Analysis of internal structure changes in black human hair keratin fibers resulting from bleaching treatments using Raman spectroscopy

NASA Astrophysics Data System (ADS)

Kuzuhara, Akio

2013-09-01

In order to investigate in detail the internal structure changes in virgin black human hair keratin fibers resulting from bleaching treatments, the structure of cross-sections at various depths of black human hair, which had been impossible due to high melanin grande content, was directly analyzed using Raman spectroscopy. The gauche-gauche-gauche (GGG) content of the sbnd SSsbnd groups existing from the cuticle region to the center of cortex region of the virgin black human hair remarkably decreased, while the gauche-gauche-trans and trans-gauche-trans contents were not changed by performing the excessive bleaching treatment. In particular, it was found that not only the β-sheet and/or random coil content, but also the α-helix content existing throughout the cortex region of virgin black human hair decreased. In addition, the transmission electron microscope observation shows that the proteins in the cell membrane complex, the cuticle and cortex of the virgin black human hair were remarkably eluted by performing the excessive bleaching treatment. From these experiments, the author concluded that the sbnd SSsbnd groups, which have a GGG conformation were decomposed and finally converted to cysteic acid, and the α-helix structure of some of the proteins existing in the keratin was changed to the random coil structure, or eluted from the cortex region, thereby leading to the reduction in the protein density of the virgin human hair after the excessive bleaching treatment.

Experimental and theoretical IR study of methyl thioglycolate, CH3OC(O)CH2SH, in different phases: Evidence of a dimer formation

NASA Astrophysics Data System (ADS)

Bava, Yanina B.; Tamone, Luciana M.; Juncal, Luciana C.; Seng, Samantha; Tobón, Yeny A.; Sobanska, Sophie; Picone, A. Lorena; Romano, Rosana M.

2017-07-01

The IR spectrum of methyl thioglycolate (MTG) was studied in three different phases, and interpreted with the aid of DFT calculations. The gas phase IR spectrum was explainable by the presence of the most stable conformer (syn-gauche-(-)gauche) only, while the IR spectrum of the liquid reveals strong intermolecular interactions, coincident with the formation of a dimeric form. The matrix-isolated spectra allow the identification of the second conformer (syn-gauche-gauche), in addition to the most stable form. The MTG dimer was also isolated by increasing the proportion of MTG in the matrix. The theoretical most stable structure of the dimer, which calculated IR spectrum agrees very well with the experimental one, is stabilized by a double interaction of the lone pair of the O atom of each of the Cdbnd O groups with the antibonding orbitals σ* (Ssbnd H).

Can acyclic conformational control be achieved via a sulfur-fluorine gauche effect?

PubMed

Thiehoff, C; Holland, M C; Daniliuc, C; Houk, K N; Gilmour, R

2015-06-01

The gauche conformation of the 1,2-difluoroethane motif is known to involve stabilising hyperconjugative interactions between donor (bonding, σ C-H ) and acceptor (antibonding, σ *C-F) orbitals. This model rationalises the generic conformational preference of F-C β -C α -X systems ( φ FCCX ≈ 60°), where X is an electron deficient substituent containing a Period 2 atom. Little is known about the corresponding Period 3 systems, such as sulfur and phosphorus, where multiple oxidation states are possible. Conformational analyses of β-fluorosulfides, -sulfoxides and -sulfones are disclosed here, thus extending the scope of the fluorine gauche effect to the 3rd Period (F-C-C-S(O) n ; φ FCCS ≈ 60°). Synergy between experiment and computation has revealed that the gauche effect is only pronounced in structures bearing an electropositive vicinal sulfur atom (S + -O - , SO 2 ).

Resolving a Long-Standing Ambiguity: the Non-Planarity of gauche-1,3-BUTADIENE Revealed by Microwave Spectroscopy

NASA Astrophysics Data System (ADS)

Martin-Drumel, Marie-Aline; McCarthy, Michael C.; Patterson, David; Eibenberger, Sandra; Buckingham, Grant; Baraban, Joshua H.; Ellison, Barney; Stanton, John F.

2016-06-01

The preferred conformation of cis-1,3-butadiene (CH_2=CH-CH=CH_2) has been of long-standing importance in organic chemistry because of its role in Diels-Alder transition states. The molecule could adopt a planar s-cis conformation, in favor of conjugations in the carbon chain, or a non-planar gauche conformation, as a result of steric interactions between the terminal H atoms. To resolve this ambiguity, we have now measured the pure rotational spectrum of this isomer in the microwave region, unambiguously establishing a significant inertial defect, and therefore a gauche conformation. Experimental measurements of gauche-1,3-butadiene and several of its isotopologues using cavity Fourier-transform microwave (FTMW) spectroscopy in a supersonic expansion and chirped-pulse FTMW spectroscopy in a 4 K buffer gas cell will be summarized, as will new quantum chemical calculations.

The Millimeterwave Spectrum of n-BUTYL Cyanide

NASA Astrophysics Data System (ADS)

Ordu, Matthias H.; Müller, Holger S. P.; Lewen, Frank; Schlemmer, Stephan; Nez, Marc Nu; Walters, Adam

2011-06-01

The rotational spectrum of n-butyl cyanide (C_4H_9CN) was measured between 75 and 130 GHz using a novel all-solid-state spectrometer with a total absorption path of 44 m. In the course of the analysis of the spectrum, about 3000 transitions were assigned and a full set of quartic centrifugal distortion parameters with some sextic and octic terms could be determined for each of the three known conformers (anti-anti, anti-gauche(methyl end) and gauche(CN end)-anti). The work was motivated by the fact that n-butyl cyanide is likely to be found in interstellar hot core environments. This is indicated by the discovery of n-propyl cyanide (C_3H_7CN), the next smaller alkyl cyanide, in the ISM. The increased accuracy of the model, which will be additionally extended by future laboratory measurements around 200 GHz, may now be employed for a prediction of the spectrum up to 300 GHz with a feasible uncertainty for astronomic line surveys. Furthermore, there are two less abundant conformers, cis-gauche-gauche and trans-gauche-gauche, which have not yet been detected in the rotational spectrum. Due to the increased sensitivity of the new spectrometer, it seems possible now for the first time to identify their sectroscopic fingerprints in the recorded data. A. Belloche, R. T. Garrod, H. S. P.Müller, K. M. Menten, C. Comito, and P. Schilke, Astronomy & Astrophysics 499, 215 (2009) R. K. Bohn, J. L. Pardus, J. August, T. Brupbacher, W. Jäger, J. Mol. Struct. 413-414, 293 (1997)

Comparison of Oxygen Gauche Effects in Poly(Oxyethylene) and Poly(ethylene terephtylene) Based on Quantum Chemistry Calculations

NASA Technical Reports Server (NTRS)

Jaffe, Richard; Han, Jie; Yoon, Do; Langhoff, Stephen R. (Technical Monitor)

1997-01-01

The so-called oxygen gauche effect in poly(oxyethylene) (POE) and its model molecules such as 1,2-dimethoxyethane (DME) and diglyme (CH3OC2H4OC2H4OCH3) is manifested in the preference for gauche C-C bond conformations over trans. This has also been observed for poly(ethylene terephthalate) (PET). Our previous quantum chemistry calculations demonstrated that the large C-C gauche population in DME is due, in part, to a low-lying tg +/- g+ conformer that exhibits a substantial 1,5 CH ... O attraction. New calculations will be described that demonstrate the accuracy of the original quantum chemistry calculations. In addition, an extension of this work to model molecules for PET will be presented. It is seen that the C-C gauche preference is much stronger in 1,2 diacetoxyethane than in DME. In addition, there exist low-lying tg +/- g+/- and g+/-g+/-g+/- conformers that exhibit 1,5 CH ... O attractions involving the carbonyl oxygens. It is expected that the -O-C-C-O- torsional properties will be quite different in these two polymers. The quantum chemistry results are used to parameterize rotational isomeric states models (RIS) and force fields for molecular dynamics simulations of these polymers.

Internal structural changes in keratin fibres resulting from combined hair waving and stress relaxation treatments: a Raman spectroscopic investigation.

PubMed

Kuzuhara, A

2016-04-01

The objective of our research was to investigate the influence of chemical treatments (reduction, stress relaxation and oxidation) on hair keratin fibres. The structure of cross-sections at various depths of virgin white human hair resulting from permanent waving treatments with stress relaxation process was directly analysed at a molecular level using Raman spectroscopy. In particular, the three disulphide (-SS-) conformations in human hair were compared by S-S band analysis. The gauche-gauche-gauche (GGG) and gauche-gauche-trans (GGT) contents of -SS- groups remarkably decreased, while the trans-gauche-trans (TGT) content was not changed by performing the reduction process with thioglycolic acid. In addition, the high-temperature stress relaxation process after reduction accelerated the disconnection of -SS- (GGG and GGT) groups in the human hair, while the low-temperature stress relaxation process after reduction accelerated the reconnection of -SS- (GGG and GGT) groups. Moreover, the S-O band intensity at 1042 cm(-1) , assigned to cysteic acid, existing in the cuticle region and the surface of the cortex region increased, while the GGG content significantly decreased by performing the oxidation process after the reduction and the high-temperature stress relaxation processes. The author concluded that the high-temperature relaxation process after reduction accelerated the disconnection of -SS- (GGG and GGT) groups, thereby leading to the remarkable local molecular disorganization (an increase in the cysteic acid content and a decrease in the GGG content) on the cuticle and cortex cells during the oxidation process. © 2015 Society of Cosmetic Scientists and the Société Française de Cosmétologie.

Different Conformations of Surface Cellulose Molecules in Native Cellulose Microfibrils Revealed by Layer-by-Layer Peeling.

PubMed

Funahashi, Ryunosuke; Okita, Yusuke; Hondo, Hiromasa; Zhao, Mengchen; Saito, Tsuguyuki; Isogai, Akira

2017-11-13

Layer-by-layer peeling of surface molecules of native cellulose microfibrils was performed using a repeated sequential process of 2,2,6,6-tetramethylpiperidine-1-oxyl radical-mediated oxidation followed by hot alkali extraction. Both highly crystalline algal and tunicate celluloses and low-crystalline cotton and wood celluloses were investigated. Initially, the C6-hydroxy groups of the outermost surface molecules of each algal cellulose microfibril facing the exterior had the gauche-gauche (gg) conformation, whereas those facing the interior had the gauche-trans (gt) conformation. All the other C6-hydroxy groups of the cellulose molecules inside the microfibrils contributing to crystalline cellulose I had the trans-gauche (tg) conformation. After surface peeling, the originally second-layer molecules from the microfibril surface became the outermost surface molecules, and the original tg conformation changed to gg and gt conformations. The plant cellulose microfibrils likely had disordered structures for both the outermost surface and second-layer molecules, as demonstrated using the same layer-by-layer peeling technique.

Rotational barriers. 1. 1,2-dihaloethanes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wiberg, K.B.; Murcko, M.A.

1987-06-18

The rotational barrier about the C-C bond of 1,2-dichloroethane has been calculated by using several basis sets (4-31G, 6-31G*, 6-31+G*, and 6-31++G**) and including electron correlation. Corrections for zero-point energy differences, and the differences in enthalpy change from 0 to 298 K, were made by using the calculated geometries and vibrational frequencies. The trans/gauche energy difference was found to be 1.39 kcal/mol as compared to the observed value, 1.1 +/- 0.1 kcal/mol. The intramolecular interactions in the several rotamers are discussed. The trans/gauche energy difference for 1,2-difluoroethane also was calculated (MP3/6-311++G**) and was found to be 0.76 kcal/mol favoring themore » gauche conformer, again in good agreement with the experimental value of 0.57 +/- 0.09 kcal/mol. The trend in trans/gauche energy differences in the series n-butane, 1,2-dichloroethane, 1,2-difluoroethane is noted.« less

Conformational analyses of 2,3-dihydroxypropanoic acid as a function of solvent and ionization state as determined by NMR spectroscopy.

PubMed

Drake, Michael D; Harsha, Alex K; Terterov, Sergei; Roberts, John D

2006-03-01

Vicinal (1)H--(1)H coupling constants were used to determine the conformational preferences of 2,3-dihydroxypropanoic acid (1) (DL-glyceric acid) in various solvents and its different carboxyl ionization states. The stereospecific assignments of J(12) and J(13) were confirmed through the point-group substitution of the C-3 hydrogen with deuterium, yielding rac-(2SR,3RS)-[3-(2)H]-1, and the observation of only J(13) in the (1)H NMR spectra. While hydrogen bonding and steric strain may be expected to drive the conformational equilibrium, their role is overshadowed by a profound gauche effect between the vicinal hydroxyl groups that mimics other substituted ethanes, such as 1,2-ethanediol and 1,2-difluoroethane. At low pH, the conformational equilibrium is heavily weighted toward the gauche-hydroxyl rotamers with a range of 81% in DMSO-d(6) to 92% in tert-butyl alcohol-d(10). At high pH, the equilibrium exhibits a larger dependence upon the polarity and solvating capability of the medium, although the gauche effect still dominates in D(2)O, 1,4-dioxane-d(8), methanol-d(4), and ethanol-d(6) (96, 89, 85, and 83% gauche-hydroxyls respectively). The observed preference for the gauche-hydroxyl rotamers is believed to stem primarily from hyperconjugative sigma(C--H) --> sigma*(C--OH) interactions.

Spectra and structure of silicon containing compounds. XXXII. Raman and infrared spectra, conformational stability, vibrational assignment and ab initio calculations of n-propylsilane-d0 and Si-d3.

PubMed

Durig, James R; Pan, Chunhua; Guirgis, Gamil A

2003-03-15

The infrared (3100-40 cm(-1)) and Raman (3100-20 cm(-1)) spectra of gaseous and solid n-propylsilane, CH(3)CH(2)CH(2)SiH(3) and the Si-d(3) isotopomer, CH(3)CH(2)CH(2)SiD(3), have been recorded. Additionally, the Raman spectra of the liquids have been recorded and qualitative depolarization values obtained. Both the anti and gauche conformers have been identified in the fluid phases but only the anti conformer remains in the solid. Variable temperature (-105 to -150 degrees C) studies of the infrared spectra of n-propylsilane dissolved in liquid krypton have been recorded and the enthalpy difference has been determined to be 220+/-22 cm(-1) (2.63+/-0.26 kJ mol(-1)) with the anti conformer the more stable form. A similar value of 234+/-23 cm(-1) (2.80+/-0.28 kJ mol(-1)) was obtained for deltaH for the Si-d(3) isotopomer. At ambient temperature it is estimated that there is 30+/-2% of the gauche conformer present. The potential function governing the conformation interchange has been estimated from the far infrared spectral data, the enthalpy difference, and the dihedral angle of the gauche conformer, which is compared to the one predicted from ab initio MP2/6-31G(d) calculations. The barriers to conformational interchange are: 942, 970 and 716 cm(-1) for the anti to gauche, gauche to gauche, and gauche to anti conformers, respectively. Relatively complete vibrational assignments are proposed for both the n-propylsilane-d(0) and Si-d(3) molecules based on the relative infrared and Raman spectral intensities, infrared band contours, depolarization ratios, and normal coordinate calculations. The geometrical parameters, harmonic force constants, vibrational frequencies, infrared intensities, Raman activities and depolarization ratios, and energy differences have been obtained for the anti and gauche conformers from ab initio MP2/6-31G(d) calculations. Structural parameters and energy differences have also been obtained utilizing the larger 6-311 + G(d,p) and 6-311 + G(2d,2p) basis sets. From the isolated Si-H stretching frequency from the Si-d(2) isotopomer the r(0) distances of 1.484 and 1.485 A have been determined for the SiH(s) and SiH(a) bonds, respectively, for the anti conformer, and 1.486 A for the SiH bond for the gauche conformer. Utilizing previously reported microwave rotational constants for the anti conformer and the determined SiH distances along with ab initio predicted parameters 'adjusted r(0)' parameters have been obtained for the anti conformer. The results are discussed and compared to those obtained for some similar molecules. Copyright 2002 Elsevier Science B.V.

Spectra and structure of silicon containing compounds. XXXII. Raman and infrared spectra, conformational stability, vibrational assignment and ab initio calculations of n-propylsilane-d 0 and Si-d 3

NASA Astrophysics Data System (ADS)

Durig, James R.; Pan, Chunhua; Guirgis, Gamil A.

2003-03-01

The infrared (3100-40 cm -1) and Raman (3100-20 cm -1) spectra of gaseous and solid n-propylsilane, CH 3CH 2CH 2SiH 3 and the Si-d 3 isotopomer, CH 3CH 2CH 2SiD 3, have been recorded. Additionally, the Raman spectra of the liquids have been recorded and qualitative depolarization values obtained. Both the anti and gauche conformers have been identified in the fluid phases but only the anti conformer remains in the solid. Variable temperature (-105 to -150 °C) studies of the infrared spectra of n-propylsilane dissolved in liquid krypton have been recorded and the enthalpy difference has been determined to be 220±22 cm -1 (2.63±0.26 kJ mol -1) with the anti conformer the more stable form. A similar value of 234±23 cm -1 (2.80±0.28 kJ mol -1) was obtained for Δ H for the Si-d 3 isotopomer. At ambient temperature it is estimated that there is 30±2% of the gauche conformer present. The potential function governing the conformation interchange has been estimated from the far infrared spectral data, the enthalpy difference, and the dihedral angle of the gauche conformer, which is compared to the one predicted from ab initio MP2/6-31G(d) calculations. The barriers to conformational interchange are: 942, 970 and 716 cm -1 for the anti to gauche, gauche to gauche, and gauche to anti conformers, respectively. Relatively complete vibrational assignments are proposed for both the n-propylsilane-d 0 and Si-d 3 molecules based on the relative infrared and Raman spectral intensities, infrared band contours, depolarization ratios, and normal coordinate calculations. The geometrical parameters, harmonic force constants, vibrational frequencies, infrared intensities, Raman activities and depolarization ratios, and energy differences have been obtained for the anti and gauche conformers from ab initio MP2/6-31G(d) calculations. Structural parameters and energy differences have also been obtained utilizing the larger 6-311+G(d,p) and 6-311+G(2d,2p) basis sets. From the isolated SiH stretching frequency from the Si-d 2 isotopomer the r0 distances of 1.484 and 1.485 Å have been determined for the SiH s and SiH a bonds, respectively, for the anti conformer, and 1.486 Å for the SiH bond for the gauche conformer. Utilizing previously reported microwave rotational constants for the anti conformer and the determined SiH distances along with ab initio predicted parameters 'adjusted r0' parameters have been obtained for the anti conformer. The results are discussed and compared to those obtained for some similar molecules.

Can acyclic conformational control be achieved via a sulfur–fluorine gauche effect?† †Electronic supplementary information (ESI) available. CCDC 1048074–1048078. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc00871a

PubMed Central

Thiehoff, C.; Holland, M. C.; Daniliuc, C.

2015-01-01

The gauche conformation of the 1,2-difluoroethane motif is known to involve stabilising hyperconjugative interactions between donor (bonding, σC–H) and acceptor (antibonding, σ*C–F) orbitals. This model rationalises the generic conformational preference of F–Cβ–Cα–X systems (φFCCX ≈ 60°), where X is an electron deficient substituent containing a Period 2 atom. Little is known about the corresponding Period 3 systems, such as sulfur and phosphorus, where multiple oxidation states are possible. Conformational analyses of β-fluorosulfides, -sulfoxides and -sulfones are disclosed here, thus extending the scope of the fluorine gauche effect to the 3rd Period (F–C–C–S(O)n; φFCCS ≈ 60°). Synergy between experiment and computation has revealed that the gauche effect is only pronounced in structures bearing an electropositive vicinal sulfur atom (S+–O–, SO2). PMID:29511517

The raman spectrum of biosynthetic human growth hormone. Its deconvolution, bandfitting, and interpretation

NASA Astrophysics Data System (ADS)

Tensmeyer, Lowell G.

1988-05-01

The Raman spectrum of amorphous biosynthetic human growth hormone, somatotropin, has been measured at high signal-to-noise ratios, using a CW argon ion laser and single channel detection. The rms signal-to-noise ratio varies from 1800:1 in the Amide I region near 1650 cm -1 region, to 500:1 in the disulfide stretch region near 500 cm -1. Component Raman bands have been extracted from the entire spectral envelope from 1800-400 cm -1, by an interactive process involving both partial deconvolution and band-fitting. Interconsistency of all bands has been achieved by multiple overlapping of adjacent regions that had been isolated for the band-fitting programs. The resulting areas of the Raman component bands have been interpreted to show the ratios of peptide conformations in the hormone: 64% α-helix, 24% β-sheet, 8% β-turns and 4% γ-turns. Analysis of the tyrosine region, usually described as a Fermi resonance doublet near ˜830-850 cm -1, shows four bands, at 825, 833, 853, and 859 cm -1 in this macromolecule. Integrated intensities of these bands (2:2:2:2) are interpreted to show that only half of the eight tyrosine residues function as hydrogen-bond bridges via the acceptance of protons. Both disulfide bridges fall within the frequency ranges for normal, unstressed SS bonds: The 511 and 529 cm -1 bands are indicative of the gauche-gauche-gauche and trans-gauche-gauche conformations, respectively.

a 480 MHz Chirped-Pulse Fourier-Transform Microwave Spectrometer: Construction and Measurement of the Rotational Spectra of Divinyl Silane and 3,3-DIFLUOROPENTANE

NASA Astrophysics Data System (ADS)

Obenchain, Daniel A.; Steber, Amanda L.; Elliott, Ashley A.; Peebles, Rebecca A.; Peebles, Sean A.; Wurrey, Charles J.; Guirgis, Gamil A.

2010-06-01

A chirped-pulse Fourier-transform microwave (CP-FTMW) spectrometer based on the original Pate design has been constructed to allow analysis of any 480 MHz region in the 7 - 18 GHz range. A 1 μs chirped-pulse (0 - 240 MHz) from an arbitrary function generator is mixed with output from a microwave synthesizer and used to polarize a supersonic gas expansion; the resulting free induction decay is collected over 20 μs and Fourier-transformed on a 500 MHz oscilloscope to produce a rotational spectrum. A variety of molecules have now been studied with this instrument and results will be presented for numerous conformers of divinyl silane (predicted μtotal = 0.6 - 0.7 D) and the more polar 3,3-difluoropentane (predicted μtotal = 2.5 - 2.8 D). Two of the three possible conformers of divinyl silane were assigned (both having a C_1=C_2-Si-C_3 dihedral angle of -120° and a {C_2-Si-C_3=C_4} dihedral of either 0° (C_1 symmetry) or -120° (C_2 symmetry)). For 3,3-difluoropentane, three of the four possible {conformers} were identified: anti-gauche (C_1), gauche-gauche (C_2) and anti-anti (C2v). While rotational spectra for only the silicon isotopologues were observed for divinyl silane, measurement of the 13C spectra of 3,3-difluoropentane allowed heavy atom structure determinations for the anti-gauche and gauche-gauche conformers. Initial assignments of all spectra were made on the CP-FTMW {spectrometer}, and a Balle-Flygare FTMW spectrometer was used to compare frequencies of measured transitions and also to provide Stark effect data. Substitution (r_s) and inertial fit (r_0) structures will be compared with computational data and instrumental details will be presented. G.G. Brown, B.C. Dian, K.O. Douglass, S.M. Geyer, S.T. Shipman, B.H. Pate, Rev. Sci. Instrum., 79, (2008), 053103.

Observation of conformational changes in ethylene glycol–water complexes by FTIR–ATR spectroscopy and computational studies

NASA Astrophysics Data System (ADS)

Guo, Yu-Cong; Cai, Chen; Zhang, Yun-Hong

2018-05-01

Attenuated total reflectance - Fourier transform infrared (ATR-FTIR) spectra of ethylene glycol-water (abbreviated as EG-H2O) mixtures were measured at 298 K with the ethylene glycol molar ratio ranging from 0.01 to 1400. The two bands at 1033 and 1082 cm-1 were assigned to be the C-C stretching vibration modes related to the trans- and gauche- conformation of EG. The absorbance of the two bands was found to be sensitive to the molar ratios. We made theoretical calculation for ten conformations of the EG molecules to understand the conformational transformation of EG molecules changing with EG-H2O molar ratios. The absorbance ratio (A1033/A1082) was used to determine the trans- and gauche- conformation ratio with the calculated (AνO-C-C-O-T/AνO-C-C-O-G) as standard. When the molar ratio of water and EG (xH2O/xEG) is smaller than 0.4, strong associations formed by the intermolecular hydrogen bonds were dominant in the solutions and the proportion of gauche- conformation was about 0.5. Within the region of 0.4< xH2O/xEG < 20, the intermolecular hydrogen bonds structure between EG molecules were broken by the water molecules and the structure of most EG molecules changed from trans- to gauche- conformation. The blue shift of the peaks indicated the increasing hydrogen bonding between water and EG. When xH2O/xEG is larger than 20, the monomers of molecules started to appear in the EG-H2O solution. The gauche- conformation was the dominated conformation in the dilute EG-H2O solution with proportion of 0.87. In the CH2 rocking vibration (δC-H) region, the computational results showed that the majority bands in this region were influenced by the gauche- conformation which can be divided into group G1 or G2. The transformation between the gauche- conformations of EG molecules can be studied by combining the experimental results and the computational results, The proportion of G1 for the EG-rich solution was about 0.71 while it decreased to 0.55 for the H2O-rich solution.

Conformational stability from temperature-dependent fourier transform infrared spectra of noble gas solutions, r0 structural parameters, and barriers to internal rotation for ethylamine.

PubMed

Durig, James R; Zheng, Chao; Gounev, Todor K; Herrebout, Wouter A; van der Veken, Benjamin J

2006-05-04

Variable temperature (-55 to -145 degrees C) studies of the infrared spectra (3500 to 100 cm(-1)) of ethylamine, CH(3)CH(2)NH(2), dissolved in liquid krypton and/or xenon have been recorded. From these data, the enthalpy differences have been determined to be 54 +/- 4 cm(-1) (0.65 +/- 0.05 kJ/mol), with the trans conformer (methyl group relative to the lone pair of electrons on nitrogen) being the more stable form. It is estimated that there is 61 +/- 1% of the doubly degenerate gauche form present at ambient temperature. The conformational energetics have been calculated with the Møller-Plesset perturbation method to the second order (MP2(full)) and the fourth order (MP4(SDTQ)) as well as with density functional theory by the B3LYP method utilizing a variety of basis sets. Basis sets with diffuse functions lead to incorrect prediction of the conformational stability. On the basis of the frequencies of the torsional transitions along with the determined experimental enthalpy difference and gauche dihedral angle, the potential function governing conformational interchange has been obtained, and the determined Fourier cosine coefficients are V(1) = -207 +/- 48, V(2) = 320 +/- 67, V(3) = 1072 +/- 25, V(4) = 55 +/- 11, and V(5) = -96 +/- 28 cm(-1), with a trans-to-gauche barrier of 1286 cm(-1), and a gauche-to-gauche barrier of 715 cm(-1). The 3-fold methyl rotational barriers have been determined to be 1241 +/- 4 and 1281 +/- 10 cm(-1) for the gauche and trans conformers, respectively. By utilizing the previously reported microwave rotational constants combined with the structural parameters predicted at the MP2(full)/6-311+ G(d,p) level, adjusted r(0) structural parameters have been obtained. A complete vibrational assignment is given for the trans conformer, which is supported by normal coordinate calculations utilizing scaled force constants from ab initio B3LYP/6-311++G(3df,3pd) calculations. Proposed assignments are also made for the fundamentals of the gauche conformer. The results of these spectroscopic and theoretical studies are discussed and compared to the corresponding results for similar molecules.

Conformational stability, barriers to internal rotation, normal coordinate analyses, and vibrational assignments of bromoacetyl halides

NASA Astrophysics Data System (ADS)

Durig, J. R.; Phan, H. V.; Little, T. S.

1989-09-01

The Raman (3200-10 cm -1) and IR (3200-30 cm -1) spectra of bromoacetyl fluoride, bromoacetyl chloride and bromoacetyl bromide in the gaseous and annealed solid phases have been recorded. Additionally, the Raman spectra and the qualitative depolarization measurements for each molecule in the liquid phase have been obtained. All of these data indicate that these bromoacetyl halides exist in mixtures of two conformers, with the trans rotamer (halogen atoms oriented trans to one another) being the thermodynamically preferred, and the gauche conformation being the high energy form. From the studies of Raman spectra at different temperatures, the enthalpy differences have been determined for the gaseous and liquid phases, respectively, to be 185 ± 23 cm -1 (0.53 ± 0.06 kcal mol -1) and 249 ± 27 cm -1 (0.71 ± 0.08 kcal mol -1) for bromoacetyl fluoride, 391 ± 130 cm -1 (1.12 ± 0.37 kcal mol -1) and 317 ± 27 cm -1 (0.91 ± 0.08 kcal mol -1) for bromoacetyl chloride, and 341 ± 48 cm -1 (0.98 ± 0.14 kcal mol -1) and 286 ± 26 cm -1 (0.82 ± 0.07 kcal mol -1) for bromoacetyl bromide. Potential functions have been calculated for the fluoride and chloride from the observed asymmetric torsional frequencies and values of 580 ± 11 cm -1 (1.66 ± 0.03 kcal mol -1), 359 ± 8 cm -1 (1.03 ± 0.02 kcal mol -1), and 387 ± 16 cm -1 (1.11 ± 0.04 kcal mol -1) for the trans to gauche, gauche to gauche to gauche and gauche to trans barrier, respectively, were determined for bromoacetyl fluoride. The corresponding quantities were 967 ± 30 cm -1 (2.76 ± 0.08 kcal mol -1), 696 ± 67 cm -1 (1.99 ± 0.19 kcal mol -1), and 663 ± 30 cm -1 (1.61 ± 0.08 kcal mol -1) for bromoacetyl chloride. These potential functions are consistent with the dihedral angle of the gauche conformation being 120° and 117° for the fluoride and chloride, respectively. Complete vibrational assignments have been carried out based on the observed IR band contours, the depolarization ratios, and group frequencies. The results are compared to those for other haloacetyl halides.

Conformational and stereoelectronic investigation in 1,2-difluoropropane: The gauche effect

NASA Astrophysics Data System (ADS)

Bitencourt, Michelle; Freitas, Matheus P.; Rittner, Roberto

2007-09-01

The effect of attaching an additional fluorine atom at C-2 in 1-fluoropropane (FP), giving 1,2-difluoropropane (DFP), on its conformational equilibrium, is theoretically evaluated. This substitution causes critical implications on the conformer stabilities of DFP (TG, GT and GG conformations) and the steric and electrostatic interactions should favor the conformer with fluorine atoms trans. However, the gauche effect plays a major role in describing the energies balance in DFP, shifting the equilibrium towards the conformation in which the two fluorine atoms are gauche. The origin of this effect is discussed through an NBO analysis, which allows the evaluation of both classical and non-classical (hyperconjugation and bent bonds) interactions as the prevailing factors governing the conformational equilibrium of molecules containing the 1,2-difluoroethane fragment.

Interplay between intramolecular and intermolecular structures of 1,1,2,2-tetrachloro-1,2-difluoroethane

NASA Astrophysics Data System (ADS)

Rovira-Esteva, M.; Murugan, N. A.; Pardo, L. C.; Busch, S.; Tamarit, J. Ll.; Pothoczki, Sz.; Cuello, G. J.; Bermejo, F. J.

2011-08-01

We report on the interplay between the short-range order of molecules in the liquid phase of 1,1,2,2-tetrachloro-1,2-difluoroethane and the possible molecular conformations, trans and gauche. Two complementary approaches have been used to get a comprehensive picture: analysis of neutron-diffraction data by a Bayesian fit algorithm and a molecular dynamics simulation. The results of both show that the population of trans and gauche conformers in the liquid state can only correspond to the gauche conformer being more stable than the trans conformer. Distinct conformer geometries induce distinct molecular short-range orders around them, suggesting that a deep intra- and intermolecular interaction coupling is energetically favoring one of the conformers by reducing the total molecular free energy.

Conformational analysis of some N,N-diethyl-2-[(4‧-substituted) phenylthio] acetamides

NASA Astrophysics Data System (ADS)

Vinhato, Elisângela; Olivato, Paulo R.; Zukerman-Schpector, Julio; Dal Colle, Maurizio

2013-11-01

The conformational analysis of some N,N-diethyl-2[(4‧-substituted)phenylthio]acetamides bearing the substituents OMe 1, Me 2, H 3, Cl 4, Br 5 and NO26, was performed by νCO IR analysis, along with B3LYP/6-311++G(d,p) and Polarisable Continuum Model (PCM) calculations, as well as NBO analysis for 1, 3, and 6 and X-ray diffraction for 4. The results of the calculations indicated the existence of two stable conformation pairs, i.e. gauche (anti; syn) (most stable) and cis (anti; syn) in the gas phase. The gauche conformers were less polar with respect to the cis ones for 1 and 3, but more polar for 6. The most intense IR carbonyl doublet component observed at the lower frequency can be ascribed to the gauche conformers g(anti; syn) for 3-6 in n-C6H14, which is in agreement with the gauche and cis relative stabilities and frequencies resulting from the PCM calculations. Similarly, the single IR band for 1 and 2 in n-hexane may be attributed to the gauche conformers. The PCM calculations compared well with the IR data for the compounds in solution, showing that there is a progressive increase of the cis/gauche population ratio as the solvent polarity increases. The NBO analysis indicated that the gauche(anti; syn) conformation in the gas phase was stabilized by the relevant LPS4 → πC 2dbnd O 1∗, πC 2dbnd O 1 → σC 3sbnd S 4∗ , σC 3sbnd S 4 → πC 2dbnd O 1∗, πC 2dbnd O 1∗ → σC 3sbnd S 4∗, and LPO1 →σ∗ C11sbnd H28 orbital interactions, which were absent in the cis(anti; syn) conformer. On the contrary, the cis conformer for derivatives 1, 3, and 6 were stabilized by the σC 3 -S 4∗ →σ∗ C2sbnd N5 orbital interaction (through bond coupling), along with the additional LPO1 →σ∗ S4sbnd C10 interaction for 6. Moreover, the electrostatic repulsion between the Cδ+sbnd Sδ- and Cδ+dbnd Oδ- dipoles (Repulsive Field Effect) contributed to both the larger destabilization and increase of the νCO frequency of the cis conformer with respect to the gauche conformer. X-ray single crystal analysis indicates that compound 4 assumes the c2(anti) conformation in the solid state, which is the conformation obtained by compound 6 in the gas phase. To obtain the largest energy gain, the molecules were arranged in the crystal in a six-molecules synthon mediated by Csbnd H⋯O and Cl⋯Cl interactions, where the chlorine atoms were related by a crystallographic inversion center.

1,2-Difluoroethane: the angular dependance on 1J(CF) coupling constants is independent of hyperconjugation.

PubMed

Freitas, Matheus P; Bühl, Michael; O'Hagan, David

2012-02-28

1,2-Difluoroethane is widely recognised to adopt a lower energy gauche rather than anti conformation; this gauche effect has its origin in hyperconjugation; however, surprisingly the (1)J(CF) coupling constant is not influenced by hyperconjugation; instead, its magnitude changes with the overall molecular dipole. This journal is © The Royal Society of Chemistry 2012

Observation of Trans-Ethanol and Gauche-Ethanol Complexes with Benzene Using Matrix Isolation Infrared Spectroscopy

NASA Astrophysics Data System (ADS)

Amicangelo, Jay; Silbaugh, Matthew J.

2016-06-01

Ethanol can exist in two conformers, one in which the OH group is trans to the methyl group (trans-ethanol) and the other in which the OH group is gauche to the methyl group (gauche-ethanol). Matrix isolation infrared spectra of ethanol deposited in 20 K argon matrices display distinct infrared peaks that can be assigned to the trans-ethanol and gauche-ethanol conformers, particularly with the O-H stretching vibrations. Given this, matrix isolation experiments were performed in which ethanol (C_2H_5OH) and benzene (C_6H_6) were co-deposited in argon matrices at 20 K in order to determine if conformer specific ethanol complexes with benzene could be observed in the infrared spectra. New infrared peaks that can be attributed to the trans-ethanol and gauche-ethanol complexes with benzene have been observed near the O-H stretching vibrations of ethanol. The initial identification of the new infrared peaks as being due to the ethanol-benzene complexes was established by performing a concentration study (1:200 to 1:1600 S/M ratios), by comparing the co-deposition spectra with the spectra of the individual monomers, by matrix annealing experiments (35 K), and by performing experiments using isotopically labeled ethanol (C_2D_5OD) and benzene (C_6D_6). Quantum chemical calculations were also performed for the C_2H_5OH-C_6H_6 complexes using density functional theory (B3LYP) and ab initio (MP2) methods. Stable minima were found for the both the trans-ethanol and gauche-ethanol complexes with benzene at both levels of theory and were predicted to have similar interaction energies. Both complexes can be characterized as H-π complexes, in which the ethanol is above the benzene ring with the hydroxyl hydrogen interacting with the π cloud of the ring. The theoretical O-H stretching frequencies for the complexes were predicted to be shifted from the monomer frequencies and from each other and these results were used to make the conformer specific infrared peak assignments. Barnes, A. J.; Hallam, H. E. Trans. Faraday Soc., 1970, 66, 1932-1940.

Acyl chain conformational ordering of individual components in liquid-crystalline bilayers of mixtures of phosphatidylcholines and phosphatidic acids. A comparative FTIR and 2H NMR study

NASA Astrophysics Data System (ADS)

Ziegler, Wolfgang; Blume, Alfred

1995-09-01

The conformational ordering of the acyl chains of all possible binary 1:1 mixtures containing the phospholipids DMPC, DMPA, DPPC, and DPPA was investigated using FTIR and 2H NMR spectroscopy. One of the components was always labelled with perdeuterated chains to be able to observe the individual behaviour of the two components. From the temperature dependence of the frequencies of the symmetric and antisymmetric CH 2- and CD 2-stretching vibrations the transition temperatures were determined. The integral intensities of the conformation sensitive CH 2-wagging bands at ca. 1368 cm -1(gtg' and gtg sequences), 1356 cm -1 (double gauche), and 1342 cm -1 (end gauche) can be converted to numbers of gauche conformers per acyl chain using calibration factors published by Senak et al. J. Phys. Chem. 95 (1991) 2565. The 2H NMR quadrupolar splittings of the CD 2-segments of the perdeuterated lipid components are affected not only by trans-gauche isomerizations but also by long axis rotations and restricted wobbling motions of the acyl chains. The values of the average gauche probability overlinep3 from FTIR spectroscopy and the average order parameters overlineSCD, the order parameter of the terminal methyl groups SCDCD 3 and the average order parameter for the plateau region overlineSCDPlat of components in the mixtures are compared to those of the pure lipids evaluated in a previous publication Tuchtenhagen et al. Eur. Biophys. J. 23 (1994) 323. The conformational behaviour of lipids in mixtures is mainly influenced by head groups interactions, PAs always being more ordered than the corresponding PCs. Depending on absolute chain length and on chain length differences between the two components different conformational behaviour is observed for the two components in the mixtures, indicating non-ideal mixing and formation of micro-domains in the liquid-crystalline phase. Increases in order at the chain ends with a concomitant decrease in probabilities for end gauche conformations give hints to chain interdigitation in the liquid-crystalline phase.

The structure of 3'-O-anthraniloyladenosine, an analogue of the 3'-end of aminoacyl-tRNA.

PubMed Central

Nawrot, B; Milius, W; Ejchart, A; Limmer, S; Sprinzl, M

1997-01-01

3'-O-Anthraniloyladenosine, an analogue of the 3'- terminal aminoacyladenosine residue in aminoacyl-tRNAs, was prepared by chemical synthesis, and its crystal structure was determined. The sugar pucker of 3'-O-anthraniloyladenosine is 2'-endo resulting in a 3'-axial position of the anthraniloyl residue. The nucleoside is insynconformation, which is stabilized by alternating stacking of adenine and benzoyl residues of the neighboring molecules in the crystal lattice. The conformation of the 5'-hydroxymethylene in 3'-O- anthraniloyladenosine is gauche-gauche. There are two intramolecular and two intermolecular hydrogen bonds and several H-bridges with surrounding water molecules. The predominant structure of 3'-O-anthraniloyladenosine in solution, as determined by NMR spectroscopy, is 2'-endo,gauche-gauche and anti for the sugar ring pucker, the torsion angle around the C4'-C5'bond and the torsion angle around the C1'-N9 bond, respectively. The 2'-endo conformation of the ribose in 2'(3')-O-aminoacyladenosine, which places the adenine and aminoacyl residues in equatorial and axial positions, respectively, could serve as a structural element that is recognized by enzymes that interact with aminoacyl-tRNA or by ribosomes to differentiate between aminoacylated and non-aminoacylated tRNA. PMID:9023103

Conformational Studies of 1-OCTYNE from Rotational Spectroscopy

NASA Astrophysics Data System (ADS)

Maturo, Mark P.; Obenchain, Daniel A.; Melchreit, Robert; Cooke, S. A.; Novick, Stewart E.

2017-06-01

Alkanes of the form CH_3(CH_2)_nCH_3 generally favor ground state geometries that have co-planar carbon atoms. In this study, we have looked at a long chain hydrocarbon with a terminal carbon-carbon triple bond, viz., 1-octyne. Guided by the results of the 1-hexyne studies, three possible low energy conformers were studied which we reference as anti-anti (AA, straight chain), anti-gauche (AG, terminal methyl group is gauche), and gauche-anti (GA, ethyl group is gauche). An initial broadband chirp-pulse was performed between 7-13 GHz and a total of sixty-eight transitions were fit. Additional measurements on a Balle Flygare cavity instrument yielded an additional seventy-three lines belonging to three of the conformers. Transitions for all 8 of the singly substituted ^{13}C isotopologues, in natural abundance, have also been observed for the AA conformer. Ab-initio optimizations at the MP2/6-311++g(2d,2p) level of theory and basis set for these three conformers will be compared to experimental rotational constants. Structure determinations of the AA conformer will also be discussed. Atticks, K.; Bohn, R. K.; Michaels H. H. Int'l J. of Quantum Chem. 2001, 85, 514-519; Utzat, K.; Bohn, R. K.; Michaels H. H. J. Mol. Struct. 2007, 841, 22-27

A study of the conformational isomerism of 1-iodobutane by high resolution rotational spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arsenault, Eric A.; Obenchain, Daniel A.; Blake, Thomas A.

2017-05-01

The first microwave study of 1-iodobutane, performed by Steinmetz et al.in 1977) led to the determination of the B + C parameter for the anti-anti­and gauche-anti-conformers. Nearly 40 years later, this reinvestigation of 1- iodobutane, by high-resolution microwave spectroscopy, led to the determina­tion of rotational constants, centrifugal distortion constants, nuclear quadrupole coupling constants (NQCCs), and nuclear-sp rotation constants belonging to both of the two previously mentioned conformers, in addition to the gauche­ gauche-conformer, which was observed in this frequency regime for the first time. Comparisons between the three conformers of 1-iodobutanc and other iodo- and bromoalkanes are made, specifically throughmore » an analysis of the nuclear quadrupole coupling constants belonging to the iodine and bromine atoms in the respective chemical environments.« less

A Study of 2-Iodobutane by Rotational Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arsenault, Eric A.; Obenchain, Daniel A.; Choi, Yoon Jeong

2016-09-15

The rotational transitions belonging to 2-iodobutane (sec-butyl-iodide, CH3CHICH2CH3) have been measured over the frequency range 5.5-16.5 GHz via jet-pulsed Fourier transform microwave (FTMW) spectroscopy. The complete nuclear quadrupole coupling tensor of iodine, ¬, has been obtained for the gauche (g)-, anti (a)-, and gauche0 (g0)-conformers, as well as the four 13C isotopologues of the gauche species. Rotational constants, centrifugal distortion constants, quadrupole coupling constants, and nuclear spin-rotation constants were determined for each species. Changes in the ¬ of the iodine nucleus, resulting from conformational and isotopic dierences, will be discussed. Isotopic substitution of g-2-iodobutane allowed for a rs structure tomore » be determined for the carbon backbone. Additionally, isotopic substitution, in conjunction with an ab initio structure, allowed for a t of various r0 structural parameters belonging to g-2-iodobutane.« less

Excited-state dynamics of bis(9-fluorenyl)methane and its derivative 9-(9-ethylfluorenyl)-9'-fluorenylmethane: steric effect on energetics and dynamics of ground- and excited-state conformations.

PubMed

Boo, Bong Hyun; Lee, Minyung; Jeon, Ki-Seok; Kim, Seung-Joon

2014-03-27

Intramolecular excimer formation of bis(9-fluorenyl)methane (BFM) and 9-(9'-ethylfluorenyl)-9-fluorenylmethane (EFFM), in which an ethyl group is substituted to a 9-H atom in BFM, was studied by means of steady-state and time-resolved fluorescence. Ab initio and DFT calculations enabled the prediction of three conformers as stable species of orthogonal, trans-gauche, and gauche-gauche. The theoretical and experimental results reveal that the substitution effect is also found to appreciably influence the energies, spectroscopy, and kinetics associated with the interconversion of various conformers of the diaryl compounds. We have not observed the rising components in the excimer fluorescence decay of BFM and EFFM in PMMA as observed in the liquid solutions probably because of the existence of the sandwich conformer responsible for the excimer fluorescence prior to the laser irradiation.

A study of the conformational isomerism of 1-iodobutane by high resolution rotational spectroscopy

DOE PAGES

Arsenault, Eric A.; Obenchain, Daniel A.; Blake, Thomas A.; ...

2017-05-01

The first microwave study of 1-iodobutane, performed by Steinmetz et al. in 1977, led to the determination of the B+C parameter for the anti-anti- and gauche-anti-conformers. Nearly 40 years later, in this paper this reinvestigation of 1-iodobutane, by high-resolution microwave spectroscopy, led to the determination of rotational constants, centrifugal distortion constants, nuclear quadrupole coupling constants (NQCCs), and nuclear-spin rotation constants belonging to both of the two previously mentioned conformers, in addition to the gauche-gauche-conformer, which was observed in this frequency regime for the first time. Finally, comparisons between the three conformers of 1-iodobutane and other iodo- and bromoalkanes are made,more » specifically through an analysis of the nuclear quadrupole coupling constants belonging to the iodine and bromine atoms in the respective chemical environments.« less

Pyélonéphrite xanthogranulomateuse bilatérale focale : à propos d’un cas

PubMed Central

El Yacoubi, Souhail; Ziouziou, Imad; Zizi, Mohamed; Jahid, Ahmed; Karmouni, Tariq; El Khader, Khalid; Koutani, Abdellatif; Andaloussi, Ahmed Iben Attya

2014-01-01

Résumé Nous présentons l’observation clinique d’un cas rare de pyélonéphrite xanthogranulomateuse (PXG) bilatérale chez un jeune patient âgé de 17 ans. La découverte progressive de l’infection a débuté par l’apparition de lombalgies bilatérales évoluant depuis un mois, sans autre signe associé. L’urotomodensitométrie penchait en faveur de deux masses rénales bilatérales, soit une masse polaire inférieure droite et une masse polaire supérieure gauche, toutes deux de densité tissulaire. Une biopsie échoguidée a suggéré la présence d’une réaction inflammatoire non spécifique. Une néphrectomie partielle polaire inférieure droite a été effectuée devant la forte présomption de tumeurs rénales malignes. Finalement, l’histologie a orienté le diagnostic vers une PXG. Il s’agit, à notre connaissance, du sixième cas de PXG focale bilatérale rapporté dans la littérature. Notre patient a reçu un traitement antibiotique à base de fluoroquinolone pendant un mois. L’évolution clinique s’est avérée bonne, et les lésions visibles à la tomodensitométrie se sont entièrement résorbées au bout d’un mois. Le patient vit toujours après un an et présente une fonction rénale normale. PMID:25295145

Inorganic Syntheses at High Temperatures and High Pressures with Special Interest in the Preparation of New Fluorine Compounds

DTIC Science & Technology

1981-05-26

produced either 1,2-gauche- and trano- difluoroethane or vinyl fluoride and hydrogen fluoride, Propylene, butadiene, and cyclohaxene reacted...Ar matrices can be explained in a number of ways. If the reaction is visualized an proceeding through a hot 1.2- difluoroethane inturmediate, one can...probability of hot 1.2- difluoroethane decomposing into vinyl fluoride. The presence of both gauche and trt!ns forms when the athylene-F 2 adduct is

L'obésité en consultation cardiologique à Lomé: prévalence et facteurs de risque cardio-vasculaire associés - étude chez 1200 patients

PubMed Central

Pessinaba, Soulemane; Yayehd, Komlavi; Pio, Machiude; Baragou, Réné; Afassinou, Yaovi; Tchérou, Tchaa; Damorou, Findibé

2012-01-01

Introduction Introduction: Les objectifs de ce travail étaient de déterminer la fréquence de l'obésité et celle des autres facteurs de risque cardio-vasculaire chez ces patients obèses à Lomé (Togo). Méthodes Il s'est agi d'une étude multicentrique transversale de prévalence. Elle s'est déroulée du 05 septembre 2005 au 04 mars 2006 et a porté sur les malades vus en consultation externe dans 3 services de cardiologie de la commune de Lomé. Ont été inclus dans cette étude les malades ayant un surpoids selon les normes de l'OMS. Résultats Parmi 1200 patients vus en consultations, 779 (64,92%) avaient une surcharge pondérale. L’âge moyen était de 49,53 ± 17,24 ans. L'obésité était plus fréquente chez les femmes (79,49%) que chez les hommes (20,51%). Un antécédent d'obésité familiale (61,8%) était le principal facteur favorisant. Les autres facteurs de risque cardio-vasculaire retrouvés étaient: sédentarité (82% vs50% chez les non obèses), hypertension artérielle (54,8% vs 39,2%), alcool (50,9% vs 43,9%), dyslipidémie (34,5% vs 20%), diabète (30,9% vs 10,7%) et tabac (14,1% vs 20,3%). La différence était statistiquement significative entre les deux groupes. Les principales complications cardiovasculaires observées chez les obèses étaient: l'ischémie myocardique (26,7%), l'hypertrophie ventriculaire gauche (46,4%), la dilatation cavitaire cardiaque (30,1%) et les accidents vasculaires cérébraux (7,1%). Conclusion L'obésité est un problème de santé publique au Togo. Sa prévalence est très élevée et elle est le plus souvent associée aux autres facteurs de risque cardio-vasculaire. Des mesures préventives doivent être mises en jeu pour lutter contre ce facteur de risque. Mots clés: Obésité, prévalence, facteurs de risque. PMID:23133699

Conformational preferences for some 2-substituted N-methoxy- N-methylacetamides through spectroscopic and theoretical studies

NASA Astrophysics Data System (ADS)

Olivato, Paulo R.; da Silva Gomes, Roberto; Rodrigues, Alessandro; Reis, Adriana K. C. A.; Domingues, Nelson L. C.; Rittner, Roberto; Dal Colle, Maurizio

2010-08-01

The analysis of the IR carbonyl band of the 2-substituted N-methoxy- N-methylacetamides Y-CH 2C(O)N(OMe)Me (Y = F 1, OMe 2, OPh 3, Cl 4), supported by B3LYP/6-311++G(3df, 3pd) calculations along with the NBO analysis for 1- 4, indicated the existence of cis- gauche conformers i.e. ( c) and ( g) for 1 and 3, ( c1,c2) and ( g1,g2) for 2, and ( c) and ( g1,g2) for 4. In the gas phase, the g conformer population prevails over the c one, for 1 and 3, the ( c1 + c2) population prevails over the ( g1 + g2) one for 2, and the ( g1 + g2) conformer population is more abundant than ( c) one for 4. In n-hexane solution, the cis conformer is more abundant for 1- 3. The occurrence of Fermi resonance in the νCO region, in n-hexane, precludes the estimative of relative populations of the ( c, g1, g2) conformers for 4. The SCI-PCM calculations agree with the solvent effect on the νCO band component relative intensities for 1- 3. NBO analysis showed that the nN → πco∗ orbital interaction is the main factor which stabilizes the gauche ( g, g1, g2) conformers for 1- 4 into a larger extent relative to the cis ( c, c1, c2) ones. The nY → πco∗, σCsbnd Y → πco∗, πco → σC sbnd Y ∗ and πco∗ → σC sbnd Y ∗ orbital interactions still contribute, but into a minor extent for the stabilization of the gauche conformers relative to the cis ones. The existence of some pyramidalization at the nitrogen atom of the Weinreb amides 1- 4 is responsible for the occurrence of Y δ-(4)···O δ-(9) and Y δ-(4)···N δ-(7) short contacts in the gauche ( g, g1, g2) conformers, which originates strong repulsive Coulombic interactions, acting in opposition to the large orbital stabilization of the gauche conformer with respect to the cis one. Therefore, a delicate balance of the Coulombic and orbital interactions seems to be responsible for the observed stabilization of the gauche ( g, g1, g2) and cis ( c, c1, c2) conformers, both in the gas phase and in the solution for 1- 4. However, the cis conformer predominance, in non polar solvents, for the 2-substituted N-methoxy- N-methyl acetamides 1- 3, bearing in α first raw (fluorine and oxygen) atoms, is in the opposite direction to the gauche conformer preference for the corresponding 2-substituted N, N-dialkyl-acetamides.

Effects of Water-Extractable Arabinoxylan on the Physicochemical Properties and Structure of Wheat Gluten by Thermal Treatment.

PubMed

Zhu, Yunping; Wang, Yu; Li, Jinlong; Li, Fang; Teng, Chao; Li, Xiuting

2017-06-14

This study investigated the effects of water-extractable arabinoxylan (WEAX) on gluten by thermal treatment. Fourier transform infrared spectroscopy (FTIR) results showed that heating significantly decreased β-sheets and β-turn structures in gluten proteins between 25 and 55 °C. The addition of WEAX caused a transition from β-turn to β-sheets at >55 °C. The ratio of weakly hydrogen-bonded β-sheets to strongly hydrogen-bonded β-sheets demonstrated an increasing trend with temperature increasing, but WEAX can hinder this process. FT-Raman results revealed that a hydrophilic environment was developed with 5% WEAX at 25 °C, and phenolic hydroxyl on ferulic acid can form new H-bonds with the phenyl groups of the nondissociated Tyr residues. A 5% WEAX content is helpful for gluten to maintain its original gauche-gauche-gauche conformation of disulfide bond upon heating. In addition, WEAX can reduce the elasticity of gluten and form a soft texture at 25, 55, and 75 °C.

Simultaneous gauche and anomeric effects in α-substituted sulfoxides.

PubMed

Freitas, Matheus P

2012-09-07

α-Substituted sulfoxides can experience both gauche and anomeric effects, since these compounds have the geometric requirements and strong electron donor and acceptor orbitals which are essential to make operative the hyperconjugative nature of these effects. Indeed, the title effects were calculated to take place for 1,3-oxathiane 3-oxide in polar solution, where dipolar effects are absent or at least minimized, while only the gauche effect is present in 2-fluorothiane 1-oxide. Since the fluorine atom is a suitable probe for structural analysis using NMR, the (1)J(CF) dependence on the rotation around the F-C-S═O dihedral angle of (fluoromethyl)methyl sulfoxide was evaluated; differently from 1,2-difluoroethane and fluoro(methoxy)methane, this coupling constant is at least not exclusively dependent on dipolar interactions (or on hyperconjugation). Because of the nonmonotonic behavior of the (1)J(CF) rotational profile, this coupling constant does not appear to be of significant diagnostic value for probing the conformations of α-fluoro sulfoxides.

Gauche effect in 1,2-difluoroethane. Hyperconjugation, bent bonds, steric repulsion.

PubMed

Goodman, Lionel; Gu, Hongbing; Pophristic, Vojislava

2005-02-17

Natural bond orbital deletion calculations show that whereas the gauche preference arises from vicinal hyperconjugative interaction between anti C-H bonds and C-F* antibonds, the cis C-H/C-F* interactions are substantial (approximately 25% of the anti interaction). The established significantly >60 degrees FCCF dihedral angle for the equilibrium conformer can then be rationalized in terms of the hyperconjugation model alone by taking into account both anti interactions that maximize near 60 degrees and the smaller cis interactions that maximize at a much larger dihedral angle. This explanation does not invoke repulsive forces to rationalize the 72 degrees equilibrium conformer angle. The relative minimum energy for the trans conformer is the consequence of a balance between decreasing hyperconjugative stabilization and decreasing steric destabilization as the FCCF torsional angle approaches 180 degrees . The torsional coordinate is predicted to be strongly contaminated by CCF bending, with the result that approximately half of the trans --> gauche stabilization energy stems from mode coupling.

Thermodynamic and spectroscopic analysis of the conformational transition of poly(vinyl alcohol) by temperature-dependent FTIR

NASA Astrophysics Data System (ADS)

Han, Shan; Luan, Ye-Mei; Pang, Shu-Feng; Zhang, Yun-Hong

2015-03-01

The conformational change of poly(vinyl alcohol) has been studied by Fourier transform infrared spectroscopy at various temperatures in the 4000-400 cm-1 region. The molecular motion and the trans/gauche content are sensitive to the Csbnd H, Csbnd C stretching modes. FTIR spectra show that the I2920/I2849 decreases from 1.84 to 1.0 with increasing temperature, companying the decrease in I1047/I1095 from 0.78 to 0.58, implying the conformational transition from trans to gauche in alkyl chain. Based on the van't Hoff relation, the enthalpies and entropies have been calculated in different temperatures, which are 4.61 kJ mol-1 and 15.23 J mol-1 K-1, respectively, in the region of 80-140 °C. From the Cdbnd O stretching mode and Osbnd H band, it can be concluded that the intermolecular hydrogen bonds decrease owing to elevating temperature, which leads to more gauche conformers.

Gas-phase Raman spectra and the potential energy function for the internal rotation of 1,3-butadiene and its isotopologues.

PubMed

Boopalachandran, Praveenkumar; Craig, Norman; Groner, Peter; Laane, Jaan

2011-08-18

The gas-phase Raman spectra of 1,3-butadiene and its 2,3-d(2), 1,1,4,4-d(4), and -d(6) isotopologues have been recorded with high sensitivity in the region below 350 cm(-1) in order to investigate the internal rotation (torsional) vibration. Based on more accurate structural information, the internal rotor constants F(n) were calculated as a function of rotation angle (ϕ). The data for all the isotopologues were then fit using a one-dimensional potential energy function of the form V = (1)/(2)∑V(n)(1 - cos ϕ). Initial V(n) values were based on those generated from theoretical calculations. The agreement between observed and calculated frequencies is very good, although bands not taken into account were present in the spectra. The energy difference between the trans and gauche forms was determined to be about 1030 cm(-1) (2.94 kcal/mol), and the barrier between the two equivalent gauche forms was determined to be about 180 cm(-1) (0.51 kcal/mol), which agrees well with high-level ab initio calculations. An alternative set of assignments also fits the data quite well for all of the isotopologues. For this model, the energy difference between the trans and gauche forms is about 1080 cm(-1) (3.09 kcal/mol), and the barrier between gauche forms is about 405 cm(-1) (1.16 kcal/mol). © 2011 American Chemical Society

Modeles de Calogero et Sutherland, fonctions speciales et symetries

NASA Astrophysics Data System (ADS)

Lapointe, Luc

La thèse comporte trois volets distincts, bien que l'utilisation de méthodes algébriques soit commune aux trois parties. Le premier volet (articles 1, 2 et 3) explore la relation entre les algèbres quantiques et les q-fonctions hypergéométriques. La connexion est d'abord faite, dans ce contexte, entre une extension à deux paramètres de l'algèbre de l'oscillateur harmonique, la (p, q)- algèbre de l'oscillateur, et les fonctions hypergéométriques bibasiques. Une formule génératrice pour des déformations à deux paramètres des polynômes de Laguerre peut ainsi être obtenue. Ensuite, la connexion entre l'algèbre sl q(n + 3) et les q-fonctions de Lauricella est étudiée et, de cette façon, plusieurs identités et relations de contiguité impliquant ces fonctions sont dérivées. Ce premier volet se termine par un court article où il est montré que certaines équations de Schrödinger en deux dimensions peuvent être résolues en termes de fonctions d'Appell, le cas à deux variables des fonctions de Lauricella. Le second volet (articles 4, 5, 6, 7 et 8) porte sur le modèle de Calogero-Sutherland et les fonctions symétriques. Le modèle de Calogero- Sutherland est un modèle intégrable décrivant N particules identiques sur un cercle dont les solutions sont esssentiellement données par des fonctions symétriques à N variables, les polynômes de Jack. Une formule permettant de construire ces polynômes à l'aide d'opérateurs de création est présentée. Cette formule permet de prouver une propriété importante des polynômes de Jack. Ces opérateurs de création sont ensuite généralisés au cas des polynômes de Macdonald. Les opérateurs obtenus dans ce cas possèdent des propriétés remarquables qui permettent notamment de prouver une forme faible d'une conjecture sur les polynômes de Macdonald. Finalement, le dernier volet (articles 9, 10 et 11) traite des algèbres dynamiques et de symétrie des modèles intégrables à plusieurs corps. Un système à N oscillateurs bosoniques sur une ligne et le modèle de Calogero avec terme harmonique sont étudiés. Une méthode générale qui permet en principe d'obtenir la structure algèbrique de ces modèles est présentée. Toutefois, seuls les cas avec N = 2 et N = 3 sont analysés en détail. Les algèbres de symétrie alors obtenues sont polynômiales.

Internal structure changes in bleached black human hair resulting from chemical treatments: A Raman spectroscopic investigation

NASA Astrophysics Data System (ADS)

Kuzuhara, Akio

2014-11-01

In order to investigate in detail the influence of chemical treatments (reduction, hydrolyzed eggwhite protein (HEWP) treatment, and oxidation) on damaged hair keratin fibers, the structure of cross-sections at various depths of excessively bleached (damaged) black human hair resulting from a permanent waving process was directly analyzed using Raman spectroscopy. It was found that L-cysteine (CYS) largely reacted with the gauche-gauche-gauche (GGG) conformation of disulfide (-SS-) groups (while CYS did not react with the trans-gauche-trans (TGT) conformation). In particular, not only the GGG content, but also the cysteic acid content existing throughout the cortex region of the excessively bleached human hair remarkably decreased by performing the oxidation process after reduction. On the other hand, the GGG content of the excessively bleached black human hair increased, while the TGT content decreased by performing the oxidation process after reduction and then HEWP treatment processes. From these experiments, the authors concluded that some of the keratin associated protein (KAP), which has a rich -SS- content and cysteic acid content was eluted from the cortex region along with the disconnection of -SS- groups, thereby leading to the remarkable reduction in the reconnection of -SS- groups of the excessively bleached black human hair after the permanent waving process (the reduction and oxidation processes). Also, the authors concluded that the HEWP treatment process in the permanent waving process caused the reconstruction of the KAP, thereby contributing to the acceleration of the reconnection of -SS- groups during the oxidation process.

Rotational Spectroscopy and Conformational Studies of 4-PENTYNENITRILE, 4-PENTENENITRILE, and Glutaronitrile

NASA Astrophysics Data System (ADS)

Hays, Brian M.; Mehta-Hurt, Deepali; Jawad, Khadija M.; Hernandez-Castillo, Alicia O.; Abeysekera, Chamara; Zhang, Di; Zwier, Timothy S.

2017-06-01

The pure rotational spectra of 4-pentynenitrile, 4-pentenenitrile, and glutaronitrile were acquired using chirped pulse Fouirer transform microwave spectroscopy. 4-pentynenitrile and 4-pentenenitrile are the recombination products of two resonance stabilized radicals, propargyl + cyanomethyl or allyl + cyanomethyl, respectively, and are thus anticipated to be significant among the more complex nitriles in Titan's atmosphere. Indeed, these partially unsaturated alkyl cyanides have been found in laboratory analogs of tholins and are also expected to have interesting photochemistry. The optimized structures of all conformers below predicted energies of 500 \\wn were calculated for each molecule. Both of the conformers, trans and gauche, for 4-pentynenitrile have been identified and assigned. Five conformers were assigned in 4-pentenenitrile. The eclipsed conformers, with respect to the vinyl group, dominate the spectrum but some population was found in the syn conformers including the syn-gauche conformer, calculated to be 324 \\wn above the global minimum. The glutaronitrile spectrum contained only the two conformers below 500 \\wn, with reduced amount of the gauche trans conformer. The assigned spectra and structural assignments will be presented.

The molecular structure and vibrational, 1H and 13C NMR spectra of lidocaine hydrochloride monohydrate

NASA Astrophysics Data System (ADS)

Badawi, Hassan M.; Förner, Wolfgang; Ali, Shaikh A.

2016-01-01

The structure, vibrational and NMR spectra of the local anesthetic drug lidocaine hydrochloride monohydrate salt were investigated by B3LYP/6-311G∗∗ calculations. The lidocaine·HCl·H2O salt is predicted to have the gauche structure as the predominant form at ambient temperature with NCCN and CNCC torsional angles of 110° and -123° as compared to 10° and -64°, respectively in the base lidocaine. The repulsive interaction between the two N-H bonds destabilized the gauche structure of lidocaine·HCl·H2O salt. The analysis of the observed vibrational spectra is consistent with the presence of the lidocaine salt in only one gauche conformation at room temperature. The 1H and 13C NMR spectra of lidocaine·HCl·H2O were interpreted by experimental and DFT calculated chemical shifts of the lidocaine salt. The RMSD between experimental and theoretical 1H and 13C chemical shifts for lidocaine·HCl·H2O is 2.32 and 8.21 ppm, respectively.

On the origin of the gauche effect. A quantum chemical study of 1,2-difluoroethane

NASA Astrophysics Data System (ADS)

Engkvist, O.; Karlström, G.; Widmark, P.-O.

1997-01-01

The conformational equilibrium of 1,2-difluoroethane has been investigated using ab initio quantum chemical calculations at the SCF, MP2 and CCSD(T) levels, with ANO basis sets. The relative stability of the gauche-conformation of 1,2-difluoroethane is found to be a consequence of the nodal structure of the singly occupied orbital in the CFH 2 radical. It is also shown that the nodal structure of the singly occupied orbitals in the CFH biradical can explain the stability of the cis conformation of 1,2-difluoroethene.

Ultrafast shock compression of self-assembled monolayers: a molecular picture.

PubMed

Patterson, James E; Dlott, Dana D

2005-03-24

Simulations of self-assembled monolayers (SAMs) are performed to interpret experimental measurements of ultrafast approximately 1 GPa (volume compression deltaV approximately 0.1) planar shock compression dynamics probed by vibrational sum-frequency generation (SFG) spectroscopy (Lagutchev, A. S.; Patterson, J. E.; Huang, W.; Dlott, D. D. J. Phys. Chem. B 2005, 109, XXXX). The SAMs investigated are octadecanethiol (ODT) and pentadecanethiol (PDT) on Au(111) and Ag(111) substrates, and benzyl mercaptan (BMT) on Au(111). In the alkane SAMs, SFG is sensitive to the instantaneous orientation of the terminal methyl; in BMT it is sensitive to the phenyl orientation. Computed structures of alkane SAMs are in good agreement with experiment. In alkanes, the energies of gauche defects increase with increasing number and depth below the methyl plane, with the exception of ODT/Au where both single and double gauche defects at the two uppermost dihedrals have similar energies. Simulations of isothermal uniaxial compression of SAM lattices show that chain and methyl tilting is predominant in PDT/Au, ODT/Ag and PDT/Ag, whereas single and double gauche defect formation is predominant in ODT/Au. Time-resolved shock data showing transient SFG signal loss of ODT/Au and PDT/Au are fit by calculations of the terminal group orientations as a function of deltaV and their contributions to the SFG hyperpolarizability. The highly elastic response of PDT/Au results from shock-generated methyl and chain tilting. The viscoelastic response of ODT/Au results from shock generation of single and double gauche defects. Isothermal compression simulations help explain and fit the time dependence of shock spectra but generally underestimate the magnitude of SFG signal loss because they do not include effects of high-strain-rate dynamics and shock front and surface irregularities.

Méningiome en plaque sphéno-orbitaire: à propos d'un cas avec revue de la littérature

PubMed Central

Abdellaoui, Meriem; Andaloussi, Idriss Benatiya; Tahri, Hicham

2015-01-01

Le méningiome intra osseux est une variété des méningiomes ectopiques dans lequel les cellules méningothéliales envahissent la paroi osseuse et entraînent une hyperostose. Le méningiome en plaque, variante macroscopique des méningiomes intra osseux, est une tumeur rare et survient fréquemment au niveau de la région sphéno-orbitaire ce qui le confond avec les tumeurs osseuses primitives. Nous rapportons le cas d'une patiente de 50 ans qui présente une exophtalmie avec cécité unilatérale gauche d'installation progressive depuis un an. L'examen trouve une exophtalmie axile, indolore et non réductible ainsi qu'une limitation de la motilité oculaire dans tous les sens du regard. La palpation montre une masse temporale gauche dure et adhérente à l'os. L'examen du fond d’œil trouve un œdème papillaire gauche. Le scanner montre une lésion ostéocondensante temporo-sphéno-orbitaire gauche avec envahissement locorégional. Le diagnostic préopératoire fut une tumeur osseuse essentiellement maligne primitive ou secondaire. L’étude histologique a révélée un méningiome meningothélial de type en plaque. La patiente a bénéficié d'une exérèse avec reconstruction chirurgicale. Aucune récidive n'a été notée après 1 an de recul. PMID:26327996

Resonant two-photon ionization and ab initio conformational analysis of haloethyl benzenes (PhCH(2)CH(2)X,X=Cl,F).

PubMed

Martin, Danielle E; Robertson, Evan G; Morrison, Richard J S; Dobney, Bruce

2007-10-07

The S(1) <-- S(0) transitions of the gaseous (2-fluoroethyl)-benzene (FEB) and (2-chloroethyl)-benzene (CEB) have been investigated using a combination of two-color resonant two-photon ionization and UV-UV hole burning spectroscopy. Both anti and gauche conformers have been identified on the basis of rotational band contour analysis supported by ab initio calculations on the ground and electronically excited states. The gauche origin band of FEB at 37,673 cm(-1) is redshifted 50 cm(-1) relative to the corresponding anti origin, while CEB origin bands overlap at 37,646 cm(-1). Relative conformational stability and populations in the jet have been estimated for both molecules, based on the intensity ratio of S(1) <-- S(0) band origin transitions. These are compared with a range of related molecules with the structural motif PhCH(2)CH(2)X (X=CH(3),CH(2)CH(3),NH(2),OH,COOH,CCH,CN). Theory and experimental results for FEB and CEB show repulsive interactions between the halogen substituents and the pi cloud of the phenyl rings destabilizing the gauche conformers, but the preference for the anti conformers is relatively modest. The gauche conformer origins show very different hybrid character: FEB is largely b type, while CEB is an ac hybrid in keeping with theoretically computed TM "rotations" (theta(elec)) of -7 degrees and -56 degrees , respectively. This difference is attributed largely to rotation of the side chain in opposite directions about the C(1)C(alpha) bond. Spectra of FEB(H(2)O) and CEB(H(2)O) single water clusters show evidence of an anti conformation in the host molecule.

Chloromethyl-oxirane and chloromethyl-thiirane in liquid phase: A joint experimental and quantum chemical study

NASA Astrophysics Data System (ADS)

Campetella, M.; Bencivenni, L.; Caminiti, R.; Zazza, C.; Di Trapani, S.; Martino, A.; Gontrani, L.

2016-07-01

The X-ray diffraction spectra of liquid chloromethyl-oxirane (ClMO) and chloromethyl-thiirane (ClMT) have been recorded for the first time. The interpretation of X-ray measurements was based on ab initio molecular dynamics simulations at finite temperature conditions. Both liquids show conformational equilibrium, which is discussed in terms of Gauche-2, Gauche-1 and Cis structures. The occurrence of the various forms estimated from X-ray and AIMD data has been compared with spectroscopy data from the literature, with the FTIR spectra of the liquids newly recorded in this work, and with theoretical in vacuo calculations.

Pressure-induced phase transition of 1-butyl-3-methylimidazolium hexafluorophosphate [bmim][PF6

NASA Astrophysics Data System (ADS)

Takekiyo, Takahiro; Hatano, Naohiro; Imai, Yusuke; Abe, Hiroshi; Yoshimura, Yukihiro

2011-03-01

We have investigated the pressure-induced Raman spectral change of 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) using Raman spectroscopy. The relative Raman intensity at 590 cm-1 of the CH2 rocking band assigned to the gauche conformer of the NCCC dihedral angle of the butyl group in the [bmim]+ cation increases when the pressure-induced liquid-crystalline phase transition occurs, while that at 610 cm-1 assigned to the trans conformer decreases. Our results show that the high-pressure phase transition of [bmim][PF6] causes the increase of the gauche conformer of the [bmim]+ cation.

Persistance de la veine cave supérieure gauche: à propos d'un cas

PubMed Central

Abidi, Kamel; Jellouli, Manel; Hammi, Yousra; Gargah, Tahar

2015-01-01

La persistance de la veine cave supérieure gauche (PVCSG) est une malformation congénitale rare et bénigne. Elle est souvent asymptomatique et sa découverte est dans la majorité des cas fortuite. Nous rapportons le cas d'un enfant chez lequel on découvre cette anomalie suite à une perte de connaissance. S.M, âgé de 9 ans, sans antécédents pathologiques notables, admis pour perte de connaissance de durée brève, sans mouvements anormaux toniques ou cloniques. L'examen physique à son admission est normal. L’électrocardiogramme est sans anomalies. La radiographie du thorax a montré un arc moyen gauche en double contour. Le Holter rythmique a montré des signes d'hyperréactivité vagale. L’échocardiographie trans-thoracique (ETT) a mis en évidence une dilatation nette du sinus coronaire et a éliminé la présence d'une cardiopathie. Une angio- IRM cardiaque a confirmé le diagnostic de PVCSG. Par ailleurs l'aorte thoracique a été normale dans ces différents segments. PMID:26664537

Microwave, infrared and Raman spectra, conformational stability and vibrational assignment of methoxyflurane

NASA Astrophysics Data System (ADS)

Li, Y. S.; Durig, J. R.

1982-05-01

The low resolution microwave spectrum of methoxyflurane, CHCl 2CF 2OCH 3, has been recorded from 26.5 to 39.0 GHz. From the spacing of the major transitions it is shown that the value of 2036 MHz for B + C is consistent with the trans-trans or gauche-trans conformers where the first term ( trans or gauche) refers to the internal rotation around the C-C bond. The infrared (40-3500 cm -1) and the Raman (20-3500 cm -1) spectra have been recorded for gaseous and solid methoxyflurane. Additionally, the Raman spectrum of the liquid has been obtained and qualitative depolarization ratios measured. From these data it is shown that the most stable form in the fluid phases at ambient temperature is the gauche-trans conformer but the trans-trans form is the most stable in the solid state. A complete vibrational analysis based on infrared band contours, depolarization values and group frequencies is proposed for this conformer. From the analysis of the low frequency vibrational data, values of some of the barriers to internal rotation are estimated. These results are compared to some similar quantities for some corresponding molecules.

Discordance gradient-surface dans le rétrécissement mitral: le gradient moyen transmitral est-il un critère de sévérité ou un indice de tolérance du rétrécissement mitral serré?

PubMed Central

Najih, Hayat; Arous, Salim; Laarje, Aziza; Baghdadi, Dalila; Benouna, Mohamed Ghali; Azzouzi, Leila; Habbal, Rachida

2016-01-01

Le rétrécissement mitral (RM) rhumatismal demeure une valvulopathie fréquente dans les pays en voie de développement. Cependant, les pays industrialisés ont vu l'émergence ces dernières années de nouvelles étiologies de RM; notamment l'origine médicamenteuse et/ou toxique responsable de valvulopathies restrictives aussi bien sténosantes que régurgitantes. Pour cette raison, l'évaluation échocardiographique du RM et surtout, la définition de critères objectifs pour conclure au caractère serré du RM reste toujours d'actualité. Les objectifs du travail sont: évaluer l'existence ou non d'une corrélation directe entre le gradient moyen transmitral (GMT) et la sévérité du RM chez les patients porteurs d'un RM serré ou très serré (critère primaire) et analyser les différents paramètres qui conditionnent le gradient moyen transmitral (GMT) (Critère secondaire). Il s'agit d'une étude transversale monocentrique incluant tous les patients admis au service de Cardiologie du CHU Ibn Rochd de Casablanca pour un RM serré ou très serré, sur une période d'une année (Janvier 2014 à Décembre 2014). Nous avons analysés séparément deux groupes de patients : ceux avec un gradient moyen transmitral<10 mmHg (groupe 1) et ceux avec un gradient>10mmHg (groupe2). 50 patients porteurs d'un RM serré ou très serré ont été inclus. L'âge moyen de nos patients est de 41,7 ans avec prédominance féminine (sex ratio: 0,25). 64% de nos patients avaient un RM serré et 36% avaient un RM très serré. 52% (26 patients) avaient un GMT <10mmHg et 48% (24 patients) avaient un gradient moyen >10mmHg, ce qui suggère l'absence de corrélation directe entre la sévérité du RM et le GMT (coefficient de Pearson R: -0,137). Pour la dyspnée, 80% des patients du groupe 1 étaient dyspnéiques stade II de la NYHA et 70% des patients du groupe 2 étaient dyspnéiques stade III (41%) ou IV (29%) de la NYHA, ce qui signifie l'existence d'une corrélation significative entre le GMT et la sévérité de la dyspnée (R: 0,586 et p: 0,001). L'étude analytique de la fréquence cardiaque et la présence d'une décompensation cardiaque par rapport au gradient moyen transmitral a montré une corrélation significative. En effet, parmi les patients du groupe 1, 96% avaient une FC entre 60 et 100 bpm et aucun patient n'était en décompensation cardiaque. Dans le groupe 2,54% (13 patients) avaient une FC >100 bpm et 7 parmi eux (53%) étaient en décompensation cardiaque gauche. L'étude de la pression artérielle pulmonaire systolique dans les deux groupes de l'étude a révélé l'existence dans notre série d'une corrélation statistiquement significative (R : 0,518 et P : 0,001) entre la PAPS et le GMT. La régularité du rythme et la fonction ventriculaire droite n'étaient pas corrélées au GMT (R : 0,038 et R :-0,002 respectivement). Le gradient moyen transmitral est un bon indicateur de la tolérance du rétrécissement mitral, mais il reflète imparfaitement sa sévérité vue qu'il dépend de plusieurs paramètres hémodynamiques. D'authentiques rétrécissements mitraux très serrés peuvent exister avec des gradients moyens transmitraux <10 mm Hg, c'est pour cette raison que la valeur du GMT ne doit jamais être interprétée isolément. PMID:28292038

The calculations of small molecular conformation energy differences by density functional method

NASA Astrophysics Data System (ADS)

Topol, I. A.; Burt, S. K.

1993-03-01

The differences in the conformational energies for the gauche (G) and trans(T) conformers of 1,2-difluoroethane and for myo-and scyllo-conformer of inositol have been calculated by local density functional method (LDF approximation) with geometry optimization using different sets of calculation parameters. It is shown that in the contrast to Hartree—Fock methods, density functional calculations reproduce the correct sign and value of the gauche effect for 1,2-difluoroethane and energy difference for both conformers of inositol. The results of normal vibrational analysis for1,2-difluoroethane showed that harmonic frequencies calculated in LDF approximation agree with experimental data with the accuracy typical for scaled large basis set Hartree—Fock calculations.

Post-Deployment Reintegration Measure: Psychometric Replication and Preliminary Validation Results

DTIC Science & Technology

2006-02-01

soudain au pays et la reprise des fonctions et activités « normales » peuvent engendrer un stress significatif chez le personnel militaire. Notre...Contexte : Après un séjour prolongé outre-mer, le retour soudain aux fonctions et activités normales peut engendrer un stress significatif chez...Johnson et al ., 1997; Wilson & Krause, 1985). For instance, participants in a focus group study of Canadian Forces (CF) personnel indicated that it

Post-deployment Reintegration Measure: Psychometric Replication and Preliminary Validation Results

DTIC Science & Technology

2006-02-01

soudain au pays et la reprise des fonctions et activités « normales » peuvent engendrer un stress significatif chez le personnel militaire. Notre...Contexte : Après un séjour prolongé outre-mer, le retour soudain aux fonctions et activités normales peut engendrer un stress significatif chez...Johnson et al ., 1997; Wilson & Krause, 1985). For instance, participants in a focus group study of Canadian Forces (CF) personnel indicated that it

Effects of Aromatic Fluorine Substitution on Protonated Neurotransmitters: The Case of 2-Phenylethylamine.

PubMed

Schütz, Markus; Bouchet, Aude; Chiavarino, Barbara; Crestoni, Maria Elisa; Fornarini, Simonetta; Dopfer, Otto

2016-06-06

Fluorination of pharmaceutical compounds is a common tool to modulate their physiochemical properties. We determine the effects of site-specific aromatic fluorine substitution on the geometric, energetic, vibrational, and electronic properties of the protonated neurotransmitter 2-phenylethylamine (xF-H(+) PEA, x=ortho, meta, para) by infrared multiphoton photodissociation (IRMPD) in the fingerprint range (600-1750 cm(-1) ) and quantum chemical calculations at the B3LYP-D3/aug-cc-pVTZ level. The IRMPD spectra of all ions are assigned to their folded gauche conformers stabilized by intramolecular NH(+) ⋅⋅⋅π hydrogen bonds (H-bonds) between the protonated amino group and the aromatic ring. H→F substitution reduces the symmetry and allows for additional NH(+) ⋅⋅⋅F interactions in oF-H(+) PEA, leading to three distinct gauche conformers. In comparison to oF-H(+) PEA, the fluorination effects on the energy landscape (energy ordering and isomerization barriers) in pF-H(+) PEA and mF-H(+) PEA with one and two gauche conformers are less pronounced. The strengths of the intramolecular NH(+) ⋅⋅⋅F and NH(+) ⋅⋅⋅π bonds are analyzed by the noncovalent interaction (NCI) method. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Conformational and Structural Studies of Isopropylamine from Temperature Dependent Raman Spectra of Xenon Solutions and {AB INITIO} Calculations

NASA Astrophysics Data System (ADS)

Klaassen, Joshua J.; Darkhalil, Ikhlas D.; Durig, James R.

2012-06-01

The Raman and infrared spectra (4000 to 50 cm-1) of the gas, liquid or solution, and solid have been recorded of isopropylamine, (CH3)2CHNH2. Variable temperature (-50 to -100oC) studies of the Raman spectra (3500 to 100 cm-1) dissolved in liquid xenon have been carried out. From these data, both the {trans} and {gauche} conformers have been identified and their relative stability obtained. The enthalpy difference has been determined from 20 band pairs at 6 temperatures to be 113 +/- 11 cm-1 (1.35 +/- 0.13 kJ mol-1) with the {trans} conformer the more stable form. The percentage of the {gauche} conformer is estimated to be 54 +/- 1 percent at ambient temperature. The conformational stabilities have been predicted from {ab initio} calculations utilizing several different basis sets up to aug-cc-pVTZ from both MP2(full) and density functional theory calculations by the B3LYP method. By utilizing previously reported microwave rotational constants along with {ab initio} MP2(full)/6-311+G(d,p) predicted structural values, adjusted r0 parameters have been obtained for the {trans} conformer. The determined heavy atom and NH2 distances in angstroms are C-C = 1.530(3), C-N = 1.465(3), N-H = 1.019(3) and angles in degrees NCC = 108.9(5), CCC = 111.0(5), HNC = 110.3(5). The structural parameters for the {gauche} conformer were estimated by using the same adjustment differences to the {gauche} form as those obtained for the corresponding {trans} parameters. Vibrational assignments have been provided for the observed bands for both conformers which are supported by MP2(full)/6-31G(d) {ab initio} calculations to predict harmonic force constants, wavenumbers, infrared intensities, Raman activities and depolarization ratios for both conformers. The results are discussed and compared to the corresponding properties of some related molecules.

Mesure de haute resolution de la fonction de distribution radiale du silicium amorphe pur

NASA Astrophysics Data System (ADS)

Laaziri, Khalid

1999-11-01

Cette these porte sur l'etude de la structure du silicium amorphe prepare par irradiation ionique. Elle presente des mesures de diffraction de rayons X sur de la poudre de silicium cristallin, du silicium amorphe relaxe et non relaxe, ainsi que tous les developpements mathematiques et physiques necessaires pour extraire la fonction de distribution radiale correspondant a chaque echantillon. Au Chapitre I, nous presentons une methode de fabrication de membranes minces de silicium amorphe pur. Il y a deux etapes majeures lors du processus de fabrication: l'implantation ionique, afin de creer une couche amorphe de plusieurs microns et l'attaque chimique, pour enlever le reste du materiau cristallin. Nous avons caracterise premierement les membranes de silicium amorphe par spectroscopie Raman pour verifier qu'il ne reste plus de trace de materiau cristallin dans les films amorphes. Une deuxieme caracterisation par detection de recul elastique (ERD-TOF) sur ces memes membranes a montre qu'il y a moins de 0.1% atomique de contaminants tels que l'oxygene, le carbone, et l'hydrogene. Au Chapitre II, nous proposons une nouvelle methode de correction de la contribution inelastique "Compton" des spectres de diffusion totale afin d'extraire les pics de diffusion elastique, responsable de la diffraction de Bragg. L'article presente tout d'abord une description simplifiee d'une theorie sur la diffusion inelastique dite "Impulse Approximation" (IA) qui permet de calculer des profils de Compton en fonction de l'energie et de l'angle de diffusion 2theta. Ces profils sont utilises comme fonction de lissage de la diffusion Compton experimentale. Pour lisser les pics de diffusion elastique, nous avons utilise une fonction pic de nature asymetrique. Aux Chapitre III, nous exposons de maniere detaillee les resultats des experiences de diffraction de rayons X sur les membranes de silicium amorphe et la poudre de silicium cristallin que nous avons preparees. Nous abordons aussi les differentes etapes experimentales, d'analyse ainsi que les methodes de determination et de filtrage des transformees de Fourier des donnees de diffraction. Une comparaison des fonctions de distribution radiale du silicium amorphe relaxe et non relaxe indique que la relaxation structurelle dans le silicium amorphe est probablement due en grande partie a une annihilation des defauts plutot qu'a une reorganisation atomique globale du reseau de silicium amorphe. La deduction de la coordination des pics correspondants au premiers voisins atomiques par lissage de fonctions gaussienne indique que la coordination du silicium amorphe relaxe est de 3.88, celle du non-relaxe est de 3.79, alors que la mesure de reference sur la poudre de silicium cristallin donne une valeur de 4 tel que prevu. La sous-coordination du silicium amorphe expliquerait pourquoi sa densite est inferieure a celle du silicium cristallin. (Abstract shortened by UMI.)

Hydrogen bonding in the neutron structure of the mononucleotide 5'-UMP disodium salt

NASA Astrophysics Data System (ADS)

Chitra, R.; Ranjan-Choudhury, R.; Ramanadham, M.

Disodium uridine 5'-monophosphate heptahydrate (5'-UMPNa2), Na2[C9H11N2O9P].7H2O, crystallises in space group C2221 with a=22.985, b=8.911 and c=19.494Å. A neutron beam of λ=1.216Å was used; Z=8 and V=3992.75Å3. Data consisted of 1785 unique reflections. Na ions were connected to the main molecule through water molecules and sugar oxygens. One of the Na ions occupied a special position, and the other at a general position was partially disordered. The uracil base was planar, and had anti conformation about the glycosidic bond. The sugar had C(2') endo conformation and was gauche-gauche.

Raman spectra of gases. XVI - Torsional transitions in ethanol and ethanethiol

NASA Technical Reports Server (NTRS)

Durig, J. R.; Bucy, W. E.; Wurrey, C. J.; Carreira, L. A.

1975-01-01

The Raman spectra of gaseous ethanol and ethanethiol have been investigated. Thiol torsional fundamentals for the gauche conformer of EtSH and EtSD have been observed and the asymmetric potential function for this vibration has been calculated. Methyl torsional transitions and overtones have also been observed for both of these molecules. Barriers to internal rotation for the methyl top are calculated to be 3.77 and 3.84 kcal/mol for the EtSH and EtSD compounds, respectively. Hydroxyl torsional fundamentals were observed at 207 and 170 per cm in the EtOH and EtOD spectra, respectively. Overtones of the methyl torsion in both molecules yield a barrier to internal rotation of 3.62 kcal/mol for the gauche conformer.

Contribution of High-Pressure-Induced Protein Modifications to the Microenvironment and Functional Properties of Rabbit Meat Sausages.

PubMed

Xue, Siwen; Yu, Xiaobo; Yang, Huijuan; Xu, Xinglian; Ma, Hanjun; Zhou, Guanghong

2017-06-01

Rabbit meat batters were subjected to high pressure (HP, 100 to 300 MPa for 3, 9, or 15 min) to elucidate their effects on proteins structures, the microenvironment, and the resulting functionalities of the subsequently heated products. To determine these effects, we investigated structural and microenvironmental changes using Raman spectroscopy and also expressible moisture content, textural characteristics, and dynamic rheological properties of batters during heating (20 to 80 °C). Untreated samples served as controls. Analysis of specific Raman spectral regions demonstrated that applications of HP to rabbit meat batters tended to induce the transformation of the all-gauche S-S conformation to gauche-gauche-trans in the batter system. HP treatment higher than 100 MPa for 9 min promoted secondary structural rearrangements, and molecular polarity enhancement in the proteins prior to cooking. Also, increases of O-H stretching intensities of rabbit meat sausages were obtained by HP treatment, denoting the strengthening of water-holding capacity. These HP-induced alterations resulted in improved texture and, perhaps, improved juiciness of rabbit meat sausages (P < 0.05), however they had relatively poorer rheological properties than the controls. Nevertheless, HP treatment, especially 200 MPa for 9 or 15 min, was an effective technique for improving the functionalities of gel-type products through modification of meat proteins. © 2017 Institute of Food Technologists®.

DISCOVERY OF METHYL ACETATE AND GAUCHE ETHYL FORMATE IN ORION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tercero, B.; Cernicharo, J.; Lopez, A.

2013-06-10

We report on the discovery of methyl acetate, CH{sub 3}COOCH{sub 3}, through the detection of a large number of rotational lines from each one of the spin states of the molecule: AA species (A{sub 1} or A{sub 2}), EA species (E{sub 1}), AE species (E{sub 2}), and EE species (E{sub 3} or E{sub 4}). We also report, for the first time in space, the detection of the gauche conformer of ethyl formate, CH{sub 3}CH{sub 2}OCOH, in the same source. The trans conformer is also detected for the first time outside the Galactic center source SgrB2. From the derived velocity ofmore » the emission of methyl acetate, we conclude that it arises mainly from the compact ridge region with a total column density of (4.2 {+-} 0.5) Multiplication-Sign 10{sup 15} cm{sup -2}. The derived rotational temperature is 150 K. The column density for each conformer of ethyl formate, trans and gauche, is (4.5 {+-} 1.0) Multiplication-Sign 10{sup 14} cm{sup -2}. Their abundance ratio indicates a kinetic temperature of 135 K for the emitting gas and suggests that gas-phase reactions could participate efficiently in the formation of both conformers in addition to cold ice mantle reactions on the surface of dust grains.« less

Photodissociation of CF2ICF2I in solid para-hydrogen: infrared spectra of anti- and gauche-˙C2F4I radicals.

PubMed

Haupa, Karolina Anna; Lim, Manho; Lee, Yuan-Pern

2018-05-09

The photolysis of 1,2-diiodotetrafluoroethane (CF2ICF2I) has served as a prototypical system in ultrafast reaction dynamics. Even though the intermediates, anti- and gauche-iodotetrafluoroethyl (˙C2F4I) radicals, have been characterized with electron diffraction and X-ray diffraction, their infrared spectra are unreported. We report the formation and infrared identification of these radical intermediates upon ultraviolet photodissociation of CF2ICF2I in solid para-hydrogen (p-H2) at 3.3 K. Lines at 1364.9/1358.5, 1283.2, 1177.1, 1162.2, 1126.8, 837.3, 658.0, 574.2, and 555.2 cm-1 are assigned to anti-˙C2F4I, and lines at 1325.9, 1259.7, 1143.4, 1063.4, 921.0, and 765.3 cm-1 to gauche-˙C2F4I. A secondary photodissociation leading to C2F4 was also observed. The assignments were derived according to behavior on secondary photolysis, comparison of the vibrational wavenumbers and the IR intensities of the observed lines with values predicted with the B3PW91/aug-cc-pVTZ-pp method. This spectral identification provides valuable information for future direct spectral probes of these important intermediates.

Measurements and Analysis of Reverberation, Target Echo and Clutter

DTIC Science & Technology

2013-12-01

réverbération pour prendre en charge les environne- ments dont les caractéristiques varient fortement en fonction de la distance ainsi que la géométrie...de faisceaux de réseaux remorqués dans un environnement dont les caractéristiques varient fortement en fonction de la distance ; (v) travaux...réverbération en mode normal pour prendre en charge la réverbération du sous-sol du fond, y compris dans les environnements dont les

Infrared spectroscopic studies of the conformation in ethyl alpha-haloacetates in the vapor, liquid and solid phases.

PubMed

Jassem, Naserallah A; El-Bermani, Muhsin F

2010-07-01

Infrared spectra of ethyl alpha-fluoroacetate, ethyl alpha-chloroacetate, ethyl alpha-bromoacetate and ethyl alpha-iodoacetate have been measured in the solid, liquid and vapor phases in the region 4000-200 cm(-1). Vibrational frequency assignment of the observed bands to the appropriate modes of vibration was made. Calculations at DFT B3LYP/6-311+G** level, Job: conformer distribution, using Spartan program '08, release 132 was made to determine which conformers exist in which molecule. The results indicated that the first compound exists as an equilibrium mixture of cis and trans conformers and the other three compounds exist as equilibrium mixtures of cis and gauche conformers. Enthalpy differences between the conformers have been determined experimentally for each compound and for every phase. The values indicated that the trans of the first compound is more stable in the vapor phase, while the cis is the more stable in both the liquid and solid phases. In the other three compounds the gauche is more stable in the vapor and liquid phases, while the cis conformer is the more stable in the solid phase for each of the second and third compound, except for ethyl alpha-iodoacetate, the gauche conformer is the more stable over the three phases. Molar energy of activation Ea and the pseudo-thermodynamic parameters of activation DeltaH(double dagger), DeltaS(double dagger) and DeltaG(double dagger) were determined in the solid phase by applying Arrhenius equation; using bands arising from single conformers. The respective E(a) values of these compounds are 5.1+/-0.4, 6.7+/-0.1, 7.5+/-1.3 and 12.0+/-0.6 kJ mol(-1). Potential energy surface calculations were made at two levels; for ethyl alpha-fluoroacetate and ethyl alpha-chloroacetate; the calculations were established at DFT B3LYP/6-311+G** level and for ethyl alpha-bromoacetate and ethyl alpha-iodoacetate at DFT B3LYP/6-311G* level. The results showed no potential energy minimum exists for the gauche conformer in ethyl alpha-fluoroacetate. Copyright 2010 Elsevier B.V. All rights reserved.

Atteinte cardiaque au cours de la dystrophie myotonique de Steinert: expérience marocaine, à propos de 18 cas

PubMed Central

Saghi, Ghita; Bouhouch, Rachida; Salaheddine, Loubna; Birouk, Nezha; Nadifi, Salama; Fellat, Ibtissam; Cherti, Mohamed

2015-01-01

La maladie de Steinert ou dystrophie myotonique de type 1 (DM1) est une maladie génétique à transmission autosomique dominante caractérisée par une myotonie et une atteinte de plusieurs organes dont le cœur. L'atteinte cardiaque est la plus grave des atteintes systémiques puisqu'elle conditionne le pronostic vital. Ce travail a pour but de déterminer les anomalies cardiaques rencontrées au cours de la DM1 et de mettre en exergue l'intérêt d'un examen cardiaque rigoureux et régulier, indépendamment de la sévérité de l'atteinte neuromusculaire, ainsi que l'apport des examens cardiaques complémentaires et notamment l'exploration électrophysiologique. 18 patients atteints de DM1 ont bénéficiés d'une exploration cardiaque systématique. Il s'agit de 9 hommes et de 9 femmes, d’âge moyen de 41,8 +/- 16,2 ans. 66 p.100 des patients sont symptomatiques sur le plan cardiovasculaire. Les anomalies électrocardiographiques sont dominées par un trouble de la conduction intra-ventriculaire dans 16 p.100 des cas et un BAV de 1er degré dans 16 p.100 des cas. L'Holter ECG objective une hyperexcitabilité à l’étage atrial et/ou ventriculaire dans 50p.100 des cas. L'ETT est normale chez 95 p.100 des patients. L'exploration électrophysiologique, réalisée chez 4 patients symptomatiques, a objectivé un bloc tronculaire dans un cas ayant conduit à l'implantation d'un PM double chambre. Un seul patient est décédé suite à une détresse respiratoire. Enfin, on n'a pas noté de corrélation entre l'atteinte cardiaque et neuromusculaire. Une exploration cardiaque est indispensable chez tout patient atteint de DM1, en dépit de l'absence de symptômes, et un bilan annuel minimal s'impose pour guetter un éventuel trouble rythmique et/ou conductif, fatal en l'absence de traitement adéquat. PMID:26097635

Isomerization reaction dynamics and equilibrium at the liquid-vapor interface of water. A molecular-dynamics study

NASA Technical Reports Server (NTRS)

Benjamin, Ilan; Pohorille, Andrew

1993-01-01

The gauche-trans isomerization reaction of 1,2-dichloroethane at the liquid-vapor interface of water is studied using molecular-dynamics computer simulations. The solvent bulk and surface effects on the torsional potential of mean force and on barrier recrossing dynamics are computed. The isomerization reaction involves a large change in the electric dipole moment, and as a result the trans/gauche ratio is considerably affected by the transition from the bulk solvent to the surface. Reactive flux correlation function calculations of the reaction rate reveal that deviation from the transition-state theory due to barrier recrossing is greater at the surface than in the bulk water. This suggests that the system exhibits non-Rice-Ramsperger-Kassel-Marcus behavior due to the weak solvent-solute coupling at the water liquid-vapor interface.

Molecular-dynamics simulation of polymethylene chain confined in cylindrical potentials. I. Nature of the conformational defects

NASA Astrophysics Data System (ADS)

Yamamoto, Takashi; Kimikawa, Yuichi

1992-10-01

The conformational motion of a polymethylene molecule constrained by a cylindrical potential is simulated up to 100 ps. The molecule consists of 60 CH2 groups and has variable bond lengths, bond angles, and dihedral angles. Our main concern here is the excitation and the dynamics of the conformational defects: kinks, jogs, etc. Under weaker constraint a number of gauche bonds are excited; they mostly form pairs such as gtḡ kinks or gtttḡ jogs. These conformational defects show no continuous drift in space. Instead they often annihilate and then recreate at different sites showing apparently random positional changes. The conformational defects produce characteristic strain fields around them. It seems that the conformational defects interact attractively through these strain fields. This is evidenced by remarkably correlated spatial distributions of the gauche bonds.

Four Structures of Tartaric Acid Revealed in the Gas Phase

NASA Astrophysics Data System (ADS)

Cortijo, Vanessa; Díez, Verónica; Alonso, Elena R.; Mata, Santiago; Alonso, José L.

2017-06-01

The tartaric acid, one of the most important organic compounds, has been transferred into the gas phase by laser ablation of its natural crystalline form (m.p.174°C) and probed in a supersonic expansion by chirped-pulse Fourier transform microwave spectroscopy (CP-FTMW). Four stable structures, two with an extended (trans) disposition of the carbon chain and two with a bent (gauche) disposition, have been unequivocally identified on the basis of the experimental rotational constants in conjunction with ab initio predictions. The intramolecular interactions that govern the conformational preferences are dominated by cooperative O-H...O=C type and O-H?O hydrogen bonds extended along the entire molecule. The observation of only μc- type spectra for one "trans" and one "gauche" conformers, support the existence of a C2 symmetry for each structure.

TCR-contacting residues orientation and HLA-DRβ* binding preference determine long-lasting protective immunity against malaria

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alba, Martha P.; Suarez, Carlos F.; Universidad del Rosario, Bogotá D. C.

Fully-protective, long-lasting, immunological (FPLLI) memory against Plasmodium falciparum malaria regarding immune protection-inducing protein structures (IMPIPS) vaccinated into monkeys previously challenged and re-challenged 60 days later with a lethal Aotus monkey-adapted P. falciparum strain was found to be associated with preferential high binding capacity to HLA-DRβ1* allelic molecules of the major histocompatibility class II (MHC-II), rather than HLA-DRβ3*, β4*, β5* alleles. Complete PPII{sub L} 3D structure, a longer distance (26.5 Å ± 1.5 Å) between residues perfectly fitting into HLA-DRβ1*PBR pockets 1 and 9, a gauche{sup −} rotamer orientation in p8 TCR-contacting polar residue and a larger volume of polar p2 residues was also found. Thismore » data, in association with previously-described p3 and p7 apolar residues having gauche{sup +} orientation to form a perfect MHC-II-peptide-TCR complex, determines the stereo-electronic and topochemical characteristics associated with FPLLI immunological memory. - Highlights: • Stereo-electronic and topochemical rules associated with FPLLI immunological memory. • Presence of very high long-lasting antibody titres against Plasmodium falciparum Spz. • Protective memory induction associated with a binding capacity to HLA-DRβ1*. • gauche{sup −} rotamer orientation in p8 polar residue is related to is related to immunological memory.« less

Structure and conformation of 1,4-difluorobutane as determined by gas-phase electron diffraction, and by molecular mechanics and ab initio calculations

NASA Astrophysics Data System (ADS)

Krosley, Kevin; Hagen, Kolbjørn; Hedberg, Kenneth

1995-06-01

Gas-phase electron diffraction data at 23°C together with molecular mechanics (MM3) and ab initio (HF/6-31G∗, gaussian 86) calculations have been used to determine the structure and conformations of 1,4-difluorobutane. The object was to ascertain whether effects similar to the gauche effect in 1,2-difluoroethane, which serves to stabilize the gauche form with the fluorine atoms in close proximity, could also operate in 1,4-difluorobutane. It was found both theoretically and experimentally that the proportion of those conformers having close fluorine atoms was small, implying the absence of effects similar to the gauche effect. The conformational composition estimated from the theoretical calculations is in good agreement with the experimental data. The experimental electron diffraction results constrained by assumptions drawn from the theoretical calculations, ED/MM3 [ED/ab initio], for the principal distances ( {r g}/{Å}) and angles ( {∠ α}/{deg}) with estimated 2σ uncertainties are as follows: r(CH) = 1.105(3) [1.106(3)], r(CF) = 1.398(2) [1.398(2)], r(C 1C 2) = 1.513(2) [1.516(2)], r(C 2C 3) = 1.537(2) [1.532(2)], ∠FCC = 110.9(3) [111.1(3)], ∠CCC = 112.9(4) [112.9(4)], and ∠HCH = 100(3) [100(3)].

Gas-phase infrared spectra of vinyl selenol and vinyl tellurol.

PubMed

Benidar, Abdessamad; Khater, Brahim; Guillemin, Jean-Claude; Gámez, José A; Yáñez, Manuel

2009-11-19

The infrared spectra (3500-500 cm(-1)) of gaseous vinyl selenol and vinyl tellurol have been recorded at 0.1 cm(-1) resolution. For the latter the spectra were obtained at room temperature, but for the former a temperature of -40 degrees C was required because of the chemical instability of vinyl selenol at room temperature. To compensate the very weak vapor pressure of vinyl tellurol at room temperature, a long optical path up to 136 m was necessary to record its spectrum. B3LYP density functional theory (DFT) calculations have been performed to assign the different absorption bands. Since an unambiguous assignment of the absorption bands requires a precise knowledge on the relative abundance of the syn and gauche rotamers of these compounds, their relative energies and their anharmonic vibrational frequencies were obtained using a very extended Def2-QZVP basis set. Two rotamers, the syn, which is planar, and a nonplanar gauche, were found to be local minima for both compounds. The gauche rotamer presents two degenerate conformers, which differ by the position of the SeH (TeH) hydrogen atom above or below the molecular plane. Our theoretical results are in good agreement with the main features of the experimental spectra. Fundamental bands and some combination bands of vinyl selenol and vinyl tellurol were assigned and compared with those of vinyl alcohol and vinyl thiol, whose spectra had been reported previously in the literature.

Gas-Phase Infrared Spectra of Vinyl Selenol and Vinyl Tellurol

NASA Astrophysics Data System (ADS)

Benidar, Abdessamad; Khater, Brahim; Guillemin, Jean-Claude; Gámez, José A.; Yáñez, Manuel

2009-10-01

The infrared spectra (3500-500 cm-1) of gaseous vinyl selenol and vinyl tellurol have been recorded at 0.1 cm-1 resolution. For the latter the spectra were obtained at room temperature, but for the former a temperature of -40 °C was required because of the chemical instability of vinyl selenol at room temperature. To compensate the very weak vapor pressure of vinyl tellurol at room temperature, a long optical path up to 136 m was necessary to record its spectrum. B3LYP density functional theory (DFT) calculations have been performed to assign the different absorption bands. Since an unambiguous assignment of the absorption bands requires a precise knowledge on the relative abundance of the syn and gauche rotamers of these compounds, their relative energies and their anharmonic vibrational frequencies were obtained using a very extended Def2-QZVP basis set. Two rotamers, the syn, which is planar, and a nonplanar gauche, were found to be local minima for both compounds. The gauche rotamer presents two degenerate conformers, which differ by the position of the SeH (TeH) hydrogen atom above or below the molecular plane. Our theoretical results are in good agreement with the main features of the experimental spectra. Fundamental bands and some combination bands of vinyl selenol and vinyl tellurol were assigned and compared with those of vinyl alcohol and vinyl thiol, whose spectra had been reported previously in the literature.

Raman spectroscopic study of leptospiral glycolipoprotein

NASA Astrophysics Data System (ADS)

Bao, PeiDi; Bao, Lang; Huang, TianQuan; Liu, XinMing

1998-04-01

The Raman scattering spectra of two different samples of Leptospiral Glycoipoprotein (GLP-1 and GLP-2) which have different toxic effects have been obtained and investigated. Leptospirosis is one of the most harmful zoonosis. It is a serious public health issue in some area of Sichusan province. The two samples offer different structural informations of GLP molecules, it would be important to find the difference in contents, structures and the amino acid side - chains environment of the molecules between the two samples of GLP for understanding the different toxic effects. The intense Am I at 1651 cm-1 and weak Am III at 1283 cm-1 show that GLP-1 has a predominantly (alpha) -helix secondary structure. The intense Am I at 1674 cm-1 and intense Am III at 1246 cm-1 show that the conformation of GLP-2 has a high content of (Beta) - sheet and a low content of random - coil secondary structure. Strong Raman scattering occurs in the range 920- 980 cm-1, belong to the C-COO vibration and the stretching of the peptide backbone. The molecules of GLP-1 has trans-gauche-trans configuration of the C-S-S-C-C linkage and the molecules of GLP-2 has trans-gauche-gauche configuration of the C-C-S-S-C-C linkage. The intensity ratio of the two tyrosine liens at 830 cm-1 and 850 cm-1 is 1.1 and 1.23, indicate their tyrosine reduces environment respectively. Other side-chain environment in the two samples were discussed.

Conformations and Barriers to Methyl Group Internal Rotation in Two Asymmetric Ethers: Propyl Methyl Ether and Butyl Methyl Ether

NASA Astrophysics Data System (ADS)

Long, B. E.; Dechirico, F.; Cooke, S. A.

2012-06-01

The conformational preferences of the O-C-C-C unit are important in many biological systems with the unit generally preferring a gauche configuration compared to an anti configuration. Butyl methyl ether and propyl methyl ether provide very simple systems for this phenomenom to manifest. Pure rotational spectra of the title molecules have been recorded using chirped pulse Fourier transform microwave spectroscopy (CP-FTMW). In the case of butyl methyl ether, only one conformer has been observed. This conformer has torsional angles of COCC = 180°, OCCC = 62° and CCCC = 180° (anti-gauche-anti) and rotational constants of A = 10259.4591(33) MHz, B = 1445.6470(13) MHz, and C = 1356.2944(14) MHz. The rotational spectrum was doubled and has been analyzed to produce an effective barrier to methyl group internal rotation of 780(35) cm-1. A prior rotational spectroscopic study on propyl methyl ether had focused only on the high energy anti-anti conformer. We have analyzed spectra from the lowest energy anti-gauche conformer and the spectroscopic constants will be presented. A summary of the differences in conformational energies and methyl group internal rotation barriers for the class of aliphatic asymmetric ethers will be presented. K. N. Houk, J. E. Eksterowicz, Y.-D. Wu, C. D. Fuglesang, D. B. Mitchell. J. Am. Chem. Soc. 115 (4170), 1993. Hiroshi Kato, Jun Nakagawa, Michiro Hayashi. J. Mol. Spectrosc. 80 (272), 1980.

Direct observation of bis(dicarbollyl)nickel conformers in solution by fluorescence spectroscopy: an approach to redox-controlled metallacarborane molecular motors.

PubMed

Safronov, Alexander V; Shlyakhtina, Natalia I; Everett, Thomas A; VanGordon, Monika R; Sevryugina, Yulia V; Jalisatgi, Satish S; Hawthorne, M Frederick

2014-10-06

As a continuation of work on metallacarborane-based molecular motors, the structures of substituted bis(dicarbollyl)nickel complexes in Ni(III) and Ni(IV) oxidation states were investigated in solution by fluorescence spectroscopy. Symmetrically positioned cage-linked pyrene molecules served as fluorescent probes to enable the observation of mixed meso-trans/dl-gauche (pyrene monomer fluorescence) and dl-cis/dl-gauche (intramolecular pyrene excimer fluorescence with residual monomer fluorescence) cage conformations of the nickelacarboranes in the Ni(III) and Ni(IV) oxidation states, respectively. The absence of energetically disfavored conformers in solution--dl-cis in the case of nickel(III) complexes and meso-trans in the case of nickel(IV)--was demonstrated based on spectroscopic data and conformer energy calculations in solution. The conformational persistence observed in solution indicates that bis(dicarbollyl)nickel complexes may provide attractive templates for building electrically driven and/or photodriven molecular motors.

Photooxidation of Trimethyl Phosphite in Nitrogen, Oxygen, and para-Hydrogen Matrixes at Low Temperatures.

PubMed

Ramanathan, N; Sundararajan, K; Gopi, R; Sankaran, K

2017-03-16

Trimethyl phosphite (TMPhite) was photooxidized to trimethyl phosphate (TMP) in N 2 , O 2 , and para-H 2 matrixes at low temperatures to correlate the conformational landscape of these two molecules. The photooxidation produced the trans (TGG)-rich conformer with respect to the ground state gauche (GGG) conformer of TMP in N 2 and O 2 matrixes, which has diverged from the conformational composition of freshly deposited pure TMP in the low-temperature matrixes. The enrichment of the trans conformer in preference to the gauche conformer of TMP during photooxidation is due to the TMPhite precursor, which exists exclusively in the trans conformer. Interestingly, whereas the photooxidized TMP molecule suffers site effects possibly due to the local asymmetry in N 2 and O 2 matrixes, in the para-H 2 matrix owing to the quantum crystal nature the site effects were observed to be self-repaired.

Structural changes evaluation with Raman spectroscopy in meat batters prepared by different processes.

PubMed

Kang, Zhuang-Li; Li, Xiang; He, Hong-Ju; Ma, Han-Jun; Song, Zhao-Jun

2017-08-01

A comprehensive study was conducted to evaluate the structural changes of meat and protein of pork batters produced by chopping or beating process through the phase-contrast micrograph, laser light scattering analyzer, scanning electronic microscopy and Raman spectrometer. The results showed that the shattered myofibrilla fragments were shorter and particle-sizes were smaller in the raw batter produced by beating process than those in the chopping process. Compared with the raw and cooked batters produced by chopping process, modifications in amide I and amide III bands revealed a significant decrease of α -helix content and an increase of β -sheet, β -turn and random coils content in the beating process. The changes in secondary structure of protein in the batter produced by beating process was thermally stable. Moreover, more tyrosine residues were buried, and more gauche-gauche-trans disulfide bonds conformations and hydrophobic interactions were formed in the batter produced by beating process.

Conformational dynamics of dry lamellar crystals of sugar based lipids: an atomistic simulation study.

PubMed

ManickamAchari, Vijayan; Bryce, Richard A; Hashim, Rauzah

2014-01-01

The rational design of a glycolipid application (e.g. drug delivery) with a tailored property depends on the detailed understanding of its structure and dynamics. Because of the complexity of sugar stereochemistry, we have undertaken a simulation study on the conformational dynamics of a set of synthetic glycosides with different sugar groups and chain design, namely dodecyl β-maltoside, dodecyl β-cellobioside, dodecyl β-isomaltoside and a C12C10 branched β-maltoside under anhydrous conditions. We examined the chain structure in detail, including the chain packing, gauche/trans conformations and chain tilting. In addition, we also investigated the rotational dynamics of the headgroup and alkyl chains. Monoalkylated glycosides possess a small amount of gauche conformers (∼20%) in the hydrophobic region of the lamellar crystal (LC) phase. In contrast, the branched chain glycolipid in the fluid Lα phase has a high gauche population of up to ∼40%. Rotational diffusion analysis reveals that the carbons closest to the headgroup have the highest correlation times. Furthermore, its value depends on sugar type, where the rotational dynamics of an isomaltose was found to be 11-15% and more restrained near the sugar, possibly due to the chain disorder and partial inter-digitation compared to the other monoalkylated lipids. Intriguingly, the present simulation demonstrates the chain from the branched glycolipid bilayer has the ability to enter into the hydrophilic region. This interesting feature of the anhydrous glycolipid bilayer simulation appears to arise from a combination of lipid crowding and the amphoteric nature of the sugar headgroups.

The vicinal difluoro motif: The synthesis and conformation of erythro- and threo- diastereoisomers of 1,2-difluorodiphenylethanes, 2,3-difluorosuccinic acids and their derivatives

PubMed Central

O'Hagan, David; Rzepa, Henry S; Schüler, Martin; Slawin, Alexandra MZ

2006-01-01

Background It is well established that vicinal fluorines (RCHF-CHFR) prefer to adopt a gauche rather than an anti conformation when placed along aliphatic chains. This has been particularly recognised for 1,2-difluoroethane and extends to 2,3-difluorobutane and longer alkyl chains. It follows in these latter cases that if erythro and threo vicinal difluorinated stereoisomers are compared, they will adopt different overall conformations if the fluorines prefer to be gauche in each case. This concept is explored in this paper with erythro- and threo- diastereoisomers of 2,3-difluorosuccinates. Results A synthetic route to 2,3-difluorosuccinates has been developed through erythro- and threo- 1,2-difluoro-1,2-diphenylethane which involved the oxidation of the aryl rings to generate the corresponding 2,3-difluorosuccinic acids. Ester and amide derivatives of the erythro- and threo- 2,3-difluorosuccinic acids were then prepared. The solid and solution state conformation of these compounds was assessed by X-ray crystallography and NMR. Ab initio calculations were also carried out to model the conformation of erythro- and threo- 1,2-difluoro-1,2-diphenylethane as these differed from the 2,3-difluorosuccinates. Conclusion In general the overall chain conformations of the 2,3-difluorosuccinates diastereoisomers were found to be influenced by the fluorine gauche effect. The study highlights the prospects of utilising the vicinal difluorine motif (RCHF-CHFR) as a tool for influencing the conformation of performance organic molecules and particularly tuning conformation by selecting specific diastereoisomers (erythro or threo). PMID:17014729

The vicinal difluoro motif: The synthesis and conformation of erythro- and threo- diastereoisomers of 1,2-difluorodiphenylethanes, 2,3-difluorosuccinic acids and their derivatives.

PubMed

O'Hagan, David; Rzepa, Henry S; Schüler, Martin; Slawin, Alexandra M Z

2006-10-02

It is well established that vicinal fluorines (RCHF-CHFR) prefer to adopt a gauche rather than an anti conformation when placed along aliphatic chains. This has been particularly recognised for 1,2-difluoroethane and extends to 2,3-difluorobutane and longer alkyl chains. It follows in these latter cases that if erythro and threo vicinal difluorinated stereoisomers are compared, they will adopt different overall conformations if the fluorines prefer to be gauche in each case. This concept is explored in this paper with erythro- and threo- diastereoisomers of 2,3-difluorosuccinates. A synthetic route to 2,3-difluorosuccinates has been developed through erythro- and threo- 1,2-difluoro-1,2-diphenylethane which involved the oxidation of the aryl rings to generate the corresponding 2,3-difluorosuccinic acids. Ester and amide derivatives of the erythro- and threo- 2,3-difluorosuccinic acids were then prepared. The solid and solution state conformation of these compounds was assessed by X-ray crystallography and NMR. Ab initio calculations were also carried out to model the conformation of erythro- and threo- 1,2-difluoro-1,2-diphenylethane as these differed from the 2,3-difluorosuccinates. In general the overall chain conformations of the 2,3-difluorosuccinates diastereoisomers were found to be influenced by the fluorine gauche effect. The study highlights the prospects of utilising the vicinal difluorine motif (RCHF-CHFR) as a tool for influencing the conformation of performance organic molecules and particularly tuning conformation by selecting specific diastereoisomers (erythro or threo).

Linking structure and vibrational mode coupling using high-resolution infrared spectroscopy: A comparison of gauche and trans 1-chloro-2-fluoroethane

NASA Astrophysics Data System (ADS)

Miller, C. Cameron; Stone, Stephen C.; Philips, Laura A.

1995-01-01

The high-resolution infrared spectrum of 1-chloro-2-fluoroethane in a molecular beam was collected over the 2975-2994 cm-1 spectral region. The spectral region of 2975-2981 cm-1 contains a symmetric C-H stretching vibrational band of the gauche conformer containing the 35Cl isotope. The spectral region of 2985-2994 cm-1 contains three vibrational bands of the trans conformer. Two of the three bands are assigned as an antisymmetric C-H stretch of each of the two different chlorine isotopes. The third band is assigned as a symmetric C-H stretch of the 35Cl isotope. The gauche conformer of 1-chloro-2-fluoroethane showed doublet patterns similar to those previously observed in 1,2-difluoroethane. The model for 1,2-difluoroethane is further refined in the present work. These refinements suggest that the coupling dark state in 1,2-difluoroethane is composed of 1 quantum C-H bend, 1 quantum C-C stretch, and 12 quanta of torsion. For 1-chloro-2-fluoroethane the dark state could not be identified due to a small data set. The trans conformer of 1-chloro-2-fluoroethane showed no evidence of mode coupling in the three vibrational bands. Including 2-fluoroethanol in this series of molecules, the extent of vibrational mode coupling did not correlate with the density of states available for coupling. Therefore, density of states alone is insufficient to explain the observed trend. A correlation was observed between the degree of intramolecular interaction and vibrational mode coupling.

Spectroscopic Signatures and Structural Motifs of Dopamine: a Computational Study

NASA Astrophysics Data System (ADS)

Srivastava, Santosh Kumar; Singh, Vipin Bahadur

2016-06-01

Dopamine (DA) is an essential neurotransmitter in the central nervous system and it plays integral role in numerous brain functions including behaviour, cognition, emotion, working memory and associated learning. In the present work the conformational landscapes of neutral and protonated dopamine have been investigated in the gas phase and in aqueous solution by MP2 and DFT (M06-2X, ωB97X-D, B3LYP and B3LYP-D3) methods. Twenty lowest energy structures of neutral DA were subjected to geometry optimization and the gauche conformer, GIa, was found to be the lowest gas phase structure at the each level of theory in agreement with the experimental rotational spectroscopy. All folded gauche conformers (GI) where lone electron pair of the NH2 group is directed towards the π system of the aromatic ring ( 'non up' ) are found more stable in the gas phase. While in aqueous solution, all those gauche conformers (GII) where lone electron pair of the NH2 group is directed opposite from the π system of the aromatic ring ('up' structures) are stabilized significantly.Nine lowest energy structures, protonated at the amino group, are optimized at the same MP2/aug-cc-pVDZ level of theory. In the most stable gauche structures, g-1 and g+1, mainly electrostatic cation - π interaction is further stabilized by significant dispersion forces as predicted by the substantial differences between the DFT and dispersion corrected DFT-D3 calculations. In aqueous environment the intra-molecular cation- π distance in g-1 and g+1 isomers, slightly increases compared to the gas phase and the magnitude of the cation- π interaction is reduced relative to the gas phase, because solvation of the cation decreases its interaction energy with the π face of aromatic system. The IR intensity of the bound N-H+ stretching mode provides characteristic 'IR spectroscopic signatures' which can reflect the strength of cation- π interaction energy. The CC2 lowest lying S1 ( 1ππ* ) excited state of neutral dopamine is significantly red shifted upon protonation at amino site. E. Dragicevic, J. Schiemann and B. Liss, Neuroscience, 2015, 284, 798. Y. T. Chien et al. Science, 2010, 330, 1091. Cabezas etal., J. Phys. Chem. Lett. 2013, 4, 486.

Autre cause de mort subite du nourrisson: à propos d'un cas clinique de syndrome du QT long congenital

PubMed Central

Seka, Zena; Mols, Pierre; Gobin, Eric; Ngatchou, William

2014-01-01

Le syndrome du QT long congénital est une maladie rythmique liée à une mutation génétique et caractérisée par un espace QT allongé sur l’électrocardiogramme, des arythmies malignes type torsade de pointe et fibrillation ventriculaire entraînant une mort subite. Les gènes impliqués dans ces mutations codent pour des sous unités des canaux ioniques responsables de l'activité électrique cardiaque. Le diagnostic est basé sur l’électrocardiogramme, une enquête familiale et l’étude génétique. Le traitement repose sur les bêtabloquants, la sympathectomie et le stimulateur cardiaque. Nous rapportons le cas d'un nourrisson de 2 ans retrouvé en état de mort apparente. Nous discutons de sa prise en charge initiale, de l'enquête familiale et de son suivi ultérieur. PMID:25667708

Methodes d'amas quantiques a temperature finie appliquees au modele de Hubbard

NASA Astrophysics Data System (ADS)

Plouffe, Dany

Depuis leur decouverte dans les annees 80, les supraconducteurs a haute temperature critique ont suscite beaucoup d'interet en physique du solide. Comprendre l'origine des phases observees dans ces materiaux, telle la supraconductivite, est l'un des grands defis de la physique theorique du solide des 25 dernieres annees. L'un des mecanismes pressentis pour expliquer ces phenomenes est la forte interaction electron-electron. Le modele de Hubbard est l'un des modeles les plus simples pour tenir compte de ces interactions. Malgre la simplicite apparente de ce modele, certaines de ses caracteristiques, dont son diagramme de phase, ne sont toujours pas bien etablies, et ce malgre plusieurs avancements theoriques dans les dernieres annees. Cette etude se consacre a faire une analyse de methodes numeriques permettant de calculer diverses proprietes du modele de Hubbard en fonction de la temperature. Nous decrivons des methodes (la VCA et la CPT) qui permettent de calculer approximativement la fonction de Green a temperature finie sur un systeme infini a partir de la fonction de Green calculee sur un amas de taille finie. Pour calculer ces fonctions de Green, nous allons utiliser des methodes permettant de reduire considerablement les efforts numeriques necessaires pour les calculs des moyennes thermodynamiques, en reduisant considerablement l'espace des etats a considerer dans ces moyennes. Bien que cette etude vise d'abord a developper des methodes d'amas pour resoudre le modele de Hubbard a temperature finie de facon generale ainsi qu'a etudier les proprietes de base de ce modele, nous allons l'appliquer a des conditions qui s'approchent de supraconducteurs a haute temperature critique. Les methodes presentees dans cette etude permettent de tracer un diagramme de phase pour l'antiferromagnetisme et la supraconductivite qui presentent plusieurs similarites avec celui des supraconducteurs a haute temperature. Mots-cles : modele de Hubbard, thermodynamique, antiferromagnetisme, supraconductivite, methodes numeriques, larges matrices

Local Anesthetics in the Gas-Phase the Rotational Spectrum of Butamben and Isobutamben

NASA Astrophysics Data System (ADS)

Vallejo-López, Montserrat; Ecija, Patricia; Caminati, Walther; Grabow, Jens-Uwe; Lesarri, Alberto; Cocinero, Emilio J.

2016-06-01

Benzocaine (BZ), butamben (BTN) and isobutamben (BTI) are local anesthetics characterized by a hydrophilic head and a lipophilic aliphatic tail linked by an aminobenzoate group. Previous rotational work on BZ (H2N-C6H4-COO-Et) showed that its ethyl aliphatic tail may adopt either in-plane (trans) or out of plane (gauche) conformations, with a low interconversion barrier below 50 cm-1. Here we extend the rotational study to BTN and BTI, isolated in a supersonic jet expansion and vaporized either by heating or UV ps-laser ablation methods. Both molecules share a 14 heavy-atoms skeleton, differing in their butyl (-(CH2)3-CH3) or isobutyl (-CH2-CH(CH3)2) four-carbon tail. We detected a single conformer for BTN and two conformers for BTI. The two molecules do not adopt an all-trans carbon skeleton. Conversely, the β-ethyl carbon in BTN is gauche. For BTI the β-carbon may be either trans or gauche. The microwave spectrum covered the cm- (BTN, BTI, 6-18 GHz) and mm-wave (BTW, 50-75 GHz) frequency ranges.In all the cases, rotational and centrifugal distortion constants as well as the diagonal elements of the 14N nuclear quadrupole coupling tensor were accurate determined and compared to the theoretical results (ab initio and DFT). No transitions belonging to configurations predicted as higher minima of the PES were found, pointing out that conformational interconversions may take place in the jet. A. Lesarri, S. T. Shipman, G. G. Brown, L. Alvarez-Valtierra, R. D. Suenram, B. H. Pate, Int. Symp. Mol. Spectrosc., 2008, Comm. RH07. E. Aguado, A. Longarte, E. Alejandro, J. A. Fernández, F. Castaño, J. Phys. Chem. A, 2006, 110, 6010.

Influences of the propyl group on the van der Waals structures of 4-propylaniline complexes with one and two argon atoms studied by electronic and cationic spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Zhijun; Gu, Quanli; Department of Chemistry, University of Oklahoma, Norman, Oklahoma 73019

2015-07-21

4-propylaniline complexes with one and two argon atoms formed in the molecular beam were studied in the first excited electronic state, S{sub 1}, using resonance enhanced two-photon ionization spectroscopy and in the cation ground state, D{sub 0}, using mass analyzed threshold ionization spectroscopy. The combination of electronic and cationic spectra of the clusters allows two conformations to be identified in both aniline-Ar{sub 1} and aniline-Ar{sub 2}, which are assigned to either the gauche configuration or anti-configuration of 4-propylaniline. The gauche isomer exhibits complex bands shifted 29 cm{sup −1} and 89 cm{sup −1} from the S{sub 1} origin bands and 83more » cm{sup −1} and 148 cm{sup −1} from the ionization potential assigned to the Ar{sub 1} and Ar{sub 2} complexes, respectively. For the anti-rotamer, the corresponding shifts actually become nearly additive, 53 cm{sup −1} and 109 cm{sup −1} for the S{sub 1} origin bands, and 61 cm{sup −1} and 125 cm{sup −1} for the ionization potentials. Ab initio calculations provide insights into the influences of the propyl and amino groups on the positions of the argon atoms within the clusters. In addition, the binding energy of one argon with the gauche isomer of 4-propylaniline has been measured to be 550 ± 5 cm{sup −1} in the D{sub 0} state, 496 ± 5 cm{sup −1} in the S{sub 1} state, and 467 ± 5 cm{sup −1} in the neutral ground state, S{sub 0}.« less

Gas Phase Conformations and Methyl Internal Rotation for 2-PHENYLETHYL Methyl Ether and its Argon Van Der Waals Complex from Fourier Transform Microwave Spectroscopy

NASA Astrophysics Data System (ADS)

Gurusinghe, Ranil M.; Tubergen, Michael

2015-06-01

A mini-cavity microwave spectrometer was used to record the rotational spectra arising from 2-phenylethyl methyl ether and its weakly bonded argon complex in the frequency range of 10.5 - 22 GHz. Rotational spectra were found for two stable conformations of the monomer: anti-anti and gauche-anti, which are 1.4 kJ mol-1 apart in energy at wB97XD/6-311++G(d,p) level. Doubled rotational transitions, arising from internal motion of the methyl group, were observed for both conformers. The program XIAM was used to fit the rotational constants, centrifugal distortion constants, and barrier to internal rotation to the measured transition frequencies of the A and E internal rotation states. The best global fit values of the rotational constants for the anti-anti conformer are A= 3799.066(3) MHz, B= 577.95180(17) MHz, C= 544.7325(3) MHz and the A state rotational constants of the gauche-anti conformer are A= 2676.1202(7) MHz, B= 760.77250(2) MHz, C= 684.78901(2) MHz. The rotational spectrum of 2-phenylethyl methyl ether - argon complex is consistent with the geometry where argon atom lies above the plane of the benzene moiety of gauche-anti conformer. Tunneling splittings were too small to resolve within experimental accuracy, likely due to an increase in three fold potential barrier when the argon complex is formed. Fitted rotational constants are A= 1061.23373(16) MHz, B= 699.81754(7) MHz, C= 518.33553(7) MHz. The lowest energy solvated ether - water complex with strong intermolecular hydrogen bonding has been identified theoretically. Progress on the assignment of the water complex will also be presented.

Fluorine substitution and nonconventional OH...pi intramolecular bond: high-resolution UV spectroscopy and ab initio calculations of 2-(p-fluorophenyl)ethanol.

PubMed

Karaminkov, Rosen; Chervenkov, Sotir; Neusser, Hans J

2008-05-21

The para-fluorinated flexible neurotransmitter analogue 2-phenylethanol has been investigated by highly resolved resonance-enhanced two-photon ionisation two-colour UV laser spectroscopy with mass resolution and ab initio structural optimisations and energy calculations. Two stable conformations, gauche and anti, separated by a high potential barrier have been identified in the cold molecular beam by rotational analysis of the vibronic band structures. The theoretically predicted higher-lying conformations most likely relax to these two structures during the adiabatic expansion. The lowest-energy gauche conformer is stabilised by an intramolecular nonconventional OH...pi-type hydrogen bond between the terminal OH group of the side chain and the pi electrons of the phenyl ring. The good agreement between the experimental and theoretical results demonstrates that even the substitution with a strongly electronegative atom of 2-phenylethanol at the para position has no noticeable effect on the strength and orientation of the OH...pi bond.

Frequency-dependent solvent friction and torsional damping in liquid 1,2-difluoroethane

NASA Astrophysics Data System (ADS)

MacPhail, Richard A.; Monroe, Frances C.

1991-04-01

We have used Raman spectroscopy to study the torsional dynamics, rotational dynamics, and conformational solvation energy of liquid 1,2-difluoroethane. From the Raman intensities, we obtain Δ H(g-t) = -2.4±0.1 kcal/mol, indicating strong dipolar solvation of the gauche conformer. We analyze the Raman linewidths of the CCF bending bands to obtain the zero-frequency torsional damping coefficient or well friction for the gauche conformer, and from the linewidth of the torsion band we obtain the friction evaluated at the torsional frequency. The zero-frequency well friction shows deviations from hydrodynamic behavior reminiscent of those observed for barrier friction, whereas the high-frequency friction is considerably smaller in magnitude and independent of temperature and viscosity. The zero-frequency torsional friction correlates linearly with the rotational friction. It is argued that the small amplitude of the torsional fluctuations emphasizes the short distance, or high wavevector components of the solvent friction. Dielectric friction apparently does not contribute to the torsional friction at the observed frequencies.

1-Methoxy-1-silacyclohexane: Synthesis, molecular structure and conformational behavior by gas electron diffraction, Raman spectroscopy and quantum chemical calculations

NASA Astrophysics Data System (ADS)

Shlykov, Sergey A.; Puchkov, Boris V.; Arnason, Ingvar; Wallevik, Sunna Ó.; Giricheva, Nina I.; Girichev, Georgiy V.; Zhabanov, Yuriy A.

2018-02-01

The synthesis and results of gas electron diffraction (GED), temperature-dependent Raman spectroscopy, along with detailed quantum chemical (QC) study of 1-methoxy-1-silacyclohexane 1 are reported. Within the series of the QC results, DFT(B3LYP, PBE0, M06, M062X), and MP2, the conformational preference predictions are rather contradictive. From the both GED and Raman experimental methods applied, the vapour and liquid phases of 1 were found to exist as a mixture of two conformers, gauche-axial and gauche-equatorial, with almost equal contributions, while the trans-forms are much less stable. In addition, theoretical calculations on the cyclohexane analog, methoxycyclohexane 2, are performed in order to compare with the conformational properties of 1. The latter is predicted not to diminish the axial/equatorial ratio, as contrasted to the expectations at switching the point of the substituent attachment from Si to C.

Rotational Spectrum of Neopentyl Alcohol, (CH_3)_3CCH_2OH

NASA Astrophysics Data System (ADS)

Kisiel, Zbigniew; Pszczołkowski, Lech; Xue, Zhifeng; Suhm, Martin A.

2012-06-01

The rotational spectrum of neopentyl alcohol (2,2-dimethyl-1-propanol, (CH_3)_3CCH_2OH) has been investigated for the first time. This molecule differs from ethanol only in having the ^tBu group instead of the methyl group, and is likewise anticipated to exhibit two spectroscopic species, with trans and gauche hydroxyl orientation. Quantum chemistry computations predict the trans to be the more stable species. Rotational transitions of both species have now been assigned in supersonic expansion cm-wave FTMW experiment and in room temperature, mm-wave spectra up to 280 GHz. The supersonic expansion measurements with Ar carrier gas confirm that trans is the global minimum species. The trans spectrum is predominantly b-type, while the gauche is predominantly a-type and the frequencies of rotational transitions in both species appear to be perturbed in different ways. The results from effective and from coupled Hamiltonian fits for neopentyl alcohol are presented, and are compared with predictions from ab initio calculations.

Investigation of the gas-phase structure and rotational barrier of trimethylsilyl trifluoromethanesulfonate and comparison with covalent sulfonates

NASA Astrophysics Data System (ADS)

Defonsi Lestard, María E.; Tuttolomondo, María E.; Varetti, Eduardo L.; Wann, Derek A.; Robertson, Heather E.; Rankin, David W. H.; Altabef, Aida Ben

2010-12-01

The molecular structure of trimethylsilyl trifluoromethanesulfonate, CF 3SO 2OSi(CH 3) 3, has been determined in the gas phase from electron-diffraction data supplemented by ab initio (MP2) and DFT calculations using 6-31G(d), 6-311++G(d,p) and 6-311G++(3df,3pd) basis sets. Both experimental and theoretical data indicate that only one gauche conformer is possible by rotating about the O-S bond. The anomeric effect is a fundamental stereoelectronic interaction and presents a profound influence on the electronic geometry. We have investigated the origin of the anomeric effect by means of NBO and AIM analysis. A natural bond orbital analysis showed that the lpπ[O bonded to Si)] → σ *[C-S] hyperconjugative interaction favors the gauche conformation. In addition, comparison of the structural and stereoelectronic properties of the title molecule with those of silyl trifluoromethanesulfonate and methyl trifluoromethanesulfonate has been carried out.

Millimeter and submillimeter wave spectroscopy of propanal

NASA Astrophysics Data System (ADS)

Zingsheim, Oliver; Müller, Holger S. P.; Lewen, Frank; Jørgensen, Jes K.; Schlemmer, Stephan

2017-12-01

The rotational spectra of the two stable conformers syn- and gauche-propanal (CH3CH2CHO) were studied in the millimeter and submillimeter wave regions from 75 to 500 GHz with the Cologne (Sub-)Millimeter wave Spectrometer. Furthermore, the first excited states associated with the aldehyde torsion and with the methyl torsion, respectively, of the syn-conformer were analyzed. The newly obtained spectroscopic parameters yield better predictions, thus fulfill sensitivity and resolution requirements in new astronomical observations in order to unambiguously assign pure rotational transitions of propanal. This is demonstrated on a radio astronomical spectrum from the Atacama Large Millimeter/submillimeter Array Protostellar Interferometric Line Survey (ALMA-PILS). In particular, an accurate description of observed splittings, caused by internal rotation of the methyl group in the syn-conformer and by tunneling rotation interaction from two stable degenerate gauche-conformers, is reported. The rotational spectrum of propanal is of additional interest because of its two large amplitude motions pertaining to the methyl and the aldehyde group, respectively.

a Comparison of the Molecular Structures of C_4H_9OCH_3, C_4H_9SCH_3, C_5H_{11}OCH_3, and C_5H_{11}SCH_3 Using Microwave Spectroscopy

NASA Astrophysics Data System (ADS)

Long, Brittany E.; Betancur, Juan; Choi, Yoon Jeong; Cooke, S. A.; Grubbs, G. S., II; Ogulnick, Jonathan; Holmes, Tara

2017-06-01

Pure rotational spectra of the title molecules have been recorded using chirped pulse Fourier transform microwave spectroscopy. Under our experimental conditions only one conformer has been observed for each of the four compounds. These conformers have torsional angles of CXCC = 180^o, XCCC = 60^o, CCCC = 180^o, and, for the C_5H_{11}-X-CH_3 species, CCCC_{Methyl} = 180^o. These angles correspond to anti-gauche-anti conformations for the butyl methyl ether/thioether species, and anti-gauche-anti-anti conformations for the pentyl methyl ether/thioether species. Splittings due to the internal rotation of the X-CH_3 group are observed in both butyl species but are not observed in the pentyl species. The barrier to the X-CH_3 internal rotation has been investigated through spectral analyses and quantum chemical calculations. The differences in the internal rotation barrier between the ethers and thioethers will be discussed and will further be compared to the barriers obtained for similar molecules.

High resolution spectroscopy of 1,2-difluoroethane in a molecular beam: A case study of vibrational mode-coupling

NASA Astrophysics Data System (ADS)

Mork, Steven W.; Miller, C. Cameron; Philips, Laura A.

1992-09-01

The high resolution infrared spectrum of 1,2-difluoroethane (DFE) in a molecular beam has been obtained over the 2978-2996 cm-1 spectral region. This region corresponds to the symmetric combination of asymmetric C-H stretches in DFE. Observed rotational fine structure indicates that this C-H stretch is undergoing vibrational mode coupling to a single dark mode. The dark mode is split by approximately 19 cm-1 due to tunneling between the two identical gauche conformers. The mechanism of the coupling is largely anharmonic with a minor component of B/C plane Coriolis coupling. Effects of centrifugal distortion along the molecular A-axis are also observed. Analysis of the fine structure identifies the dark state as being composed of C-C torsion, CCF bend, and CH2 rock. Coupling between the C-H stretches and the C-C torsion is of particular interest because DFE has been observed to undergo vibrationally induced isomerization from the gauche to trans conformer upon excitation of the C-H stretch.

Conformational Analysis of Retinoic Acids: Effects of Steric Interactions on Nonplanar Conjugated Polyenes

PubMed Central

Cox, Bryan D.; Muccio, Donald D.; Hamilton, Tracy P.

2013-01-01

Retinoic acids and other vitamin A analogs contain a trimethylcyclohexenyl ring in conjugation with a polyene chain joined at carbon-6 (C6) and carbon-7 (C7). A MP2-SCS/cc-pVDZ// B3LYP/6-31G(d) 2-D potential energy surface was computed for all-trans retinoic acid, which had 6 minima (3 enantiomeric pairs). The global minima were distorted s-gauche enantiomers (6–7 = 53°) with half-chair conformations of the ring. Distorted s-gauche enantiomers (6–7 = 55°) with inverted half-chair ring conformations were 1.7 kJ/mol above the global minima. The s-trans enantiomers (6–7 = 164°) were 11.3 kJ/mol above the global minima. Steric energies were computed by the method of Guo and Karplus to identify key structural elements in retinoic acids which determines their conformation. Small molecule crystal structures in the CCDC database with trimethylcyclohexenyl ring and exocyclic double bonds have ring-chain geometries near to one of the 6 energy minima of retinoic acids, except for retinaldehyde iminium cations. PMID:25798372

Conformational Analysis of Retinoic Acids: Effects of Steric Interactions on Nonplanar Conjugated Polyenes.

PubMed

Cox, Bryan D; Muccio, Donald D; Hamilton, Tracy P

2013-05-01

Retinoic acids and other vitamin A analogs contain a trimethylcyclohexenyl ring in conjugation with a polyene chain joined at carbon-6 (C6) and carbon-7 (C7). A MP2-SCS/cc-pVDZ// B3LYP/6-31G(d) 2-D potential energy surface was computed for all- trans retinoic acid, which had 6 minima (3 enantiomeric pairs). The global minima were distorted s-gauche enantiomers ( 6-7 = 53°) with half-chair conformations of the ring. Distorted s-gauche enantiomers ( 6-7 = 55°) with inverted half-chair ring conformations were 1.7 kJ/mol above the global minima. The s-trans enantiomers ( 6-7 = 164°) were 11.3 kJ/mol above the global minima. Steric energies were computed by the method of Guo and Karplus to identify key structural elements in retinoic acids which determines their conformation. Small molecule crystal structures in the CCDC database with trimethylcyclohexenyl ring and exocyclic double bonds have ring-chain geometries near to one of the 6 energy minima of retinoic acids, except for retinaldehyde iminium cations.

Molecular structure and conformational composition of methyl chloroacetate: An electron-diffraction and ab initio molecular orbital investigation

NASA Astrophysics Data System (ADS)

Aarset, Kirsten; Boldermo, Kjell Gunnar; Hagen, Kolbjørn

2010-08-01

The molecular structure and conformational composition of methyl chloroacetate, H 2ClC sbnd C( dbnd O) sbnd O sbnd CH 3, have been determined by gas-phase electron-diffraction (GED), using results from ab initio molecular orbital calculations (HF, MP2 and MP3/6-311+G(d,p)) to obtain constraints on some of the structural parameters. The molecules exist in the gas-phase at 25 °C as a mixture of two stable conformers: syn with C sbnd Cl eclipsing C dbnd O and gauche with C sbnd H approximately eclipsing C dbnd O. In both of these conformers O sbnd CH 3 is also eclipsing C dbnd O. The experimentally observed conformational composition at 25 °C was 36(8)% syn and 64(8)% gauche (parenthesised values are 2 σ), corresponding to a free energy difference between conformers of ΔGexp° = 1.4(9) kJ/mol. The corresponding theoretical values obtained for Δ G° are 1.1 kJ/mol (HF), 2.3 kJ/mol (MP2), and 2.4 kJ/mol (MP3). The results for the principal distances ( rh1) and angles ( ∠h1) for the major gauche conformer obtained from the combined GED/ ab initio study (2 σ uncertainties) are r(CO sbnd CCl) = 1.502(9) Å, r(C sbnd H) = 1.084(6) Å (average value), r(C sbnd Cl) = 1.782(4) Å, r(C dbnd O) = 1.213(4) Å, r(CO sbnd O) = 1.346(4) Å, r(CH 3sbnd O) = 1.468(10) Å, ∠C sbnd C sbnd Cl = 110.0(6)°, ∠C sbnd C dbnd O = 124.7(6)°, ∠C sbnd C sbnd O = 108.3(10)°, ∠C sbnd O sbnd C = 115.9(8)°, ϕ(Cl sbnd C sbnd C dbnd O) = 111(2)°, ϕ(C sbnd O sbnd C dbnd O) = 3(3)°.

Exploration of a Variety of Copper Molybdate Coordination Hybrids Based on a Flexible Bis(1,2,4-triazole) Ligand: A Look through the Composition-Space Diagram.

PubMed

Senchyk, Ganna A; Lysenko, Andrey B; Domasevitch, Konstantin V; Erhart, Oliver; Henfling, Stefan; Krautscheid, Harald; Rusanov, Eduard B; Krämer, Karl W; Decurtins, Silvio; Liu, Shi-Xia

2017-11-06

We investigated the coordination ability of the bis(1,2,4-triazolyl) module, tr 2 pr = 1,3-bis(1,2,4-triazol-4-yl)propane, toward the engineering of solid-state structures of copper polyoxomolybdates utilizing a composition space diagram approach. Different binding modes of the ligand including [N-N]-bridging and N-terminal coordination and the existence of favorable conformation forms (anti/anti, gauche/anti, and gauche/gauche) resulted in varieties of mixed metal Cu I /Mo VI and Cu II /Mo VI coordination polymers prepared under hydrothermal conditions. The composition space analysis employed was aimed at both the development of new coordination solids and their crystallization fields through systematic changes of the reagent ratios [copper(II) and molybdenum(VI) oxide precursors and the tr 2 pr ligand]. Nine coordination compounds were synthesized and structurally characterized. The diverse coordination architectures of the compounds are composed of cationic fragments such as [Cu II 3 (μ 2 -OH) 2 (μ 2 -tr) 2 ] 4+ , [Cu II 3 (μ 2 -tr) 6 ] 6+ , [Cu II 2 (μ 2 -tr) 3 ] 4+ , etc., connected to polymeric arrays by anionic species (molybdate MoO 4 2- , isomeric α-, δ-, and β-octamolybdates {Mo 8 O 26 } 4- or {Mo 8 O 28 H 2 } 6- ). The inorganic copper(I,II)/molybdenum(VI) oxide matrix itself forms discrete or low-dimensional subtopological motifs (0D, 1D, or 2D), while the organic spacers interconnect them into higher-dimensional networks. The 3D coordination hybrids show moderate thermal stability up to 230-250 °C, while for the 2D compounds, the stability of the framework is distinctly lower (∼190 °C). The magnetic properties of the most representative samples were investigated. The magnetic interactions were rationalized in terms of analyzing the planes of the magnetic orbitals.

Dimensions rénales en Service de Néphrologie Clinique, Befelatanana, Antananarivo

PubMed Central

Ramilitiana, Benja; Dodo, Mihary; Rakotoarimanga, Henintsoa Nirina; Randriamboavonjy, Rado Lalao; Randriamarotia, Willy Franck

2016-01-01

La connaissance des dimensions rénales pour tout individu et pour toute ethnie, aide à une décision médicale d'ordre diagnostique et thérapeutique. Pour un pays à faible revenu comme Madagascar, l’échographie constitue un outil idéal à cette fin. Ce travail a comme objectifs de recueillir les dimensions rénales, puis de chercher la corrélation entre ces dernières et les paramètres démographiques ou anthropométriques des Malgaches. Il s'agit d'une étude rétrospective, s’étalant sur une période de 3 ans, effectuée dans le service de Néphrologie du centre hospitalier de Befelatanana, Antananarivo, recrutant 200 patients non diabétiques, sans maladie rénale chronique. L’âge moyen de nos patients était de 45 ans ±16, avec un sex ratio de 0,9. En moyenne, les dimensions (longueur × largeur × épaisseur) étaient de 98 mm × 42 mm × 30 mm pour le rein droit et 99 mm × 45 mm × 31 mm pour le rein gauche. Nous avons retrouvé une différence significative entre le rein droit et gauche sur la longueur (p<0,00001) et la largeur (p = 0,03). Une relation significative était aussi retrouvée entre la longueur rénale et l’âge (p = 0,0016 et p = 0,04 respectivement pour le rein droit et le rein gauche). Aucune relation significative n'a été établie entre les dimensions rénales et la taille ni le poids de nos patients. Malgré ses limites, notre étude apporterait une aide sur le plan pratique clinique ainsi que pour une étude ultérieure. PMID:27642455

Direct Quantum Mechanical Simulations of Shocked Energetic Materials

DTIC Science & Technology

2008-12-01

dynamics (QMD) simulations of shocked pentaerythritol tetranitrate (PETN), a conventional high explosive , and the polymeric cubic gauche phase of...nitrogen (cg-N), proposed as an environmentally acceptable energetic alternative to conventional explosive formulations. These simulations, made...stored structural potential energy can be liberated quickly enough, it is possible that explosion can occur with energies several orders of magnitude

Validation d’indicateurs de la prise en charge des atteintes des fonctions cognitives dans les unités d’évaluation gériatrique

PubMed Central

Payot, Isabelle; Latour, Judith; Massoud, Fadi; Kergoat, Marie-Jeanne

2007-01-01

RÉSUMÉ OBJECTIF Analyser et adapter des indicateurs de qualité pour l’évaluation et la prise en charge des personnes avec atteinte des fonctions cognitives, dont la prévalence est très élevée dans les unités d’évaluation gériatrique au Québec. DEVIS Une méthode de type Delphi-modifiée. CONTEXTE Province de Québec. PARTICIPANTS Sept praticiens de milieux hospitaliers affiliés à 3 universités du Québec choisis pour leur compétence reconnue en démence et soins gériatriques. MÉTHODE Parmi les indicateurs développés en 2001 par la méthode RAND, 22 items sélectionnés pour leur pertinence au cours du processus d’évaluation et de prise en charge d’une atteinte des fonctions cognitives ont été adaptés aux conditions de pratique du milieu hospitalier québécois. Les indicateurs, accompagnés d’évidences de la littérature, ont été soumis, par la poste, à un panel d’experts. Chaque expert a coté, sur une échelle de 1 à 9, son degré d’accord à des affirmations concernant la validité, la qualité et la nécessité d’être inscrit dans le dossier médical. Pour qu’un indicateur soit retenu, il devait faire consensus selon les valeurs médianes, être situé dans le tertile supérieur et recevoir l’agrément des experts. Les indicateurs incertains étaient modifiés en fonction des commentaires des experts, puis soumis au même panel pour un second tour. RÉSULTATS Des 22 indicateurs soumis au premier tour, 21 ont été validés. Ils prenaient en compte le dépistage, l’investigation, l’évaluation, le traitement et le suivi. L’indicateur considéré comme incertain a été modifié puis accepté lors du second tour. CONCLUSION Cette étude a identifié 22 indicateurs pertinents pour l’évaluation et la prise en charge de l’atteinte des fonctions cognitives dans une unité d’évaluation gériatrique. Ils serviront de base à l’appréciation de la problématique de la démence, dans une étude ayant cours sur la qualité des soins dans l’ensemble des unités de courte durée gériatriques des hôpitaux généraux duQuébec. PMID:18000272

Analyse de L'ancrage des Vortex Intergrains pour le Yttrium BARYUM(2) CUIVRE(3) OXYGENE(7) Polycristallin

NASA Astrophysics Data System (ADS)

Fournier, Patrick

Le Modele de l'Etat Critique Generalise (MECG) est utilise pour decrire les proprietes magnetiques et de transport du YBa_2Cu_3O _7 polycristallin. Ce modele empirique permet de relier la densite de courant critique a la densite de lignes de flux penetrant dans la region intergrain. Deux techniques de mesures sont utilisees pour caracteriser nos materiaux. La premiere consiste a mesurer le champ au centre d'un cylindre creux en fonction du champ magnetique applique pour des temperatures comprises entre 20 et 85K. En variant l'epaisseur de la paroi du cylindre creux, il est possible de suivre l'evolution des cycles d'hysteresis et de determiner des champs caracteristiques qui varient en fonction de cette dimension. En utilisant un lissage des resultats experimentaux, nous determinons J _{co}, H_ {o} et n, les parametres du MECG. La forme des cylindres, avec une longueur comparable au diametre externe, entrai ne la presence d'un champ demagnetisant qui peut etre inclus dans le modele theorique. Ceci nous permet d'evaluer la fraction du volume ecrante, f _{g}, ainsi que le facteur demagnetisant N. Nous trouvons que J_{ co}, H_{o} et f_{g} dependent de la temperature, tandis que n et N (pour une epaisseur de paroi fixe) n'en dependent pas. La deuxieme technique consiste a mesurer le courant critique de lames minces en fonction du champ applique pour differentes temperatures. Nous utilisons un montage que nous avons developpe permettant d'effectuer ces mesures en contact direct avec le liquide refrigerant, i.e. dans l'azote liquide. Nous varions la temperature du liquide en variant la pression du gaz au-dessus du bain d'azote. Cette methode nous permet de balayer des temperatures entre 65K et la temperature critique du materiau ({~ }92K). Nous effectuons le lissage des courbes de courant critique en fonction du champ applique encore a l'aide du MECG, pour a nouveau obtenir ses parametres. Pour trois echantillons avec des traitements thermiques differents, les parametres sont differents confirmant que la variation des proprietes macroscopiques de ces supraconducteurs est intimement reliee a la nature des jonctions entre les grains et de la surface des grains. L'oxygenation prolongee retablit les proprietes initiales des echantillons qui se sont degrades durant le recuit des contacts.

Jean Vigo's "Zéro De Conduite" and the Spaces of Revolt

ERIC Educational Resources Information Center

Vanobbergen, Bruno; Grosvenor, Ian; Simon, Frank

2014-01-01

In this article we will contribute to the contemporary theoretical debate about film by considering, from a history-of-education perspective, the film "Zéro de conduite" by Jean Vigo (1905--1934). This film is classified under the umbrella of "poetic realism": a product of "cinéma de gauche" and an avant-gardist,…

Transition State Gauche Effects Control the Torquoselectivities of the Electrocyclizations of Chiral 1-Azatrienes.

PubMed

Patel, Ashay; Vella, Joseph R; Ma, Zhi-Xiong; Hsung, R P; Houk, K N

2015-12-04

Hsung et al. have reported a series of torquoselective electrocyclizations of chiral 1-azahexa-1E,3Z,5E-trienes that yield functionalized dihydropyridines. To understand the origins of the torquoselectivities of these azaelectrocyclizations, we modeled these electrocyclic ring closures using the M06-2X density functional. A new stereochemical model that rationalizes the observed 1,2 stereoinduction emerges from these computations. This model is an improvement and generalization of the "inside-alkoxy" model used to rationalize stereoselectivities of the 1,3-dipolar cycloaddition of chiral allyl ethers and emphasizes a stabilizing hyperconjugative effect, which we have termed a transition state gauche effect. This stereoelectronic effect controls the conformational preferences at the electrocyclization transition states, and only in one of the allowed disrotatory electrocyclization transition states is the ideal stereoelectronic arrangement achieved without the introduction of a steric clash. Computational experiments confirm the role of this effect as a stereodeterminant since substrates with electropositive groups and electronegative groups have different conformational preferences at the transition state and undergo ring closure with divergent stereochemical outcomes. This predicted reversal of stereoselectivity for the ring closures of several silyl substituted azatrienes have been demonstrated experimentally.

Conformational polymorphs of a novel TCNQ derivative carrying an acetylene group

NASA Astrophysics Data System (ADS)

Iida, Yuki; Kataoka, Makoto; Okuno, Tsunehisa

2018-01-01

TCNQ is one of the most important organic acceptors and lots of its derivatives have been prepared. However the reports on their crystal polymorphs are limited to their complexes, and simple polymorphs of TCNQ derivatives are uncommon. We succeeded in preparation of a novel TCNQ derivative, 2,2'-(2-(prop-2-yn-1-yloxy)cyclohexa-2,5-diene-1,4-diylidene)dimalononitrile, having a propynyloxy group on a substituent. This compound was found to have two crystal polymorphs depending on a solvent for recrystallization. In polymorph I, dimeric hydrogen bonds are formed between acetylenic hydrogens and cyano nitrogens with the molecule in an inversion symmetry. While, in polymorph II, the molecules make intermolecular hydrogen bonds between acetylenic hydrogens and cyano nitrogens with the molecule in 21 symmetry, forming a hydrogen bonded molecular helix along the b axis. Besides patterns of the intermolecular hydrogen bonds, difference was recognized in conformation of propynyloxy group. The molecule has an anti conformation in polymorph I and a gauche conformation in polymorph II. DFT calculation indicates that the anti conformer is less stable than the gauche one. But a solvation model suggests the anti conformer is estimated to be more stable in a toluene solution.

The Millimeter-Wave Spectrum of Propanal

NASA Astrophysics Data System (ADS)

Zingsheim, Oliver; Müller, Holger S. P.; Lewen, Frank; Schlemmer, Stephan

2017-06-01

The microwave spectrum of propanal, also known as propionaldehyde, CH_3CH_2CHO, has been investigated in the laboratory already since 1964^1 and has also been detected in space^2. Recently, propanal was detected with the Atacama Large Millimeter/submillimeter Array (ALMA), Protostellar Interferometric Line Survey (PILS)^3. The high sensitivity and resolution of ALMA indicated small discrepancies between observed and predicted rotational spectra of propanal. As higher accuracies are desired the spectrum of propanal was measured up to 500 GHz with the Cologne (Sub-)Millimeter spectrometer. Propanal has two stable conformers, syn and gauche, which differ mainly in the rotation of the aldehyd group with respect to the rigid C-atom framework of the molecule. We extensively studied both of them. The lower syn-conformer shows small splittings caused by the internal rotation of the methyl group, whereas the spectrum of gauche-propanal is complicated due to the tunneling rotation interaction from two stable degenerate conformers. Additionally, we analyzed vibrationally excited states. ^1 Butcher et al., J. Chem. Phys. 40 6 (1964) ^2 Hollis et al., Astrophys. J. 610 L21 (2004) ^3 Lykke et al., A&A 597 A53 (2017)

Molecular dynamics study of the conformational properties of cyclohexadecane

NASA Astrophysics Data System (ADS)

Zhang, Renshi; Mattice, Wayne L.

1993-06-01

Molecular dynamics has been used for the first time for the study of the conformational properties of cyclohexadecane, c-C16H32. By analyzing a long molecular dynamics trajectory (14.5 ns) at 450 K, equilibrium statistics such as the relative populations of different isomeric conformers and the probability ratios, p(gt)/p(tt), p(gg)/p(tt), and p(gg)/p(gtg), of different conformational segments, have been studied. The dynamic properties including the transition modes of gauche migration and gauche-pair creation, which have been reported before in n-alkanes, and the auto- and cross-correlations of the bond dihedral angles, have also been obtained. It was possible to make direct comparisons on some of the statistics with theory and experiment. Most of the results extracted from the molecular dynamics trajectory lie in between previously reported experimental and theoretical values. Many previously predicted conformers have been confirmed by our simulations. The results of the population probability of the most populated conformer seems to suggest that an earlier discrepancy between the theoretical works and an experimental work originates from insufficient samplings in earlier theoretical works, rather than from their inaccurate force field.

Application d'une technique de modelisation aerodynamique conceptuelle sur la simulation d'un pilote automatique a commande optimale pour un avion d'affaires

NASA Astrophysics Data System (ADS)

Pollender-Moreau, Olivier

Ce document présente, dans le cadre d'un contexte conceptuel, une méthode d'enchaînement servant à faire le lien entre les différentes étapes qui permettent de réaliser la simulation d'un aéronef à partir de ses données géométriques et de ses propriétés massiques. En utilisant le cas de l'avion d'affaires Hawker 800XP de la compagnie Hawker Beechcraft, on démontre, via des données, un processus de traitement par lots et une plate-forme de simulation, comment (1) modéliser la géométrie d'un aéronef en plusieurs surfaces, (2) calculer les forces aérodynamiques selon une technique connue sous le nom de Vortex Lattice Method, (3) construire un modèle de vol servant à la simulation des aéronefs pour leur enveloppe de vol en ajoutant des fonctions supplémentaires, (4) construire un modèle de turbosoufflante simplifié, (5) développer un algorithme d'équilibre (trim) du mouvement longitudinal, (6) développer des algorithmes de contrôle à commande moderne, (7) développer certaines fonctions d'un système de pilotage automatique, et (8) rassembler le tout sous une même plate-forme de simulation. Afin de supporter ce travail, une application publique Matlab, connue sous le nom de Tornado, est utilisée conjointement avec d'autres fonctions pour la conception du modèle de vol aérodynamique. D'ailleurs, il sera démontré que le modèle de vol, quoiqu'il soit quand même crédible, ne concorde pas tout à fait avec les données de référence. Par contre, puisque le modèle des moteurs fonctionne bien, que l'algorithme d'équilibrage du mouvement longitudinal fonctionne bien et que les pôles des systèmes dynamiques concordent avec la littérature, les tests dynamiques effectués au sein de la plate-forme de simulation permettent d'obtenir des résultats fonctionnels et crédibles. D'ailleurs, deux systèmes d'augmentation de la stabilité basés sur la méthode de contrôle moderne LQR et couvrant l'enveloppe de vol de l'aéronef via un système d'ordonnancement des gains sont implémentés respectivement selon les mouvements longitudinal et latéral. Ces fonctions fonctionnent bien et permettent de rencontrer les qualités de vol requises pour un avion d'affaires. Finalement, certaines fonctions concernant un système de pilotage automatique sont implémentées. Dans le cas du mouvement latéral, ces fonctions sont basées sur les méthodes de contrôle modernes et couvrent la totalité de l'enveloppe de vol; mais en ce qui concerne le mouvement longitudinal, elles sont basées sur des algorithmes d'équilibre difficile à gérer pour implémenter sur toute l'enveloppe de vol, c'est pourquoi les tests présentés sont limités à des scénarios bien précis. Dans les deux cas, les essais effectués donnent d'assez bons résultats.

Les pyélonephrites aigues de la femme enceinte: place du traitement médical et indications d'un drainage de la voie excrétrice supérieure (y'a-t-il des facteurs prédictifs cliniques, biologiques et radiologiques pour rendre le drainage licite?)

PubMed Central

El Bahri, Abdessamad; Janane, Abdellatif; Chafiki, Jaouad; Arnaud, Tayiri; Ghadouane, Mohammed; Ameur, Ahmed; Abbar, Mohammed

2015-01-01

Les pyélonéphrites aigues gravidiques (PNAg) sont fréquentes et peuvent avoir des conséquences maternelles et fœtales graves. Le but de notre étude était de déterminer les facteurs prédictifs cliniques, biologiques et radiologiques qui permettent de se limiter au traitement médical ou d'associer un drainage de la voie excrétrice supérieure dans la prise en charge des PNAg. Nous rapportons, de façon rétrospective une série de 26 cas dans les services d'Urologie et de Gynécologie de l'Hôpital Militaire d'Instruction Mohamed V de Rabat (Maroc) sur une période allant du 1er Janvier 2010 au 30 Aout 2012. Toutes les patientes avaient une PNAg symptomatique objectivée par l'ECBU et/ou l’échographie rénale. La fréquence de la pyélonéphrite aigue gravidique par rapport aux pyélonéphrites aigues en général a été de 27,95% avec une prédominance chez les primipares de 53,84%. Son pic de fréquence se situe à 73,08% pour les gestantes âgées de 19 à 37 ans ainsi qu'au troisième trimestre (77%) de la grossesse. La triade clinique fièvre, lombalgie, troubles mictionnels et l’échographie rénale sont les éléments importants du diagnostic. L'antibiothérapie probabiliste a été débuté d'emblée et adaptée en fonctions des résultats de l'examen cytobactériologique des urines. Sa durée est de trois à six semaines en fonction de l’évolution clinique. La protéine C réactive est un marqueur de progression de la maladie ou de l'efficacité thérapeutique. Les principaux facteurs prédictifs du drainage de la voie excrétrice supérieure sont: persistance de la symptomatologie clinique, du syndrome infectieux et des anomalies visibles à l’échographie rénale ainsi que l'altération de la fonction rénale. La montée de la sonde JJ est le principal traitement urologique. Le traitement médical repose sur l'antibiothérapie probabiliste qui sera adaptée Ultérieurement en fonction des résultats de l'antibiogramme. Les facteurs prédictifs d'un drainage de la VES sont: la persistance de la symptomatologie clinique, du syndrome infectieux et des anomalies visibles à l’échographie rénale ainsi que l'altération de la fonction rénale. PMID:26977232

Rotational Spectroscopy of Two Tellurol Compounds : Ethyl and Vinyl-Tellurol

NASA Astrophysics Data System (ADS)

Motiyenko, R.; Margulès, L.; Goubet, M.; Møllendal, H.; Guillemin, J. C.

2009-06-01

Among the compounds containing a chalcogen, the tellurols (R-TeH) have been poorly investigated previously. Only H_2Te was studied in rotational spectroscopy. This fact can be explained by high toxicity and high chemical reactivity of these compounds. However quite recently, a new method allowing easily obtention of pure samples has been reported. Thanks to this approach, very high acidity of these tellurols in gas phase has been measured and photoelectron spectra have been recorded. It should be noted that, even if simple derivatives are known since a long time, no microwave spectrum of these compounds has been recorded previously. The determination of their rotational constants is however a determining step to have a quite complete knowledge of such systems and to be able to perform comparisons of their physicochemical properties with those of the corresponding thiols and selenols which have been more extensively studied. The rotational spectra of vinyl and ethyl-tellurol have been recorded in the frequency range up to 210 GHz. For both compounds gauche forms have been assigned due to rather distinguishable patterns of a-type transitions. The assignments were confirmed by comparison with the results of ab initio calculations. For ethyl-tellurol the rotational transitions were observed as doublets. The splittings are probably caused by tunneling effect between two equivalent configurations (gauche^+, gauche^-). The assignment and analysis of the rotational spectra of both molecules is in progress. The latest results will be reported. I. N. Kozin, P. Jensen, O. Polanz, S. Klee, L. Poteau, and J. Demaison, J. Mol. Spectrosc., 180 402-413 (1996) J. C. Guillemin, A. Bouayard, D. Vijaykumar, D. Chem. Commun., 1163-1164 (2000) J. C. Guillemin, El. H. Riague, J. F. Gal, P. C. Marris, O. Mo., M. Yanez, Chem. Eur. J. 11, 2145-2153 (2005) B. Khater, J. C. Guillemin, G. Bajor, T. Veszprémi, P. C. Marris, O. Mo., M. Yanez, Inorg. Chem. 112, 3053-3060 (2008) A. Baroni, Atti Accad. Naz. Lincei, Cl. Sci. Fis., Mat. Nat., Rend. 27, 238-242 (1938)

Molecular-dynamics simulations of self-assembled monolayers (SAM) on parallel computers

NASA Astrophysics Data System (ADS)

Vemparala, Satyavani

The purpose of this dissertation is to investigate the properties of self-assembled monolayers, particularly alkanethiols and Poly (ethylene glycol) terminated alkanethiols. These simulations are based on realistic interatomic potentials and require scalable and portable multiresolution algorithms implemented on parallel computers. Large-scale molecular dynamics simulations of self-assembled alkanethiol monolayer systems have been carried out using an all-atom model involving a million atoms to investigate their structural properties as a function of temperature, lattice spacing and molecular chain-length. Results show that the alkanethiol chains tilt from the surface normal by a collective angle of 25° along next-nearest neighbor direction at 300K. At 350K the system transforms to a disordered phase characterized by small tilt angle, flexible tilt direction, and random distribution of backbone planes. With increasing lattice spacing, a, the tilt angle increases rapidly from a nearly zero value at a = 4.7A to as high as 34° at a = 5.3A at 300K. We also studied the effect of end groups on the tilt structure of SAM films. We characterized the system with respect to temperature, the alkane chain length, lattice spacing, and the length of the end group. We found that the gauche defects were predominant only in the tails, and the gauche defects increased with the temperature and number of EG units. Effect of electric field on the structure of poly (ethylene glycol) (PEG) terminated alkanethiol self assembled monolayer (SAM) on gold has been studied using parallel molecular dynamics method. An applied electric field triggers a conformational transition from all-trans to a mostly gauche conformation. The polarity of the electric field has a significant effect on the surface structure of PEG leading to a profound effect on the hydrophilicity of the surface. The electric field applied anti-parallel to the surface normal causes a reversible transition to an ordered state in which the oxygen atoms are exposed. On the other hand, an electric field applied in a direction parallel to the surface normal introduces considerable disorder in the system and the oxygen atoms are buried inside.

Very high resolution far infrared synchrotron radiation spectrum of methanol-D1 (CH2DOH) in the first three torsional-vibrational modes

NASA Astrophysics Data System (ADS)

Mukhopadhyay, Indra; Billinghurst, B. E.

2016-11-01

In our effort to systematically study the far infrared (FIR) spectra of asymmetrically mono deuterated methanol (CH2DOH) and thereby obtain the transition wavenumbers with better and better accuracy (Mukhopadhyay, 2016a,b), the complete Fourier transform (FT) spectra from FIR to infrared (IR) vibrational bands (in the range 50-1190 cm-1) have been re-recorded using the Synchrotron Radiation Source at the Canadian Light Sources in Saskatchewan, Canada. The resolution of the spectrum is unprecedented, reaching beyond the Doppler limited resolution as low as about 0.0008 cm-1 with a signal to noise (S/N) ratio is many fold better than that can be obtained by commercially available FT spectrometer using thermal sources (e.g., Globar). Spectra were also recorded beyond 1190 cm-1 to about 5000 cm-1 at a somewhat lower resolution of 0.002-0.004 cm-1. In this report the analysis of the b-type and c-type torsional - rotational spectra in the ground vibrational state corresponding to gauche- (e1/o1) to gauche- (e1/o1) and gauche- (e1/o1) to trans- (e0) states in the ground vibrational state are reported and an atlas of the wavenumber for about 2500 FIR assigned absorption lines has been prepared. The transitions within a given sub-band are analyzed using state dependent expansion parameters and the Q-branch origins. The data from previous results (Mukhopadhyay, 2016a,b) along with the present work allowed a global analysis yielding a complete set of molecular parameters. The state dependent molecular parameters reproduce the experimental wavenumbers within experimental uncertainty. In addition, the sensitivity of the spectrum allowed observation of forbidden transitions previously unobserved and helped reassignment of rotational angular momentum quantum numbers of some ΔK = ±1, Q-branch transitions in highly excited states recently reported in the literature. To our knowledge the wavenumbers reported in the present work are the most accurate so far reported in the literature and represent the highest resolution spectra for this molecular species.

Vegetation and soils

USGS Publications Warehouse

Burke, M.K.; King, S.L.; Eisenbies, M.H.; Gartner, D.

2000-01-01

Intro paragraph: Characterization of bottomland hardwood vegetation in relatively undisturbed forests can provide critical information for developing effective wetland creation and restoration techniques and for assessing the impacts of management and development. Classification is a useful technique in characterizing vegetation because it summarizes complex data sets, assists in hypothesis generation about factors influencing community variation, and helps refine models of community structure. Hierarchical classification of communities is particularly useful for showing relationships among samples (Gauche 1982).

Early structural development in melt-quenched polymer PTT from atomistic molecular dynamic simulations

NASA Astrophysics Data System (ADS)

Hsieh, Min-Kang; Lin, Shiang-Tai

2009-12-01

Molecular dynamics simulations are performed to study the initial structural development in poly(trimethylene terephthalate) (PTT) when quenched below its melting point. The development of local ordering has been observed in our simulations. The thermal properties, such as the glass transition temperature (Tg) and the melting temperature (Tm), determined from our simulations are in reasonable agreement with experimental values. It is found that, between these two temperatures, the number of local structures quickly increases during the thermal relaxation period soon after the system is quenched and starts to fluctuate afterwards. The formation and development of local structures is found to be driven mainly by the torsional and van der Waals forces and follows the classical nucleation-growth mechanism. The variation of local structures' fraction with temperature exhibits a maximum between Tg and Tm, resembling the temperature dependence of the crystallization rate for most polymers. In addition, the backbone torsion distribution for segments within the local structures preferentially reorganizes to the trans-gauche-gauche-trans (t-g-g-t) conformation, the same as that in the crystalline state. As a consequence, we believe that such local structural ordering could be the baby nuclei that have been suggested to form in the early stage of polymer crystallization.

Weak Intramolecular Interactions Effcts on the Structure and the Torsional Spectra of Ethylene Glycol, AN Astrophysical Species

NASA Astrophysics Data System (ADS)

Senent, Maria Luisa S.; Boussessi, Rahma

2016-06-01

A variational procedure of reduced dimensionality based on CCSD(T)-F12 calculations is applied to understand the far infrared spectrum of Ethylene-Glycol. This molecule can be classified in the double molecular symmetry group G8 and displays nine stable conformers, gauche and trans. In the gauche region, the effect of the potential energy surface anisotropy due to the formation of intramolecular hydrogen bonds is relevant. For the primary conformer, the ground vibrational state rotational constants are computed at 6.3 MHz, 7.2 MHz and 3.5 MHz from the experimental parameters. Ethylene glycol displays very low torsional energy levels whose classification is not straightforward. Given the anisotropy, tunneling splittings are significant and unpredictable. The ground vibrational state splits into 16 sublevels separated approximately 142 cm-1. Transitions corresponding to the three internal rotation modes allow assign previous observed Q branches. Band patterns, calculated between 362.3 cm-1 and 375.2 cm-1, between 504 cm-1 and 517 cm-1 and between 223.3 cm-1 and 224.1 cm-1, that correspond to the tunnelling components of the v21 fundamental (ν21 = OH-torsional mode), are assigned to the prominent experimental Q branches.

Evidence of conformational exchange averaging in the thermal rotational spectrum of ethyl cyanoformate.

PubMed

True, Nancy S

2006-06-15

The Stark modulated low resolution microwave spectrum of ethyl cyanoformate between 21.5 and 24.0 GHz at 210, 300, and 358 K, which shows the J + 1 <-- J = 8 <-- 7 bands of three species, is compared to simulations based on electronic structure calculations at the MP2/6-311++G theory level. Calculations at this theory level reproduce the relative energies of the syn-anti and syn-gauche conformers, obtained in a previous study, and indicate that the barrier to conformer exchange is approximately 360 cm(-1) higher in energy than the syn-anti minimum. Simulated spectra of the eigenstates of the calculated O-ethyl torsional potential function reproduce the relative intensities and shapes of the lower and higher frequency bands which correspond to transitions of the syn-anti and syn-gauche conformers, respectively, but fail to reproduce the intense center band in the experimental spectra. A model incorporating exchange averaging reproduces the intensity of the center band and its temperature dependence. These simulations indicate that a large fraction of the thermal population at all three temperatures undergoes conformational exchange with an average energy specific rate constant, , of approximately 25 GHz. This model can explain anomalies present in rotational spectra of many other compounds composed of mixtures of conformers.

Characterization of crystallinity in PET bottles by IR spectroscopy

NASA Astrophysics Data System (ADS)

Nguyen, Tuan Q.; Christopher, Plummer J. G.

2000-03-01

PET is a semicrystalline thermoplastic widely used to package foods and beverages. Most of these applications rely on the barrier properties of the polymer, which improve with the proportion of crystalline phase. It is therefore important for the industries concerned to develop a fast, simple and reliable technique to quantify the degree of crystallization. Current FTIR and Raman spectroscopy correlate cristallinity with the trans to gauche ratio of the ethylene conformational isomers. Such a procedure, however, is based on the naive assumption that the proportion of trans isomers in the crystalline regions and that of the trans/gauche isomers in the amorphous regions vary linearly with the total crystallinity. By combining density measurements with DSC, WAXS and FTIR, we have shown the conformer technique to work well for isotropic PET sheets, but not for bottles. Biaxial extension of the preform during processing results in strain-induced cristallinity with a different morphology to that induced thermally. As a result, PET should be treated as a three-component mixture with distinct physical and spectroscopic properties for each phase. Using ATR, micro-transmission FTIR and factor analysis, our primary goal has been to develop a routine technique which allows one to identify the contribution of each component in the spectra of commercial PET bottles.

Alpha-helix to beta-sheet transition in long-chain poly-l-lysine: Formation of alpha-helical fibrils by poly-l-lysine.

PubMed

Cieślik-Boczula, Katarzyna

2017-06-01

The temperature-induced α-helix to β-sheet transition in long-chain poly-l-lysine (PLL), accompanied by the gauche-to-trans isomerization of CH 2 groups in the hydrocarbon side chains of Lys amino acid residues, and formation of β-sheet as well as α-helix fibrillar aggregates of PLL have been studied using Fourier-transform infrared (FT-IR) and vibrational circular dichroism (VCD) spectroscopy, and transmission electron microscopy (TEM). In a low-temperature alkaline water solution or in a methanol-rich water mixture, the secondary structure of PLL is represented by α-helical conformations with unordered and gauche-rich hydrocarbon side chains. Under these conditions, PLL molecules aggregate into α-helical fibrils. PLLs dominated by extended antiparallel β-sheet structures with highly ordered trans-rich hydrocarbon side chains are formed in a high-temperature range at alkaline pD and aggregate into fibrillar, protofibrillar, and spherical forms. Presented data support the idea that fibrillar aggregation is a varied phenomenon possible in repetitive structural elements with not only a β-sheet-rich conformation, but also an α-helical-rich conformation. Copyright © 2017 Elsevier B.V. and Société Française de Biochimie et Biologie Moléculaire (SFBBM). All rights reserved.

Conformational stability, r(0) structural parameters, vibrational assignments and ab initio calculations of ethyldichlorophosphine.

PubMed

Darkhalil, Ikhlas D; Paquet, Charles; Waqas, Mohammad; Gounev, Todor K; Durig, James R

2015-02-05

Variable temperature (-60 to -100 °C) studies of ethyldichlorophosphine, CH3CH2PCl2, of the infrared spectra (4000-400 cm(-1)) dissolved in liquid xenon have been carried out. From these data, the two conformers have been identified and the enthalpy difference has been determined between the more stable trans conformer and the less stable gauche form to be 88±9 cm(-1) (1.04±0.11 kJ/mol). The percentage of abundance of the gauche conformer is estimated to be 57% at ambient temperature. The conformational stabilities have been predicted from ab initio calculations by utilizing many different basis sets up to aug-cc-pVTZ for both MP2(full) and density functional theory calculations by the B3LYP method. Vibrational assignments have been provided for both conformers which have been predicted by MP2(full)/6-31G(d) ab initio calculations to predict harmonic force fields, wavenumbers of the fundamentals, infrared intensities, Raman activities and depolarization ratios for both conformers. Estimated r0 structural parameters have been obtained from adjusted MP2(full)/6-311+G(d,p) calculations. The results are discussed and compared to the corresponding properties of some related molecules. Copyright © 2014 Elsevier B.V. All rights reserved.

Fonctions Discursives et Communication Ecrite (Discursive Functions and Written Communication). Melanges Pedagogiques, 1974.

ERIC Educational Resources Information Center

Duda, R.

This article describes discursive functions in the three major areas of non-literary written communication: (1) official or personal correspondence; (2) technical reading or editing; and (3) the press. Illocutionary acts are examined under their three aspects: graphic, lexical, enunciative. This description is intended to result in training…

Syndrome coronarien aigue suite à une injection accidentelle intraveineuse de Bupivacaine

PubMed Central

Koita, Siriman Abdoulaye; Bouhabba, Najib; Salaheddine, Fjouji; Bensghir, Mustapha; Charki, Haimeur

2015-01-01

Les erreurs médicamenteuses constituent une complication très redoutable en anesthésie. La fréquence des erreurs médicamenteuses par administration serait de l'ordre 1/10 000 à 1/1000. Nous rapportons un cas d'injection accidentelle de bupivacaine en intraveineuse directe. Il s'agissait d'un jeune patient classé ASA I qui était prévu pour cure chirurgicale d'une hydrocèle unilatérale sous rachianesthésie. Une injection de 12,5 mg de bupivacaine et 25 µg de fentanyl étaient injectés après un reflux net du liquide céphalorachidien sans incident. Après installation de la rachianesthésie, le début de l'intervention était autorisé sans incidents. Une sédation de confort était décidée. Juste après apparaissait des troubles de rythme à type tachycardie ventriculaire avec une élévation de taux de troponines en post opératoire. L’évolution était marquée par une normalisation de la troponine au troisième jour post opératoire et sorti de l'hôpital au cinquième jour. PMID:26889325

1H and 13C NMR studies of molecular dynamics in the biocopolymer of glycolide and epsilon-caprolactone.

PubMed

Nozirov, Farhod; Szczesniak, Eugeniusz; Fojud, Zbigniew; Dobrzynski, Piotr; Klinowski, Jacek; Jurga, Stefan

2002-08-01

Copolymers of glycolide and epsilon-caprolactone were studied using differential scanning calorimetry and solid-state NMR. The variation of the T1 relaxation time with temperature reflects local disorder and can be quantified in terms of the distribution of correlation times predicted by the Davidson-Cole model. T, relaxation is dominated by trans-gauche isomerisation, with an activation energy of 34-35 kJ mol(-1).

Comparative matrix isolation infrared spectroscopy study of 1,3- and 1,4-diene monoterpenes (α-phellandrene and γ-terpinene).

PubMed

Marzec, K M; Reva, I; Fausto, R; Proniewicz, L M

2011-05-05

In the present work, γ-terpinene (a 1,4-diene derivative) and α-phellandrene (1,3-diene derivative) were isolated in cryogenic argon matrices and their structures, vibrational spectra, and photochemistries were characterized with the aid of FTIR spectroscopy and quantum chemical calculations performed at the DFT/B3LYP/6-311++G(d,p) level of approximation. The molecules bear one conformationally relevant internal rotation axis, corresponding to the rotation of the isopropyl group. The calculations provide evidence of three minima on the potential energy surfaces of the studied molecules, where the isopropyl group assumes the trans, gauche+, and gauche- conformations (T, G+, G-). The signatures of all these conformers were identified in the experimental matrix infrared spectra, with the T forms dominating, in agreement with the theoretical predicted abundances in gas phase at room temperature. In situ UV (λ > 200 nm) irradiation of matrix-isolated α-phellandrene led to its isomerization into an open-ring species. The photoproduct was found to exhibit the ZE configuration of its backbone, which to be formed from the reactant molecule does not require extensive structural rearrangements of both the reagent and matrix. γ-Terpinene was photostable when subjected to irradiation under the same experimental conditions. In addition, the liquid compounds at room temperature were also investigated by FTIR-ATR and FT-Raman spectroscopies.

Conformational Characteristics of Poly(tetrafluoroethylene) (PTFE) Based Upon Ab Initio Electronic Structure Calculations on Model Molecules

NASA Technical Reports Server (NTRS)

Smith, Grant D.; Jaffe, R. L.; Yoon, D. Y.; Arnold, James O. (Technical Monitor)

1994-01-01

Conformational energy contours of perfluoroalkanes, determined from ab initio calculations, confirm the well-known spitting of trans states into two minima at plus or minus 17 degrees but also show that the gauche states split as well, with minima at plus or minus 124 degrees and plus or minus 84 in order to relieve steric crowding. The directions of such split distortions from the perfectly staggered states are strongly coupled for adjacent pairs of bonds in a manner identical to the intradyad pair for poly (isobutylene) chains. These conformational characteristics are fully represented by a six-state rotational isomeric state (RIS) model for PTFE comprised of t(+), t(-), g(sup +)+, g(sup +)-, g(sup -) + and g(sup -)-states, located at the split energy minima. The resultant 6 x 6 statistical weight matrix is described by first-order interaction parameters for the g+(+) (ca. 0.6 kcal/mol) and g+- (ca. 2.0 kcal/mol) states, and second order parameters for the g(sup +)+g(sup +)+ (ca 0.6 kcal/mol) and g(sup +)+g(sup -)+ (ca. 1.0 kcal/mol) states. This six-state RIS model, without adjustment of the geometric or energy parameters as determined from the ab initio calculations, predicts the unperturbed chain dimensions and the fraction of gauche bonds as a function of temperature for PTFE in good agreement with available experimental values.

[Study of selegiline and related compounds with x-ray diffraction].

PubMed

Simon, K; Böcskei, Z; Török, Z

1992-09-01

Selegiline and its parent compounds were studied by X-ray diffraction. It was established that the racemates of primary and secondary amines (p-fluoro-amphetamine, methamphetamine, p-fluoro-methamphetamine) hydrochloride do not form racemic compounds but crystalline as conglomerates, at the same time tertiary amines like selegiline and p-fluoro-selegiline hydrochlorides do. The crystalline structure of five enantiomeric hydrochlorides were determined, the CPhe-C-C-N torsion angle is anti-periplanar in all cases but in p-fluoro-amphetamine where it is gauche.

Ethane-1,1,2-trisphosphonic acid hemihydrate.

PubMed

Delain-Bioton, Lise; Lohier, Jean François; Villemin, Didier; Sopková-de Oliveira Santos, Jana; Hix, Gary; Jaffrès, Paul Alain

2008-02-01

Ethane-1,1,2-trisphosphonic acid crystallizes as a hemihydrate, C(2)H(9)O(9)P(3).0.5H(2)O, in which the water O atom lies on an inversion centre in the space group P2(1)/c. The acid component, which contains a short but noncentred O-H...O hydrogen bond, adopts a gauche conformation. The acid components are linked by an extensive series of O-H...O hydrogen bonds to form layers, which are linked into pairs by the water molecules.

An Expert System for Searching in Full-Text

DTIC Science & Technology

1989-12-01

2 An Expert System for Searching in Full-Text 00~ TR89-043 -December, 1989 cc D IF L, ~r." T M~ EA 13~ 1991ON- The University of North Carolina at...Full-Text by Susan Evalyn Gauch A dissertation submitted to the faculty of The University of North Carolina at Chapel Hill in partial fulfillment of...MICROARRAS, the retrieval software. MICROARRAS developed at the University of North Carolina under the direction of John B. Smith and Stephen Weiss [Smith et

Etude vibroacoustique d'un systeme coque-plancher-cavite avec application a un fuselage simplifie

NASA Astrophysics Data System (ADS)

Missaoui, Jemai

L'objectif de ce travail est de developper des modeles semi-analytiques pour etudier le comportement structural, acoustique et vibro-acoustique d'un systeme coque-plancher-cavite. La connection entre la coque et le plancher est assuree en utilisant le concept de rigidite artificielle. Ce concept de modelisation flexible facilite le choix des fonctions de decomposition du mouvement de chaque sous-structure. Les resultats issus de cette etude vont permettre la comprehension des phenomenes physiques de base rencontres dans une structure d'avion. Une approche integro-modale est developpee pour calculer les caracteristiques modales acoustiques. Elle utilise une discretisation de la cavite irreguliere en sous-cavites acoustiques dont les bases de developpement sont connues a priori. Cette approche, a caractere physique, presente l'avantage d'etre efficace et precise. La validite de celle-ci a ete demontree en utilisant des resultats disponibles dans la litterature. Un modele vibro-acoustique est developpe dans un but d'analyser et de comprendre les effets structuraux et acoustiques du plancher dans la configuration. La validite des resultats, en termes de resonance et de fonction de transfert, est verifiee a l'aide des mesures experimentales realisees au laboratoire.

Gas Phase Raman Spectra of Butadiene and BUTADIENE-d_{6} and the Internal Rotation Potential Energy Function

NASA Astrophysics Data System (ADS)

Boopalachandran, Praveenkumar; Laane, Jaan; Craig, Norman C.

2009-06-01

The Raman spectrum of butadiene has been previously reported by Carreira and by Engeln and co-workers. Both studies reported a series of bands corresponding to double quantum jumps of ν_{13}, the internal rotation vibration, of the trans rotamer. Both studies also reported weaker bands assigned to the higher energy conformer. Carriera assigned these to the cis form while Engeln assigned them to the gauche form. Recent high level calculations by Feller and Craig also assign the higher energy form as gauche. In the present study we report the gas phase Raman spectrum of butadiene and its d_{6} isotopomer at both 25^°C and 260^°C. Several new spectral features in the 330 to 210 cm^{-1} region were observed and the effect of heating on the band intensities was studied. In addition, combination bands were observed in the 630 to 690 cm^{-1} (ν_{12} + ν_{13}) and 1130 to 1180 cm^{-1} (ν_{10} + ν_{13}) regions. A periodic potential energy function with V_{1}, V_{2}, V_{3}, V_{4}, and V_{6} terms was utilized to fit the data. This function was compared to the results from previous work and to the theoretical calculation. L. Carreira, J. Phys. Chem. 62, 3851 (1975). R. Engeln, D. Consalvo, and J. Reuss, J. Chem. Phys. 160, 427 (1992). D. Feller and N. C. Craig, J. Phys. Chem. 113, 1601 (2009).

Dynamic behaviors and transport properties of ethanol molecules in transmembrane cyclic peptide nanotubes.

PubMed

Li, Rui; Fan, Jianfen; Li, Hui; Yan, Xiliang; Yu, Yi

2015-07-07

Classical molecular dynamics simulations have been performed to investigate the dynamic behaviors and transport properties of ethanol molecules in transmembrane cyclic peptide nanotubes (CPNTs) with various radii, i.e., 8×(WL¯)n=3,4,5/POPE. The results show that ethanol molecules spontaneously fill the octa- and deca-CPNTs, but not the hexa-CPNT. In the octa-CPNT, ethanol molecules are trapped at individual gaps with their carbon skeletons perpendicular to the tube axis and hydroxyl groups towards the tube wall, forming a broken single-file chain. As the channel radius increases, ethanol molecules inside the deca-CPNT tend to form a tubular layer and the hydroxyl groups mainly stretch towards the tube axis. Computations of diffusion coefficients indicate that ethanol molecules in the octa-CPNT nearly lost their diffusion abilities, while those in the deca-CPNT diffuse as 4.5 times as in a (8, 8) carbon nanotube with a similar tube diameter. The osmotic and diffusion permeabilities (pf and pd, respectively) of the octa- and deca-CPNTs transporting ethanol were deduced for the first time. The distributions of the gauche and trans conformers of ethanol molecules in two CPNTs are quite similar, both with approximately 57% gauche conformers. The non-bonded interactions of channel ethanol with a CPNT wall and surrounding ethanol were explored. The potential of mean force elucidates the mechanism underlying the transporting characteristics of channel ethanol in a transmembrane CPNT.

Sum frequency generation spectroscopy of tetraalkylphosphonium ionic liquids at the air-liquid interface

NASA Astrophysics Data System (ADS)

Peñalber-Johnstone, Chariz; Adamová, Gabriela; Plechkova, Natalia V.; Bahrami, Maryam; Ghaed-Sharaf, Tahereh; Ghatee, Mohammad Hadi; Seddon, Kenneth R.; Baldelli, Steven

2018-05-01

Sum frequency generation (SFG) spectroscopy is a nonlinear vibrational spectroscopic technique used in the study of interfaces, due to its unique ability to distinguish surface molecules that have preferential ordering compared to the isotropic bulk. Here, a series of alkyltrioctylphosphonium chloride ionic liquids, systematically varied by cation structure, were characterized at the air-liquid interface by SFG. The effect on surface structure resulting from molecular variation (i.e., addition of cyano- and methoxy-functional groups) of the cation alkyl chain was investigated. SFG spectra in the C—H stretching region (2750-3100 cm-1) for [P8 8 8 n][Cl], where n = 4, 5, 8, 10, 12, or 14, showed characteristic changes as the alkyl chain length was increased. Spectral profiles for n = 4, 5, 8, or 10 appeared similar; however, when the fourth alkyl chain was sufficiently long (as in the case of n = 12 or n = 14), abrupt changes occurred in the spectra. Molecular dynamics (MD) simulation of a slab of each ionic liquid (with n = 8, 10, or 12) confirmed gauche defects, with enhancement for the long alkyl chain and an abrupt increase of gauche occurrence from n = 8 to n = 10. A comparison of the tilt angle distribution from the simulation and the SFG analysis show a broad distribution of angles. Using experimental SFG spectra in conjunction with MD simulations, a comprehensive molecular picture at the surface of this unique class of liquids is presented.

The Free Jet Microwave Spectrum of 2-PHENYLETHYLAMINE-WATER

NASA Astrophysics Data System (ADS)

Melandri, Sonia; Giuliano, B. Michela; Maris, Assimo; Caminati, Walther

2009-06-01

2-Phenylethylamine (PEA) is the parent structure for a variety of important compounds including dopamine, tyrosine, anphetamine and adrenaline. Due to the flexibility of the side chain, the conformational hypersurface of the isolated molecule contains several minima at relatively low energy. The conformational surface was studied by various spectroscopic and theoretical techniques and four of the five stable conformers were detected. The most stable conformers observed in isolated conditions are those in which the methylene side chain is folded into a gauche structure and the amino hydrogen is oriented towards the aromatic ring to form a weakly hydrogen bonded structure, while in the less stable conformers the amino group is in the anti position, thus the energy difference between the gauche and anti conformers (ca 4 kJ mol^{-1}) represents the energy associated with this weak interaction. Since bioactive molecules can be found in different environments including aqueous media and rotational spectroscopy coupled with high level ab initio calculations gives the most detailed structural picture, we studied the free jet microwave spectrum of the adducts formed between PEA and water in the region 60-78 GHz. The dominant spectrum is that of the 1:1 adduct of PEA and water where PEA is in its most stable gauche conformation and the water molecole is bound to the nitrogen lone pair. The orientation of the water molecole is such that the oxygen atom is closest (ca 2.5 Å) and equidistant from the ring and chain hydrogen atoms. The experimental data were complemented by ab initio calculations at the MP2/6311++G** level of theory; several stable conformations of the PEA-W have been characterized and the observed structure corresponds to the global minimum. The bonding of water seems to affect only slightly the structure of isolated PEA and the main structural parameters of the flexible amino side chain remain basically unaltered. Some lines still remain unassigned in the spectrum and we are hoping to assign them to a second conformational species of PEA-W. (a) S. J. Martinez, J. C. Alfano and D. H. Levy J. Mol. Struct. 158 82 1993. (b)P. D. Godfrey,L. D. Hatherley and R. D. Brown J. Am. Chem. Soc. 117 8204 1995. (c)S. Sun and E. R. Bernstein J. Am. Chem. Soc. 118 5086 1996. (d) J. A. Dickinson, M. R. Hockridge, R. T. Kroemer, E. G. Robertson, J. P. Simons, J. McCombie and M. Walker J. Am. Chem. Soc. 120 2622 1998. (e) J. C. Lopez, V. Cortijo, S. Blanco and J. Alonso PCCP 9 4521 2007.

Computing the melting point and thermodynamic stability of the orthorhombic and monoclinic crystalline polymorphs of the ionic liquid 1-n-butyl-3-methylimidazolium chloride

NASA Astrophysics Data System (ADS)

Jayaraman, Saivenkataraman; Maginn, Edward J.

2007-12-01

The melting point, enthalpy of fusion, and thermodynamic stability of two crystal polymorphs of the ionic liquid 1-n-butyl-3-methylimidazolium chloride are calculated using a thermodynamic integration-based atomistic simulation method. The computed melting point of the orthorhombic phase ranges from 365 to 369 K, depending on the classical force field used. This compares reasonably well with the experimental values, which range from 337 to 339 K. The computed enthalpy of fusion ranges from 19 to 29 kJ/mol, compared to the experimental values of 18.5-21.5 kJ/mol. Only one of the two force fields evaluated in this work yielded a stable monoclinic phase, despite the fact that both give accurate liquid state densities. The computed melting point of the monoclinic polymorph was found to be 373 K, which is somewhat higher than the experimental range of 318-340 K. The computed enthalpy of fusion was 23 kJ/mol, which is also higher than the experimental value of 9.3-14.5 kJ/mol. The simulations predict that the monoclinic form is more stable than the orthorhombic form at low temperature, in agreement with one set of experiments but in conflict with another. The difference in free energy between the two polymorphs is very small, due to the fact that a single trans-gauche conformational difference in an alkyl sidechain distinguishes the two structures. As a result, it is very difficult to construct simple classical force fields that are accurate enough to definitively predict which polymorph is most stable. A liquid phase analysis of the probability distribution of the dihedral angles in the alkyl chain indicates that less than half of the dihedral angles are in the gauche-trans configuration that is adopted in the orthorhombic crystal. The low melting point and glass forming tendency of this ionic liquid is likely due to the energy barrier for conversion of the remaining dihedral angles into the gauche-trans state. The simulation procedure used to perform the melting point calculations is an extension of the so-called pseudosupercritical path sampling procedure. This study demonstrates that the method can be effectively applied to quite complex systems such as ionic liquids and that the appropriate choice of tethering potentials for a key step in the thermodynamic path can enable first order phase transitions to be avoided.

The free jet microwave spectrum of 2-phenylethylamine-water.

PubMed

Melandri, Sonia; Maris, Assimo; Giuliano, Barbara M; Favero, Laura B; Caminati, Walther

2010-09-21

We observed the rotational spectrum of the 1:1 molecular adduct between 2-phenylethylamine and water (normal and H(2)(18)O species) by free jet absorption microwave spectroscopy in the frequency region 60-78 GHz. The dominant spectrum belongs to the structure where the PEA moiety is in the most stable gauche conformation and the water molecule is hydrogen bound to the nitrogen lone pair. The orientation of the water molecule is such that the oxygen atom is almost equidistant (ca. 2.5 A) from the closest methylenic and aromatic hydrogen atoms.

(2SR,3RS)-Benz­yl[4-chloro-1-(4-chloro­phen­yl)-1-methoxy­carbon­yl-2-but­yl]­ammonium chloride

PubMed Central

Kaupang, Åsmund; Bolsønes, Marianne; Gamadeku, Thywill; Hansen, Tore; Hennum, Martin Johanson; Görbitz, Carl Henrik

2008-01-01

In the racemic hydro­chloride salt of the title ester, C19H22Cl2NO2 +·Cl−, the penta­noic acid chain shows a mixture of trans and gauche orientations to give an overall helical conformation. The dihedral angle between the two aromatic rings is 26.11 (10)°. The charged secondary amine function participates in two N—H⋯Cl hydrogen bonds. PMID:21201230

Identification of two conformationally trapped n-propanol-water dimers in a supersonic expansion

NASA Astrophysics Data System (ADS)

Mead, Griffin J.; Alonso, Elena R.; Finneran, Ian A.; Carroll, P. Brandon; Blake, Geoffrey A.

2017-05-01

Two conformers of the n-propanol-water dimer have been observed in a supersonic expansion using chirped-pulse Fourier-transform microwave (CPFTMW) spectroscopy. Structural assignments reveal the n-propanol sub-unit is conformationally trapped, with its methyl group in both Gauche and Trans orientations. Despite different carbon backbone conformations, both dimers display the same water-donor/alcohol-acceptor hydrogen bonding motif. This work builds upon other reported alcohol-water dimers and upon previous work detailing the trapping of small molecules into multiple structural minima in rare gas supersonic expansions.

Diethyl 4,4'-(3,6-dioxaoctane-1,8-diyl-dioxy)dibenzoate.

PubMed

Ma, Zhen; Qin, Haisha; Lai, Gang; Fan, Jingjie

2012-03-01

The title compound, C(24)H(30)O(8), was obtained by reaction of ethyl 4-hy-droxy-benzoate with 1,2-dichloro-ethane. The mol-ecule occupies a crystallographic inversion center, with its central ethyl-ene bridge in an anti conformation. The other ethyl-ene bridge has a gauche conformation, with the corresponding O-C-C-O torsion angle being 74.2 (1)°. The benzene rings are almost coplanar with the adjacent eth-oxy-carbonyl groups, with an r.m.s. deviation of 0.078 Å.

Melting line of polymeric nitrogen

NASA Astrophysics Data System (ADS)

Yakub, L. N.

2013-05-01

We made an attempt to predict location of the melting line of polymeric nitrogen using two equations for Helmholtz free energy: proposed earlier for cubic gauche-structure and developed recently for liquid polymerized nitrogen. The P-T relation, orthobaric densities and latent heat of melting were determined using a standard double tangent construction. The estimated melting temperature decreases with increasing pressure, alike the temperature of molecular-nonmolecular transition in solid. We discuss the possibility of a triple point (solid-molecular fluid-polymeric fluid) at ˜80 GPa and observed maximum of melting temperature of nitrogen.

Conformer-specific microwave spectroscopy of 3-phenylpropionitrile by strong field coherence breaking

NASA Astrophysics Data System (ADS)

Fritz, Sean M.; Hernandez-Castillo, A. O.; Abeysekera, Chamara; Hays, Brian M.; Zwier, Timothy S.

2018-07-01

Strong field coherence breaking (SFCB) was used with a chirped-pulse Fourier Transform microwave spectrometer to obtain conformer-specific rotational spectra of 3-phenylpropionitrile in the 8-18 GHz region. Transitions belonging to anti and gauche conformers were identified and assigned and accurate experimental rotational constants were determined to provide insight to the molecular structure. Experimental rotational transitions provided relative abundances in the supersonic expansion. A modified line picking scheme was developed in the process to modulate more transitions and improve the overall efficiency of the SFCB multiple selective excitation technique.

Software for Avionics.

DTIC Science & Technology

1983-01-01

fonctions gfinbrales et lea uti- litaires fournis en particulier grice 41 UNIX, sont intfigrfs aelon divers points de vue: - par leur accas 41 travers le...Are They Really A Problem? Proceedings, 2nd International Conference On Software Engineering, pp 91-68. Long acCA : IEEE Computer Society. Britton...CD The Hague. Nc KLEINSCIIMIDT, M. Dr Fa. LITEF. Poatfach 774. 7800 Freiburg i. Br., Ge KLEMM, R. Dr FGAN- FFM , D 5 307 Watchberg-Werthhoven. Ge KLENK

Evolution des contraintes résiduelles dans des films minces de tungstène en fonction de l'irradiation

NASA Astrophysics Data System (ADS)

Durand, N.; Badawi, K. F.; Goudeau, P.; Naudon, A.

1994-01-01

The influence of the irradiation dose upon the residual stresses in 1 000 Å tungsten thin films has been studied by two different techniques. Results show a relaxation of the strong initial compressive stresses σ=- 4,5 GPa) in virgin samples when the irradiation dose increases. The existence of a relaxation threshold is also clearly evidenced, it indicates a strong correlation between the thin film microstructure (point defects, grain size) and the relaxation phenomenon, and consequently, the residual stresses. Nous avons étudié, par deux méthodes différentes, l'évolution des contraintes résiduelles dans des couches minces de 1 000 Å de W en fonction de la dose d'irradiation. Ces expériences mettent en évidence une relaxation des fortes contraintes de compression (σ=- 4,5 GPa) observées dans les échantillons vierges quand la dose de l'irradiation augmente. Notre étude montre par ailleurs, l'existence d'un seuil de relaxation et relie de façon indiscutable, la microstructure de la couche mince (défauts ponctuels, taille de grains) au phénomène de relaxation, donc aux contraintes elles-mêmes.

THE CM-, MM-, AND SUB-MM-WAVE SPECTRUM OF ALLYL ISOCYANIDE AND RADIOASTRONOMICAL OBSERVATIONS IN ORION KL AND THE SgrB2 LINE SURVEYS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Haykal, I.; Margulès, L.; Huet, T. R.

2013-11-10

Organic isocyanides have an interesting astrochemistry and some of these molecules have been detected in the interstellar medium (ISM). However, rotational spectral data for this class of compounds are still scarce. We provide laboratory spectra of the four-carbon allyl isocyanide covering the full microwave region, thus allowing a potential astrophysical identification in the ISM. We assigned the rotational spectrum of the two cis (synperiplanar) and gauche (anticlinal) conformations of allyl isocyanide in the centimeter-wave region (4-18 GHz), resolved its {sup 14}N nuclear quadrupole coupling (NQC) hyperfine structure, and extended the measurements into the millimeter and submillimeter-wave (150-900 GHz) ranges formore » the title compound. Rotational constants for all the monosubstituted {sup 13}C and {sup 15}N isotopologues are additionally provided. Laboratory observations are supplemented with initial radioastronomical observations. Following analysis of an extensive dataset (>11000 rotational transitions), accurate ground-state molecular parameters are reported for the cis and gauche conformations of the molecule, including rotational constants, NQC parameters, and centrifugal distortion terms up to octic contributions. Molecular parameters have also been obtained for the two first excited states of the cis conformation, with a dataset of more than 3300 lines. The isotopic data allowed determining substitution and effective structures for the title compound. We did not detect allyl isocyanide either in the IRAM 30 m line survey of Orion KL or in the PRIMOS survey toward SgrB2. Nevertheless, we provided an upper limit to its column density in Orion KL.« less

The Molecular Structure of Phenetole Studied by Microwave Spectroscopy and Quantum Chemical Calculations

NASA Astrophysics Data System (ADS)

Ferres, Lynn; Stahl, Wolfgang; Nguyen, Ha Vinh Lam

2016-06-01

A pulsed molecular beam Fourier transform microwave spectrometer operating in the frequency range 2 - 26.5 GHz was used to measure the spectrum of phenetole (ethyl phenyl ether or ethoxybenzene, C6H5OC2H5). The conformational landscape is completely determined by the orientations of the phenyl ring and the ethyl group. A two-dimensional potential energy surface was calculated at the MP2/6-311++G(d,p) level of theory. Two conformers were found: The trans conformer has a Cs symmetry, and the gauche conformer has the ethyl group tilted out of the phenyl plane by about 70°. Totally 186 rotational transitions were assigned to the more stable planar trans conformer, and fitted using a semi-rigid rotor model to measurement accuracy of 2 kHz. Highly accurate rotational and centrifugal distortion constants were determined. Several method and basis set combinations were applied to check for convergence and to compare with the experimentally deduced molecular parameters. The inertial defect of the observed conformer Δc = (Ic - Ia - Ib) = -6.718 uÅ2 confirms that the heavy atom skeleton is planar with two pairs of hydrogen atoms out of plane. All lines in the spectrum could be assigned to the trans conformer, which confirms that the gauche conformer cannot be observed under our measurement conditions. In agreement with the rather high torsional barrier of the methyl group (V3 = 1168 wn) calculated by quantum chemical methods, all assigned lines appeared sharp and no signs of splittings were observed for the methyl internal rotation.

CF CIMIC Operations 1990-2010: An Annotated Bibliography

DTIC Science & Technology

2010-12-01

those who will be involved in negotiations during their deployments. Canada, Department of National Defence, “Operation Assistance: Lessons ...publications cover the period from 1990 to 2010. As a whole, the books, articles, monographs, and manuals listed below provide a partial history ...activités de la COCIM ainsi qu’une analyse de ses fonctions durant la période de l’après- guerre froide. Les articles choisis traitent de la planification

Determination de la Distribution Granulometrique des Particules par la Mesure de la Transmission d’un Aerosol Sedimentant (Aerosol Size Distribution Using the Extinction-Sedimentation Inversion Technique),

DTIC Science & Technology

1982-11-01

est la longueur du chemin optique. La fonction K(xn, n) peut Stre evaluee 1 l’aide de la theorie de Mie. Elle est du type oscillant et tend vers 2...Directeur, Division de l1informatlque - Directeur, Division de la Propulsion 10 - Bibliotheque - M. G. Roy ( auteur ) - Dr R. Lavertu - Dr B.T.N

Raman spectroscopic study of reaction dynamics

NASA Astrophysics Data System (ADS)

MacPhail, R. A.

1990-12-01

The Raman spectra of reacting molecules in liquids can yield information about various aspects of the reaction dynamics. The author discusses the analysis of Raman spectra for three prototypical unimolecular reactions, the rotational isomerization of n-butane and 1,2-difluoroethane, and the barrierless exchange of axial and equatorial hydrogens in cyclopentane via pseudorotation. In the first two cases the spectra are sensitive to torsional oscillations of the gauche conformer, and yield estimates of the torsional solvent friction. In the case of cyclopentane, the spectra can be used to discriminate between different stochastic models of the pseudorotation dynamics, and to determine the relevant friction coefficients.

An Information Handbook for Contracting and Manufacturing Officers.

DTIC Science & Technology

1988-01-01

11 - _ _1L~ ~ IIIfl~ 550 ___ Ow 1*1 lllll~=. urn,,. .5... liii, __ m:~ 5~ b _______ L ,uII1.Q 0~ S. -A. S .5,. b .1~ S .5.. 0 0’ .5-. .5 0 5%’ E * I...CfO FI ropy 00E ,. 77 t6 ODTIC ELECTE JUN 08 18 AIR COMMANI) STFFCOLLEGE ~.mriS-AT: !- E ;-rL AI Ap"ps hed iint public teleasw" Distribution Unlimited 5 A...M. KING, USAF FACULTY ADVISOR MAJOR TRACEY L. GAUCH, ACSC/EDC SPONSOR MAJOR DANIEL E . ELDRIDGE AFMPC/DPMRSA2 Submitted to the faculty in partial

Spectra and structure of small ring molecules. XLV. Microwave, infrared, and Raman spectra, conformational stability, dipole moment and vibrational assignment of cyclobutylcarboxaldehyde

NASA Astrophysics Data System (ADS)

Durig, J. R.; Badawi, H. M.

1990-12-01

The microwave spectrum of cyclobutylcarboxaldehyde, c-C 4H 7CHO, has been recorded from 12.4 to 39.0 GHz. Two sets of a-type R-branch transitions were observed and assigned, on the basis of the rigid rotor model, to the equatorial-trans and the equatorial-gauche conformers. The rotational constants for the ground state for the equatorial-trans conformer are: A=9653.70 ± 0.47, B=2224.15 ± 0.01 and C=1986.68 ± 0.01 MHz. The lines for the first excited state of the asymmetric torsion for the equatorial-trans conformer have also been identified and assigned and, from relative intensity measurements, the frequency of the asymmetric torsion of this conformer is estimated to be 71 ± 10 cm -1. For the equatorial-gauche conformer in addition to the R-branch assignments, Q-branch assignments have been made for b- and c-type transitions for the ground state. The rotational constants for this conformer are: A=8108.08 ± 0.05, B=2554.89 ± 0.01, and C=2215.78 ± 0.01 MHz. From the Stark effect the dipole moment components for both conformers were determined. For the equatorial-trans conformer the dipole moment components were determined to be: &|μ a&| = 1.65 ± 0.01 D, &|μ b&|=0.00 (by symmetry), &|μ c&|=1.23 ± 0.01 &|μ t&|=2.06 ± 0.01 D. For the equatorial-gauge conformer the dipole moment components were determined to be: &|μ a&|=2.03 ± &|μ b&|=1.52 ± 0.04, &|μ c&|=0.83 ± 0.06 and &|μ t&|=2.66 ± 0.02 D. The infrared (3500-30 cm -1 and Raman have been recorded for the gaseous and solid states of cyclobutylcarboxaldehyde. Additionally, the Raman spectrum of the liquid phase has been recorded and qualitative depolarization values have been obtained. From variable temperature measurements of the microwave and Raman spectra, for the gaseous and liquid phases, respectively, the equatorial-gauche conformer was found to be thermodynamically preferred for the gas phase; however, it is the equatorial-trans rotamer which is most stable in the liquid. Furthermore, the only conformation present in the annealed solid is the equatorial-trans rotamer. From these data a complete vibrational assignment is proposed. The observed splitting of many of the fundamentals in the solid state indicates that there are at least two molecules per primitive cell. These results are compared to similar quantities in some related molecules.

Réseaux minces de diffraction en régime de Bragg

NASA Astrophysics Data System (ADS)

Moreau, A.; Zaquine, I.; Maruani, A.; Frey, R.

2006-10-01

Le régime de diffraction d'un réseau infiniment mince inséré dans une cavité Fabry-Pérot est étudié, en particulier en fonction de la longueur de la cavité. Un régime de Bragg très efficace est possible même en utilisant des cavités micrométriques, ce qui peut être utile pour le traitement optique de l'information.

Analysis of vibrational spectra of 3-halo-1-propanols CH(2)XCH(2)CH(2)OH (X is Cl and Br).

PubMed

Badawi, Hassan M; Förner, Wolfgang

2008-12-01

The conformational stability and the three rotor internal rotations in 3-chloro- and 3-bromo-1-propanols were investigated by DFT-B3LYP/6-311+G and ab initio MP2/6-311+G, MP3/6-311+G and MP4(SDTQ)//MP3/6-311+G levels of theory. On the calculated potential energy surface twelve distinct minima were located all of which were not predicted to have imaginary frequencies at the B3LYP level of theory. The calculated lowest energy minimum in the potential curves of both molecules was predicted to correspond to the Gauche-gauche-trans (Ggt) conformer in excellent agreement with earlier microwave and electron diffraction results. The equilibrium constants for the conformational interconversion of the two 3-halo-1-propanols were calculated at the B3LYP/6-311+G level of calculation and found to correspond to an equilibrium mixture of about 32% Ggt, 18% Ggg1, 13% Tgt, 8% Tgg and 8% Gtt conformations for 3-chloro-1-propanol and 34% Ggt, 15% Tgt, 13% Ggg1, 9% Tgg and 7% Gtt conformations for 3-bromo-1-propanol at 298.15K. The nature of the high energy conformations was verified by carrying out solvent experiments using formamide ( epsilon=109.5) and MP3 and MP4//MP3 calculations. The vibrational frequencies of each molecule in its three most stable forms were computed at the B3LYP level and complete vibrational assignments were made based on normal coordinate calculations and comparison with experimental data of the molecules.

Organization of lipids in avian stratum corneum: Changes with temperature and hydration.

PubMed

Champagne, Alex M; Allen, Heather C; Bautista-Jimenez, Robin C; Williams, Joseph B

2016-02-01

In response to increases in ambient temperature (Ta), many animals increase total evaporative water loss (TEWL) through their skin and respiratory passages to maintain a constant body temperature, a response that compromises water balance. In birds, cutaneous water loss (CWL) accounts for approximately 65% of TEWL at thermoneutral temperatures. Although the proportion of TEWL accounted for by CWL decreases to only 25% at high Ta, the magnitude of CWL still increases, suggesting changes in the barrier function of the skin. The stratum corneum (SC) is composed of flat, dead cells called corneocytes embedded in a matrix of lipids, many of which arrange in layers called lamellae. The classes of lipids that comprise these lamellae, and their attendant physical properties, determine the rate of CWL. We measured CWL at 25, 30, 35, and 40 °C in House Sparrows (Passer domesticus) caught in the winter and summer, and in sparrows acclimated to warm and cold lab environments. We then used Fourier transform infrared spectroscopy to measure lipid-lipid and lipid-water interactions in the SC under different conditions of temperature and hydration, and correlated these results with lipid classes in the SC. As CWL increased at higher temperatures, the amount of gauche defects in lipid alkyl chains increased, indicating that lipid disorder is partially responsible for higher CWL at high temperatures. However, variation in CWL between groups could not be explained by the amount of gauche defects, and this remaining variation may be attributed to greater amounts of cerebrosides in birds with low CWL, as the sugar moieties of cerebrosides lie outside lipid lamellae and form strong hydrogen bonds with water molecules. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

Structural variability in Cu(I) and Ag(I) coordination polymers with a flexible dithione ligand: Synthesis, crystal structure, microbiological and theoretical studies

NASA Astrophysics Data System (ADS)

Beheshti, Azizolla; Nozarian, Kimia; Babadi, Susan Soleymani; Noorizadeh, Siamak; Motamedi, Hossein; Mayer, Peter; Bruno, Giuseppe; Rudbari, Hadi Amiri

2017-05-01

Two new compounds namely [Cu(SCN)(μ-L)]n (1) and {[Ag (μ2-L)](ClO4)}n (2) have been synthesized at room temperature by one-pot reactions between the 1,1-(1,4-butanediyl)bis(1,3-dihydro-3-methyl-1H-imidazole- 2-thione) (L) and appropriate copper(I) and silver(I) salts. These polymers have been characterized by single crystal X-ray diffraction, XRPD, TGA, elemental analysis, infrared spectroscopy, antibacterial activity and scanning probe microscopy studies. In the crystal structure of 1, copper atoms have a distorted trigonal planar geometry with a CuS2N coordination environment. Each of the ligands in the structure of 1 acting as a bidentate S-bridging ligand to form a 1D chain structure. Additionally, the adjacent 1D chains are interconnected by the intermolecular C-H…S interactions to create a 2D network structure. In contrast to 1, in the cationic 3D structure of 2 each of the silver atoms exhibits an AgS4 tetrahedral geometry with 4-membered Ag2S2 rings. In the structure of 2, the flexible ligand adopts two different conformations; gauche-anti-gauche and anti-anti-anti. The antibacterial studies of these polymers showed that polymer 2 is more potent antibacterial agent than 1. Scanning probe microscopy (SPM) study of the treated bacteria was carried out to investigate the structural changes cause by the interactions between the polymers and target bacteria. Theoretical study of polymer 1 investigated by the DFT calculations indicates that observed transitions at 266 nm and 302 nm in the UV-vis spectrum could be attributed to the π→π* and MLCT transitions, respectively.

Some general aspects of torsional sensitivity and the GG-effect

NASA Astrophysics Data System (ADS)

Yu, C.-H.; Schäfer, L.; Ramek, M.; Miller, D. M.; Teppen, B. J.

1999-08-01

The geometries of 28 compounds of type X-C1-C2-C3-Y, with X,Y=CH 3, F, Cl, OH, NH 2, COH, and COOH, were fully optimized by ab initio HF/4-21G calculations at 30° grid points in their respective φ(X-C1-C2-C3), ψ(C1-C2-C3-Y)-torsional spaces. The results make it possible to construct parameter surfaces and their gradients in φ, ψ-space. The magnitude of the gradient, |∇ P|=[( ∂P/ ∂φ) 2+( ∂P/ ∂ψ) 2] 1/2, of a structural parameter P (a bond length, bond angle, or non-bonded distance) in φ, ψ-torsional space is a measure of torsional sensitivity (TS); i.e. a measure of the extent to which bond lengths, bond angles, and non-bonded distances change at a point in φ, ψ-space with backbone torsional angles. It is found that TS is not constant throughout the conformational space of a molecule, but varies in a characteristic way. It seems that, regardless of the nature of X or Y, extended forms are typically in regions of low TS; puckered conformations, of high TS. Conformations with two sequential gauche torsional angles (GG sequences) are characterized by high TS of 1,5-non-bonded distances concomitant with relatively low TS of other internal coordinates. This property of GG sequences is the source of a stabilizing and cooperative energy increment that is not afforded by other torsional sequences, such as trans- trans or trans- gauche. A structural data base, consisting of thousands of HF/4-21G structures of X-C-C-Y and X-C-C-C-Y systems has been assembled and is available on a CD.

Diethyl 4,4′-(3,6-dioxaoctane-1,8-diyl­dioxy)dibenzoate

PubMed Central

Ma, Zhen; Qin, Haisha; Lai, Gang; Fan, Jingjie

2012-01-01

The title compound, C24H30O8, was obtained by reaction of ethyl 4-hy­droxy­benzoate with 1,2-dichloro­ethane. The mol­ecule occupies a crystallographic inversion center, with its central ethyl­ene bridge in an anti conformation. The other ethyl­ene bridge has a gauche conformation, with the corresponding O—C—C—O torsion angle being 74.2 (1)°. The benzene rings are almost coplanar with the adjacent eth­oxy­carbonyl groups, with an r.m.s. deviation of 0.078 Å. PMID:22412598

2'-O-[2-[2-(N,N-Dimethylamino)ethoxy]ethyl] Modified Antisense Oligonucleotides: Symbiosis of Charge Interaction Factors and Stereoelectronic Effects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prhavc, M.; Prakash, T.P.; Minasov, G.

Oligonucleotides with a novel, 2'-O-[2-[2-(N,N-dimethylamino)ethoxy]ethyl] (2'-O-DMAEOE) modification have been synthesized. This modification, a cationic analogue of the 2'-O-(2-methoxyethyl) (2'-O-MOE) modification, exhibits high binding affinity to target RNA (but not to DNA) and exceptional resistance to nuclease degradation. Analysis of the crystal structure of a self-complementary oligonucleotide containing a single 2'-O-DMAEOE modification explains the importance of charge factors and gauche effects on the observed antisense properties. 2'-O-DMAEOE modified oligonucleotides are ideal candidates for antisense drugs.

The Aerodynamcis of Parachutes

DTIC Science & Technology

1987-07-01

saine pour cc qui faisait I’objet de son livre ’Les parachutes". Les fonctions remplies par les matiriels qu’il y d&crivait itaient d’abord r’emport...port le titre, cet "AGARDographe eat considdre comme Ia suite directe du livre "Les parachutes" de Brown, car il insiste sur le maine themne: ’lea...reconnaitre au passage lea apports inestimablemn qu’clles ont faits A cette publication qui eat l’aboutissenient de tous nos efforts conjuguis. David

Assessing Vulnerability of Biometric Technologies for Identity Management Applications

DTIC Science & Technology

2011-10-01

de vulnérabilité et d’analyse de la relation entre la performance du système et la force de sécurité de la fonction. En Octobre 2010, IBG-Canada...Les agences et ministères du gouvernement du Canada ont besoin d’information sur la performance , les vulnérabilités et l’efficacité des solutions...négligent des éléments humains qui peuvent stimuler la performance , de sécurité et les

Static Aeroelastic Effects on High Performance Aircraft

DTIC Science & Technology

1987-06-01

davis la rffrence 9. L’avion est instrurnent6, en plus des capteurs classiques des param~tres de n~ca- nique du vol. de plusleurs centaines de jauges de...crites §2.3.5, et lensemble dv l’analyse, pernet- tent le calcul des r~ponues des jauges en fonction dv X soit ar ( X) , lv procesnus de d~rivation...travissonique. Rema rque La smine technique d’identification par rtponne dv jauges s’applique (plus simple- ment) sur len essais en soufflerie, pour la

Modelling Broadband Scattering From Shelled Spheres in a Waveguide

DTIC Science & Technology

2007-10-01

profonde. Le contenu spectral de l’echo produit par une cible peut varier de fagon appreciable en fonction de sa profondeur et de sa distance dans le...Canada’s leader in defence and National Security Science and Technology R&D pour la defense Canada Chef de file au Canada en matiere de science et...Copy No. nent Development Canada pour la defense Canada • ^g, M Defence Research and Recherche et deyeloppem r£ m> DEFENCE I « M

Optical Propagation in the Atmosphere

DTIC Science & Technology

1976-05-01

I (r~) oil v out la friquance, r Is rayon...diroctement transmis des sources. La fux et n a pont ~)A travers un plan perpondiculairo I la direction i ~sera F (4r) co 44, (3) -Fgý’r) F- (’r) (4 oil F...forme oil la fonction source J s𔄀crit ;0(r) 4. JOU~ - I p(’r;4,’n’) I (’r,ý’) dwt +’(.r*,4) + (1-w (r)) B(r) ; (6) 1. premier terms correspond

Measurement of the Spatial Distribution of the Spectral Response Variation in the Field of View of the ASD Spectrometer Input Optics

DTIC Science & Technology

2014-12-01

development. It will be used for the measurement of the spectro-polarimetric BRDF (Bidirectional Reflectance Distribution function). For practical reasons...goniomètre est en développement. Il sera utilisé pour les mesures de BRDF (fonction de distribution de réflectance bidirectionnelle) spectrales et...by the independent measurements of the spectral and Bidirectional Reflectance Distribution Function ( BRDF ). The BRDF is the measurement of the

Analytical Solutions for Predicting Underwater Explosion Gas Bubble Behaviour

DTIC Science & Technology

2010-11-01

donne les meilleures prévisions comparativement aux ajustements avec les données expérimentales. Le modèle à fluide incompressible exige d’utiliser une...couplage des mouvements radial et migratoire. L’étude montre que, comparativement aux résultats d’expérience, la réduction du rayon de la bulle... comparativement aux ajustements avec les données expérimentales. Le modèle à fluide incompressible exige d’utiliser une fonction empirique de perte d’énergie

Airframe/Propulsion Interference

DTIC Science & Technology

1975-03-01

elancee, en incidence, est prcsenic figure 14. L’intrados se caracterise par une divergence des lignes dc courant, et par une reducti.in ’es nombres...ale de la zone dissipative en R et A/S une fonction du nombre de Hach au recollement Mq et d’un parametre de forme Hiq caracterisant le...extralte d’une Etude expE- rimentale prEsentEe rEf. [13]. Bile se caractErise par un elancement assez important et un rapport de tronoature ft^ /\\M.t

[Relations between biomedical variables: mathematical analysis or linear algebra?].

PubMed

Hucher, M; Berlie, J; Brunet, M

1977-01-01

The authors, after a short reminder of one pattern's structure, stress on the possible double approach of relations uniting the variables of this pattern: use of fonctions, what is within the mathematical analysis sphere, use of linear algebra profiting by matricial calculation's development and automatiosation. They precise the respective interests on these methods, their bounds and the imperatives for utilization, according to the kind of variables, of data, and the objective for work, understanding phenomenons or helping towards decision.

Comparison of the One-electron Oxidations of CO-Bridged vs Unbridged Bimetallic Complexes: Electron-transfer Chemistry of Os2Cp2(CO)4 and Os2Cp*2(μ-CO)2(CO)2 (Cp = η5-C5H5, Cp* = η5-C5Me5)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Laws, Derek R.; Bullock, R. Morris; Lee, Richmond

The one-electron oxidations of two dimers of half-sandwich osmium carbonyl complexes have been examined by electrochemistry, spectro-electrochemistry, and computational methods. The all-terminal carbonyl complex Os2Cp2(CO)4 (1, Cp = η5-C5H5) undergoes a reversible one-electron anodic reaction at E1/2 = 0.41 V vs ferrocene in CH2Cl2/0.05 M [NBu4][B(C6F5)4], giving a rare example of a metal-metal bonded radical cation unsupported by bridging ligands. The IR spectrum of 1+ is consistent with an approximately 1:1 mixture of anti and gauche structures for the 33 e- radical cation in which it has retained all-terminal bonding of the CO ligands. DFT calculations, including orbital-occupancy-perturbed Mayer bond-ordermore » analyses, show that the HOMOs of anti-1 and gauche-1 are metal-ligand delocalized. Removal of an electron from 1 has very little effect on the Os-Os bond order, accounting for the resistance of 1+ to heterolytic cleavage. The Os-Os bond distance is calculated to decrease by 0.10 Å and 0.06 Å as a consequence of one-electron oxidation of anti-1 and gauche-1, respectively. The CO-bridged complex Os2Cp*2(μ-CO)2(CO)2 (Cp* = η5-C5Me5), trans-2, undergoes a more facile oxidation, E1/2 = - 0.11 V, giving a persistent radical cation shown by solution IR analysis to preserve its bridged-carbonyl structure. However, ESR analysis of frozen solutions of 2+ is interpreted in terms of the presence of two isomers, most likely anti-2+ and trans-2+, at low temperature. Calculations show that the HOMO of trans-2 is highly delocalized over the metal-ligand framework, with the bridging carbonyls accounting for about half of the orbital makeup. The Os-Os bond order again changes very little with removal of an electron, and the Os-Os bond length actually undergoes minor shortening. Calculations suggest that the second isomer of 2+ has both the trans CO-bridged and the anti all-terminal CO structures. DRL and WEG acknowledge the support of the National Science Foundation under grant CHE-0808909. K-WH acknowledges financial support from KAUST. RMB thanks the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Biosciences and Geosciences for support. Pacific Northwest National Laboratory is a multiprogram national laboratory operated by Battelle for the U.S. Department of Energy. We thank Dr. S. I. Gorelsky for the discussion on the OOP analysis.« less

Reconstruction de la surface de Fermi dans l'etat normal d'un supraconducteur a haute Tc: Une etude du transport electrique en champ magnetique intense

NASA Astrophysics Data System (ADS)

Le Boeuf, David

Des mesures de resistance longitudinale et de resistance de Hall en champ magnetique intense transverse (perpendiculaire aux plans CuO2) ont ete effectuees au sein de monocristaux de YBa2Cu3Oy (YBCO) demacles, ordonnes et de grande purete, afin d'etudier l'etat fondamental des supraconducteurs a haute Tc dans le regime sous-dope. Cette etude a ete realisee en fonction du dopage et de l'orientation du courant d'excitation J par rapport a l'axe orthorhombique b de la structure cristalline. Les mesures en champ magnetique intense revelent par suppression de la supraconductivite des oscillations magnetiques des resistances longitudinale et de Hall dans YBa2Cu 3O6.51 et YBa2Cu4O8. La conformite du comportement de ces oscillations quantiques au formalisme de Lifshitz-Kosevich, apporte la preuve de l'existence d'une surface de Fermi fermee a caractere quasi-2D, abritant des quasiparticules coherentes respectant la statistique de Fermi-Dirac, dans la phase pseudogap d'YBCO. La faible frequence des oscillations quantiques, combinee avec l'etude de la partie monotone de la resistance de Hall en fonction de la temperature indique que la surface de Fermi d'YBCO sous-dope comprend une petite poche de Fermi occupee par des porteurs de charge negative. Cette particularite de la surface de Fermi dans le regime sous-dope incompatible avec les calculs de structure de bande est en fort contraste avec la structure electronique presente dans le regime surdope. Cette observation implique ainsi l'existence d'un point critique quantique dans le diagramme de phase d'YBCO, au voisinage duquel la surface de Fermi doit subir une reconstruction induite par l'etablissement d'une brisure de la symetrie de translation du reseau cristallin sous-jacent. Enfin, l'etude en fonction du dopage de la resistance de Hall et de la resistance longitudinale en champ magnetique intense suggere qu'un ordre du type onde de densite (DW) est responsable de la reconstruction de la surface de Fermi. L'analogie de la phenomenologie entourant le comportement des resistances longitudinale et de Hall dans YBa2Cu3Oy, avec des systemes dans lesquels l'existence d'un ordre du type DW est etablie, notamment des cuprates a structure tetragonale a basse temperature ("Low Temperature Tetragonal", LTT), indique que l'ordre causant la reconstruction de la surface de Fermi est stabilise au voisinage du dopage p = 1/8, et est en competition directe avec la supraconductivite.

Le modele de Hubbard bidimensionnel a faible couplage: Thermodynamique et phenomenes critiques

NASA Astrophysics Data System (ADS)

Roy, Sebastien

Une etude systematique du modele de Hubbard en deux dimensions a faible couplage a l'aide de la theorie Auto-Coherente a Deux Particules (ACDP) dans le diagramme temperature-dopage-interaction-sauts permet de mettre en evidence l'influence des fluctuations magnetiques sur les proprietes thermodynamiques du systeme electronique sur reseau. Le regime classique renormalise a temperature finie pres du dopage nul est marque par la grandeur de la longueur de correlation de spin comparee a la longueur thermique de de Broglie et est caracterisee par un accroissement drastique de la longueur de correlation de spin. Cette croissance exponentielle a dopage nul marque la presence d'un pic de chaleur specifique en fonction de la temperature a basse temperature. Une temperature de crossover est alors associee a la temperature a laquelle la longueur de correlation de spin est egale a la longueur thermique de de Broglie. C'est a cette temperature caracteristique, ou est observee l'ouverture du pseudogap dans le poids spectral, que se situe le maximum du pic de chaleur specifique. La presence de ce pic a des consequences sur l'evolution du potentiel chimique avec le dopage lorsque l'uniformite thermodynamique est respectee. Les contraintes imposees par les lois de la thermodynamique font en sorte que l'evolution du potentiel chimique avec le dopage est non triviale. On demontre entre autres que le potentiel chimique est proportionnel a la double occupation qui est reliee au moment local. Par ailleurs, une derivation de la fonction de mise a l'echelle de la susceptibilite de spin a frequence nulle au voisinage d'un point critique marque sans equivoque la presence d'un point critique quantique en dopage pour une valeur donnee de l'interaction. Ce point critique, associe a une transition de phase magnetique en fonction du dopage a temperature nulle, induit un comportement non trivial sur les proprietes physiques du systeme a temperature finie. L'approche quantitative ACDP permet de calculer une echelle de temperature concrete pour laquelle ce point critique a des repercussions. Dans le regime critique, la longueur de correlation enregistre plutot une dependance en 1T Finalement, une synthese de ces resultats permet d'aborder une mise en application pratique de ces methodes d'analyse pour les supraconducteurs a haute temperature critique dopes aux electrons tels que le Nd2--xCe xCuO4+/-delta. Une comparaison entre les resultats theoriques et les mesures experimentales pour ce materiau est effectuee.

Nanocylindrical confinement imparts highest structural order in molecular self-assembly of organophosphonates on aluminum oxide.

PubMed

Pathak, Anshuma; Bora, Achyut; Braunschweig, Björn; Meltzer, Christian; Yan, Hongdan; Lemmens, Peter; Daum, Winfried; Schwartz, Jeffrey; Tornow, Marc

2017-05-18

We report the impact of geometrical constraint on intramolecular interactions in self-assembled monolayers (SAMs) of alkylphosphonates grown on anodically oxidized aluminum (AAO). Molecular order in these films was determined by sum frequency generation (SFG) spectroscopy, a more sensitive measure of order than infrared absorption spectroscopy. Using SFG we show that films grown on AAO are, within detection limits, nearly perfectly ordered in an all-trans alkyl chain configuration. In marked contrast, films formed on planar, plasma-oxidized aluminum oxide or α-Al 2 O 3 (0001) are replete with gauche defects. We attribute these differences to the nanocylindrical structure of AAO, which enforces molecular confinement.

Can Helical Peptides Unwind One Turn at a Time? - Controlled Conformational Transitions in α,β(2,3)-Hybrid Peptides.

PubMed

Balamurugan, Dhayalan; Muraleedharan, Kannoth M

2015-06-22

Unfolding of helical trans-β(2,3) -hybrid peptides with (α-β)n α composition, when executed by increasing solvent polarity or temperature, proceeded in a systematic manner with the turns unwinding sequentially; C-terminal region of these peptides were first to unwind and the process propagated towards N terminus with more and more β residues equilibrating from the gauche to the anti rotameric state across Cα-Cβ . This is evidenced by clear change in their Cβ H signal splitting, (3)JCαH-CβH values, and sequential disappearance of i,i+2 NOEs. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Guidance and Control Technology for Highly Integrated Systems.

DTIC Science & Technology

1981-02-08

fonctions. 11 s’agit en fait d’un probl ~me 6conomique de redondance du mat6riel et de redondance entre les sysemes - en ce qui concerne lea pannes, la...le brouillage pour lingual ii ne se pose qua le probl ~me de compatibilit6. 3 - La NIS bande L eat par contra envisag6 pour assurer in haut nivesu de... management considerably. The 5INTAC-3 is in the global system catenory : NIS L BAND + 3TID5 DTDMA optimized : - the message is distributed both For

A Literature Review of Disinfectants: Effects When Used by CF Divers in Cleaning Rebreather Sets

DTIC Science & Technology

2002-11-01

Cavicide ) and all were evaluated against the same criteria. In order to be recommended for use two mandatory criteria had to be complied with; the...Listerine, Cavicide ); ces produits ont tous 6t6 6valu6s en fonction des m~mes crit~res. Pour que l’utilisation d’un produit donn6 soit recommand6e... Cavicide ) and all were evaluated against the same criteria. In order to be recommended for use two mandatory criteria had to be complied with; the

Ocean Thermal Analysis and Related Naval Operational Considerations in the Ionian Sea - June 1980.

DTIC Science & Technology

1981-09-01

oceanography and XBT sampl- ing procedures are made. 4 RESUME L’analyse synoptique de la mer Ionienne en Juin 1980 r~v~le des structures thermiques...varides, et en particulier, un tourbillon chaud comparable en taille et position A celui trouv6 aui cours de MILOC-68. Les fonctions de corr~1ation...spatiale en temp~rature sont anisotropiques dans la partie sud, avec des 6chelles respectives de 30 et 40 A 80 km dans les directions Est/Quest et Nord/Sud

Application of Hierarchical Goal Analysis to the Halifax Class Frigate Operations Room: A Case Study

DTIC Science & Technology

2007-11-01

actuelle en fonction de son niveau de soutien pour ces diverses dépendances. Les auteurs prévoient que la même méthode peut être utilisée pour décrire...analysis. The focus of this paper is on the practice rather than the theory of HGA. Therefore, the next section contains only a brief summary of the...is based on Perceptual Control Theory [17], which posits that humans operate as perceptually driven, goal referenced, feedback systems, in that all

Helicopter Propulsion Systems

DTIC Science & Technology

1981-09-01

doessais do torborsotour MAKILA nous avons choisi trois easais gui ont pour objet die asiuier qoolguos ones des conditions oxposees prece6demisont et gui...46laLore one lin dv d~bit. Los ossais ao banc consistent A 6rablir cette loi poor 6n fonictionnement aui eol do sorte I cqutiie couvrei lensemble du...laisserons de c6t6 le facteur de ddcroissanco du prix en fonction du rang de s6rie ( loi de Wright) parce que, do par sa g6ndralit6, il n’est pas influenc6

Syndrome de poland: à propos d’un cas et revue de la litterature

PubMed Central

Benzalim, Meriam; Berghalout, Laila; Elfakir, Sophia; Jalal, Hicham

2017-01-01

Le syndrome de Poland est une malformation congénitale rare associant à des degrés divers des anomalies thoraciques et du membre supérieur homolatéral. Nous rapportons le cas d'une fillette de 7 ans, explorée pour dépression de l'hémithorax gauche avec masse sous claviculaire homolatérale. La tomodensitométrie a montré que la déformation de la paroi thoracique était liée à l'absence des chefs à insertion sterno-costale du muscle pectoralis major gauche avec agénésie du pectoralis minor et hypoplasie des arcs antérieurs des six premières côtes correspondantes. Ces anomalies étaient rapportées à un syndrome de Poland. Un bilan général fait d'échographie abdominale, radiographies des deux mains, a été réalisé chez la patiente n'ayant révélé aucune malformation associée. Le syndrome de Poland résulte d'un défaut d'approvisionnement sanguin des éléments musculosquelettiques de la paroi thoracique pendant la vie fœtale. Il existe de nombreuses variantes du syndrome de Poland qui peuvent être mieux détectées par la TDM qui doit être réalisée chaque fois qu'il est disponible, sans omettre le rôle de la radiologie général dans la détection des malformations associées. La caractéristique de ce syndrome est l'agénésie des faisceaux sternocostaux du muscle pectoralis major. Son étiologie reste inconnue et discutée. Une anomalie vasculaire en serait la cause, sans que le primum movens de cette anomalie vasculaire soit connu. PMID:28450991

Le carcinome parathyroïdien: à propos d’un cas et revue de la literature

PubMed Central

kolsi, Naourez; Jellali, Sondos; Koubaa, Jamel

2017-01-01

Le carcinome parathyroïdien est une tumeur maligne, très rare, de la glande parathyroïde. Cliniquement, ce cancer se présente souvent par un tableau d'hyperparathyroïdie primaire sévère. Le diagnostic est histologique mais n'est pas toujours aisé. Le traitement est basé sur la chirurgie. Femme âgée de 59 ans, aux antécédents d'hypertension artérielle, et de lithiases rénales récidivantes, consultait pour des douleurs osseuses diffuses avec asthénie. L'examen du cou a trouvé une tuméfaction basi-cervicale dure et à bord inférieur non palpable. A la biologie: hypercalcémie à 4,1 mmol/l, une hyperparathyroïdie avec valeur de parathormone (PTH) très élevée à 1088 pg/ml soit 13 fois la normale. La scintigraphie au Technétium-99m-sestamibi a montré une plage de fixation anormale de MIBI en projection de la parathyroïde inférieure gauche. Une parathyroïdectomie inférieure gauche, avec évidement médiastino-récurrentiel homolatéral ont été réalisés. Les suites opératoires étaient marquées par la normalisation de la calcémie et de la PTH. L'anatomopathologie était en faveur d'un carcinome parathyroïdien. Le diagnostic de carcinome parathyroïdien est généralement établi sur la conjonction de signes radiologiques biologiques et histologiques. La gravité de cette pathologie est due à l'hypercalcémie sévère et au risque de récidive et de métastases à distance justifiant la surveillance prolongée. PMID:28819506

Multipoint anchoring of the [2.2.2.2]metacyclophane motif to a gold surface via self-assembly: coordination chemistry of a cyclic tetraisocyanide revisited.

PubMed

Toriyama, Masaharu; Maher, Tiffany R; Holovics, Thomas C; Vanka, Kumar; Day, Victor W; Berrie, Cindy L; Thompson, Ward H; Barybin, Mikhail V

2008-04-21

A one-pot transformation of bis(2-isocyano-3-methylphenyl)ethane affords gram quantities of 8,16,24,32-tetraisocyano[2.2.2.2]metacyclophane ( 3). The solid state structure of 3 is remarkably close to the lowest energy conformation found on the potential energy landscape for 3 by DFT. In solution, the structure of metacyclophane 3 is mobile but can be locked in a rectangular gauche- anti- gauche- anti conformation by coordination of the isocyanide substituents to the [W(CO) 5] units to give [M] 4(mu 4-eta (1):eta (1):eta (1):eta (1)- 3) ( 5). The tetranuclear [M] 4(mu 4-eta (1):eta (1):eta (1):eta (1)- 3) motif featured in crystallographically characterized 5 may be present in several insoluble complexes of 3 previously described as mononuclear eta (4) species. A self-assembled monolayer of metacyclophane 3 is formed upon exposing a solution of 3 to the gold(111) surface with no precautions to exclude air or light. The monolayer nature of the film was confirmed by optical ellipsometry. The isocyanide stretching band for 3 shifts from 2119 cm (-1) in solution to 2175 cm (-1) upon chemisorption to metallic gold. The FTIR spectrum of the film indicates interaction of 3 with the gold surface via all four of its isocyanide anchors. No gold-facilitated oxidation of the -NC junctions was detected under ambient conditions. The energy cost associated with accessing the conformations of 3 suitable for mu 4-eta (1):eta (1):eta (1):eta (1) interaction of the molecule with the Au(111) surface is under 8 kcal/mol, a value that can be easily offset by formation of a gold-isocyanide bond. Two different mu 4-eta (1):eta (1):eta (1):eta (1) coordination arrangements of 3 with respect to gold atoms on the (111) face of the fcc Au lattice are suggested.

Weak intramolecular interaction effects on the torsional spectra of ethylene glycol, an astrophysical species

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boussessi, R., E-mail: rahma.boussesi@iem.cfmac.csic.es; Laboratoire de Spectroscopie Atomique, Moléculaire et Applications-LSAMA LR01ES09, Faculté des sciences de Tunis, Université de Tunis El Manar, 2092 Tunis; Senent, M. L., E-mail: ml.senent@csic.es

2016-04-28

An elaborate variational procedure of reduced dimensionality based on explicitly correlated coupled clusters calculations is applied to understand the far infrared spectrum of ethylene-glycol, an astrophysical species. This molecule can be classified in the double molecular symmetry group G{sub 8} and displays nine stable conformers, gauche and trans. In the gauche region, the effect of the potential energy surface anisotropy due to the formation of intramolecular hydrogen bonds is relevant. For the primary conformer, stabilized by a hydrogen bond, the ground vibrational state rotational constants are computed to be A{sub 0} = 15 369.57 MHz, B{sub 0} = 5579.87 MHz, andmore » C{sub 0} = 4610.02 MHz corresponding to differences of 6.3 MHz, 7.2 MHz, and 3.5 MHz from the experimental parameters. Ethylene glycol displays very low torsional energy levels whose classification is not straightforward and requires a detailed analysis of the torsional wavefunctions. Tunneling splittings are significant and unpredictable due to the anisotropy of the potential energy surface PES. The ground vibrational state splits into 16 sublevels separated ∼142 cm{sup −1}. The splitting of the “G1 sublevels” was calculated to be ∼0.26 cm{sup −1} in very good agreement with the experimental data (0.2 cm{sup −1} = 6.95 MHz). Transitions corresponding to the three internal rotation modes allow assignment of previously observed Q branches. Band patterns, calculated between 362.3 cm{sup −1} and 375.2 cm{sup −1}, 504 cm{sup −1} and 517 cm{sup −1}, and 223.3 cm{sup −1} and 224.1 cm{sup −1}, that correspond to the tunnelling components of the v{sub 21} fundamental (v{sub 21} = OH-torsional mode), are assigned to the prominent experimental Q branches.« less

Transferred nuclear Overhauser enhancement experiments show that the monoclonal antibody strep 9 selects a local minimum conformation of a Streptococcus group A trisaccharide-hapten.

PubMed

Weimar, T; Harris, S L; Pitner, J B; Bock, K; Pinto, B M

1995-10-17

Transferred nuclear Overhauser enhancement (TRNOE) experiments have been performed to investigate the bound conformation of the trisaccharide repeating unit of the Streptococcus Group A cell-wall polysaccharide. Thus, the conformations of propyl 3-O-(2-acetamido-2-deoxy-beta-D-glucopyranosyl)-2-O-(alpha-L-rhamnopyran osyl)- alpha-L-rhamnopyranoside [C(A')B] (1) as a free ligand and when complexed to the monoclonal antibody Strep 9 were examined. Improved insights about the conformational preferences of the glycosidic linkages of the trisaccharide ligand showed that the free ligand populates various conformations in aqueous solution, thus displaying relatively flexible behavior. The NOE HNAc-H2A', which was not detected in previous work, accounts for a conformation at the beta-(1-->3) linkage with a phi angle of approximately 180 degrees. Observed TRNOEs for the complex are weak, and their analysis was further complicated by spin diffusion. With the use of transferred rotating-frame Overhauser enhancement (TRROE) experiments, the amount of spin diffusion was assessed experimentally, proving that all of the observed long-range TRNOEs arose through spin diffusion. Four interglycosidic distances, derived from the remaining TRNOEs and TRROEs, together with repulsive constraints, derived from the absence of TRROE effects, were used as input parameters in simulated annealing and molecular mechanics calculations to determine the bound conformation of the trisaccharide. Complexation by the antibody results in the selection of one defined conformation of the carbohydrate hapten. This bound conformation, which is a local energy minimum on the energy maps calculated for the trisaccharide ligand, shows only a change from a +gauche to a -gauche orientation at the psi angle of the alpha-(1-->2) linkage when compared to the global minimum conformation. The results infer that the bound conformation of the Streptococcus Group A cell-wall polysaccharide is different from its previously proposed solution structure (Kreis et al., 1995).

Conformational preferences of γ-aminobutyric acid in the gas phase and in water

NASA Astrophysics Data System (ADS)

Song, Il Keun; Kang, Young Kee

2012-09-01

The conformational study of γ-aminobutyric acid (GABA) has been carried out at the M06-2X/cc-pVTZ level of theory in the gas phase and the SMD M06-2X/cc-pVTZ level of theory in water. In the gas phase, the folded conformation gG1 with gauche- and gauche+ conformations for the Cβsbnd Cα and Cγsbnd Cβ bonds, respectively, is found to be lowest in energy and enthalpy, which can be ascribed to the favored hyperconjugative n → π* interaction between the lone electron pair of the amine nitrogen atom and the Cdbnd O bond of the carboxylic group and the favored antiparallel dipole-dipole interaction between the Nsbnd H bond and the Cdbnd O bond. In addition, the intramolecular hydrogen bonds between the carboxylic group and the amine Nsbnd H group have contributed to stabilize some low-energy conformers. However, the most preferred conformation is found to be tG1 and more stable by 0.4 kcal/mol in ΔG than the conformer gG1, in which the favored entropic term due to the conformational flexibility and the other favored n → σ*, σ → σ*, and π → σ* interactions seem to play a role. The conformational preferences of the neutral GABA calculated by ΔG's are reasonably consistent with the populations deduced from FT microwave spectroscopy in supersonic jets combined with laser ablation. In water, the two folded conformers Gg and gG of the zwitterionic GABA are dominantly populated, each of which has the population of 47%, and the hydrogen bond between the ammonium Nsbnd H group and the lone electron pair of the Csbnd O- group seems to be crucial in stabilizing these conformers. Our calculated result that the folded conformers preferentially exist in water is consistent with the 1H NMR experiments in D2O.

High resolution synchrotron radiation Fourier transform infrared spectrum of the COH-bending mode in methanol-D1 (CH2DOH)

NASA Astrophysics Data System (ADS)

Mukhopadhyay, Indra; Billinghurst, B. E.

2017-09-01

In this work the high resolution synchrotron radiation Fourier transform spectrum in the range 1180-1300 cm-1 corresponding to the COH-bending vibrational mode has been recorded and analyzed. The spectrum shows a structure analogous to a parallel band. Since the COH bending motion is one of the main contributors to the asymmetry in the torsional hindering potential barrier, the torsional barrier height in the excited state is expected to be quite different from that of the ground state. This makes the spectrum to spread over a wide region. Although the spectrum corresponding to the P- and R-branch looks very complicated, the Q-branches are well resolved and can be identified without much difficulty. It was possible to assign the spectra for K = 0 to 10 for the trans- (e0) species. The interesting feature of the spectra is the absence of the lines for two other lower lying gauche symmetry species e1 and o1. The spectra due to any perpendicular transitions were absent as well. However some weak c-type transitions from gauche states (o1 and e1) in the ground state to the trans-species (e0) in the COD bending mode for low K-values ΔK = 0 have been seen to be present in the spectra. These along with similar transitions for the OCD vibrational band are under investigation and the results will be communicated elsewhere. In the present work, analysis of the spectrum has been carried out to obtain precise term values and molecular parameters in the excited COH-bending state for the trans-species. The results will be shown valuable to assign similar spectra for the methanol-D2. This work represents the first reported high resolution study of this illusive vibrational mode in methanol-D1.

Contrôle de la température durant le processus de dégradation d'un acier Z12CNS20 en frottement avec un acier Z200C13

NASA Astrophysics Data System (ADS)

Khanafi-Benghalem, N.; Loucif, K.; Benghalem, K.; Boudoukha, H.; Louahdi, R.

2005-05-01

La température de contact lors des essais d'usure varie d'une manière spontanée et aléatoire. Cette température de contact dépend essentiellement de la nature du couple des matériaux en contact de la charge et de la vitesse. Cependant la mesure de la température est très difficile à effectuer compte tenu du choix de l'endroit de prise de la température et des phénomènes d'évacuation de la chaleur et de la dissipation de l'énergie. Dans ce travail nous exposons une méthode très simple de mesure de la température et nous étudions par conséquent la variation de la température du Z12CNS20 / Z200C13. Au cours des essais d'usure pour différentes vitesses de glissement, nous montrons en effet que la température augmente d'une manière progressive en fonction de la vitesse puis elle s'élève brutalement au fur et à mesure qu'on se rapproche du point de contact, et enfin nous prouvons par observation métallographique que l'échantillon subit un écoulement plastique provoqué par l'élévation de la température en fonction de la vitesse.

Lésions bulleuses et purpuriques unilatérales: pathomimie cutanée

PubMed Central

Zinoun, Mouna; Chiheb, Soumia; Marnissi, Farida; Kadiri, Nadia; Benchikhi, Hakima

2015-01-01

La pathomimie cutanée est une forme particulière de troubles factices relativement rare, et constitue l'un des problèmes les plus complexes pour le dermatologue. Nous rapportons un cas de pathomimie révélée par des lésions cutanées unilatérales, mimant une brûlure. Une jeune femme de 27 ans, était suivie depuis 4 ans pour une dépression. Elle a présenté 15j avant sa 1ère hospitalisation un placard inflammatoire du sein gauche compliqué de lésions bulleuses et d’érosions superficielles. La biopsie cutanée avait montré une dermite non spécifique. Une cicatrisation rapide sous traitement local a été notée. Elle a présenté 10 jours plus tard de nouvelles lésions similaires étagées au membre inférieur gauche, évoluant vers le décollement bulleux spontané. La biopsie cutanée avait montré un décollement bulleux jonctionnel et des foyers de nécrose ischémique. L'IFD était négative. Devant les données anamnestiques, cliniques, la négativité du bilan paraclinique, et la guérison des lésions sous pansements occlusifs seuls, le diagnostic de pathomimie a été évoqué et retenu. La patiente a été adressée en psychiatrie où une thérapie cognitivo-comportementale a été préconisée. Notre observation correspond à un tableau de pathomimie de présentation clinique particulière par sa localisation unilatérale et son caractère bulleux. Chez notre patiente qui est droitière, la localisation unilatérale gauche sur des zones accessibles, l'absence de lésions spécifiques à l'examen histologique, la cicatrisation rapide des lésions sous traitement local occlusif seul et leur récurrence malgré des soins adaptés étaient en faveur d'une pathologie factice. Néanmoins, la localisation au niveau des seins peut être très déroutante. Le caractère bulleux des lésions dans le cadre d'une pathomimie a été rarement rapporté. Dans notre cas, la pathomimie s'associe à des troubles anxieux et dépressifs très importants. Leur prise en charge demande un investissement pluridisciplinaire le plus précoce possible. La prise en charge des pathomimies est complexe. Le traitement médical associé à une prise en charge psychologique de type thérapie cognitivo-comportementale, qui est une première expérience, peut aider cette patiente à contrôler son comportement et éviter les récidives qui sont fréquentes dans ce type de pathologie. PMID:26161224

Le don après un décès d'origine cardiocirculatoire au Canada

PubMed Central

Shemie, Sam D.; Baker, Andrew J.; Knoll, Greg; Wall, William; Rocker, Graeme; Howes, Daniel; Davidson, Janet; Pagliarello, Joe; Chambers-Evans, Jane; Cockfield, Sandra; Farrell, Catherine; Glannon, Walter; Gourlay, William; Grant, David; Langevin, Stéphan; Wheelock, Brian; Young, Kimberly; Dossetor, John

2006-01-01

Résumé Ces recommandations sont le fruit d'un processus multidisciplinaire national ayant duré un an et visant à déterminer si et comment l'on pourrait procéder au don d'organes après un décès d'origine cardiocirculatoire («don après le décès cardiocirculatoire», ou DDC) au Canada. Le forum national organisé en février 2005 a permis aux participants de discuter et d'élaborer des recommandations sur les principes, interventions et pratiques se rapportant au DDC. Les aspects éthiques et juridiques ont été abordés dans les discussions. À la fin du Forum, la majorité des participants ont été favorables à l'implantation de programmes de DDC au Canada. Les participants du Forum ont également convenu qu'il fallait formuler et prôner des valeurs fondamentales pour orienter l'élaboration de programmes et de protocoles basés sur le cadre médical, éthique et juridique établi lors de cette réunion. Même si la possibilité d'un don d'organes et de tissus doit faire partie intégrante des soins de fin de vie, il faut insister sur le fait que le devoir de diligence envers les patients mourants et leurs familles doit demeurer la priorité des équipes soignantes. La complexité et les répercussions profondes du décès sont reconnues et doivent être respectées, de même que les différences personnelles, ethnoculturelles et religieuses face à la mort et au don d'organes. Les décisions d'arrêter le traitement de maintien des fonctions vitales, la prise en charge des derniers moments de la vie et le diagnostic de décès selon des critères cardiocirculatoires doivent être distincts et indépendants des processus de don et transplantation. Ce rapport contient des recommandations destinées aux gestionnaires de program, aux autorités sanitaires régionales et aux instances appelés à élaborer les protocoles de DDC. Les programmes doivent être conçus en fonction des éléments suivants : direction et planification locales, éducation et engagement des intervenants, mécanismes d'assurance de la sécurité et de la qualité et information du public. Il est recommandé de commencer par un program de DDC contrôlé à l'unité de soins intensifs où, après une décision par consentement mutuel de cesser le traitement de maintien des fonctions vitales, la mort est attendue, mais n'est pas survenue, ce qui rend possible des discussions non précipitées sur le consentement. Un don non contrôlé, en cas de décès après un arrêt cardiaque non prévu, doit être envisagé seulement une fois que le program de DDC contrôlé a été établi. Bien qu'il soit recommandé de restreindre le programme initial au don de reins, le don d'autres organes peut aussi être envisagé selon l'expertise régionale en matière de transplantation. Les répercussions d'un DDC, y compris les interventions pratiquées avant et après le décès, sur la famille du donneur, la disponibilité des organes, la fonction du greffon et la survie du receveur doivent être documentées de façon méthodique et examinées.

An ab initio study of the conformational energy map of acetylcholine

NASA Astrophysics Data System (ADS)

Segall, M. D.; Payne, M. C.; Boyes, R. N.

An ab initio density functional theory study is reported of the conformational energy map of acetylcholine, with respect to the two central dihedral angles of the molecule. The acetylcholine molecule pays a central role in neurotransmission and has been studied widely using semi-empirical computational modelling. The ab initio results are compared with a number of previous investigations and with experiment. The ab initio data indicate that the most stable conformation of acetylcholine is the trans , gauche arrangement of the central dihedral angles. Furthermore, Mulliken population analysis of the electronic structure of the molecule in this conformation indicates that the positive charge of the molecule is spread over the exterior of the cationic head of the molecule.

Initial stages of aggregation in aqueous solutions of ionic liquids: molecular dynamics studies.

PubMed

Bhargava, B L; Klein, Michael L

2009-07-16

Structures formed by 1-alkyl-3-methylimidazolium bromide aqueous solutions with decyl, dodecyl, tetradecyl, and hexadecyl chains have been studied using molecular dynamics (MD) simulations. Spontaneous self-assembly of the amphiphilic cations to form quasi-spherical polydisperse aggregates has been observed in all of the systems, with the size and nature of the aggregates varying with chain length. In all systems, the cation alkyl tails are buried deep inside the aggregates with the polar imidazolium group exposed to exploit the favorable interactions with water. Aggregation numbers steadily increase with the chain length. The hexadecyl aggregates have the most ordered internal structure of the systems studied, and the alkyl chains in these cations show the least number of gauche defects.

Nitriles as directionally tolerant hydrogen bond acceptors: IR-UV ion depletion spectroscopy of benzenepropanenitrile and its hydrate clusters

NASA Astrophysics Data System (ADS)

Robertson, Patrick A.; Lobo, Isabella A.; Wilson, David J. D.; Robertson, Evan G.

2016-09-01

Benzenepropanenitrile (BPN) and its hydrate clusters are studied by R2PI and IR-UV ion-depletion spectroscopy in the CH/OH stretch regions, aided by theoretical calculations. A single water molecule binds to the terminal nitrile 'lone-pair' of the anti-BPN host, but there is also evidence for a side-type structure with OH donating to the nitrile π-electrons. In the gauche-BPN cluster, water is located at an intermediate angle that facilitates O⋯HC(ortho) interaction. A wide range of attachment angles is possible, as the intrinsic preference for linear hydrogen bonding is mediated by additional CH⋯O interactions that depend on molecular geometry near the nitrile group.

Anesthetic-dependent changes in the chain-melting phase transition of DPPG liposomes studied using near-infrared spectroscopy supported by PCA

NASA Astrophysics Data System (ADS)

Kuć, Marta; Cieślik-Boczula, Katarzyna; Rospenk, Maria

2017-11-01

The effect of inhalation anesthetics (enflurane, isoflurane, sevoflurane or halothane) on the lipid chain-melting phase transition of negatively charged phospholipid membranes was studied using near-infrared (NIR) spectroscopy supported by Principal Component Analysis (PCA). NIR spectra of anesthetics-mixed dipalmitoylphosphatidylglycerol (DPPG) membranes were recorded in a range of the first overtone of the symmetric and antisymmetric stretching vibrations of CH2 groups of lipid aliphatic chains as a function of increasing temperature. Anesthetic-dependent changes in the trans to gauche conformers ratio of CH2 groups in the hydrocarbon lipid chains were characterized in detail and compared with the zwitterionic lipid membranes, which were built of dipalmitoylphosphatidylcholine (DPPC) molecules.

Research Using In Vivo Simulation of Meta-Organizational Shared Decision-making (SDM). Task 4: Modeling of Communication and Decision Functions within a Shared Decision-making (SDM) Framework

DTIC Science & Technology

2011-12-01

la Reine (en droit du Canada), telle que représentée par le ministre de la Défense nationale 2011, Abstract...modélisation des fonctions de communication et de prise de décision dans le cadre de la prise de décision partagée (PDP) du volet de travail « Recherche par... la simulation in-vivo sur la prise de décision partagée des méta-organisations ». Cette composante du programme

Contractor Final Report: For the Technology Demonstration of the Joint Network Defence and Management System (JNDMS)

DTIC Science & Technology

2013-10-01

opérationnel. Importance: Nous avons démontré des fonctions cruciales en utilisant des outils d’entreprise pour comprendre en profondeur un domaine...by the Minister of National Defence, 2009 © Sa Majesté la Reine ( en droit du Canada), telle que représentée par le ministre de la Défense nationale...interarmées de défense et de gestion des réseaux (SIDGR), en vertu du contrat W7714-04-0875/001/SV. Il touche l’exécution et les résultats de cette

Telemetre Laser a Onde Entretenue a 10.6 micrometers avec Postdetection non Lineaire: Etude d’un Systeme a un Laser (A 10.6 micrometer Amplitude Modulated Telemeter Laser with Nonlinear Postdetection: Study of a Single Laser System),

DTIC Science & Technology

1981-04-01

Courbes de variation de u et de la profondeur de modulation a en fonction de la tension appliquge V FIGURE - 4 jo NON CLASSIFIE 14 On peut donc...ET DEVELOPPEMENT RESEARCH AND DEVELOPMENT BRANCH MINISTERE DE LA DEFENSE NATIONALE UNCLASSIFIED DEA CETO AINADEFNC CANADA UNI. IMITED DISTRIBUTiIN CND...RECHERCHES POUR LA DEFENSE DEFENCE RESEARCH ESTABLISHMENT VALCARTIER Tel: (418) 844-4271 Quebec, Canada April/avril 1981 UNCLASSIFIED, /41/7z *I .. , NON

Developpement d'outils quantitatifs pour le suivi par imagerie TEP/TDM de la reponse a la chimiotherapie et de sa toxicite

NASA Astrophysics Data System (ADS)

Croteau, Etienne

L'objectif de ce projet de doctorat est de developper des outils quantitatifs pour le suivi des traitements de chimiotherapie pour le cancer du sein et de leurs effets cardiotoxiques a l'aide de l'imagerie TEP dynamique. L'analyse cinetique en TEP dynamique permet l'evaluation de parametres biologiques in vivo. Cette analyse peut etre utilise pour caracteriser la reponse tumorale a la chimiotherapie et les effets secondaires nefastes qui peuvent en resulter. Le premier article de cette these decrit la mise au point des techniques d'analyse cinetique qui utilisent la fonction d'entree d'un radiotraceur derive de l'image dynamique. Des corrections de contamination radioactive externe (epanchement) et de l'effet de volume partiel ont ete necessaires pour standardiser l'analyse cinetique et la rendre quantitative. Le deuxieme article porte sur l'evaluation d'un nouveau radiotraceur myocardique. Le 11C-acetoacetate, un nouveau radiotraceur base sur un corps cetonique, a ete compare au 11C-acetate, couramment utilise en imagerie cardiaque TEP. L'utilisation de 3H-acetate et 14C-acetoacetate ont permis d'elucider la cinetique de ces traceurs depuis la fonction d'entree et la captation par les mitochondries cardiaques qui reflete la consommation en oxygene, jusqu'a la liberation de leurs principaux metabolites reciproques (3H20 et 14CO2). Le troisieme et dernier article de cette these presente l'integration d'un modele qui evalue la reserve cardiaque de perfusion et de consommation en oxygene. Un modele de cardiomyopathie a ete etabli a l'aide d'un agent chimiotherapeutique contre le cancer du sein, la doxorubicine, reconnu comme etant cardiotoxique. Un protocole de repos/effort a permis d'evaluer la capacite d'augmentation de perfusion et de consommation en oxygene par le coeur. La demonstration d'une reserve cardiaque reduite caracterise la cardiotoxicite. La derniere contribution de cette these porte sur la mise au point de methodes peu invasives pour mesurer la fonction d'entree en modele animal avec l'utilisation de l'artere caudale et un compteur microvolumetrique, la bi-modalite TEP/IRM dynamique avec le Gd-DTPA et l'etablissement d'un modele d'evaluation simultane de cardiotoxicite et reponse tumorale chez la souris. Le developpement d'outils d'analyse TEP dans l'evaluation de la cardiotoxicite lors de traitements du canter du sein permet de mieux comprendre la relation entre les dommages mitochondriaux et la diminution de la fraction d'ejection. Mots cles : Tomographie d'emission par positrons (TEP), analyses cinetiques, IIC-acetate, 11Cacetoacetate, cardiotoxicite.

Developpement de techniques de diagnostic non intrusif par tomographie optique

NASA Astrophysics Data System (ADS)

Dubot, Fabien

Que ce soit dans les domaines des procedes industriels ou de l'imagerie medicale, on a assiste ces deux dernieres decennies a un developpement croissant des techniques optiques de diagnostic. L'engouement pour ces methodes repose principalement sur le fait qu'elles sont totalement non invasives, qu'elle utilisent des sources de rayonnement non nocives pour l'homme et l'environnement et qu'elles sont relativement peu couteuses et faciles a mettre en oeuvre comparees aux autres techniques d'imagerie. Une de ces techniques est la Tomographie Optique Diffuse (TOD). Cette methode d'imagerie tridimensionnelle consiste a caracteriser les proprietes radiatives d'un Milieu Semi-Transparent (MST) a partir de mesures optiques dans le proche infrarouge obtenues a l'aide d'un ensemble de sources et detecteurs situes sur la frontiere du domaine sonde. Elle repose notamment sur un modele direct de propagation de la lumiere dans le MST, fournissant les predictions, et un algorithme de minimisation d'une fonction de cout integrant les predictions et les mesures, permettant la reconstruction des parametres d'interet. Dans ce travail, le modele direct est l'approximation diffuse de l'equation de transfert radiatif dans le regime frequentiel tandis que les parametres d'interet sont les distributions spatiales des coefficients d'absorption et de diffusion reduit. Cette these est consacree au developpement d'une methode inverse robuste pour la resolution du probleme de TOD dans le domaine frequentiel. Pour repondre a cet objectif, ce travail est structure en trois parties qui constituent les principaux axes de la these. Premierement, une comparaison des algorithmes de Gauss-Newton amorti et de Broyden- Fletcher-Goldfarb-Shanno (BFGS) est proposee dans le cas bidimensionnel. Deux methodes de regularisation sont combinees pour chacun des deux algorithmes, a savoir la reduction de la dimension de l'espace de controle basee sur le maillage et la regularisation par penalisation de Tikhonov pour l'algorithme de Gauss-Newton amorti, et les regularisations basees sur le maillage et l'utilisation des gradients de Sobolev, uniformes ou spatialement dependants, lors de l'extraction du gradient de la fonction cout, pour la methode BFGS. Les resultats numeriques indiquent que l'algorithme de BFGS surpasse celui de Gauss-Newton amorti en ce qui concerne la qualite des reconstructions obtenues, le temps de calcul ou encore la facilite de selection du parametre de regularisation. Deuxiemement, une etude sur la quasi-independance du parametre de penalisation de Tikhonov optimal par rapport a la dimension de l'espace de controle dans les problemes inverses d'estimation de fonctions spatialement dependantes est menee. Cette etude fait suite a une observation realisee lors de la premiere partie de ce travail ou le parametre de Tikhonov, determine par la methode " L-curve ", se trouve etre independant de la dimension de l'espace de controle dans le cas sous-determine. Cette hypothese est demontree theoriquement puis verifiee numeriquement sur un probleme inverse lineaire de conduction de la chaleur puis sur le probleme inverse non-lineaire de TOD. La verification numerique repose sur la determination d'un parametre de Tikhonov optimal, defini comme etant celui qui minimise les ecarts entre les cibles et les reconstructions. La demonstration theorique repose sur le principe de Morozov (discrepancy principle) dans le cas lineaire, tandis qu'elle repose essentiellement sur l'hypothese que les fonctions radiatives a reconstruire sont des variables aleatoires suivant une loi normale dans le cas non-lineaire. En conclusion, la these demontre que le parametre de Tikhonov peut etre determine en utilisant une parametrisation des variables de controle associee a un maillage lâche afin de reduire les temps de calcul. Troisiemement, une methode inverse multi-echelle basee sur les ondelettes associee a l'algorithme de BFGS est developpee. Cette methode, qui s'appuie sur une reformulation du probleme inverse original en une suite de sous-problemes inverses de la plus grande echelle a la plus petite, a l'aide de la transformee en ondelettes, permet de faire face a la propriete de convergence locale de l'optimiseur et a la presence de nombreux minima locaux dans la fonction cout. Les resultats numeriques montrent que la methode proposee est plus stable vis-a-vis de l'estimation initiale des proprietes radiatives et fournit des reconstructions finales plus precises que l'algorithme de BFGS ordinaire tout en necessitant des temps de calcul semblables. Les resultats de ces travaux sont presentes dans cette these sous forme de quatre articles. Le premier article a ete accepte dans l'International Journal of Thermal Sciences, le deuxieme est accepte dans la revue Inverse Problems in Science and Engineering, le troisieme est accepte dans le Journal of Computational and Applied Mathematics et le quatrieme a ete soumis au Journal of Quantitative Spectroscopy & Radiative Transfer. Dix autres articles ont ete publies dans des comptes-rendus de conferences avec comite de lecture. Ces articles sont disponibles en format pdf sur le site de la Chaire de recherche t3e (www.t3e.info).

Effets non lineaires transversaux dans les guides d'ondes plans

NASA Astrophysics Data System (ADS)

Dumais, Patrick

Les effets non lineaires transversaux dus a l'effet Kerr optique non resonant sont etudies dans deux types de guides a geometrie plane. D'abord (au chapitre 2), l'emission de solitons spatiaux d'un guide de type canal est etudie historiquement, analytiquement et numeriquement dans le but d'en faire la conception et la fabrication, en AlGaAs, dans la region spectrale en deca de la moitie de la bande interdite de ce materiau, soit autour de 1,5 microns. Le composant, tel que concu, comporte une structure de multipuits quantiques. Le desordonnement local de cette structure permet une variation locale du coefficient Kerr dans le guide, ce qui mene a l'emission d'un soliton spatial au-dela d'une puissance optique de seuil. L'observation experimentale d'un changement en fonction de l'intensite du profil de champ a la sortie du guide realise est presentee. Deuxiemement (au chapitre 3) une technique de mesure du coefficient Kerr dans un guide plan est presentee. Cette technique consiste a mesurer le changement de transmission au travers d'un cache place a la sortie du guide en fonction de l'intensite crete a l'entree du guide plan. Une methode pour determiner les conditions optimales pour la sensibilite de la mesure est presentee, illustree de plusieurs exemples. Finalement, la realisation d'un oscillateur parametrique optique basee sur un cristal de niobate de lithium a domaines periodiquement inverses est presentee. La theorie des oscillateurs parametriques optiques est exposee avec une emphase sur la generation d'impulsions intenses a des longueurs d'onde autour de 1,5 microns a partir d'un laser Ti:saphir, dans le but d'obtenir une source pour faire les experiences sur l'emission solitonique.

Cardiomyopathie du péripartum: à propos d’une observation et revue de la littérature

PubMed Central

Bouzerda, Abdelmajid

2016-01-01

La cardiomyopathie du péripartum ou cardiomyopathie gravidique primitive, est une entité rare et méconnue définie comme une insuffisance cardiaque systolique survenant le dernier mois de la grossesse ou les cinq premiers mois du postpartum en l'absence d'étiologie connue ou de cardiopathie préexistante. Nous rapportons l'observation d'une jeune patiente de 31 ans sans antécédents pathologiques particuliers admise pour une poussée d'insuffisance cardiaque gauche 1mois après son accouchement. Le contexte de péripartum nous a fait penser au diagnostic et a motivé la réalisation d'une Echocardiographie qui a confirmé cette entité. PMID:28154713

DOE Office of Scientific and Technical Information (OSTI.GOV)

Medvedev, Ivan R.; De Lucia, Frank C.; Herbst, Eric

Since methyl formate (HCOOCH{sub 3}) is found to have a high abundance in hot molecular cores and other types of clouds in the galactic center, it is reasonable to search among such sources for detectable abundances of the more complex analog ethyl formate (HCOOC{sub 2}H{sub 5}). Following a previous study of the millimeter-wave spectrum of ethyl formate, we have extended the analysis of the vibrational ground state of the trans and gauche conformers of ethyl formate into the submillimeter-wave range. Over 2200 new spectral lines have been measured and analyzed at frequencies up to 380 GHz. Fitting the data formore » each conformer to a Watson A-reduced asymmetric-top Hamiltonian has allowed us to predict the frequencies and intensities of many more transitions through 380 GHz.« less

Raman study of vibrational dynamics of aminopropylsilanetriol in gas phase

NASA Astrophysics Data System (ADS)

Volovšek, V.; Dananić, V.; Bistričić, L.; Movre Šapić, I.; Furić, K.

2014-01-01

Raman spectrum of aminopropylsilanetriol (APST) in gas phase has been recorded at room temperature in macro chamber utilizing two-mirror technique over the sample tube. Unlike predominantly trans molecular conformation in condensed phase, the spectra of vapor show that the molecules are solely in gauche conformation with intramolecular hydrogen bond N⋯Hsbnd O which reduces the molecular energy in respect to trans conformation by 0.152 eV. The assignment of the molecular spectra based on the DFT calculation is presented. The strong vibrational bands at 354 cm-1, 588 cm-1 and 3022 cm-1 are proposed for verifying the existence of the ring like, hydrogen bonded structure. Special attention was devoted to the high frequency region, where hydrogen bond vibrations are coupled to stretchings of amino and silanol groups.

An ab-initio study of the relative stability of the ggg and the gtg conformer in hexane

NASA Astrophysics Data System (ADS)

Koglin, Eckhard; Meier, Robert J.

1999-10-01

Earlier ab-initio work suggested, on the basis of MP2 level calculations, that the hexane ggg conformer is more stable than the gtg conformer. Because this is unexpected and if true might have a significant impact on force field parametrisations, we have applied Hartree-Fock and post-HF methods to evaluate the relative stability of these conformers. We find that at levels higher than MP2 the gtg conformer is more stable than the ggg conformer, in agreement with the conventional idea that each additional gauche bond causes a further decrease in stability of the conformer. DFT methods were also applied, but although DFT methods including gradient corrections show correct qualitative behaviour, quantitatively the relative energies are far off compared to the post-HF results.

Guidance-Control-Navigation Automation for Night All-Weather Tactical Operations Held at Hague (Netherlands) on 21-24 May 1985.

DTIC Science & Technology

1985-11-01

1 1 f, 1,1"u’t I r -I irmat tor related to the weapon system as a whole can [1--1 Th t- it: as growth pot enS lal to Interface a Mission Planning...taictical decisions4 1n" 1 w 1I ’ depenid en the? core avionics to varying dog re-n. It is Important .i.h, h11~ knew whether any equipment or system ...toot en limitant le poids. le volume et le coOt des eguipements. Des fonctions nouvelles sont introduites. Peu A peu, le systeme de navigation se

Unifying the microscopic picture of His-containing turns: from gas phase model peptides to crystallized proteins.

PubMed

Sohn, Woon Yong; Habka, Sana; Gloaguen, Eric; Mons, Michel

2017-07-14

The presence in crystallized proteins of a local anchoring between the side chain of a His residue, located in the central position of a γ- or β-turn, and its local main chain environment, was assessed by the comparison of protein structures with relevant isolated model peptides. Gas phase laser spectroscopy, combined with relevant quantum chemistry methods, was used to characterize the γ- and β-turn structures in these model peptides. A conformer-selective NH stretch infrared study provided evidence for the formation in vacuo of two types of short-range H-bonded motifs, labelled ε-6 δ and δ- δ 7/π H , bridging the His side chain (in its gauche+ rotamer) to the neighbouring NH(i) and CO(i) sites of the backbone; each side chain-backbone motif was found to be specific of the tautomer (ε or δ) adopted by the His side chain in its neutral form. A close comparison between β- and γ-turns, selected from the Protein Data Bank, and the gas phase models demonstrated that a significant proportion of the gauche+ His rotamer distribution of proteins was well described by the corresponding gas phase H-bonded structures. This is consistent with the persistence of local 6 δ and δ 7/π H intramolecular interactions in proteins, emphasizing the relevance of gas phase data to secondary structures that are poorly accessible to solvents, e.g., in the case of a specific compact topology (Xxx-His β-turns). Deviations from the gas phase structures were also observed, mainly in His-Xxx β-turns, and assigned to solvent accessible turn structures. They were well accounted for by theoretical models of microhydrated turns, in which a few solvent molecules take over the gas phase motifs, constituting a water-mediated local anchoring of the His side chain to the backbone. Finally, the present gas phase benchmark models also pinpointed weaknesses in the protein structure determination by X-ray diffraction analysis; in particular, besides the lack of tautomer information, inaccuracies in the description of imidazole ring flip rotamerism were identified.

The Enantiomers of 4-Amino-3-fluorobutanoic Acid as Substrates for γ-Aminobutyric Acid Aminotransferase. Conformational Probes for GABA Binding†

PubMed Central

Clift, Michael; Ji, Haitao; Deniau, Gildas P.; O’Hagan, David; Silverman, Richard B.

2008-01-01

γ-Aminobutyric acid aminotransferase (GABA-AT), a pyridoxal 5’-phosphate dependent enzyme, catalyzes the degradation of the inhibitory neurotransmitter γ-aminobutyric acid (GABA) to succinic semialdehyde with concomitant conversion of pyridoxal 5’-phosphate (PLP) to pyridoxamine 5’-phosphate (PMP). The enzyme then catalyzes the conversion of α-ketoglutarate to the excitatory neurotransmitter L-glutamate. Racemic 4-amino-3-fluorobutanoic acid (3-F-GABA) was shown previously to act as a substrate for GABA-AT, not for transamination, but for HF elimination. Here we report studies of the reaction catalyzed by GABA-AT on (R)- and (S)-3-F-GABA. Neither enantiomer is a substrate for transamination. Very little elimination from the (S)-enantiomer was detected using a coupled enzyme assay; The rate of elimination of HF from the (R)-enantiomer is at least 10 times greater than that for the (S)-enantiomer. The (R)-enantiomer is about 20 times more efficient as a substrate for GABA-AT catalyzed HF elimination than GABA is a substrate for transamination. The (R)-enantiomer also inhibits the transamination of GABA 10 times more effectively than the (S)-enantiomer. Using a combination of computer modeling and the knowledge that vicinal C-F and C-NH3+ bonds have a strong preference to align gauche rather than anti to each other, it is concluded that on binding of free 3-F-GABA to GABA-AT the optimal conformation places the C-NH3+ and C-F bonds gauche in the (R)-enantiomer but anti in the (S)-enantiomer. Furthermore, the dynamic binding process and the bioactive conformation of GABA bound to GABA-AT have been inferred based on the different biological behavior of the two enantiomers of 3-F-GABA when they bind to the enzyme. The present study suggests that the C-F bond can be utilized as a conformational probe to explore the dynamic binding process and provide insight into the bioactive conformation of substrates, which cannot be easily determined by other biophysical approaches. PMID:17988152

Direct dynamics simulation of dioxetane formation and decomposition via the singlet .O-O-CH2-CH2. biradical: Non-RRKM dynamics

NASA Astrophysics Data System (ADS)

Sun, Rui; Park, Kyoyeon; de Jong, Wibe A.; Lischka, Hans; Windus, Theresa L.; Hase, William L.

2012-07-01

Electronic structure calculations and direct chemical dynamics simulations are used to study the formation and decomposition of dioxetane on its ground state singlet potential energy surface. The stationary points for 1O2 + C2H4, the singlet .O-O-CH2-CH2. biradical, the transition state (TS) connecting this biradical with dioxetane, and the two transition states and gauche .O-CH2-CH2-O. biradical connecting dioxetane with the formaldehyde product molecules are investigated at different levels of electronic structure theory including UB3LYP, UMP2, MRMP2, and CASSCF and a range of basis sets. The UB3LYP/6-31G* method was found to give representative energies for the reactive system and was used as a model for the simulations. UB3LYP/6-31G* direct dynamics trajectories were initiated at the TS connecting the .O-O-CH2-CH2. biradical and dioxetane by sampling the TS's vibrational energy levels, and rotational and reaction coordinate energies, with Boltzmann distributions at 300, 1000, and 1500 K. This corresponds to the transition state theory model for trajectories that pass the TS. The trajectories were directed randomly towards both the biradical and dioxetane. A small fraction of the trajectories directed towards the biradical recrossed the TS and formed dioxetane. The remainder formed 1O2 + C2H4 and of these ˜ 40% went directly from the TS to 1O2 + C2H4 without getting trapped and forming an intermediate in the .O-O-CH2-CH2. biradical potential energy minimum, a non-statistical result. The dioxetane molecules which are formed dissociate to two formaldehyde molecules with a rate constant two orders of magnitude smaller than that predicted by Rice-Ramsperger-Kassel-Marcus theory. The reaction dynamics from dioxetane to the formaldehyde molecules do not follow the intrinsic reaction coordinate or involve trapping in the gauche .O-CH2-CH2-O. biradical potential energy minimum. Important non-statistical dynamics are exhibited for this reactive system.

Odd-even chain packing, molecular and thermal models for some long chain sodium(I) n-alkanoates

NASA Astrophysics Data System (ADS)

Nelson, Peter N.; Ellis, Henry A.

2014-10-01

A homologous series of sodium(I) n-alkanoates, NaCnH2n-1O2, with chain lengths n = 8-18, inclusive, have been synthesized and their structural and thermal properties investigated via Fourier Transform Infrared and Solid State 13C NMR spectroscopies, X-ray powder diffraction, Thermogravimetry, Differential Scanning Calorimetry, Polarizing light microscopy and variable temperature Infrared spectroscopy. The measurements show that metal-carboxylate coordination is via asymmetric chelating bidentate bonding with extensive carboxyl group inter-molecular interactions in which four oxygen atoms are bonded tetrahedrally to a sodium atom. Furthermore, the compounds crystallize in a monoclinic crystal system with the hydrocarbon chains in the fully extended all-trans conformation, advancing along the c-axis. Moreover, the chains are packed as tilted (θ ∼ 63°), non-overlapping, tail-to-tail lamellar bilayers that are not in the same plane, within a lamellar. Though these compounds are nearly isostructural, there are subtle differences in the packing of the hydrocarbon chains in the crystal lattice, resulting in odd-even alternation in the terminal methyl group asymmetric stretching vibration and chemical shift. These differences arise from the relative vertical distances between hydrocarbon planes within the lamellar; such that, for odd-chain compounds, larger inter-planar distances result in less efficient packing in the crystal lattice and hence, lower inter-planar van der Waals interactions between hydrocarbon chains. Thermal traces, for all compounds, show several partially reversible solid-solid pre-melting transitions associated with different degrees of gauche conformers in the alkyl chains. The reversible gauche-trans isomerism, of the methylene groups, is kinetically controlled; hence, super-cooling of the melt and other transitions, are observed for all compounds. The kinetics of chain reversion follow the exponential law of nucleation, though complicated by competing processes. Thermogravimetric data show that all compounds decompose at temperatures in excess of 690 K; therefore, free radical thermal cracking of the hydrocarbon chains, in conjunction with decarboxylation is proposed for their non-oxidative degradation mechanism.

Benefit of a topical slimming cream in conjunction with dietary advice

PubMed Central

Escudier, B; Fanchon, C; Labrousse, E; Pellae, M

2011-01-01

Synopsis The aim of this study was to determine how worthwhile it would be to combine a newly developed topical slimming product with customized dietary habits not based on calorie restriction, so as to improve the cellulite appearance of the skin. At the beginning of the study, a nutritionist recorded the dietary habits of each participant and gave recommendations to each of them according to their food consumption. The chosen methodology was a right/left comparison, one thigh and hip being treated with the new topical slimming product and the other one left untreated to serve as a random control. Objective evaluations were performed by blind assessors. Control of food intake improved the cellulite score after 4 weeks when compared with the base value, but this reduction was significantly greater and earlier on the treated side than on the untreated side, indicating an objective additional benefit derived from the new slimming cream. This result corroborated the slimming effect assessed by measurement in centimetres of the circumference of the upper thighs and the reconstructed volume of the thigh between two fixed horizontal slices. Furthermore, skin tonicity, a major component of cellulite visibility, was also significantly improved on the treated side after only 2 weeks. This new topical cream thus enhances the benefit of a dietetic control for the treatment of the visible aspect of cellulite on the skin. Résumé Cette étude avait pour objectif d’étudier l'intérêt éventuel d'associer une nouvelle crème amincissante à des conseils nutritionnels personnalisés, non basés sur la restriction calorique mais sur un meilleur équilibre alimentaire afin d'améliorer l'aspect cellulitique de la peau. Au début de l’étude un médecin nutritionniste a enregistré les habitudes alimentaires de chaque sujet et a donné des recommandations à chacun en fonction de leur consommation alimentaire. La méthodologie contrôlée en hémi corps, gauche/droite a été choisie, une cuisse, une fesse ayant été traités par le produit à l’étude, l'autre partie du corps étant restée sans traitement selon la randomisation. Les évaluations objectives ont été réalisées par des investigateurs en aveugle. Le contrôle des aliments a permis une réduction du score de cellulite après 4 semaines mais cette réduction est statistiquement plus importante et plus rapide du côté traité avec le produit topique que du côté non traité, ce qui correspond à un effet additionnel objectivé du produit topique. Ce résultat est conforté par l'effet amincissant évalué par la mesure centimétrique de la circonférence de la partie supérieure de la cuisse et l’évolution du volume reconstruit de la cuisse entre deux niveaux. De plus la tonicité de la peau, composante importante de la visibilité de la cellulite, est améliorée significativement dès 2 semaines du coté traité; Cette nouvelle crème apporte donc un bénéfice complémentaire au contrôle diététique pour le traitement de la cellulite. PMID:21284660

Persistance du 5ème arc aortique associé à une interruption de l’arche aortique

PubMed Central

Houssa, Mahdi Ait; Atmani, Noureddine; Bamous, Mehdi; Abdou, Abdessamad; Nya, Fouad; Seghrouchni, Anis; Amahzoune, Brahim; El Bekkali, Youssef; Drissi, Mohamed; Boulahya, Abdelatif

2017-01-01

Les auteurs rapportent un cas de persistance du 5ème arc aortique associé à une interruption totale de l'arche aortique. Ce cas clinique montre le piège diagnostic posé par la persistance du 5ème arc aortique et son effet bénéfique hémodynamique. Le tableau clinique était trompeur en préopératoire en raison de la persistance des pouls fémoraux et des signes cliniques d'un shunt gauche-droite via un large canal artériel. Le diagnostic a été redressé en peropératoire grâce au monitorage de la pression artérielle par un cathéter placé dans l'artère fémorale. PMID:29187934

Molecular interaction of (ethanol)2-water heterotrimers.

PubMed

Mejía, Sol M; Espinal, Juan F; Restrepo, Albeiro; Mondragón, Fanor

2007-08-23

The potential energy surface of the (ethanol)2-water heterotrimers for the trans and gauche conformers of ethanol was studied using density functional theory. The same approximation was used for characterizing representative clusters of (ethanol)3, (methanol)3, and (methanol)2-water. Trimerization energies and enthalpies as well as the analysis of geometric parameters suggest that the structures with a cyclic pattern in the three hydrogen bonds of the type O-H---O (primary hydrogen bonds), where all molecules are proton donor-acceptor at the same time, are more stable than those with just two primary hydrogen bonds. Additionally, we propose the formation of "secondary hydrogen bonds" between hydrogen atoms of the methyl group of ethanol and the oxygen atom of water or other ethanol molecule (C-H---O), which were found to be weaker than the primary hydrogen bonds.

Mercury coordination polymers with flexible ethane-1,2-diyl-bis-(pyridyl-3-carboxylate): Synthesis, structures, thermal and luminescent properties

NASA Astrophysics Data System (ADS)

Vallejos, Javier; Brito, Iván; Cárdenas, Alejandro; Llanos, Jaime; Bolte, Michael; López-Rodríguez, Matías

2015-03-01

The reaction of the flexible ligand, ethane-1,2-diyl-bis-(pyridyl-3-carboxylate), (L) with HgI2 and HgBr2 salts under the same experimental conditions leads to the formation of two coordination polymers with different motifs: {[Hg(L)(Br2)]}n(1) and {[Hg(L)(I2)]}n(2). In both compounds, the ligand, (L) acts in a μ2-N:N‧-bidentate fashion to link HgBr2 and HgI2 units to form a linear and helical chain motif, along [1 0 0] for (1) and [0 0 1] for (2). The ethylene moiety of (L) has gauche and trans conformation in compounds (1) and (2), respectively. The flexible conformation of L produces differences in the optical and crystal properties of the two compounds.

Structural and conformational properties of 1-decyl-3-methylimidazolium tetrafluoroborate under high pressure

NASA Astrophysics Data System (ADS)

Chen, Liucheng; Li, Haining; Zhu, Xiang; Su, Lei; Yang, Kun; Yuan, Chaosheng; Yang, Guoqiang; Li, Xiaodong

2017-06-01

In situ crystalization of 1-decyl-3-methylimidazolium tetrafluoroborate ([C10MIM][BF4]) from melt has been investigated under high pressure up to 3.4 GPa at room temperature by using Raman spectroscopy and synchrotron X-ray diffraction measurement. Raman spectral analysis indicated that [C10MIM][BF4] experienced two successive phase transitions at about 0.3 GPa and 1.6 GPa. And the polymorphism was also discussed in view of the conformational isomerism of [C10MIM]+ cation between gauche and trans conformers. Notably, liquid-crystal and crystal-crystal phase transitions were further confirmed by synchrotron X-ray diffraction measurement. Moreover, it also indicated that high structural flexibility of the cations with long alkyl chain might have effect on the degree of disorder of pressure-induced crystallization for ionic liquids.

A new approach to explore the binding space of polysaccharide-based ligands: selectin antagonists.

PubMed

Calosso, Mickael; Charpentier, Daniel; Vaillancourt, Marc; Bencheqroun, Mohammed; St-Pierre, Gabrielle; Wilkes, Brian C; Guindon, Yvan

2012-12-13

The discovery of molecules that interfere with the binding of a ligand to a receptor remains a topic of great interest in medicinal chemistry. Herein, we report that a monosaccharide unit of a polysaccharide ligand can be replaced advantageously by a conformationally locked acyclic molecular entity. A cyclic component of the selectin ligand Sialyl Lewis(x), GlcNAc, is replaced by an acyclic tether, tartaric esters, which link two saccharide units. The conformational bias of this acyclic tether originates from the minimization of intramolecular dipole-dipole interaction and the gauche effect. The evaluation of the binding of these derivatives to P-selectin was measured by surface plasmon resonance spectroscopy. The results obtained in our pilot study suggest that the discovery of tunable tethers could facilitate the exploration of the carbohydrate recognition domain of various receptors.

Impact of Emerging NDE-NDI Methods on Aircraft Design, Manufacture and Maintenance (L’Impact des Nouvelles Methodes d’Examen Non Destructif et de Controle Non Destructif (NDE-NDI) sur la Conception, la Fabrication et la Maintenance des Aeronefs)

DTIC Science & Technology

1990-03-01

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Évaluation des caractéristiques mécaniques du polissoir en polyuréthanne utilisé comme porte abrasifs durant le processus du polissage du verre optique

NASA Astrophysics Data System (ADS)

Aliouane, T.; Bouzid, D.; Belkhir, N.; Bouzid, S.; Herold, V.

2005-05-01

La fabrication des composants en verre optique nécessite des moyens de grande précision dans les procédés de finition vue l'importance accordée à leur qualité.
Durant le processus de polissage des verres optiques, le polissoir est un élément clé et a un impact direct sur les performances des composants optiques, non seulement il est utilisé comme support de grains abrasifs mais il doit posséder la fonction de transmission de la pression aux grains. La connaissance de ses propriétés, essentiellement mécanique, est impérative afin d'obtenir un état de surface optimal des composants optiques destinés à remplir des fonctions très précises dans des appareils optiques très performants.
Dans cette étude, nous avons constaté que les propriétés des polissoirs en polyuréthanne tel que la dureté, le module d'élasticité et la densité varient au cours du polissage. Ce changement a des effets sur l'état de surface de verre optique, causé par le changement microstructural de la surface du polissoir (distribution et dimensions des pores) et par conséquent sur la quantité des abrasifs (en oxyde de cérium) insérée dans les pores, ce qui influe sur la quantité de verre enlevée et sur l'état de surface du composant.
Sur la base des résultats obtenus, il a été prouvé que le polissoir subit des modifications très importantes ce qui influe considérablement sur son efficacité de polissage.

Transverse magnetic field effects on the resonant tunneling current

NASA Astrophysics Data System (ADS)

Cury, L. A.; Celeste, A.; Goutiers, B.; Portal, J. C.; Sivco, D. L.; Cho, A. Y.

1991-04-01

Resonant tunneling process in an (InGa)As-(InAI)As symmetric double-barrier structure subjected to a transverse magnetic field B_{perp} (perpendicular to the current) is investigated. We particularly focus on the experimental behaviour of V_p, the voltage at the current peak position, as a function of the magnetic field B_{perp}. For strong magnetic fields a clear dependence on B_{perp}^2 is observed, as expected. However, an original result is obtained at small magnetic fields where a deviation from the parabolic behaviour is observed. The more complicated dependence on B_{perp} of V_p is obtained from a numerical fit. A qualitative discussion is proposed on the basis of a previous publication (L. A. Cury, A. Celeste, J. C. Portal, Solid-States Electron. 32 (1989) 1689) and the differences with the results of other authors are pointed out. Un système à double barrière à semiconducteurs basé sur les alliages (InGa)As(InAI)As est étudié sous un fort champ magnétique transverse B_{perp} (perpendiculaire au courant). On étudie plus particulièrement la variation expérimentale de la tension V_p associée au courant pic en fonction du champ magnétique B_{perp}. A très fort champ, le comportement attendu de V_p en B_{perp}^2 est observé. Dans le domaine des bas champs magnétiques une déviation du comportement quadratique est mise en évidence. Le comportement plus compliqué de V_p en fonction de B_{perp} est obtenu au travers d'un lissage numérique. Nous proposons une discussion qualitative, de ces résultats, fondée sur notre travail antérieur (L. A. Cury, A. Celeste, J. C. Portal, Solid-States Electron. 32 (1989) 1689) ainsi qu'une comparaison avec les résultats d'autres auteurs.

L'effet de p53 sur la radiosensibilité des cellules humaines normales et cancéreuses

NASA Astrophysics Data System (ADS)

Little, J. B.; Li, C. Y.; Nagasawa, H.; Huang, H.

1998-04-01

The radiosensitivity of normal human fibroblasts in p53 dependent and associated with the loss of cells from the cycling population as the result of an irreversible G1 arrest; cells lacking normal p53 function show no arrest and are more radioresistant. Under conditions in which the repair potentially lethal radiation damage is facilitated, the fraction of cells arrested in G1 is reduced and survival is enhanced. The response of human tumor cells differs significantly. The radiation-induced G1 arrest is minimal or absent in p53+ tumor cells, and loss of normal p53 function has no consistent effect on their radiosensitivity. These results suggest that p53 status may not be a useful predictive marker for the response of human solid tumors to radiation therapy. La radiosensibilité des fibroblastes diploïdes humains est liée à l'expression de p53, et à la perte de cellules en cycle résultant d'un arrêt irréversible en phase G1 ; dans les cellules n'ayant pas une fonction p53 normale, on ne constate aucun arrêt, et elles sont plus radio-résistantes. Dans des conditions favorables à la réparation de lésions potentiellement léthales dues à l'irradiation, la proportion de cellules bloquées en phase G1 baisse, et les chances de survie sont accrues. Bien différente est la réaction des cellules cancéreuses humaines. Le blocage par irradiation en phase G1 est minime ou inexistant dans les cellules cancéreuses p53^+, et la perte de la fonction normale p53 n'a pas d'effet constant sur leur radiosensibilité. Ces résultats laissent penser que l'expression de p53 n'est pas un indice fiable permettant de prévoir la réaction des tumeurs solides à la radiothérapie.

Investigation of a van der Waals complex with C 1 symmetry: the free-jet rotational spectrum of 1,2-difluoroethane-Ar

NASA Astrophysics Data System (ADS)

Melandri, Sonia; Velino, Biagio; Favero, Paolo G.; Dell'Erba, Adele; Caminati, Walther

2000-04-01

The van der Waals complex between Ar and 1,2-difluoroethane has been investigated by free-jet absorption millimeter-wave spectroscopy in the frequency range 60-78 GHz. The analysis of the spectroscopic constants derived from the rotational spectrum allowed the determination of the dimer's structure. 1,2-Difluoroethane is in the gauche conformation and the Ar atom is in a position stabilized by the interaction with one fluorine and the two carbon atoms. The distance between Ar and the center of mass (CM) of the monomer is 3.968 Å, the angle between the Ar-CM line and the C-C bond is 65° and the dihedral angle Ar-CM-C-C is 99°. From centrifugal distortion effects the dissociation energy of the complex has been estimated to be 2.1 kJ/mol.

Structural characterization and Hirshfeld surface analysis of racemic baclofen

NASA Astrophysics Data System (ADS)

Maniukiewicz, Waldemar; Oracz, Monika; Sieroń, Lesław

2016-11-01

The crystal structure of baclofen, (R,S) [4-amino-3-(4-chlorophenyl)butanoic acid], (C10H12ClNO2, Mr = 213.66) has been determined by single crystal X-ray diffraction analysis. The title compound crystallizes in the orthorhombic space group Pbca (No. 61) with a = 9.2704(5), b = 7.0397(4), c = 30.4015(15) Å, V = 1984.0(2) Å3 and Z = 8. The molecules exist as zwitterions, adopting a gauche conformation with respect to the Cαsbnd Cβ bond, and held in a cross-linked chain arrangement by strong Nsbnd H⋯O hydrogen bonds and Csbnd Cl⋯π interactions. The electrostatic molecular potential as well as the intermolecular interactions of the title compound were analyzed by the Hirshfeld surfaces. The FT-IR spectrum is also reported. The DTA, TG and DTG results indicate that baclofen is stable up to 205 °C.

Diethyl 2,2'-(ethane-1,2-diyldi-oxy)di-benzo-ate.

PubMed

Shi, Huaduan; Qin, Haisha; Ma, Zhen

2014-05-01

The mol-ecular title compound, C20H22O6, was obtained by the reaction of ethyl 2-hy-droxy-benzoate with 1,2-di-chloro-ethane. The mol-ecule lies on a twofold rotation axis which passes through the middle of the central ethyl-ene bridge. This group exhibits a gauche conformation with the corresponding O-C-C-O torsion angle being 73.2 (2)°. The C atoms of the carboxyl group, the aryl and the O-CH2 group are coplanar, with an r.m.s. deviation of 0.01 Å. The two aryl rings form a dihedral angle of 67.94 (4)°. The ester ethyl group is disordered over two sets of sites with an occupancy ratio of 0.59 (2):0.41 (2). The crystal packing is dominated by van der Waals forces.

Imaging phospholipid conformational disorder and packing in giant multilamellar liposome by confocal Raman microspectroscopy

NASA Astrophysics Data System (ADS)

Noothalapati, Hemanth; Iwasaki, Keita; Yoshimoto, Chikako; Yoshikiyo, Keisuke; Nishikawa, Tomoe; Ando, Masahiro; Hamaguchi, Hiro-o.; Yamamoto, Tatsuyuki

2017-12-01

Liposomes are closed phospholipid bilayer systems that have profound applications in fundamental cell biology, pharmaceutics and medicine. Depending on the composition (pure or mixture of phospholipids, presence of cholesterol) and preparation protocol, intra- and inter-chain molecular interactions vary leading to changes in the quality (order and packing) of liposomes. So far it is not possible to image conformational disorders and packing densities within a liposome in a straightforward manner. In this study, we utilized confocal Raman microspectroscopy to visualize structural disorders and packing efficiency within a giant multilamellar liposome model by focusing mainly on three regions in the vibrational spectrum (Csbnd C stretching, Csbnd H deformation and Csbnd H stretching). We estimated properties such as trans/gauche isomers and lateral packing probability. Interestingly, our Raman imaging studies revealed gel phase rich domains and heterogeneous lateral packing within the giant multilamellar liposome.

Rotationally Resolved Electronic Spectroscopy of Biomolecules in the Gas Phase. Melatonin.

NASA Astrophysics Data System (ADS)

Yi, John T.; Pratt, David W.; Brand, Christian; Wollenhaupt, Miriam; Schmitt, Michael; Meerts, W. Leo

2011-06-01

Rotationally resolved electronic spectra of the A and B bands of melatonin have been analyzed using an evolutionary strategy approach. From a comparison of the ab initio calculated structures of energy selected conformers to the experimental rotational constants, the A band could be shown to be due to a gauche structure of the side chain, while the B band is an anti structure. Both bands show a complicated pattern due to a splitting from the three-fold internal rotation of the methyl rotor in the N-acetyl group of the molecules. From a torsional analysis we additionally were able to determine the barriers of the methyl torsion in both electronic states. The electronic nature of the lowest excited singlet state could be determined to be 1LB (as in the chromophore indole) from comparison to the results of ab initio calculations.

A peptide co-solvent under scrutiny: self-aggregation of 2,2,2-trifluoroethanol.

PubMed

Scharge, Tina; Cézard, Christine; Zielke, Philipp; Schütz, Anne; Emmeluth, Corinna; Suhm, Martin A

2007-08-28

Trifluoroethanol (TFE) and its aggregates are studied via supersonic jet FTIR and Raman spectroscopy as well as by quantum chemistry and simple force field approaches. A multi-slit nozzle is introduced to study collisionally excited clusters. Efforts are made to extract harmonic frequencies from experiment for better comparison to theory. Based on deuteration, the OH stretching anharmonicity changes weakly upon dimerization, but increases for trimers. Among the possible dimer conformations, only an all-gauche, homoconfigurational, compact, OH-F connected structure is observed in an extreme case of chiral discrimination. Quantum tunneling assisted pathways for this surprising helicity synchronization are postulated. The oscillator coupling in hydrogen-bonded trimers is analyzed. Trans conformations of TFE start to become important for trimers and probably persist in the liquid state. Simple force fields can be refined to capture some molecular recognition features of TFE dimer, but their limitations are emphasized.

Dibenzo-18-crown-6–picric acid–water (1/2/3)

PubMed Central

Saleh, Muhammad Idiris; Kusrini, Eny; Rosli, Mohd Mustaqim; Fun, Hoong-Kun

2008-01-01

In the crown ether ring of the title compound, C20H24O6·2C6H3N3O7·3H2O, the O—C(H2)—C(H2)—O torsion angles indicate a gauche conformation of the ethyl­eneoxy units, while the C—O—C—C torsion angles indicate planarity of these segments; the dihedral angle between the two benzene rings is 44.53 (13)°. In both picric acid mol­ecules, one of the nitro groups is twisted away from the attached ring. The mol­ecules are linked into chains along the b axis via inter­molecular O—H⋯O hydrogen bonds. In addition, the crystal structure is stabilized by C—H⋯O hydrogen bonds and π–π inter­actions [centroid–centroid distance between benzene rings = 3.5697 (16) Å]. PMID:21202944

Etude de la formation de resonances electroniques et de leur role dans la fragmentation neutre de molecules d'interet biologique

NASA Astrophysics Data System (ADS)

Lepage, Martin

1998-12-01

Cette these est presentee a la Faculte de medecine de l'Universite de Sherbrooke en vue de l'obtention du grade de Ph.D. en Radiobiologie. Elle contient des resultats experimentaux enregistres avec un spectrometre d'electrons a haute resolution. Ces resultats portent sur la formation de resonances electroniques en phase condensee et de differents canaux pour leur decroissance. En premier lieu, nous presentons des mesures d'excitations vibrationnelles de l'oxygene dilue en matrice d'argon pour des energies des electrons incidents de 1 a 20 eV. Les resultats suggerent que le temps de vie des resonances de l'oxygene est modifie par la densite d'etats d'electrons dans la bande de conduction de l'argon. Nous presentons aussi des spectres de pertes d'energie d'electrons des molecules de tetrahydrofuranne (THF) et d'acetone. Dans les deux cas, la position en energie des pertes associees aux excitations vibrationnelles est en excellent accord avec les resultats trouves dans la litterature. Les fonctions d'excitation de ces modes revelent la presence de plusieurs nouvelles resonances electroniques. Nous comparons les resonances du THF et celles de la molecule de cyclopentane en phase gazeuse. Nous proposons une origine commune aux resonances ce qui implique qu'elles ne sont pas necessairement attribuees a l'excitation des electrons non-apparies de l'oxygene du THF. Nous proposons une nouvelle methode basee sur la spectroscopie par pertes d'energie des electrons pour detecter la production de fragments neutres qui demeurent a l'interieur d'un film mince condense a basse temperature. Cette methode se base sur la detection des excitations electroniques du produit neutre. Nous presentons des resultats de la production de CO dans un film de methanol. Le taux de production de CO en fonction de l'energie incidente des electrons est calibre en termes d'une section efficace totale de diffusion des electrons. Les resultats indiquent une augmentation lineaire du taux de production de CO en fonction de l'epaisseur du film et de la dose d'electrons incidente sur le film. Ces donnees experimentales cadrent dans un modele simple ou un electron cause la fragmentation de la molecule sans reaction avec les molecules avoisinantes. Le mecanisme propose pour la fragmentation unimoleculaire du methanol est la formation de resonances qui decroissent dans un etat electronique excite. Nous suggerons l'action combinee de la presence d'un trou dans une orbitale de coeur du methanol et de la presence de deux electrons dans la premiere orbitale vide pour expliquer la dehydrogenation complete du methanol pour des energies des electrons entre 8 et 18 eV. Pour des energies plus grandes, la fragmentation par l'intermediaire de l'ionisation de la molecule a deja ete suggeree. La methode de detection des etats electroniques offre une alternative a la detection des excitations vibrationnelles puisque les spectres de pertes d'energie des electrons sont congestionnes dans cette region d'energie pour les molecules polyatomiques.

Le syndrome d’Usher: à propos d’une observation

PubMed Central

Daoudi, Chama; boutimzine, Noureddine; Haouzi, Samia El; Lezrek, Omar; Tachfouti, Samira; Lezrek, Mounir; Laghmari, Mina; Daoudi, Rajae

2017-01-01

Résumé Le syndrome d'Usher est une maladie génétique comportant une double atteinte sensorielle (auditive et visuelle) appelée surdicécité. Nous rapportons l'observation d'un patient de 50 ans, issue d'un mariage consanguin présentant une surdité congénitale avec une fonction vestibulaire normale et une rétinopathie pigmentaire responsable d'une baisse bilatérale de l'acuité visuelle apparue vers l'âge de 16 ans. Cette association compose le type 2 du syndrome d'Usher, affection rare de transmission autosomique récessive. La chirurgie de la cataracte a permis une amélioration de l'acuité visuelle chez ce patient. PMID:28979619

Conformers, infrared spectrum and UV-induced photochemistry of matrix-isolated furfuryl alcohol.

PubMed

Araujo-Andrade, C; Gómez-Zavaglia, A; Reva, I D; Fausto, R

2012-03-08

The infrared spectra of furfuryl alcohol (2-furanmethanol, FFA) were investigated for FFA monomers isolated in low-temperature argon matrices. The structural interpretation of the obtained experimental spectra was assisted by analysis of the molecule's conformational landscape. According to the DFT(B3LYP)/6-311++G(d,p) calculations, five different minimum energy structures were found on the potential energy surface of the molecule. They can be defined by the orientation of the OCCO and CCOH dihedral angles: GG', GG, TG, TT, GT (G = +gauche, G' = -gauche, T = trans) and have a symmetry equivalent configuration: GG' = G'G, GG = G'G', TG = TG', GT = G'T. When zero-point energies are taken into account, only three (GG', GG, and TT) out of the five unique minima correspond to stable structures. The most stable conformer GG' (OCCO, 72.7°; CCOH, -59.3°), which in gas phase at room temperature accounts for ∼65% of the total population, was the only form isolated in the argon matrices at 14 K. The other two relevant forms convert into conformer GG' during matrix deposition. The low temperature glassy and crystalline states of FFA were also obtained and their infrared spectra assigned, suggesting the sole existence of the GG' conformer also in these phases. The photochemical behavior of FFA induced in situ, by tunable UV-laser, was also studied. The longest wavelength resulting in photochemical changes in the structure of the irradiated sample was found to be λ = 229 nm. Such UV irradiation of the matrix-isolated FFA led to production of formaldehyde and different isomeric C(4)H(4)O species. Cycloprop-2-ene-1-carbaldehyde and buta-2,3-dienal (two conformers) are the main initial C(4)H(4)O photoproducts formed upon short-time excitation at λ = 229 nm. But-3-ynal (two conformers) was the principal photoproduct resulting from prolonged excitation at λ= 229 nm, being consumed upon irradiation at shorter wavelengths (λ < 227.5 nm). Vinyl ketene is produced from FFA in the trans conformation and undergoes isomerization to the cis form upon irradiation at λ < 227.5 nm. Cyclopropene, propyne, allene, and CO were also identified in the irradiated matrices (in particular at the later stages of irradiation), suggesting that the photoproduced aldehydes partially decarbonylate during the performed photochemical experiments.

Pseudarthrose de l'extrémité inférieure du fémur traitée par mégaprothèse: à propos d'un cas et revue de la littérature

PubMed Central

Elidrissi, Mohammed; Hammou, Nassereddine; Shimi, Mohammed; Elibrahimi, Abdelhalim; Elmrini, Abdelmajid

2013-01-01

Les pseudarthroses de l'extrémité distale du fémur sont relativement rares du fait de la qualité de la vascularisation de cette région. La prise en charge d'une telle complication pose un certain nombre de difficultés. Le traitement chirurgical fait appel à plusieurs techniques conservatrices, le traitement par prothèse peut s'avérer utile quand la perte de substance est importante chez le sujet âgé. L'objectif de ce travail est de discuter l'intérêt de la mégaprothèse du genou dans le traitement de la pseudarthrose de l'extrémité distale du fémur, à travers l’étude de l'observation d'une patiente et revue de la littérature. Il s'agit d'une patiente âgée de 62 ans qui présente une pseudarthrose de l'extrémité distale du fémur gauche. Sur le plan clinique la patiente présente des douleurs du genou gauche, avec gène fonctionnelle importante. Le score de l'IKS préopératoire était de 60. Elle a bénéficié d'un remplacement prothétique par une mégaprothèse du genou. En postopératoire la flexion du genou était à 90°, le score de l'IKS était de 130. A travers l’étude de cette observation, et la revue de la littérature, nous pensons que l'utilisation de mégaprothèse du genou, constitue une solution efficace et durable pour le traitement des pseudarthroses du fémur distal et particulièrement chez le sujet âgé. Cette technique permet de répondre aux impératifs d'un tel aléa de la consolidation: lutter contre la douleur et garantir une mobilité satisfaisante permettant de répondre aux besoins de la vie quotidienne du patient et ainsi améliorer sa qualité de vie. PMID:24396555

Neutron Depolarization in Superconductors

NASA Astrophysics Data System (ADS)

Zhuchenko, N. K.

1995-04-01

The dependences of neutron depolarization on applied magnetic field are deduced along the magnetization hysteresis loop in terms of the Bean model of the critical state. The depolarization in uniaxial superconductors with the reversible magnetization, including uniaxial magnetic superconductors, is also considered. A strong depolarization is expected if the neutrons travel along the vortex lines. On calcule la dépendance en champ magnétique de la dépolarisation des neutrons le long du cycle d'hystérésis en termes du modèle critique de Bean. On considère aussi la dépolarisation dans les supraconducteurs uniaxiaux en fonction de l'aimantation réversible, y compris pour les supraconducteurs magnétiques. On attend une forte dépolarisation si les neutrons se propagent le long des vortex.

Aspects épidémiologiques des fractures de membres liées à l'exercice de la fonction militaire au Togo

PubMed Central

Akpoto, Yao Messanvi; Abalo, Anani; Gnandi-pio, Faré; Sonhaye, Lantam; Tchaou, Mazamaesso; Sama, Hamza Doles; Assenouwe, Sarakawabalo; Lamboni, Damessane; Amavi, Kossigan Adodossi; Adam, Saliou; Kpelao, Essossinam; Tengue, Kodjo; Songne-Gnamkoulamba, Badjona

2015-01-01

Le but de notre étude était de déterminer la fréquence des fractures de membres liées à l'exercice de la fonction militaire au sein des Forces de Défense et de Sécurité en milieu africain en vue de ressortir l'impact des différentes circonstances de survenue. Nous avons entrepris une étude rétrospective descriptive allant du 1er janvier 2004 au 31 décembre 2013. Elle a concerné les agents des forces de défense et de sécurité traités pour des fractures de membres au cours de cette période. Sept cent quatre (704) cas de fractures de membres ont été dénombrés. L’âge moyen des patients était de 30,57 ans avec des extrêmes de 19 et 55 ans. La prédominance masculine était nette (95,71%). L'Armée de Terre (51,05%) et la Gendarmerie Nationale (38,86%) étaient les plus représentées. Les hommes du rang étaient majoritaires (43,08%), suivis des sous-officiers (32,59%). La fréquence annuelle des fractures de membres en rapport avec la profession militaire était de 63 cas. Les fractures de jambe étaient les lésions les plus recensées (32,96%). Les Formations et les stages militaires ont été les circonstances de survenue les plus rencontrées (42,60%), suivies des accidents de la circulation (39,43%). La perte des journées de service liée à ces lésions était estimée à 14009 jours par an. Les fractures de jambes occupent le premier rang des fractures de membres en rapport avec l'exercice de la profession militaire. Les formations-stages militaires et les accidents de la voie publique en sont les deux grandes circonstances de survenue. PMID:27081434

Silence et divulgation dans des familles d’adolescents vivant avec le VIH depuis la naissance : une exploration qualitative

PubMed Central

Proulx-Boucher, Karène; Blais, Martin; Fernet, Mylène; Richard, Marie-Ève; Otis, Joanne; Josy Lévy, Joseph; Samson, Johanne; Lapointe, Normand; Morin, Guylaine; Thériault, Jocelyne; Trottier, Germain

2011-01-01

OBJECTIF : Les études ciblant les enfants nés avec le VIH se sont principalement intéressées à la période précédant l’annonce du diagnostic à l’enfant. L’objectif de cette étude est d’explorer les dynamiques de communication intrafamiliale suivant l’annonce du diagnostic. MÉTHODOLOGIE : Vingt-neuf jeunes (de dix à 18 ans) vivant avec le VIH depuis la naissance ont accordé des entrevues individuelles semi-dirigées portant sur : 1) le dévoilement du statut sérologique, 2) leurs relations familiales et 3) l’éducation sexuelle en milieu familial. Les témoignages ont fait l’objet d’une analyse de contenu. RÉSULTATS : Les jeunes ont appris en moyenne à l’âge de 11 ans leur diagnostic VIH+. La dynamique qui s’installe après cette annonce apparaît régie par le silence : les échanges qui s’ensuivent portent en majorité sur des questions relatives à la médication et à la prévention d’une transmission sexuelle du virus. Ce silence préserverait l’équilibre familial en occupant trois fonctions : protéger la mère d’un sentiment de culpabilité à l’égard de la transmission, assurer l’harmonie familiale, se sentir normal face aux autres. Le diagnostic de l’adolescent n’est généralement pas révélé à la famille élargie, préservant ainsi leur intégration au sein de la famille en les protégeant du rejet, de la trahison et du jugement. EXPOSÉ : Les fonctions du silence et du secret occupent une place stabilisatrice importante au sein de la famille. Toutefois, elles contribuent à isoler les adolescents d’une forme de soutien affectif dont ils ont pourtant besoin. Des pistes d’intervention sont suggérées. PMID:22851894

Approche structurée en pratique familiale pour les patients ayant des problèmes de mémoire

PubMed Central

Lee, Linda; Weston, W. Wayne; Heckman, George; Gagnon, Micheline; Lee, F. Joseph; Sloka, Scott

2013-01-01

Résumé Objectif Présenter aux médecins de famille une approche structurée pour les patients qui présentent des problèmes de mémoire. Sources des données Cette approche se fonde sur un programme agréé de formation clinique sur la mémoire, élaboré par le Centre for Family Medicine Memory Clinic en partenariat avec le Collège des médecins de famille de l’Ontario. Message principal Le recours à une approche structurée de raisonnement clinique peut aider les médecins à poser un diagnostic exact chez des patients qui présentent des problèmes de mémoire. Le délirium, la dépression et les causes réversibles doivent être exclus, pour ensuite faire une différenciation entre le vieillissement cognitif normal, la déficience cognitive légère et la démence. Il est essentiel de procéder à une anamnèse collatérale et à une évaluation fonctionnelle exacte. Les formes courantes de la démence peuvent être cliniquement différenciées par la séquence dans laquelle les symptômes apparaissent et par la façon dont les déficits cognitifs évoluent avec le temps. Habituellement, les signes précoces de la démence d’Alzheimer comportent une déficience de la mémoire épisodique, tandis que la démence due principalement à des causes vasculaires peut se présenter par une perte précoce de la fonction exécutive et de la fonction visuospatiale, ainsi que des caractéristiques cliniques particulières. Conclusion Une approche de raisonnement clinique peut aider les médecins à poser des diagnostics précoces et exacts qui peuvent orienter une prise en charge appropriée et améliorer les soins aux patients qui ont des problèmes de mémoire.

Torsion d'annexe en cours de grossesse: à propos d'un cas à l'Hôpital Central de Yaoundé, Cameroun

PubMed Central

Fouedjio, Jeanne Hortence; Fouogue, Jovanny Tsuala; Fouelifack, Florent Ymele; Nangue, Charlette; Sando, Zacharie; Enow Mbu, Robinson

2014-01-01

Les kystes ovariens sont dans la majorité des cas asymptomatiques et peuvent être de découverte fortuite lors d'une échographie. Ils ne deviennent symptomatiques que lorsque survient une complication. Nous présentons un cas de torsion d'annexe gauche diagnostiqué à 8 semaines et 4 jours de grossesse. Nous avons réalisé une annexectomie Suivie de l'administration de progestérone retard à la dose 500 mg par jour. L'évolution a été marquée par la survenue d'un avortement au cinquième jour post opératoire. L'analyse anatomopathologique de la masse chirurgicale a conclu à une apoplexie ovarienne. L'ablation chirurgicale du corps jaune au premier trimestre de la grossesse pose le problème du maintien de celle - ci et devrait être présente à l'esprit des praticiens avant toute chirurgie pelvienne pendant cette période. PMID:24932350

Molecular dynamics simulations of polyethers and a quaternary ammonium ionic liquid as CO2 absorbers

NASA Astrophysics Data System (ADS)

Cardoso, Piercarlo Fortunato; Fernandez, Juan S. L. C.; Lepre, Luiz Fernando; Ando, Rômulo Augusto; Costa Gomes, Margarida F.; Siqueira, Leonardo J. A.

2018-04-01

The properties of mixtures of butyltrimethylammonium bis(trifluoromethylsulfonyl)imide, [N4111][NTf2], with poly(ethyleneglycol) dimethyl ether, PEO, were described as a function of PEO chain size by molecular dynamics simulations. Both PEO chain size and mixture composition revealed to play a significant role in determining the structure and the dynamics of the fluids. The remarkably higher viscosity observed for mixtures composed by 0.25 mole fraction of PEO was attributed to the increase in the gauche population of OCCO dihedral of the polyether of longer chains. The negative solvation enthalpy (ΔsolH < 0) and entropy (ΔsolS < 0) revealed a favorable CO2 absorption by the neat and mixture systems. The CO2 absorption was higher in neat PEO, particularly considering longer chains. The gas solubility in the mixtures presented intermediate values in comparison to the neat PEO and neat ionic liquid. The CO2 solutions had their structures discussed in the light of the calculated radial and spatial distribution functions.

Conformational study of 2-phenylethylamine by molecular-beam Fourier transform microwave spectroscopy.

PubMed

López, Juan C; Cortijo, Vanessa; Blanco, Susana; Alonso, Jose L

2007-08-28

The conformational preferences of the simplest amine neurotransmitter 2-phenylethylamine have been investigated using molecular beam Fourier transform microwave (MB-FTMW) spectroscopy. Two new conformers have been observed together with the two previously reported by Godfrey et al. [J. Am. Chem. Soc., 1995, 117, 8204]. The (14)N nuclear quadrupole hyperfine structure has been resolved for all four conformers. Comparison of the experimental rotational and quadrupole coupling constants with those calculated theoretically provides a conclusive test for the identification of all conformers. The two most stable conformers present a gauche (folded) disposition of the alkyl-amine chain and are stabilised by a weak NH...pi interaction between the amino group and the aromatic ring. The other two conformers show an anti (extended) arrangement of the alkyl-amine chain. Tunnelling splittings have been observed in the spectrum of one of the anti conformers. The post expansion relative abundances in the supersonic jet have been also investigated and related to the conformer energies.

Structural and spectroscopic characterization of various isotopologues of 2-hydroxyacetonitrile using highly correlated ab initio methods

NASA Astrophysics Data System (ADS)

Dalbouha, Samira; Domínguez-Gómez, Rosa M.; Senent, Maria Luisa

2017-06-01

Various isotopologues of 2-hydroxyacetonitrile (OHCH2CN), a detectable astrophysical molecule, are characterized using explicitly correlated coupled cluster theory (CCSD(T)-F12/AVTZ-F12). Rovibrational parameters and far infrared transitions are computed to help the interpretation of the rotational spectra and radioastronomical observations. OHCH2CN displays non-rigid properties. The OH internal rotation intertransforms two conformers, gauche and trans, whose energy separation reaches 1.41 kcal/mol. The process is restricted by energy barriers of V t = 645 cm-1 and V g → g = 425 cm-1. Isotopic effects on the rotational constants and on the torsional energy levels are evaluated for isotopic varieties containing the most abundant cosmological isotopes (13C, 18C, 15N and D). Effects are relevant for ODCH2CN where the ground vibrational state splits in two components separated by 0.51 cm-1. This gap has been evaluated to be 3.20 cm-1 for the main isotopologue.

Host–guest complexes between cryptophane-C and chloromethanes revisited

PubMed Central

Takacs, Z; Soltesova, M; Kowalewski, J; Lang, J; Brotin, T; Dutasta, J-P

2013-01-01

Cryptophane-C is composed of two nonequivalent cyclotribenzylene caps, one of which contains methoxy group substituents on the phenyl rings. The two caps are connected by three OCH2CH2O linkers in an anti arrangement. Host–guest complexes of cryptophane-C with dichloromethane and chloroform in solution were investigated in detail by nuclear magnetic resonance techniques and density functional theory (DFT) calculations. Variable temperature proton and carbon-13 spectra show a variety of dynamic processes, such as guest exchange and host conformational transitions. The guest exchange was studied quantitatively by exchange spectroscopy measurements or by line-shape analysis. The conformational preferences of the guest-containing host were interpreted through cross-relaxation measurements, providing evidence of the gauche+2 and gauche−2 conformations of the linkers. In addition, the mobility of the chloroform guest inside the cavity was studied by carbon-13 relaxation experiments. Combining different types of evidence led to a detailed picture of molecular recognition, interpreted in terms of conformational selection. Copyright © 2012 John Wiley & Sons, Ltd. PMID:23132654

A Comparison of the ab Initio Calculated and Experimental Conformational Energies of Alkylcyclohexanes

NASA Astrophysics Data System (ADS)

Freeman, Fillmore; Tsegai, Zufan M.; Kasner, Marc L.; Hehre, Warren J.

2000-05-01

Ab initio 6-31G(d) and MP2/6-31G(d)//6-31G(d) methods were used to calculate the energies of the rotamers of the chair conformers of alkylcyclohexanes and trimethylsilylcyclohexane. The MP2/6-31G(d)//6-31G(d) calculated conformational energies ( ? or A values, in kcal/mol) of the alkylcyclohexanes (Me = 1.96; Et = 1.80; Pr = 1.73 iso-Pr = 1.60; t-Bu = 5.45; neo-pent = 1.32) and trimethylsilylcyclohexane (SiMe3 = 2.69) are similar to the experimental values. Plots of the calculated conformational energies for the alkylcyclohexanes and trimethylsilylcyclohexane versus their experimental values are linear (slope = 1.253 and r = .993 for 6-31G(d) and slope = 1.114 and r = .982 for MP2/6-31G(d)//6-31G(d)). The conformational energies are determined primarily by steric effects which include gauche (synclinal) interactions and repulsive nonbonded interactions in both the axial and equatorial conformers.

Kyste épidermoïde du testicule : Étude de cas

PubMed Central

Diarra, Alkadri; Elammari, Jalal Eddine; Kassogue, Amadou; El Fassi, Mohammed Jamal; Farih, My Hassan

2013-01-01

Résumé Le kyste épidermoïde (KE) du testicule est une tumeur bénigne rare. Le diagnostic peut être évoqué par l’échographie et l’IRM. En cas de lésion unique de petite taille, il est possible d’effectuer une chirurgie conservatrice. Ce traitement nécessite une confirmation anatomopathologique. Le présent article fait état de l’observation d’un patient de 34 ans ayant été admis en consultation d’urologie pour désir d’enfant. Le diagnostic de KE associé à une varicocèle gauche a été retenu. L’énucléation du kyste avec cure de varicocèle a été réalisée sans complications postopératoires. Une revue de la littérature nous a permis de mettre en évidence les différents aspects du KE du testicule et les méthodes thérapeutiques envisageables. PMID:24282476

Odd-Even Alternation in Tautomeric Porous Organic Cages with Exceptional Chemical Stability.

PubMed

Bera, Saibal; Basu, Arghya; Tothadi, Srinu; Garai, Bikash; Banerjee, Subhrashis; Vanka, Kumar; Banerjee, Rahul

2017-02-13

Amine-linked (C-NH) porous organic cages (POCs) are preferred over the imine-linked (C=N) POCs owing to their enhanced chemical stability. In general, amine-linked cages, obtained by the reduction of corresponding imines, are not shape-persistent in the crystalline form. Moreover, they require multistep synthesis. Herein, a one-pot synthesis of four new amine-linked organic cages by the reaction of 1,3,5-triformylphloroglucinol (Tp) with different analogues of alkanediamine is reported. The POCs resulting from the odd diamine (having an odd number of -CH 2 groups) is conformationally eclipsed, while the POCs constructed from even diamines adopt a gauche conformation. This odd-even alternation in the conformation of POCs has been supported by computational calculations. The synthetic strategy hinges on the concept of Schiff base condensation reaction followed by keto-enol tautomerization. This mechanism is the key for the exceptional chemical stability of cages and facilitates their resistance towards acids and bases. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular dynamics simulations of polyethers and a quaternary ammonium ionic liquid as CO2 absorbers.

PubMed

Cardoso, Piercarlo Fortunato; Fernandez, Juan S L C; Lepre, Luiz Fernando; Ando, Rômulo Augusto; Costa Gomes, Margarida F; Siqueira, Leonardo J A

2018-04-07

The properties of mixtures of butyltrimethylammonium bis(trifluoromethylsulfonyl)imide, [N 4111 ][NTf 2 ], with poly(ethyleneglycol) dimethyl ether, PEO, were described as a function of PEO chain size by molecular dynamics simulations. Both PEO chain size and mixture composition revealed to play a significant role in determining the structure and the dynamics of the fluids. The remarkably higher viscosity observed for mixtures composed by 0.25 mole fraction of PEO was attributed to the increase in the gauche population of OCCO dihedral of the polyether of longer chains. The negative solvation enthalpy (Δ sol H < 0) and entropy (Δ sol S < 0) revealed a favorable CO 2 absorption by the neat and mixture systems. The CO 2 absorption was higher in neat PEO, particularly considering longer chains. The gas solubility in the mixtures presented intermediate values in comparison to the neat PEO and neat ionic liquid. The CO 2 solutions had their structures discussed in the light of the calculated radial and spatial distribution functions.

Free Energy Landscape of GAGA and UUCG RNA Tetraloops.

PubMed

Bottaro, Sandro; Banáš, Pavel; Šponer, Jiří; Bussi, Giovanni

2016-10-20

We report the folding thermodynamics of ccUUCGgg and ccGAGAgg RNA tetraloops using atomistic molecular dynamics simulations. We obtain a previously unreported estimation of the folding free energy using parallel tempering in combination with well-tempered metadynamics. A key ingredient is the use of a recently developed metric distance, eRMSD, as a biased collective variable. We find that the native fold of both tetraloops is not the global free energy minimum using the Amberχ OL3 force field. The estimated folding free energies are 30.2 ± 0.5 kJ/mol for UUCG and 7.5 ± 0.6 kJ/mol for GAGA, in striking disagreement with experimental data. We evaluate the viability of all possible one-dimensional backbone force field corrections. We find that disfavoring the gauche + region of α and ζ angles consistently improves the existing force field. The level of accuracy achieved with these corrections, however, cannot be considered sufficient by judging on the basis of available thermodynamic data and solution experiments.

Diethyl 2,2′-(ethane-1,2-diyldi­oxy)di­benzo­ate

PubMed Central

Shi, Huaduan; Qin, Haisha; Ma, Zhen

2014-01-01

The mol­ecular title compound, C20H22O6, was obtained by the reaction of ethyl 2-hy­droxy­benzoate with 1,2-di­chloro­ethane. The mol­ecule lies on a twofold rotation axis which passes through the middle of the central ethyl­ene bridge. This group exhibits a gauche conformation with the corresponding O—C—C—O torsion angle being 73.2 (2)°. The C atoms of the carboxyl group, the aryl and the O—CH2 group are coplanar, with an r.m.s. deviation of 0.01 Å. The two aryl rings form a dihedral angle of 67.94 (4)°. The ester ethyl group is disordered over two sets of sites with an occupancy ratio of 0.59 (2):0.41 (2). The crystal packing is dominated by van der Waals forces. PMID:24860360

Crystal structure of octane-1,8-diaminium 4,4′-(diazene-1,2-di­yl)dibenzoate monohydrate

PubMed Central

Elkin, Igor; Christopherson, Jan-Constantin; Borchers, Tristan H.; Barrett, Christopher J.

2018-01-01

The title salt, C8H22N2 2+·C14H8N2O4 2−·H2O, represents a pseudo-polymer ionic material, resulting from the self-organizing behavior of 4,4′-azinodibenzoate dianions and doubly protonated, 1,8-diaminium-octane cations in aqueous solution. The asymmetric unit consists of two halves of octane 1,8-diaminium cations (the complete cations are both generated by crystallographic inversion symmetry), a 4,4′-azinodibenzoate anion [dihedral angle between the aromatic rings = 10.22 (4)°] and a water mol­ecule of crystallization. One of the cations is in a fully extended linear conformation while the second one has a terminal C—C—C—N gauche conformation. In the crystal, the cations, anions and water mol­ecules are linked into a three-dimensional network via a complex pattern of charge-assisted N—H⋯O and O—H⋯O hydrogen bonds. PMID:29850100

Rotationally resolved electronic spectroscopy of biomolecules in the gas phase. Melatonin

NASA Astrophysics Data System (ADS)

Yi, John T.; Brand, Christian; Wollenhaupt, Miriam; Pratt, David W.; Leo Meerts, W.; Schmitt, Michael

2011-07-01

Rotationally resolved electronic spectra of the A and B bands of melatonin have been analyzed using an evolutionary strategy approach. From a comparison of the ab initio calculated structures of energy selected conformers to the experimental rotational constants, the A band could be shown to be due to a gauche structure of the side chain, while the B band is an anti structure. Both bands show a complicated pattern due to a splitting from the threefold internal rotation of the methyl rotor in the N-acetyl group of the molecules. From a torsional analysis we additionally were able to determine the barriers of the methyl torsion in both electronic states of melatonin B and give an estimate for the change of the barrier upon electronic excitation in melatonin A. The electronic nature of the lowest excited singlet state could be determined to be 1Lb (as in the chromophore indole) from comparison to the results of ab initio calculations.

Identifying stereoisomers by ab-initio calculation of secondary isotope shifts on NMR chemical shieldings.

PubMed

Böhm, Karl-Heinz; Banert, Klaus; Auer, Alexander A

2014-04-23

We present ab-initio calculations of secondary isotope effects on NMR chemical shieldings. The change of the NMR chemical shift of a certain nucleus that is observed if another nucleus is replaced by a different isotope can be calculated by computing vibrational corrections on the NMR parameters using electronic structure methods. We demonstrate that the accuracy of the computational results is sufficient to even distinguish different conformers. For this purpose, benchmark calculations for fluoro(2-2H)ethane in gauche and antiperiplanar conformation are carried out at the HF, MP2 and CCSD(T) level of theory using basis sets ranging from double- to quadruple-zeta quality. The methodology is applied to the secondary isotope shifts for 2-fluoronorbornane in order to resolve an ambiguity in the literature on the assignment of endo- and exo-2-fluoronorbornanes with deuterium substituents in endo-3 and exo-3 positions, also yielding insight into mechanistic details of the corresponding synthesis.

Quantum mechanical origin of the conformational preferences of 4-thiaproline and its S-oxides

PubMed Central

Choudhary, Amit; Pua, Khian Hong

2010-01-01

The saturated ring and secondary amine of proline spawn equilibria between pyrrolidine ring puckers as well as peptide bond isomers. These conformational equilibria can be modulated by alterations to the chemical architecture of proline. For example, Cγ in the pyrrolidine ring can be replaced with sulfur, which can be oxidized either stereoselectively to yield diastereomeric S-oxides or completely to yield a sulfone. Here, the thiazolidine ring and peptide bond conformations of 4-thiaproline and its S-oxides were analyzed in an Ac-Xaa-OMe system by using NMR spectroscopy, X-ray crystallography, and hybrid density functional theory. The results indicate that the ring pucker of the S-oxides is governed by the gauche effect, and the prolyl peptide bond conformation is determined by the strength of the n→π* interaction between the amide oxygen and the ester carbonyl group. These findings, which are consistent with those for isologous 4-hydroxyprolines and 4-fluoroprolines, substantiate the importance of electron delocalization in amino-acid conformation. PMID:20221839

Force fields and scoring functions for carbohydrate simulation.

PubMed

Xiong, Xiuming; Chen, Zhaoqiang; Cossins, Benjamin P; Xu, Zhijian; Shao, Qiang; Ding, Kai; Zhu, Weiliang; Shi, Jiye

2015-01-12

Carbohydrate dynamics plays a vital role in many biological processes, but we are not currently able to probe this with experimental approaches. The highly flexible nature of carbohydrate structures differs in many aspects from other biomolecules, posing significant challenges for studies employing computational simulation. Over past decades, computational study of carbohydrates has been focused on the development of structure prediction methods, force field optimization, molecular dynamics simulation, and scoring functions for carbohydrate-protein interactions. Advances in carbohydrate force fields and scoring functions can be largely attributed to enhanced computational algorithms, application of quantum mechanics, and the increasing number of experimental structures determined by X-ray and NMR techniques. The conformational analysis of carbohydrates is challengeable and has gone into intensive study in elucidating the anomeric, the exo-anomeric, and the gauche effects. Here, we review the issues associated with carbohydrate force fields and scoring functions, which will have a broad application in the field of carbohydrate-based drug design. Copyright © 2014 Elsevier Ltd. All rights reserved.

Synthesis, spectroscopic characterization and theoretical calculations of ClF2CC(O)NPCl3 ([chloro(difluor)acetyl]phosphorimidic trichloride).

PubMed

Iriarte, Ana G; Cutin, Edgardo H; Argüello, Gustavo A

2014-01-01

The synthesis of [chloro(difluor)acetyl]phosphorimidic trichloride (ClF2CC(O)NPCl3), together with a tentative assignment of the vibrational, NMR and mass spectra, are reported. Quantum chemical calculations (MP2 and B3LYP methods with 6-311+G(d) and 6-311+G(2df,p) basis sets) predict three stable conformers in the gas phase (syn, gauche and anti, defined according to the rotation around both the ClCCN and the CCNP dihedral angles). However, only a single C1 symmetry conformer is observed in the liquid phase, possessing the CO double bond in synperiplanar orientation with respect to the PN double bond, and the ClC bond distorted from the plane defined by the CC(O)NP entity. A Natural Bond Orbital (NBO) analysis was carried out for the title compound and related molecules in order to provide an explanation about the electronic properties. Copyright © 2013 Elsevier B.V. All rights reserved.

Dynamics of liquids, molecules, and proteins measured with ultrafast 2D IR vibrational echo chemical exchange spectroscopy.

PubMed

Fayer, M D

2009-01-01

A wide variety of molecular systems undergo fast structural changes under thermal equilibrium conditions. Such transformations are involved in a vast array of chemical problems. Experimentally measuring equilibrium dynamics is a challenging problem that is at the forefront of chemical research. This review describes ultrafast 2D IR vibrational echo chemical exchange experiments and applies them to several types of molecular systems. The formation and dissociation of organic solute-solvent complexes are directly observed. The dissociation times of 13 complexes, ranging from 4 ps to 140 ps, are shown to obey a relationship that depends on the complex's formation enthalpy. The rate of rotational gauche-trans isomerization around a carbon-carbon single bond is determined for a substituted ethane at room temperature in a low viscosity solvent. The results are used to obtain an approximate isomerization rate for ethane. Finally, the time dependence of a well-defined single structural transformation of a protein is measured.

Structural variability in Cu(I) and Ag(I) coordination polymers with a flexible dithione ligand: Synthesis, crystal structure, microbiological and theoretical studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beheshti, Azizolla, E-mail: a.beheshti@scu.ac.ir; Nozarian, Kimia; Babadi, Susan Soleymani

Two new compounds namely [Cu(SCN)(µ-L)]{sub n} (1) and ([Ag (µ{sub 2}-L)](ClO{sub 4})){sub n} (2) have been synthesized at room temperature by one-pot reactions between the 1,1-(1,4-butanediyl)bis(1,3-dihydro-3-methyl-1H-imidazole- 2-thione) (L) and appropriate copper(I) and silver(I) salts. These polymers have been characterized by single crystal X-ray diffraction, XRPD, TGA, elemental analysis, infrared spectroscopy, antibacterial activity and scanning probe microscopy studies. In the crystal structure of 1, copper atoms have a distorted trigonal planar geometry with a CuS{sub 2}N coordination environment. Each of the ligands in the structure of 1 acting as a bidentate S-bridging ligand to form a 1D chain structure. Additionally, themore » adjacent 1D chains are interconnected by the intermolecular C-H…S interactions to create a 2D network structure. In contrast to 1, in the cationic 3D structure of 2 each of the silver atoms exhibits an AgS{sub 4} tetrahedral geometry with 4-membered Ag{sub 2}S{sub 2} rings. In the structure of 2, the flexible ligand adopts two different conformations; gauche-anti-gauche and anti-anti-anti. The antibacterial studies of these polymers showed that polymer 2 is more potent antibacterial agent than 1. Scanning probe microscopy (SPM) study of the treated bacteria was carried out to investigate the structural changes cause by the interactions between the polymers and target bacteria. Theoretical study of polymer 1 investigated by the DFT calculations indicates that observed transitions at 266 nm and 302 nm in the UV–vis spectrum could be attributed to the π→π* and MLCT transitions, respectively. - Graphical abstract: Two new Cu(I) and Ag(I) coordination polymers have been have been synthesized by one-pot reactions. Copper complex has a 2D non-covalent structure, but silver compound is a 3D coordination compound. These compounds have effective antibacterial activity. - Highlights: • Cu(I) and Ag(I) based coordination polymers have different network structures. • Ag(I) polymer has more antibacterial activity than Cu(I) polymer. • DFT calculations of Cu(I) polymer has been investigated. • Cu(I) and Ag(I) polymers can destroy the structure of chromosomal and plasmid DNA.« less

Fluorine Substitution in Neurotransmitters: Microwave Spectroscopy and Modelling of the Conformational Space and Non Bonding Interactions

NASA Astrophysics Data System (ADS)

Melandri, S.; Maris, A.; Merloni, A.

2011-06-01

Fluorine substitution in molecules is a common practice in bio-organic chemistry in order to modulate physicochemical properties and biological activity of molecules and an increasing number of drugs on the market contain fluorine, the presence of which is often of major importance to modify pharmacokinetics properties and molecular activity. The rationale for such a strategy is that fluorine is generally a stronger electron acceptor than the other halogen atoms and its size is intermediate between that of hydrogen and oxygen. We have studied two fluorinated analogs of 2-phenylethylamine (PEA), the prototype molecule for adrenergic neurotransmitters, namely: 4-Fluoro (4FPEA) and 2-Fluoro-2-phenylethylamine (2FPEA) by Molecular Beam Fourier Transform Microwave Spectroscopy in the frequency range 6-18 GHz and ab initio calculations at the MP2/6311++G** level. The aim is to obtain information on the spatial arrangement of the ethylamine side chain and the effects of fluorination on the energy landscape. The conformational space is dominated by low energy gauche conformations stabilized by weak interactions between the aminic hydrogens and the electron cloud of the benzene ring and anti conformations higher in energy. In 2FPEA the presence of the fluorine atom almost duplicate the number of possible conformation with respect to 4FPEA. We observed two conformers of 4FPEA and five conformers of 2FPEA which have been classified with the guide provided by accurate ab initio calculations. The identification of the conformational species was helped by the analysis of the quadrupole hyperfine pattern which is greatly influenced by the orientation of the amino group and acts as a fingerprint for each conformation. The orientation of the dipole moment within the principal axis frame and the order of stability of the different conformations are other independent pieces of evidence for the unambiguous assignment and identification of the conformers. The order of stability was found to be altered in both molecules with respect to the prototype PEA molecule, especially in the case of 2FPEA where we observe a stabilization of some of the anti forms and great destabilization of some of the gauche forms. These observations are in agreement with the results of the theoretical calculation and can be rationalized in terms of the effect of the fluorine atom on the electron density of the molecule and in particular on the electron cloud on the benzene ring.

Noble-Gas Difluoride Complexes of Mercury(II): The Syntheses and Structures of Hg(OTeF 5) 2·1.5NgF 2 (Ng = Xe, Kr) and Hg(OTeF 5) 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

DeBackere, John R.; Mercier, Helene P. A; Schrobilgen, Gary J.

2014-02-03

The synthesis of high-purity Hg(OTeF 5) 2 has resulted in its structural characterization in the solid state by Raman spectroscopy and single-crystal X-ray diffraction (XRD) and in solution by 19F NMR spectroscopy. The crystal structure of Hg(OTeF 5) 2 (-173 °C) consists of discrete Hg(OTeF 5) 2 units having gauche-conformations that interact through long Hg---O and Hg---F intramolecular contacts to give a chain structure. Furthermore, the Lewis acidity of Hg(OTeF 5) 2 toward NgF 2 (Ng = Xe, Kr) was investigated in SO 2ClF solvent and shown to form stable coordination complexes with NgF 2 at -78 °C. Both complexesmore » were characterized by low-temperature Raman spectroscopy (-155 °C) and single-crystal XRD. The complexes are isostructural and are formulated as Hg(OTeF 5) 2·1.5NgF 2. The Hg(OTeF 5) 2 units of Hg(OTeF 5) 2·1.5NgF 2 also have gauche-conformations and are linked through bridging NgF 2 molecules, also resulting in chain structures. The complexes represent the only examples of coordination compounds where NgF 2 coordinates to mercury in a neutral covalent compound and the only example of mercury coordinated to KrF 2. Moreover, the Hg(OTeF 5) 2·1.5KrF 2 complex is the only KrF 2 complex known to contain a bridging KrF 2 ligand. Energy-minimized gas-phase geometries and vibrational frequencies for the model compounds, [Hg(OTeF5) 2] 3 and [Hg(OTeF 5) 2] 3·2NgF 2, were obtained and provide good approximations of the local environments of Hg(OTeF 5) 2 and NgF 2 in the crystal structures of Hg(OTeF5)2 and Hg(OTeF 5) 2·1.5NgF 2. Assignments of the Raman spectra of Hg(OTeF 5) 2 and Hg(OTeF 5) 2·1.5NgF 2 are based on the calculated vibrational frequencies of the model compounds. Natural bond orbital analyses provided the associated bond orders, valencies, and natural population analysis charges.« less

Macro-adénome surrénalien masquant une hyperplasie micronodulaire des surrénales au cours d’un syndrome de Cushing ACTH indépendant et hypokaliémie réfractaire

PubMed Central

Alaya, Wafa; Bouchahda, Haifa; Fradi, Asma; Zantour, Baha; Sfar, Mohamed Habib

2017-01-01

L’association d’une hyperplasie micronodulaire des surrénales à un macro-adénome surrénalien au cours d’un syndrome de Cushing (SC) ACTH-indépendant est rare et suscite beaucoup de questions. Nous en rapportons un cas. Patiente âgée de 35 ans nous a été adressée pour suspicion d’un SC devant une obésité facio-tronculaire avec hypokaliémie d’origine rénale. Les explorations hormonales ont objectivé un SC ACTH-indépendant et le scanner abdominal a montré macro-adénome surrénalien gauche de 2cm avec une surrénale droite normale. La patiente a eu une surrénalectomie gauche. Cependant, l’hypercortisolisme et l’hypokaliémie ont persisté. L’examen anatomopathologique a permis de conclure à un adénome corticosurrénalien de 2,5cm, avec une hyperplasie micronodulaire non pigmentée des surrénales (i-MAD). La patiente a eu une surrénalectomie droite, suivie d’une insuffisance surrénalienne. Paradoxalement, l’hypokaliémie a persisté sans autres anomalies ni explication évidente (magnésémie, pH sanguin et urinaire, bilan phosphocalcique et échographie rénale normaux) nécessitant une supplémentation parentérale puis orale par du KCl. The association between micronodular adrenal hyperplasia and macro-adrenal adenoma in patients with ACTH-independent Cushing’s syndrome (CS) is rare and raises a lot of questions. We here report the case of a 35-year old female patient referred to us for suspected CS due to central obesity associated with renal hypokalaemia. Hormonal explorations objectified ACTH-independent CS and abdominal CT scan showed left macro-adrenal adenoma measuring 2cm in diameter associated with normal right adrenal gland. The patient underwent left adrenalectomy. However, hypercortisolism and hypokalaemia persisted. Anatomo-pathological examination allowed the diagnisis of adrenocortical adenoma measuring 2,5cm in diameter associated with unpigmented micronodular adrenal hyperplasia (i-Mad). The patient underwent right adrenalectomy followed by adrenal insufficiency. Paradoxically, the hypokalaemia persisted without other abnormalities nor obvious explanation (normal magnesium, urine pH, blood pH, phosphocalcic assessment and renal ultrasound) requiring parenteral and oral KCl supplementation. PMID:28690744

L’embolie pulmonaire au centre hospitalier universitaire Campus de Lomé (Togo): étude rétrospective à propos de 51 cas

PubMed Central

Pessinaba, Soulemane; Atti, Yaovi Dodzi Molba; Baragou, Soodougoua; Pio, Machihude; Afassinou, Yaovi; Kpélafia, Mohamed; Goeh-Akué, Edem; Damorou, Findibé

2017-01-01

Introduction L’objectif était d’étudier les aspects épidémiologiques, cliniques et évolutifs de l’embolie pulmonaire au CHU Campus de Lomé. Méthodes C’est une étude rétrospective, analytique et descriptive sur une période de 39 mois (1erNovembre 2011- 31 Janvier 2015). Etaient inclus, tous les dossiers des patients hospitalisés dans le service de cardiologie du CHU Campus pour une EP. Résultats La prévalence de l’EP était de 3,1%. Le sex ratio femme/homme était de 2,2. L’âge moyen des patients était de 52,7 ± 14,4 ans. Les facteurs de risque de MTEV étaient dominés par: l’obésité (54,9%), l’alitement (25,5%) et le long voyage (17,6%). Les principaux symptômes étaient: dyspnée (98,0%), douleur thoracique (78,4%) et toux (60,8%). Le score de Wells était élevé dans 29,4%. L’ECG notait: tachycardie (78,4%), HVD (49,0%), aspect S1Q3T3 (47,1%) et bloc droit (39,2%). L’échodoppler cardiaque transthoracique montrait une dilatation cavitaire droite et thrombus intra ventriculaire droit dans 5,6%. L’angioscanner thoracique était normal dans 9,8% et objectivait un embole dans 82,4%. Le traitement était fait d’HBPM à dose curative avec relais par un AVK. Une thrombolyse était effectuée chez 8 malades. L’évolution était favorable dans 86,3%. Le taux de létalité était de 13,7%. Conclusion La prévalence de l’EP est relativement faible chez nous mais probablement sous estimée. L’EP pose un problème thérapeutique au Togo à cause du coût élevé des examens complémentaires et de la thrombolyse. La prévention reste donc l’arme efficace. PMID:28904659

Aspects of Quantum Theory

NASA Astrophysics Data System (ADS)

Salam, Abdus; Wigner, E. P.

2010-03-01

Preface; List of contributors; Bibliography of P. A. M. Dirac; 1. Dirac in Cambridge R. J. Eden and J. C. Polkinghorne; 2. Travels with Dirac in the Rockies J. H. Van Vleck; 3. 'The golden age of theoretical physics': P. A. M. Dirac's scientific work from 1924 to 1933 Jagdish Mehra; 4. Foundation of quantum field theory Res Jost; 5. The early history of the theory of electron: 1897-1947 A. Pais; 6. The Dirac equation A. S. Wightman; 7. Fermi-Dirac statistics Rudolph Peierls; 8. Indefinite metric in state space W. Heisenberg; 9. On bras and kets J. M. Jauch; 10. The Poisson bracket C. Lanczos; 11. La 'fonction' et les noyaux L. Schwartz; 12. On the Dirac magnetic poles Edoardo Amadli and Nicola Cabibbo; 13. The fundamental constants and their time variation Freeman J. Dyson; 14. On the time-energy uncertainty relation Eugene P. Wigner; 15. The path-integral quantisation of gravity Abdus Salam and J. Strathdee; Index; Plates.

Modelling and Caracterisation of sea salt aerosols during ChArMEx-ADRIMED campaign in Ersa

NASA Astrophysics Data System (ADS)

Claeys, Marine; Roberts, Greg; Mallet, Marc; Sciare, Jean; Arndt, Jovanna; Mihalopoulos, Nikos

2015-04-01

During ChArMEx-ADRIMED campaign (June and July 2013), aerosol particles measurements were conducted in Ersa (600 m asl), Cap Corsica. The in-situ instrumentation allowed to characterize sea salt aerosols (SSA) by their physico-chemical and optical properties and their size distribution. This study concentrates particularly on a period of a few days where the concentration of sea salt aerosols was higher. The chemistry results indicate that the SSA measured during this period were mostly aged. The comparison of the number size distributions of air masses allow to determine the SSA size mode. These data are used to evaluate the sea salt aerosol emission scheme implemented in the regional scale Meso-Nh model. A new emission scheme based on available source fonctions is tested for different sea state conditions to evaluate the direct radiative impact of sea salt aerosols over the Mediterranean basin.

Émission spontanée amplifiée (ÉSA) dans une structure à double cavité verticale (Bi-VCSEL)

NASA Astrophysics Data System (ADS)

Boucher, Y.; Gayraud, L.

2004-11-01

Nous présentons une étude théorique de l'Émission Spontanée Amplifiée dans une structure verticale à double cavité, décrite en termes de couplage d'ondes. Chaque cavité y est représentée par un saut de phase, tandis que les puits quantiques sont assimilés à des singularités de Dirac de la permittivité. Les sources sont prises en compte dans le cadre du formalisme des matrices de transfert étendues (3 × 3), qui inclut la saturation des zones actives sous l'effet du champ interne. Dans le plan spectral, celui-ci apparaît, au même titre que le champ émis, filtré par la fonction de transfert bimode de la structure.

Reseaux Neuronaux Optiques

NASA Astrophysics Data System (ADS)

Bergeron, Alain

Cette recherche vise a la mise en oeuvre optique de reseaux neuronaux. Deux architectures differentes sont proposees. La premiere est la memoire associative permettant d'associer a un objet quelconque une sortie arbitraire tout en preservant l'information sur sa position. La seconde architecture, le classificateur neuronal pour le controle robotique, permet l'identification d'une entree et son classement selon differentes categories. La sortie est compatible avec les systemes numeriques standard. Pour realiser ces architectures, une approche modulaire est privilegiee. Le correlateur constitue le module de base des realisations. Differents modules sont de plus introduits pour realiser convenablement les operations neuronales. Le premier de ces modules est le seuil optoelectronique permettant de realiser une fonction non lineaire, element essentiel des reseaux neuronaux. Le second module a etre introduit est l'encodeur optonumerique, utile au classement des objets. Le probleme de l'enregistrement de la memoire est aborde a l'aide du codage iteratif global.

Sum frequency generation (SFG) vibrational spectroscopy of planar phosphatidylethanolamine hybrid bilayer membranes under water.

PubMed

Kett, Peter J N; Casford, Michael T L; Davies, Paul B

2010-06-15

Sum frequency generation (SFG) spectroscopy has been used to study the structure of phosphatidylethanolamine hybrid bilayer membranes (HBMs) under water at ambient temperatures. The HBMs were formed using a modified Langmuir-Schaefer technique and consisted of a layer of dipalmitoyl phosphatidylethanolamine (DPPE) physisorbed onto an octadecanethiol (ODT) self-assembled monolayer (SAM) at a series of surface pressures from 1 to 40 mN m(-1). The DPPE and ODT were selectively deuterated so that the contributions to the SFG spectra from the two layers could be determined separately. SFG spectra in both the C-H and C-D stretching regions confirmed that a monolayer of DPPE had been adsorbed to the ODT SAM and that there were gauche defects within the alkyl chains of the phospholipid. On adsorption of a layer of DPPE, methylene modes from the ODT SAM were detected, indicating that the phospholipid had partially disordered the alkanethiol monolayer. SFG spectra recorded in air indicated that removal of water from the surface of the HBM resulted in disruption of the DPPE layer and the formation of phospholipid bilayers.

Halocarbons as hydrogen bond acceptors: a spectroscopic study of haloethylbenzenes (PhCH2CH2X, X = F, Cl, Br) and their hydrate clusters.

PubMed

Robertson, Patrick A; Villani, Luigi; Dissanayake, Uresha L M; Duncan, Luke F; Abbott, Belinda M; Wilson, David J D; Robertson, Evan G

2018-03-28

The electronic spectra of 2-bromoethylbenzene and its chloro and fluoro analogues have been recorded by resonant two-photon ionisation (R2PI) spectroscopy. Anti and gauche conformers have been assigned by rotational band contour analysis and IR-UV ion depletion spectroscopy in the CH region. Hydrate clusters of the anti conformers have also been observed, allowing the role of halocarbons as hydrogen bond acceptors to be examined in this context. The donor OH stretch of water bound to chlorine is red-shifted by 36 cm -1 , or 39 cm -1 in the case of bromine. Although classed as weak H-bond acceptors, halocarbons are favourable acceptor sites compared to π systems. Fluorine stands out as the weakest H-bond acceptor amongst the halogens. Chlorine and bromine are also weak H-bond acceptors, but allow for more geometric lability, facilitating complimentary secondary interactions within the host molecule. Ab initio and DFT quantum chemical calculations, both harmonic and anharmonic, aid the structural assignments and analysis.

Molecular recognition in the gas phase: benzocaine-phenol as a model of anaesthetic-receptor interaction.

PubMed

Aguado, Edurne; León, Iker; Cocinero, Emilio J; Lesarri, Alberto; Fernández, José A; Castaño, Fernando

2009-12-28

The benzocaine-phenol complex is proposed as a model system of the interaction between the local anaesthetic benzocaine and the tyrosine residue. The complex has been generated by supersonic expansion of benzocaine and phenol in helium and probed by 1- and 2-color mass-resolved laser spectroscopies. The electronic excitation spectrum of the 1 : 1 complex spans some approximately 700 cm(-1) and includes well resolved bands from at least two isomers, as demonstrated using UV-UV hole burning spectroscopy. The combination of ion dip infrared spectroscopy (IDIRS) and ab initio calculations shows that both isomers are stabilized by an OH...N hydrogen bond between the phenol hydroxyl group and the benzocaine amino moiety, differing only in the conformation adopted by the benzocaine monomer (trans and gauche). The application of the fragmentation threshold method to benzocaine-phenol suggests the existence of chemical reactions in the electronic excited state of the complex and/or in the ion. Such hypothesis is also supported by the calculated potential energy curves along the hydrogen bond coordinate.

IR spectrum of the protonated neurotransmitter 2-phenylethylamine: dispersion and anharmonicity of the NH3(+)-π interaction.

PubMed

Bouchet, Aude; Schütz, Markus; Chiavarino, Barbara; Crestoni, Maria Elisa; Fornarini, Simonetta; Dopfer, Otto

2015-10-21

The structure and dynamics of the highly flexible side chain of (protonated) phenylethylamino neurotransmitters are essential for their function. The geometric, vibrational, and energetic properties of the protonated neutrotransmitter 2-phenylethylamine (H(+)PEA) are characterized in the N-H stretch range by infrared photodissociation (IRPD) spectroscopy of cold ions using rare gas tagging (Rg = Ne and Ar) and anharmonic calculations at the B3LYP-D3/(aug-)cc-pVTZ level including dispersion corrections. A single folded gauche conformer (G) protonated at the basic amino group and stabilized by an intramolecular NH(+)-π interaction is observed. The dispersion-corrected density functional theory calculations reveal the important effects of dispersion on the cation-π interaction and the large vibrational anharmonicity of the NH3(+) group involved in the NH(+)-π hydrogen bond. They allow for assigning overtone and combination bands and explain anomalous intensities observed in previous IR multiple-photon dissociation spectra. Comparison with neutral PEA reveals the large effects of protonation on the geometric and electronic structure.

Long-timescale motions in glycerol-monopalmitate lipid bilayers investigated using molecular dynamics simulation.

PubMed

Laner, Monika; Horta, Bruno A C; Hünenberger, Philippe H

2015-02-01

The occurrence of long-timescale motions in glycerol-1-monopalmitate (GMP) lipid bilayers is investigated based on previously reported 600 ns molecular dynamics simulations of a 2×8×8 GMP bilayer patch in the temperature range 302-338 K, performed at three different hydration levels, or in the presence of the cosolutes methanol or trehalose at three different concentrations. The types of long-timescale motions considered are: (i) the possible phase transitions; (ii) the precession of the relative collective tilt-angle of the two leaflets in the gel phase; (iii) the trans-gauche isomerization of the dihedral angles within the lipid aliphatic tails; and (iv) the flipping of single lipids across the two leaflets. The results provide a picture of GMP bilayers involving a rich spectrum of events occurring on a wide range of timescales, from the 100-ps range isomerization of single dihedral angles, via the 100-ns range of tilt precession motions, to the multi-μs range of phase transitions and lipid-flipping events. Copyright © 2014 Elsevier Inc. All rights reserved.

2H{ 19F} REDOR for distance measurements in biological solids using a double resonance spectrometer

NASA Astrophysics Data System (ADS)

Grage, Stephan L.; Watts, Jude A.; Watts, Anthony

2004-01-01

A new approach for distance measurements in biological solids employing 2H{ 19F} rotational echo double resonance was developed and validated on 2H, 19F- D-alanine and an imidazopyridine based inhibitor of the gastric H +/K +-ATPase. The 2H- 19F double resonance experiments presented here were performed without 1H decoupling using a double resonance NMR spectrometer. In this way, it was possible to benefit from the relatively longer distance range of fluorine without the need of specialized fluorine equipment. A distance of 2.5 ± 0.3 Å was measured in the alanine derivative, indicating a gauche conformation of the two labels. In the case of the imidazopyridine compound a lower distance limit of 5.2 Å was determined and is in agreement with an extended conformation of the inhibitor. Several REDOR variants were compared, and their advantages and limitations discussed. Composite fluorine dephasing pulses were found to enhance the frequency bandwidth significantly, and to reduce the dependence of the performance of the experiment on the exact choice of the transmitter frequency.

Kyste hydatique mammaire primitive

PubMed Central

Boufettal, Houssine; Samouh, Naïma

2015-01-01

La localisation mammaire du kyste hydatique est exceptionnelle. De ce fait, le diagnostic est difficile avant l'examen anatomopathologique. Nous rapportons une observation d'un cas de kyste hydatique du sein chez une femme de 32 ans, qui consultait pour un nodule du sein, dont l'imagerie montrait une lésion en rétro-aréolaire du sein gauche, homogène, ovalaire et de contours réguliers. L'examen anatomopathologique objectivait un kyste hydatique à localisation mammaire. Les suites opératoires étaient simples. L'hydatidose est une maladie ubiquitaire, pouvant atteindre tous les organes. Le diagnostic peut être évoqué devant une masse kystique du sein avec des aspects très évocateurs à l'imagerie. La confirmation du diagnostic n'est confirmée qu'après une cytoponction ou une chirurgie d'exérèse qui réalise le traitement de cette pathologique. La négativité du bilan d'extension hydatique permet de retenir une localisation primitive de l’échinococcose. PMID:26185575

Zwitterionic 4-bromo-6-meth-oxy-2-{[tris-(hy-droxy-meth-yl)methyl]-iminiumyl-meth-yl}phenolate: crystal structure and Hirshfeld surface analysis.

PubMed

Lee, See Mun; Lo, Kong Mun; Tan, Sang Loon; Tiekink, Edward R T

2016-08-01

In the solid state, the title compound, C12H16BrNO5 [systematic name: 4-bromo-2-((1E)-{[1,3-dihy-droxy-2-(hy-droxy-meth-yl)propan-2-yl]iminium-yl}meth-yl)-6-meth-oxy-benzen-1-olate], C12H16BrNO5, is found in the keto-amine tautomeric form, with an intra-molecular iminium-N-H⋯O(phenolate) hydrogen bond and an E conformation about the C=N bond. Both gauche (two) and anti relationships are found for the methyl-hydroxy groups. In the crystal, a supra-molecular layer in the bc plane is formed via hy-droxy-O-H⋯O(hy-droxy) and charge-assisted hy-droxy-O-H⋯O(phenolate) hydrogen-bonding inter-actions; various C-H⋯O inter-actions provide additional cohesion to the layers, which stack along the a axis with no directional inter-actions between them. A Hirshfeld surface analysis confirms the lack of specific inter-actions in the inter-layer region.

Crystal structure of benzyl 3-(3-methyl-phen-yl)di-thio-carbazate.

PubMed

Aziz, NurFadhilah Abdul; Yusof, Enis Nadia Md; Ravoof, Thahira Begum S A; Tiekink, Edward R T

2015-04-01

In the title compound, C15H16N2S2, the central CN2S2 residue is almost planar (r.m.s. deviation = 0.0354 Å) and forms dihedral angles of 56.02 (4) and 75.52 (4)° with the phenyl and tolyl rings, respectively; the dihedral angle between the aromatic rings is 81.72 (5)°. The conformation about the N-N bond is gauche [C-N-N-C = -117.48 (15)°]. Overall, the mol-ecule has the shape of the letter L. In the crystal packing, supra-molecular chains along the a axis are formed by N-H⋯S(thione) hydrogen bonds whereby the thione S atom accepts two such bonds. The hydrogen bonding leads to alternating edge-shared eight-membered {⋯HNCS}2 and 10-membered {⋯HNNH⋯S}2 synthons. The chains are connected into layers by phen-yl-tolyl C-H⋯π inter-actions; the layers stack along the c axis with no specific inter-actions between them.

NMR crystallography of oxybuprocaine hydrochloride, Modification II degrees.

PubMed

Harris, Robin K; Cadars, Sylvian; Emsley, Lyndon; Yates, Jonathan R; Pickard, Chris J; Jetti, Ram K R; Griesser, Ulrich J

2007-01-21

The (13)C CPMAS spectrum is presented for the polymorph of oxybuprocaine hydrochloride which is stable at room temperature, i.e. Mod. II degrees . It shows crystallographic splittings arising from the fact that there are two molecules, with substantially different conformations, in the asymmetric unit. An INADEQUATE two-dimensional experiment was used to link signals for the same independent molecule. The chemical shifts are discussed in relation to the crystal structure. Of the four ethyl groups attached to NH(+) nitrogens, one gives rise to unusually low chemical shifts, very different from those of the other three ethyl groups. This is attributed empirically to gamma-gauche conformational effects, as is confirmed by shielding computations. These considerations allow (13)C signals to be assigned to specific carbons in the two crystallographically inequivalent molecules in the crystal structure. Indeed, information about the conformations is inherent in the NMR spectrum, which thus provides data of crystallographic significance. A (13)C/(1)H HETCOR experiment enabled resolution to be obtained in the (1)H dimension and allowed (1)H and (13)C signals for the same independent molecule to be linked.

Crystal structures of 1-hy­droxy-4-prop­yloxy-9,10-anthra­quinone and its acetyl derivative

PubMed Central

Nakagawa, Hidemi; Kitamura, Chitoshi

2017-01-01

1-Hy­droxy-4-prop­yloxy-9,10-anthra­quinone, C17H14O4, (I), and its acetyl derivative, 4-acet­yloxy-4-prop­yloxy-9,10-anthra­quinone, C19H16O5, (II), were synthesized from the commercially available dye quinizarin. In both compounds, the anthra­quinone frameworks are close to planarity. There is a large difference in the conformation of the prop­yloxy group; the mol­ecule of (I) adopts a gauche conformation [O—C—C—C = −64.4 (2)°], although the mol­ecule of (II) takes a trans-planar conformation (zigzag) [O—C—C—C = 176.1 (3)°]. In the mol­ecule of (I), there is an intra­molecular O—H⋯O hydrogen bond. In both crystals, the mol­ecules are linked by C—H ⋯O hydrogen bonds. A difference in the mol­ecular arrangements of (I) and (II) is found along the stacking directions. PMID:29250400

Optical and Raman microspectroscopy of nitrogen and hydrogen mixtures at high pressures

NASA Astrophysics Data System (ADS)

Ciezak, Jennifer; Jenkins, T.; Hemley, R.

2009-06-01

Extended phases of molecular solids formed from simple molecules have led to polymeric materials under extreme conditions with advanced optical, mechanical and energetic properties. Although the existence of extended phases has been demonstrated in N2, CO and CO2, recovery of the materials to ambient conditions has posed considerable difficulty. Recent molecular dynamics simulations have predicted that the addition of hydrogen to nitrogen may increase the stability of the cubic-gauche nitrogen polymer and thereby offer the possibility of synthesis at lower pressures and temperatures. Here we present optical and Raman microspectroscopy measurements performed on nitrogen and hydrogen mixtures to 85 GPa. To pressures of 30 GPa, large deviations in the internal molecular stretching modes of the mixtures relative to those of the pure material reveal unusual phase behavior. After an unusual phase separation near 35 GPa, a phase assemblage of consisting of a phase rich in both nitrogen and hydrogen, a phase of relatively amorphous nitrogen and a mixture of the two is observed. Near this pressure, Raman bands attributed to the N-N single bonded stretch were observed.

L’enclouage centromédullaire dans les fractures complexes de l’extrémité supérieure de l’humérus: résultats préliminaire à propos de 6 cas

PubMed Central

Jamal, Louaste; Cherrad, Taoufik; Bousbaa, Hicham; Wahidi, Mohammed; Amhajji, Larbi; Rachid, Khalid

2016-01-01

L’enclouage centromédullaire antérograde s’est imposé comme un des traitements de référence des fractures céphalotubérositaires à deux, trois et quatre fragments. Nous présentons une étude rétrospective de 06 patients ayant bénéficié d’un enclouage centromédullaire depuis janvier 2012. Le Recul moyen est de 12 mois, l’âge moyen était de 57 ans. Evaluation clinique se basait sur le score de Constant et Murley, en brut et pondéré en fonction de l’âge et du sexe, avec un comparatif avec le coté sain. Le bilan radiologique nous a permis d’évaluer la consolidation osseuse, l’apparition d’Ostéonécrose de la tête ou arthrose post traumatique. Surveille aussi l’Etat des tubérosités avec l’existence ou non d’ostéolyse du trochiter. Elle recherche aussi les critères de bonne réduction à savoir l’angle calotte céphalique et l’axe diaphysaire (αF) sur les clichés de face. Tous les patients ont été traités selon la même technique chirurgicale. Le score de Constant et Murley sur l’ensemble des patients était de 64.13 points. Le score pondéré en fonction de l’age et du sexe était de 73%. Les mobilités articulaires étaient en moyenne sur l’ensemble des patients 116° en élévation antérieure, 99.9° en élévation latérale, et 42° en rotation externe. Angle αF moyen s’élève à 42°. Tous les patients présentaient des critères de bonne réduction à savoir αF. L’enclouage centromédullaire permet une synthèse osseuse simple et au prix d’un abord limité avec des résultats fonctionnels très prometteurs. La comminution fracturaire et l’ostéoporose peuvent limiter ces indications. PMID:28250878

Transitions de phase dans le oxyde de yttrium vanadium

NASA Astrophysics Data System (ADS)

Roberge, Benoit

Dans le mémoire qui suit, les ordres structural, magnétiques et orbital dans le YVO3 sont étudiés avec l'aide de la diffraction des rayons X,de la spectroscopie Raman et de la technique de la cavité résonnante hyperfréquence. L'objectif premier consiste à observer l'évolution de ces ordres en fonction de la température. Le mémoire met ensuite en évidence le couplage entre les différents ordres cohabitants dans le YVO3 . Les mesures effectuées par la diffraction des rayons X permettent de mesurer le caractère polycrystallin des échantillons du YVO 3. Une comparaison de nos mesures avec des mesures de diffraction des rayons X faites sur la poudre de YVO3 indique la faible présence de maclage. Les mesures effectuées avec la technique de résonnance hyperfréquence permettent de suivre l'évolution de la constante diélectrique en fonction de la température. Les changements impliquant l'ordre orbital se manifestent de manière évidente dans la constante diélectrique à 200 K et à 77 K. La transition diélectrique détectée à 77 K est une transition de premier ordre. Un couplage entre les propriétés diélectriques et magnétiques est observable à la température de Néel à 114 K. L'effet d'un champ magnétique fixe sur la température de transition de l'ordre orbital survenant à 77 K est également remarquable. Cela indique un couplage magnétodiélectrique démontrant ainsi le caractère multiferroïque du YVO 3. Finalement, l'observation d'un mécanisme de relaxation pouvant être modélisé par le modèle d'Havriliak-Negami est observé en dessous de 77 K. En utilisant le modèle d'Arrhénius et le modèle d'Havriliak-Negami, on peut caractériser le mécanisme avec son énergie d'activation et son temps de relaxation. Les mesures effectuées en spectroscopie Raman permettent de suivre l'évolution de la structure du YVO3 en fonction de la température. Les deux changements structuraux survenant à 200 K et 77 K sont observés. Le couplage entre le réseau et l'ordre orbital se manifeste par une augmentation de l'anharmonicité qui se traduit par une augmentation de l'intensité des processus de deuxième et troisième ordres. Les différentes théories expliquant comment l'ordre orbital interagit avec le réseau cristallin seront abordées en mettant l'accent sur la théorie de Van den Brink ['] qui réflète le mieux la réalité. Une comparaison de nos mesures avec d'autres travaux en spectroscopie Raman effectués sur le YVO3 sera également effectuée. Le couplage entre le réseau et l'ordre magnétique s'observe par la présence d'excitations magnétiques dans les spectres Raman et par la présence d'un ramollissement/durcissement survenant à la température de Néel. La théorie de Granado expliquant le phénomène de durcissement/ramollissement sera discutée.

Introduction à une théorie des systèmes composites : exemples simples de matériaux lamellaires

NASA Astrophysics Data System (ADS)

Akjouj, A.; Sylla, B.; Dobrzynski, L.

This review paper is mostly an introduction to the linear response theory for composite systems. The composite materials are defined here as being formed by different homogeneous parts connected together by interfaces. This type of material can be constructed with the help of homogeneous "bricks" cuted out from infinite materials. This cutting procedures are realized with the help of cleavage operators. The "bricks" are then put together by a coupling operator. This construction manner enables to obtain for any composite system a general equation relating the composite response function (called also Green's function) to the elements of the infinite material response functions and to the cleavage and coupling operators. A general and unified formulation valid as well in matrix algebra as in the algebra of differential equations results from this approach. Any general theory is abstract ; simple examples help very much to understand it. The principal aim of this review paper is the introduction of a general theory for composite systems through simple and analytical examples from the fields of phonons, magnons and electrons in the lamellar composite materials. In order to achieve this goal, the algebra of the examples is as explicit as possible. The references of what was already realized in theory of composite response are discussed also. A prospective and non exhaustive study of all the fields where such a theory can prove to be helpful is given also in this review paper. Cet article de revue est essentiellement une introduction à la théorie de la réponse linéaire dans les systèmes composites. Les matériaux composites sont définis ici comme étant formés de parties homogènes différentes reliées par des interfaces. Ce type de matériaux peut être construit à partir de "briques" homogènes découpées dans des matériaux infinis. Ces opérations de découpage sont effectuées par l'intermédiaire d'opérateurs de clivage. Les "briques" sont ensuite assemblées grâce à un opérateur de couplage. Cette façon de construire un système composite permet d'obtenir une équation générale reliant la fonction réponse (appelée aussi fonction de Green) du système composite aux éléments des fonctions réponses des matériaux infinis et aux opérateurs de clivage et de couplage. Une formulation générale unifiée valable aussi bien en algèbre des matrices pour les systèmes discrets qu'en algèbre différentielle pour les systèmes continus en résulte. Toute théorie générale est abstraite ; sa compréhension est grandement facilitée par la pratique d'exemples simples. Le but principal de cet article de revue est d'introduire une théorie générale des systèmes composites grâce à des exemples simples et analytiques empruntés au domaine des phonons, des magnons et des électrons dans les matériaux composites lamellaires (multicouches). Afin d'atteindre ce but, les développements mathématiques des exemples sont donnés le plus explicitement possible. Une revue bibliographique de ce qui a été déjà réalisé en théorie de la réponse dans les matériaux composites est donnée également. Une étude prospective et non exhaustive des très nombreux domaines où cette théorie peut être utile prolonge la revue bibliographique.

Low field scaling properties of high Tc superconductor glasses

NASA Astrophysics Data System (ADS)

Giovannella, C.; Fruchter, L.; Chappert, C.

We show that the zero field cooling (ZFC) M/H curves of both the YBaCuO and the LaSrCuO granular superconductor glasses (SuG) are subjected to scaling when plotted against the reduced variable t/H1/ψ . The breaking of the scaling for too weak or too strong magnetic fields is discussed and justified by the introduction of a phenomenological fractal picture, describing the behaviour of the disordered intergranular junction network. Nous montrons que les courbes M/H caractéristiques des verres de supraconducteurs granulaires sont sujettes à une loi d'échelle lorsqu'elles sont tracées en fonction de la variable réduite t/H1/ψ. La brisure de la loi d'échelle pour des champs trop forts ou trop faibles est justifiée par l'introduction d'un modèle phénoménologique fractal capable de décrire le comportement d'un réseau désordonné des jonctions.

Epanchement pleuro-péricardique liquidien révélant un lymphome lymphoblastique

PubMed Central

N'goran, Yves N'da Kouakou; Soya, Kossa Esaïe; Beossin, Sylvanus Koui; Angoran, Ines; Traore, Fatou; Tano, Micesse; Afassinou, Yaovi; Ekou, Arnaud; Koffi, Florent; Yao, Hermann; Kramoh, Euloge Kouadio; Kakou, Maurice Guikahue

2014-01-01

L'atteinte cardiaque au cours des lymphomes lymphoblastiques est rare. Il s'agissait d'un patient de 17 ans de race noire qui a été admis pour une douleur médiothoracique. Le patient avait des signes d'insuffisance cardiaque droite; un syndrome d’épanchement pleural liquidien gauche; des adénopathies superficielles et une splénomégalie de type IV de Hackett. La biopsie ganglionnaire a été réalisée pour la confirmation du diagnostic par analyse histologique et immuno-histochimique. Des ponctions pleurale et péricardique ont été effectuées. Le patient a été confié au service d'oncologie pédiatrique pour la chimiothérapie. L’évolution a été marquée par le décès du patient 18 jours après. La manifestation cardiaque est une entité rare et très souvent méconnue.la confirmation histologique est parfois difficile à obtenir du vivant de la plupart des patients. Le pronostic est souvent réservé à court terme. PMID:25419294

Biophysical characterization of gold nanoparticles-loaded liposomes.

PubMed

Mady, Mohsen Mahmoud; Fathy, Mohamed Mahmoud; Youssef, Tareq; Khalil, Wafaa Mohamed

2012-10-01

Gold nanoparticles were prepared and loaded into the bilayer of dipalmitoylphosphatidylcholine (DPPC) liposomes, named as gold-loaded liposomes. Biophysical characterization of gold-loaded liposomes was studied by transmission electron microscopy (TEM) and Fourier transform infrared (FTIR) spectroscopy as well as turbidity and rheological measurements. FTIR measurements showed that gold nanoparticles made significant changes in the frequency of the CH(2) stretching bands, revealing that gold nanoparticles increased the number of gauche conformers and create a conformational change within the acyl chains of phospholipids. The transmission electron micrographs (TEM) revealed that gold nanoparticles were loaded in the liposomal bilayer. The zeta potential of DPPC liposomes had a more negative value after incorporating of Au NPs into liposomal membranes. Turbidity studies revealed that the loading of gold nanoparticles into DPPC liposomes results in shifting the temperature of the main phase transition to a lower value. The membrane fluidity of DPPC bilayer was increased by loading the gold nanoparticles as shown from rheological measurements. Knowledge gained in this study may open the door to pursuing liposomes as a viable strategy for Au NPs delivery in many diagnostic and therapeutic applications. Copyright © 2011 Associazione Italiana di Fisica Medica. Published by Elsevier Ltd. All rights reserved.

A computational study of vicinal fluorination in 2,3-difluorobutane: implications for conformational control in alkane chains.

PubMed

Fox, Stephen J; Gourdain, Stephanie; Coulthurst, Anton; Fox, Clare; Kuprov, Ilya; Essex, Jonathan W; Skylaris, Chris-Kriton; Linclau, Bruno

2015-01-19

A comprehensive conformational analysis of both 2,3-difluorobutane diastereomers is presented based on density functional theory calculations in vacuum and in solution, as well as NMR experiments in solution. While for 1,2-difluoroethane the fluorine gauche effect is clearly the dominant effect determining its conformation, it was found that for 2,3-difluorobutane there is a complex interplay of several effects, which are of similar magnitude but often of opposite sign. As a result, unexpected deviations in dihedral angles, relative conformational energies and populations are observed which cannot be rationalised only by chemical intuition. Furthermore, it was found that it is important to consider the free energies of the various conformers, as these lead to qualitatively different results both in vacuum and in solvent, when compared to calculations based only on the electronic energies. In contrast to expectations, it was found that vicinal syn-difluoride introduction in the butane and by extension, longer hydrocarbon chains, is not expected to lead to an effective stabilisation of the linear conformation. Our findings have implications for the use of the vicinal difluoride motif for conformational control. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Infrared spectra of molecules and materials of astrophysical interest

NASA Technical Reports Server (NTRS)

Durig, J. R.

1978-01-01

The Raman spectra of gaseous, liquid and solid, and infrared spectra of gaseous and solid isopropylamine-d sub 0 and -d sub 2 was investigated between 4000 and 50 cm superscript -1. Differences between the spectrum of the solid phase and that of the fluid phases were interpreted in terms of an equilibrium between low energy s-trans and high energy gauche conformers, and a complete vibrational assignment was proposed for the s-trans conformer. The far infrared spectra of the gaseous compounds contained bands due to the asymmetric amino and coupled methyl torsions; the assignment of these bands was aided by observation of a number of two quantum transitions for each vibrational mode. The asymmetric potential functions were calculated, which resulted in values for the enthalpy differences between conformers in the gaseous phase of 446 and 523 callmole for the sub 0 -d and -d sub 2 compounds, respectively. The methyl torsional potential function of isopropylamine-d sub 0 was calculated which led to a value for the barrier height to internal rotation of the methyl rotors of 4.23 + or - 0.06 kcal/mole. Values for the ideal gas thermodynamic functions were calculated over a range of temperatures.

Solution structure and thermodynamics of 2',5' RNA intercalation.

PubMed

Horowitz, Eric D; Lilavivat, Seth; Holladay, Benjamin W; Germann, Markus W; Hud, Nicholas V

2009-04-29

As a means to explore the influence of the nucleic acid backbone on the intercalative binding of ligands to DNA and RNA, we have determined the solution structure of a proflavine-bound 2',5'-linked octamer duplex with the sequence GCCGCGGC. This structure represents the first NMR structure of an intercalated RNA duplex, of either backbone structural isomer. By comparison with X-ray crystal structures, we have identified similarities and differences between intercalated 3',5' and 2',5'-linked RNA duplexes. First, the two forms of RNA have different sugar pucker geometries at the intercalated nucleotide steps, yet have the same interphosphate distances. Second, as in intercalated 3',5' RNA, the phosphate backbone angle zeta at the 2',5' RNA intercalation site prefers to be in the trans conformation, whereas unintercalated 2',5' and 3',5' RNA prefer the -gauche conformation. These observations provide new insights regarding the transitions required for intercalation of a phosphodiester-ribose backbone and suggest a possible contribution of the backbone to the origin of the nearest-neighbor exclusion principle. Thermodynamic studies presented for intercalation of both structural RNA isomers also reveal a surprising sensitivity of intercalator binding enthalpy and entropy to the details of RNA backbone structure.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Avazbaeva, Zaure; Sung, Woongmo; Lee, Jonggwan

In this paper, it has been reported that an octadecylamine (ODA) Langmuir monolayer becomes unstable at low pH values with no measurable surface pressure at around pH 3.5, suggesting significant dissolution of the ODA molecule into the subphase solution (Albrecht, Colloids Surf. A 2006, 284–285, 166–174). However, by lowering the pH further, ODA molecules reoccupy the surface, and a full monolayer is recovered at pH 2.5. Using surface sum-frequency spectroscopy and pressure–area isotherms, it is found that the recovered monolayer at very low pH has a larger area per molecule with many gauche defects in the ODA molecules as comparedmore » to that at high pH values. This structural change suggests that the reappearance of the monolayer is due to the adsorbed Cl– counterions to the protonated amine groups, leading to partial charge neutralization. This proposition is confirmed by intentionally adding monovalent salts (i.e., NaCl, NaBr, or NaI) to the subphase to recover the monolayer at pH 3.5, in which the detailed structure of the monolayer is confirmed by sum frequency spectra and the adsorbed anions by X-ray reflectivity.« less

Photothermal microfluidic cantilever deflection spectroscopy reflecting clustering mechanism of ethanol water mixtures

NASA Astrophysics Data System (ADS)

Ghoraishi, Maryam; Hawk, John; Thundat, Thomas

Aqueous mixture of alcohol is a typical prototype for biomolecules, micelle formation, and structural stability of proteins. Therefore, Short chain alcohols such as EtOH have been used as a simple model for understanding of more complex aqueous biomolecules. Here we study vibrational energy peaks of EtOH water binary mixtures using micromechanical calorimetric spectroscopy using bimaterial microfluidic cantilevers (BMC). The IR spectra of EtOH-water are experimentally collected employing a BMC as concentration of EtOH changes from 20-100 wt%. As concentration of EtOH varies in the mixture, considerable shifts in the wavenumber at IR absorption peak maxima are reported. The experimentally measured shifts in the wavenumber at IR absorption peak maxima are related to changes in dipole moment (μ) of EtOH at different concentration. The relationship between IR absorption wavenumber for both anti and gauche conformers of EtOH, and inverse dipole moment, 1/ μ, of EtOH at different concentrations follows a power law dependence. Our technique offers a platform to investigate dipole effect on molecular vibrations of mixtures in confined picoliter volumes, previously unexplored with other analytical techniques due to limitations of volume under study.

The distribution of conformational disorder in the high-temperature phases of the crystalline n-alkanes

NASA Astrophysics Data System (ADS)

Maroncelli, M.; Strauss, H. L.; Snyder, R. G.

1985-03-01

The distributions of conformational defects that exist in the high-temperature phase II (also referred to as the hexagonal or rotator phase) of the crystalline n-alkanes C21 and C29 have been measured by an infrared CD2-substitution technique and have been accounted for in terms of a lattice model that provides freedom for longitudinal displacement of the chains. The defects consist almost entirely of gtg' kinks distributed nonuniformly along the chain. The uneven distribution is indicated in the variation in the concentration of gauche bonds measured at various sites along the chain. The highest concentration is at the chain ends, and the concentrations at interior sites decrease exponentially in going toward the middle. To explain the distribution we used a modification of a lattice model that had been successfully applied to the lipid bilayer. Comparison of observed distributions with those computed from the model indicates that the factors that determine the shape of the distribution are quite different in the n-alkane and bilayer cases. For the bilayer, the dominant factor is the variation in the lateral density of chains; for the n-alkane, the dominant factor is associated with longitudinal displacement of the chains.

Constant-pH molecular dynamics using stochastic titration

NASA Astrophysics Data System (ADS)

Baptista, António M.; Teixeira, Vitor H.; Soares, Cláudio M.

2002-09-01

A new method is proposed for performing constant-pH molecular dynamics (MD) simulations, that is, MD simulations where pH is one of the external thermodynamic parameters, like the temperature or the pressure. The protonation state of each titrable site in the solute is allowed to change during a molecular mechanics (MM) MD simulation, the new states being obtained from a combination of continuum electrostatics (CE) calculations and Monte Carlo (MC) simulation of protonation equilibrium. The coupling between the MM/MD and CE/MC algorithms is done in a way that ensures a proper Markov chain, sampling from the intended semigrand canonical distribution. This stochastic titration method is applied to succinic acid, aimed at illustrating the method and examining the choice of its adjustable parameters. The complete titration of succinic acid, using constant-pH MD simulations at different pH values, gives a clear picture of the coupling between the trans/gauche isomerization and the protonation process, making it possible to reconcile some apparently contradictory results of previous studies. The present constant-pH MD method is shown to require a moderate increase of computational cost when compared to the usual MD method.

Production du baryon Sigma+ dans les collisions e+e- au LEP

NASA Astrophysics Data System (ADS)

Joly, Andre

Les mécanismes de production des baryons dans les interactions e+e- font l'objet de nombreuses études. De plus, les modes de production des baryons étranges semblent faire appel A des processus spécifiques, qui sont encore mal compris. Notre étude de la production des baryons Σ+ dans les interactions e+e- nous permet de formuler certaines remarques sur l'état des connaîssances acquises sur le sujet. Une methode de reconstruction originale et des critères de sélection spécifiques ont été développés afin d'identifier des baryons Σ+ de haute Energie ( ES+ > 5 GeV), partir de leur canal de désintégration en un proton et un π0 (S+-->p+p0 ). Trois mesures principales sont réalisées à partir de notre échantillon de baryons reconstruits. Le nombre mesuré de baryons Σ+ produits par événement e +e- à 91 GeV est de: =0.102+/-0.006(stat.) +/-0.008(syst.) +/-0.003(extrap.) où les erreurs sont dues à la statistique, aux systématiques et à la procédure d'extrapolation. Ce résultat est en accord avec ceux obtenus précédemment, mais avec des erreurs réduites. La section efficace différentielle en fonction de l'energie est mesurée et comparée aux prédictions des principaux générateurs Monte-Carlo (JETSET7.4(MOPS), JETSET7.4 et HERWIG5.9). A haute énergie, HERWIG ne semble pas reproduire les mesures, aussi bien que les deux versions de JETSET. Enfin, la position du maximum de la section efficace différentielle de production des baryons Σ+ en fonction de l'impulsion est mesurée. On trouve: overlinexoverlineS+=2.32+/- 0.47 Une étude spécifique du générateur JETSET7.4(MOPS) est réalisee, afin de mieux comprendre les mécanismes de production de l'étrangeté et du spin dans la production des baryons. Aucun générateur ne semble capable de décrire de manière simultanée la production du spin et de l'étrangeté.

Les fluctuations supraconductrices dans le compose praseodyme-cerium-oxyde de cuivre

NASA Astrophysics Data System (ADS)

Renaud, Jacques

Ce travail etudie les fluctuations supraconductrices dans le compose supraconducteur a haute temperature critique dope aux electrons Pr2-xCe xCuO4+delta. La technique utilisee pour sonder ces fluctuations est le transport electrique DC dans le plan ab. Il s'agit, a notre connaissance, de la premiere etude de ce type dans la classe generale des supraconducteurs a haute temperature critique dopes aux electrons et, plus particulierement, dans Pr2-xCe xCuO4+delta. De plus, l'etude est effectuee pour trois regimes de dopage, soit sous-dope x = 0.135, dopage optimal x = 0.15 et surdope x = 0.17. Les echantillons etudies sont des couches minces d'epaisseur plus grande que 100 nm crues par ablation laser. Les mesures electriques DC effectuees dans ce travail sont la resistance en reponse lineaire et les courbes IV en reponse non lineaire en fonction de la temperature. La mise en oeuvre experimentale de ces mesures a necessite une grande attention au filtrage et aux effets de chauffage a haut courant. Nous montrons que, sans cette attention, les donnees experimentales sont toujours erronees dans le regime pertinent pour nos echantillons. Les resultats pour le dopage optimal x = 0.15 sont expliques de facon tres convaincante dans le cadre de fluctuations purement 2D. D'abord, le regime des fluctuations gaussiennes est tres bien decrit par le modele d'Aslamazov-Larkin en deux dimensions. Ensuite, le regime de fluctuations critiques, se trouvant a plus basse temperature que le regime gaussien, est tres bien decrit par la physique 2D de Kosterlitz-Thouless. Dans cette analyse, les deux regimes ont des temperatures critiques coherentes entre elles, ce qui semble confirmer ce scenario 2D. Une analyse des donnees dans le cadre de fluctuations 3D est exploree mais donne des conclusions incoherentes. Les resultats pour les autres dopages sont qualitativement equivalents avec le dopage optimal et permettent donc une explication purement 2D. Par contre, contrairement au dopage optimal, les effets du desordre semblent etre tres importants. Une analyse detaillee de tous ces resultats semble indiquer que les signatures 2D in identifiees proviennent vraisemblablement de plans paralleles decouples formes d'environ 4 plans CuO2 couples. On discute de cette mise en ordre partielle comme une possible consequence d'une separation de phase isolante antiferromagnetique/supraconducteur. La largeur de la transition en fonction du dopage est aussi analysee dans le but de mettre en lumiere un possible effet du pseudogap. On montre que nos mesures ne supportent pas une telle interpretation.

Caracterisation environnementale des emissions atmospheriques d'une source fixe et creation d'un outil de gestion dynamique =

NASA Astrophysics Data System (ADS)

Fournier, Marie-Claude

Une caracterisation des emissions atmospheriques provenant des sources fixes en operation, alimentees au gaz et a l'huile legere, a ete conduite aux installations visees des sites no.1 et no.2. La caracterisation et les calculs theoriques des emissions atmospheriques aux installations des sites no.1 et no.2 presentent des resultats qui sont en dessous des valeurs reglementaires pour des conditions d'operation normales en periode hivernale et par consequent, a de plus fortes demandes energetiques. Ainsi, pour une demande energetique plus basse, le taux de contaminants dans les emissions atmospheriques pourrait egalement etre en dessous des reglementations municipales et provinciales en vigueur. Dans la perspective d'une nouvelle reglementation provinciale, dont les termes sont discutes depuis 2005, il serait souhaitable que le proprietaire des infrastructures visees participe aux echanges avec le Ministere du Developpement Durable, de l'Environnement et des Parcs (MDDEP) du Quebec. En effet, meme si le principe de droit acquis permettrait d'eviter d'etre assujetti a la nouvelle reglementation, l'application de ce type de principe ne s'inscrit pas dans ceux d'un developpement durable. L'âge avance des installations etudiees implique la planification d'un entretien rigoureux afin d'assurer les conditions optimales de combustion en fonction du type de combustible. Des tests de combustion sur une base reguliere sont donc recommandes. Afin de supporter le processus de suivi et d'evaluation de la performance environnementale des sources fixes, un outil d'aide a la gestion de l'information environnementale a ete developpe. Dans ce contexte, la poursuite du developpement d'un outil d'aide a la gestion de l'information environnementale faciliterait non seulement le travail des personnes affectees aux inventaires annuels mais egalement le processus de communication entre les differents acteurs concernes tant intra- qu'inter-etablissement. Cet outil serait egalement un bon moyen pour sensibiliser le personnel a leur consommation energetique ainsi qu'a leur role dans la lutte contre les emissions polluantes et les gaz a effets de serre. En outre, ce type d'outil a pour principale fonction de generer des rapports dynamiques pouvant s'adapter a des besoins precis. Le decoupage coherent de l'information associe a un developpement par modules offre la perspective d'application de l'outil pour d'autres types d'activites. Dans ce cas, il s'agit de definir la part commune avec les modules existants et planifier les activites de developpement specifiques selon la meme demarche que celle presentee dans le present document.

Vecteurs Singuliers des Theories des Champs Conformes Minimales

NASA Astrophysics Data System (ADS)

Benoit, Louis

En 1984 Belavin, Polyakov et Zamolodchikov revolutionnent la theorie des champs en explicitant une nouvelle gamme de theories, les theories quantiques des champs bidimensionnelles invariantes sous les transformations conformes. L'algebre des transformations conformes de l'espace-temps presente une caracteristique remarquable: en deux dimensions elle possede un nombre infini de generateurs. Cette propriete impose de telles conditions aux fonctions de correlations qu'il est possible de les evaluer sans aucune approximation. Les champs des theories conformes appartiennent a des representations de plus haut poids de l'algebre de Virasoro, une extension centrale de l'algebre conforme du plan. Ces representations sont etiquetees par h, le poids conforme de leur vecteur de plus haut poids, et par la charge centrale c, le facteur de l'extension centrale, commune a toutes les representations d'une meme theorie. Les theories conformes minimales sont constituees d'un nombre fini de representations. Parmi celles-ci se trouvent des theories unitaires dont les representation forment la serie discrete de l'algebre de Virasoro; leur poids h a la forme h_{p,q}(m)=[ (p(m+1) -qm)^2-1] (4m(m+1)), ou p,q et m sont des entiers positifs et p+q<= m+1. L'entier m parametrise la charge centrale: c(m)=1 -{6over m(m+1)} avec n>= 2. Ces representations possedent un sous-espace invariant engendre par deux sous-representations avec h_1=h_{p,q} + pq et h_2=h_{p,q} + (m-p)(m+1-q) dont chacun des vecteurs de plus haut poids portent le nom de vecteur singulier et sont notes respectivement |Psi _{p,q}> et |Psi_{m-p,m+1-q}>. . Les theories super-conformes sont une version super-symetrique des theories conformes. Leurs champs appartiennent a des representation de plus haut poids de l'algebre de Neveu-Schwarz, une des deux extensions super -symetriques de l'algebre de Virasoro. Les theories super -conformes minimales possedent la meme structure que les theories conformes minimales. Les representations sont elements de la serie h_{p,q}= [ (p(m+2)-qm)^2-4] /(8m(m+2)) ou p,q et m sont des entiers positifs, p et q etant de meme parite, et p+q<= m+2. La charge centrale est donnee par c(m)={3over 2}-{12over m(m+2)} avec m >= 2. Les vecteurs singuliers | Psi_{p,q}> et |Psi_{m-p,m+2-q} > sont respectivement de poids h _{p,q}+pq/2 et h_ {p,q}+(m-p)(m+2-q)/2.. Les vecteurs singuliers ont une norme nulle et on doit les eliminer des representations pour que celles -ci soient unitaires. Cette elimination engendrent des equations (super-)differentielles qui dependent directement de la forme explicite des vecteurs singuliers et auxquelles doivent obeir les fonctions de correlations de la theorie. Ainsi la connaissance de ces vecteurs singuliers est intimement reliee au calcul des fonctions de correlation. Les equations definissant les vecteurs singuliers forment un systeme lineaire surdetermine dont le nombre d'equations est de l'ordre de N(pq), le nombre de partitions de l'entier pq. Puisque les vecteurs singuliers jouent un role capital en theorie conforme, il est naturel de chercher des formes explicites pour les vecteurs (ou pour des familles infinies de ceux -ci). Nous donnons ici la forme explicite pour la famille infinie de vecteurs singuliers ayant un de ses indices egal a 1, pour les algebres de Virasoro et de Neveu-Schwarz. Depuis ces decouvertes, d'autres techniques de construction des vecteurs singuliers ont ete developpees, dont celle de Bauer, Di Francesco, Itzykson et Zuber pour l'algebre de Virasoro qui reproduit directement l'expression explicite des vecteurs singuliers |Psi _{1,q}> et |Psi_{p,1}>. Ils ont utilise l'algebre des produits d'operateurs et la fusion entre representations irreductibles pour engendrer des relations de recurence produisant les vecteurs singuliers. Dans le dernier chapitre de cette these nous adaptons cet algorithme a la construction des vecteurs singuliers de l'algebre de Neveu-Schwarz.

Etude des phenomenes dynamiques ultrarapides et des caracteristiques impulsionnelles d'emission terahertz du supraconducteur YBCO

NASA Astrophysics Data System (ADS)

Savard, Stephane

Les premieres etudes d'antennes a base de supraconducteurs a haute temperature critique emettant une impulsion electromagnetique dont le contenu en frequence se situe dans le domaine terahertz remontent a 1996. Une antenne supraconductrice est formee d'un micro-pont d'une couche mince supraconductrice sur lequel un courant continu est applique. Un faisceau laser dans le visible est focalise sur le micro-pont et place le supraconducteur dans un etat hors-equilibre ou des paires sont brisees. Grace a la relaxation des quasiparticules en surplus et eventuellement de la reformation des paires supraconductrices, nous pouvons etudier la nature de la supraconductivite. L'analyse de la cinetique temporelle du champ electromagnetique emis par une telle antenne terahertz supraconductrice s'est averee utile pour decrire qualitativement les caracteristiques de celle-ci en fonction des parametres d'operation tels que le courant applique, la temperature et la puissance d'excitation. La comprehension de l'etat hors-equilibre est la cle pour comprendre le fonctionnement des antennes terahertz supraconductrices a haute temperature critique. Dans le but de comprendre ultimement cet etat hors-equilibre, nous avions besoin d'une methode et d'un modele pour extraire de facon plus systematique les proprietes intrinseques du materiau qui compose l'antenne terahertz a partir des caracteristiques d'emission de celle-ci. Nous avons developpe une procedure pour calibrer le spectrometre dans le domaine temporel en utilisant des antennes terahertz de GaAs bombarde aux protons H+ comme emetteur et detecteur. Une fois le montage calibre, nous y avons insere une antenne emettrice dipolaire de YBa 2Cu3O7-delta . Un modele avec des fonctions exponentielles de montee et de descente du signal est utilise pour lisser le spectre du champ electromagnetique de l'antenne de YBa 2Cu3O7-delta, ce qui nous permet d'extraire les proprietes intrinseques de ce dernier. Pour confirmer la validite du modele choisi, nous avons mesure les proprietes intrinseques du meme echantillon de YBa2Cu3O7- delta avec la technique pompe-visible et sonde-terahertz donnant, elle aussi, acces aux temps caracteristiques regissant l'evolution hors-equilibre de ce materiau. Dans le meilleur scenario, ces temps caracteristiques devraient correspondre a ceux evalues grace a la modelisation des antennes. Un bon controle des parametres de croissance des couches minces supraconductrices et de fabrication du dispositif nous a permis de realiser des antennes d'emission terahertz possedant d'excellentes caracteristiques en terme de largeur de bande d'emission (typiquement 3 THz) exploitables pour des applications de spectroscopie resolue dans le domaine temporel. Le modele developpe et retenu pour le lissage du spectre terahertz decrit bien les caracteristiques de l'antenne supraconductrice pour tous les parametres d'operation. Toutefois, le lien avec la technique pompe-sonde lors de la comparaison des proprietes intrinseques n'est pas direct malgre que les deux techniques montrent que le temps de relaxation des porteurs augmente pres de la temperature critique. Les donnees en pompe-sonde indiquent que la mesure du temps de relaxation depend de la frequence de la sonde, ce qui complique la correspondance des proprietes intrinseques entre les deux techniques. De meme, le temps de relaxation extrait a partir du spectre de l'antenne terahertz augmente en s'approchant de la temperature critique (T c) de YBa2Cu 3O7-delta. Le comportement en temperature du temps de relaxation correspond a une loi de puissance qui est fonction de l'inverse du gap supraconducteur avec un exposant 5 soit 1/Delta 5(T). Le travail presente dans cette these permet de mieux decrire les caracteristiques des antennes supraconductrices a haute temperature critique et de les relier aux proprietes intrinseques du materiau qui les compose. De plus, cette these presente les parametres a ajuster comme le courant applique, la puissance de la pompe, la temperature d'operation, etc, afin d'optimiser l'emission et les performances de ces antennes supraconductrices entre autres pour maximiser leur etendue en frequence dans une perspective d'application en spectroscopie terahertz. Cependant, plusieurs des resultats obtenus soulevent la difficulte de decrire l'etat hors-equilibre et la necessite de developper une theorie pour le supraconducteur YBa2 Cu3O7-delta

Nébulisation d’épinéphrine chez les jeunes enfants atteints de bronchiolite

PubMed Central

Sakulchit, Teeranai; Goldman, Ran D.

2016-01-01

Résumé Question Tous les ans, durant l’hiver, je vois des nourrissons qui présentent des symptômes pseudo-grippaux et des sibilances. Je pose souvent un diagnostic de bronchiolite en fonction du tableau clinique. Serait-il prudent d’envoyer ces nourrissons à l’urgence la plus proche pour recevoir un traitement par nébulisation d’épinéphrine? Réponse La nébulisation d’épinéphrine ne doit pas être administrée systématiquement aux nourrissons atteints de bronchiolite. C’est une option à envisager chez les patients qui manifestent des symptômes graves. S’il n’y a aucun signe d’amélioration après l’administration d’épinéphrine, les doses subséquentes sont déconseillées. Il est nécessaire de poursuivre les études sur l’épinéphrine associée à d’autres agents (p. ex. solution saline hypertonique, dexaméthasone par voie orale) pour en confirmer les bienfaits. PMID:27965346

La réfrigération des grandes machines supraconductrices

NASA Astrophysics Data System (ADS)

Gistau, Guy

1991-02-01

The large scale superconducting devices which are now in operation for deviation of heavy particles, acceleration of light particles or plasma confinement need very large powers of refrigeration. After a short survewing of the different functions of refrigerators and the special requirements for large units, the paper describes some existing or envisaged cooling systems which have an equivalent cooling power in the range of 5 kW at 4.5 K. Les grands appareils de physique utilisant les supraconducteurs demandent des puissances cryogéniques de plus en plus importantes. Après un examen des fonctions élémentaires assurées par un réfrigérateur liées au cahier des charges spécifique à chaque utilisation, les spécificités des grosses unités de réfrigération (fiabilité, efficacité, flexibilité, automatisme) sont mises en évidence. Les solutions proposées dans plusieurs grands projets nécessitant des puissances froides supérieures à 5 kW à 4,5 K sont discutées.

Reconstruction d’une Carbonisation du Pouce par Lambeau Chinois

PubMed Central

Khales, A.; Achbouk, J.A.; Moussaoui, A.; Belmir, R.; Tourabi, K.; Oufkir, A.; Ihrai, H.

2010-01-01

Summary La main en tant qu’organe majeur de la préhension peut être le siège de brûlures graves qui compromettent sa fonction. Bien qu’elle ne représente que 2% de la surface corporelle la brûlure de la main est grave et difficile à traiter, vu la vulnérabilité et la complexité de son appareil locomoteur. Nous rapportons dans ce travail le cas d’un patient victime d’une carbonisation de la main. Huit mois après le parage et la couverture par lambeau inguinal, le patient bénéficie d’une reconstruction du pouce par lambeau chinois associé à une greffe osseuse. Le résultat s’est avéré satisfaisant. Le lambeau chinois prouve par son apport vasculaire et par sa facilité technique qu’il est un moyen très intéressant dans la reconstruction du pouce - ou des doigts en général - surtout dans un contexte de brûlure. PMID:21991226

Le Laser A Argon Ionise : Applications Therapeutiques

NASA Astrophysics Data System (ADS)

Brunetaud, J. M.; Mosquet, L.; Mordon, S.; Rotteleur, G.

1984-03-01

Le laser a argon ionise est un laser a emission continue, reglee en general en multiraies de 487 a 544 nm. Le rayonnement de ce laser est bien absorbe par les tissus vivants, avec une action preferentielle au niveau des pigments rouges (hemoglobine, myoglobine) et noirs (melanine). Le laser a argon est princi-palement utilise en therapeutique pour ses effets thermiques : en fonction du choix des parametres (puissance optique, surface exposee, temps d'exposition) on peut obtenir une coagulation (temperature optimale au niveau des tissus 60° - 80°) ou une volatisation (temperature superieure a 100°). Si la zone volatilisee est tres etroite (inferieure a 0,5 mm) on obtient un effet de coupe. Par rapport aux deux autres lasers egalement utilises pour leurs effets thermiques (CO2 et Nd. YAG) l'argon a des effets intermediaires : la coagulation sera plus superficielle qu'avec le Nd. YAG et la volatisation plus profonde qu'avec le CO2. Lors de la coupe, la necrose sur les berges sera egalement plus importante qu'avec le CO2.

Effects of molecular and lattice structure on the thermal behaviours of some long chain length potassium(I) n-alkanoates

NASA Astrophysics Data System (ADS)

Nelson, Peter N.; Ellis, Henry A.; Taylor, Richard A.

2014-01-01

Lattice structures and thermal behaviours for some long chain potassium carboxylates (nc = 8-18, inclusive) are investigated using Fourier Transform Infrared spectroscopy, X-ray Powder Diffraction, Solid State spin decoupled 13C NMR spectroscopy, Differential Scanning Calorimetry and Thermogravimetry. The measurements show that the carboxyl groups are coordinated to potassium atoms via asymmetric chelating bidentate bonding, with extensive carboxyl intermolecular interactions to yield tetrahedral metal centers, irrespective of chain length. Furthermore, the hydrocarbon chains are crystallized in the fully extended all-trans configuration and are arranged as non-overlapping lamellar bilayer structures with closely packed methyl groups from opposite layers. Additionally, odd-even alternation, observed in density and methyl group chemical shift, is ascribed to the relative vertical distances between layers in the bilayer, that are not in the same plane. Therefore, for even chain homologues, where this distances is less than for odd chain adducts, more intimate packing is indicated. The phase sequences for all compounds show several reversible crystal-crystal transition associated with kinetically controlled gauche-trans isomerism of the polymethylene chains which undergo incomplete fusion when heated to the melt. The compounds degrade above 785 K to yield carbon dioxide, water, potassium oxide and an alkene.

Paul de Kruif's Microbe Hunters and an outraged Ronald Ross.

PubMed

Chernin, E

1988-01-01

Paul de Kruif's book, Microbe Hunters, published in New York in 1926, was a romanticized medical "history," written in a breathless style, that describes the lives and works of a dozen famous figures, ranging from Leeuwenhoek to Sir Ronald Ross. Ross, who received the Nobel Prize in 1902 for his discovery that certain mosquitoes transmit malaria, resented de Kruif's personal remarks and his version of the malaria story, especially concerning the disputes with Italian workers over priorities. In a little-known polemic "review" of Microbe Hunters, Ross castigated de Kruif for statements he considered libelous. While Ross could not sue for libel across the Atlantic, his threatened action for libel forced the publisher of the British edition of Microbe Hunters to delete the chapter about Ross and one about David Bruce, Ross's countryman. de Kruif's book, a best-seller in its day and influential among the young for a generation, now seems gauche and anachronistic. While Ross seems to have been justified in some of his complaints about Microbe Hunters, the bitter tone of his reactions all but confirms de Kruif's opinion of him. Ross died in 1932 with a permanent niche in medical history; de Kruif died in 1971 and is little remembered except, perhaps, for Microbe Hunters.

Choriorétinite extensive bilatérale révélant une infection par le virus de l'immunodéficience humaine (VIH)

PubMed Central

El Yamouni, Oubaida; Tzili, Nazih; El Hassan, Abdallah; Slassi, Nadia; El Khaoua, Mahfoud; Jebbar, Zakaria; Berraho, Amina

2014-01-01

Au cours de l'infection par le virus de l'immunodéficience humaine(VIH), Les atteintes oculaires sont polymorphes, pouvant compromettre le pronostic fonctionnel. Nous rapportons l'observation d'un patient présentant une choriorétinite infectieuse sévère révélant une infection par le VIH. Patient âgé de 35 ans avec antécédent de tuberculose pulmonaire en 2007, consulte pour BAV bilatérale progressive depuis 6 mois. Une acuité visuelle à compte les doigts au niveau de l'oeil droit et à mouvement des doigts au niveau de l'oeil gauche, avec présence de foyers choriorétiniens diffus visualisés au fond d'oeil et à l'angiographie. Les sérologies VIH, toxoplasmose et CMV sont positives. Le patient a été mis sous traitement anti-toxoplasmose (Sulfadiazine et pyriméthamine) et anti-CMV (Ganciclovir per os). L’évolution sous traitement a été marquée par une régression de la hyalite avec la persistance des foyers choriorétiniens évolutifs et une acuité visuelle réduite à perception lumineuse. PMID:25709723

Role of calcium in phosphoinositide metabolism and inhibition of norepinephrine transport into synaptic vesicles by amphetamine analogs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Knepper, S.M.

1985-01-01

Norepinephrine-(NE) and calcium ionophore A23187-stimulated phosphoinositide (PIn) metabolism in rat brain slices was studied under varying calcium conditions. Tissue was labelled with /sup 3/H-myo-inositol and /sup 3/H-inositol phosphates (IPn), products of PIn metabolism were measured. In the absence of media calcium the response to NE was decreased while that to A23187 was little affected A23187 can release calcium from intracellular stores. Basal and stimulated accumulation of /sup 3/H-IPn was reversibly antagonized with EGTA by addition of calcium. Using calcium buffers, approximately 10/sup -7/ M free calcium was required to support hydrolysis. Free intracellular calcium is maintained at approximately this level.more » Thus calcium is required for PIn hydrolysis but appears to play a permissive role, basal levels being sufficient to support metabolism. Conformationally-defined (rigid) and -restricted (semi-rigid) analogs of the most stable conformations of amphetamine, antiperiplanar (exo) and gauche (endo), were utilized to probe the conformational requirements of vesicular NE transport. Analogs tested were 2-aminotetralin (2AT), 3-methyltetrahydroisoquinoline, anti- and syn-9-aminobenzobicyclo(2.2.1)heptene, and endo and exo conformers of 2-aminobenzobicyclo(2.2.1)heptene and 2-aminobenzobicyclo(2.2.2)octene.« less

Crystal structure of allyl­ammonium hydrogen succinate at 100 K

PubMed Central

Dziuk, Błażej; Zarychta, Bartosz; Ejsmont, Krzysztof

2014-01-01

The asymmetric unit of the title compound, C2H8N+·C4H5O4 −, consists of two allyl­ammonium cations and two hydrogen succinate anions (Z′ = 2). One of the cations has a near-perfect syn-periplanar (cis) conformation with an N—C—C—C torsion angle of 0.4 (3)°, while the other is characterized by a gauche conformation and a torsion angle of 102.5 (3)°. Regarding the anions, three out of four carboxilic groups are twisted with respect to the central C–CH2–CH2–C group [dihedral angles = 24.4 (2), 31.2 (2) and 40.4 (2)°], the remaining one being instead almost coplanar, with a dihedral angle of 4.0 (2)°. In the crystal, there are two very short, near linear O—H⋯O hydrogen bonds between anions, with the H atoms shifted notably from the donor O towards the O⋯O midpoint. These O—H⋯O hydrogen bonds form helical chains along the [011] which are further linked to each other through N—H⋯O hydrogen bonds (involving all the available NH groups), forming layers lying parallel to (100). PMID:25309251

Molecular dynamics study of intermediate phase of long chain alkyl sulfonate/water systems.

PubMed

Poghosyan, Armen H; Arsenyan, Levon H; Shahinyan, Aram A

2013-01-08

Using atomic level simulation we aimed to investigate various intermediate phases of the long chain alkyl sulfonate/water system. Overall, about 800 ns parallel molecular dynamics simulation study was conducted for a surfactant/water system consisting of 128 sodium pentadecyl sulfonate and 2251 water molecules. The GROMACS software code with united atom force field was applied. Despite some differences, the analysis of main structural parameters is in agreement with X-ray experimental findings. The mechanism of self-assembly of SPDS molecules was also examined. At T = 323 K we obtained both tilted fully interdigitated and liquid crystalline-like disordered hydrocarbon chains; hence, the presence of either gel phase that coexists with a lamellar phase or metastable gel phase with fraction of gauche configuration can be assumed. Further increase of temperature revealed that the system underwent a transition to a lamellar phase, which was clearly identified by the presence of fully disordered hydrocarbon chains. The transition from gel-to-fluid phase was implemented by simulated annealing treatment, and the phase transition point at T = 335 K was identified. The surfactant force field in its presented set is surely enabled to fully demonstrate the mechanism of self-assembly and the behavior of phase transition making it possible to get important information around the phase transition point.

Physicochemical interactions among α-eleostearic acid-loaded liposomes applied to the development of drug delivery systems

NASA Astrophysics Data System (ADS)

Nogueira, Alessandro Oliveira de Moraes; de Sousa, Robson Simplício; Pereira, Luiza Silveira; Mallmann, Christian; da Silva Ferreira, Ailton; Clementin, Rosilene Maria; de Lima, Vânia Rodrigues

2018-02-01

In this study, α-eleostearic acid-loaded (α-ESA-loaded) dimyristoylphosphatidylcholine (DMPC) liposomes had their physicochemical properties characterized by horizontal attenuated total reflectance Fourier transform infrared (HATR-FTIR) spectroscopy, nuclear magnetic resonance (NMR) and differential scanning calorimetry (DSC). In vitro thiobarbituric acid reactive substance (TBARS) assays were performed to obtain preliminary information on the oxidative potential of the system. An α-ESA-promoted ordering effect in the lipid phosphate region was observed. It was associated with a rotation restriction due to an increase in the amount of lipid group hydrogen bonds. The fatty acid was responsible for the reduction in the degree of hydration of carbonyl groups located in the interfacial region of lipids. α-ESA disordered the DMPC methylene acyl chains by trans-gauche isomerization and increased its rotation rate. TBARS results showed pro-oxidant behavior on liposomes, induced by α-ESA. The discussion about the responses considered the degree of saturation of phosphatidylcholines and suggested that the α-ESA oxidative effects may be modulated by the liposome lipid composition. The versatility of liposomal carriers may be promising for the development of efficacious α-ESA-based drug delivery systems. Results described in this study contribute to the selection of adequate material to produce them.

Origin of the instability of octadecylamine Langmuir monolayer at low pH

DOE PAGES

Avazbaeva, Zaure; Sung, Woongmo; Lee, Jonggwan; ...

2015-11-30

In this paper, it has been reported that an octadecylamine (ODA) Langmuir monolayer becomes unstable at low pH values with no measurable surface pressure at around pH 3.5, suggesting significant dissolution of the ODA molecule into the subphase solution (Albrecht, Colloids Surf. A 2006, 284–285, 166–174). However, by lowering the pH further, ODA molecules reoccupy the surface, and a full monolayer is recovered at pH 2.5. Using surface sum-frequency spectroscopy and pressure–area isotherms, it is found that the recovered monolayer at very low pH has a larger area per molecule with many gauche defects in the ODA molecules as comparedmore » to that at high pH values. This structural change suggests that the reappearance of the monolayer is due to the adsorbed Cl– counterions to the protonated amine groups, leading to partial charge neutralization. This proposition is confirmed by intentionally adding monovalent salts (i.e., NaCl, NaBr, or NaI) to the subphase to recover the monolayer at pH 3.5, in which the detailed structure of the monolayer is confirmed by sum frequency spectra and the adsorbed anions by X-ray reflectivity.« less

Crystal structure of a new alpha-cyclodextrin hydrate form. Molecular geometry and packing features: disordered solvent contribution.

PubMed

Puliti, R; Mattia, C A; Paduano, L

1998-08-01

The crystallographic study of a new hydrated form of alpha-cyclodextrin (cyclohexaamylose) is reported. C36H60O30 . 11H2O; space group P2(1)2(1)2(1) with cell constants a = 13.839(3), b = 15.398(3), c = 24.209(7) A; final discrepancy index R = 0.057 for the 5182 observed reflections and 632 refined parameters. Besides four ordered water molecules placed outside alpha-cyclodextrins, the structure shows regions of severely disordered solvent mainly confined in the oligosaccharide cavities. The contribution of the observed disorder has been computed via Fourier inversions of the residual electron density and incorporated into the structure factors in further refinements of the ordered part. The alpha-cyclodextrin molecule assumes a relaxed round shape stabilised by a ring sequence of all the six possible O2 ... O3 intramolecular hydrogen bonds. The four ordered water molecules take part in an extensive network of hydrogen bonds (infinite chains and loops) without modifying the scheme of intramolecular H-bonds or the (-)gauche conformation of O-6-H hydroxyl groups. The structure shows a new molecular arrangement, for an "empty" hydrated alpha-cyclodextrin, like that "brick-type" observed for alpha-CD in the iodoanilide trihydrate complex crystallising in an isomorphous cell.

Zwitterionic 4-bromo-6-meth­oxy-2-{[tris­(hy­droxy­meth­yl)methyl]­iminiumyl­meth­yl}phenolate: crystal structure and Hirshfeld surface analysis

PubMed Central

Lee, See Mun; Lo, Kong Mun; Tan, Sang Loon; Tiekink, Edward R. T.

2016-01-01

In the solid state, the title compound, C12H16BrNO5 [systematic name: 4-bromo-2-((1E)-{[1,3-dihy­droxy-2-(hy­droxy­meth­yl)propan-2-yl]iminium­yl}meth­yl)-6-meth­oxy­benzen-1-olate], C12H16BrNO5, is found in the keto–amine tautomeric form, with an intra­molecular iminium-N—H⋯O(phenolate) hydrogen bond and an E conformation about the C=N bond. Both gauche (two) and anti relationships are found for the methyl­hydroxy groups. In the crystal, a supra­molecular layer in the bc plane is formed via hy­droxy-O—H⋯O(hy­droxy) and charge-assisted hy­droxy-O—H⋯O(phenolate) hydrogen-bonding inter­actions; various C—H⋯O inter­actions provide additional cohesion to the layers, which stack along the a axis with no directional inter­actions between them. A Hirshfeld surface analysis confirms the lack of specific inter­actions in the inter-layer region. PMID:27536419

Submillimeterwave Spectroscopy of Highly Astrophysical Interest Molecule: Hydroxyacetonitrile

NASA Astrophysics Data System (ADS)

Margules, L.; Motiyenko, R. A.; Guillemin, J.-C.

2013-06-01

Hydroxyacetonitrile is a simple derivative of methanol. This molecule has a strong astrophysical interest. In astrophysical environment, the formation of hydroxyacetonitrile (HOCH_2CN), has been shown to compete with aminomethanol (NH_2CH_2OH), a glycine precursor, through the Strecker synthesis, in addition its photochemistry leads to the formation of formylcyanide (CHOCN), ketenimine (CH_2CNH), formaldehyde (CH_2O), hydrogen cyanide (HCN), carbon monoxyde (CO). Its detection in the ISM will provide crucial hints in the formation process of complex organic molecules. The lack of data about this molecule, only studied up to 50 GHz, is mainly due to two reasons. First, this is not commercially available, the synthesis should be perform. Second, the most stable conformer is the gauche one. This exhibits large amplitude motion due to the two equivalent configurations possible. Due to tunneling effect, each level is split into 0^+ and 0^- substates. This makes the analysis of the spectra delicate. We will report here the very first results obtained. This work was supported by the CNES and the Action sur Projets de l'INSU, PCMI. Danger, G. et al.ApJ {756}, (2012) 11 Danger, G. et al.A&A {549}, (2012) A93 Cazzoli, G. et al.J. Chem. Soc., Faraday Trans. 2 {69}, (1973) 569

Effect of Varying the 1-4 Intramolecular Scaling Factor in Atomistic Simulations of Long-Chain N-alkanes with the OPLS-AA Model

DOE Office of Scientific and Technical Information (OSTI.GOV)

de Almeida, Valmor F; Ye, Xianggui; Cui, Shengting

2013-01-01

A comprehensive molecular dynamics simulation study of n-alkanes using the Optimized Potential for Liquid Simulation-All Atoms (OPLS-AA) force field at ambient condition has been performed. Our results indicate that while simulations with the OPLS-AA force field accurately predict the liquid state mass density for n-alkanes with carbon number equal or less than 10, for n-alkanes with carbon number equal or exceeding 12, the OPLS-AA force field with the standard scaling factor for the 1-4 intramolecular Van der Waals and electrostatic interaction gives rise to a quasi-crystalline structure. We found that accurate predictions of the liquid state properties are obtained bymore » successively reducing the aforementioned scaling factor for each increase of the carbon number beyond n-dodecane. To better un-derstand the effects of reducing the scaling factor, we analyzed the variation of the torsion potential pro-file with the scaling factor, and the corresponding impact on the gauche-trans conformer distribution, heat of vaporization, melting point, and self-diffusion coefficient for n-dodecane. This relatively simple procedure thus allows for more accurate predictions of the thermo-physical properties of longer n-alkanes.« less

Mercury coordination polymers with flexible ethane-1,2-diyl-bis-(pyridyl-3-carboxylate): Synthesis, structures, thermal and luminescent properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vallejos, Javier; Brito, Iván, E-mail: ivanbritob@yahoo.com; Cárdenas, Alejandro

2015-03-15

The reaction of the flexible ligand, ethane-1,2-diyl-bis-(pyridyl-3-carboxylate), (L) with HgI{sub 2} and HgBr{sub 2} salts under the same experimental conditions leads to the formation of two coordination polymers with different motifs: ([Hg(L)(Br{sub 2})]){sub n}(1) and ([Hg(L)(I{sub 2})]){sub n}(2). In both compounds, the ligand, (L) acts in a μ2-N:N′-bidentate fashion to link HgBr{sub 2} and HgI{sub 2} units to form a linear and helical chain motif, along [1 0 0] for (1) and [0 0 1] for (2). The ethylene moiety of (L) has gauche and trans conformation in compounds (1) and (2), respectively. The flexible conformation of L produces differencesmore » in the optical and crystal properties of the two compounds. - Graphical abstract: This work demonstrates how the HgX{sub 2} units are coordinates by bi-dentate ligand forming polymeric coordination complexes by self-assembly of both chemical units.- Highlights: • News 1-D d{sup 10} transition metal coordination polymers. • The photoluminescent properties have been measured. • The thermal properties have been measured.« less

Lower bounds on entropy for polymer chains on a square and a cubic lattice

NASA Astrophysics Data System (ADS)

Gujrati, P. D.

1982-07-01

Rigorous lower bounds on the entropy per particle as a function of the fraction g of the gauche bonds of a system of semiflexible polymer chains is obtained in the thermodynamic limit. Only square and cubic lattices are considered. For the case of a single chain having l monomers, the bound is obtained for all g⩽g=2/3. For the case of p>1 chains, each having l monomers, where l is a multiple of 4, the bound is obtained for all g⩽g'=13/90. In both cases, it is shown that the entropy is always nonzero for all 0< g

Formation des etoiles massives dans les galaxies spirales

NASA Astrophysics Data System (ADS)

Lelievre, Mario

Le but de cette thèse est de décrire la formation des étoiles massives dans les galaxies spirales appartenant à divers types morphologiques. L'imagerie Hα profonde combinée à une robuste méthode d'identification des régions HII ont permis de détecter et de mesurer les propriétés (position, taille, luminosité, taux de formation d'étoiles) de plusieurs régions HII situées dans le disque interne (R < R25) de dix galaxies mais aussi à leur périphérie (R ≥ R 25). De façon générale, la répartition des régions HII ne montre aucune évidence de structure morphologique à R < R25 (bras spiraux, anneau, barre) à moins de limiter l'analyse aux régions HII les plus grosses ou les plus lumineuses. La répartition des régions HII, de même que leur taille et leur luminosité, sont toutefois sujettes à de forts effets de sélection qui dépendent de la distance des galaxies et qu'il faut corriger en ramenant l'échantillon à une résolution spatiale commune. Les fonctions de luminosité montrent que les régions HII les plus brillantes ont tendance à se former dans la portion interne du disque. De plus, l'analyse des pentes révèle une forte corrélation linéaire par rapport au type morphologique. Aucun pic n'est observé dans les fonctions de luminosité à log L-37 qui révèlerait la transition entre les régions HII bornées par l'ionisation et par la densité. Une relation cubique est obtenue entre la taille et la luminosité des régions HII, cette relation variant toutefois de façon significative entre le disque interne et la périphérie d'une même galaxie. La densité et la dynamique du gaz et des étoiles pourraient influencer de façon significative la stabilité des nuages moléculaires face à l'effondrement gravitationnel. D'une part, l'étendue du disque de régions HII pour cinq galaxies de l'échantillon coïncide avec celle de l'hydrogène atomique. D'autre part, en analysant la stabilité des disques galactiques, on conclue qu'en incluant la densité des étoiles vieilles présentes, on arrive à mieux contraindre le rayon à partir duquel aucune formation d'étoiles ne devrait se produire dans les galaxies.

Etude thermo-hydraulique de l'ecoulement du moderateur dans le reacteur CANDU-6

NASA Astrophysics Data System (ADS)

Mehdi Zadeh, Foad

Etant donne la taille (6,0 m x 7,6 m) ainsi que le domaine multiplement connexe qui caracterisent la cuve des reacteurs CANDU-6 (380 canaux dans la cuve), la physique qui gouverne le comportement du fluide moderateur est encore mal connue de nos jours. L'echantillonnage de donnees dans un reacteur en fonction necessite d'apporter des changements a la configuration de la cuve du reacteur afin d'y inserer des sondes. De plus, la presence d'une zone intense de radiations empeche l'utilisation des capteurs courants d'echantillonnage. En consequence, l'ecoulement du moderateur doit necessairement etre etudie a l'aide d'un modele experimental ou d'un modele numerique. Pour ce qui est du modele experimental, la fabrication et la mise en fonction de telles installations coutent tres cher. De plus, les parametres de la mise a l'echelle du systeme pour fabriquer un modele experimental a l'echelle reduite sont en contradiction. En consequence, la modelisation numerique reste une alternative importante. Actuellement, l'industrie nucleaire utilise une approche numerique, dite de milieu poreux, qui approxime le domaine par un milieu continu ou le reseau des tubes est remplace par des resistances hydrauliques distribuees. Ce modele est capable de decrire les phenomenes macroscopiques de l'ecoulement, mais ne tient pas compte des effets locaux ayant un impact sur l'ecoulement global, tel que les distributions de temperatures et de vitesses a proximite des tubes ainsi que des instabilites hydrodynamiques. Dans le contexte de la surete nucleaire, on s'interesse aux effets locaux autour des tubes de calandre. En effet, des simulations faites par cette approche predisent que l'ecoulement peut prendre plusieurs configurations hydrodynamiques dont, pour certaines, l'ecoulement montre un comportement asymetrique au sein de la cuve. Ceci peut provoquer une ebullition du moderateur sur la paroi des canaux. Dans de telles conditions, le coefficient de reactivite peut varier de maniere importante, se traduisant par l'accroissement de la puissance du reacteur. Ceci peut avoir des consequences majeures pour la surete nucleaire. Une modelisation CFD (Computational Fluid Dynamics) detaillee tenant compte des effets locaux s'avere donc necessaire. Le but de ce travail de recherche est de modeliser le comportement complexe de l'ecoulement du moderateur au sein de la cuve d'un reacteur nucleaire CANDU-6, notamment a proximite des tubes de calandre. Ces simulations servent a identifier les configurations possibles de l'ecoulement dans la calandre. Cette etude consiste ainsi a formuler des bases theoriques a l'origine des instabilites macroscopiques du moderateur, c.-a-d. des mouvements asymetriques qui peuvent provoquer l'ebullition du moderateur. Le defi du projet est de determiner l'impact de ces configurations de l'ecoulement sur la reactivite du reacteur CANDU-6.

Modélisation de la dynamique de la chaîne peptidique des protéines en solution par RMN à travers les couplages dipolaires

NASA Astrophysics Data System (ADS)

Bouvignies, G.; Bernadó, P.; Blackledge, M.

2005-11-01

L'activité d'une protéine est liée non seulement à sa structure, mais également à sa dynamique, et il est important de connaître la nature de ses mouvements pour comprendre sa fonction biologique. La résonance magnétique nucléaire est particulièrement utile pour étudier la dynamique d'une molécule en solution sur une gamme de temps de corrélation très large. En particulière, la relaxation des spins 15N ou 13C donne accès aux mouvements moléculaires avec les temps caractéristiques entre les dizaines de picosecondes et le temps de corrélation rotationelle de la molécule (autour de 10ns pour une protéine monomérique de 20 kD à 300 K). Les vitesses de relaxation dépendent de la flexibilité de chaque site, et peuvent être caractérisé en termes d'amplitude et de temps caractéristique locale. La précision de ces paramètres et sa compréhension en termes de fonction exigent que la réorientation globale de la molécule soit correctement prise en compte. Ces méthodes expérimentales, qui seront présentées ici brièvement, font maintenant partie de la panoplie d'expériences appliquées dans l'étude de la relation structure-dynamique d'une protéine et ses partenaires. Néanmoins les mouvements plus lents, entre la nano et la milliseconde, sont plus difficiles à étudier, et il y a très peu d'information disponible sur la nature de la dynamique de la chaîne peptidique dans cette gamme de temps par RMN. Très récemment de nouvelles méthodologies ont été proposées, basées sur l'alignement préférentiel d'une protéine par rapport au champ magnétique, induit par dissolution de la molécule dans un cristal liquide très dilué. Dans ces conditions les changements conformationels sur des temps caractéristique plus lents (jusqu'au millisecondes) peuvent être étudiés. Nous présenterons cette technique, et quelques résultats, comparant la dynamique rapide (ps-ns), et plus lente le long de la chaîne peptidique de quatre protéines.

Profil épidémiologique et clinique de la tuberculose dans la zone de santé de Lubumbashi (RD Congo)

PubMed Central

Ngama, Christian Kakisingi; Muteya, Michel Manika; Lukusha, Yves Isango Idi; Kapend, Serge Matanda; Tshamba, Henri Mundongo; Makinko, Paul Ilunga; Mulumba, Claude Mwamba; Kalala, Liévin Kapend a

2014-01-01

Introduction L'objectif de notre travail était de déterminer la distribution sociodémographique des patients tuberculeux, les types de tuberculose en fonction de la localisation de la maladie et déterminer l'issue thérapeutique des patients en fonction de différentes localisations. Méthodes C'est une étude descriptive transversale des patients diagnostiqués et traités pour tuberculose du 1er Janvier 2010 au 30 Juin 2011 dans la zone de santé de Lubumbashi. Une de 11 zones de santé du District de Lubumbashi dans la province du Katanga(RD Congo). Ont été inclus tous les patients tuberculeux de nationalité congolaise consultés dans la zone de santé pendant la période d’étude. L’âge, le sexe, la commune de résidence, le tableau clinique à la première consultation et les résultats des examens de laboratoire des crachats par la coloration Ziehl-Neelsen ont été les paramètres d'analyse. Résultats Nous avons enregistré 708 patients tuberculeux soit une prévalence de 0.5%. Le sexe masculin représentait 58.78% contre 41.25% de sexe féminin avec un sexe ratio de 1.42 en faveur du sexe masculin. La moyenne d’âge était de 33±;15 ans. La majorité des patients soit 54.79 appartiennent à la tranche d’âge entre 21 et 40 ans. La tuberculose extra pulmonaire a représenté 51.8% contre 50.2% de tuberculose pulmonaire dont 31.9% à bacilloscopie positive. Le décès a intéressé les patients bacillifères puis qu'il y a 5 fois plus de décès liés à une tuberculose pulmonaire à microscopie positive qu'aux autres formes de tuberculose (OR (IC 95%): 5.27 (2.92-9.59, p = 0.00). La majorité des patients résidaient les communes Lubumbashi (41.7%) et Kampemba (23.2%). Conclusion La tuberculose extrapulmonaire (pleurale) a été plus rencontrée que la tuberculose pulmonaire et c'est cette dernière forme de tuberculose qui a entrainé beaucoup plus de décès. Ce qui nécessite une amélioration du système de santé de prise en charge des tuberculeux dans les démarches diagnostique, le suivi des patients bacilliformes et encourager l'adhérence au traitement. PMID:25018820

Étude par RMN à l'état solide de catalyseurs oxydes du type Mo-P-Al

NASA Astrophysics Data System (ADS)

Quartararo, J.; Rigole, M.; Guelton, M.; Amoureux, J. P.; Grimblot, J.

1999-10-01

Solid state 27Al NMR and especially 27Al MQMAS is used to characterize the oxide Mo-P-Al hydrotreating catalysts. This application shows that NMR is an efficient method to determine the local structure of the elements in the amorphous catalysts. So, this permits to conclude that the association of the Mo and the P leads to the formation of aluminium phosphates and that differences in the structure depend on the method of preparation. La RMN du solide et notamment la méthode “MQMAS" de 27Al est utilisée pour caractériser en détail les catalyseurs d'hydrotraitement du type Mo-P-Al sous forme oxyde. Cette application montre que la RMN est un outil efficace pour déterminer la structure locale des éléments introduits dans les catalyseurs de caractère amorphe. Ainsi, elle permet d'établir que le Mo associé au P induit la formation de phosphates d'aluminium. Des différences de structure en fonction de la méthode de préparation sont également observées.

Evolution de films de cuivre sur un substrat de cordiérite au cours de traitements thermiques

NASA Astrophysics Data System (ADS)

Guille, Jean-Louis; Gondolf, Marc

1993-04-01

Copper films were applied on low sintering temperature cordierite substrates either by sputtering or screen printing. Their behaviour during thermal treatments was studied as a function of various parameters : deposition technique, thickness, firing atmosphere, physical state of the substrate (green or sintered). Films were most often broken during the treatment. In the case of screen printed films the effects of an oxydation-reduction cycle of copper are pointed out. Des films de cuivre ont été déposés sur un substrat de cordiérite à basse température de frittage par deux techniques, pulvérisation cathodique et sérigraphie. On étudie leur comportement au cours de traitements thermiques en fonction de différents paramètres : technique de déposition, épaisseur, atmosphère de traitement, état physique du substrat (cru ou fritté). On constate le plus souvent une fragmentation du film. Dans le cas des films sérigraphiés on met en évidence les effets dus à l'oxydation et à la réduction du cuivre.

[Evaluation of soy bean proteins obtained by pressure].

PubMed

Bau, H M; Poullain, B; Debry, G

1978-01-01

Besides the processes of extrusion and protein fiber spinning, analogous utilization research with a range of protein sources is continuing at an accelerated pace. However, the pressure forming process, an attractive process for producing protein foods, has not received the attention as it merits. The fabrication techniques contribute the advantages of nutritional value, economic and simplicity in manufacture; it can be extend to utilize in the development of useful textured vegetable protein foods. Here, we present a pressure forming process for producing protein foods with soybean grains. In this paper, we evaluated the composition, and the yield of the products obtained by this process; the trypsin inhibitor and enzymatic proteolyse of the products were also studied. The product obtained contents soluble and insoluble proteins of soybean, 45 p. 100 of protein (N x 6,25), 20-25 p. 100 of carbohydrates of which the fibers are included; moreover it contents 6-7 p. 100 of ash and 20-22 p. 100 of fat. It does not content any starch, the oligosaccharides and antinutritional factors were almost eliminated. This product presents in acceptable textural form resembling traditional animal protein foodstuffs; its fonctional and nutritional properties can meet different utilizations in foodstuffs such as dietetic products and protein complements.

43Ca NMR in solid state

NASA Astrophysics Data System (ADS)

Bellot, P.-V.; Trokiner, A.; Zhdanov, Yu.; Yakubovskii, A.

1998-02-01

In this paper we show that 43Ca is a suitable NMR probe to study the properties of high-Tc superconducting oxides. In the normal state, we report the temperature and doping dependencies of the spin susceptibility measured by 43Ca NMR. In the superconducting state and more exactly in the mixed state, by analysing 43Ca NMR linewidth, we have studied the magnetic induction distribution due to the presence of vortices and deduced λ, the penetration depth. Dans cet article, on montre que l'isotope 43 du calcium est une bonne sonde RMN pour l'étude des propriétés des oxydes supraconducteurs à haute température. Dans l'état normal, par la détermination du déplacement de la raie, en fonction de la température, on accède à la variation thermique de la susceptibilité de spin. Dans l'état supraconducteur et plus particulièrement dans l'état mixte, la largeur de raie RMN permet d'étudier la distribution d'induction magnétique due à la présence des vortex et de déterminer λ, la longueur de pénétration.

Etude expérimentale des écoulements darcéens à travers un lit de fibres rigides empilées aléatoirement: influence de la porosité

NASA Astrophysics Data System (ADS)

Rahli, O.; Tadrist, L.; Miscevic, M.; Santini, R.

1995-11-01

Experimental studies have been carried out on fluid flow through porous media made up of randomly packed monodisperse fibers. The fibers of fixed diameter have an aspect ratio (L/d) varying between 4 and 70 given porosities of the porous media varying between 0.35 and 0.90. The relationships between friction losses and superficial velocity have been systematically determined for each porous medium. A detailed analysis is carried out for low fluid velocities. The influence of flow direction on pressure drop is studied along two perpendicular directions: it is found that fibrous media behave globally in isotropic manner. The permeability and the Kozeny Carman parameter k_k are deduced from experimental results. The variations of the permeability increase exponentially with the porosity. The Kozeny Carman parameter k_k is a decreasing function of the porosity ɛ(L/d) and tends asymptotically to a value close to that deduced from a modified Ergun relation. The important decrease, observed for small aspect ratios, is certainly an effect of the cut sections of fibers. This effect becomes negligible for larger aspect ratios. The results in terms of permeability and of Kozeny Carman parameter k_k are systematically compared to those deduced from various theoretical models. Generally, these models consider cylinders arranged in simple network, the flow being either parallel or perpendicular to the axis of cylinders. The variation laws of the parameter k_k, deduced from different models, present important discrepancies with our experimental results. The theoretical models, established for regular arrays of fibers do not correctly describe the behavior of randomly packed fibers. Des études expérimentales de l'écoulement d'un fluide à travers un milieu poreux constitué de fibres monodisperses empilées aléatoirement sont réalisées. Les milieux fibreux étudiés ont des porosités variant de 0,35 à 0,90. Ces porosités sont obtenues à l'aide de fibres dont le rapport d'aspect L/d varie de 4 à 70. Les lois de perte de charge en fonction de la vitesse du fluide sont déterminées systématiquement pour chaque milieu poreux. Une analyse détaillée est effectuée pour les faibles vitesses d'écoulement. L'influence de la direction de l'écoulement sur les lois de perte de charge est étudiée. Celles-ci sont établies suivant deux directions perpendiculaires. Les résultats obtenus mettent en évidence un comportement du milieu fibreux globalement isotrope vis à vis de l'écoulement du fluide. La perméabilité et le paramètre de Kozeny Carman k_k sont déduits des résultats expérimentaux. Les variations de la perméabilité en fonction de la porosité suivent une loi de type exponentiel. Le paramètre de Kozeny Carman k_k décroît en fonction de la porosité ɛ(L/d) et tend asymptotiquement vers une valeur proche de celle déduite de la relation d'Ergun modifiée. La décroissance importante, observée pour les petits rapports d'aspect, est sans doute due aux effets induits par les surfaces de base des fibres. Ces effets deviennent négligeables pour les grands rapports d'aspect. Les résultats en terme de perméabilité et de paramètre de Kozeny Carman sont comparés systématiquement avec les modèles proposés dans la littérature. Généralement, ces modèles supposent des cylindres de grande longueur, disposés en réseaux simples. L'écoulement est soit parallèle, soit perpendiculaire à l'axe des cylindres. Les lois de variation du paramètre k_k, déduites des différents modèles, présentent des écarts importants avec les résultats expérimentaux. Ces résultats semblent montrer qu'une disposition des fibres en réseaux simples ne permet pas une description convenable des écoulements à travers les empilements aléatoires de fibres.

Tératome immature de l’ovaire: à propos d’un cas

PubMed Central

Bouzoubaa, Wail; Jayi, Sofia; Alaoui, Fatima Zohra Fdili; Chaara, Hikmat; Melhouf, Moulay Abdelilah

2017-01-01

Les tératomes ovariens sont des tumeurs issues des cellules germinales pluripotentes, on décrit 3 types de tératomes: tératome mature, immature et monodermique. Le tératome immature constitue moins de 1% des cancers ovariens, et touche préférentiellement les sujets jeunes. Nous rapportons le cas d'une patiente de 25 ans, admise pour prise en charge d'une masse abdomino-pelvienne pour laquelle elle a bénéficiée d'une échographie et d'un scanner pelvien suivie d'un traitement conservateur a base d'une annexectomie gauche, avec multiples biopsies, dont le résultat anatomo-pathologique était en faveur d'un tératome ovarien immature. Par la suite le traitement a été complété par une hystérectomie avec curage lombo-aortique et omentectomie. Nous insistons à travers cette observation et sous la lumière d'une revue de la littérature sur les terrains particuliers prédisposant à ce type de tumeur rare et grave et sur les différents critères radiologiques orientant vers ce type histologique rare des tumeurs ovariennes, afin d'améliorer le pronostic et la prise en charge de cette pathologie qui reste multidisciplinaires. PMID:29187932

Charge transport with single molecules--an electrochemical approach.

PubMed

Li, Chen; Mishchenko, Artem; Pobelov, Ilya; Wandlowski, Thomas

2010-01-01

After an introduction and brief review of charge transport in nanoscale molecular systems we report on experimental studies in gold / (single) molecule / gold junctions at solid / liquid interfaces employing a scanning tunneling microscopy (STM)-based 'break junction' technique. We demonstrate attempts in developing basic relationships between molecular structure, conductance properties and nanoscale electrochemical concepts based on four case studies from our own work. In experiments with alpha, omega-alkanedithiol and biphenyldithiol molecular junctions we address the role of sulfur-gold couplings and molecular conformation, such as gauche defects in the alkyl chains and the torsion angle between two phenyl rings. Combination with quantum chemistry calculations enabled a detailed molecular-level understanding of the electronic structure and transport characteristics of both systems. Employing the concept of 'electrolyte gating' with redox-active molecules, such as thiol-terminated derivatives of viologens (HS-6V6-SH or (HS-6V6)) we demonstrate the construction of symmetric and asymmetric active molecular junctions with transistor- or diode-like behavior upon polarization in an electrochemical environment. The experimental data could be represented quantitatively by the Kutznetsov/Ulstrup model assuming a two-step electron transfer with partial vibration relaxation. Finally, we show that surface-immobilized gold nanoparticles with a diameter of (2.4 +/- 0.5) nm exhibit features of locally addressable multi-state electronic switching upon electrolyte gating, which appears to be reminiscent of a sequential charging through several 'oxidation/reduction states'.

Expanding the peptide beta-turn in alphagamma hybrid sequences: 12 atom hydrogen bonded helical and hairpin turns.

PubMed

Chatterjee, Sunanda; Vasudev, Prema G; Raghothama, Srinivasarao; Ramakrishnan, Chandrasekharan; Shamala, Narayanaswamy; Balaram, Padmanabhan

2009-04-29

Hybrid peptide segments containing contiguous alpha and gamma amino acid residues can form C(12) hydrogen bonded turns which may be considered as backbone expanded analogues of C(10) (beta-turns) found in alphaalpha segments. Exploration of the regular hydrogen bonded conformations accessible for hybrid alphagamma sequences is facilitated by the use of a stereochemically constrained gamma amino acid residue gabapentin (1-aminomethylcyclohexaneacetic acid, Gpn), in which the two torsion angles about C(gamma)-C(beta) (theta(1)) and C(beta)-C(alpha) (theta(2)) are predominantly restricted to gauche conformations. The crystal structures of the octapeptides Boc-Gpn-Aib-Gpn-Aib-Gpn-Aib-Gpn-Aib-OMe (1) and Boc-Leu-Phe-Val-Aib-Gpn-Leu-Phe-Val-OMe (2) reveal two distinct conformations for the Aib-Gpn segment. Peptide 1 forms a continuous helix over the Aib(2)-Aib(6) segment, while the peptide 2 forms a beta-hairpin structure stabilized by four cross-strand hydrogen bonds with the Aib-Gpn segment forming a nonhelical C(12) turn. The robustness of the helix in peptide 1 in solution is demonstrated by NMR methods. Peptide 2 is conformationally fragile in solution with evidence of beta-hairpin conformations being obtained in methanol. Theoretical calculations permit delineation of the various C(12) hydrogen bonded structures which are energetically feasible in alphagamma and gammaalpha sequences.

Revisiting imidazolium based ionic liquids: Effect of the conformation bias of the [NTf2] anion studied by molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Neumann, Jan; Golub, Benjamin; Odebrecht, Lisa-Marie; Ludwig, Ralf; Paschek, Dietmar

2018-05-01

We study ionic liquids composed of 1-alkyl-3-methylimidazolium cations and bis(trifluoromethyl-sulfonyl)imide anions ([CnMIm][NTf2]) with varying chain-length n = 2, 4, 6, 8 by using molecular dynamics simulations. We show that a reparametrization of the dihedral potentials as well as charges of the [NTf2] anion leads to an improvement of the force field model introduced by Köddermann, Paschek, and Ludwig [ChemPhysChem 8, 2464 (2007)] (KPL-force field). A crucial advantage of the new parameter set is that the minimum energy conformations of the anion (trans and gauche), as deduced from ab initio calculations and Raman experiments, are now both well represented by our model. In addition, the results for [CnMIm][NTf2] show that this modification leads to an even better agreement between experiment and molecular dynamics simulation as demonstrated for densities, diffusion coefficients, vaporization enthalpies, reorientational correlation times, and viscosities. Even though we focused on a better representation of the anion conformation, also the alkyl chain-length dependence of the cation behaves closer to the experiment. We strongly encourage to use the new NGOLP (Neumann, Golub, Odebrecht, Ludwig, Paschek) force field for the [NTf2] anion instead of the earlier KPL parameter set for computer simulations aiming to describe the thermodynamics, dynamics, and also structure of imidazolium-based ionic liquids.

Décision d'amputation dans la prise en charge initiale d'une luxation ouverte grave de la cheville à propos d'un cas observé à l'Hôpital Laquintinie de Douala suite à un accident par moto-taxi

PubMed Central

Tsatedem, Faustin Atemkeng; Tsiagadigui, Jean Gustave; Ndando, Richard Polle; Arabo, Mohamadou Saidou; Bayiha, Alphonse; Kenfack, Bruno

2012-01-01

La décision d'amputation pour traumatisme grave de membre n'est pas toujours facile à prendre. Les auteurs rapportent le cas d'un traumatisme ouvert de la cheville gauche avec luxation tibiotalienne complète, référé pour amputation. Il s'agit d'une passagère d'une moto-taxi percutée par une voiture. A l'admission, le pouls tibial postérieur était présent et le score dit MESS (Mangled Extremity Severity Score) côté à 5, ce qui a permis et d'éviter l'amputation. Après débridement et réduction, une broche transplantaire a permis d'immobiliser la cheville et de faire les pansements. L'amputation a été évitée. La cicatrisation dirigée de la peau a été suivie par la kinésithérapie. La mobilité de la cheville autorise une marche avec cannes au quatrième mois post-opératoire. Les auteurs recommandent l'utilisation du MESS dans la décision d'amputation après traumatisme grave de membre. PMID:23396997

The effect of furazolidone on the physico-chemical properties of dimyristoylphosphatidylcholine bilayers: Relevance to anti-leishmanial therapy

NASA Astrophysics Data System (ADS)

Martins, Victor Hugo Giendruczak; Rodrigues, Marisa Raquel; Mascarenhas, Layoan Dantas; de Azambuja, Carla Roberta Lopes; Londoño, Julian Londoño; de Lima, Vânia Rodrigues

2014-02-01

In this study, the influence of furazolidone, an anti-leishmanial drug, on dimyristoylphosphatidylcholine (DMPC) liposome hydration degree, mobility and thermodynamics was investigated by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR) and differential scanning calorimetry (DSC). FTIR results showed that furazolidone was responsible for an increase in the hydrogen bound number and mobility of the lipid phosphate group. Furazolidone also affected the lipid choline group by increasing its motional freedom, as shown by FTIR and 1H NMR spin-lattice relaxation time measurements. At the DMPC interfacial region, FTIR results showed a drug-induced reduction of the carbonyl hydration and order degrees. Very weak interaction among furazolidone and the hydrophobic lipid chains was also observed. However, no furazolidone-induced changes on thermodynamical parameters, such as phase transition temperature (Tm) and enthalpy variation (ΔH), were detected by the DSC technique. Thus, furazolidone seems to interact preferentially with lipid polar and interfacial regions, enhancing the freedom for gauche-trans isomerization of the first methylene groups of DMPC acyl chains. Responses described in this paper may explain the improved activity of furazolidone-encapsulated liposomes by comparison with the effect of the free drug, described in literature. The findings can also improve further strategies for the potential therapeutic application of liposomal furazolidone as a drug delivery system and minimize the risk of drug resistance and collateral effects related to high toxicity.

Organofluorine chemistry: synthesis and conformation of vicinal fluoromethylene motifs.

PubMed

O'Hagan, David

2012-04-20

The C-F bond is the most polar bond in organic chemistry, and thus the bond has a relatively large dipole moment with a significant -ve charge density on the fluorine atom and correspondingly a +ve charge density on carbon. The electrostatic nature of the bond renders it the strongest one in organic chemistry. However, the fluorine atom itself is nonpolarizable, and thus, despite the charge localization on fluorine, it is a poor hydrogen-bonding acceptor. These properties of the C-F bond make it attractive in the design of nonviscous but polar organic compounds, with a polarity limited to influencing the intramolecular nature of the molecule and less so intermolecular interactions with the immediate environment. In this Perspective, the synthesis of aliphatic chains carrying multivicinal fluoromethylene motifs is described. It emerges that the dipoles of adjacent C-F bonds orientate relative to each other, and thus, individual diastereoisomers display different backbone carbon chain conformations. These conformational preferences recognize the influence of the well-known gauche effect associated with 1,2-difluoroethane but extend to considering 1,3-fluorine-fluorine dipolar repulsions. The synthesis of carbon chains carrying two, three, four, five, and six vicinal fluoromethylene motifs is described, with an emphasis on our own research contributions. These motifs obey almost predictable conformational behavior, and they emerge as candidates for inclusion in the design of performance organic molecules. © 2012 American Chemical Society

Crystal structure, conformation, vibration and optical band gap analysis of bis[ rac-propranolol nitrate

NASA Astrophysics Data System (ADS)

Franklin, S.; Balasubramanian, T.; Nehru, K.; Kim, Youngmee

2009-06-01

The crystal structure of the title rac-propranolol salt, CHNO2+·NO3-, consists of two protonated propranolol residues and nitrate anions. Three virtually flat fragments, characteristics of most of the β-adrenolytics with oxy-methylene bridge are present in both the cations (A and B). The plane of the propranolol chain is twisted with respect to the plane of the aromatic ring in both the cations. Present study investigates the conformation and hydrogen bonding interactions, which play an important role in biological functions. A gauche conformation is observed for the oxo-methylene bridge of cation A, while a trans conformation prevails in cation B. These conformations are found in majority of β-blockers. Presence of twenty intermolecular hydrogen bonds mediating through the anions stabilizes the crystal packing. Vibration analysis and earlier theoretical predictions complement the structure analysed. From the UV-Vis spectral analysis for the crystal, the optical band gap is found to be Eg = 5.12 eV, where as the chloride salt has Eg = 3.81 eV. The increase in the band gap may be attributed by the increase in the number of intermolecular hydrogen bonds. Good optical transmittance in the entire visible region and the direct band gap property suggest that it is a suitable candidate for optical applications in UV region.

Solid-state transformations in the β-form of chlorpropamide on cooling to 100 K.

PubMed

Drebushchak, Tatiana N; Drebushchak, Valeri A; Boldyreva, Elena V

2011-04-01

A single-crystal X-ray diffraction study of the effect of cooling down to 100 K on the β-form of chlorpropamide, 4-chloro-N-(propylaminocarbonyl)benzenesulfonamide, has revealed reversible phase transitions at ∼257 K and between 150 and 125 K: β (Pbcn, Z' = 1) ⇔ β(II) (P2/c, Z' = 2) ⇔ β(III) (P2/n, a' = 2a, Z' = 4); the sequence corresponds to cooling. Despite changes in the space group and number of symmetry-independent molecules, the volume per molecule changes continuously in the temperature range 100-300 K. The phase transition at ∼257 K is accompanied by non-merohedral twinning, which is preserved on further cooling and through the second phase transition, but the original single crystal does not crack. DSC (differential scanning calorimetry) and X-ray powder diffraction investigations confirm the phase transitions. Twinning disappears on heating as the reverse transformations take place. The second phase transition is related to a change in conformation of the alkyl tail from trans to gauche in 1/4 of the molecules, regularly distributed in the space. Possible reasons for the increase in Z' upon cooling are discussed in comparison to other reported examples of processes (crystallization, phase transitions) in which organic crystals with Z' > 1 have been formed. Implications for pharmaceutical applications are discussed. © 2011 International Union of Crystallography

The first 3':5'-cyclic nucleotide-amino acid complex: L-His-cIMP.

PubMed

Slepokura, Katarzyna

2012-08-01

In the crystal structure of the L-His-cIMP complex, i.e. L-histidinium inosine 3':5'-cyclic phosphate [systematic name: 5-(2-amino-2-carboxyethyl)-1H-imidazol-3-ium 7-hydroxy-2-oxo-6-(6-oxo-6,9-dihydro-1H-purin-9-yl)-4a,6,7,7a-tetrahydro-4H-1,3,5,2λ(5)-furo[3,2-d][1,3,2λ(5)]dioxaphosphinin-2-olate], C(6)H(10)N(3)O(2)(+)·C(10)H(10)N(4)O(7)P(-), the Hoogsteen edge of the hypoxanthine (Hyp) base of cIMP and the Hyp face are engaged in specific amino acid-nucleotide (His···cIMP) recognition, i.e. by abutting edge-to-edge and by π-π stacking, respectively. The Watson-Crick edge of Hyp and the cIMP phosphate group play a role in nonspecific His···cIMP contacts. The interactions between the cIMP anions (anti/C3'-endo/trans-gauche/chair conformers) are realized mainly between riboses and phosphate groups. The results for this L-His-cIMP complex, compared with those for the previously reported solvated L-His-IMP crystal structure, indicate a different nature of amino acid-nucleotide recognition and interactions upon the 3':5'-cyclization of the nucleotide phosphate group.

Otite externe maligne à Candida Albicans

PubMed Central

Elayoubi, Fahd; Lachkar, Azeddine; Aabach, Ahmed; Chouai, Mohamed; Ghailan, Mohamed Rachid

2016-01-01

L’otite externe maligne est une ostéomyélite de la base du crane. Le Pseudomonas aeruginosa est le germe le plus incriminé. Cependant l’origine fongique n’est pas rare. Patiente âgée de 80 ans avait présenté une otalgie gauche persistante depuis deux mois malgré un traitement bien conduit. L’examen otologique mettait en évidence des signes inflammatoires au niveau du pavillon, une sténose du conduit avec des granulomes, et otorrhée d’allure purulente. Le scanner montrait un comblement otomastoïdien, un processus inflammatoire extensif des tissus pré et rétro-auriculaire et une lyse du tympanal. Vu l’absence d’amélioration un examen mycologique a été réalisé et qui a révélé la présence de Candida Albicans. Les cas d’otite externe maligne à Candida Albicans sont rarement rapportés. L’origine fongique doit être suspecté devant la négativité des prélèvements bactériologiques et la non amélioration malgré un traitement antibiotique bien conduit, et confirmée par des prélèvements mycologiques parfois multiples. L’otite externe maligne à Candida Albicans est une infection rare potentiellement mortelle. PMID:28154677

Crystal structure of bis­[trans-(ethane-1,2-di­amine-κ2 N,N′)bis­(thio­cyanato-κN)chromium(III)] tetra­chlorido­zincate from synchrotron data

PubMed Central

Moon, Dohyun; Choi, Jong-Ha

2015-01-01

The structure of the title compound, [Cr(NCS)2(C2H8N2)2]2[ZnCl4], has been determined from synchrotron data. In the asymmetric unit, there are four independent halves of the CrIII complex cations, each of which lies on an inversion centre, and one tetra­chlorido­zincate anion in a general position. The CrIII atoms are coordinated by the four N atoms of two ethane-1,2-di­amine (en) ligands in the equatorial plane and two N-bound NCS− anions in a trans arrangement, displaying a slightly distorted octa­hedral geometry with crystallographic inversion symmetry. The Cr—N(en) and Cr—N(NCS) bond lengths range from 2.0653 (10) to 2.0837 (10) Å and from 1.9811 (10) to 1.9890 (10) Å, respectively. The five-membered metalla-rings are in stable gauche conformations. The [ZnCl4]2− anion has a distorted tetra­hedral geometry. The crystal structure is stabilized by inter­molecular hydrogen bonds involving the en NH2 or CH2 groups as donors and chloride ligands of the anion and S atoms of NCS− ligands as acceptors. PMID:25705463

From Intermolecular Interactions to Texture in Polycrystalline Surfaces of 1,ω-alkanediols (ω = 10-13).

PubMed

Luis-Raya, Gilgamesh; Ramírez-Cardona, Màrius; Luna-Bárcenas, Gabriel; Hernández-Landaverde, Martín A; Jiménez-Nieto, Adair; García-Rivas, Jose Luis; España-Sánchez, Beatriz Liliana; Sanchez, Isaac C

2017-06-08

Differences on herringbone molecular arrangement in two forms of long-chain 1,ω-alkanediols (C n H 2 n +2 O₂ with n = 10, 11, 12, 13) are explained from the analysis of O-H···O hydrogen-bond sequences in infinite chains and the role of a C-H···O intramolecular hydrogen-bond in stabilization of a gauche defect, as well as the inter-grooving effectiveness on molecular packing. GIXD (Glancing Incidence X-ray Diffraction) experiments were conducted on polycrystalline monophasic samples. Diffracted intensities were treated with the multi-axial March-Dollase method to correlate energetic and geometrical features of molecular interactions with the crystalline morphology and textural pattern of samples. The monoclinic (P 2 ₁/ c , Z = 2) crystals of the even-numbered members ( n = 10, 12; DEDOL and DODOL, respectively) are diametrical prisms with combined form {104}/{-104}/{001} and present a two-fold platelet-like preferred orientation, whereas orthorhombic (P 2 ₁ 2 ₁ 2 ₁, Z = 4) odd-numbered members ( n = 11, 13; UNDOL and TRDOL, respectively) present a dominant needle-like orientation on direction [101] (fiber texture). We show that crystalline structures of medium complexity and their microstructures can be determined from rapid GIXD experiments from standard radiation, combined with molecular replacement procedure using crystal structures of compounds with higher chain lengths as reference data.

Synthesis and characterization of two new zinc(II) coordination polymers with bidentate flexible ligands: Formation of a 2D structure with (44.62)-sql topology

NASA Astrophysics Data System (ADS)

Lalegani, Arash; Khaledi Sardashti, Mohammad; Gajda, Roman; Woźniak, Krzysztof

2017-12-01

Zinc(II) coordination polymers [Zn(bip)2(NCS)2]n (1) and [Zn(μ-bbd)(N3)2]n (2) were synthesized by using the neutral flexible bidentate N-donor ligands 1,4-bis(3,5-dimethylpyrazolyl)butane (bbd) and 1,3-bis(imidazolyl)propane (bip), mono-anionic NCS- or N3-ligand and zinc(II) chloride salts. The results of the X-ray analyses demonstrate that in the structure of 1, the zinc(II) ion is located on an inversion center and exhibits an ZnN6 octahedral arrangement while, in the structure of 2, the zinc(II) ion adopts an ZnN4 tetrahedral geometry. In the polymer 1, the NCS groups are terminally N-bonded to the metal center and the each bip with anti-gauche conformation acts as bridging connecting four zinc(II) ions to form a two-dimensional network with a sql [point symbol (44.62)] topology while, in the polymer 1, the N3 groups are terminally bonded to the metal center and each bbd with anti-anti-anti conformation acts as bridging ligand connecting two zinc(II) ions to form a one-dimensional zig-zag chain. Coordination compounds 1 and 2 have been characterized by infrared spectroscopy, elemental analyses and single-crystal X-ray diffraction. Thermal analyses of polymers were also presented.

Synthesis and conformational analysis of hybrid α/β-dipeptides incorporating S-glycosyl-β(2,2)-amino acids.

PubMed

García-González, Iván; Mata, Lara; Corzana, Francisco; Jiménez-Osés, Gonzalo; Avenoza, Alberto; Busto, Jesús H; Peregrina, Jesús M

2015-01-12

We synthesized and carried out the conformational analysis of several hybrid dipeptides consisting of an α-amino acid attached to a quaternary glyco-β-amino acid. In particular, we combined a S-glycosylated β(2,2)-amino acid and two different types of α-amino acid, namely, aliphatic (alanine) and aromatic (phenylalanine and tryptophan) in the sequence of hybrid α/β-dipeptides. The key step in the synthesis involved the ring-opening reaction of a chiral cyclic sulfamidate, inserted in the peptidic sequence, with a sulfur-containing nucleophile by using 1-thio-β-D-glucopyranose derivatives. This reaction of glycosylation occurred with inversion of configuration at the quaternary center. The conformational behavior in aqueous solution of the peptide backbone and the glycosidic linkage for all synthesized hybrid glycopeptides was analyzed by using a protocol that combined NMR experiments and molecular dynamics with time-averaged restraints (MD-tar). Interestingly, the presence of the sulfur heteroatom at the quaternary center of the β-amino acid induced θ torsional angles close to 180° (anti). Notably, this value changed to 60° (gauche) when the peptidic sequence displayed aromatic α-amino acids due to the presence of CH-π interactions between the phenyl or indole ring and the methyl groups of the β-amino acid unit. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spectroscopic Study and Astronomical Detection of Vibrationally Excited n-PROPYL Cyanide

NASA Astrophysics Data System (ADS)

Müller, Holger S. P.; Wehres, Nadine; Wilkins, Olivia H.; Lewen, Frank; Schlemmer, Stephan; Walters, Adam; Vicente, Rémi; Liu, Delong; Garrod, Robin T.; Belloche, Arnaud; Menten, Karl M.

2016-06-01

We have obtained ALMA data of Sagittarius (Sgr for short) B2(N) between 84.0 and 114.4 GHz in its Early Science Cycles 0 and 1. We have focused our analyses on the northern, secondary hot molecular core Sgr B2(N2) because of the smaller line widths. The survey led to the first detection of a branched alkyl compound, iso-propyl cyanide, i-C_3H_7CN, in space besides the ˜2.5 times more abundant straight chain isomer n-propyl cyanide, a molecule which we had detected in our IRAM 30 m survey. We suspected to be able to detect n-propyl cyanide in vibrationally excited states in our ALMA data. We have recorded laboratory rotational spectra of this molecule in three large frequency regions and identified several excited vibrational states. The analyses of these spectra have focused on the 36 to 70 GHz and 89 to 127 GHz regions and on the four lowest excited vibrational states of both the lower lying gauche- and the slightly higher lying anti-conformer for which rotational constants had been published. We will present results of our laboratory spectroscopic investigations and will report on the detection of these states toward Sgr B2(N2). A. Belloche et al., Science 345 (2014) 1584. A. Belloche et al., A&A 499 (2009) 215. E. Hirota, J. Chem. Phys. 37 (1962) 2918.

Defect Passivation of Organic–Inorganic Hybrid Perovskites by Diammonium Iodide toward High-Performance Photovoltaic Devices

DOE PAGES

Zhao, Ting; Chueh, Chu-Chen; Chen, Qi; ...

2016-09-12

The polycrystalline feature of solutionprocessed perovskite film and its ionic nature inevitably incur substantial crystallographic defects, especially at the film surface and the grain boundaries (GBs). Here, a simple defect passivation method was exploited by post-treating CH 3NH 3PbI 3 (MAPbI 3) film with a rationally selected diammonium iodide. The molecular structure of the used diammonium iodide was discovered to play a critical role in affecting the phase purity of treated MAPbI 3. Both NH 3I(CH 2) 4NH 3I and NH 3I(CH 2) 2O(CH 2) 2NH 3I (EDBE) induce three-dimensional (3D) to two-dimensional (2D) perovskite phase transformation during the treatmentmore » while only NH 3I(CH 2) 8NH 3I (C 8) successfully passivates perovskite surface and GBs without forming 2D perovskite because of the elevated activation energy arising from its unique anti-gauche isomerization. In conclusion, defect passivation of MAPbI 3 was clearly confirmed by scanning Kelvin probe microscopy (SKPM) and time-resolved photoluminescence (TRPL) studies, which results in the reduced recombination loss in derived devices. Consequently, the perovskite solar cell with C 8 passivation showed a much improved power conversion efficiency (PCE) of 17.60% compared to the control device PCE of 14.64%.« less

Extended Generation Profile - E.B.I.C. Model

NASA Astrophysics Data System (ADS)

Guermazi, S.; Toureille, A.; Grill, C.; El Jani, B.; Lakhoua, N.

1996-04-01

We have developed a model for the calculation of the induced current due to an electron beam with an extended profile. As well as the number of absorbed and diffuse electrons as a function of the depth, the generation profile takes into account the lateral diffusion and the effect of defects, dislocations and recombination surfaces. The expression from the Electron Beam Induced Current (EBIC) is obtained by solving the continuity equation in permanent regime by the Green function method. In the case of a Schottky diode Au/InP, obtained by ionic scattering followed by a quick thermal treatment, the induced current profile is compared to the theoretical profiles whose analytical expressions are given by Van Roosbroeck and Bresse. The experimental current profile, measured by S.E.M provided us with the calculation of the diffusion length of the minority carriers, L_n=1 μm. The theoretical curve obtained from the proposed model is in good agreement with the experimental one for a surface recombination velocity of 104 cm s^{-1}. Our results are found to be consistent with those obtained by other experimental techniques on the same samples. Nous avons développé un modèle de calcul du courant induit par un faisceau d'électrons avec un profil de génération élargi. Le profil de génération tient compte, en plus du nombre d'électrons absorbés et du nombre d'électrons diffusés en fonction de la profondeur, de la diffusion latérale (en prenant en considération la diffusion angulaire), de l'effet des défauts, des dislocations et de la recombinaison à la surface. L'expression analytique du courant induit E.B.I.C est déterminée par résolution de l'équation de continuité en régime permanent par la méthode des fonctions de Green. Le profil de courant induit obtenu dans le cas d'une diode Schottky Au/InP dopé p et fabriqué par implantation suivit d'un recuit, est comparé au profil de courant théorique dont l'expression analytique est explicité par Van Roosbroeck et Bresse. Le profil de courant expérimental, mesuré par un microscope électronique à balayage, nous a permis de calculer la longueur de diffusion des porteurs minoritaires L_n=1 μm. La courbe théorique, tracée à partir du modèle proposé, est en bon accord avec la courbe expérimental pour une vitesse de recombinaison à la surface de 104 cm s^{-1}. Ces résultats sont conformes avec ceux obtenus par d'autres techniques expérimentales sur les mêmes échantillons.

Les facteurs prédictifs de morbimortalité chez les patients sous ballon de contre pulsion intra-aortique en chirurgie cardiaque

PubMed Central

Elahmadi, Brahim; Motiaa, Youssef; Hatim, Abdedaim Elghadbane; Atmani, Noureddine; Moutakillah, Younes; Wahid, Fouad Amal; Elbekkali, Youssef; Houssa, Mahdi Ait; Razine, Rachid; Boulahya, Abdelatif; Drissi, Mohammed

2015-01-01

Le ballon de contre pulsion intra-aortique (BCPIA) est fréquemment utilisé en chirurgie cardiaque, comme moyen d'assistance circulatoire en cas de bas débit cardiaque. Il est d'intérêt clinique de déterminer les facteurs pronostiques chez les patients porteurs d'un BCPIA en chirurgie cardiaque, et qui restent un sujet rarement élucidé dans la littérature. L'objectif de notre travail est de déterminer les facteurs prédictifs de morbi-mortalité chez les patients sous ballon de contre pulsion intraortique en périopératoire d'une chirurgie cardiaque. Il s'agit d'une étude rétrospective portant sur l'ensemble des patients opérés en chirurgie cardiaque sous circulation extracorporelle, et ayant bénéficiés de la mise en place d'un ballon de contre pulsion intra-aortique en périopératoire, au service de chirurgie cardiovasculaire de l'Hôpital Militaire Mohamed V de Rabat, entre le mois de janvier 2005 et le mois d'aout 20014. Soixante dix patients ont été inclus dans notre étude. En analyse univariée l'âge, la dyspnée de stade III et IV, l'insuffisance cardiaque, la présence d'un infarctus du myocarde, d'une coronaropathie mono et bitronculaire, les anomalies du doppler de trons supra-aortique et du membre inférieur, le caractère urgent de la chirurgie, la durée de la circulation extracorporelle, l'instabilité hémodynamique postopératoire, le saignement et l'insuffisance rénale postopératoire étaient statistiquement associés à une mortalité postopératoire élevée. La dyskinésie préopératoire et la sortie de circulation extracorporelle sous drogues étaient associées à une morbidité globale élevée. En analyse multi variée, seule l'âge, constituait un facteur de risque indépendant de mortalité dans notre série avec un Odds Ratio (OR): 1,89 ; un Intervalle de Confiance (IC) 95% de (1,52-4,97) et un p =0,045. Au terme de notre étude, le taux de mortalité était de 48,57% et de morbidité globale était de 87,1%. Il nous parait donc nécessaire pour diminuer l'incidence de cette morbimortalité dans notre population, d'agir sur les facteurs que nous jugeons modifiables tels l'amélioration de la fonction cardiaque préopératoire, l'optimisation de la fonction rénale, la réduction de la durée de CEC et le contrôle du saignement. PMID:26587158

Pressure-induced stable BeN4 as a high-energy density material

NASA Astrophysics Data System (ADS)

Zhang, Shoutao; Zhao, Ziyuan; Liu, Lulu; Yang, Guochun

2017-10-01

Polynitrogens are the ideal rocket fuels or propellants. Due to strong triple N≡N bond in N2, the direct polymerization of nitrogen is rather difficult (i.e. extreme high temperature and high pressure). However, the use of nitrides as precursors or the reaction of N2 with other elements has been proved to be an effective way to obtain polynitrogens. Here, with assistance of the advanced first-principles swarm-intelligence structure searches, we found that P 1 bar -BeN4, containing infinite zigzag-like polymeric nitrogen chains, can be synthesized by compressing the mixture of Be3N2 and N2 at 25.4 GPa, which is greatly lower than 110 GPa for synthesizing cubic gauche nitrogen and other polynitrogen compounds (e.g. bulk CNO at 52 GPa and SN4 at 49 GPa). Its structural stability can be attributed to the coexistence of ionic Be-N and covalent N-N bonds. Intriguingly, this phase has high kinetic stability and remains metastable at ambient pressure. The exceptional properties, including high energy density (3.60 kJ g-1), high nitrogen content (86.1%), high dynamical stability, and low polymerization pressure, make P 1 bar -structured BeN4 a promising high energy material. Infinite nitrogen chains in P 1 bar -BeN4 transform to N10 rings network in P21/c phase at 115.1 GPa. P 1 bar -BeN4 is metallic, while P21/c-BeN4 is an insulator.

Conditional solvation thermodynamics of isoleucine in model peptides and the limitations of the group-transfer model.

PubMed

Tomar, Dheeraj S; Weber, Valéry; Pettitt, B Montgomery; Asthagiri, D

2014-04-17

The hydration thermodynamics of the amino acid X relative to the reference G (glycine) or the hydration thermodynamics of a small-molecule analog of the side chain of X is often used to model the contribution of X to protein stability and solution thermodynamics. We consider the reasons for successes and limitations of this approach by calculating and comparing the conditional excess free energy, enthalpy, and entropy of hydration of the isoleucine side chain in zwitterionic isoleucine, in extended penta-peptides, and in helical deca-peptides. Butane in gauche conformation serves as a small-molecule analog for the isoleucine side chain. Parsing the hydrophobic and hydrophilic contributions to hydration for the side chain shows that both of these aspects of hydration are context-sensitive. Furthermore, analyzing the solute-solvent interaction contribution to the conditional excess enthalpy of the side chain shows that what is nominally considered a property of the side chain includes entirely nonobvious contributions of the background. The context-sensitivity of hydrophobic and hydrophilic hydration and the conflation of background contributions with energetics attributed to the side chain limit the ability of a single scaling factor, such as the fractional solvent exposure of the group in the protein, to map the component energetic contributions of the model-compound data to their value in the protein. But ignoring the origin of cancellations in the underlying components the group-transfer model may appear to provide a reasonable estimate of the free energy for a given error tolerance.

Crystal structure of bis­[trans-(1,4,8,11-tetra­aza­cyclo­tetra­decane-κ4 N)bis­(thio­cyanato-κN)chromium(III)] tetra­chlorido­zincate from synchrotron data

PubMed Central

Moon, Dohyun; Ryoo, Keon Sang; Choi, Jong-Ha

2015-01-01

The structure of the title compound, [Cr(NCS)2(cyclam)]2[ZnCl4] (cyclam = 1,4,8,11-tetra­aza­cyclo­tetra­decane, C10H24N4), has been determined from synchrotron data. The asymmetric unit contains two independent halves of the CrIII complex cations and half of a tetra­chlorido­zincate anion. In each complex cation, the CrIII atom is coordinated by the four N atoms of the cyclam ligand in the equatorial plane and by two N-bound NCS− anions in a trans axial arrangement, displaying a distorted octa­hedral geometry with crystallographic inversion symmetry. The mean Cr—N(cyclam) and Cr—N(NCS) bond lengths are 2.065 (4) and 1.995 (6) Å, respectively. The macrocyclic cyclam moieties adopt centrosymmetric trans-III configurations with six- and five-membered chelate rings in chair and gauche configurations, respectively. The [ZnCl4]2− anion, which lies about a twofold rotation axis, has a slightly distorted tetra­hedral geometry. The crystal packing is stabilized by hydrogen-bonding inter­actions between the N—H groups of the cyclam ligands, the S atoms of the NCS− groups and the Cl− ligands of the anion. PMID:25995875

Structural and conformational analysis of pentostatin (2'-deoxycoformycin), a potent inhibitor of adenosine deaminase.

PubMed

Cox, M B; Arjunan, P; Arora, S K

1990-08-01

X-ray, NMR and molecular mechanics studies on pentostatin (C11H16N4O4), a potent inhibitor of the enzyme adenosine deaminase, have been carried out to study the structure and conformation. The crystals belong to the monoclinic space group P21 with the cell dimensions of a = 4.960(1), b = 10.746(3), c = 11.279(4)A, beta = 101.18(2) degrees and Z = 2. The structure was solved by direct methods and difference Fourier methods and refined to an R value of 0.047 for 997 reflections. The trihydrodiazepine ring is nonplanar and adopts a distorted sofa conformation with C(7) deviated from the mean plane by 0.66A. The deoxyribose ring adopts a C3'-endo conformation, different from coformycin where the sugar has a C2'-endo conformation. The observed glycosidic torsion angle (chi = -119.5 degrees) is in the anti range. The conformation about the C(4')-C(5') bond is gauche+. The conformation of the molecule is compared with that of coformycin and 2-azacoformycin. 1 and 2D NMR studies have been carried out and the dihedral angles obtained from coupling constants have been compared with those obtained from the crystal structure. The conformation of deoxyribose in solution is approximately 70% S and 30% N. Molecular mechanics studies were performed to obtain the energy minimized conformation, which is compared with X-ray and NMR results.

We are Family: the Conformations of 1-FLUOROALKANES, C_nH2n+1F (n = 2,3,4,5,6,7,8)

NASA Astrophysics Data System (ADS)

Obenchain, Daniel A.; Orellana, W.; Cooke, S. A.

2016-06-01

he pure rotational spectra of the n = 5, 6, 7, and 8 members of the 1-fluoroalkane family have been recorded between 7 GHz and 14 GHz using chirped pulse Fourier transform microwave spectroscopy. The spectra have been analyzed and results will be presented and compared with previous work on the n= 2, 3, and 4 members. The lowest energy conformer for all family members has the common feature that the fluorine is in a gauche position relative to the alkyl tail for which all other heavy atom dihedral angles, where appropriate, are 180 degrees. For the n = 3 and higher family members the second lowest energy conformer has all heavy atom dihedral angles equal to 180 degrees. For each family member transitions carried by both low energy conformers were observed in the collected rotational spectra. Quantum chemical calculations were performed and trends in the energy separations between these two common conformers will be presented as a function of chain length. Furthermore, longer chain lengths have been examined using only quantum chemical calculations and results will be presented. M. Hayashi, M. Fujitake, T. Inagusa, S. Miyazaki, J.Mol.Struct., 216, 9-26, 1990 W. Caminati, A. C. Fantoni, F. Manescalchi, F. Scappini, Mol.Phys., 64, 1089 ,1988 L. B. Favero, A. Maris, A. Degli Esposti, P. G. Favero, W. Caminati, G. Pawelke, Chem.Eur.J., 6(16), 3018-3025, 2000

Poussée de maladie de Kaposi et élévation du CA 19-9: penser à la tuberculose!

PubMed Central

Ajili, Faida; Hariz, Héla; Souissi, Asmahen; Abid, Rim; Boussetta, Najeh; Laabidi, Besma; Battikh, Riadh; Louzir, Bassem; Othmani, Salah

2013-01-01

La maladie de Kaposi (MK) est une entité pathologique qui peut survenir chez les patients VIH positifs et dans le cadre d'une immunodépression, d'origine tuberculeuse très rarement. On décrit le cas d'une MK chez un patient VIH négatif au décours d'une tuberculose. Nous rapportons le cas d'un patient âgé de 81 ans, VIH négatif, ayant présenté deux nodules angiomateux de l'avant bras gauche dont la biopsie cutanée était en faveur d'une MK. L’évolution était marquée 2 mois plus tard, par l'apparition de placards angiomateux extensifs des deux membres supérieurs et d'adénopathies cervicales jugulo-carotidiennes bilatérales. La biopsie ganglionnaire était en faveur d'une tuberculose ganglionnaire. Par ailleurs, il avait un taux sérique élevé des CA 19-9. La régression de l’étendue des lésions au niveau des membres supérieurs et la normalisation du taux sérique des CA 19-9 ont été obtenues sous traitement anti-tuberculeux. Chez les patients atteints d'une MK avec une élévation des CA 19-9, il faut penser à la tuberculose. PMID:24711871

Equivalent Thermal Conductivities for Twisted Flat Windings

NASA Astrophysics Data System (ADS)

Glises, R.; Bernard, R.; Chamagne, D.; Kauffmann, J. M.

1996-10-01

The authors of this paper intend to develop a method of determination of equivalent thermal conductivities for twisted flat windings. The conductivities determined are radial and parallel to the principal directions of the windings. A design has been realized thanks to the thermal modulus of the computation software Flux2D using a finite elements method. Following that phase, numerical correlations permitting to express the radial conductivities as a function of temperature, filling rate and insulation conductivities are proposed. Les auteurs de cet article se proposent de développer une étude de détermination de conductivités thermiques équivalentes d'empilements de bobinages plats torsadés. Les conductivités sont déterminées dans le plan radial (perpendiculaire à l'axe des bobinages) et parallèlement aux directions principales de la structure. La méthode utilisée est exclusivement numérique et est réalisée à l'aide du logiciel de calculs bidimensionnels par éléments finis Flux2D. Des corrélations numériques exploitables permettent d'obtenir directement les conductivités radiales en fonction du taux de remplissage, de la température du milieu et des conductivités des isolants électriques.

Oscillator strengths of the optical transitions in a semiconductor superlattice under an electric field

NASA Astrophysics Data System (ADS)

Tronc, P.

1992-04-01

The oscillator strengths of the optical transitions in a semiconductor superlattice under an electric field parallel to the growth axis can be calculated using a perturbative model with Bloch envelope functions. The applied electric field and the electron-hole interaction inducing formation of indirect excitons both induce strength asymmetry between the oblique +p and -p transitions of the Wannier-Stark ladder. Features of the photocurrent spectra recorded at low temperature can be accounted for by the present model in a very simple manner. Les forces d'oscillateur des transitions optiques dans un superréseau semiconducteur soumis à un champ électrique parallèle à la direction de croissance, peuvent être calculées à l'aide d'un modèle de perturbation avec des fonctions enveloppes de Bloch. Le champ électrique appliqué ainsi que l'interaction électron-trou, qui induit la formation d'excitons indirects, entraînent une asymétrie entre les forces d'oscillateur des transitions +p et -p dans l'échelle de Wannier-Stark. Certaines caractéristiques des spectres de photocourant enregistrés à basse température peuvent être prévues d'une manière très simple.

Influence des interactions entre écrans de soutènement sur le calcul de la butée

NASA Astrophysics Data System (ADS)

Magnan, Jean-Pierre; Meyer, Grégory

2018-05-01

La mobilisation de la butée devant un écran implique un volume de sol important, sur une distance plus grande que la fiche et qui dépend des paramètres du calcul. L'article passe en revue les méthodes de calcul utilisées pour évaluer la butée, en insistant sur la distance nécessaire au libre développement du mécanisme de butée. Il évalue ensuite de différentes façons l'effet de l'interaction entre deux écrans placés face à face de part et d'autre d'une excavation. La méthode recommandée pour calculer la butée mobilisable consiste à faire un calcul en éléments finis avec des valeurs réduites des paramètres de résistance au cisaillement dans la zone où se développera la butée. Cette démarche permet de déterminer des facteurs correctifs à appliquer au calcul de la butée d'un écran isolé en fonction du rapport de la distance entre écrans à leur fiche.

Portage vaginal du streptocoque du groupe B chez la femme enceinte au niveau de la région de Marrakech

PubMed Central

Bassir, Ahlam; Dhibou, Hanane; Farah, Majdi; Mohamed, Lharmis; Amal, Addebous; Nabila, Souraa; Abderahim, Aboulfalah; Asmouki, Hamid; Soummani, Abderraouf

2016-01-01

Introduction Le streptocoque du groupe B est le principal agent impliqué dans les infections materno-fœtales, les septicémies et les méningites du nouveau-né à terme. L'objectif est de déterminer le taux de portage maternel du streptocoque du groupe B (SGB) à terme. Méthodes Un prélèvement vaginal a été réalisé de manière prospective chez 275 parturientes lors de l'entrée en salle d'accouchement sur une période de 06 mois. Résultats Le taux de portage était de 20,2%. Le portage était variable en fonction de l’âge gestationnel, il constitue 57.5% entre 37 et 38 semaines d'aménorrhée. Aucun des facteurs de risque n'a était statistiquement prédictif du portage maternel du SGB. Conclusion Le dépistage doit être réalisé à partir de 37 semaines d'aménorrhée, et comme le portage est intermittent, un prélèvement négatif ne garantirait pas que le portage soit négatif à l'accouchement. PMID:27222693

Effets potentiels d’un modèle rationnel de prescription sur les dépenses nationales en santé

PubMed Central

Littman, Jordan; Halil, Roland

2016-01-01

Résumé Objectif Estimer les économies que pourrait engendrer la mise en œuvre d’un modèle rationnel de prescription pour des classes de médicaments équivalents sur les plans de l’efficacité, de la toxicité et de la commodité. Conception L’Institut canadien d’information sur la santé a fourni des renseignements sur les 10 principales classes de médicaments en fonction des dépenses annuelles qui leur sont attribuables. Ces classes ont été examinées en vue de leur inclusion potentielle dans l’étude selon qu’il était possible de comparer les médicaments à l’intérieur d’une même classe. Lorsqu’à la suite d’une recherche documentaire, une équivalence a été établie en fonction de l’efficacité, de la toxicité et de la commodité des médicaments, les données annuelles sur les prescriptions ont été recueillies à partir de la base de données du Système national d’information sur l’utilisation des médicaments prescrits. Les économies potentielles de coûts ont ensuite été calculées en comparant les parts de marché actuelles avec les parts potentielles futures de ce marché. Contexte Le Canada. Principaux paramètres à l’étude Les différences estimées dans les dépenses que produirait un modèle rationnel de prescription. Résultats Une équivalence a été établie sur les plans de l’efficacité, de la toxicité et de la commodité dans les classes de statines, d’inhibiteurs de la pompe à protons, d’inhibiteurs de l’enzyme de conversion de l’angiotensine et d’inhibiteurs sélectifs du recaptage de l’angiotensine. Les dépenses annuelles totales dans ces classes se situent à 856 millions $ dans les programmes publics de médicaments et à 1,97 milliard $ environ à l’échelle nationale. Grâce à des prescriptions rationnelles, on estime que les économies annuelles pourraient atteindre 222 millions $ pour les programmes publics et 521 millions $ à l’échelle nationale. Conclusion La majorité des économies potentielles seraient attribuables à l’abandon des médicaments les plus récents protégés par un brevet dans chaque classe. En évitant de prescrire les plus récents médicaments intraclasses, en particulier en l’absence de recherche établissant leur supériorité dans les résultats cliniques pertinents, on pourrait réaliser des économies considérables dans les dépenses en santé et inciter l’industrie pharmaceutique à innover plutôt qu’à imiter.

Elastin-like Polypeptide Linkers for Single-Molecule Force Spectroscopy.

PubMed

Ott, Wolfgang; Jobst, Markus A; Bauer, Magnus S; Durner, Ellis; Milles, Lukas F; Nash, Michael A; Gaub, Hermann E

2017-06-27

Single-molecule force spectroscopy (SMFS) is by now well established as a standard technique in biophysics and mechanobiology. In recent years, the technique has benefitted greatly from new approaches to bioconjugation of proteins to surfaces. Indeed, optimized immobilization strategies for biomolecules and refined purification schemes are being steadily adapted and improved, which in turn has enhanced data quality. In many previously reported SMFS studies, poly(ethylene glycol) (PEG) was used to anchor molecules of interest to surfaces and/or cantilever tips. The limitation, however, is that PEG exhibits a well-known trans-trans-gauche to all-trans transition, which results in marked deviation from standard polymer elasticity models such as the worm-like chain, particularly at elevated forces. As a result, the assignment of unfolding events to protein domains based on their corresponding amino acid chain lengths is significantly obscured. Here, we provide a solution to this problem by implementing unstructured elastin-like polypeptides as linkers to replace PEG. We investigate the suitability of tailored elastin-like polypeptides linkers and perform direct comparisons to PEG, focusing on attributes that are critical for single-molecule force experiments such as linker length, monodispersity, and bioorthogonal conjugation tags. Our results demonstrate that by avoiding the ambiguous elastic response of mixed PEG/peptide systems and instead building the molecular mechanical systems with only a single bond type with uniform elastic properties, we improve data quality and facilitate data analysis and interpretation in force spectroscopy experiments. The use of all-peptide linkers allows alternative approaches for precisely defining elastic properties of proteins linked to surfaces.

Structure of water at zwitterionic copolymer film-liquid water interfaces as examined by the sum frequency generation method.

PubMed

Kondo, Takuya; Nomura, Kouji; Gemmei-Ide, Makoto; Kitano, Hiromi; Noguchi, Hidenori; Uosaki, Kohei; Saruwatari, Yoshiyuki

2014-01-01

A copolymer film composed of zwitterionic carboxymethylbetaine (CMB) and n-butyl methacrylate (BMA), Poly(CMB-r-BMA), was cast on a flat plane of an octadecyltrichlorosilane (ODS)-modified fused quartz prism with a semi-cylindrical shape. CH stretching of the polymer film and O-H stretching of water at the surface of the film were examined using the sum frequency generation (SFG) technique. The C-H stretching band of the cast film, indicating a gauche defect of the film, was affected by the contact medium including dry nitrogen, water vapor-saturated nitrogen and liquid water. In contrast, the C-H stretching of an octadecyl group introduced onto the quartz prism for stable attachment of the cast film was not significantly changed by the contact medium. The O-H stretching band indicated that water molecules at the surface of the Poly(CMB-r-BMA) film in contact with liquid water were not greatly oriented in comparison with those at the surfaces of a bare prism, an ODS SAM-modified prism, and a prism covered with a PolyBMA film or a copolymer film of BMA and methacrylic acid or 2-(dimethylamino)ethyl methacrylate. A similar small perturbation of the structure of water was previously observed in the vicinity of water-soluble zwitterionic polymers and zwitterionic copolymer films using Raman and attenuated total reflection infrared spectroscopies, respectively. A distinct effect of charge neutralization to diminish the perturbation of the structure of interfacial water around polymer materials was suggested. Copyright © 2013 Elsevier B.V. All rights reserved.

Conditional Solvation Thermodynamics of Isoleucine in Model Peptides and the Limitations of the Group-Transfer Model

PubMed Central

2015-01-01

The hydration thermodynamics of the amino acid X relative to the reference G (glycine) or the hydration thermodynamics of a small-molecule analog of the side chain of X is often used to model the contribution of X to protein stability and solution thermodynamics. We consider the reasons for successes and limitations of this approach by calculating and comparing the conditional excess free energy, enthalpy, and entropy of hydration of the isoleucine side chain in zwitterionic isoleucine, in extended penta-peptides, and in helical deca-peptides. Butane in gauche conformation serves as a small-molecule analog for the isoleucine side chain. Parsing the hydrophobic and hydrophilic contributions to hydration for the side chain shows that both of these aspects of hydration are context-sensitive. Furthermore, analyzing the solute–solvent interaction contribution to the conditional excess enthalpy of the side chain shows that what is nominally considered a property of the side chain includes entirely nonobvious contributions of the background. The context-sensitivity of hydrophobic and hydrophilic hydration and the conflation of background contributions with energetics attributed to the side chain limit the ability of a single scaling factor, such as the fractional solvent exposure of the group in the protein, to map the component energetic contributions of the model-compound data to their value in the protein. But ignoring the origin of cancellations in the underlying components the group-transfer model may appear to provide a reasonable estimate of the free energy for a given error tolerance. PMID:24650057

Ostéo-arthrite tuberculeuse tarsienne: à propos d’un cas

PubMed Central

Yacoubi, Hicham; Erraji, Moncef; Abdelillah, Rachid; Abbassi, Najib; Abdeljawad, Najib; Daoudi, Abdelkrim

2012-01-01

Nous rapportons le cas d’une patiente de 45 ans sans antécédents médicaux particuliers, qui a présenté une atteinte inflammatoire du pied gauche, sans notion de traumatisme ni de fièvre, avec apparition secondaire d’une fistule cutanée purulente à la face externe du cou de pied. Les radiographies standards et la Tomodensitométrie de la cheville mettaient en évidence une ostéite calcanéenne avec atteinte articulaire subtalienne. Une biopsie chirurgicale associée à une excision des tissus inflammatoires et nécrotiques et l’ablation du trajet fistuleux, ont été réalisées. L’analyse histologique montrait une image de granulome épithélio-giganto-cellulaire avec une nécrose caséeuse et les prélèvements bactériologiques (retrouvaient Mycobacterium tuberculosis. Une chimiothérapie antituberculeuse a été administrée pendant 12 mois. À 24 mois, la patiente ne présentait pas de récidive mais une arthropathie dégénérative secondaire subtalienne. Il nous semble intéressant de rappeler que tout tableau clinique traînant ou toute lésion osseuse suspecte et de présentation atypique doit faire évoquer le diagnostic de tuberculose afin d’éviter des retards de diagnostic. Ceci permet une prise en charge thérapeutique précoce de la pathologie. PMID:22655098

Schwannome benin primitif retrovesical: une tumeur très rare à propos d'un cas

PubMed Central

Beddouche, Ali; Fahsi, Othemane; Kallat, Adil; El Bote, Hicham; Ziani, Idriss; El Sayegh, Hachem; Iken, Ali; Benslimane, Lounis; Nouini, Yassine

2016-01-01

Le schwannome est une tumeur le plus souvent bénigne, d'origine nerveuse se développant à partir des cellules de la gaine de Schwann. C'est une tumeur très rare tant par sa fréquence que par sa localisation rétrovésicale. L'examen anatomopathologique et immunohistochimique confirme le type histologique ainsi que le caractère bénin ou malin du schwannome. En raison des récidives, et du risque de transformation maligne, l'exérèse doit être complète. Nous rapportons le cas d'un patient âgé de 39 ans, admis pour une douleur pelvienne chronique à type de pesanteur, des signes irritatifs du bas appareil urinaire, et des troubles de transit. L'imagerie (échographie, TDM, IRM) a révélé la présence d'une masse pelvienne rétrovésicale, à paroi fine, latéralisée à gauche, mesurant 68x70x70 mm, exerçant un effet de masse sur la vessie et le sigmoïde. L'intervention chirurgicale menée par une laparotomie médiane a permis l'exérèse d'une masse retrovésicale bien encapsulée. L'examen anatomopathologique et immunohistochimique ont conclu à un schwannome bénin. La récidive et la transformation maligne bien que rare après chirurgie impose une surveillance post opératoire clinique et tomodensitométrique annuelle. PMID:27217902

PyCPR - a python-based implementation of the Conjugate Peak Refinement (CPR) algorithm for finding transition state structures.

PubMed

Gisdon, Florian J; Culka, Martin; Ullmann, G Matthias

2016-10-01

Conjugate peak refinement (CPR) is a powerful and robust method to search transition states on a molecular potential energy surface. Nevertheless, the method was to the best of our knowledge so far only implemented in CHARMM. In this paper, we present PyCPR, a new Python-based implementation of the CPR algorithm within the pDynamo framework. We provide a detailed description of the theory underlying our implementation and discuss the different parts of the implementation. The method is applied to two different problems. First, we illustrate the method by analyzing the gauche to anti-periplanar transition of butane using a semiempirical QM method. Second, we reanalyze the mechanism of a glycyl-radical enzyme, namely of 4-hydroxyphenylacetate decarboxylase (HPD) using QM/MM calculations. In the end, we suggest a strategy how to use our implementation of the CPR algorithm. The integration of PyCPR into the framework pDynamo allows the combination of CPR with the large variety of methods implemented in pDynamo. PyCPR can be used in combination with quantum mechanical and molecular mechanical methods (and hybrid methods) implemented directly in pDynamo, but also in combination with external programs such as ORCA using pDynamo as interface. PyCPR is distributed as free, open source software and can be downloaded from http://www.bisb.uni-bayreuth.de/index.php?page=downloads . Graphical Abstract PyCPR is a search tool for finding saddle points on the potential energy landscape of a molecular system.

Searching for trans ethyl methyl ether in Orion KL★,★★

PubMed Central

Tercero, B.; Cernicharo, J.; López, A.; Brouillet, N.; Kolesniková, L.; Motiyenko, R. A.; Margulès, L.; Alonso, J. L.; Guillemin, J.-C.

2015-01-01

We report on the tentative detection of trans ethyl methyl ether (tEME), t-CH3CH2OCH3, through the identification of a large number of rotational lines from each one of the spin states of the molecule towards Orion KL. We also search for gauche-trans-n-propanol, Gt-n-CH3CH2CH2OH, an isomer of tEME in the same source. We have identified lines of both species in the IRAM 30 m line survey and in the ALMA Science Verification data. We have obtained ALMA maps to establish the spatial distribution of these species. Whereas tEME mainly arises from the compact ridge component of Orion, Gt-n-propanol appears at the emission peak of ethanol (south hot core). The derived column densities of these species at the location of their emission peaks are ≤(4.0 ± 0.8) × 1015 cm−2 and ≤(1.0 ± 0.2)× 1015 cm−2 for tEME and Gt-n-propanol, respectively. The rotational temperature is ~100 K for both molecules. We also provide maps of CH3OCOH, CH3CH2OCOH, CH3OCH3, CH3OH, and CH3CH2OH to compare the distribution of these organic saturated O-bearing species containing methyl and ethyl groups in this region. Abundance ratios of related species and upper limits to the abundances of non-detected ethers are provided. We derive an abundance ratio N(CH3OCH3)/N(tEME) ≥ 150 in the compact ridge of Orion. PMID:26869726

Searching for trans ethyl methyl ether in Orion KL.

PubMed

Tercero, B; Cernicharo, J; López, A; Brouillet, N; Kolesniková, L; Motiyenko, R A; Margulès, L; Alonso, J L; Guillemin, J-C

2015-10-01

We report on the tentative detection of trans ethyl methyl ether (tEME), t-CH 3 CH 2 OCH 3 , through the identification of a large number of rotational lines from each one of the spin states of the molecule towards Orion KL. We also search for gauche-trans-n-propanol, Gt-n-CH 3 CH 2 CH 2 OH, an isomer of tEME in the same source. We have identified lines of both species in the IRAM 30 m line survey and in the ALMA Science Verification data. We have obtained ALMA maps to establish the spatial distribution of these species. Whereas tEME mainly arises from the compact ridge component of Orion, Gt-n-propanol appears at the emission peak of ethanol (south hot core). The derived column densities of these species at the location of their emission peaks are ≤(4.0 ± 0.8) × 10 15 cm -2 and ≤(1.0 ± 0.2)× 10 15 cm -2 for tEME and Gt-n-propanol, respectively. The rotational temperature is ~100 K for both molecules. We also provide maps of CH 3 OCOH, CH 3 CH 2 OCOH, CH 3 OCH 3 , CH 3 OH, and CH 3 CH 2 OH to compare the distribution of these organic saturated O-bearing species containing methyl and ethyl groups in this region. Abundance ratios of related species and upper limits to the abundances of non-detected ethers are provided. We derive an abundance ratio N (CH 3 OCH 3 )/ N (tEME) ≥ 150 in the compact ridge of Orion.

Confocal Raman spectroscopy: In vivo biochemical changes in the human skin by topical formulations under UV radiation.

PubMed

Tosato, M G; Orallo, D E; Ali, S M; Churio, M S; Martin, A A; Dicelio, L

2015-12-01

A new approach to the study of the effects on human skin of mycosporine-like amino acids (MAAs) and gadusol (Gad) incorporated in polymer gel is proposed in this work. The depth profile and photoprotector effects of Pluronic F127® gels containing each of the natural actives were evaluated by in vivo confocal Raman spectroscopy aiming at the analysis of the biochemical changes on human skin. Hierarchical cluster analysis (HCA) showed that the data corresponding to different depths of the skin, from surface to 4 μm, and from 6 to 16 μm, remained in the same cluster. In vivo Raman spectra, classified into five different layers of epidermis according to their similarities, indicated that the amount of Gad gel increased by about 26% in the outermost layer of the stratum corneum (SC) and that MAAs gel at 2 μm depth was 103.4% higher than in the outermost layer of the SC. Variations in the SC of urocanic acid at 1490-1515 cm(-1) and 1652 cm(-1) and histidine at 1318 cm(-1) were calculated, before and after UV exposure with or without gels. With the application of gels the vibrational modes that correspond to lipids in trans conformation (1063 and 1128 cm(-1)) increased with respect to normal skin, whereas gauche conformation (1085 cm(-1)) disappeared. Our studies suggest that gels protected the skin against the stress of the natural defense mechanism caused by high levels of UV exposure. Copyright © 2015 Elsevier B.V. All rights reserved.

Pressure dependence of side chain 13C chemical shifts in model peptides Ac-Gly-Gly-Xxx-Ala-NH2.

PubMed

Beck Erlach, Markus; Koehler, Joerg; Crusca, Edson; Munte, Claudia E; Kainosho, Masatsune; Kremer, Werner; Kalbitzer, Hans Robert

2017-10-01

For evaluating the pressure responses of folded as well as intrinsically unfolded proteins detectable by NMR spectroscopy the availability of data from well-defined model systems is indispensable. In this work we report the pressure dependence of 13 C chemical shifts of the side chain atoms in the protected tetrapeptides Ac-Gly-Gly-Xxx-Ala-NH 2 (Xxx, one of the 20 canonical amino acids). Contrary to expectation the chemical shifts of a number of nuclei have a nonlinear dependence on pressure in the range from 0.1 to 200 MPa. The size of the polynomial pressure coefficients B 1 and B 2 is dependent on the type of atom and amino acid studied. For H N , N and C α the first order pressure coefficient B 1 is also correlated to the chemical shift at atmospheric pressure. The first and second order pressure coefficients of a given type of carbon atom show significant linear correlations suggesting that the NMR observable pressure effects in the different amino acids have at least partly the same physical cause. In line with this observation the magnitude of the second order coefficients of nuclei being direct neighbors in the chemical structure also are weakly correlated. The downfield shifts of the methyl resonances suggest that gauche conformers of the side chains are not preferred with pressure. The valine and leucine methyl groups in the model peptides were assigned using stereospecifically 13 C enriched amino acids with the pro-R carbons downfield shifted relative to the pro-S carbons.

Population shuffling between ground and high energy excited states.

PubMed

Sabo, T Michael; Trent, John O; Lee, Donghan

2015-11-01

Stochastic processes powered by thermal energy lead to protein motions traversing time-scales from picoseconds to seconds. Fundamental to protein functionality is the utilization of these dynamics for tasks such as catalysis, folding, and allostery. A hierarchy of motion is hypothesized to connect and synergize fast and slow dynamics toward performing these essential activities. Population shuffling predicts a "top-down" temporal hierarchy, where slow time-scale conformational interconversion leads to a shuffling of the free energy landscape for fast time-scale events. Until now, population shuffling was only applied to interconverting ground states. Here, we extend the framework of population shuffling to be applicable for a system interconverting between low energy ground and high energy excited states, such as the SH3 domain mutants G48M and A39V/N53P/V55L from the Fyn tyrosine kinase, providing another tool for accessing the structural dynamics of high energy excited states. Our results indicate that the higher energy gauche - rotameric state for the leucine χ2 dihedral angle contributes significantly to the distribution of rotameric states in both the major and minor forms of the SH3 domain. These findings are corroborated with unrestrained molecular dynamics (MD) simulations on both the major and minor states of the SH3 domain demonstrating high correlations between experimental and back-calculated leucine χ2 rotameric populations. Taken together, we demonstrate how fast time-scale rotameric side-chain population distributions can be extracted from slow time-scale conformational exchange data further extending the scope and the applicability of the population shuffling model. © 2015 The Protein Society.

Atomistic Simulation Studies of Cholesteryl Oleates: Model for the Core of Lipoprotein Particles

PubMed Central

Heikelä, Mikko; Vattulainen, Ilpo; Hyvönen, Marja T.

2006-01-01

We have conducted molecular dynamics simulations to gain insight into the atomic-scale properties of an isotropic system of cholesteryl oleate (CO) molecules. Cholesteryl esters are major constituents of low density lipoprotein particles, the key players in the formation of atherosclerosis, as well as the storage form of cholesterol. Here the aim is to clarify structural and dynamical properties of CO molecules under conditions, which are suggestive of those in the core of low density lipoprotein particles. The simulations in the fluid phase indicate that the system of CO molecules is characterized by an absence of translational order, as expected, while the orientational order between distinct CO molecules is significant at short distances, persisting over a molecular size. As for intramolecular properties, the bonds along the oleate chain are observed to be weakly ordered with respect to the sterol structure, unlike the bonds along the short hydrocarbon chain of cholesterol where the ordering is significant. The orientational distribution of the oleate chain as a whole with respect to the sterol moiety is of broad nature, having a major amount of extended and a less considerable proportion of bended structures. Distinct transient peaks at specific angles also appear. The diffusion of CO molecules is found to be a slow process and characterized by a diffusion coefficient of the order of 2 × 10−9 cm2/s. This is considerably slower than diffusion, e.g., in ordered domains of lipid membranes rich in sphingomyelin and cholesterol. Analysis of the rotational diffusion rates and trans-to-gauche transition rates yield results consistent with experiments. PMID:16399839

Peptide crystal simulations reveal hidden dynamics

PubMed Central

Janowski, Pawel A.; Cerutti, David S.; Holton, James; Case, David A.

2013-01-01

Molecular dynamics simulations of biomolecular crystals at atomic resolution have the potential to recover information on dynamics and heterogeneity hidden in the X-ray diffraction data. We present here 9.6 microseconds of dynamics in a small helical peptide crystal with 36 independent copies of the unit cell. The average simulation structure agrees with experiment to within 0.28 Å backbone and 0.42 Å all-atom rmsd; a model refined against the average simulation density agrees with the experimental structure to within 0.20 Å backbone and 0.33 Å all-atom rmsd. The R-factor between the experimental structure factors and those derived from this unrestrained simulation is 23% to 1.0 Å resolution. The B-factors for most heavy atoms agree well with experiment (Pearson correlation of 0.90), but B-factors obtained by refinement against the average simulation density underestimate the coordinate fluctuations in the underlying simulation where the simulation samples alternate conformations. A dynamic flow of water molecules through channels within the crystal lattice is observed, yet the average water density is in remarkable agreement with experiment. A minor population of unit cells is characterized by reduced water content, 310 helical propensity and a gauche(−) side-chain rotamer for one of the valine residues. Careful examination of the experimental data suggests that transitions of the helices are a simulation artifact, although there is indeed evidence for alternate valine conformers and variable water content. This study highlights the potential for crystal simulations to detect dynamics and heterogeneity in experimental diffraction data, as well as to validate computational chemistry methods. PMID:23631449

Parametrization of 2,2,2-trifluoroethanol based on the generalized AMBER force field provides realistic agreement between experimental and calculated properties of pure liquid as well as water-mixed solutions.

PubMed

Vymětal, Jiří; Vondrášek, Jiří

2014-09-04

We present a novel force field model of 2,2,2-trifluoroethanol (TFE) based on the generalized AMBER force field. The model was exhaustively parametrized to reproduce liquid-state properties of pure TFE, namely, density, enthalpy of vaporization, self-diffusion coefficient, and population of trans and gauche conformers. The model predicts excellently other liquid-state properties such as shear viscosity, thermal expansion coefficient, and isotropic compressibility. The resulting model describes unexpectedly well the state equation of the liquid region in the range of 100 K and 10 MPa. More importantly, the proposed TFE model was optimized for use in combination with the TIP4P/Ew and TIP4P/2005 water models. It does not manifest excessive aggregation, which is known for other models, and therefore, it is supposed to more realistically describe the behavior of TFE/water mixtures. This was demonstrated by means of the Kirkwood-Buff theory of solutions and reasonable agreement with experimental data. We explored a considerable part of the parameter space and systematically tested individual combinations of parameters for performance in combination with the TIP4P/Ew and TIP4P/2005 water models. We observed ambiguity in parameters describing pure liquid TFE; however, most of them failed for TFE/water mixtures. We clearly demonstrated the necessity for balanced TFE-TFE, TFE-water, and water-water interactions which can be acquired only by employing implicit polarization correction in the course of parametrization.

Two-step recrystallization of water in concentrated aqueous solution of poly(ethylene glycol).

PubMed

Gemmei-Ide, Makoto; Motonaga, Tetsuya; Kasai, Ryosuke; Kitano, Hiromi

2013-02-21

Crystallization behavior of water in a concentrated aqueous solution of poly(ethylene glycol) (PEG) with a water content of 37.5 wt % was investigated by temperature variable mid-infrared (mid-IR) spectroscopy in a temperature range of 298-170 K. The mid-IR spectrum of water at 298 K showed that a large water cluster was not formed and that most of the water molecules were associated with the PEG chain. Ice formation, however, occurred as found in previous studies by differential scanning calorimetory. Ice formations were grouped into three types: crystallization at 231 K during cooling, that at 198 K during heating, and that at 210 K during heating. The latter two were just recrystallization. These ice formations were the direct transition from hydration species to ice without condensation regardless of crystallization or recrystallization. This means that the recrystallized water in the present system was not generated from low-density amorphous solid water. At a low cooling rate, nearly complete crystallization at 231 K during cooling and no recrystallization were observed. At a high cooling rate, no crystallization and two-step recrystallization at 198 and 210 K were observed. The former and latter recrystallizations were found to be generated from water associated with the PEG chains with ttg (the sequence -O-CH(2)-CH(2)-O- having a trans (t) conformation about the -C-O- bond and a gauche (g) conformation about the -C-C- bond) and random conformations, respectively. These results indicate that recrystallizable water does not have a single specific water structure.

Parotidite aigue néonatale suppurative: à propos de trois cas cliniques avec revue de la littérature

PubMed Central

Isfaoun, Zineb; Radouani, Mohammed Amine; Azzaoui, Sihame; Knouni, Houria; Aguenaou, Hassan; Barkat, Amina

2016-01-01

Cet article fait mention de trois cas de parotidite bactérienne néonatale observés pendant une période de sept mois. Ce diagnostic est souvent clinique: on retrouve classiquement hyperthermie, tuméfaction, érythème, chaleur ainsi que sensibilité locale et écoulement purulent au niveau du canal de Sténon lors du massage de la parotide. Le diagnostic clinique est confirmé par échographie et culture de la sécrétion parotidienne purulente. Elles sont le plus souvent d’origine nosocomiale, favorisées par la prématurité et la déshydratation. Traitées précocement, leur évolution est favorable. Les risques liés à l’âge doivent faire débuter une antibiothérapie empirique puis fonction de l'examen direct du pus extrait du canal de Sténon. On isole le plus communément le Staphylocoque aureus; le Streptocoque Viridans et les germes anaérobies. Les parotidites aigues sont très rares en période néonatale: moins de 50 cas ont été rapportés dans la littérature. Nous rapportons trois observations assez particulières. Le diagnostic avait été suspecté sur les signes inflammatoires locaux. PMID:28154641

Élaboration d'un bronze Cu-8%Sn fritté sous pression et l'étude de son aptitude à l'absorption

NASA Astrophysics Data System (ADS)

Loucif, K.; Keraghel, F.; Alem, S.

2005-05-01

L'introduction des píeces miniatures dans le domaine de l'informatique et la microélectronique nécessite une grande précision et un environnement propre. D'autre part, la conservation d'énergie exige des pièces légères et une bonne longévité. Pour résoudre ces problèmes, des pièces autolubrifiées ont été proposées. En effet, plusieurs disciplines peuvent s'ingérer pour élaborer ces pièces: la métallurgie des poudres pour produire des pièces poreuses, la tribologie pour caractériser la pièce en fonctionnement et la mécanique des fluides pour évaluer le comportement échantillon -lubrifiant.
Dans ce présent travail, nous présentons l'évolution de la densité des échantillons élaborés en fonction de: la température d'élaboration, la pression de compactage, et le temps de maintien et l'évolution de l'absorption des lubrifiants par un alliage Cu-8% Sn fritté sous pression. Les lubrifiants choisis sont l'eau et une huile de machine à usage domestique et leur aptitude à l'autolubrification.

Quand le malheur frappe les bénéficiaires de la sécurité du revenu. Sur qui peuvent-ils s’appuyer ?

PubMed Central

Tousignant, Michel; Caron, Jean

2013-01-01

Cette étude analyse les conditions de réalisation du soutien social dans les quartiers de Saint-Henri et de la Pointe Saint-Charles, en comparant un groupe de 61 prestataires de la sécurité du revenu avec un échantillon de 21 personnes de la population vivant au-dessus du seuil de la pauvreté, et en fonction du degré de détresse dans chaque groupe. Elle vise également à décrire comment une adversité vécue par les prestataires avec ou sans détresse vient briser ou modifier le réseau de soutien. Les résultats indiquent que le réseau social est moins fiable en présence de détresse qu’en son absence, que les personnes en détresse se sont vues plus fréquemment refuser du soutien ou être abandonnées et qu’elles ont davantage de personnes nuisibles dans leur entourage. De plus, les événements vécus comportent souvent une atteinte à leur réputation, des menaces, des trahisons et des refus à un droit légitime. Les personnes en détresse sont aussi davantage isolées. PMID:16505926

CR extension from hypersurfaces of higher type

NASA Astrophysics Data System (ADS)

Baracco, Luca

2007-07-01

We prove extension of CR functions from a hypersurface M of in presence of the so-called sector property. If M has finite type in the Bloom-Graham sense, then our result is already contained in [C. Rea, Prolongement holomorphe des fonctions CR, conditions suffisantes, C. R. Acad. Sci. Paris 297 (1983) 163-166] by Rea. We think however, that the argument of our proof carries an expressive geometric meaning and deserves interest on its own right. Also, our method applies in some case to hypersurfaces of infinite type; note that for these, the classical methods fail. CR extension is treated by many authors mainly in two frames: extension in directions of iterated of commutators of CR vector fields (cf., for instance, [A. Boggess, J. Pitts, CR extension near a point of higher type, Duke Math. J. 52 (1) (1985) 67-102; A. Boggess, J.C. Polking, Holomorphic extension of CR functions, Duke Math. J. 49 (1982) 757-784. ; M.S. Baouendi, L. Rothschild, Normal forms for generic manifolds and holomorphic extension of CR functions, J. Differential Geom. 25 (1987) 431-467. ]); extension through minimality towards unprecised directions [A.E. Tumanov, Extension of CR-functions into a wedge, Mat. Sb. 181 (7) (1990) 951-964. ; A.E. Tumanov, Analytic discs and the extendibility of CR functions, in: Integral Geometry, Radon Transforms and Complex Analysis, Venice, 1996, in: Lecture Notes in Math., vol. 1684, Springer, Berlin, 1998, pp. 123-141].

Multiplicative Process in Turbulent Velocity Statistics: A Simplified Analysis

NASA Astrophysics Data System (ADS)

Chillà, F.; Peinke, J.; Castaing, B.

1996-04-01

A lot of models in turbulence links the energy cascade process and intermittency, the characteristic of which being the shape evolution of the probability density functions (pdf) for longitudinal velocity increments. Using recent models and experimental results, we show that the flatness factor of these pdf gives a simple and direct estimate for what is called the deepness of the cascade. We analyse in this way the published data of a Direct Numerical Simulation and show that the deepness of the cascade presents the same Reynolds number dependence as in laboratory experiments. Plusieurs modèles de turbulence relient la cascade d'énergie et l'intermittence, caractérisée par l'évolution des densités de probabilité (pdf) des incréments longitudinaux de vitesse. Nous appuyant aussi bien sur des modèles récents que sur des résultats expérimentaux, nous montrons que la Curtosis de ces pdf permet une estimation simple et directe de la profondeur de la cascade. Cela nous permet de réanalyser les résultats publiés d'une simulation numérique et de montrer que la profondeur de la cascade y évolue de la même façon que pour les expériences de laboratoire en fonction du nombre de Reynolds.

Theorie de la Levitation Radiative a L'equilibre dans les Etoiles Naines Blanches Chaudes

NASA Astrophysics Data System (ADS)

Chayer, Pierre

1995-01-01

Les resultats de nouveaux calculs detailles de levitation radiative dans des naines blanches chaudes utilisant la base de donnees atomiques TOPBASE sont presentes. Des accelerations radiatives et des abondances d'equilibre ont ete calculees pour C, N, O, Ne, Na, Mg, Al, Si, S, Ar, Ca, et Fe, sur des grilles de modeles d'enveloppes stellaires riches en hydrogene et riches en helium. La grille des modeles de DA a des gravites telles que log g = 7.0, 7.5, 8.0, et 8.5, et couvre les temperatures effectives pour lesquelles 100,000K >= T_ {rm eff} >= 20,000K par sauts de 2,500K. La grille des modeles de DO/DB est similaire mais se prolonge a T_{rm eff } = 130,000K. Les resultats d'abondances d'equilibre de Ni dans des DA utilisant la base de donnees de Kurucz sont aussi presentes. Nous discutons dans les moindres details de la physique incluse dans les calculs afin de fournir une bonne comprehension physique de la levitation radiative sous les conditions rencontrees dans les naines blanches. Nous discutons aussi de la forme et de la dependance en fonction de la profondeur des reservoirs des elements, crees par un equilibre entre l'acceleration radiative et la gravite locale effective dans differentes enveloppes stellaires. Nous soulignons le role important joue dans la morphologie de ces reserviors par les etats d'ionisation dominants se trouvant dans la configuration gaz noble. Nos resultats centraux sont presentes sous forme de figures montrant le comportement de l'abondance photospherique estimee pour chaque element en fonction de la temperature effective et de la gravite de surface. Nous apportons egalement des ameliorations aux calculs de levitation radiative en utilisant une approche de modeles d'atmospheres pour les etoiles riches en hydrogene. Nous mettons l'emphase, en particulier, sur le role des traces d'elements lourds qui peuvent etre presents dans le plasma. Nous utilisons une table d'opacite monochromatique detaillee calculee pour un plasma compose de H contenant de faibles quantites de C, N, O, et Fe pour illustrer comment les abondances d'equilibre des elements supportes reagissent a la redistribution du flux causee par l'addition de ces traces de matiere opaque. Nous traitons ce probleme, en premier lieu, selon une approche basee sur des modeles d'enveloppes et, en second lieu, selon une approche basee sur des modeles d'atmospheres. Nous considerons aussi deux autres ameliorations concernant, premierement, un traitement plus sophistique de la redistribution de la quantite de mouvement d'un ion suite a l'absorption d'un photon, et deuxiemement, l'utilisation d'une meilleure valeur de la largeur du profil de raie associee a l'elargissement par pression. Bien qu'une poignee d'abondances soient disponibles a partir de l'analyse des observations qui ont ete faites jusqu'a maintenant, nous sommes neanmoins capables de conclure, a l'aide de comparaisons detaillees, que la theorie de la levitation radiative a l'equilibre ne reussit pas a expliquer quantitativement les patrons d'abondances des elements lourds observes dans les naines blanches chaudes. Au moins un autre mecanisme doit competionner avec la levitation radiative et le triage gravitationnel dans les atmospheres/enveloppes des naines blanches chaudes. Nous suggerons la possibilite d'un vent stellaire ou encore la possibilite d'accretion.

Mesures experimentales de l'impact des revetements hydrophobeset superhydrophobes sur la trainee et la portance d'un profil aerodynamique propre et glace

NASA Astrophysics Data System (ADS)

Villeneuve, Eric

Ce projet, realise a la demande du Laboratoire International des Materiaux Antigivre, a pour but de mesurer et definir experimentalement l'impact de revetements hydrophobes sur les coefficients de trainee et de portance d'un profil NACA 0012. Pour ce faire, la balance aerodynamique du LIMA devait tout d'abord etre amelioree afin d'offrir une sensibilite suffisante pour realiser le projet. Plusieurs ameliorations ont ete faites, comme le changement des cellules de charge, la diminution du nombre de cellules de charge, le changement du cadre de la balance, etc. Une fois ces ameliorations terminees, la reproductibilite, l'exactitude et la sensibilite ont ete valides afin de s'assurer de la fiabilite des resultats offerts par la balance. Pour les angles d'attaque etudies avec les revetements, soient -6° et 0°, la balance a une reproductibilite de +/-2,06% a 360 000 de nombre de Reynolds. Pour valider la sensibilite, des essais a -6° et 0° d'angle d'attaque et des nombres de Reynolds de 360 000 et 500 000 ont ete faits avec des papiers sables. Les resultats de ces essais ont permis de, tracer des courbes de tendances du coefficient de trainee du NACA 0012 en fonction de la rugosite de surface et d'etablir la valeur de la sensibilite de la balance a +/-8 mu m. Cinq revetements populaires ont ete choisis pour l'experimentation, soient le Wearlon, le Staclean, le Hirec, le Phasebreak ainsi que le Nusil. Les revetements sont soumis aux memes conditions experimentales que les papiers sables, et une rugosite equivalente est trouvee par extrapolation des resultats. Cependant, les rugosites equivalentes de surfaces different entre -6° et 0°. Les essais avec le Staclean et le Hirec donnent des coefficients de trainee equivalent a ceux avec l'aluminium, alors que le Wearlon, le Nusil et le Phasebreak donnent une augmentation du coefficient de trainee de 13%, 17% et 25% respectivement par rapport a l'aluminium. Pour les coefficients de portance, la balance ne detecte pas l'effet des revetements, ni des papiers sables, sur la force de portance ce qui signifie qu'il entre dans l'insensibilite de la balance. La derniere etape experimentale consistait a mesurer l'impact des revetements sur la formation de la glace ainsi que sur l'evolution des coefficients de trainee et de portance du NACA 0012 en fonction de l'accumulation de glace sur celui-ci. Le Wearlon a ete choisi comme revetement en raison de sa grande popularite. Des essais a -5°C et -20°C ont ete faits et les resultats ont montres que le Wearlon n'apporte pas d'effet benefique au NACA 0012 en conditions d'accumulations de glace. L'augmentation du coefficient de trainee du profil muni du Wearlon debutait plus rapidement que sur l'aluminium et de l'eau gelait legerement plus loin vers l'arriere du profil pendant les essais, ce qui n'est pas souhaitable. Le coefficient de trainee est superieur d'environ 13% pour le Wearlon par rapport a l'aluminium pendant toute l'accumulation de glace, ce qui correspond au meme ecart lorsque la glace n'est pas en cause. Pour le coefficient de portance, les resultats ne peuvent etre utilises pour une raison qui doit etre investiguee.

Etude exploratoire des conceptions de la circulation sanguine aupres d'eleves de l'ordre collegial

NASA Astrophysics Data System (ADS)

Robitaille, Jean-Marc

Il existe peu d'etudes sur les conceptions touchant les domaines de la biologie, notamment sur les conceptions de la circulation sanguine Nous avons observe egalement l'absence de recherche menee aupres d'eleves de l'ordre collegial sur cette question. Nous avons voulu combler une lacune en menant une recherche sur les conceptions de la circulation sanguine aupres d'eleves de l'ordre collegial. Pour mener cette recherche nous nous sommes inspires d'une methode developpee par Treagust (1988). Le premier niveau de formulation didactique etablit l'architecture du systeme et la fonction nutritive de la circulation. Le second niveau de formulation didactique decrit et relie les parametres de la dynamique de la circulation et leur relation: Pression, Debit et Resistance. Le troisieme niveau de formulation didactique s'interesse au controle de la circulation du sang dans un contexte d'homeostasie qui implique la regulation de la pression arterielle. Nous avons construit un questionnaire en nous guidant sur les niveaux de formulation didactique et l'analyse des entrevues menees aupres de dix-huit eleves, representatifs de la population cible. Ce questionnaire fut administre a un echantillon de 2300 eleves disperses dans six colleges de la region de Montreal. Notre echantillon comprend des eleves inscrits a des programmes de l'ordre collegial en Sciences de la nature et en Techniques de la sante et qui n'ont pas suivi le cours sur la circulation sanguine. Notre analyse des reponses des eleves de notre echantillon aux questions sur le premier niveau de formulation didactique revele que la majorite des eleves considerent que le systeme circulatoire relie les organes les uns aux autres dans un circuit en serie. Notre analyse revele egalement que la majorite des eleves estiment que les nutriments sont extraits du sang par les organes selon un processus de selection base sur les besoins determines par la fonction de l'organe. Ces besoins sont differents selon les organes qui ne prelevent que les nutriments necessaires. Au second niveau les reponses des eleves de la population indiquent une conception de la dynamique cardio-vasculaire axee d'abord sur le coeur, laissant aux vaisseaux un role passif de canaux. Ces reponses indiquent egalement que la dynamique circulatoire est reduite a une sequence d'etapes ponctuelles sans relation les unes avec les autres. Au troisieme niveau les reponses des eleves de la population font etat d'une conception du controle qui privilegie la satisfaction de besoins locaux, sans relation systemique. Nos resultats suggerent que les eleves de notre echantillon affichent une plus grande concordance avec l'expert pour les questions du premier niveau (70%) que pour les niveaux II (54%) et III (50%). Notre analyse des donnees revele que l'accord avec l'expert est eleve lorsque la questions touchent la description des structures et la definition de leurs roles et plus faible lorsque les questions touchent la dynamique et le controle. Il existerait donc un niveau de formulation qui correspond a la description de structures et un autre niveau qui recoupe toute la dynamique de la circulation et son controle. Du point de vue didactique lanalyse des donnees suggere que nous ne retrouvons pas une correspondance entre les niveaux de formulation didactique et les conceptions des eleves. (Abstract shortened by UMI.)

Canadian Thesis Abstracts: Synthèse spectrale de jeunes populations stellaires dans; l'ultraviolet lointain

NASA Astrophysics Data System (ADS)

Pellerin, Anne

2005-02-01

Le but de cette thèse était de développer et tester la technique de synthè;se spectrale évolutive aux longueurs d'onde de l'ultraviolet lointain. Jusquà récemment, cette technique n'était appliqué quà des données au-delà de 1200 Å. Le lancement du satellite FUSE en 1999 a permis d'explorer le domaine de l'ultraviolet lointain (900-1200 Å) avec une grande résolution spectrale. J'ai donc utilisé les spectres du satellite FUSE de 228 étoiles chaudes de type O et B, de 24 galaxies à sursauts de formation d'étoiles et de quatre galaxies Seyfert. Dans un premier temps, j'ai caractérisé le comportement des profils de raies stellaires en fonction du type spectral, de la classe de luminosité et de la métallicité des étoiles. Les raies O vi >>1031.9, 1037.6, S iv >>1062.7, 1073.0, 1073.5, P v>>1118.0, 1128.0 et C iii >1175.6 ont été identifiées comme étant des indicateurs stellaires potentiellement intéressants pour la synthèse spectrale. Le domaine de longueur d'onde inférieur à 1000 Å couvert par FUSEmontre aussi des signatures stellaires mais qui sont peu intéressantes pour la synthèse en raison de la contamination interstellaire. J'ai ensuite crééé; une bibliothèque de spectres FUSE qui a été intégrée au code de synthèse LavalSBafin de produire des spectres de synthèse dans l'ultraviolet lointain pour diverses populations stellaires théoriques. Il s'est avéré que les raies de P vet de C iii sont d'excellents indicateurs d'âge, de métallicité et de fonction de masse initiale de la population stellaire, tandis que les raies de O vi et de S ivne sont pas aussi efficaces. La comparaison des spectres FUSEde galaxies avec les spectres synthétiques a révèlé des âges entre 2.5 et 18 millions d'années pour un large éventail de métallicités. On trouve aussi une forte dominance du mode instantané de formation stellaire. Ce travail a aussi permis d'estimer quantitativement l'extinction interne et les masses stellaires impliquées dans les sursauts. La synthèse des raies de l'ultraviolet lointain s'est avérée beaucoup plus précise que la synthèse à > 1200 Å en raison de la résolution spectrale exceptionnelle de FUSE et parce que les raies stellaires n'ont pas de profils saturés, même aux métallicités élevées. Les propriétés physiques globales des 24 galaxies à sursauts ont aussi été étudiées dans leur ensemble afin de mieux décrire le phénomène des sursauts de formation stellaires.

Torsion d'annexe au second trimestre de la grossesse, à propos de deux cas

PubMed Central

Ayachi, Amira; Blel, Zeineb; Khelifa, Nahed; Mkaouer, Lassaad; Bouchahda, Rim; Mourali, Mechaal

2016-01-01

Les douleurs pelviennes aigues pendant la grossesse peuvent poser un problème de diagnostic différentiel.Nous rapportons deux cas de torsion d'annexes au deuxième trimestre de la grossesse afin d'attirer l'attention sur ce diagnostic, dont seule une prise en charge précoce permet d'éviter des lésions irréversibles dues à l'ischémie, pouvant mettre en jeu le pronostic ultérieur de fertilité. La première patiente, G1P0, enceinte à 20 SA, s'est présenté initialement pour un syndrome appendiculaire. Une incision de Mac Burney, au cours de l'exploration, a montré un ovaire droit nécrosé et une ovariectomie a été faite. Les suites post opératoires étaient simples. La seconde patiente, G2P2, s'est présenté aux urgences avec des douleurs aigues de la fosse iliaque gauche à 26 SA. La laparotomie a mis en évidence une torsion d'une hydatide de Morgani, dont l'aspect nécrosé dû à une torsion, a orienté vers une ablation de l'hydatide. Pour les deux patientes, aucune complication postopératoire n'a été relevée. La torsion d'annexe est une urgence à ne pas méconnaître devant toute douleur pelvienne aigue chez la femme enceinte. Le traitement conservateur est actuellement le gold standard et une prise en charge appropriée est nécessaire pour éviter d'éventuelles complications maternelles et fœtales. PMID:28292076

Science, Worldviews and Education: An Introduction

NASA Astrophysics Data System (ADS)

Matthews, Michael R.

2009-06-01

This special issue of Science & Education deals with the theme of ‘Science, Worldviews and Education’. The theme is of particular importance at the present time as many national and provincial education authorities are requiring that students learn about the Nature of Science (NOS) as well as learning science content knowledge and process skills. NOS topics are being written into national and provincial curricula. Such NOS matters give rise to questions about science and worldviews: What is a worldview? Does science have a worldview? Are there specific ontological, epistemological and ethical prerequisites for the conduct of science? Does science lack a worldview but nevertheless have implications for worldviews? How can scientific worldviews be reconciled with seemingly discordant religious and cultural worldviews? In addition to this major curricular impetus for refining understanding of science and worldviews, there are also pressing cultural and social forces that give prominence to questions about science, worldviews and education. There is something of an avalanche of popular literature on the subject that teachers and students are variously engaged by. Additionally the modernisation and science-based industrialisation of huge non-Western populations whose traditional religions and beliefs are different from those that have been associated with orthodox science, make very pressing the questions of whether, and how, science is committed to particular worldviews. Hugh Gauch Jr. provides a long and extensive lead essay in the volume, and 12 philosophers, educators, scientists and theologians having read his paper, then engage with the theme. Hopefully the special issue will contribute to a more informed understanding of the relationship between science, worldviews and education, and provide assistance to teachers who are routinely engaged with the subject.

An activation switch in the rhodopsin family of G protein-coupled receptors: the thyrotropin receptor.

PubMed

Urizar, Eneko; Claeysen, Sylvie; Deupí, Xavier; Govaerts, Cedric; Costagliola, Sabine; Vassart, Gilbert; Pardo, Leonardo

2005-04-29

We aimed at understanding molecular events involved in the activation of a member of the G protein-coupled receptor family, the thyrotropin receptor. We have focused on the transmembrane region and in particular on a network of polar interactions between highly conserved residues. Using molecular dynamics simulations and site-directed mutagenesis techniques we have identified residue Asn-7.49, of the NPxxY motif of TM 7, as a molecular switch in the mechanism of thyrotropin receptor (TSHr) activation. Asn-7.49 appears to adopt two different conformations in the inactive and active states. These two states are characterized by specific interactions between this Asn and polar residues in the transmembrane domain. The inactive gauche+ conformation is maintained by interactions with residues Thr-6.43 and Asp-6.44. Mutation of these residues into Ala increases the constitutive activity of the receptor by factors of approximately 14 and approximately 10 relative to wild type TSHr, respectively. Upon receptor activation Asn-7.49 adopts the trans conformation to interact with Asp-2.50 and a putatively charged residue that remains to be identified. In addition, the conserved Leu-2.46 of the (N/S)LxxxD motif also plays a significant role in restraining the receptor in the inactive state because the L2.46A mutation increases constitutive activity by a factor of approximately 13 relative to wild type TSHr. As residues Leu-2.46, Asp-2.50, and Asn-7.49 are strongly conserved, this molecular mechanism of TSHr activation can be extended to other members of the rhodopsin-like family of G protein-coupled receptors.

Adsorption of normal pentane on the surface of rutile. Experimental results and simulations.

PubMed

Rakhmatkariev, G U; Carvalho, A J Palace; Ramalho, J P Prates

2007-07-03

Adsorption isotherms and differential heats of normal pentane adsorption on microcrystalline rutile were measured at 303 K. The heat of adsorption of n-pentane on rutile at zero occupancy is 64 kJ/mol. The differential heats have three descending segments, corresponding to the adsorption of n-pentane on three types of surfaces. At low coverage (first segment), the adsorption is restricted to the rows A of the (110) faces along the 5-fold coordinatively unsaturated (cus) Ti(4+) ions with differential heat showing a linear decrease with increasing occupancy. The second segment is attributed to bonding with atoms of the rows along the remaining faces exposed, (101) and (100). The third segment is related to a multilayer adsorption. The mean molar adsorption entropy of n-pentane is ca. -25 J/mol K less than the entropy of the bulk liquid, thus revealing a hindered state of motion of the n-pentane molecules on the surface of rutile. Simulations of the adsorption of n-pentane on the three most abundant crystallographic faces of rutile were also performed. The adsorption isotherm obtained from the combination of each face's isotherm weighted by the respective abundance was found to be in a good agreement with the experimental data. A structural characterization of n-pentane near the surface was also conducted, and it was found that the substrate, especially for the (110) face, strongly perturbs the distribution of n-pentane conformations, compared to those found for the gas phase. Adsorbed molecules are predominantly oriented with their long axes and their backbone zigzag planes parallel to the surface and are also characterized by fewer gauche conformations than observed in the bulk phase.

Novel Cu(I)-selective chelators based on a bis(phosphorothioyl)amide scaffold.

PubMed

Amir, Aviran; Ezra, Alon; Shimon, Linda J W; Fischer, Bilha

2014-08-04

Bis(dialkyl/aryl-phosphorothioyl)amide (BPA) derivatives are versatile ligands known by their high metal-ion affinity and selectivity. Here, we synthesized related chelators based on bis(1,3,2-dithia/dioxaphospholane-2-sulfide)amide (BTPA/BOPA) scaffolds targeting the chelation of soft metal ions. Crystal structures of BTPA compounds 6 (N(-)R3NH(+)) and 8 (NEt) revealed a gauche geometry, while BOPA compound 7 (N(-)R3NH(+)) exhibited an anti-geometry. Solid-state (31)P magic-angle spinning NMR spectra of BTPA 6-Hg(II) and 6-Zn(II) complexes imply a square planar or tetrahedral geometry of the former and a distorted tetrahedral geometry of the latter, while both BTPA 6-Ni(II) and BOPA 7-Ni(II) complexes possibly form a polymeric structure. In Cu(I)-H2O2 system (Fenton reaction conditions) BTPA compounds 6, 8, and 10 (NCH2Ph) were identified as most potent antioxidants (IC50 32, 56, and 29 μM, respectively), whereas BOPA analogues 7, 9 (NEt), and 11 (NCH2Ph) were found to be poor antioxidants. In Fe(II)-H2O2 system, IC50 values for both BTPA and BOPA compounds exceeded 500 μM indicating high selectivity to Cu(I) versus the borderline Fe(II)-ion. Neither BTPA nor BOPA derivatives showed radical scavenging properties in H2O2 photolysis, implying that inhibition of the Cu(I)-induced Fenton reaction by both BTPA and BOPA analogues occurred predominantly through Cu(I)-chelation. In addition, NMR-monitored Cu(I)- and Zn(II)-titration of BTPA compounds 8 and 10 showed their high selectivity to a soft metal ion, Cu(I), as compared to a borderline metal ion, Zn(II). In summary, lipophilic BTPA analogues are promising highly selective Cu(I) ion chelators.

Group 13 ligand supported heavy-metal complexes: first structural evidence for gallium-lead and gallium-mercury bonds.

PubMed

Prabusankar, Ganesan; Gemel, Christian; Winter, Manuela; Seidel, Rüdiger W; Fischer, Roland A

2010-05-25

Heavy-metal complexes of lead and mercury stabilized by Group 13 ligands were derived from the oxidative addition of Ga(ddp) (ddp=HC(CMeNC(6)H(3)-2,6-iPr(2))(2), 2-diisopropylphenylamino-4-diisopropyl phenylimino-2-pentene) with corresponding metal precursors. The reaction of Me(3)PbCl and Ga(ddp) afforded compound [{(ddp)Ga(Cl)}PbMe(3)] (1) composed of Ga-Pb(IV) bonds. In addition, the monomeric plumbylene-type compound [{(ddp)Ga(OSO(2)CF(3))}(2)Pb(thf)] (2a) with an unsupported Ga-Pb(II)-Ga linkage was obtained by the reaction of [Pb(OSO(2)CF(3))(3)] with Ga(ddp) (2 equiv). Compound 2a falls under the rare example of a discrete plumbylene-type compound supported by a nonclassical ligand. Interesting structural changes were observed when [Pb(OSO(2)CF(3))(3)]2.H(2)O was treated with Ga(ddp) in a 1:2 ratio to yield [{(ddp)Ga(mu-OSO(2)CF(3))}(2)(OH(2))Pb] (2b) at below -10 degrees C. Compound 2b consists of a bent Ga-Pb-Ga backbone with a bridging triflate group between the Ga-Pb bond and a weakly interacting water molecule at the gallium center. Similarly, the reaction of mercury thiolate Hg(SC(6)F(5)) with Ga(ddp) (2 equiv) produced the bimetallic homoleptic compounds anti-[{(ddp)Ga(SC(6)F(5))}(2)Hg] (3a) and gauche-[{(ddp)Ga(SC(6)F(5))}(2)Hg] (3b), respectively, with a linear Ga-Hg-Ga linkage. Compounds 1-3 were structurally characterized and these are the first examples of compounds comprised of Ga-Pb(II), Ga-Pb(IV), and Ga-Hg bonds.

Propargyl + O 2 Reaction in Helium Droplets: Entrance Channel Barrier or Not?

DOE PAGES

Moradi, Christopher P.; Morrison, Alexander M.; Klippenstein, Stephen J.; ...

2013-09-09

A combination of liquid He droplet experiments and multireference electronic structure calculations is used to probe the potential energy surface for the reaction between the propargyl radical and O 2. Infrared laser spectroscopy is used to probe the outcome of the low temperature, liquid He-mediated reaction. Bands in the spectrum are assigned to the acetylenic CH stretch (ν 1), the symmetric CH 2 stretch (ν 2), and the antisymmetric CH 2 stretch (ν 13) of the trans-acetylenic propargyl peroxy radical (•OO—CH 2—C≡CH). The observed band origins are in excellent agreement with previously reported anharmonic frequency computations for this species. Themore » Stark spectrum of the ν 1 band provides further evidence that the reaction leads only to the trans-acetylenic species. There are no other bands in the CH 2 stretching region that can be attributed to any of the other three propargyl peroxy isomers/conformers that are predicted to be minimum energy structures ( gauche-acetylenic, cis-allenic, and trans-allenic). There is also no evidence for the kinetic stabilization of a van der Waals complex between propargyl and O 2. A combination of multireference and coupled-cluster electronic structure calculations is used to probe the potential energy surface in the neighborhood of the transition state connecting reactants with the acetylenic adduct. The multireference based evaluation of the doublet-quartet splitting added to the coupled-cluster calculated quartet state energies yields what are likely the most accurate predictions for the doublet potential curve. As a result, this calculation suggests that there is no saddle point for the addition process, in agreement with the experimental observations. Other calculations suggest the possible presence of a small submerged barrier.« less

Standardissimo. Les limitations théoriques du Modèle Standard. Quelles réponses y apporter?

NASA Astrophysics Data System (ADS)

Renard, F. M.

Nous présentons I 'état du Modèle Standard des interactions fortes, faibles et électromagnétiques. Après une description rapide de ses 3 secteurs, secteur de jauge (radiation), secteur fermionique (matière) et secteur scalaire (génération des masses), nous insistons sur le grand nombre de paramètres libres et sur les choix arbitraires qu'il a fallu faire dans l'élaboration du modèle. Nous faisons ressortir les problèmes techniques non résolus et nous dressons la liste des questions fondamentales restées sans réponses. Nous passons ensuite en revue les idées et méthodes proposées pour répondre à ces questions. Elles utilisent essentiellement 3 voies différentes. La première consiste à requérir plus de symétrie (extension du modèle, symétrie Gauche-Droite, Grandes Unifications, Supersymétrie,...). La seconde contient les diverses alternatives au Modèle Standard impliquant des modifications dans certains secteurs (par exemple le secteur scalaire avec le modèle de la Technicouleur) ou de façon plus violente l'hypothèse d'une sous-structure des leptons, des quarks et des bosons W et Z eux-mêmes. Une dernière voie cherche à justifier les particularités du Modèle Standard et relier ses paramètres libres en se basant sur des principes de cohérence interne du modèle. Les conséquences observables de ces diverses approches sont dans chaque cas mentionnées.

Conformation analysis and molecular mobility of ethylene and tetrafluoroethylene copolymer using solid-state 19F MAS and 1H --> 19F CP/MAS NMR spectroscopy.

PubMed

Aimi, Keitaro; Ando, Shinji

2004-07-01

The changes in the conformation and molecular mobility accompanied by a phase transition in the crystalline domain were analyzed for ethylene (E) and tetrafluoroethylene (TFE) copolymer, ETFE, using variable-temperature (VT) solid-state 19F magic angle spinning (MAS) and 1H --> 19F cross-polarization (CP)/MAS NMR spectroscopy. The shifts of the signals for fluorines in TFE units to higher frequency and the continuing decrease and increase in the T1rho(F) values suggest that conformational exchange motions exist in the crystalline domain between 42 and 145 degrees C. Quantum chemical calculations of magnetic shielding constants showed that the high-frequency shift of TFE units should be induced by trans to gauche conformational changes at the CH2-CF2 linkage in the E-TFE unit. Although the 19F signals of the crystalline domain are substantially overlapped with those of the amorphous domain at ambient probe temperature (68 degrees C), they were successfully distinguished by using the dipolar filter and spin-lock pulse sequences at 145 degrees C. The dipolar coupling constants for the crystalline domain, which can be estimated by fitting the dipolar oscillation behaviors in the 1H --> 19F CP curve, showed a significant decrease with increasing temperature from 42 to 145 degrees C. This is due to the averaging of 1H-19F dipolar interactions originating from the molecular motion in the crystalline domain. The increase in molecular mobility in the crystalline domain was clearly shown by VT T1rho(F) and 1H --> 19F CP measurements in the phase transition temperature range. Copyright 2004 John Wiley & Sons, Ltd.

Properties of Self-Assembled Monolayers Revealed via Inverse Tensiometry.

PubMed

Chen, Jiahao; Wang, Zhengjia; Oyola-Reynoso, Stephanie; Thuo, Martin M

2017-11-28

Self-assembled monolayers (SAMs) have emerged as a simple platform technology and hence have been broadly studied. With advances in state-of-the-art fabrication and characterization methods, new insights into SAM structure and related properties have been delineated, albeit with some discrepancies and/or incoherencies. Some discrepancies, especially between experimental and theoretical work, are in part due to the misunderstanding of subtle structural features such as phase evolution and SAM quality. Recent work has, however, shown that simple techniques, such as the measurement of static contact angles, can be used to delineate otherwise complex properties of the SAM, especially when complemented by other more advanced techniques. In this article, we highlight the effect of nanoscale substrate asperities and molecular chain length on the SAM structure and associated properties. First, surfaces with tunable roughness are prepared on both Au and Ag, and their corresponding n-alkanethiolate SAMs are characterized through wetting and spectroscopy. From these data, chain-length- and substrate-morphology-dependent limits to the odd-even effect (structure and properties vary with the number of carbons in the molecules and the nature of the substrate), parametrization of gauche defect densities, and structural phase evolution (liquidlike, waxy, crystalline interfaces) are deduced. An evaluation of the correlation between the effect of roughness and the components of surface tension (polar-γ p and dispersive-γ d ) reveals that wetting, at nanoscale rough surfaces, evolves proportionally with the ratio of the two components of surface tension. The evolution of conformational order is captured over a range of molecular lengths and parametrized through a dimensionless number, χ c . By deploying a well-known tensiometry technique (herein the liquid is used to characterize the solid, hence the term inverse tensiometry) to characterize SAMs, we demonstrate that complex molecular-level phenomena in SAMs can be understood through simplicity.

Rotational Spectroscopy of 4-HYDROXY-2-BUTYNENITRILE

NASA Astrophysics Data System (ADS)

Motiyenko, R. A.; Margulès, L.; Guillemin, J.-C.

2015-06-01

Recently we studied the rotational spectrum of hydroxyacetonitrile (HOCH_2CN, HAN) in order to provide a firm basis for its possible detection in the interstellar medium Different plausible pathways of the formation of HAN in the interstellar conditions were proposed; however, up to now, the searches for this molecule were unsuccessful. To continue the study of nitriles that represent an astrophysical interest we present in this talk the analysis of the rotational spectrum of 4-hydroxy-2-butynenitrile (HOCH_2CC-CN, HBN), the next molecule in the series of hydroxymethyl nitriles. Using the Lille spectrometer the spectrum of HBN was measured in the frequency range 50 -- 500 GHz. From the spectroscopic point of view HBN molecule is rather similar to HAN, because of -OH group tunnelling in gauche conformation. As it was previously observed for HAN, due to this large amplitude motion, the splittings in the rotational spectra of HBN are easily resolved making the spectral analysis more difficult. Additional difficulties arise from the near symmetric top character of HBN (κ = -0.996), and very dense spectrum because of relatively small values of rotational constants and a number of low-lying excited vibrational states. The analysis carried out in the frame of reduced axis system approach of Pickett allows to fit within experimental accuracy all the rotational transitions in the ground vibrational state. Thus, the results of the present study provide a reliable catalog of frequency predictions for HBN. The support of the Action sur Projets de l'INSU PCMI, and ANR-13-BS05-0008-02 IMOLABS is gratefully acknowledged Margulès L., Motiyenko R.A., Guillemin J.-C. 68th ISMS, 2013, TI12. Danger G. et al. Phys. Chem. Chem. Phys. 2014, 16, 3360. Pickett H.M. J. Chem. Phys. 1972, 56, 1715.

Chemically Realistic Tetrahedral Lattice Models for Polymer Chains: Application to Polyethylene Oxide.

PubMed

Dietschreit, Johannes C B; Diestler, Dennis J; Knapp, Ernst W

2016-05-10

To speed up the generation of an ensemble of poly(ethylene oxide) (PEO) polymer chains in solution, a tetrahedral lattice model possessing the appropriate bond angles is used. The distance between noncovalently bonded atoms is maintained at realistic values by generating chains with an enhanced degree of self-avoidance by a very efficient Monte Carlo (MC) algorithm. Potential energy parameters characterizing this lattice model are adjusted so as to mimic realistic PEO polymer chains in water simulated by molecular dynamics (MD), which serves as a benchmark. The MD data show that PEO chains have a fractal dimension of about two, in contrast to self-avoiding walk lattice models, which exhibit the fractal dimension of 1.7. The potential energy accounts for a mild hydrophobic effect (HYEF) of PEO and for a proper setting of the distribution between trans and gauche conformers. The potential energy parameters are determined by matching the Flory radius, the radius of gyration, and the fraction of trans torsion angles in the chain. A gratifying result is the excellent agreement of the pair distribution function and the angular correlation for the lattice model with the benchmark distribution. The lattice model allows for the precise computation of the torsional entropy of the chain. The generation of polymer conformations of the adjusted lattice model is at least 2 orders of magnitude more efficient than MD simulations of the PEO chain in explicit water. This method of generating chain conformations on a tetrahedral lattice can also be applied to other types of polymers with appropriate adjustment of the potential energy function. The efficient MC algorithm for generating chain conformations on a tetrahedral lattice is available for download at https://github.com/Roulattice/Roulattice .

Molecular dynamics simulation study of solvent effects on conformation and dynamics of polyethylene oxide and polypropylene oxide chains in water and in common organic solvents.

PubMed

Hezaveh, Samira; Samanta, Susruta; Milano, Giuseppe; Roccatano, Danilo

2012-03-28

In this paper, the conformation and dynamics properties of polyethylene oxide (PEO) and polypropylene oxide (PPO) polymer chains at 298 K have been studied in the melt and at infinite dilution condition in water, methanol, chloroform, carbon tetrachloride, and n-heptane using molecular dynamics simulations. The calculated density of PEO melt with chain lengths of n = 2, 3, 4, 5 and, for PPO, n = 7 are in good agreement with the available experimental data. The conformational properties of PEO and PPO show an increasing gauche preference for the O-C-C-O dihedral in the following order water>methanol>chloroform>carbon tetrachloride = n-heptane. On the contrary, the preference for trans conformation has a maximum in carbon tetrachloride and n-heptane followed in the order by chloroform, methanol, and water. The PEO conformational preferences are in qualitative agreement with results of NMR studies. PEO chains formed different types of hydrogen bonds with polar solvent molecules. In particular, the occurrence of bifurcated hydrogen bonding in chloroform was also observed. Radii of gyration of PEO chains of length larger than n = 9 monomers showed a good agreement with light scattering data in water and in methanol. For the shorter chains the observed deviations are probably due to the enhanced hydrophobic effects caused by the terminal methyl groups. For PEO the fitting of end-to-end distance distributions with the semi-flexible chain model at 298 K provided persistence lengths of 0.375 and 0.387 nm in water and methanol, respectively. Finally, the radius of gyration of Pluronic P85 turned out to be 2.25 ± 0.4 nm at 293 K in water in agreement with experimental data.

Molecular dynamics simulation study of solvent effects on conformation and dynamics of polyethylene oxide and polypropylene oxide chains in water and in common organic solvents

NASA Astrophysics Data System (ADS)

Hezaveh, Samira; Samanta, Susruta; Milano, Giuseppe; Roccatano, Danilo

2012-03-01

In this paper, the conformation and dynamics properties of polyethylene oxide (PEO) and polypropylene oxide (PPO) polymer chains at 298 K have been studied in the melt and at infinite dilution condition in water, methanol, chloroform, carbon tetrachloride, and n-heptane using molecular dynamics simulations. The calculated density of PEO melt with chain lengths of n = 2, 3, 4, 5 and, for PPO, n = 7 are in good agreement with the available experimental data. The conformational properties of PEO and PPO show an increasing gauche preference for the O-C-C-O dihedral in the following order water>methanol>chloroform>carbon tetrachloride = n-heptane. On the contrary, the preference for trans conformation has a maximum in carbon tetrachloride and n-heptane followed in the order by chloroform, methanol, and water. The PEO conformational preferences are in qualitative agreement with results of NMR studies. PEO chains formed different types of hydrogen bonds with polar solvent molecules. In particular, the occurrence of bifurcated hydrogen bonding in chloroform was also observed. Radii of gyration of PEO chains of length larger than n = 9 monomers showed a good agreement with light scattering data in water and in methanol. For the shorter chains the observed deviations are probably due to the enhanced hydrophobic effects caused by the terminal methyl groups. For PEO the fitting of end-to-end distance distributions with the semi-flexible chain model at 298 K provided persistence lengths of 0.375 and 0.387 nm in water and methanol, respectively. Finally, the radius of gyration of Pluronic P85 turned out to be 2.25 ± 0.4 nm at 293 K in water in agreement with experimental data.

Mimicking the properties of antifreeze glycoproteins: synthesis and characterization of a model system for ice nucleation and antifreeze studies.

PubMed

Hederos, Markus; Konradsson, Peter; Borgh, Annika; Liedberg, Bo

2005-08-25

Synthesis of beta-D-Gal-(1 --> 3)-beta-D-GalNAc coupled to HOC2H4NHCOC15H30SH is described. This compound was coadsorbed at various proportions with C2H5OC2H4NHCOC15H30SH to form statistically mixed self-assembled monolayers (SAMs) on gold in an attempt to mimic the properties of the active domain in antifreeze glycoproteins (AFGPs). The monolayers were characterized by null ellipsometry, contact angle goniometry, X-ray photoelectron spectroscopy, and infrared reflection-absorption spectroscopy. The disaccharide compound adsorbed preferentially, and SAMs prepared at a solution molar ratio >0.3 displayed total wetting. The mixed SAMs showed well-organized alkyl chains up to a disaccharide surface fraction of 0.8. The amount of gauche conformers in the alkyls increased rapidly above this point, and the monolayers became disordered and less densely packed. Furthermore, the generated mixed SAMs were subjected to water vapor at constant relative humidity and the subsequent ice crystallization on a cooled substrate was monitored via an optical microscope. Interestingly, rapid crystallization occurred within a narrow range of temperatures on mixed SAMs with a high disaccharide content, surface fraction >0.3. The reported crystallization temperatures and the ice layer topography were compared with results obtained for a much simpler reference system composed of -OH/-CH3 terminated n-alkanethiols in order to account for changes in topography of the water/ice layer with surface energy. Although preliminary, the obtained results can be useful in the search for the molecular mechanism behind the antifreeze activity of AFGPs.

Eicosapentaenoic acid and docosahexaenoic acid have distinct membrane locations and lipid interactions as determined by X-ray diffraction.

PubMed

Sherratt, Samuel C R; Mason, R Preston

2018-01-31

Eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) differentially influence lipid oxidation, signal transduction, fluidity, and cholesterol domain formation, potentially due in part to distinct membrane interactions. We used small angle X-ray diffraction to evaluate the EPA and DHA effects on membrane structure. Membrane vesicles composed of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) and cholesterol (C) (0.3C:POPC mole ratio) were prepared and treated with vehicle, EPA, or DHA (1:10 mol ratio to POPC). Electron density profiles generated from the diffraction data showed that EPA increased membrane hydrocarbon core electron density over a broad area, up to ± 20 Å from the membrane center, indicating an energetically favorable extended orientation for EPA likely stabilized by van der Waals interactions. By contrast, DHA increased electron density in the phospholipid head group region starting at ± 12 Å from the membrane center, presumably due to DHA-surface interactions, with coincident reduction in electron density in the membrane hydrocarbon core centered ± 7-9 Å from the membrane center. The membrane width (d-space) decreased by 5 Å in the presence of vehicle as the temperature increased from 10 °C to 30 °C due to increased acyl chain trans-gauche isomerizations, which was unaffected by addition of EPA or DHA. The influence of DHA on membrane structure was modulated by temperature changes while the interactions of EPA were unaffected. The contrasting EPA and DHA effects on membrane structure indicate distinct molecular locations and orientations that may contribute to observed differences in biological activity. Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.

First-principle simulations of electronic structure in semicrystalline polyethylene

NASA Astrophysics Data System (ADS)

Moyassari, A.; Unge, M.; Hedenqvist, M. S.; Gedde, U. W.; Nilsson, F.

2017-05-01

In order to increase our fundamental knowledge about high-voltage cable insulation materials, realistic polyethylene (PE) structures, generated with a novel molecular modeling strategy, have been analyzed using first principle electronic structure simulations. The PE structures were constructed by first generating atomistic PE configurations with an off-lattice Monte Carlo method and then equilibrating the structures at the desired temperature and pressure using molecular dynamics simulations. Semicrystalline, fully crystalline and fully amorphous PE, in some cases including crosslinks and short-chain branches, were analyzed. The modeled PE had a structure in agreement with established experimental data. Linear-scaling density functional theory (LS-DFT) was used to examine the electronic structure (e.g., spatial distribution of molecular orbitals, bandgaps and mobility edges) on all the materials, whereas conventional DFT was used to validate the LS-DFT results on small systems. When hybrid functionals were used, the simulated bandgaps were close to the experimental values. The localization of valence and conduction band states was demonstrated. The localized states in the conduction band were primarily found in the free volume (result of gauche conformations) present in the amorphous regions. For branched and crosslinked structures, the localized electronic states closest to the valence band edge were positioned at branches and crosslinks, respectively. At 0 K, the activation energy for transport was lower for holes than for electrons. However, at room temperature, the effective activation energy was very low (˜0.1 eV) for both holes and electrons, which indicates that the mobility will be relatively high even below the mobility edges and suggests that charge carriers can be hot carriers above the mobility edges in the presence of a high electrical field.

Franz Joseph Gall and music: the faculty and the bump.

PubMed

Eling, Paul; Finger, Stanley; Whitaker, Harry

2015-01-01

The traditional story maintains that Franz Joseph Gall's (1758-1828) scientific program began with his observations of schoolmates with bulging eyes and good verbal memories. But his search to understand human nature, in particular individual differences in capacities, passions, and tendencies, can also be traced to other important observations, one being of a young girl with an exceptional talent for music. Rejecting contemporary notions of cognition, Gall concluded that behavior results from the interaction of a limited set of basic faculties, each with its own processes for perception and memory, each with its own territory in both cerebral or cerebellar cortices. Gall identified 27 faculties, one being the sense of tone relations or music. The description of the latter is identical in both his Anatomie et Physiologie and Sur les Fonctions du Cerveau et sur Celles de Chacune de ses Parties, where he provided positive and negative evidences and discussed findings from humans and lower animals, for the faculty. The localization of the cortical faculty for talented musicians, he explained, is demonstrated by a "bump" on each side of the skull just above the angle of the eye; hence, the lower forehead of musicians is broader or squarer than in other individuals. Additionally, differences between singing and nonsinging birds also correlate with cranial features. Gall even brought age, racial, and national differences into the picture. What he wrote about music reveals much about his science and creative thinking. © 2015 Elsevier B.V. All rights reserved.

Caractérisation aérodynamique d'un rotor éolien en site naturel

NASA Astrophysics Data System (ADS)

Fabre, B.; Coudeville, H.

1991-03-01

The C_p/V_s curve (aerodynamic power coefficient versus tip-speed ratio) may be obtained in the field, therefore with different windspeeds, and to varying rotor speed, whithout selection of measures by steady state criterion. Experimentation is made on a small windmill with a straight blades Darrieus turbine and an eddy current converter. It allows us to display the conditions for a satisfying characterisation. So, the histogram of tip-speed ratio's instantaneous values must be as flat as it is possible, this on both sides of the tip-speed ratio's value for which the power coefficient is maximum. La courbe du coefficient de puissance aérodynamique (C_p) en fonction de la vitesse spécifique (V_s) peut être obtenue en champ libre, à vitesse de rotation variable et sans sélection des mesures par des critères de stabilité. L'expérimentation sur un système éolien composé d'un rotor Darrieus à pales droites associé à un convertisseur mécano-thermique nous a permis de mettre en évidence les conditions d'une caractérisation correcte. Notamment, l'histogramme des valeurs instantanées, acquises et traitées, de la vitesse spécifique doit être le plus plat possibie sur une large zone de part et d'autre de la valeur donnant le coefficient de puissance maximal.

"The Electric City": Sherbrooke et son paysage hydroelectrique (1880--1930)

NASA Astrophysics Data System (ADS)

Guillemette, Remi

Ce memoire presente l'imbrication des elements hydroelectrique au sein du paysage de la ville de Sherbrooke entre 1880 et 1930. Nous cherchons a comprendre comment les nouveaux elements energetiques s'integrent a celui-ci et comment la population sherbrookoise se represente ces espaces transformes. Comment le paysage hydroelectrique, en tant qu'espace vu et vecu, interagit-il avec la societe sherbrookoise ? A l'interieur de cette problematique generale, nous chercherons a repondre a trois sous-questions. Quelles sont les transformations physiques et materielles engendrees par l'implantation de cette nouvelle technologie hydroelectrique sur le paysage urbain sherbrookois ? Qu'est-ce que les differents groupes valorisent au sein du paysage ? Quel sens prennent ces nouveaux paysages pour les Sherbrookois ? En effet, l'etude du developpement rapide du potentiel hydroelectrique de la riviere Magog nous amene a demontrer que l'exploitation des ressources energetiques a profondement transforme le paysage de Sherbrooke : vastes modifications du trace des cours d'eau, apparition de batiments specifiques a la production energetique, structures de distributions et infrastructures permettant l'illumination de la ville. Nous avancons aussi que differents groupes d'individus ne valorisent pas les memes elements paysagers. Finalement, nous proposons que le regard porte par les citoyens sur le paysage energetique est tributaire de l'usage qu'ils en font. Comme la fonction des elements energetiques paysagers evolue, le regard qu' ils portent vers ces structures se transforme lui aussi. Mots cles: histoire de Sherbrooke, paysage, hydroelectricite, electricite, transformation de l'espace, histoire environnementale

Les métamatériaux, des micro-ondes à l'optique : théorie et applications

NASA Astrophysics Data System (ADS)

Kante, B.

2010-04-01

Cet article constitue une contribution originale et importante à la compréhension à la fois théorique et expérimentale des métamatériaux en micro-ondes et en infrarouge. Nous avons réalisé et caractérisé sur silicium des nano-structures metallo-diélectriques, briques de base des métamatériaux infrarouge et optique. Des caractérisations optiques exhaustives ont été réalisées pour la première fois sur ces structures en amplitude et en phase par interférométrie. Des topologies plus simples de métamatériaux d’un point de vue technologique et des performances optiques ont été introduites, et leur potentiel démontré dans la réalisation de fonctions aussi complexes que la réfraction négative, le couplage de mode plasmoniques, les nano senseurs pour la biologie et l’invisibilité électromagnétique en infrarouge. Les transformations d’espace, et le nouveau paradigme qu’elles offrent à l’optique, rendant possible une ingénierie de l’espace pour les photons ainsi que leur implémentation par métamatériaux ont été présentés par la première démonstration expérimentale d’une cape d’invisibilité non magnétique.

Antioxidant effect of naturally occurring xanthines on the oxidative damage of DNA bases

NASA Astrophysics Data System (ADS)

Vieira, A. J. S. C.; Telo, J. P.; Pereira, H. F.; Patrocínio, P. F.; Dias, R. M. B.

1999-01-01

The repair of the oxidised radicals of adenine and guanosine by several naturally occurring xanthines was studied. Each pair of DNA purine/xanthine was made to react with the sulphate radical and the decrease of the concentration of both compounds was measured by HPLC as a function of irradiation time. The results show that xanthine efficiently prevents the oxidation of the two DNA purines. Theophyline and paraxanthine repair the oxidised radical of adenine but not the one from guanosine. Theobromine and caffeine do not show any protecting effect. An order of the oxidation potentials of all the purines studied is proposed. La réparation des radicaux oxydés de l'adénine et de la guanosine par des xanthines naturelles a été étudiée en soumettant chaque paire base de l'ADN/xanthine à l'oxydation par le radical sulfate et en mesurant par HPLC la disparition des deux composés en fonction du temps d'irradiation. Les résultats montrent que la xanthine joue un rôle protecteur efficace contre l'oxydation des deux purines de l'ADN. La théophyline et la paraxanthine réparent le radical oxydé de l'adénine mais pas celui de la guanosine. La théobromine et la cafeíne n'ont pas d'effet protecteur. Un ordre de potentiels d'oxydation des purines étudiées est proposé.

Dust Evolution in Low-Metallicity Environments: Bridging the Gap Between Local Universe and Primordial Galaxies

NASA Astrophysics Data System (ADS)

Galliano, Frederic; Barlow, Mike; Bendo, George; Boselli, Alessandro; Buat, Veronique; Chanial, Pierre; Clements, David; Davies, Jon; Eales, Steve; Gomez, Haley; Isaak, Kate; Madden, Suzanne; Page, Mathew; Perez Fournon, Ismael; Sauvage, Marc; Spinoglio, Luigi; Vaccari, Mattia; Wilson, Christine

2008-03-01

The local galaxy Science Advisory Group (SAG 2) in the Herschel/SPIRE consortium, has constructed a Guaranteed Time Key Program using the PACS and SPIRE insruments to obtain 60 to 550 micron photometry of a statistically significant sample of 51 dwarf galaxies in our local universe chosen to cover an impressivly broad range of physical conditions. Here we propose the necessary complementary IRAC, MIPS and IRS Spitzer observations which together with the Herschel GT database will provide a rich database to the community to perform the dust and gas analyses in unprecedented detail in low metallicity galaxies ranging between 1/50 to 1 solar metallicity. Due to their chemical youth, and to the extreme conditions they experience, low metallicity environments constitute a keystone to understand dust evolution. The primary goal of this combined Herschel and Spitzer project is to study in details the physical processes at play within the ISM of these galaxies. We will take advantage of the powerful combination of Spitzer, Herschel and ancillary data to decompose the SED into the emission coming from the main phases of the ISM. Such a decomposition will provide reliable estimate of the abundances of the principal dust species, as a fonction of metallicity and physical conditions. These results will be exploited to compare the various evolutionary processes affecting the dust content of galaxies. All these outstanding scientific advances will be the true legacy value that this project brings to the community.

Estimating continuous floodplain and major river bed topography mixing ordinal coutour lines and topographic points

NASA Astrophysics Data System (ADS)

Bailly, J. S.; Dartevelle, M.; Delenne, C.; Rousseau, A.

2017-12-01

Floodplain and major river bed topography govern many river biophysical processes during floods. Despite the grow of direct topographic measurements from LiDARS on riverine systems, it still room to develop methods for large (e.g. deltas) or very local (e.g. ponds) riverine systems that take advantage of information coming from simple SAR or optical image processing on floodplain, resulting from waterbodies delineation during flood up or down, and producing ordered coutour lines. The next challenge is thus to exploit such data in order to estimate continuous topography on the floodplain combining heterogeneous data: a topographic points dataset and a located but unknown and ordered contourline dataset. This article is comparing two methods designed to estimate continuous topography on the floodplain mixing ordinal coutour lines and continuous topographic points. For both methods a first estimation step is to value each contourline with elevation and a second step is next to estimate the continuous field from both topographic points and valued contourlines. The first proposed method is a stochastic method starting from multigaussian random-fields and conditional simualtion. The second is a deterministic method based on radial spline fonction for thin layers used for approximated bivariate surface construction. Results are first shown and discussed from a set of synoptic case studies presenting various topographic points density and topographic smoothness. Next, results are shown and discuss on an actual case study in the Montagua laguna, located in the north of Valparaiso, Chile.

Appareillage automatisé de mesure simultanée du pouvoir thermoélectrique et de la conductivité électrique. Application à l'étude de couches polymères semi-conductrices

NASA Astrophysics Data System (ADS)

Moliton, A.; Ratier, B.; Moreau, C.; Froyer, G.

1991-05-01

In this paper, we present an automatized system for simultaneous measurement of conductivity σ, and thermoelectric power S : measurements are allowed for temperatures ranging from 130 K to 360 K on brittle semiconductor layers. As an example of the application, results obtained in the case of polymer (PPP) layers implanted with Na ions are presented : with high energy implantation (E = 250 keV) we observe only a defect semiconduction of p type while at low energy (30 keV) an electronic n type conduction appears. Nous présentons dans cet article un système de mesure simultanée de la conductivité σ, et du pouvoir thermoélectrique S : il permet des mesures en fonction de la température (entre 130 K et 360 K) dans le cas de couches semi-conductrices relativement fragiles. A titre d'application, nous indiquons les résultats que nous avons obtenus dans le cas de couches polymères (PPP) implantées avec des ions sodium: alors que seule une semi-conduction par défaut est générée par de fortes énergies d'implantation (E = 250 keV ), il apparaît une semiconduction induite par le dopage n lors d'implantations à basse énergie (E = 30 keV ).

Estimating continuous floodplain and major river bed topography mixing ordinal coutour lines and topographic points

NASA Astrophysics Data System (ADS)

Brown, T. G.; Lespez, L.; Sear, D. A.; Houben, P.; Klimek, K.

2016-12-01

Floodplain and major river bed topography govern many river biophysical processes during floods. Despite the grow of direct topographic measurements from LiDARS on riverine systems, it still room to develop methods for large (e.g. deltas) or very local (e.g. ponds) riverine systems that take advantage of information coming from simple SAR or optical image processing on floodplain, resulting from waterbodies delineation during flood up or down, and producing ordered coutour lines. The next challenge is thus to exploit such data in order to estimate continuous topography on the floodplain combining heterogeneous data: a topographic points dataset and a located but unknown and ordered contourline dataset. This article is comparing two methods designed to estimate continuous topography on the floodplain mixing ordinal coutour lines and continuous topographic points. For both methods a first estimation step is to value each contourline with elevation and a second step is next to estimate the continuous field from both topographic points and valued contourlines. The first proposed method is a stochastic method starting from multigaussian random-fields and conditional simualtion. The second is a deterministic method based on radial spline fonction for thin layers used for approximated bivariate surface construction. Results are first shown and discussed from a set of synoptic case studies presenting various topographic points density and topographic smoothness. Next, results are shown and discuss on an actual case study in the Montagua laguna, located in the north of Valparaiso, Chile.

l en configuration dite de "Bridgman verticale" avec un tirage vers le haut. Pour des valeurs élevées du nombre de Rayleigh solutal, nous suivons les diverses branches de solutions stationnaires jusqu'aux seuils d'apparition des phénomènes instationnaires. Ces transitions à l'instationnarité sont étudiées en fonction du confinement et, le long de ces nouvelles branches de solution, nous estimons l'ordre de grandeur de la fluctuation temporelle de la composition à l'interface. Cette dernière étant responsable d'une striation qui est incorporée par le solide lors de sa croissance, nous caractérisons ce phénomène en termes d'amplitude de striation (i.e. intensité de la fluctuation de composition) et de période spatiale de striation.

NASA Astrophysics Data System (ADS)

Haldenwang, P.; Guérin, R.; Le Marec, C.

1999-06-01

2-D unsteady flow patterns in upward Bridgman solidification are numerically investigated. The alloy under study is Pb-30%Tl. The purpose of the contribution is to characterise the striations induced by unsteadiness in the growing crystal. Unsteady solution branches are studied from onset threshold of unsteadiness to chaos. We report two examples for which time behaviour of a given solution branch is studied versus Rayleigh number. We then estimate the magnitude of the time fluctuations in solute composition that the crystal incorporates. The period of the striations is also discussed. Nous étudions numériquement les structures hydrodynamiques de la convection solutale dans le bain fondu, lors de la solidification dirigée d'alliages binaires. Plus précisément, cette étude porte

Quasi-elastic neutron scattering study of a re-entrant side-chain liquid-crystal polyacrylate

NASA Astrophysics Data System (ADS)

Benguigui, L.; Noirez, L.; Kahn, R.; Keller, P.; Lambert, M.; Cohen de Lara, E.

1991-04-01

We present a first investigation of the dynamics of a side chain liquid crystal polyacrylate in the isotropic (I), nematic (N), smectic A (SA), and re-entrant nematic (NRe) phases by means of quasi-elastic neutron scattering. The motion or/and the mobility of the mesogen protons decreases as soon as the temperature decreases after the isotropic-nematic transition. The I-N and SA-NRe transitions corrspond to a jump in the curve of the Elastic Incoherent Structure Factor (ratio: elastic scattering/ total scattering) versus temperature, on the other hand the transition N-SA occurs without any change of slope. We conclude that the local order is very similar in the nematic and the smectic A phases. Nous présentons une première étude dynamique par diffusion quasi-élastique des neutrons, d'un échantillon de polyacrylate mésomorphe en peigne dans chacune des phases : isotrope, nématique, smectique et nématique rentrante. On montre que le mouvement et/ou la mobilité des protons du mésogène se restreint à mesure que la température diminue après la transition isotrope-nématique. Contrairement à la transition N-SA, les transitions I-N et SA-NRe correspondent à une discontinuité dans la courbe du Facteur de Structure Incohérent Elastique (rapport : intensité élastique/intensité totale) en fonction de la température ; l'ordre local semble donc très proche pour les phases nématique et smectique.

Prise en charge d’un afflux massif de brûles lors d’une situation de catastrophe par incendie au Maroc

PubMed Central

Siah, S.; Hatimi, E.M.; Ihrai, H.; Drissi Kamili, N.

2012-01-01

Summary La brûlure est l’une des lésions les plus fréquemment rencontrées lors de catastrophes naturelles ou lors de catastrophes d’origine humaine (incendies de lieux publics d’origine accidentelle, ou en temps de guerre ou encore lors d’attentats terroristes). La prise en charge et le triage de brûlés en nombre reste un problème difficile; ceci souligne la nécessité d’une réflexion et de prévisions de ces crises en insistant sur la formation des médecins et des soignants. Les défis à relever sont multiples: les soins aux brûlés requièrent un nombre important de personnel qualifié; les évacuations doivent être planifiées en fonction de la gravité de la brûlure et des lésions associées; les stocks et lots de dotation (en particulier en topiques anti-infectieux et en cristalloïdes) doivent être suffisants et adéquats. Les services hospitaliers de l’Hôpital Militaire d’Instruction Mohammed V de Rabat doivent pouvoir être rapidement adaptés pour accueillir et surtout isoler ces patients. L’hypothèse d’une catastrophe par incendie avec afflux massif de brûlés à l’hôpital militaire d’instruction Mohammed V de Rabat ne doit laisser place à aucune improvisation. PMID:23467075

L'Amsaga (Mauritanie), fragment Archéen du Craton Ouest-Africain: observations et hypothèses nouvelles

NASA Astrophysics Data System (ADS)

Auvray, B.; Burg, J. P.; Caruba, Ch.; Dars, R.; Lo, K.

1992-02-01

L'Amsaga (R.I. Mauritanie) au NW du Craton Ouest-Africain, constitue la partie méridionale du soubassement de la Dorsale Reguibat. Cette région est constituée de deux ensembles principaux séparés par und grand accident mylonitique SW-NE. A l'Ouest, il s'agit d'un domaine granulitique (granulites ortho et para avec intrusions charnockitiques) et migmatitiques (migmatites ortho de type TTG); a l'Est, on retrouve les mêmes migmatites dont les produits de fusion (monzogranites a muscovite) recoupent et metamorphisent une série volcano-sedimentaire située dans le faciès amphibolite. Les contrastes pétrologiques et structuraux entre ces deux domaines sont discutés en fonction de la signification et de l'âge de l'accident qui les sépare (chevauchement ou décrochement). Dans le bloc ouest, les relations entre granulites et migmatites conduisent a envisager deux hypothèses (1) Un socle granodioritique (TTG) et sa couverture volcano-sédimentaire sont impliqués dans un même événement tectonométamorphique, mais dans des conditions de PH 2O variables. (2) Un seul ensemble supra-crustal (à soubassement inconnu) est intrudé, au cours d'une même phase de tectogenèse, par des magmas à caractères géochimiques voisins, mais cristallisant sous forme de TTG ou de charnockites suivant les conditions de leur mise en place.

Rupture utérine sur utérus bicorne à 12 semaines d'aménorrhée: à propos d'un cas

PubMed Central

Itchimouh, Sanaa; Khabtou, Karima; Mahdaoui, Sakher; Boufettal, Houssine; Samouh, Naima

2016-01-01

La fréquence des malformations utérines ayant un impact sur la reproduction est difficile à apprécier. Leur mise en évidence nécessite un bilan spécifique (hystérosalpingographie, hystéroscopie, cœlioscopie). La fertilité spontanée peut être altérée en fonction du type d'anomalie utérine. Toutes ces anomalies peuvent avoir des répercussions sur l’évolution de la conception à type de fausses couches précoces et tardives, de grossesse extra utérine, de menace d'accouchement prématuré, d'accouchement prématuré, de pathologies vasculaires gravidiques et de retard de croissance intra-utérin. L'utérus bicorne est la plus connue des malformations et représente environ la moitié des anomalies de l'utérus. La survenue d'une telle grossesse constitue une situation à risque pouvant entraîner une mort maternelle, mais le diagnostic précoce et un bon suivi peut mener des grossesses à terme sur des utérus malformé. Le dépistage échographique devrait permettre la détection systématique de ce genre de cas afin de prendre préventivement les mesures qui s'imposent. Nous rapportons un cas de rupture utérine sur utérus bicorne unicervical sur grossesse à 12 semaines d'aménorrhée. PMID:27642490

La plastie en rail dans le traitement des brides rétractiles du creux poplite

PubMed Central

Achbouk, A.; Khales, A.; Bourra, K.; Tourabi, K.; Ababou, K.; Ihrai, H.

2011-01-01

Summary Les Auteurs décrivent le cas d’un patient âgé de 45 ans atteint de brûlures thermiques par flammes suite à la déflagration d’une bonbonne de gaz. Les lésions initiales intéressaient les quatre membres (en particulier, le genou) et le tronc. La prise en charge initiale a consisté en une excision-greffe précoce des membres. L’évolution a été marquée par la survenue de cicatrices hypertrophiques au niveau des zones non greffées et à la bordure de la greffe ainsi que la survenue de brides rétractiles. Devant l’handicap fonctionnel engendré par la bride à cause de la limitation importante de l’extension, le patient a été admis pour cure chirurgicale. Grâce à la technique en rail décrite, le patient a pu récupérer une fonction normale du genou. Les suites ont été simples avec une durée d’hospitalisation d’un mois. Le résultat esthétique est relativement satisfaisant. La technique en rail est un moyen parmi l’arsenal thérapeutique qui permet de traiter la bride du creux poplité. Sa simplicité, sa facilité technique et son résultat satisfaisant ainsi que ses suites simples permettent de la rendre une technique très prisée dans le traitement de ce type de bride. PMID:21991240

Relevé postnatal Rourke 2014

PubMed Central

Riverin, Bruno; Li, Patricia; Rourke, Leslie; Leduc, Denis; Rourke, James

2015-01-01

Résumé Objectif Mettre à jour la version de 2011 du Relevé postnatal Rourke (RPR) à la suite d’une révision des meilleures données probantes récentes sur le suivi de la santé des nourrissons et des enfants de la naissance jusqu’à l’âge de 5 ans. Qualité des données La qualité des données a été cotée en fonction de l’ancien système de classification du Groupe d’étude canadien sur les soins de santé préventifs (jusqu’à 2006) et l’approche de détermination, d’élaboration et d’évaluation des recommandations (GRADE). Message principal De nouveaux faits scientifiques ont été pris en compte dans les recommandations du RPR 2014 en ce qui a trait au suivi de la croissance, à la nutrition, à l’éducation et aux conseils, au développement, à l’examen physique et à l’immunisation. La croissance est surveillée à l’aide des courbes de l’Organisation mondiale de la Santé qui ont été révisées en 2014. On devrait introduire les aliments solides en fonction de l’état de préparation du nourrisson et ces produits devraient contenir du fer. Il n’est actuellement plus recommandé de retarder l’introduction des allergènes alimentaires courants pour prévenir les allergies. Il faut promouvoir l’utilisation d’une tasse sans couvercle au lieu d’une tasse à bec dès l’âge de 12 mois. La section sur l’éducation et les conseils porte sur les blessures causées par du mobilier instable, ainsi que l’utilisation d’un siège d’auto orienté vers l’arrière jusqu’à 2 ans. Elle comporte aussi de l’information sur les saines habitudes de sommeil, la prévention de la maltraitance des enfants, la vie saine et active et la sédentarité de la famille, de même que l’hygiène buccale. On a aussi ajouté à cette section une nouvelle catégorie consacrée à la santé environnementale pour tenir compte des effets des dangers environnementaux sur la santé des enfants. Le RPR a recours à une surveillance développementale globale pour reconnaître les enfants qui pourraient être à risque de retards de développement. La vérification de la mobilité de la langue et de la perméabilité de l’anus est incluse dans l’examen physique du premier bilan de santé du bébé. Le RPR présente aussi les mises à jour concernant le vaccin contre la rougeole, les oreillons et la rubéole, le vaccin atténué vivant contre la grippe et celui contre le virus du papillome humain. Conclusion Le RPR 2014 représente la mise à jour de l’outil d’application pratique des connaissances, fondé depuis longtemps sur des données probantes, accompagné de ses ressources connexes dans le web, à l’intention des professionnels de la santé et des parents pour les soins de santé préventifs durant la petite enfance. La Société canadienne de pédiatrie, le Collège des médecins de famille du Canada et Les diététistes du Canada ont donné leur aval au RPR 2014. Des versions nationales et adaptées à l’Ontario du RPR sont accessibles en français et en anglais.

Characterization of beta-turn and Asx-turns mimicry in a model peptide: stabilization via C--H . . . O interaction.

PubMed

Thakur, A K; Kishore, R

2006-04-15

The chemical synthesis and single-crystal X-ray diffraction analysis of a model peptide, Boc-Thr-Thr-NH2 (1) comprised of proteinogenic residues bearing an amphiphilic Cbeta -stereogenic center, has been described. Interestingly, the analysis of its molecular structure revealed the existence of a distinct conformation that mimics a typical beta-turn and Asx-turns, i.e., the two Thr residues occupy the left- and right-corner positions. The main-chain torsion angles of the N- and C-terminal residues i.e., semiextended: phi = -68.9 degrees , psi = 128.6 degrees ; semifolded: phi = -138.1 degrees , psi = 2.5 degrees conformations, respectively, in conjunction with a gauche- disposition of the obligatory C-terminus Thr CgammaH3 group, characterize the occurrence of the newly described beta-turn- and Asx-turns-like topology. The preferred molecular structure is suggested to be stabilized by an effective nonconventional main-chain to side-chain Ci=O . . . H--Cgamma(i+2)-type intraturn hydrogen bond. Noteworthy, the observed topology of the resulting 10-membered hydrogen-bonded ring is essentially similar to the one perceived for a classical beta-turn and the Asx-turns, stabilized by a conventional intraturn hydrogen bond. Considering the signs as well as magnitudes of the backbone torsion angles and the orientation of the central peptide bond, the overall mimicked topology resembles the type II beta-turn or type II Asx-turns. An analysis of Xaa-Thr sequences in high-resolution X-ray elucidated protein structures revealed the novel topology prevalence in functional proteins (unpublished). In view of indubitable structural as well as functional importance of nonconventional interactions in bioorganic and biomacromolecules, we intend to highlight the participation of Thr CgammaH in the creation of a short-range C=O . . . H--Cgamma -type interaction in peptides and proteins. Copyright 2006 Wiley Periodicals, Inc.

The Rotational Spectrum of Anti-Ethylamine (CH3CH2NH2) from 10 to 270 GHz: A Laboratory Study and Astronomical Search in Sgr B2(N)

NASA Astrophysics Data System (ADS)

Apponi, A. J.; Sun, M.; Halfen, D. T.; Ziurys, L. M.; Müller, H. S. P.

2008-02-01

The pure rotational spectrum of the lowest energy (anti-) conformer of ethylamine (CH3CH2NH2) has been measured in the frequency range of 10-270 GHz. The spectrum was recorded using both millimeter-wave absorption spectroscopy and Fourier transform microwave (FTMW) techniques. Ten rotational transitions of this molecule were recorded in the frequency range of 10-40 GHz using FTMW methods, resulting in the assignment of 53 quadrupole-resolved hyperfine lines; in the millimeter-wave region (48-270 GHz), nearly 600 transitions were assigned to the ground (anti-) state. The amine group in CH3CH2NH2 undergoes inversion, resulting in a doubling that is frequently small and most apparent in the low-frequency K-doubling transitions. In addition, seemingly random rotational levels of this molecule were found to be significantly perturbed. The cause of these perturbations is presently uncertain, but torsion-rotation interactions with the higher lying gauche conformers seem to be a likely explanation. An astronomical search was conducted for ethylamine toward Sgr B2(N) using the Kitt Peak 12 m antenna and the Sub-Millimeter Telescope (SMT) of the Arizona Radio Observatory. Frequencies of 70 favorable rotational transitions were observed in this search, which covered the range 68-263 GHz. Ethylamine was not conclusively detected in Sgr B2(N), with an upper limit to the column density of (1-8) × 1013 cm-2 with f(CH3CH2NH2/H2) ~ (0.3-3) × 10-11, assuming a rotational temperature of 50-220 K. These observations indicate a gas-phase CH3CH2NH2/CH3NH2 ratio of <0.001-0.01, in contrast to the nearly equal ratio suggested by the acid hydrolysis of cometary solids from the Stardust mission.

Experimentally driven atomistic model of 1,2 polybutadiene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gkourmpis, Thomas, E-mail: thomas.gkourmpis@borealisgroup.com; Mitchell, Geoffrey R.; Centre for Rapid and Sustainable Product Development, Institute Polytechnic Leiria, Marinha Grande

2014-02-07

We present an efficient method of combining wide angle neutron scattering data with detailed atomistic models, allowing us to perform a quantitative and qualitative mapping of the organisation of the chain conformation in both glass and liquid phases. The structural refinement method presented in this work is based on the exploitation of the intrachain features of the diffraction pattern and its intimate linkage with atomistic models by the use of internal coordinates for bond lengths, valence angles, and torsion rotations. Atomic connectivity is defined through these coordinates that are in turn assigned by pre-defined probability distributions, thus allowing for themore » models in question to be built stochastically. Incremental variation of these coordinates allows for the construction of models that minimise the differences between the observed and calculated structure factors. We present a series of neutron scattering data of 1,2 polybutadiene at the region 120–400 K. Analysis of the experimental data yields bond lengths for Cî—¸C and C î—» C of 1.54 Å and 1.35 Å, respectively. Valence angles of the backbone were found to be at 112° and the torsion distributions are characterised by five rotational states, a three-fold trans-skew± for the backbone and gauche± for the vinyl group. Rotational states of the vinyl group were found to be equally populated, indicating a largely atactic chan. The two backbone torsion angles exhibit different behaviour with respect to temperature of their trans population, with one of them adopting an almost all trans sequence. Consequently, the resulting configuration leads to a rather persistent chain, something indicated by the value of the characteristic ratio extrapolated from the model. We compare our results with theoretical predictions, computer simulations, RIS models and previously reported experimental results.« less

Polymorphism in R-tamsulosin (an alpha blocker): The unexpected manifestation of a sulfonamide⋯o-diethoxybenzene heterosynthon

NASA Astrophysics Data System (ADS)

Nanubolu, Jagadeesh Babu; Sridhar, Balasubramanian; Ravikumar, Krishnan

2014-12-01

A two point Nsbnd H⋯O dimer or an infinite catemer are the most preferred motifs/synthons for sulfonamide structures. Such synthons are known to be so robust that they are only disrupted in the presence of highly activated O acceptors such as pyridine-N-oxide and sulfoxide. We demonstrate in this article that a multi-point synthon offered by much weaker ethoxy O and amine N acceptors can however strongly compete and disrupt the robust sulfonamide homosynthons. This has been illustrated with the synthon analysis in three polymorphic crystal structures of R-tamsulosin, an active drug used in the treatment of Benign Prostatic Hyperplasia (BPH) and its hydrochloride salt. These crystalline solids are characterized by Single crystal X-ray diffraction (SC-XRD), powder X-ray diffraction (PXRD), Fourier Transform Infrared (FT-IR) and Raman spectroscopy. Forms I, II of the free base and hydrochloride salt crystallize in the monoclinic P21, C2, and P21 space groups respectively with two molecules in the asymmetric unit (Z‧ = 2), whereas, form III of freebase crystallize in the orthorhombic P212121 space group with Z‧ = 1. Remarkably, all four crystal structures contain a totally unexpected sulfonamide⋯o-diethoxybenzene heterosynthon. The multi-point motifs observed in polymorphs are relatively stronger than those in the hydrochloride salt because of the gauche conformation of the tamsulosin linker chain which renders an additional hydrogen bond interaction with amine N acceptor, and resemble the crown ether sulfonamide recognition pattern. Observation of this new heterosynthon offers potential scope in the design of pharmaceutical cocrystals for sulfonamide bearing drug molecules. The present study also presents a detailed hydrogen bond motif analysis in 310 primary sulfonamide structures culled from the latest version of Cambridge Structural Database (CSD). The role of various competing groups is discussed in the context of understanding the most recurring sulfonamide homo and heterosynthons.

Understanding the factors affecting the activation of alkane by Cp′Rh(CO)2 (Cp′ = Cp or Cp*)

PubMed Central

George, Michael W.; Hall, Michael B.; Jina, Omar S.; Portius, Peter; Sun, Xue-Zhong; Towrie, Michael; Wu, Hong; Yang, Xinzheng; Zarić, Snežana D.

2010-01-01

Fast time-resolved infrared spectroscopic measurements have allowed precise determination of the rates of activation of alkanes by Cp′Rh(CO) (Cp′ = η5-C5H5 or η5-C5Me5). We have monitored the kinetics of C─H activation in solution at room temperature and determined how the change in rate of oxidative cleavage varies from methane to decane. The lifetime of CpRh(CO)(alkane) shows a nearly linear behavior with respect to the length of the alkane chain, whereas the related Cp*Rh(CO)(alkane) has clear oscillatory behavior upon changing the alkane. Coupled cluster and density functional theory calculations on these complexes, transition states, and intermediates provide the insight into the mechanism and barriers in order to develop a kinetic simulation of the experimental results. The observed behavior is a subtle interplay between the rates of activation and migration. Unexpectedly, the calculations predict that the most rapid process in these Cp′Rh(CO)(alkane) systems is the 1,3-migration along the alkane chain. The linear behavior in the observed lifetime of CpRh(CO)(alkane) results from a mechanism in which the next most rapid process is the activation of primary C─H bonds (─CH3 groups), while the third key step in this system is 1,2-migration with a slightly slower rate. The oscillatory behavior in the lifetime of Cp*Rh(CO)(alkane) with respect to the alkane’s chain length follows from subtle interplay between more rapid migrations and less rapid primary C─H activation, with respect to CpRh(CO)(alkane), especially when the CH3 group is near a gauche turn. This interplay results in the activation being controlled by the percentage of alkane conformers. PMID:21048088

Determination of molecular structure of succinic acid in a very complex conformational landscape: Gas-phase electron diffraction (GED) and ab initio studies

NASA Astrophysics Data System (ADS)

Vogt, Natalja; Abaev, Maxim A.; Rykov, Anatolii N.; Shishkov, Igor F.

2011-06-01

The molecular structure of succinic acid has been investigated by the gas-phase electron diffraction (GED) method for the first time. According to predictions of MP2/cc-pVTZ calculations, the molecule has 18 stable conformers with the C sbnd C sbnd C sbnd C chain in the gauche ( G) or anti ( A) configuration, and four of them, I ( G), II ( A), III ( G) and IV ( A) belonging to the C 2, C 2h, C 1 and C 1 point groups, respectively, with relative energies ΔE ZPE within 2.2 kcal/mol can be present at the experimental temperature of 445 K in noticeable amounts. The ratio of the conformers I:II:III:IV = 45(15):20(15):10(assumed):25(15) (in %) has been determined in the GED analysis guided by theoretical predictions. To take into account vibrational effects, the corrections Δ( r e - r a) to the experimental r a bond lengths were calculated from the MP2/cc-pVTZ quadratic and cubic force constants. The obtained equilibrium structural parameters of the dominant conformer I are the following (bond lengths in Å, angles in degrees): r e(C sp3sbnd C sp3) = 1.508(3), r e(C sp3sbnd C sp2) = 1.499(2), r e(C sbnd O) = 1.343(2), r e(C dbnd O) = 1.202(1), e(C sbnd C sbnd C) = 111.8(4), e(C sbnd C sbnd O) = 112.0(4), e(O sbnd C dbnd O) = 123.0(1), τ(C sbnd C sbnd C sbnd C) = 69.9(11). Yielding the best agreement with the GED structure, the MP2/cc-pVQZ approximation overestimates the C sbnd O and C dbnd O bond lengths by ca. 0.005(2) Å.

Crystal structure of trans-diammine(1,4,8,11-tetra­aza­cyclo­tetra­decane-κ4 N)chromium(III) tetra­chlorido­zincate chloride monohydrate from synchrotron data

PubMed Central

Moon, Dohyun; Choi, Jong-Ha

2016-01-01

The asymmetric unit of the title complex salt, [Cr(C10H24N4)(NH3)2][ZnCl4]Cl·H2O, is comprised of four halves of the CrIII complex cations (the counterparts being generated by application of inversion symmetry), two tetra­chlorido­zincate anions, two chloride anions and two water mol­ecules. Each CrIII ion is coordinated by the four N atoms of the cyclam (1,4,8,11-tetra­aza­cyclo­tetra­deca­ne) ligand in the equatorial plane and by two N atoms of ammine ligands in axial positions, displaying an overall distorted octa­hedral coordination environment. The Cr—N(cyclam) bond lengths range from 2.0501 (15) to 2.0615 (15) Å, while the Cr—(NH3) bond lengths range from 2.0976 (13) to 2.1062 (13) Å. The macrocyclic cyclam moieties adopt the trans-III conformation with six- and five-membered chelate rings in chair and gauche conformations. The [ZnCl4]2− anions have a slightly distorted tetra­hedral shape. In the crystal, the Cl− anions link the complex cations, as well as the solvent water mol­ecules, through N—H⋯Cl and O—H⋯Cl hydrogen-bonding inter­actions. The supra­molecular set-up also includes N—H⋯Cl, C—H⋯Cl, N—H⋯O and O—H⋯Cl hydrogen bonding between N—H or C—H groups of cyclam, ammine N—H and water O—H donor groups, and O atoms of the water mol­ecules, Cl− anions or Cl atoms of the [ZnCl4]2− anions as acceptors, leading to a three-dimensional network structure. PMID:27375863

The equilibrium molecular structures of cross-conjugated alkenes with particular reference to [3]- and [4]-dendralene from ab initio studies of various conformers

NASA Astrophysics Data System (ADS)

Palmer, Michael H.; Blair-Fish, John A.; Sherwood, Paul

1997-07-01

A study of the equilibrium structures and relative energies for the conformers of 3-methylenepenta-1,4-diene (MPD) and bis(3,4-methylene)-1,5-hexadiene (MHD) have been obtained by SCF and MP2 correlated methods; a double zeta+polarisation basis set (DZP) was used. Both planar and non-planar forms were evaluated for a variety of point groups. The force constants for each conformer were obtained, in order to determine whether the minima were saddle points rather than genuine minima owing to the constraints of molecular symmetry. For both molecules, all the non-planar forms studied were of lower energy than the best planar-forms. Indeed the planar structures are all saddle-points between the interconverting pairs of non-planar forms, as shown by one or more negative vibration frequencies for the planar molecules. The relative energies and structures of the different conformers of MPD and MHD are almost identical between the SCF and MP2 series, the MP2 calculations merely leading to slight extensions of the C=C bonds, minor changes in dihedral angles, and small changes otherwise. Because of the H⋯H interactions, all the planar forms showed considerable in-plane angle bending, and small but consistent H-C bond compressions were also obtained in the most hindered cases. The lowest energy conformer of MPD is a gauche-trans conformer, with symmetry C 1, but a second conformer of trans-trans type and C 2 symmetry lies only 6 kJ mol -1 above. The C 2 non-planar conformer of MHD containing (basically) trans-butadiene units is the lowest energy by a significant amount, but several trans-cis and cis-cis conformers were all identified as potential species for gas phase mixtures.

Conformation, dynamics, solvation and relative stabilities of selected beta-hexopyranoses in water: a molecular dynamics study with the GROMOS 45A4 force field.

PubMed

Kräutler, Vincent; Müller, Martin; Hünenberger, Philippe H

2007-10-15

The present article reports long timescale (200 ns) simulations of four beta-D-hexopyranoses (beta-D-glucose, beta-D-mannose, beta-D-galactose and beta-D-talose) using explicit-solvent (water) molecular dynamics and vacuum stochastic dynamics simulations together with the GROMOS 45A4 force field. Free-energy and solvation free-energy differences between the four compounds are also calculated using thermodynamic integration. Along with previous experimental findings, the present results suggest that the formation of intramolecular hydrogen-bonds in water is an 'opportunistic' consequence of the close proximity of hydrogen-bonding groups, rather than a major conformational driving force promoting this proximity. In particular, the conformational preferences of the hydroxymethyl group in aqueous environment appear to be dominated by 1,3-syn-diaxial repulsion, with gauche and solvation effects being secondary, and intramolecular hydrogen-bonding essentially negligible. The rotational dynamics of the exocyclic hydroxyl groups, which cannot be probed experimentally, is found to be rapid (10-100 ps timescale) and correlated (flip-flop hydrogen-bonds interconverting preferentially through an asynchronous disrotatory pathway). Structured solvent environments are observed between the ring and lactol oxygen atoms, as well as between the 4-OH and hydroxymethyl groups. The calculated stability differences between the four compounds are dominated by intramolecular effects, while the corresponding differences in solvation free energies are small. An inversion of the stereochemistry at either C(2) or C(4) from equatorial to axial is associated with a raise in free energy. Finally, the particularly low hydrophilicity of beta-D-talose appears to be caused by the formation of a high-occurrence hydrogen-bonded bridge between the 1,3-syn-diaxial 2-OH and 4-OH groups. Overall, good agreement is found with available experimental and theoretical data on the structural, dynamical, solvation and energetic properties of these compounds. However, this detailed comparison also reveals some discrepancies, suggesting the need (and providing a solid basis) for further refinement.

Structure and phase transitions of monolayers of intermediate-length n-alkanes on graphite studied by neutron diffraction and molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Diama, A.; Matthies, B.; Herwig, K. W.; Hansen, F. Y.; Criswell, L.; Mo, H.; Bai, M.; Taub, H.

2009-08-01

We present evidence from neutron diffraction measurements and molecular dynamics (MD) simulations of three different monolayer phases of the intermediate-length alkanes tetracosane (n-C24H50 denoted as C24) and dotriacontane (n-C32H66 denoted as C32) adsorbed on a graphite basal-plane surface. Our measurements indicate that the two monolayer films differ principally in the transition temperatures between phases. At the lowest temperatures, both C24 and C32 form a crystalline monolayer phase with a rectangular-centered (RC) structure. The two sublattices of the RC structure each consists of parallel rows of molecules in their all-trans conformation aligned with their long axis parallel to the surface and forming so-called lamellas of width approximately equal to the all-trans length of the molecule. The RC structure is uniaxially commensurate with the graphite surface in its [110] direction such that the distance between molecular rows in a lamella is 4.26 Å=√3 ag, where ag=2.46 Å is the lattice constant of the graphite basal plane. Molecules in adjacent rows of a lamella alternate in orientation between the carbon skeletal plane being parallel and perpendicular to the graphite surface. Upon heating, the crystalline monolayers transform to a "smectic" phase in which the inter-row spacing within a lamella expands by ˜10% and the molecules are predominantly oriented with the carbon skeletal plane parallel to the graphite surface. In the smectic phase, the MD simulations show evidence of broadening of the lamella boundaries as a result of molecules diffusing parallel to their long axis. At still higher temperatures, they indicate that the introduction of gauche defects into the alkane chains drives a melting transition to a monolayer fluid phase as reported previously.

Structure and phase transitions of monolayers of intermediate-length n-alkanes on graphite studied by neutron diffraction and molecular dynamics simulation.

PubMed

Diama, A; Matthies, B; Herwig, K W; Hansen, F Y; Criswell, L; Mo, H; Bai, M; Taub, H

2009-08-28

We present evidence from neutron diffraction measurements and molecular dynamics (MD) simulations of three different monolayer phases of the intermediate-length alkanes tetracosane (n-C(24)H(50) denoted as C24) and dotriacontane (n-C(32)H(66) denoted as C32) adsorbed on a graphite basal-plane surface. Our measurements indicate that the two monolayer films differ principally in the transition temperatures between phases. At the lowest temperatures, both C24 and C32 form a crystalline monolayer phase with a rectangular-centered (RC) structure. The two sublattices of the RC structure each consists of parallel rows of molecules in their all-trans conformation aligned with their long axis parallel to the surface and forming so-called lamellas of width approximately equal to the all-trans length of the molecule. The RC structure is uniaxially commensurate with the graphite surface in its [110] direction such that the distance between molecular rows in a lamella is 4.26 A=sqrt[3a(g)], where a(g)=2.46 A is the lattice constant of the graphite basal plane. Molecules in adjacent rows of a lamella alternate in orientation between the carbon skeletal plane being parallel and perpendicular to the graphite surface. Upon heating, the crystalline monolayers transform to a "smectic" phase in which the inter-row spacing within a lamella expands by approximately 10% and the molecules are predominantly oriented with the carbon skeletal plane parallel to the graphite surface. In the smectic phase, the MD simulations show evidence of broadening of the lamella boundaries as a result of molecules diffusing parallel to their long axis. At still higher temperatures, they indicate that the introduction of gauche defects into the alkane chains drives a melting transition to a monolayer fluid phase as reported previously.

NMR analyses of the conformations of L-isoleucine and L-valine bound to Escherichia coli isoleucyl-tRNA synthetase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kohda, D.; Kawai, G.; Yokoyama, S.

1987-10-06

The 400-MHz /sup 1/H NMR spectra of L-isoleucine and L-valine were measured in the presence of Escherichia coli isoleucyl-tRNA synthetase (IleRS). Because of chemical exchange of L-isoleucine or L-valine between the free state and the IleRS-bound state, a transferred nuclear Overhauser effect (TRNOE) was observed among proton resonances of L-isoleucine or L-valine. However, in the presence of isoleucyl adenylate tightly bound to the amino acid activation site of IleRS, no TRNOE for L-isoleucine or L-valine was observed. This indicates that the observed TRNOE is due to the interaction of L-isoleucine or L-valine with the amino acid activation site of IleRS.more » The conformations of these amino acids in the amino acid activation site of IleRS were determined by the analyses of time dependences of TRNOEs and TRNOE action spectra. The IleRS-bound L-isoleucine takes the gauche/sup +/ form about the C/sub ..cap alpha../-C/sub ..beta../ bond and the trans form about the C/sub ..beta../-C/sub ..gamma../sub 1// bond. The IleRS-bound L-valine takes the guache/sup -/ form about the C/sub ..cap alpha../-C/sub ..beta../ bond. Thus, the conformation of the IleRS-bound L-valine is the same as that of IleRS-bound L-isoleucine except for the delta-methyl group. The side chain of L-isoleucine or L-valine lies in an aliphatic hydrophobic pocket of the active site of IleRS. Such hydrophobic interaction with IleRS is more significant for L-isoleucine than for L-valine. The TRNOE analysis is useful for studying the amino acid discrimination mechanism of aminoacyl-tRNA synthetases.« less

Using Symmetry Group Correlation Tables to Explain why Erham (and Other Programs) cannot BE Used to Analyze Torsional Splittings of Some Molecules

NASA Astrophysics Data System (ADS)

Groner, Peter

2016-06-01

ERHAM has been used to analyze rotational spectra of many molecules with torsional splitting caused by one or two internal rotors. The gauche form of dimethyl ether-d1 whose equilibrium structure has C1 symmetry is an example of a molecule for which ERHAM could not model additional small splittings resolvable for many transitions, whereas the spectrum of the symmetric (anti, trans) form with a C{_s} equilibrium structure could be analyzed successfully with ERHAM. A more recent example where ERHAM failed is pinacolone CH_3-CO-C(CH_3)_3. In this case, the barriers to internal rotation of the methyl groups within the -C(CH_3)_3 unit are too high to produce observable internal rotation splittings, but the splittings due to the CH_3-CO methyl group could not be modeled correctly with ERHAM nor with any other available program (XIAM, BELGI-Cs, BELGI-C1, RAM36). In the paper, it was speculated that BELGI-Cs-2tops might be able to the job, but arguments against this possibility have also been put forward. The correlation between irreducible representations of groups and their subgroups according to Watson can be used not only to determine the total number of substates (components) to be expected but also to help decide which particular program has a chance for a successful analysis. As it turns out, the number of components of split lines depends on the molecular symmetry at equilibrium in relation to the highest possible symmetry for a given molecular symmetry group. Therefore, for pinacolone, the vibrational ground state is split into 10 torsional substates. P. Groner, J. Mol. Spectrosc. 278 (2012) 52-67. C. Richard et al. A&A 552 (2013), A117. Y. Zhao et al., J. Mol. Spectrosc. 318 (2015) 91-100, with references to all other programs mentioned in the abstract. J. K. G. Watson, Can. J. Physics 43 (1965) 1996-2007.

Thermally induced conformational changes in polyethylene studied by two-dimensional near-infrared infrared hetero-spectral correlation spectroscopy

NASA Astrophysics Data System (ADS)

Watanabe, Shin; Noda, Isao; Ozaki, Yukihiro

2008-07-01

The amount of nonplanar gauche bonds was monitored as a function of increasing temperature in three different polyethylene (PE) samples by means of mid-infrared (MIR) and near-infrared (NIR) spectroscopy. The hetero-spectral two-dimensional (2D) correlation analysis was carried out between the NIR spectral region of 4365-4235 cm -1 and the well-established MIR spectral region of 1375-1265 cm -1, where bands due to nonplanar conformer are detected. This approach allowed us to identify the NIR band at 4265 cm -1, which behaves in a way similar to MIR bands originating from conformational-defect sequences. By combining the result of our current study and that of our previous report obtained on different types of PE, it is suggested that the NIR band originates from conformational-defect sequences in PE. This finding opens up a unique and useful way to study the state of conformational disorder in PE crystal by NIR spectroscopy, monitoring the intensity of the NIR band at 4265 cm -1. The use of NIR spectroscopy allows researchers to directly probe the degree in the formation of conformational-defect sequences in thick, real-world PE samples that cannot be studied by conventional MIR spectroscopy. The 2D correlation spectroscopy analysis among the MIR CH 2 wagging conformational-defect-mode bands on linear low-density PE (LLDPE) and low-density PE (LDPE) revealed the formation of nonplanar conformer represented by the band at 1368 cm -1 proceeds prior to those by other band at 1308 cm -1. This result agrees well with our previous finding on high-density PE (HDPE). We therefore propose with strong confidence that the bands at 1368 and 1308 cm -1 arise from different conformational-defect sequences, even though both of the bands have been proposed to arise from the same conformer of gtg' ( kink) + gtg sequence.

Estimation of crystallinity in isotropic isotactic polypropylene with Raman spectroscopy.

PubMed

Minogianni, Chrysa; Gatos, Konstantinos G; Galiotis, Costas

2005-09-01

The Raman spectrum of isotactic polypropylene (iPP) has been found to exhibit vibrational peaks in the region of 750 to 880 cm(-1) that are sensitive to the degree of crystallinity. These features are broadly assigned to various modes of methyl group rocking, rho(CH2), and there have been various attempts to assess crystallinity based on the integrated intensities of these bands. Various vibrational analyses performed in the past in combination with experimental studies have concluded that the presence of crystalline order with trans-gauche conformation gives rise to a peak at 809 cm(-1), which is assigned to a rho(CH2) mode coupled with the skeletal stretching mode. However, the presence of additional peaks at 830 cm(-1), 841 cm(-1), and 854 cm(-1), within the same envelope, have been the subject of controversy. In this work isotropic films of iPP derived from the same precursor of identical tacticity have been subjected to various degrees of annealing and the integrated intensities of the Raman bands were measured. The results showed that true 3d crystallinity in isotropic iPP can only be expressed by the 809 cm(-1) band whereas the band at 841 cm(-1) corresponds to an uncoupled rho(CH2) fundamental mode and thus is a measure of the amorphous content. The less intense satellite bands at 830 cm(-1) and 854 cm(-1) of solid iPP cannot be distinguished from the 841 cm(-1) band in the melt and are generally considered as intermediate phases possibly related to non-crystalline components with 3(1)-helical conformations. Independent differential scanning calorimetry (DSC) crystallinity measurements were in broad agreement with the Raman measurements based on the normalized intensity of the 809 cm(-1) Raman band. By comparing the Raman with the DSC data a new value for the theoretical heat of fusion for the 100% crystalline iPP has been proposed.

Métastase pleurale et pulmonaire d’une polyadénofibromatose dégénéréé: à propos d’un cas

PubMed Central

El Hachimi, Kawtar; Benjelloun, Hanane; Zaghba, Nahid; Yassine, Najiba

2017-01-01

La polyadénofibromatose ou l’adénofibromatose est définie par la présence d’au moins 3 adénofibromes, uni ou bilatéraux atteignant une taille importante responsable de troubles trophiques. Nous rapportons une observation colligée au service des maladies respiratoires du Centre Hospitalier Universitaire Ibn Rochd de Casablanca. Il s’agit d’une patiente âgée de 46ans, suivie depuis l’âge de 30 ans pour une adénofibromatose bilatérale opérée à 4 reprises. Suite à un bilan préopératoire d’une mastectomie bilatérale, une radio du thorax a été réalisée objectivant un hémithorax droit opaque avec refoulement des éléments du médiastin. L’examen clinique retrouvait un syndrome d’épanchement liquidien de l’hémithorax droit et une adénopathie cervicale sus claviculaire gauche. La ponction biopsie pleurale confirmait la localisation pleurale d’un carcinome peu différencié et invasif compatible avec une origine mammaire. La bronchoscopie après évacuation pleurale objectivait un aspect infiltré de tout l’arbre bronchique, dont les biopsies concluaient au même résultat anatomopathologique. Le traitement préconisé était une polychimiothérapie. L’évolution était marquée par l’apparition de métastases hépatiques. A travers cette observation, nous concluons que les adénofibromes nécessitent une surveillance régulière vu le risque de dégénérescence vers le cancer du sein qui est une cause fréquente de métastases pleuropulmonaires. PMID:29515733

Evaluation of antidiabetic effect of total calystegines extracted from Hyoscyamus albus.

PubMed

Bourebaba, Lynda; Saci, Souaad; Touguit, Damia; Gali, Lynda; Terkmane, Schahinez; Oukil, Naima; Bedjou, Fatiha

2016-08-01

Hyoscyamus albus L. (Solanaceae) an old medicinal plant is a rich source of tropane and nortropane alkaloids which confers to this plant a number of very interesting and beneficial therapeutic effects. Calystegines that are polyhydroxylated alkaloids and imino-sugars poccess significant glycosidases inhibitory activities and are therefore good candidats for the treatment of diabetes mellitus. Calystegines extracted from Hyoscyamys albus seeds were tested for teir acute oral toxicity and investigated for their in-vivo antidiabetic effect on Streptozotocine induced diabetes in mice. Calystegines were extracted from the seeds plant using an Ion exchange column; the remaining extract was then administrated orally to mice at several single doses for acute toxicity assay. A dose of 130mg/kg streptozotocine was injected to mice to induce diabetes mellitus, and diabetic mice were treated orally during 20days with 10mg/kg and 20mg/kg calystegines and 20mg/kg glibenclamide as the reference drug. Acute oral toxicity showed that calystegines are not toxic up to a dose of 2000mg/kg with absence of any signs of intoxication and damages in Liver and kidney tissues. The nortropane alkaloids markedly reduced blood glucose levels and lipid parameters of diabetic mice to normal concentrations after 20days of treatment at 10mg/kg and 20mg/kg (p<0.05). Histopathological study of diabetic mice pancreas indicated that calystegines of Hyoscyamus albus have minimized streptozotocine damages on β-cells of islets of langerhans, stimulated β-cells regeneration and improved with this insulin secretion. The findings of this study suggest that calystegines are potent antidiabetic agents with antihyperglicemic and hypolipidemic effects, and a protective fonction on pancreas in streptozotocin induced diabetes in mice. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Outbursts formation on low carbon and trip steel grades during hot-dip galvanisation

NASA Astrophysics Data System (ADS)

Petit, E. J.; Lamm, L.; Gilles, M.

2004-12-01

Low carbon and TRIP grade steels have been hot dip galvanised in order to study outbursts formation. Microstructure and texture of intermetallic phases have been observed after selective electrochemical etching by scanning electron microscopy. Potential versus time (chronopotentiometric) characteristics were recorded in order to monitor surface modifications. This combination of techniques enable to quantify and observe intermetallic phase one by one. The overall thickness of coating on both substrates are similar. However, microstructures of Fe-Zn intermetallic phases are very different on both grades. In particular, the V phase is dense on standard steel but develops a highly branched filament structure on TRIP steel. The transformation of V phase to d and G1 are limited on TRIP steel. Differences of texture provide clues for understanding mechanisms of formation of outbursts. They can account for the differences of mechanical properties and corrosion resistance. Silicon from the substrate influences the reactivity of TRIP steels due to capping and local reactions. La formation des outbursts a été étudiée sur un acier bas carbone et sur un acier TRIP galvanisés. Les épaisseurs des revêtements sont similaires. Néanmoins, les observations microscopiques et les érosions électrochimiques montrent que la répartition des phases intermétalliques et leurs microstructures diffèrent sensiblement en fonction de la nature du substrat. Ces différences expliquent les propriétés mécaniques et anticorrosions. L’encapsulation de la surface par les oxydes de silicium freine la transformation de la phase dzêta en delta et gamma sur l’acier TRIP.

Offset fémoral et le fonctionnement de la hanche dans la prothèse totale de la hanche

PubMed Central

Rachid, Abdelillah; Moncef, Erraji; Najib, Abbassi; Abdeljaouad, Najib; Abdelkarim, Daudi; Hicham, Yacoubi

2014-01-01

L'offset fémoral est l’élément pronostic le plus important dans l'arthroplastie de la hanche. Sa restauration est devenue de plus en plus une obligation. Toute modification de la valeur native de l'offset retenti sur la qualité du fonctionnement clinique de la hanche. Le but de notre travail était d’évaluer le fonctionnement clinique de la hanche en fonction de la valeur de l'offset fémoral après une arthroplastie. C'est une étude rétrospective effectuée entre 2010 et 2013, comportant 27 patients ayant bénéficiés d'une arthroplastie totale de la hanche. Les patients ayant eu un geste chirurgicale antérieur sur la même hanche ou sur la hanche controlatérale ont été exclus. Les mesures ont été effectuées sur des radiographies standards de la hanche en rotation interne d'environ 15°, avec un agrandissement à 100%. Les résultats cliniques étaient évalués au moyen du score de WOMAC qui était en moyenne de 15,2 points, et le score de Merle d'Aubigné-Postel avec une moyenne de 15 points. Deux autres tests ont été évalués dans notre étude qui sont le step et le hop test. Les meilleurs résultats fonctionnels ont été obtenus chez les patients ayant eu une latéralisation de la tige fémoral avec un offset augmenté. PMID:25400835

Poumon du puisatier

PubMed Central

Elidrissi, Amal Moustarhfir; Zaghba, Nahid; Benjelloun, Hanane; Yassine, Najiba

2016-01-01

Le puisatier a pour profession le creusement et l'entretien des puits pour fournir de l'eau. Il est au contact de divers minerais, particulièrement la silice, particule qui présente un risque certain de développement des maladies pulmonaires connues sous le nom de silicose. Le but de notre travail est de préciser le profil épidémiologique, clinique, radiologique et évolutif des patients puisatiers silicotiques. C'est une étude rétrospective concernant 54 cas de puisatiers ayant une silicose, colligés au service des maladies respiratoires du CHU Ibn Rochd de Casablanca, de Mars 1997 à Janvier 2016. Tous les malades étaient des puisatiers, de sexe masculin, avec une moyenne d'âge de 50 ans. Le tabagisme était retrouvé dans 36 cas et un antécédent de tuberculose était noté dans huit cas. La radiographie thoracique retrouvait des grandes opacités dans 39 cas, des petites opacités dans 15 cas, et un épaississement des septats dans 11 cas. Ce tableau de silicose s'était compliqué d'une surinfection bactérienne dans 37% des cas, d' un pneumothorax dans 4% des cas et d'une tuberculose dans 20% des cas. La prise en charge thérapeutique était celle des complications. La déclaration de la maladie professionnelle et de l'indemnisation était faite. L'évolution était bonne dans 12 cas, stationnaire dans 17 cas et mauvaise dans 16 cas. La silicose est une pneumoconiose fréquente chez les puisatiers. Elle retentit sur la fonction respiratoire. Nous soulignons l'association fréquente de tuberculose et nous insistons sur la prévention qui reste le meilleur traitement. PMID:28292119

Influence of water vapour and permanent gases on the atmospheric optical depths and transmittance

NASA Astrophysics Data System (ADS)

Badescu, V.

1991-05-01

The influence of the atmospheric state on the extinction of direct solar radiation has been studied by using a four layer atmospheric model. Simple analytical formulae are established for the spectral optical depths of permanent gases and water vapour. These formulae use the ground level values of air pressure, temperature and relative huniidity. An additional parameter, related to the vertical distribution of the hunmidity content, is used for a better estimation of the water vapour optical depth. Good agreement between theory and measurements is found. The paper shows the dependence of the atmospheric spectral transmittance on the above mentioned parameters. L'influence de l'état atmosphérique sur l'extinction de la radiation solaire directe a été étudiée à l'aide d'un modèle atmosphérique développé antérieurement par l'auteur. Des formules simples ont été établies pour l'épaisseur optique spectrale des gaz et de la vapeur d'eau. Ces formules utilisent les valeurs de la pression atmosphérique, de la température et de l'humidité relative, mesurées au niveau du sol. Un paramètre supplémentaire, lié à la distribution verticale du contenu d'humidité, est utilisé pour calculer l'épaisseur optique due à la vapeur d'eau. La théorie est en bon accord avec les résultats des mesures. Le travail montre la dépendance de la transmittance atmosphérique spectrale en fonction des paramètres spécifiés ci-dessus.

Grammaire de l’expérience romantique adolescente au Québec: une analyse sociosémantique des idéaux amoureux

PubMed Central

Blais, Martin; Hébert-Ratté, Roxanne; Hébert, Martine; Lavoie, Francine

2016-01-01

Cette étude vise à décrire, à travers les thèmes qu’évoque la plus belle expérience amoureuse chez de jeunes Québécois âgés de 14 à 19 ans, les formes sémantiques de l’amour contemporain ainsi que les attentes et les paradoxes dont elles témoignent sur le plan communicationnel. Au total, 6 961 jeunes Québécois âgés de 14 à 18 ans recrutés dans les milieux scolaires ont décrit leur plus belle expérience amoureuse vécue ou souhaitée. Une analyse des champs lexicaux, réalisée avec le logiciel Sémato, a permis de dégager six (6) formes sémantiques dominantes: 1) la fidélité, le respect et l’authenticité, 2) les références à la sensualité (embrasser et enlacement), 3) l’ancrage de l’amour idéal dans la compagnie de l’autre et des activités concrètes, 4) l’importance de la passion, de la magie (pour les deux genres) et, surtout pour les garçons, du plaisir, 5) l’ancrage de l’idéal amoureux dans des projets d’union et d’enfants, et 6) l’ancrage du couple dans des lieux précis, dans un quotidien ou des souvenirs tangibles. Ces formes sémantiques sont discutées en fonction des problèmes qu’elles ont pu résoudre et ceux qu’elles font émerger. Les différences de genre sont aussi discutées. PMID:27917004

Lévitation magnétique par association d'aimants permanents et de supraconducteurs à haute température critique

NASA Astrophysics Data System (ADS)

Hiebel, P.; Tixador, P.; Chaud, X.

1995-06-01

Since their discovery in the years 1986/87, the high critical temperature superconductors have reached nowadays performances interesting enough to conceive passive magnetic bearings and suspensions which would combined permanent magnets and naturally stable superconducting pellets. After underlining the principal factors that affect the superconductormagnet interaction, different experimental results are given about vertical and axial forces with some stiffness values. The magnetization curve of a superconductor help to understand the hysteretic behavior of the force as a function of the distance between superconductor and magnet. So called simple and hybrid structures of superconducting magnetic suspension are presented. Finally simple numerical simulations allow to draw some interesting conclusions about both geometry and best fitting structure of permanent magnets. Depuis leur découverte dans les années 1986/87, les supraconducteurs à haute température critique ont désormais atteint des performances intéressantes et rendent envisageables des paliers et suspensions magnétiques passives associant aimants permanents et pastilles supraconductrices naturellement stables. Après avoir indiqué les termes importants influençant l'interaction supraconducteur - aimant, différents relevés expérimentaux sont donnés pour les forces verticales et transversales avec quelques valeurs de raideurs. La courbe d'aimantation d'un supraconducteur permet de comprendre le comportement hystérétique de la force en fonction de la distance supraconducteur-aimant. Les structures dites simple et hybride des suspensions magnétiques supraconductrices sont présentées. Enfin quelques simulations numériques simples permettent de dégager quelques conclusions intéressantes quant aux géométries respectives et aux structures d'aimants permanents les mieux adaptées.

Épidémiologie des brûlures de la main chez les enfants vus dans le Centre National des Brûlés et de Chirurgie Plastique de Casablanca, Maroc

PubMed Central

Rafik, A.; Lahlou, M.; Diouri, M.; Bahechar, N.; Chlihi, A.

2015-01-01

Summary Les brûlures de la main chez l’enfant constituent une source de séquelles invalidantes. A cet régard, la conservation et la restauration complète de la fonction de la main demeurent le but primordial de la prise en charge. Afin de répertorier les caractéristiques épidémiologiques, cliniques et évolutives des mains brûlées, nous avons réalisé une étude rétrospective étalée sur 4 ans, de janvier 2011 à janvier 2015. Cette étude a permis de colliger les cas de 313 enfants atteints de brûlure de la main vus dans le Centre National des Brulés et de Chirurgie Plastique du CHU Ibn Rochd de Casablanca. La majorité des brûlures touche les enfants de 3 à 6 ans (70% des cas), avec une légère prédominance masculine. La principale cause des brûlures survenant à cet âge est l’ébouillantement. Les brûlures par flamme représentent 33% des cas, celles par électricité 4,5%. Les brûlures chimiques et par contact sont anecdotiques (1 cas chacune). L’accident survient le plus souvent à domicile. Soixante douze pour cent des brûlures ont guéri spontanément. Afin de diminuer l’incidence de ces accidents, une approche préventive faite de sensibilisation et d’éducation devrait faire partie du cursus scolaire. PMID:27777543

Etude par émission acoustique de la dynamique des dislocations pendant la déformation cyclique de polycristaux d'aluminium

NASA Astrophysics Data System (ADS)

Slimani, A.; Fleischmann, P.; Fougères, R.

1992-06-01

The cyclic plasticity of 5N polycrystalline aluminium have been studied at room temperature by measuring the continuous acoustic emission (A.E.) due to dislocations movements in the metal. In this study, original data have been obtained in the understanding of continuous A.E. sources. In comparison with classical interpretation given in the literature, the fact that dislocations are arranged according to a dislocation cell structure from the first cycle has been included in the analysis of the results. From this, it has been shown that the amplitude of the A.E. signal is not directly connected with the plastic strain rate prescribed to the fatigue sample and that the probability density function of dislocation loops created during the cycling can be determined. La plasticité cyclique de l'AI 5N polycristallin a été étudiée à la température ambiante à partir de mesures d'émission acoustique continue (E.A.). L'application de la technique de l'E.A. nous a permis d'obtenir des données originales quant aux mécanismes sources d'E.A. Par rapport aux interprétations classiques de la littérature, nous avons fait intervenir le fait que, dès les premiers cycles, une structure cellulaire de dislocations est établie. Nous montrons que l'amplitude du signal d'E.A. n'est plus liée directement à la vitesse de déformation plastique macroscopique. A partir de cette donnée, l'analyse des résultats d'E.A. permet d'obtenir des informations sur la fonction distribution des boucles de dislocations créées au cours de la déformation cyclique.

Radar response to crop residue cover and tillage application on postharvest agricultural surfaces

NASA Astrophysics Data System (ADS)

McNairn, Heather

Les informations sur les pratiques de conservation des sols comme le labourage et la gestion des residus de culture sont requises afin d'estimer avec exactitude les risques d'erosion des sols. Quoique les micro-ondes soient sensibles aux conditions d'humidite et aux proprietes geometriques des surfaces, il n'en demeure pas moins que l'on connait encore peu sur la sensibilite des micro-ondes polarisees lineaires ou des parametres polarimetriques du ROS en fonction des caracteristiques des residus. A partir de donnees prises a l'aide d'un diffusometre monte sur un camion en 1996 et lors d'une mission SIR-C menee en 1994, cette recherche a demontre que les micro-ondes sont sensibles a la fois a la quantite et au type de couverture de residus, de meme qu'a la teneur en eau des residus. La reponse des polarisations croisees lineaires et de plusieurs parametres polarimetriques, incluant la hauteur pedestre, a permis d'observer qu'une diffusion volumique importante avait lieu en presence de vegetation senescente qui se tenait debout et pour les champs non laboures. La diffusion de surface dominait cependant pour les champs avec de faibles quantites de residus et des residus plus fins. La recherche a toutefois demontre que des conditions de surface complexes etaient crees par differentes combinaisons de residus et de pratiques de labourage. Par consequent, il faudra attendre que des donnees multi-polarisees ou polarimetriques soient acquises par les capteurs prevus a bord du satellite canadien RADARSAT-2 et du satellite ENVISAT de l'Agence spatiale europeenne avant de pouvoir completement caracteriser les champs apres la recolte.

Etude de la dynamique des porteurs dans des nanofils de silicium par spectroscopie terahertz

NASA Astrophysics Data System (ADS)

Beaudoin, Alexandre

Ce memoire presente une etude des proprietes de conduction electrique et de la dynamique temporelle des porteurs de charges dans des nanofils de silicium sondes par rayonnement terahertz. Les cas de nanofils de silicium non intentionnellement dopes et dopes type n sont compares pour differentes configurations du montage experimental. Les mesures de spectroscopie terahertz en transmission montre qu'il est possible de detecter la presence de dopants dans les nanofils via leur absorption du rayonnement terahertz (˜ 1--12 meV). Les difficultes de modelisation de la transmission d'une impulsion electromagnetique dans un systeme de nanofils sont egalement discutees. La detection differentielle, une modification au systeme de spectroscopie terahertz, est testee et ses performances sont comparees au montage de caracterisation standard. Les instructions et des recommendations pour la mise en place de ce type de mesure sont incluses. Les resultats d'une experience de pompe optique-sonde terahertz sont egalement presentes. Dans cette experience, les porteurs de charge temporairement crees suite a l'absorption de la pompe optique (lambda ˜ 800 nm) dans les nanofils (les photoporteurs) s'ajoutent aux porteurs initialement presents et augmentent done l'absorption du rayonnement terahertz. Premierement, l'anisotropie de l'absorption terahertz et de la pompe optique par les nanofils est demontree. Deuxiemement, le temps de recombinaison des photoporteurs est etudie en fonction du nombre de photoporteurs injectes. Une hypothese expliquant les comportements observes pour les nanofils non-dopes et dopes-n est presentee. Troisiemement, la photoconductivite est extraite pour les nanofils non-dopes et dopes-n sur une plage de 0.5 a 2 THz. Un lissage sur la photoconductivite permet d'estimer le nombre de dopants dans les nanofils dopes-n. Mots-cles: nanofil, silicium, terahertz, conductivite, spectroscopie, photoconductivite.

Les tuberculomes intracraniens: à propos de 125 cas

PubMed Central

Moufid, Faycal; Oulali, Noureddine; El Fatemi, Nizare; Gana, Rachid; Maaqili, Rachid; Bellakhdar, Fouad

2012-01-01

Les tuberculomes intracrâniens représentent l'une des localisations les plus graves de la tuberculose, leur incidence varie en fonction du contexte représentant 0,2% des processus intracrâniens dans les pays occidentaux et 5 à 10% des masses intracrâniennes dans les pays en voie de développement. Nous rapportons une étude rétrospective de 125 cas. L'hypertension intracrânienne (45%) et le déficit neurologique (36%) sont les signes cliniques les plus fréquents. La lésion était localisée dans 60% des cas en sus-tentoriel et dans 40% des cas en sous-tentoriel. L'approche thérapeutique a consisté en un abord direct du tuberculome dans 67 cas (53%), une biopsie stéréotaxique dans 32 cas (25%), le traitement médical en première intention sans confirmation histologique dans 26 cas (20%). Avant 1993 notre service ne disposait pas de cadre de stéréotaxie, notre attitude thérapeutique consistait soit en un abord direct de la lésion dans 70% des cas, soit un traitement antituberculeux en première intention sans confirmation histologique (30%). Cette attitude était corrélée à une mortalité et morbidité non négligeables respectivement 3% et 10%. Après 1993; le taux d'abords direct a chuté a 38%, avec 47% de biopsies stéréotaxiques et seulement 13% des patients traités par antibacillaires sans preuve histologique. Ceci s'est accompagné d'une réduction significative de mortalité a 1,4% (p = 0,0003) et de morbidité a 2% (p = 0,0027). PMID:22937196

PubMed

Black, Amanda; Guilbert, Edith; Costescu, Dustin; Dunn, Sheila; Fisher, William; Kives, Sari; Mirosh, Melissa; Norman, Wendy V; Pymar, Helen; Reid, Robert; Roy, Geneviève; Varto, Hannah; Waddington, Ashley; Wagner, Marie-Soleil; Whelan, Anne Marie

2017-04-01

Mettre à la disposition des fournisseurs de soins des lignes directrices concernant le recours à des méthodes contraceptives pour prévenir la grossesse et la promotion d'une sexualité saine. Efficacité globale des méthodes contraceptives citées : évaluation de l'innocuité, des effets indésirables et de la baisse du taux de grossesse; effet des méthodes contraceptives citées sur la santé sexuelle et le bien-être général; disponibilité des méthodes contraceptives citées au Canada. RéSULTATS: Des recherches ont été effectuées dans MEDLINE et la base de données Cochrane afin d'en tirer les articles en anglais publiés entre janvier 1994 et décembre 2015 traitant de sujets liés à la contraception, à la sexualité et à la santé sexuelle, dans le but de mettre à jour le consensus canadien sur la contraception paru de février à avril 2004. Nous avons également passé en revue les publications pertinentes du gouvernement canadien, ainsi que les déclarations de principes issues d'organisations compétentes vouées à la santé et à la planification familiale. La qualité des résultats a été évaluée au moyen des critères décrits par le Groupe d'étude canadien sur les soins de santé préventifs. Les recommandations quant à la pratique sont classées en fonction de la méthode décrite dans le rapport du Groupe. DéCLARATIONS SOMMAIRES: RECOMMANDATIONS. Copyright © 2017. Published by Elsevier Inc.

Conforming discretizations of boundary element solutions to the electroencephalography forward problem

NASA Astrophysics Data System (ADS)

Rahmouni, Lyes; Adrian, Simon B.; Cools, Kristof; Andriulli, Francesco P.

2018-01-01

In this paper, we present a new discretization strategy for the boundary element formulation of the Electroencephalography (EEG) forward problem. Boundary integral formulations, classically solved with the Boundary Element Method (BEM), are widely used in high resolution EEG imaging because of their recognized advantages, in several real case scenarios, in terms of numerical stability and effectiveness when compared with other differential equation based techniques. Unfortunately, however, it is widely reported in literature that the accuracy of standard BEM schemes for the forward EEG problem is often limited, especially when the current source density is dipolar and its location approaches one of the brain boundary surfaces. This is a particularly limiting problem given that during an high-resolution EEG imaging procedure, several EEG forward problem solutions are required, for which the source currents are near or on top of a boundary surface. This work will first present an analysis of standardly and classically discretized EEG forward problem operators, reporting on a theoretical issue of some of the formulations that have been used so far in the community. We report on the fact that several standardly used discretizations of these formulations are consistent only with an L2-framework, requiring the expansion term to be a square integrable function (i.e., in a Petrov-Galerkin scheme with expansion and testing functions). Instead, those techniques are not consistent when a more appropriate mapping in terms of fractional-order Sobolev spaces is considered. Such a mapping allows the expansion function term to be a less regular function, thus sensibly reducing the need for mesh refinements and low-precisions handling strategies that are currently required. These more favorable mappings, however, require a different and conforming discretization, which must be suitably adapted to them. In order to appropriately fulfill this requirement, we adopt a mixed discretization based on dual boundary elements residing on a suitably defined dual mesh. We devote also a particular attention to implementation-oriented details of our new technique that will allow the rapid incorporation of our finding in one's own EEG forward solution technology. We conclude by showing how the resulting forward EEG problems show favorable properties with respect to previously proposed schemes, and we show their applicability to real-case modeling scenarios obtained from Magnetic Resonance Imaging (MRI) data. xml:lang="fr" Malheureusement, il est également reconnu dans la littérature que leur précision diminue particulièrement lorsque la source de courant est dipolaire et se situe près de la surface du cerveau. Ce défaut constitue une importante limitation, étant donné qu'au cours d'une session d'imagerie EEG à haute résolution, plusieurs solutions du problème direct EEG sont requises, pour lesquelles les sources de courant sont proches ou sur la surface de cerveau. Ce travail présente d'abord une analyse des opérateurs intervenant dans le problème direct et leur discrétisation. Nous montrons que plusieurs discrétisations couramment utilisées ne conviennent que dans un cadre L2, nécessitant que le terme d'expansion soit une fonction de carré intégrable. Dès lors, ces techniques ne sont pas cohérentes avec les propriétés spectrales des opérateurs en termes d'espaces de Sobolev d'ordre fractionnaire. Nous développons ensuite une nouvelle stratégie de discrétisation conforme aux espaces de Sobolev avec des fonctions d'expansion moins régulières, donnant lieu à une nouvelle formulation intégrale. Le solveur résultant présente des propriétés favorables par rapport aux méthodes existantes et réduit sensiblement le recours à un maillage adaptatif et autres stratégies actuellement requises pour améliorer la précision du calcul. Les résultats numériques présentés corroborent les développements théoriques et mettent en évidence l'impact positif de la nouvelle approche.

Systeme microfluidique d'analyse sanguine en temps reel pour l'imagerie moleculaire chez le petit animal

NASA Astrophysics Data System (ADS)

Convert, Laurence

De nouveaux radiotraceurs sont continuellement développés pour améliorer l'efficacité diagnostique en imagerie moléculaire, principalement en tomographie d'émission par positrons (TEP) et en tomographie d'émission monophotonique (TEM) dans les domaines de l'oncologie, de la cardiologie et de la neurologie. Avant de pouvoir être utilisés chez les humains, ces radiotraceurs doivent être caractérisés chez les petits animaux, principalement les rats et les souris. Pour cela, de nombreux échantillons sanguins doivent être prélevés et analysés (mesure de radioactivité, séparation de plasma, séparation d'espèces chimiques), ce qui représente un défi majeur chez les rongeurs à cause de leur très faible volume sanguin (˜1,4 ml pour une souris). Des solutions fournissant une analyse partielle sont présentées dans la littérature, mais aucune ne permet d'effectuer toutes les opérations dans un même système. Les présents travaux de recherche s'insèrent dans le contexte global d'un projet visant à développer un système microfluidique d'analyse sanguine complète en temps réel pour la caractérisation des nouveaux radiotraceurs TEP et TEM. Un cahier des charges a tout d'abord été établi et a permis de fixer des critères quantitatifs et qualitatifs à respecter pour chacune des fonctions de la puce. La fonction de détection microfluidique a ensuite été développée. Un état de l'art des travaux ayant déjà combiné la microfluidique et la détection de radioactivité a permis de souligner qu'aucune solution existante ne répondait aux critères du projet. Parmi les différentes technologies disponibles, des microcanaux en résine KMPR fabriqués sur des détecteurs semiconducteurs de type p-i-n ont été identifiés comme une solution technologique pour le projet. Des détecteurs p-i-n ont ensuite été fabriqués en utilisant un procédé standard. Les performances encourageantes obtenues ont mené à initier un projet de maîtrise pour leur optimisation. En parallèle, les travaux ont été poursuivis avec des détecteurs du commerce sous forme de gaufres non découpées. Un premier dispositif intégrant des canaux en KMPR sur ces gaufres a permis de valider le concept démontrant le grand potentiel de ces choix technologiques et incitant à poursuivre les développements dans cette voie, notamment en envisageant des expériences animales. L'utilisation prolongée des canaux avec du sang non dilué est cependant particulièrement exigeante pour les matériaux artificiels. Une passivation à l'albumine a permis d'augmenter considérablement la compatibilité sanguine de la résine KMPR. Le concept initial, incluant la passivation des canaux, a ensuite été optimisé et intégré dans un système de mesure complet avec toute l'électronique et l'informatique de contrôle. Le système final a été validé chez le petit animal avec un radiotraceur connu. Ces travaux ont donné lieu à la première démonstration d'un détecteur microfluidique de haute efficacité pour la TEP et la TEM. Cette première brique d'un projet plus global est déjà un outil innovant en soi qui permettra d'augmenter l'efficacité du développement d'outils diagnostiques plus spécifiques principalement pour l'oncologie, la cardiologie et la neurologie. Mots clefs : imagerie moléculaire, tomographie d'émission par positrons (TEP), tomographie d'émission monophotonique (TEM), microfluidique, détecteur de radioactivité, KMPR, diodes p-i-n, hémocompatibilité.

Semiconducting perovskites (2-XC6H4C2H4NH3)2SnI4 (X = F, Cl, Br): steric interaction between the organic and inorganic layers.

PubMed

Xu, Zhengtao; Mitzi, David B; Dimitrakopoulos, Christos D; Maxcy, Karen R

2003-03-24

Two new semiconducting hybrid perovskites based on 2-substituted phenethylammonium cations, (2-XC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) (X = Br, Cl), are characterized and compared with the previously reported X = F compound, with a focus on the steric interaction between the organic and inorganic components. The crystal structure of (2-ClC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) is solved in a disordered subcell [C2/m, a = 33.781(7) A, b = 6.178(1) A, c = 6.190(1) A, beta = 90.42(3)(o), and Z = 2]. The structure is similar to the known (2-FC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) structure with regard to both the conformation of the organic cations and the bonding features of the inorganic sheet. The (2-BrC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) system adopts a fully ordered monoclinic cell [P2(1)/c, a = 18.540(2) A, b = 8.3443(7) A, c = 8.7795(7) A, beta = 93.039(1)(o), and Z = 2]. The organic cation adopts the anti conformation, instead of the gauche conformation observed in the X = F and Cl compounds, apparently because of the need to accommodate the additional volume of the bromo group. The steric effect of the bromo group also impacts the perovskite sheet, causing notable distortions, such as a compressed Sn-I-Sn bond angle (148.7(o), as compared with the average values of 153.3 and 154.8(o) for the fluoro and chloro compounds, respectively). The optical absorption features a substantial blue shift (lowest exciton peak: 557 nm, 2.23 eV) relative to the spectra of the fluoro and chloro compounds (588 and 586 nm, respectively). Also presented are transport properties for thin-film field-effect transistors (TFTs) based on spin-coated films of the two hybrid semiconductors.

Theoretical spectroscopic characterization at low temperatures of detectable sulfur-organic compounds: Ethyl mercaptan and dimethyl sulfide

NASA Astrophysics Data System (ADS)

Senent, M. L.; Puzzarini, C.; Domínguez-Gómez, R.; Carvajal, M.; Hochlaf, M.

2014-03-01

Highly correlated ab initio methods are used for the spectroscopic characterization of ethyl mercaptan (CH3CH232SH, ETSH) and dimethyl sulfide (CH332SCH3, DMS), considering them on the vibrational ground and excited torsional states. Since both molecules show non-rigid properties, torsional energy barriers and splittings are provided. Equilibrium geometries and the corresponding rotational constants are calculated by means of a composite scheme based on CCSD(T) calculations that accounts for the extrapolation to the complete basis set limit and core-correlation effects. The ground and excited states rotational constants are then determined using vibrational corrections obtained from CCSD/cc-pVTZ force-field calculations, which are also employed to determine anharmonic frequencies for all vibrational modes. CCSD(T) and CCSD force fields are employed to predict quartic and sextic centrifugal-distortion constants, respectively. Equilibrium rotational constants are also calculated using CCSD(T)-F12. The full-dimensional anharmonic analysis does not predict displacements of the lowest torsional excited states due to Fermi resonances with the remaining vibrational modes. Thus, very accurate torsional transitions are calculated by solving variationally two-dimensional Hamiltonians depending on the CH3 and SH torsional coordinates of ethyl mercaptan or on the two methyl groups torsions of dimethyl-sulfide. For this purpose, vibrationally corrected potential energy surfaces are computed at the CCSD(T)/aug-cc-pVTZ level of theory. For ethyl mercaptan, calculations show large differences between the gauche (g) and trans (t) conformer spectral features. Interactions between rotating groups are responsible for the displacements of the g-bands with respect to the t-bands that cannot therefore be described with one-dimensional models. For DMS, the CCSD(T) potential energy surface has been semi-empirically adjusted to reproduce experimental data. New assignments are suggested for the methyl torsion bands of ETSH and a reassignment is proposed for the infrared bands of DMS (0 3 → 0 4 and 1 0 → 1 1). Our accurate spectroscopic data should be useful for the analysis of the microwave and far infrared spectra of ETSH and DMS recorded, at low temperatures, either in laboratory or in the interstellar medium.

a Study of Vibrational Mode Coupling in 2-FLUOROETHANOL and 1,2-DIFLUOROETHANE Using High-Resolution Infrared Spectroscopy.

NASA Astrophysics Data System (ADS)

Mork, Steven Wayne

High resolution infrared spectroscopy was used to examine intramolecular vibrational interactions in 2 -fluoroethanol (2FE) and 1,2-difluoroethane (DFE). A high resolution infrared spectrophotometer capable of better than 10 MHz spectral resolution was designed and constructed. The excitation source consists of three lasers: an argon-ion pumped dye laser which pumps a color -center laser. The infrared beam from the color-center laser is used to excite sample molecules which are rotationally and vibrationally cooled in a supersonic molecular beam. Rovibrational excitation of the sample molecules is detected by monitoring the kinetic energy of the molecular beam with a bolometer. The high resolution infrared spectrum of 2FE was collected and analyzed over the 2977-2990 cm^ {-1}^ectral region. This region contains the asymmetric CH stretch on the fluorinated carbon. The spectrum revealed extensive perturbations in the rotational fine structure. Analysis of these perturbations has provided a quantitative measure of selective vibrational mode coupling between the C-H stretch and its many neighboring dark vibrational modes. Interestingly, excitation of the C-H stretch is known to induce a photoisomerization reaction between 2FE's Gg^' and Tt conformers. Implications of the role of mode coupling in the reaction mechanism are also addressed. Similarly, the high resolution infrared spectrum of DFE was collected and analyzed over the 2978-2996 cm ^{-1}^ectral region. This region contains the symmetric combination of asymmetric C-H stretches in DFE. Perturbations in the rotational fine structure indicate vibrational mode coupling to a single dark vibrational state. The dark state is split by approximately 19 cm^{-1} due to tunneling between two identical gauche conformers. The coupling mechanism is largely anharmonic with a minor component of B/C-plane Coriolis coupling. Effects of centrifugal distortion along the molecular A-axis are also observed. The coupled vibrational mode has been identified as containing C-C torsion, CCF bend and CH_2 rock. As in 2FE, DFE undergoes an isomerization reaction upon excitation of the C-H stretch. Coupling between the C-H stretch and C-C torsion is addressed with respect to the reaction mechanism.

Impact de la varicocèle sur le volume testiculaire et les paramètres spermatiques

PubMed Central

Benazzouz, Mohamed Hicham; Essatara, Younes; El Sayegh, Hachem; Iken, Ali; Benslimane, Lounis; Nouini, Yassine

2014-01-01

Introduction La varicocèle est une pathologie masculine fréquente dont l'incidence est encore plus importante dans dans la population des hommes infertiles. Si ses mécanismes sont à ce jour incomplètement expliqués il semble acquis que la varicocèle peut être associée a une dysfonction testiculaire avec diminution du volume testiculaire et de la concentration en spermatozoïde de l’éjaculat. Méthodes Dans un premier temps nous exposons les résultats d'une étude rétrospective sur 5 ans (de Mars 2009 à Mars 2014), réalisée au service d'urologie A de l'hôpital Ibn Sina de Rabat et ayant comme objectif d’évaluer l'impact de la varicocèle palpable sur le volume testiculaire et les paramètres spermatiques. Tous les patients inclus dans notre étude avaient une varicocèle palpable. Dans un deuxième temps, et à travers une revue de la littérature nous discutons l'impact du traitement de la varicocèle sur la fertilité. Résultats 39 patients ont été inclus dans notre étude. L’âge moyen était de 29,71 ans et la varicocèle siégeait dans 89,74% des cas du coté gauche. Une atrophie testiculaire homolatérale à la varicocèle était retrouvée dans 7% des cas alors que des anomalies du spermogramme se voyaient dans 69,23% des cas. Conclusion L'impact de la varicocèle sur l'altération des paramètres spermatiques a été clairement établi bien que sa physio pathogénie ne soit pas bien élucidée. Le traitement chirurgical de la varicocèle semble indiqué chez les hommes infertiles présentant une varicocèle clinique et une altération significative du sperme. PMID:25918574

Use of beta-methylphenylalanine (beta MeF) residues to probe the nature of the interaction of substance P with its receptor: effects of beta MeF-containing substance P analogs on rabbit iris smooth muscle contraction.

PubMed

Birney, D M; Cole, D C; Crosson, C E; Kahl, B F; Neff, B W; Reid, T W; Ren, K; Walkup, R D

1995-06-23

The effects of substituting (2S,3S)-beta-methylphenylalanine (S-beta MeF) or (2S,3R)-beta-methylphenylalanine (R-beta MeF) for the Phe7 and/or Phe8 residues of the tachykinin substance P (SP, RPKPQQFFGLM-NH2) upon the ability of SP to stimulate contraction of the rabbit iris smooth muscle were investigated. The eight beta MeF-containing SP analogs (four monosubstituted analogs, four disubstituted analogs) 1-8 were synthesized and found to be agonsts of SP in the smooth muscle contraction assay, having EC50 values ranging from 0.15 to 10.0 nM. Three analogs are significantly more active than SP [8R-(beta MeF)SP (4), 7S,8S-(beta MeF)2SP (5), and 7R,8S-(beta MeF)2SP (6)], three analogs are approximately equipotent with SP [7S-(beta MeF)SP (1), 7R-(beta MeF)SP (2), and 7S,8R-(beta MeF)2SP (8)], and two analogs are significantly less active than SP [8S-(beta MeF)SP (3) and 7R,8R-(beta MeF)2SP (7)]. The effects of the beta MeF substitutions upon the activity of SP are not additive and cannot be explained using simple conformational models which focus only on the side chain conformations of the beta MeF residues. It is postulated that the beta MeF residues induce minor distortions in the peptide backbone with resultant consequences upon peptide-receptor binding which are not dictated soley by the side chain conformations. This idea is consistent with 1H-NMR data for the monosubstituted analogs 1-4, which imply that the beta MeF substitutions cause slight distortions in the peptide backbone and that the beta MeF side chains are assuming trans or gauche(-) conformations.

Thermodynamic properties of {Delta}H{sub f 298}{degree}, S{sub 298}{degree}, and C{sub p}(T) for 2-fluoro-2-methylpropane, {Delta}H{sub f 298}{degree} of fluorinated ethanes, and group additivity for fluoroalkanes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yamada, Takahiro; Bozzelli, J.W.

1999-09-09

G2(MP2) composite calculations are performed to obtain thermodynamic properties ({Delta}H{sub f 298}{degree}, S{sub 298}{degree} and C{sub p}(T)'s) of 2-fluoro-2-methylpropane. {Delta}H{sub f 298}{degree} is calculated from the G2(MP2) calculated enthalpy of reaction ({Delta}H{sub rxn 298}{degree}) and use of isodesmic reactions. Standard entropy (S{sub 298}{degree} in cal/(mol{center{underscore}dot}K)) and heat capacities (C{sub p}(T)'s in cal/(mol{center{underscore}dot}K)) are calculated using the rigid-rotor--harmonic-oscillator approximation with direct integration over energy levels of the intermolecular rotation potential energy curve. These thermodynamic properties are used to estimate data for the C/C3/F group. Enthalpies of formation ({Delta}H{sub f 298}{degree} in kcal/mol) for 1,2-difluoroethane ({minus}102.7), 1,1,2-trifluoroethane ({minus}156.9), 1,1,2,2- and 1,1,1,2-tetrafluoroethane (209.6more » and 213.3), and pentafluoroethane ({minus}264.1), are calculated using total energies obtained from G2(MP2) composite ab initio methods. Isodesmic reactions with existing literature values of {Delta}H{sub f 298}{degree} for ethane, 1-fluoroethane, 1,1-difjuoroethane and 1,1,1-trifluoroethane are used. Fluorine/fluorine interaction terms, F/F, 2F/F, 3F/F, 2F/2F, and 3F/2F, where ``/'' indicates interaction for alkane compounds, for {Delta}H{sub f 298}{degree} are reevaluated based on {Delta}H{sub f 298}{degree} of the above five fluoroethanes. Thermodynamic properties ({Delta}H{sub f 298}{degree}, S{sub 298}{degree} and C{sub p}(T)'s (300 {le} T/K {le} 1500)) for fluorinated carbon groups, C/C3F, C/C2/F/H, C/C2/F2, are calculated using data from ab initio methods and existing literature data. Fluorine-methyl (alkyl) group additivity corrections for gauche interactions are also evaluated.« less

Searching for trans ethyl methyl ether in Orion KL⋆

NASA Astrophysics Data System (ADS)

Tercero, B.; Cernicharo, J.; López, A.; Brouillet, N.; Kolesniková, L.; Motiyenko, R. A.; Margulès, L.; Alonso, J. L.; Guillemin, J.-C.

2015-10-01

We report on the tentative detection of trans ethyl methyl ether (tEME), t-CH3CH2OCH3, through the identification of a large number of rotational lines from each one of the spin states of the molecule towards Orion KL. We also search for gauche-trans-n-propanol, Gt-n-CH3CH2CH2OH, an isomer of tEME in the same source. We have identified lines of both species in the IRAM 30 m line survey and in the ALMA Science Verification data. We have obtained ALMA maps to establish the spatial distribution of these species. Whereas tEME mainly arises from the compact ridge component of Orion, Gt-n-propanol appears at the emission peak of ethanol (south hot core). The derived column densities of these species at the location of their emission peaks are ≤(4.0 ± 0.8) × 1015 cm-2 and ≤(1.0 ± 0.2) × 1015 cm-2 for tEME and Gt-n-propanol, respectively. The rotational temperature is ~100 K for both molecules. We also provide maps of CH3OCOH, CH3CH2OCOH, CH3OCH3, CH3OH, and CH3CH2OH to compare the distribution of these organic saturated O-bearing species containing methyl and ethyl groups in this region. Abundance ratios of related species and upper limits to the abundances of non-detected ethers are provided. We derive an abundance ratio N(CH3OCH3)/N(tEME) ≥ 150 in the compact ridge of Orion. This paper makes use of the following ALMA data: ADS/JAO.ALMA#2011.0.00009.SV. ALMA is a partnership of ESO (representing its member states), NSF (USA), and NINS (Japan) with NRC (Canada), NSC, and ASIAA (Taiwan), and KASI (Republic of Korea), in cooperation with the Republic of Chile. The Joint ALMA Observatory is operated by ESO, AUI/NRAO, and NAOJ. This work was also based on observations carried out with the IRAM 30-m telescope. IRAM is supported by INSU/CNRS (France), MPG (Germany), and IGN (Spain).Appendix A is available in electronic form at http://www.aanda.org

Three isomers detected for the whisky lactone: 5-butyl-4-methyl tetrahydrofuran-2-one by Fourier transform microwave spectroscopy and quantum chemical calculations

NASA Astrophysics Data System (ADS)

Kawashima, Yoshiyuki; Katsuragi, Ryusuke; Hirota, Eizi

2017-05-01

The ground-state rotational spectra of the whisky lactone (WL) : 5-butyl-4-methyl tetrahydrofuran-2-one were observed and analyzed by molecular beam Fourier transform microwave spectroscopy combined with quantum chemical calculations. We have detected three stereo-isomers: the trans-TTT form with a methyl CH3 group attached to C(4) in an equatorial position (eq) and a butyl C4H9 group to C(5) in an eq position, for which 110 b-type and 113 a-type transitions were assigned, the cis-TTT form with a CH3 to C(4) in an axial position (ax) and a C4H9 to C(5) in eq, for which 96 a-type, 101 b-type, and 45 c-type transitions were observed, and the cis-GTT form with a CH3 to C(4) in ax and a C4H9 to C(5) in eq, for which 158 a-type, 52 b-type, and 17 c-type transitions were observed, where TTT and GTT denote the conformations about the C(6)sbnd C(5), C(7)sbnd C(6), and C(8)sbnd C(7) bonds, with T and G designating trans and gauche, respectively. The rotational constants thus derived agree with the predictions made by quantum chemical calculations, MP2/6-311++G(d, p) within 1.2%. The trans-TTT form was calculated to be the most stable. The splittings due to internal rotation of the terminal methyl in the butyl group were observed for all the three stereo-isomers and were analyzed by the XIAM program to determine the threefold potential barrier V3 to be 966.4 (25), 978.8 (11), and 1098.7 (48) in cm-1 for the trans-TTT (eq, eq), the cis-TTT (ax, eq), and the cis-GTT (ax, eq) forms, respectively, to be compared with quantum chemically calculated values: 1055, 1055, and 1053 in cm-1.

IR low-temperature matrix, X-ray and ab initio study on L-isoserine conformations.

PubMed

Dobrowolski, Jan Cz; Jamróz, Michał H; Kołos, Robert; Rode, Joanna E; Cyrański, Michał K; Sadlej, Joanna

2010-09-28

The IR low-temperature Ar and Kr matrix spectra of l-isoserine were registered for the first time and interpreted by means of the anharmonic DFT frequencies calculated at the B3LYP/aug-cc-pVTZ and B3LYP/aug-cc-pVDZ levels. 54 l-isoserine conformers were predicted to be stable at the B3LYP/aug-cc-pVDZ level. Population of the 8 most stable conformers was based on the QCISD/aug-cc-pVDZ energies, corrected for thermal anharmonic factors obtained at the B3LYP/aug-cc-pVDZ level. We found several conformers to be present in the measured matrices and conformer 1 to be dominating. Presence of the conformer 2 is well confirmed by the nu(C=O) band at 1790 cm(-1) and two bands at 1380 and 1350 cm(-1). Presence of the conformer 4 is quite well confirmed by the nu(C-O) bands at 1120 and 1095 cm(-1). Slightly weaker arguments are found for the observation of conformers 6 and 3. Calculations on 54 neutral and 5 zwitterionic conformers in water at the IEF-PCM/B3LYP/aug-cc-pVDZ level suggest that one neutral and one zwitterionic conformer co-exist in the aqueous environment. The crystal structure of l-isoserine was solved by X-ray diffraction analysis. The compound crystallizes without solvent in the chiral P2(1)2(1)2 space group. The asymmetric unit contains a single molecule. The molecule is in its zwitterionic form with the CH(2)-NH(3) side chain in the gauche conformation with respect to the hydroxyl group and in the anti conformation with respect to the carboxylate group. The structure of l-isoserine is dominated by a set of intermolecular hydrogen bonds. The strongest one appears between the OH and COOH groups of two neighbouring molecules: the O...H contact is of 1.66(2) A, which is amongst the shortest H-bonds of this kind observed in amino acid crystal structures.

Facile preparation of an alternating copolymer-based high molecular shape-selective organic phase for reversed-phase liquid chromatography.

PubMed

Mallik, Abul K; Noguchi, Hiroki; Rahman, Mohammed Mizanur; Takafuji, Makoto; Ihara, Hirotaka

2018-06-22

The synthesis of a new alternating copolymer-grafted silica phase is described for the separation of shape-constrained isomers of polycyclic aromatic hydrocarbons (PAHs) and tocopherols in reversed-phase high-performance liquid chromatography (RP-HPLC). Telomerization of the monomers (octadecyl acrylate and N-methylmaleimide) was carried out with a silane coupling agent; 3-mercaptopropyltrimethoxysilane (MPS), and the telomer (T) was grafted onto porous silica surface to prepare the alternating copolymer-grafted silica phase (Sil-alt-T). The new hybrid material was characterized by elemental analyses, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, and solid-state 13 C and 29 Si cross-polarization magic-angle spinning (CP/MAS) NMR spectroscopy. The results of 13 C CP/MAS NMR demonstrated that the alkyl chains of the grafted polymers in Sil-alt-T remained disordered, amorphous, and mobile represented by gauche conformational form. Separation abilities and molecular-shape selectivities of the prepared organic phase were evaluated by the separation of PAHs isomers and Standard Reference Material 869b, Column Selectivity Test Mixture for Liquid Chromatography, respectively and compared with commercially available octadecylsilylated silica (ODS) and C 30 columns as well as previously reported alternating copolymer-based column. The effectiveness of this phase is also demonstrated by the separation of tocopherol isomers. Oriented functional groups along the polymer main chains and cavity formations are investigated to be the driving force for better separation with multiple-interactions with the solutes. One of the advantages of the Sil-alt-T phase to that of the previously reported phase is the synthesis of the telomer first and then immobilized onto silica surface. In this case, the telomer was characterized easily with simple spectroscopic techniques and the molecular mass and polydispersity index of the telomer were determined by size exclusion chromatography (SEC) before grafting onto silica surface. Moreover, both of the monomers were commercially available. Therefore, the technique of preparation was very facile and better separation was achieved with the Sil-alt-T phase compared to the ODS, C 30 and other previously reported alternating copolymer-based columns. Copyright © 2018 Elsevier B.V. All rights reserved.

Solid state 13C-NMR, infrared, X-ray powder diffraction and differential thermal studies of the homologous series of some mono-valent metal (Li, Na, K, Ag) n-alkanoates: A comparative study

NASA Astrophysics Data System (ADS)

Nelson, Peter N.; Ellis, Henry A.; White, Nicole A. S.

2015-06-01

A comparative study of the molecular packing, lattice structures and phase behaviors of the homologous series of some mono-valent metal carboxylates (Li, Na, K and Ag) is carried out via solid state FT-infrared and 13C-NMR spectroscopes, X-rays powder diffraction, density measurements, differential scanning calorimetry, polarizing light microscopy and variable temperature infrared spectroscopy. It is proposed that, for lithium, sodium and potassium carboxylates, metal-carboxyl coordination is via asymmetric chelating bidentate bonding with extensive intermolecular interactions to form tetrahedral metal centers, irrespective of chain length. However, for silver n-alkanoates, carboxyl moieties are bound to silver ions via syn-syn type bridging bidentate coordination to form dimeric units held together by extensive head group inter-molecular interactions. Furthermore, the fully extended hydrocarbon chains which are crystallized in the all-trans conformation are tilted at ca. 30°, 27°, 15° and 31° with respect to a normal to the metal plane, for lithium, sodium, silver and potassium carboxylates, respectively. All compounds are packed as lamellar bilayer structures, however, lithium compounds are crystallized in a triclinic crystal system whilst silver, sodium and potassium n-alkanoates are all monoclinic with possible P1 bravais lattice. Odd-even alternation observed in various physical features is associated with different inter-planar spacing between closely packed layers in the bilayer which are not in the same plane; a phenomenon controlled by lattice packing symmetry requirements. All compounds, except silver carboxylates, show partially reversibly first order pre-melting transitions; the number of which increases with increasing chain length. These transitions are associated, for the most part, with lamellar collapse followed by increased gauche-trans isomerism in the methylene group assembly, irrespective of chain length. It is proposed that the absence of mesomorphic transitions in their phase sequences is due to a lack of sufficient balance between attractive and repulsive electrostatic and van der Waals forces during phase change. The evidence presented in this study shows that phase behaviors of mono-valent metal carboxylates are controlled, mainly, by head group bonding.

Spectra and structure of organophosphorus compounds. LI. IR and Raman spectra, conformational stability, barriers to internal rotation, vibrational assignment, and ab initio calculations of n-propylphosphine

NASA Astrophysics Data System (ADS)

Durig, J. R.; Gounev, T. K.; Lee, M. S.; Little, T. S.

1994-10-01

The Raman (3100 to 50 cm -1) and IR (3100 to 50 cm -1) spectra of gaseous and solid n-propylphosphine, C 3H 7PH 2, and the corresponding P- d2 isotopomer have been recorded. Additionally, the Raman spectra of the liquids have been obtained with qualitative depolarization ratios. From these data, all five possible conformers have been identified in the fluid states and the trans-trans conformer is shown to be the most stable rotamer in both the gaseous and liquid states and it is the only conformer present in the solid. The first trans refers to the orientation of the lone pair to the ethylene group (rotation around the PC bond) whereas the second trans refers to the orientation of the methyl group relative to the PC bond (rotation around the -CH 2CH 2 bond). The next most stable conformer is the gauche-trans rotamer where the enthalpy difference has been determined from variable-temperature Raman studies to be 140 ± 5 cm -1 (400 ± 14 cal mol -1) for the vapor and 351 ± 20 cm -1 (1004 ± 57 cal mol -1) for the liquid. The other three conformers have nearly the same stabilities but significantly higher energies than the two more stable rotamers. From the far-IR data and relative conformer stabilities, some of the coefficients of the potential function governing conformer interconversion are estimated. A complete vibrational assignment is proposed for the trans-trans conformer and for the fundamentals for most of the heavy atom motions for the other conformers. The conformational stabilities, barriers to internal rotation, and fundamental vibrational frequencies which have been determined experimentally are compared to those obtained from ab initio calculations employing the RHF/3-21G* and/or RHF/6-31G* basis sets. Additionally, the conformational stabilities and structural parameters have been determined with the 6-31G* basis set with electron correlation at the MP2 level. These results are compared with the corresponding quantities for some similar molecules.

La prise en charge du pneumothorax spontané: à propos de 138 cas

PubMed Central

Habibi, Bouchra; Achachi, Leila; Hayoun, Sohaib; Raoufi, Mohammed; Herrak, Laila; Ftouh, Mustapha El

2017-01-01

Le pneumothorax est définit par la présence d’air dans la cavité pleurale. L’objectif de notre étude rétrospective du pneumothorax spontanés au servie de pneumologie à l’hôpital Ibn Sina rabat (2009-2011) est de déterminer le profil épidémiologique, clinique, radiologique, thérapeutique et évolutif. Il s’agit de 138 patients: 128 hommes et 10 femmes (17 à 83 ans), un âge moyen de 44,5 +/- 17,4 ans; sexe ratio 12/8. Le tabagisme est noté chez 81,2%. La symptomatologie clinique est la douleur thoracique (92%), la dyspnée (60%). Et sur la radiographie thoracique: on trouve un PNO (pneumothorax) unilatéral total (110 cas); partiel (10 cas); localisé (6 cas); bilatéral (4 cas); à droite dans 51,4% et à gauche dans 45,7%. On a recensé 70% de pneumothorax spontanés primitifs et 30% de PNO secondaire à (BPCO 44%, et tuberculose pulmonaire 39%). La prise en charge initiale est l’hospitalisation de tous les patients : le drainage thoracique (95%), l’exsufflation à l’aiguille (1%). Le repos et l’O2 (4%). Le retour du poumon à la paroi a été obtenu avant 10 jours chez 63%. L’évolution est favorable chez 89%. Et les complications immédiates: l’emphysème sous cutané (5 cas); une infection (6 cas) et 3 décès (arrêt cardio-respiratoire); les complications à distance sont les récidives dans 11,6%; une 1ère récidive chez 13 cas (drainage thoracique chez 11 cas et oxygénothérapie chez 2 cas) et une 2ème récidive chez 3 cas (recours à la chirurgie). Ce travail montre l’intérêt du drainage thoracique et la surveillance dans la prise en charge du pneumothorax pour éviter les complications et surtout pour éviter les récidives avec un éventuel recours à la chirurgie. PMID:28533875

Cancer du sein au Cameroun, profil histo-épidémiologique: à propos de 3044 cas

PubMed Central

Engbang, Jean Paul Ndamba; Essome, Henri; Koh, Valère Mve; Simo, Godefroy; Essam, Jean Daniel Sime; Mouelle, Albert Sone; Essame, Jean Louis Oyono

2015-01-01

Décrire les caractéristiques épidémiologiques et histo-pathologiques des tumeurs malignes du sein au Cameroun. Il s'agissait d'une étude rétrospective descriptive portant sur les tumeurs malignes du sein, colligées, dans les registres des différents laboratoires d'Anatomie Pathologique publiques et privés repartis dans cinq régions (centre, littoral, Ouest, Nord-ouest, Sud-ouest), pendant une période de 10 ans (2004-2013). Les paramètres étudiés étaient la fréquence, l’âge, le sexe, la localisation, le type et le grade histologique, et les récepteurs hormonaux. Un total de 3044 cas de cancers du sein a été recensé, soit une fréquence annuelle de 304,4 cas en moyenne. Le sexe féminin était le plus représenté avec 2971 cas (97,60%) et les hommes avec 73 cas (2,40%), soit un sexe ratio (H/F) de 0,02. L’âge moyen des patients était de 46±15,87 ans, avec des extrêmes de 13 et 95 ans. Selon la localisation, le sein gauche était atteint dans 1244 cas (52%) et le sein droit dans 1115 cas (47%). Au plan histologique, on retrouvait essentiellement des carcinomes avec 96,50% des cas, des sarcomes 1,39%, des lymphomes 1,07% et la maladie de Paget du mamelon, 1,03%. Les tumeurs épithéliales étaient infiltrantes dans 2049 cas (84,46%), avec une prédominance du carcinome canalaire infiltrant (1870 cas) et non infiltrantes dans 377 cas (15,54%). Le grade histo-pronostic de SBR avait révélé une prédominance du grade II dans 66% des cas. Les cancers du sein restent une pathologie fréquente au Cameroun et atteignent principalement la population féminine en âge de procréer. Ils sont caractérisés par la prédominance du carcinome canalaire infiltrant. PMID:26523182

Doppler transcranien au cours de la drépanocytose chez l'enfant Malagasy

PubMed Central

Herinirina, Nicolas Fanantenana; Rajaonarison, Lova Hasina Ny Ony Narindra; Herijoelison, Andry Roussel; Rakoto, Olivat Aimée Alson; Ahmad, Ahmad

2016-01-01

Introduction Le doppler transcrânien est un outil efficace permettant de dépister les enfants drépanocytaires à risque d'AVC. Méthodes Nous avons réalisé une étude descriptive transversale sur des enfants Malagasy âgés entre 24 mois et 15 ans (groupe 1: 57 drépanocytaires, groupe 2: 43 témoins) afin d’évaluer le profil vélocimétrique des artères cérébrales chez les drépanocytaires. Un examen Doppler transcrânien a été réalisé avec étude des flux sanguins cérébraux chez les enfants des deux groupes. Résultats Pour les sujets drépanocytaires, la vitesse moyenne (VM) de l'artère cérébrale moyenne était de 100,9 ± 26,8 cm/s, l'indice de pulsatilité (IP) de 0,73 ± 0,20, la différence entre les artères cérébrales moyennes droite et gauche (ACMr) de 19,8 ± 21,5 cm/s, le rapport des vitesses de l'artère cérébrale antérieure/artère cérébrale moyenne (ACA/ACM) de 0,7 ± 0,2. Pour les enfants non drépanocytaires, VM: 80,6 ± 19,3 cm/s, IP: 0,79 ± 0,14, ACMr: 17 ± 20,1 cm/s, ACA/ACM: 0,8 ± 0,2. La vélocité des enfants drépanocytaires était supérieure au groupe contrôle. Les vitesses ont été corrélées avec le taux d'hémoglobine et l’âge et non pas avec le sexe et le volume globulaire moyen. Conclusion Les vitesses circulatoires cérébrales sont élevées chez les drépanocytaires que les enfants non drépanocytaires et sont influencées par le taux d'hémoglobine et l’âge. PMID:27516829

Structural characterization and mutational assessment of podocin - a novel drug target to nephrotic syndrome - an in silico approach.

PubMed

Tabassum, Asra; Rajeshwari, Tadigadapa; Soni, Nidhi; Raju, D S B; Yadav, Mukesh; Nayarisseri, Anuraj; Jahan, Parveen

2014-03-01

Non-synonymous single nucleotide changes (nSNC) are coding variants that introduce amino acid changes in their corresponding proteins. They can affect protein function; they are believed to have the largest impact on human health compared with SNCs in other regions of the genome. Such a sequence alteration directly affects their structural stability through conformational changes. Presence of these conformational changes near catalytic site or active site may alter protein function and as a consequence receptor-ligand complex interactions. The present investigation includes assessment of human podocin mutations (G92C, P118L, R138Q, and D160G) on its structure. Podocin is an important glomerular integral membrane protein thought to play a key role in steroid resistant nephrotic syndrome. Podocin has a hairpin like structure with 383 amino acids, it is an integral protein homologous to stomatin, and acts as a molecular link in a stretch-sensitive system. We modeled 3D structure of podocin by means of Modeller and validated via PROCHECK to get a Ramachandran plot (88.5% in most favored region), main chain, side chain, bad contacts, gauche and pooled standard deviation. Further, a protein engineering tool Triton was used to induce mutagenesis corresponding to four variants G92C, P118L, R138Q and D160G in the wild type. Perusal of energies of wild and mutated type of podocin structures confirmed that mutated structures were thermodynamically more stable than wild type and therefore biological events favored synthesis of mutated forms of podocin than wild type. As a conclusive part, two mutations G92C (-8179.272 kJ/mol) and P118L (-8136.685 kJ/mol) are more stable and probable to take place in podocin structure over wild podocin structure (-8105.622 kJ/mol). Though there is lesser difference in mutated and wild type (approximately, 74 and 35 kJ/mol), it may play a crucial role in deciding why mutations are favored and occur at the genetic level.

Evaluation of the new infrastructure for French Permanent Broadband Stations in Auvergne (France).

NASA Astrophysics Data System (ADS)

Douchain, J. M.; Regis, E.; Battaglia, J.; Vergne, J.

2017-12-01

French seismologic and geodetic network (RESIF) is a national equipment for the observation and understanding of the solid Earth. It is an instrument aimed at acquiring new top-quality data for disciplines like seismology, geodesy and gravimetry to advance the understanding of the dynamics of our planet. The seismology component of RESIF, with its homogeneous coverage of the territory, will allow better localisation and characterisation of seismic activityover a wide range of magnitudes as well as provide high quality data for research The Auvergne Seismic Network (ASN) manages seismic stations in the center of france since the beginning of the 80's and continuously ugrades them. Nowadays, 21 stations (velocimeters and accelerometers) are deployed to monitor the Massif Central seismic activity. In the future, the ASN will run 15 broadband stations that will be part of RESIF network. Six of theses sites already have former generation instrumentation (short period sensors buried in the ground, low dynamic) but others are completely new. In june 2017, 4 permanent seismic stations have been upgraded to the new standard installation type for open environment. The chozen infrastructure is a 5 meter drilling equiped with a posthole broadband sensor. Prior to these final installations, on each site, Trillium 120 PA have been installed for 2 temporary experiments. The first one consisted of a direct burial installations at about 80 centimeters depth and lasted for 1 or 2 months. The second dataset was recorded in shallow seismic vaults, during 6 months.In this study, we compare, for each site, data recorded with the 3 configurations in order to evaluate the profits of the new RESIF installations. For this purpose, we compare the probability density fonctions to evaluate noise levels, as well as sprectrograms and hourly detection number. Our results show that the installation of sensors in drillings greatly improves the quality of data at low and high frequencies.

Modélisation de matériaux chiraux à structures hétérogènes (modèle MTWC) : théorie, validations expérimentales et applications

NASA Astrophysics Data System (ADS)

Mariotte, F.; Sauviac, B.; Héliot, J. Ph.

1995-10-01

After a brief overview of the concept of electromagnetic chirality, this paper deals with a numerical simulation of isotropic composites with metallic chiral inclusions: computations of permittivity, permeability and chirality parameter as functions of frequency are presented. The theoretical results are, step by step, compared with measurements of chiral composites at microwave frequencies. The application of such media in Radar Cross-Section (RCS) management and control is discussed. The introduction of chiral inclusions seems to make impedance matching possible and may lead to attractive shields with lower reflectivity and larger bandwidth. However the optimization of material characteristics necessary to get a specific absorber remains a difficult task. Après un bref rappel du principe de la chiralité, cet article présente une modélisation des propriétés effectives des matériaux hétérogènes à inclusions chirales métalliques : calcul de la permittivité, perméabilité et coefficient de chiralité du composite en fonction de la fréquence. Les résultats théoriques sont validés, pas à pas, par des mesures effectuées sur des composites chiraux de natures différentes. L'application de tels matériaux à la conception de matériaux absorbant les ondes électromagnétiques est ensuite envisagée. Les inclusions chirales semblent offrir la possibilité de régler l'impédance à l'interface air-milieu absorbant permettant ainsi de concevoir des absorbants micro-ondes plus performants en terme d'atténuation ou de largeur de bande. L'optimisation des caractéristiques des matériaux pour obtenir des performances données restent néanmoins très délicate.

Corrosion influencée par les micro-organismes : influence du biofilm sur la corrosion des aciers, techniques et résultats recents

NASA Astrophysics Data System (ADS)

Feugeas, F.; Magnin, J. P.; Cornet, A.; Rameau, J. J.

1997-03-01

Microbiologically Influenced Corrosion (M.I.C.) studied since the beginning of this century, is responsible for the degradation of many metallic equipments. This study is a review of results dealing with M.I.C. on several types of steels as: carbon steels, stainless steels, welded steels and covered steels. M.I.C. occurs only in presence of a biofilm. The first part of this study describes chemical and physical factors involved in its development, technical methods for studying biofilms, and its contribution in the corrosion process. The second part is devoted to the study of M.I.C. cases linked with metal nature and different aqueous environments and the last part reviews the mainly mecanisms of biocorrosion. La Corrosion Influencée par les Micro-organismes (C.I.M.) ou biocorrosion, phénomène étudié depuis le début du siècle, est responsable de la dégradation d'un grand nombre d'ouvrages métalliques. Cette étude a pour but de faire le point des connaissances sur la corrosion influencée microbiologiquement de divers types d'aciers au carbone, d'aciers inoxydables, d'assemblages soudés et d'aciers revêtus. La C.I.M. n'apparaît qu'en présence d'un biofilm. La première partie de cette étude décrit les facteurs physico-chimiques impliqués dans la formation du biofilm, ces moyens d'études ainsi que son action dans le processus de biocorrosion. La seconde partie est consacrée à la description des cas de biocorrosion classés en fonction de la nature des métaux et des milieux avec lesquels ils sont en contact. La dernière partie de ce document passe en revue les principaux mécanismes de biocorrosion décrits.

Extraction of water and solutes from argillaceous rocks for geochemical characterisation: Methods, processes and current understanding

NASA Astrophysics Data System (ADS)

Sacchi, Elisa; Michelot, Jean-Luc; Pitsch, Helmut; Lalieux, Philippe; Aranyossy, Jean-François

2001-01-01

This paper summarises the results of a comprehensive critical review, initiated by the OECD/NEA "Clay Club," of the extraction techniques available to obtain water and solutes from argillaceous rocks. The paper focuses on the mechanisms involved in the extraction processes, the consequences on the isotopic and chemical composition of the extracted pore water and the attempts made to reconstruct its original composition. Finally, it provides some examples of reliable techniques and information, as a function of the purpose of the geochemical study. Résumé. Cet article résume les résultats d'une synthèse critique d'ensemble, lancée par le OECD/NEA "Clay Club", sur les techniques d'extraction disponibles pour obtenir l'eau et les solutés de roches argileuses. L'article est consacré aux mécanismes impliqués dans les processus d'extraction, aux conséquences sur la composition isotopique et chimique de l'eau porale extraite et aux tentatives faites pour reconstituer sa composition originelle. Finalement, il donne quelques exemples de techniques fiables et d'informations, en fonction du but de l'étude géochimique. Resúmen. Este artículo resume los resultados de una revisión crítica exhaustiva (iniciada por el "Clay Club" OECD/NEA) de las técnicas de extracción disponibles para obtener agua y solutos en rocas arcillosas. El artículo se centra en los mecanismos involucrados en los procesos extractivos, las consecuencias en la composición isotópica y química del agua intersticial extraída, y en los intentos realizados para reconstruir su composición original. Finalmente, se presentan algunos ejemplos de técnicas fiables e información, en función del propósito del estudio geoquímico.

Intérêt de l’imagerie dans les tumeurs osseuses bénignes chez l’enfant

PubMed Central

Traoré, Ousmane; Chban, Kamilia; Hode, Alzavine Fleur; Diarra, Yaya; Salam, Siham; Ouzidane, Lachen

2016-01-01

Les tumeurs osseuses bénignes sont beaucoup plus fréquentes que les tumeurs malignes en milieu pédiatrique. L’exostose (ostéchondrome) en est la plus fréquente. Les différentes techniques d'imagerie occupent une place déterminante dans l'étude de ses tumeurs notamment la radiographie standard. Le but de ce travail est de souligner l’intérêt de l’imagerie dans la prise en charge diagnostique des tumeurs bénignes osseuses chez l’enfant à travers une étude rétrospective portant sur 169 patients. Tous ces patients ont été explorés par la radiographie standard, un complément scanner avec reconstruction multiplanaires avant et après injection de PDC et/ouune IRM 1.5 Tesla a été réalisé en fonction de l’indication. L’âge moyen est de 6 ans avec une légère prédominance masculine. Cliniquement, la tuméfaction est présente dans 35% des cas. La douleur dans 29 %des cas. La localisation la plus fréquente est la métaphyse sur les os long: fémur: 25% des cas, humérus: 17 % des cas, tibia: 21% des cas. Les principales tumeurs bénignes retrouvées sont l’exostose (20,12 %), le kyste osseux (31,95%) et l’ostéoblastome (16, 57%). L’imagerie permet de préciser la topographie et l’extension de la lésion dans l’os, apporter des arguments en faveur de la bénignité et parfois, en faveur de l’origine de la lésion. La radiographie standard seule permet souvent de poser un diagnostic de certitude dans certains cas. PMID:27795776

Étude du comportement structural de l'alliage NC 19 Fe Nb (Inconel 718)

NASA Astrophysics Data System (ADS)

Slama, C.; Cizeron, G.

1997-03-01

In the as-received state (following a double treatment at 720 and 620 °C), the structure of INC 718 consists of a γ matrix, intergranular β precipitates and (Nb,Ti)C carbides; moreover, γ{'} and γ{''} phases have precipitated in the matrix. Using different methods, the structural behaviour was analyzed which led to distinguish the temperature ranges in which occurs precipitation or dissolution of β, γ{'} and γ{''} phases on heating and to define the optimum conditions of homogeneization. Furthermore a CCT diagram for INC 718 has been drawn showing the respective precipitation of γ{'}, γ{''} and β phases as a function of the cooling rate applied from 990 °C. L'étude de l'alliage Inconel 718 (NC 19 Fe Nb) a permis de montrer que sa structure, dans l'état de livraison (après double revenu à 720 puis 620 °C), consiste en une matrice γ avec des précipités β intergranulaires et des carbures du type (Nb,Ti) C ; en outre, la matrice contient des précipités des phases γ{''} et γ{'}. L'analyse du comportement structural de l'alliage à l'aide de différentes méthodes physiques a conduit à délimiter les domaines de température dans lesquels interviennent, au chauffage, la précipitation ou la dissolution des phases β, γ{'}, γ{''} et de définir les conditions optimales d'homogénéisation. Le diagramme T.R.C. de l'Inconel 718 a ensuite été tracé : les intervalles de température dans lesquels interviennent les précipitations respectives des phases γ{'}, γ{''} et β en fonction de la vitesse de refroidissement imposée depuis 990 °C, ont ainsi pu être précisés.

Le HELLP syndrome: à propos de 61 cas et revue de la littérature

PubMed Central

Mamouni, Nisrine; Bougern, Hakima; Derkaoui, Ali; Bendahou, Karima; Fakir, Samira; Bouchikhi, Chehrazad; Chaara, Hikmat; Banani, Abdelaziz; Abdelilah, Moulay Melhouf

2012-01-01

Introduction L’objectif de ce travail etait d’étudier et comparer les paramètres épidémiologiques, cliniques, paracliniques et évolutifs des patientes présentant un HELLP syndrome complet et incomplet. (Hemolysis, Elevated Liver enzymes, Low Platelets count). Méthodes Une enquête rétrospective sur la période du 1er janvier 2005 au 31octobre 2008 et incluant tous les cas de HELLP syndrome colligés au service de Gynécologie obstétrique du CHU HASSAN II de Fès, incluant toutes les patientes ayant présenté un HELLP syndrome. Les patientes ont été classées en deux groupes en fonction de la forme du HELLP syndrome (complète ou incomplète). Résultats 61 patientes ont été incluses, dont 29 ont présenté un HELLP syndrome complet (groupe 1) et 32 ont présenté une forme incomplète de ce syndrome (groupe 2). La moyenne d’âge était de 29,7 ± 7 ans pour le groupe 1 et de 28,5 ± 7 ans pour le groupe 2.La gestité moyenne était de 2,8, Pour le groupe 1et de 2,5 pour le groupe 2.Les complications maternelles ont été notées chez 68,9% des patientes avec HELLP complet et 53% avec HELLP incomplet. On a recensés trois cas de décès maternel dans le groupe HELLP complet contre aucun cas dans la forme incomplète. Conclusion D’après les résultats de notre étude, le HELLP complet n’expose pas les patientes à un risque plus élevé de complications maternelles que dans la forme incomplète. PMID:22514764

PubMed

Vila Masse, Samantha

2018-01-22

Examiner le lien entre les conditions de travail et la santé mentale des travailleurs-euses de la restauration.MÉTHODE : L'échantillon se compose de 652 travailleurs-euses de la restauration issus de l'ESCC-SM de 2012. Des analyses de régression linéaire hiérarchique sont effectuées et ajustées en fonction de divers facteurs sélectionnés (sociodémographiques, habitudes de vie). Les conditions de travail sont mesurées en partie selon le Job Content Questionnaire (JCQ) de Karasek et Theorell. La détresse psychologique est mesurée à partir de l'échelle K6 de Kessler. La santé mentale positive est mesurée à partir du Continuum de santé mentale-version abrégée (MHC-SF) de Keyes.RÉSULTATS : Les fortes exigences psychologiques, le travail à temps partiel et les fortes exigences physiques sont associés de façon positive à la détresse psychologique des travailleurs-euses de la restauration, alors que le soutien social des collègues y est associé de façon inverse. Pour la santé mentale positive des travailleurs-euses de la restauration, l'insécurité d'emploi, les fortes exigences psychologiques et la faible latitude décisionnelle sont associées de façon négative tandis que le soutien social des collègues y est associé inversement. Cette étude souligne l'importance de considérer à la fois les aspects positifs et négatifs de la santé mentale. En effet, les facteurs associés à la santé mentale positive et à la détresse psychologique des travailleurs-euses de la restauration sont différents, voire associés en direction inverse.

Élimination du bore du silicium par plasma inductif sous champ électrique

NASA Astrophysics Data System (ADS)

Combes, R.; Morvan, D.; Picard, G.; Amouroux, J.

1993-05-01

We analyzed purification mechanisms of silicon by inductive plasma with a fluoride slag. The aim is to study boron elimination from doped electronic grade silicon in function of the nature of the slag to obtain a photovoltaic grade silicon. The steady began with the calculation and the comparison of the stability diagram of boron compounds in presence of CaF2, BaF2 and MgF2. This study led us to conclude that BaF2 is the better slag for silicon purification. This has been confirmed by experience. In a second time, we made purifications under electric bias to enhance slag efficiency. We noticed that BaF2 is more sensitive to electric bias than other slags. Nous avons analysé le mécanisme de purification du silicium sous plasma inductif en présence d'un laitier fluoré. L'objectif principal est d'étudier l'élimination du bore du silicium électronique dopé en fonction de la nature du fluorure pour obtenir un silicium de qualité photovoltaïque. L'étude a commencé par l'établissement et la comparaison de diagrammes des composés du bore en présence de CaF2, de MgF2 et de BaF2. Nous avons déduit de cette première étude que BaF2 est le meilleur laitier pour la purification du silicium. Ceci a été corroboré par l'expérience. Nous avons ensuite opéré en présence d'un champ électrique dans le but d'améliorer encore l'efficacité des laitiers. Nous avons constaté que BaF2 est plus sensible au champ électrique que les deux autres laitiers utilisés.

Synthèse bibliographique : micro-texturation et microinjection de thermoplastiques

NASA Astrophysics Data System (ADS)

Vera, Julie; Brulez, Anne-Catherine; Contraires, Elise; Larochette, Mathieu; Valette, Stéphane; Benayoun, Stéphane

2017-12-01

La fonctionnalisation de surface des matériaux et notamment des polymères fait l'objet de recherches intenses dans de nombreux secteurs tels que l'industrie du biomédical ou du transport afin de conférer aux pièces des propriétés spécifiques comme l'antibuée, la réduction du frottement ou le dégivrage… Dans le cas d'une production en grande série de pièces polymères fonctionnalisées, il est préférable, pour des questions de coûts, de générer des textures, au moyen d'une technique de reproduction d'empreinte comme l'injection plastique. Toutefois les fonctions requises nécessitent parfois la reproduction de dimensions microniques voire submicroniques poussant à ses limites la maîtrise du procédé conventionnel, avec les caractéristiques de l'injection de micro-pièces, mais aussi des spécificités propres à la micro-texturation. L'objet de cette revue bibliographique est de couvrir le large spectre des problèmes techniques et scientifiques associés à la micro-texturation des pièces plastiques. Les techniques d'usinage de ces micro-motifs sur les outillages et le rôle des revêtements est particulièrement décrit ainsi que le besoin de mettre en œuvre des approches spécifiques de caractérisation topographique des textures. L'influence des paramètres du procédé d'injection est aussi discutée, soulignant la nécessité d'appréhender la micro-texturation des pièces plastiques avec une nouvelle grille de lecture de la microinjection.

Soins primaires aux adultes ayant des déficiences intellectuelles et développementales

PubMed Central

Sullivan, William F.; Diepstra, Heidi; Heng, John; Ally, Shara; Bradley, Elspeth; Casson, Ian; Hennen, Brian; Kelly, Maureen; Korossy, Marika; McNeil, Karen; Abells, Dara; Amaria, Khush; Boyd, Kerry; Gemmill, Meg; Grier, Elizabeth; Kennie-Kaulbach, Natalie; Ketchell, Mackenzie; Ladouceur, Jessica; Lepp, Amanda; Lunsky, Yona; McMillan, Shirley; Niel, Ullanda; Sacks, Samantha; Shea, Sarah; Stringer, Katherine; Sue, Kyle; Witherbee, Sandra

2018-01-01

Résumé Objectif Mettre à jour les Lignes directrices consensuelles canadiennes 2011 en matière de soins primaires aux adultes ayant une déficience développementale. Méthodes Des médecins de famille et d’autres professionnels de la santé expérimentés dans les soins aux personnes ayant des DID ont examiné et synthétisé les récentes connaissances empiriques, d’écosystèmes, expertes et expérientielles. Un système a été conçu pour catégoriser la qualité des recommandations. Recommandations Les adultes ayant des DID sont un groupe hétérogène de patients qui présentent des affections médicales et des facteurs qui influent sur leur santé, qui diffèrent de ceux qui touchent les autres membres de la communauté de par leur nature, leurs manifestations, leur gravité ou leur complexité. Ces personnes nécessitent une approche de soins et des interventions adaptées à leurs besoins. Les présentes lignes directrices offrent des conseils en matière de normes de soins. Nous avons incorporé des références à des outils cliniques et à d’autres ressources pratiques. Les approches de soins décrites ici s’appliquent aussi à d’autres groupes de patients ayant un déficit cognitif ou de la communication, ou d’autres déficits des fonctions adaptatives. Conclusion À titre de fournisseurs de soins de première ligne, les médecins de famille jouent un rôle vital de promotion de la santé et de bien-être auprès des adultes ayant des DID. Ces lignes directrices peuvent les aider à prendre des décisions avec les patients et les aidants naturels. PMID:29650617

Study of the chain conformation of thermotropic nematic main chain polyesters

NASA Astrophysics Data System (ADS)

Li, M. H.; Brûlet, A.; Cotton, J. P.; Davidson, P.; Strazielle, C.; Keller, P.

1994-10-01

The conformation of main chain mesomorphic polyesters is studied by small angle neutron scattering (SANS) in the isotropic and in the nematic phases, by using mixtures of deuterated and undeuterated polymers. Particular attention is given to neglect the transesterification effects occurring mainly at high temperature for these LC polymers. In the isotropic phase, despite the presence of long rigid mesogenic groups, the LC polyester chains have a Gaussian conformation shown by the variation of the radius of gyration as a function of the molecular weight. This result is confirmed from the scattering variation in the intermediate range of the scattering vector. In the nematic phase, the SANS data are well fitted to a model of cylinder, in which the main chain polymer is confined. In the unoriented phase, the measurements in the intermediate range give the values of the radii of cylinders : they lie in between 10 Å and 19 Å depending on the degree of polymerization of chains. In the oriented nematic phase, the scattering patterns are highly anisotropic : they correspond to very long, thin and well-oriented cylinders. We have calculated the fully extended chain lengths using for the monomer length that measured in situ by X-ray diffraction. Then the comparison of this length with the measured height of the cylinders gives the existence of hairpins and their number per chain. For the short chain, the conformation is almost completely elongated in the nematic direction, whereas hairpin defects appear in longer chains. Their number decreases slightly with decreasing temperature. The orientational fluctuations of cylinders relatively to the nematic director are weak as shown from the high values of their order parameter (P_2 > 0.9). These results are discussed for two spacer lengths as a function of the molecular weight and of the temperature. La conformation de polyesters linéaires mésomorphes est étudiée par diffusion de neutrons aux petits angles (DNPA) dans les phases isotrope et nématique sur des mélanges de polymères hydrogénés et deutériés. Les conditions expérimentales ont été choisies afin de pouvoir négliger les effets de la transestérification obtenus à haute température avec cette famille de polymères cristaux liquides. Dans la phase isotrope, en dépit de la présence de longs et rigides groupements mésogènes, les chaînes de polymères ont une conformation gaussienne, comme le montre la variation du rayon de giration en fonction de la masse moléculaire. Ce résultat est confirmé par les mesures faites dans le domaine intermédiaire du vecteur de diffusion. Dans la phase nématique, les données de DNPA sont bien ajustées par un modèle de cylindre dans lequel la chaîne de polymère est confinée. Dans la phase non orientée, les mesures faites dans le domaine intermédiaire donnent les valeurs des rayons des cylindres (compris entre 10 Å et 19 Å selon le degré de polymérisation des chaînes). Dans la phase nématique orientée, les figures de diffusion sont très anisotropes et correspondent à de longs et étroits cylindres bien orientés. La longueur de la chaîne totalement étirée est calculée à partir de la longueur du monomère mesurée par diffraction de rayons X. Par comparaison avec la hauteur du cylindre mesurée en DNPA, nous déduisons l'existence des épingles à cheveux et leur nombre par chaîne. La conformation d'une chaîne courte est complètement étirée dans la direction du champ nématique, alors que des défauts du type épingles à cheveux apparaissent dans les chaînes plus longues. Le nombre de ces défauts décroît légèrement en diminuant la température. Les fluctuations d'orientation des cylindres autour de la direction du champ nématique sont faibles comme le montrent les valeurs élevées des paramètres d'ordre des cylindres (P_2 > 0,9). Les résultats sont discutés, pour deux longueurs d'espaceur, en fonction de la masse moléculaire et de la température.

Nouvelles approches en theorie du champ moyen dynamique: le cas du pouvoir thermoelectrique et celui de l'effet orbital d'un champ magnetique

NASA Astrophysics Data System (ADS)

Arsenault, Louis-Francois

Les applications reliees a la generation d'energie motivent la recherche de materiaux ayant un fort pouvoir thermoelectrique (S). De plus, S nous renseigne sur certaines proprietes fondamentales des materiaux, comme, par exemple, la transition entre l'etat coherent et incoherent des quasi-particules lorsque la temperature augmente. Empiriquement, la presence de fortes interactions electron-electron peut mener a un pouvoir thermoelectrique geant. Nous avons donc etudie le modele le plus simple qui tient compte de ces fortes interactions, le modele de Hubbard. La theorie du champ moyen dynamique (DMFT) est tout indiquee dans ce cas. Nous nous sommes concentres sur un systeme tridimensionnel (3d) cubique a face centree (fcc), et ce, pour plusieurs raisons. A) Ce type de cristal est tres commun dans la nature. B) La DMFT donne de tres bons resultats en 3d et donc ce choix sert aussi de preuve de principe de la methode. C) Finalement, a cause de la frustration electronique intrinseque au fcc, celui-ci ne presente pas de symetrie particule-trou, ce qui est tres favorable a l'apparition d'une grande valeur de S. Ce travail demontre que lorsque le materiau est un isolant a demi-remplissage a cause des fortes interactions (isolant de Mott), il est possible d'obtenir de grands pouvoirs thermoelectriques en le dopant legerement. C'est un resultat pratique important. Du point de vue methodologique, nous avons montre comment la limite de frequence infinie de S et l'approche dite de Kelvin, qui considere la limite de frequence nulle avant la limite thermodynamique pour S, donnent des estimations fiables de la vraie limite continue (DC) dans les domaines de temperature appropriee. Ces deux approches facilitent grandement les calculs en court-circuit ant la necessite de recourir a de problematiques prolongements analytiques. Nous avons trouve que la methode de calcul a frequence infinie fonctionne bien lorsque les echelles d'energie sont relativement faibles. En d'autres termes, cette approche donne une bonne representation de S lorsque le systeme devient coherent. Les calculs montrent aussi que la formule Kelvin est precise lorsque la fonction spectrale des electrons devient incoherente, soit a plus haute temperature. Dans la limite Kelvin, S est essentiellement l'entropie par particule, tel que propose il y a longtemps. Nos resultats demontrent ainsi que la vision purement entropique de S est la bonne dans le regime incoherent, alors que dans le regime coherent, l'approche a frequence infinie est meilleure. Nous avons utilise une methode a la fine pointe, soit le Monte-Carlo quantique en temps continu pour resoudre la DMFT. Pour permettre une exploration rapide du diagramme de phase, nous avons du developper une nouvelle version de la methode des perturbations iterees pour qu'elle soit applicable aussi a forte interaction au-dela de la valeur critique de la transition de Mott. Un autre sujet a aussi ete aborde. L'effet orbital du champ magnetique dans les systemes electroniques fortement correles est une question tres importante et peu developpee. Cela est d'autant plus essentiel depuis la decouverte des oscillations quantiques dans les supraconducteurs a haute temperature (haut- Tc). Par desir de developper une methode la moins biaisee possible, nous avons derive la DMFT lorsqu'un champ se couplant a l'operateur energie cinetique par la substitution de Peierls est present. Ce type d'approche est necessaire pour comprendre entre autres l'effet de la physique de Mott sur des phenomenes tels que les oscillations quantiques. Nous avons obtenu un resultat tres important en demontrant rigoureusement que la relation d'auto-coherence de la DMFT et le systeme intermediaire d'impurete quantique restent les memes. L'effet du champ peut etre contenu dans la fonction de Green locale, ce qui constitue la grande difference avec le cas habituel. Ceci permet de continuer a utiliser les solutionneurs d'impuretes standards, qui sont de plus en plus puissants. Nous avons aussi developpe la methode pour le cas d'un empilement de plans bidimensionnels selon z, ce qui permet d'etudier l'effet orbital du champ dans des nanostructures et meme dans les materiaux massifs, si le nombre de plans est suffisant pour obtenir la limite tridimensionnelle. Mots cles : Pouvoir thermoelectrique, Theorie du Champ Moyen Dynamique, Modele de Hubbard, Effet orbital du champ magnetique, Electrons fortement correles, Materiaux quantiques, Theorie des perturbations iterees

Consistent force field modeling of matrix isolated molecules. V. Minimum energy path potential to the conformer conversion of 1,2-difluoroethane: Ar 364, ab initio calculation of electric multipole moments and electric polarization contribution to the conversion barrier

NASA Astrophysics Data System (ADS)

Gunde, R.; Ha, T.-K.; Günthard, H. H.

1990-08-01

In this paper results of consistent force field modeling (CFF) of the potential function to conversion of the gauche (g) to the trans (t) conformer of 1,2-difluoroethane (DFE) isolated in an argon matrix will be reported. Starting point are locally stable configurations gDFE:Ar 364 (defect GH1) and tDFE:Ar 364 (TH1) obtained in previous work from CFF modeling of a cube shaped Ar 364 fragment containing one DFE molecule in its center. Using the dihedral angle of DFE as an independent parameter the minimum energy path of the conversion process gDFE:Ar 364→tDFE:Ar 364 will be determined by CFF energy minimization. Determination of the minimum energy path is found to require large numbers of energy minimization steps and to lead to a rather complicated motion of the molecule with respect to the crystal fragment. Surprisingly the molecule-matrix interactions lead to a reduction of the g-t barrier by ≈500 cal/mol and to a stabilization of the trans species by ≈500 cal/mol. This finding is a consequence of a delicate interplay of matrix-molecule and matrix-matrix interactions. Calculation of the electric polarization energy (induced dipole-first-order polarization approximation) is based on extended ab initio calculations of dipole and quadrupole moments and a bond polarizability estimate of the first-order polarizability of DFE as a function of the internal rotation angle, on Fourier expansion of multipole components and use of symmetry for reduction of the order of the linear system defining the (self-consistent) induced dipole moments of all Ar atoms. Electric polarization is found to alter the potential function of the conversion process in a profound way: the g-t barrier and the t-g energy difference are increased to ≈3000 cal/mol and to ≈1500 cal/mol respectively (≈2500 and ≈530 cal/mol respectively for free DFE). Further applications of the technique developed in this work to related problems of matrix isolated molecules, e.g., vibrational matrix shifts will be discussed.

Solid state ¹³C-NMR, infrared, X-ray powder diffraction and differential thermal studies of the homologous series of some mono-valent metal (Li, Na, K, Ag) n-alkanoates: a comparative study.

PubMed

Nelson, Peter N; Ellis, Henry A; White, Nicole A S

2015-06-15

A comparative study of the molecular packing, lattice structures and phase behaviors of the homologous series of some mono-valent metal carboxylates (Li, Na, K and Ag) is carried out via solid state FT-infrared and (13)C-NMR spectroscopes, X-rays powder diffraction, density measurements, differential scanning calorimetry, polarizing light microscopy and variable temperature infrared spectroscopy. It is proposed that, for lithium, sodium and potassium carboxylates, metal-carboxyl coordination is via asymmetric chelating bidentate bonding with extensive intermolecular interactions to form tetrahedral metal centers, irrespective of chain length. However, for silver n-alkanoates, carboxyl moieties are bound to silver ions via syn-syn type bridging bidentate coordination to form dimeric units held together by extensive head group inter-molecular interactions. Furthermore, the fully extended hydrocarbon chains which are crystallized in the all-trans conformation are tilted at ca. 30°, 27°, 15° and 31° with respect to a normal to the metal plane, for lithium, sodium, silver and potassium carboxylates, respectively. All compounds are packed as lamellar bilayer structures, however, lithium compounds are crystallized in a triclinic crystal system whilst silver, sodium and potassium n-alkanoates are all monoclinic with possible P1 bravais lattice. Odd-even alternation observed in various physical features is associated with different inter-planar spacing between closely packed layers in the bilayer which are not in the same plane; a phenomenon controlled by lattice packing symmetry requirements. All compounds, except silver carboxylates, show partially reversibly first order pre-melting transitions; the number of which increases with increasing chain length. These transitions are associated, for the most part, with lamellar collapse followed by increased gauche-trans isomerism in the methylene group assembly, irrespective of chain length. It is proposed that the absence of mesomorphic transitions in their phase sequences is due to a lack of sufficient balance between attractive and repulsive electrostatic and van der Waals forces during phase change. The evidence presented in this study shows that phase behaviors of mono-valent metal carboxylates are controlled, mainly, by head group bonding. Copyright © 2015 Elsevier B.V. All rights reserved.

Statistical Mechanical Foundation for the Two-State Transition in Protein Folding of Small Globular Proteins

NASA Astrophysics Data System (ADS)

Iguchi, Kazumoto

We discuss the statistical mechanical foundation for the two-state transition in the protein folding of small globular proteins. In the standard arguments of protein folding, the statistical search for the ground state is carried out from astronomically many conformations in the configuration space. This leads us to the famous Levinthal's paradox. To resolve the paradox, Gō first postulated that the two-state transition - all-or-none type transition - is very crucial for the protein folding of small globular proteins and used the Gō's lattice model to show the two-state transition nature. Recently, there have been accumulated many experimental results that support the two-state transition for small globular proteins. Stimulated by such recent experiments, Zwanzig has introduced a minimal statistical mechanical model that exhibits the two-state transition. Also, Finkelstein and coworkers have discussed the solution of the paradox by considering the sequential folding of a small globular protein. On the other hand, recently Iguchi have introduced a toy model of protein folding using the Rubik's magic snake model, in which all folded structures are exactly known and mathematically represented in terms of the four types of conformations: cis-, trans-, left and right gauche-configurations between the unit polyhedrons. In this paper, we study the relationship between the Gō's two-state transition, the Zwanzig's statistical mechanics model and the Finkelsteinapos;s sequential folding model by applying them to the Rubik's magic snake models. We show that the foundation of the Gō's two-state transition model relies on the search within the equienergy surface that is labeled by the contact order of the hydrophobic condensation. This idea reproduces the Zwanzig's statistical model as a special case, realizes the Finkelstein's sequential folding model and fits together to understand the nature of the two-state transition of a small globular protein by calculating the physical quantities such as the free energy, the contact order and the specific heat. We point out the similarity between the liquid-gas transition in statistical mechanics and the two-state transition of protein folding. We also study morphology of the Rubik's magic snake models to give a prototype model for understanding the differences between α-helices proteins and β-sheets proteins.

Etude du strabisme chez des enfants de 0 à 15 ans suivis a Lubumbashi, République Démocratique du Congo: analyse des aspects épidémiologiques et cliniques

PubMed Central

Bienvenu, Yogolelo Asani; Angel, Musau Nkola; Sebastien, Mbuyi Musanzayi; Philippe, Cilundika Mulenga; Léon, Kabamba Ngombe; Eugene, Twite Kabange; Chami, Cham Lubamba; Prosper, Kalenga Muenze Kayamba; Claude, Speeg-Schatz; Gaby, Chenge Borasisi

2015-01-01

Introduction Le strabisme est défini comme un syndrome à double composante: motrice et sensorielle. Le but de ce travail est de décrire les aspects épidémiologiques et cliniques du strabisme chez l'enfant congolais de 0 à 15 ans dans la ville de Lubumbashi. Méthodes Il s'agit d'une étude descriptive longitudinale sur les aspects épidémiologiques et cliniques du strabisme chez l'enfant congolais de 0 à 15 ans dans la ville de Lubumbashi entre Décembre 2012 à Décembre 2013. Nous avons recueilli l’âge des patients, leur sexe, leur provenance, le type de strabisme, la réfraction, le fond d'oeil, les antécédents (hérédité) ainsi que le type de la déviation strabique observé sur 70 patients. Résultats Nous avons observé 70 cas de strabisme manifeste dont 31 cas (44,28%) étaient dans la tranche d’âge comprise entre 0 et 5 ans. L’âge moyen de nos patients était de 6,7 ans avec une prédominance du sexe féminin, soit 51,42%. Le strabisme était convergent dans 65,71%, divergent dans 30%, et vertical dans 4,28%. Les ésotropies représentaient 65 cas (92,85%), quatre cas (5,71%) avaient un antécédent familial de strabisme au premier degré de parenté, 21 cas (30%) au second degré de parenté, 45 cas (64,28%) n'avaient pas cet antécédent. L'oeil gauche était le plus dominé dans 30% des cas. Les facteurs favorisant le strabisme étaient inconnus dans 54 cas (77,14%). Le strabisme était secondaire à l'hypermétropie chez 32 patients (42,71%). Conclusion La fréquence du strabisme dans la ville de Lubumbashi chez les enfants âgés de 0 à 15 ans est de 0,50%. Comme dans la plupart des études sur le strabisme de l'enfant, c'est l’ésotropie qui est la déviation la plus commune. PMID:26834919

Effets du stress familial lié au diabète sur le contrôle glycémique chez les jeunes diabétiques de type 1

PubMed Central

Tsiouli, Elina; Alexopoulos, Evangelos C.; Stefanaki, Charikleia; Darviri, Christina; Chrousos, George P.

2013-01-01

Objectif Examiner la façon dont le stress familial influence le contrôle glycémique chez les patients diabétiques de moins de 18 ans. Sources des données Une recherche des études pertinentes publiées depuis 1990 a été réalisée dans PubMed et Scopus à l'aide des mots-clés suivants en anglais: diabetes type 1, glycemic control, family stress, family conflict et family function. Sélection des études La recension initiale a permis de cerner un total de 1 478 articles. La synthèse finale portrait sur 6 études de cohortes, 3 études transversales et 1 étude qualitative dans lesquelles le stress familial était évalué à l'aide d'instruments de mesure des conflits spécifiquement reliés au diabète et le contrôle glycémique était mesuré en fonction de l'hémoglobine glycosylée. Synthèse Dans la plupart des études, il existait une corrélation négative entre le stress familial et le contrôle glycémique des patients. Le bon fonctionnement familial était fortement relié à un bon contrôle glycémique des patients, tandis que les conflits familiaux étaient associés à un mauvais contrôle glycémique. Les familles dont la situation socioéconomique était défavorisée, celles ayant des adolescents atteints de diabète et les familles monoparentales étaient plus enclines à vivre un stress relié au diabète et étaient, par conséquent, plus susceptibles de connaître un moins bon contrôle glycémique. Conclusion Les interventions psychologiques thérapeutiques et les programmes éducatifs peuvent aider à atténuer le stress familial relié au diabète et amélioreront probablement le contrôle glycémique.

Particularité de la cystinose infantile chez l'enfant tunisien

PubMed Central

Jellouli, Manel; Turkia, Hadhami Ben; Abidi, Kamel; Hammi, Yosra; Gargah, Tahar

2015-01-01

La cystinose est une maladie rare qui résulte d'un défaut d'expression de la cystinosine transporteur de la cystine du lysosome. La forme infantile est la plus fréquente et la plus sévère. Elle conduit en dehors du traitement à l'insuffisance rénale chronique terminale au cours de la première décade de la vie. Nous rapportons l'expérience tunisienne de la cystinose infantile. Une étude rétrospective sur une période de 25 ans (1990-2014) était menée. Nous avons colligé 8 dossiers de cystinose infantile dans les services de pédiatrie des hôpitaux Charles Nicolle de Tunis et la Rabta de Tunis. Il s'agissait de 5garçons et de 3 filles. L’âge moyen au début des symptômes était de 6,37 mois (2-14 mois). L’âge moyen au moment du diagnostic était de 4 ans (7 mois-6 ans). Les dépôts cornéens de cystine étaient observés chez 7 patients. Sept patients présentaient une hypothyroïdie. La cystéamine était prescrite chez 6 patients. L’âge moyen au moment de la prescription de cystéamine était de 5,12 ans (8 mois- 13 ans). L’âge moyen lors de passage en insuffisance rénale chronique était de 3,4 ans. L’âge moyen lors du passage en insuffisance rénale chronique terminale était de 6,37 ans Actuellement, un patient garde une fonction rénale normale, trois patients sont en insuffisance rénale, deux patients sont décédés et un patient était transplanté. Il faut instaurer dans notre pays les moyens de diagnostic pour traiter tôt la maladie. PMID:26985266

Analyse des facteurs histo-pronostiques du cancer du rectum non métastatique dans une série ouest Algérienne de 58 cas au CHU-Tlemcen

PubMed Central

Mesli, Smain Nabil; Regagba, Derbali; Tidjane, Anisse; Benkalfat, Mokhtar; Abi-Ayad, Chakib

2016-01-01

Introduction L'objectif de notre travail est d'analyser les facteurs histo-pronostiques des cancers du rectum non métastatique opérés au service de chirurgie «A» de Tlemcen à ouest Algérien durant une période de six ans. Méthodes Etude rétrospective de 58 patients qui avait un adénocarcinome rectal. Le critère de jugement était la survie. Les paramètres étudiés, le sexe, l’âge, stade tumoral, et les récidives tumorales. Résultats L’âge moyen était de 58 ans. Avec 52% d'hommes contre 48% femmes avec sex-ratio (1,08). Le siège tumoral était: moyen rectum avec 41,37%, 34,48% au bas rectum et dans 24,13% au haut rectum. La classification TNM avec 17,65% au stade I, 18,61% au stade II, 53, 44% au stade III et 7,84% au stade IV. La survie médiane globale était de 40 mois ±2,937 mois. La survie en fonction du stade tumoral, le stade III et IV avait un faible taux de survie (19%) a 3 ans contre le stade I, II avait un taux de survie de (75%) (P = 0,000) (IC 95%). Les patients avec récidives tumorales avaient un taux de survie faible à 3 ans par rapport à ceux n'ayant pas eu de récidive (30,85% Vs 64,30% P = 0,043). Conclusion Dans cette série, l’étude uni varié des différents facteurs pronostiques conditionnant la survie n'a permis de retenir que trois facteurs influençant la survie, à savoir la taille tumorale, le stade, et les récidives tumorales. En analyse multi variée en utilisant le modèle Cox un seul facteur été retenu la récidive tumorale. PMID:27583069

Conductivite dans le modele de Hubbard bi-dimensionnel a faible couplage

NASA Astrophysics Data System (ADS)

Bergeron, Dominic

Le modele de Hubbard bi-dimensionnel (2D) est souvent considere comme le modele minimal pour les supraconducteurs a haute temperature critique a base d'oxyde de cuivre (SCHT). Sur un reseau carre, ce modele possede les phases qui sont communes a tous les SCHT, la phase antiferromagnetique, la phase supraconductrice et la phase dite du pseudogap. Il n'a pas de solution exacte, toutefois, plusieurs methodes approximatives permettent d'etudier ses proprietes de facon numerique. Les proprietes optiques et de transport sont bien connues dans les SCHT et sont donc de bonne candidates pour valider un modele theorique et aider a comprendre mieux la physique de ces materiaux. La presente these porte sur le calcul de ces proprietes pour le modele de Hubbard 2D a couplage faible ou intermediaire. La methode de calcul utilisee est l'approche auto-coherente a deux particules (ACDP), qui est non-perturbative et inclue l'effet des fluctuations de spin et de charge a toutes les longueurs d'onde. La derivation complete de l'expression de la conductivite dans l'approche ACDP est presentee. Cette expression contient ce qu'on appelle les corrections de vertex, qui tiennent compte des correlations entre quasi-particules. Pour rendre possible le calcul numerique de ces corrections, des algorithmes utilisant, entre autres, des transformees de Fourier rapides et des splines cubiques sont developpes. Les calculs sont faits pour le reseau carre avec sauts aux plus proches voisins autour du point critique antiferromagnetique. Aux dopages plus faibles que le point critique, la conductivite optique presente une bosse dans l'infrarouge moyen a basse temperature, tel qu'observe dans plusieurs SCHT. Dans la resistivite en fonction de la temperature, on trouve un comportement isolant dans le pseudogap lorsque les corrections de vertex sont negligees et metallique lorsqu'elles sont prises en compte. Pres du point critique, la resistivite est lineaire en T a basse temperature et devient progressivement proportionnelle a T 2 a fort dopage. Quelques resultats avec sauts aux voisins plus eloignes sont aussi presentes. Mots-cles: Hubbard, point critique quantique, conductivite, corrections de vertex

Minimisation des inductances propres des condensateurs à film métallisé

NASA Astrophysics Data System (ADS)

Joubert, Ch.; Rojat, G.; Béroual, A.

1995-07-01

In this article, we examine the different factors responsible for the equivalent series inductance in metallized capacitors and we propose structures for capacitors that reduce this inductance. After recalling the structure of metallized capacitors we compare, by experimental measurements, the inductance due to the winding and that one added by the connections. The latter can become preponderant. In order to explain the experimental evolution of the winding impedance vs. frequency, we describe an analytical model which gives the current density in the winding and its impedance. This model enables us to determine the self resonant frequency for different types of capacitors. From where, we can infer the influence of the height of capacitors and their internal and external radius upon performances, It appears that to reduce the equivalent series inductance, it is better to use flat windings and annular windings. Dans cet article nous examinons les différents facteurs responsables de l'inductance équivalente série dans les condensateurs à film métallisé et proposons des géométries de condensateurs qui réduisent cette inductance. Après avoir rappelé la structure des condensateurs à film métallisé, nous comparons, par des mesures expérimentales, l'inductance due au bobinage et l'inductance ajoutée par les connexions. Cette dernière peut devenir prépondérante. Afin d'expliquer l'évolution de l'impédance du bobinage en fonction de la fréquence, nous décrivons un modèle analytique qui donne la densité du courant dans le bobinage et l'impédance de ce dernier. En outre, ce modèle permet de déterminer la fréquence de résonance série de divers types de condensateurs ce qui permet de déduire l'influence de la hauteur des condensateurs et de leurs rayons interne et externe sur les performances. Il apparaît ainsi que, pour diminuer l'inductance équivalente série, il vaut mieux employer des bobinages plats et des bobinages annulaires.

Les effets des interfaces sur les proprietes magnetiques et de transport des multicouches nickel/iron et cobalt/silver

NASA Astrophysics Data System (ADS)

Veres, Teodor

Cette these est consacree a l'etude de l'evolution structurale des proprietes magnetiques et de transport des multicouches Ni/Fe et nanostructures a base de Co et de l'Ag. Dans une premiere partie, essentiellement bibliographique, nous introduisons quelques concepts de base relies aux proprietes magnetiques et de transport des multicouches metalliques. Ensuite, nous presentons une breve description des methodes d'analyse des resultats. La deuxieme partie est consacree a l'etude des proprietes magnetiques et de transport des multicouches ferromagnetiques/ferromagnetiques Ni/Fe. Nous montrerons qu'une interpretation coherente de ces proprietes necessite la prise en consideration des effets des interfaces. Nous nous attacherons a mettre en evidence, a evaluer et a etudier les effets de ces interfaces ainsi que leur evolution, et ce, suite a des traitements thermiques tel que le depot a temperature elevee et l'irradiation ionique. Les analyses correlees de la structure et de la magnetoresistance nous permettront d'emettre des conclusions sur l'influence des couches tampons entre l'interface et le substrat ainsi qu'entre les couches elles-memes sur le comportement magnetique des couches F/F. La troisieme partie est consacree aux systemes a Magneto-Resistance Geante (MRG) a base de Co et Ag. Nous allons etudier l'evolution de la microstructure suite a l'irradiation avec des ions Si+ ayant une energie de 1 MeV, ainsi que les effets de ces changements sur le comportement magnetique. Cette partie debutera par l'analyse des proprietes d'une multicouche hybride, intermediaire entre les multicouches et les materiaux granulaires. Nous analyserons a l'aide des mesures de diffraction, de relaxation superparamagnetique et de magnetoresistance, les evolutions structurales produites par l'irradiation ionique. Nous etablirons des modeles qui nous aideront a interpreter les resultats pour une serie des multicouches qui couvrent un large eventail de differents comportements magnetiques et ceci en fonction de l'epaisseur de la couche magnetique de Co. Nous verrons que dans ces systemes les effets de l'irradiation ionique sont fortement influences par l'energie de surface ainsi que par l'enthalpie de formation, largement positive pour le systeme Co/Ag.

Les séquelles de brûlures cervicales: aspects épidémiologique, clinique et thérapeutique au Maroc

PubMed Central

Rafik, Amine; Chabak, Hakim; Diouri, Mounia; Bahechar, Naïma; Chlihi, Abdessamad

2015-01-01

Les séquelles de brûlures cervicales représentent une entité fréquente des séquelles de brûlure, elles affectent la fonction, l'esthétique et l’état psychologique des patients et peuvent être de traitement difficile. Il s'agit d'une étude rétrospective étalée sur 5 ans de Mars 2009 au Octobre2014, réalisée au centre national des brûlés et de chirurgie plastique au CHU Ibn Rochd Casablanca. Nous avons analysé les caractéristiques épidémiologiqueset cliniques ainsi que les indications et les résultats thérapeutiques chez 300 patients présentant des rétractions cervicales post-brûlure, suivis dans notre formation. Les jeunes femmes étaient le plus souvent touchées (56%). la brûlure thermique par flamme de butane dans le cadre d'accident domestique était l’étiologie la plus fréquente (91%).75% des patients ont été pris en charge dans un délai de 18 mois après avoir présenté une incapacité fonctionnelle. Les brides cervicales modérées et sévères sont les plus fréquentes et représentent respectivement 60% et 16% des cas. Le traitement chirurgical a fait appel aux greffes cutanées dans 67%des cas, aux plasties locales dans 24%des cas et aux lambeaux dans 24% des cas, les résultats sont jugés bons dans 75%des cas et moyens dans 18% des cas, tandis que les cas restants (7%) ont nécessité une reprise chirurgicale. Le traitement des brides cervicales doit être associé à un programme de rééducation adapté, afin d'assurer la pérennité des résultats fonctionnels et esthétiques. PMID:26301017

Médecine des voyages

PubMed Central

Aw, Brian; Boraston, Suni; Botten, David; Cherniwchan, Darin; Fazal, Hyder; Kelton, Timothy; Libman, Michael; Saldanha, Colin; Scappatura, Philip; Stowe, Brian

2014-01-01

Résumé Objectif Définir la pratique de la médecine des voyages, présenter les éléments fondamentaux d’une consultation complète préalable aux voyages à des voyageurs internationaux et aider à identifier les patients qu’il vaudrait mieux envoyer en consultation auprès de professionnels de la médecine des voyages. Sources des données Les lignes directrices et les recommandations sur la médecine des voyages et les maladies liées aux voyages publiées par les autorités sanitaires nationales et internationales ont fait l’objet d’un examen. Une recension des ouvrages connexes dans MEDLINE et EMBASE a aussi été effectuée. Message principal La médecine des voyages est une spécialité très dynamique qui se concentre sur les soins préventifs avant un voyage. Une évaluation exhaustive du risque pour chaque voyageur est essentielle pour mesurer avec exactitude les risques particuliers au voyageur, à son itinéraire et à sa destination et pour offrir des conseils sur les interventions les plus appropriées en gestion du risque afin de promouvoir la santé et prévenir les problèmes médicaux indésirables durant le voyage. Des vaccins peuvent aussi être nécessaires et doivent être personnalisés en fonction des antécédents d’immunisation du voyageur, de son itinéraire et du temps qu’il reste avant son départ. Conclusion La santé et la sécurité d’un voyageur dépendent du degré d’expertise du médecin qui offre le counseling préalable à son voyage et les vaccins, au besoin. On recommande à ceux qui donnent des conseils aux voyageurs d’être conscients de l’ampleur de cette responsabilité et de demander si possible une consultation auprès de professionnels de la médecine des voyages pour tous les voyageurs à risque élevé.

L’expérience d’une patiente qui reçoit des soins pour la démence

PubMed Central

Frank, Christopher; Forbes, Rev Faye

2017-01-01

Résumé Objectif Permettre aux médecins de famille de comprendre « l’expérience vécue » de la démence de la bouche d’une personne atteinte de démence—Faye Forbes, ministre anglicane de 64 ans atteinte de la maladie d’Alzheimer, qui donne son point de vue sur comment vivre avec la démence—et utiliser cette information pour améliorer les soins et les résultats. Sources d’information Une recherche a été effectuée dans MEDLINE sur Ovid entre janvier 2005 et février 2015, à l’aide des mots-clés anglais suivants : dementia, caregiver, perspectives et quality of health care. Les articles qui s’adressaient aux médecins de famille ont été sélectionnés. Des revues pertinentes et des articles de recherche originaux ont été utilisés, le cas échéant, s’ils s’appliquaient aux personnes atteintes de démence et à leurs soignants. Message principal Plusieurs cadres de référence organisent les principales expériences décrites par les patients et leurs soignants. Nous avons utilisé une revue de la littérature qualitative pour fournir un cadre de référence résumant l’expérience de Faye, en fonction des thèmes suivants : tenter d’obtenir un diagnostic, accéder au soutien et aux services, besoins en matière d’information, prise en charge de la maladie, et communication et attitudes. Conclusion Les médecins doivent tenir compte de ces thèmes lorsqu’ils planifient la prise en charge des personnes atteintes de démence. Il importe de tenter de comprendre l’expérience et le point de vue des personnes atteintes de démence et de leurs soignants afin de pouvoir dispenser des soins optimaux. PMID:28115451

Hématome sous capsulaire de foie compliquant une pré-éclampsie: à propos de 6 cas

PubMed Central

Mamouni, Nisrine; Derkaoui, Ali; Bougern, Hakima; Bouchikhi, Chehrazad; Chaara, Hikmat; Banani, Abdelaziz; Abdelilah, Melhouf Moulay

2011-01-01

L'hématome sous capsulaire du foie (HSCF) est une complication rare mais gravissime de la grossesse. Devant une symptomatologie clinique souvent non spécifique et un tableau biologique retardé, son diagnostic est basé essentiellement sur les moyens de l'imagerie (échographie, TDM, IRM). Son traitement est fonction de l'intégrité ou non de la capsule de Glisson. Nous rapportons les observations de 6 patientes, à travers une étude rétrospective s’étalant sur la période du Janvier 2005 à Octobre 2008, incluant tous les cas de preeclampsie colligés au service de gynécologie obstétrique du CHU Hassan II. Durant la période d’étude, L'incidence de l'hématome sous capsulaire de foie chez les patientes préeclamptiques admises durant la période d’étude est de 1,49 %. Aucune des patientes n'a benificié d'un suivi prénatal au sein de notre formation. La moyenne d’âge des patientes est de 37,6 ans avec des extrêmes allant de 33 à 45 ans. La gestité moyenne était de 4,8 avec une parité moyenne de 4,5.l'hematome sous capsulaire est survenu en post partum chez tous nos cas avec un délai moyen de 4 jours et des extrêmes allant de J0 et J10 du post partum .Toutes les patientes ont présenté un HELLP syndrome concomitant à la survenue de cette complication gravissime.Le diagnostic positif s'est basé sur les données échographiques dans 5 cas (hemoperitoine –HSCF).l’équipe a opté pour une abstention thérapeutique avec surveillance armée chez 2 cas et l'exploration chirurgicale a été indiquée chez quatre patientes en instabilité hemodynamique.Nous avons déploré deux cas de décès maternel. PMID:22145072

Les neuropathies liées au VIH/SIDA: une étude clinique chez les patients infectés par le VIH au Centre d'Excellence VIH/SIDA de l'Université de Lubumbashi

PubMed Central

Kabongo, Joe Katabwa; Kaputu-Kalala-Malu, Célestin; Luboya, Oscar; Mutombo, Valerien; Ntambwe, Abel; Mapatano, Mala Ali; Mukendi, Kavulu Mayamba

2015-01-01

Introduction En vue d'améliorer la prise en charge des patients souffrant de neuropathie (NP) associées à l'infection HIV, nous avons essayé de déterminer le profil clinique des personnes souffrant de NP au cours du suivi thérapeutique de leur infection HIV. Méthodes Il s'agit d'une étude transversale (n= 101) menée au centre d'excellence depuis 1 an. Notre analyse est essentiellement clinique. Par un examen clinique minutieux, nous avons recherché tous les symptômes et signes cliniques des NP. Subjectivement, les douleurs dominent le tableau. Pour affiner leur diagnostic, nous avons utilisé l’échelle DN4 (Diagnostic des douleurs neuropathiques) et l’échelle EVA (Evaluation de la gravité des douleurs). Nous avons ensuite analysé nos données en fonction de certains autres facteurs épidémiologiques tels que le taux des CD4, le traitement anti-HIV etc. Résultats Les 101 patients représentent 3,12% de la cohorte générale; 53,3% des patients présentent une abolition des réflexes ostéotendineux des membres inférieurs; 77,89% présentent une hypoesthésie thermo algique en chaussette et en gants; 25% ont présenté une amyotrophie des membres inférieurs; 76,5% ont été soumis à un traitement antirétroviral contenant la stavudine; 11,7% ont pris la didanosine (DDI) et Abacavir (ABC). 84% ont une moyenne de CD4 de 292 cel/mm3. Conclusion La NP altère la qualité de vie de nos patients et diminue l'adhérence au traitement antirétroviral. Plusieurs facteurs sont incriminés dans la survenue de la NP, l'effet direct des antirétroviraux, l'effet inflammatoire dysimmunitaire, l'effet infectieux lié aux infections opportunistes. D'autres facteurs seront recherchés et analysés ultérieurement. PMID:26185582

Influence of non-contextual auditory stimuli on navigation in a virtual reality context involving executive functions among patients after stroke.

PubMed

Cogné, Mélanie; Violleau, Marie-Hélène; Klinger, Evelyne; Joseph, Pierre-Alain

2018-01-31

Topographical disorientation is frequent among patients after a stroke and can be well explored with virtual environments (VEs). VEs also allow for the addition of stimuli. A previous study did not find any effect of non-contextual auditory stimuli on navigational performance in the virtual action planning-supermarket (VAP-S) simulating a medium-sized 3D supermarket. However, the perceptual or cognitive load of the sounds used was not high. We investigated how non-contextual auditory stimuli with high load affect navigational performance in the VAP-S for patients who have had a stroke and any correlation between this performance and dysexecutive disorders. Four kinds of stimuli were considered: sounds from living beings, sounds from supermarket objects, beeping sounds and names of other products that were not available in the VAP-S. The condition without auditory stimuli was the control. The Groupe de réflexion pour l'évaluation des fonctions exécutives (GREFEX) battery was used to evaluate executive functions of patients. The study included 40 patients who have had a stroke (n=22 right-hemisphere and n=18 left-hemisphere stroke). Patients' navigational performance was decreased under the 4 conditions with non-contextual auditory stimuli (P<0.05), especially for those with dysexecutive disorders. For the 5 conditions, the lower the performance, the more GREFEX tests were failed. Patients felt significantly disadvantaged by the non-contextual sounds sounds from living beings, sounds from supermarket objects and names of other products as compared with beeping sounds (P<0.01). Patients' verbal recall of the collected objects was significantly lower under the condition with names of other products (P<0.001). Left and right brain-damaged patients did not differ in navigational performance in the VAP-S under the 5 auditory conditions. These non-contextual auditory stimuli could be used in neurorehabilitation paradigms to train patients with dysexecutive disorders to inhibit disruptive stimuli. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

Le traumatisme du colon: l'expérience du CHU Hassan II de Fès

PubMed Central

Benjelloun, El Bachir; Hafid, Hasnai; Karim, Ibnmajdoub; Ousadden, Abdelmalek; Mazaz, Khalid; Taleb, Kahlid Ait

2012-01-01

Introduction Les traumatismes du colon sont associés à un risque majeur de complications septiques et de mortalité. Le but de notre étude est d’évaluer les circonstances, la prise en charge, le suivi et les facteurs pronostic de morbidité postopératoire des malades victimes d'un traumatisme colique. Méthodes Il s'agit d'une étude rétrospective sur une série de 49 patients opérés pour des plaies coliques aux services de chirurgie viscérale du CHU HASSAN II de Fès sur une période de 8 ans de juillet 2003 à juillet 2011. Résultats L’âge moyen de nos patients était de 25ans (16-70) avec une nette prédominance masculine (93.8%). Les plaies coliques secondaires à un traumatisme par arme blanche représentent 85% des cas (42 patients), suivi par les plaies iatrogènes au cours d'une coloscopie chez 6 patients (13%), puis les contusions abdominales chez 1 patient (2%). Les parties du cadre colique les plus touchées étaient le colon transverse chez 19 patients (38%) et le colon descendant chez 12 patients (24, 5%). Le colon sigmoïde était le segment le plus touché au cours d'une coloscopie4/6. Quarante-deux patients (85%) ont eu une suture primaire des plaies coliques, six patients (13%) une diversion fécale et un patient (2%) une résection-anastomose. Deux patients (4%) sont décédés suite à un choc septique. La morbidité globale était de 38,7% dominé essentiellement par l'infection de la paroi chez 14 patients et une péritonite post opératoire chez 3 patients. L'analyse univarié a montré une différence significatif en terme d'infection de la paroi entre le groupe colostomie versus suture simple (50% vs 20,9% p<0,05). L'atteinte du colon gauche et la réalisation d'une colostomie sont associés à un risque plus élevés de complications postopératoires. Conclusion La suture primaire peut être effectuée avec un faible taux de complications postopératoire chez la majorité des patients suite à un traumatisme du colon. PMID:23346275

Forced-Unfolding and Force-Quench Refolding of RNA Hairpins

PubMed Central

Hyeon, Changbong; Thirumalai, D.

2006-01-01

Nanomanipulation of individual RNA molecules, using laser optical tweezers, has made it possible to infer the major features of their energy landscape. Time-dependent mechanical unfolding trajectories, measured at a constant stretching force (fS) of simple RNA structures (hairpins and three-helix junctions) sandwiched between RNA/DNA hybrid handles show that they unfold in a reversible all-or-none manner. To provide a molecular interpretation of the experiments we use a general coarse-grained off-lattice Gō-like model, in which each nucleotide is represented using three interaction sites. Using the coarse-grained model we have explored forced-unfolding of RNA hairpin as a function of fS and the loading rate (rf). The simulations and theoretical analysis have been done both with and without the handles that are explicitly modeled by semiflexible polymer chains. The mechanisms and timescales for denaturation by temperature jump and mechanical unfolding are vastly different. The directed perturbation of the native state by fS results in a sequential unfolding of the hairpin starting from their ends, whereas thermal denaturation occurs stochastically. From the dependence of the unfolding rates on rf and fS we show that the position of the unfolding transition state is not a constant but moves dramatically as either rf or fS is changed. The transition-state movements are interpreted by adopting the Hammond postulate for forced-unfolding. Forced-unfolding simulations of RNA, with handles attached to the two ends, show that the value of the unfolding force increases (especially at high pulling speeds) as the length of the handles increases. The pathways for refolding of RNA from stretched initial conformation, upon quenching fS to the quench force fQ, are highly heterogeneous. The refolding times, upon force-quench, are at least an order-of-magnitude greater than those obtained by temperature-quench. The long fQ-dependent refolding times starting from fully stretched states are analyzed using a model that accounts for the microscopic steps in the rate-limiting step, which involves the trans to gauche transitions of the dihedral angles in the GAAA tetraloop. The simulations with explicit molecular model for the handles show that the dynamics of force-quench refolding is strongly dependent on the interplay of their contour length and persistence length and the RNA persistence length. Using the generality of our results, we also make a number of precise experimentally testable predictions. PMID:16473903

On the chemical ladder of esters. Detection and formation of ethyl formate in the W51 e2 hot molecular core

NASA Astrophysics Data System (ADS)

Rivilla, V. M.; Beltrán, M. T.; Martín-Pintado, J.; Fontani, F.; Caselli, P.; Cesaroni, R.

2017-03-01

Context. In recent years, the detection of organic molecules with increasing complexity and potential biological relevance is opening the possibility to understand the formation of the building blocks of life in the interstellar medium. One of the families of molecules of substantial astrobiological interest are the esters. The simplest ester, methyl formate (CH3OCHO), is rather abundant in star-forming regions. The next step in the chemical complexity of esters is ethyl formate, C2H5OCHO. Despite the increase in sensitivity of current telescopes, the detection of complex molecules with more than ten atoms such as C2H5OCHO is still a challenge. Only two detections of this species have been reported so far, which strongly limits our understanding of how complex molecules are formed in the interstellar medium. New detections towards additional sources with a wide range of physical conditions are crucial to differentiate between competing chemical models based on dust grain surface and gas-phase chemistry. Aims: We have searched for ethyl formate towards the W51 e2 hot molecular core, one of the most chemically rich sources in the Galaxy and one of the most promising regions to study prebiotic chemistry, especially after the recent discovery of the P-O bond, key in the formation of DNA. Methods: We have analyzed a spectral line survey towards the W51 e2 hot molecular core, which covers 44 GHz in the 1, 2 and 3 mm bands, carried out with the IRAM 30 m telescope. Results: We report the detection of the trans and gauche conformers of ethyl formate. A local thermodynamic equilibrium analysis indicates that the excitation temperature is 78 ± 10 K and that the two conformers have similar source-averaged column densities of (2.0 ± 0.3) × 10-16 cm-2 and an abundance of 10-8. We compare for the first time the observed molecular abundances of ethyl formate with different competing chemical models based on grain surface and gas-phase chemistry. Conclusions: We propose that grain-surface chemistry may have a dominant role in the formation of ethyl formate (and other complex organic molecules) in hot molecular cores, rather than reactions in the gas phase. Based on observations carried out with the IRAM 30 m Telescope. IRAM is supported by INSU/CNRS (France), MPG (Germany) and IGN (Spain).