Density functional theory study of hydrogen atom abstraction from a series of para-substituted phenols: why is the Hammett σ(p)+ constant able to represent radical reaction rates?

PubMed

Yoshida, Tatsusada; Hirozumi, Koji; Harada, Masataka; Hitaoka, Seiji; Chuman, Hiroshi

2011-06-03

The rate of hydrogen atom abstraction from phenolic compounds by a radical is known to be often linear with the Hammett substitution constant σ(+), defined using the S(N)1 solvolysis rates of substituted cumyl chlorides. Nevertheless, a physicochemical reason for the above "empirical fact" has not been fully revealed. The transition states of complexes between the 2,2-diphenyl-1-picrylhydrazyl radical (dpph·) and a series of para-substituted phenols were determined by DFT (Density Functional Theory) calculations, and then the activation energy as well as the homolytic bond dissociation energy of the O-H bond and charge distribution in the transition state were calculated. The heterolytic bond dissociation energy of the C-Cl bond and charge distribution in the corresponding para-substituted cumyl chlorides were calculated in parallel. Excellent correlations among σ(+), charge distribution, and activation and bond dissociation energies revealed quantitatively that there is a strong similarity between the two reactions, showing that the electron-deficiency of the π-electron system conjugated with a substituent plays a crucial role in determining rates of the two reactions. The results provide a new insight into and physicochemical understanding of σ(+) in the hydrogen abstraction from substituted phenols by a radical.

Nitrogen Molecule-Dimethyl Sulfide Complex Investigated by Fourier Transform Microwave Spectroscopy and AB Initio Calculation

NASA Astrophysics Data System (ADS)

Kawashima, Yoshiyuki; Iwano, Sakae; Hirota, Eizi

2016-06-01

This paper presents an extension of the preceding talk on the FTMW spectroscopy of N_2-ES (ethylene sulfide), namely the results on N_2-DMS (dimethyl sulfide). We have previously investigated two N_2 complexes: N_2-DME (dimethyl ether), for which we reported a prelimanary result, and N_2-EO (ethylene oxide). We have observed the ground-state rotational spectrum of the N_2-DMS complex, i.e. c-type transitions in the frequency region from 5 to 24 GHz, which we assigned to the normal, 15N_2-DMS, and 15NN-DMS species of the N_2-DMS. We have found both the ortho and para states for the 14N_2-DMS and 15N_2-DMS species. In the case of the 15N_2-DMS, some transitions with Ka = 2 and 3 were observed slightly split by the internal rotation of the two methyl tops of the DMS. The observed spectra of the 15N_2-DMS were analyzed by using the XIAM program. In the case of the para state of the 15N_2-DMS, three rotational and five centrifugal distortion constants with the V3 barrier to the methyl group internal rotation, whereas, in the case of the ortho state of the 15N_2-DMS, two more centrifugal distortion constants, ΦJK and ΦKJ, were needed to reproduce the observed spectra. For the N_2-DMS complex, we concluded that the N_2 moiety was located in a plane perpendicular to the C-S-C plane and bisecting the CSC angle of the DMS. We have carried out ab initio molecular orbital calculations at the level of MP2 with basis sets 6-311++G(d, p), aug-cc-pVDZ, and aug-cc-pVTZ, to complement the information on the intracomplex motions obtained from the observed rotational spectra. We have applied a natural bond orbital (NBO) analysis to the N_2-DMS and N_2-ES to calculate the stabilization energy CT (=Δ Eσσ*), which was closely correlated with the binding energy EB, as found for other related complexes. Y. Kawashima, Y. Tatamitani, Y. Morita, and E. Hirota, 61st International Symposium on Molecular Spectroscopy, TE10 (2006) Y. Kawashima and E. Hirota, J. Phys. Chem. A 2013 117, 13855

The origin of the Hox/ParaHox genes, the Ghost Locus hypothesis and the complexity of the first animal.

PubMed

Ferrier, David E K

2016-09-01

A key aim in evolutionary biology is to deduce ancestral states to better understand the evolutionary origins of clades of interest and the diversification process(es) that has/have elaborated them. These ancestral deductions can hit difficulties when undetected loss events are misinterpreted as ancestral absences. With the ever-increasing amounts of animal genomic sequence data, we are gaining a much clearer view of the preponderance of differential gene losses across animal lineages. This has become particularly clear with recent progress in our understanding of the origins of the Hox/ParaHox developmental control genes relative to the earliest branching lineages of the animal kingdom: the sponges (Porifera), comb jellies (Ctenophora) and placozoans (Placozoa). These reassessments of the diversity and complexity of developmental control genes in the earliest animal ancestors need to go hand-in-hand with complementary advances in comparative morphology, phylogenetics and palaeontology to clarify our understanding of the complexity of the last common ancestor of all animals. The field is currently undergoing a shift from the traditional consensus of a sponge-like animal ancestor from which morphological and molecular elaboration subsequently evolved, to a scenario of a more complex animal ancestor, with subsequent losses and simplifications in various lineages. © The Author 2015. Published by Oxford University Press. All rights reserved. For permissions, please email: journals.permissions@oup.com.

Diimine triscarbonyl Re(I) of isomeric pyridyl-fulvene ligands: an electrochemical, spectroscopic, and computational investigation.

PubMed

Chartrand, Daniel; Castro Ruiz, Carlos A; Hanan, Garry S

2012-12-03

The synthesis and characterization of a novel family of positively charged fac-[Re(bpy)(CO)(3)(L)]PF(6) (bpy = 2,2'-bipyridine) complexes are reported, where L is a pyridine functionalized in para or meta position with a fulvene moiety, namely, 4-fluoren-9-ylidenemethyl-pyridine (pFpy) and 3-fluoren-9-ylidenemethyl-pyridine (mFpy). The complexes were prepared in high yield (86%) by direct addition at room temperature of the corresponding pyridine to the tetrahydrofuran (THF) adduct fac-[Re(bpy)(CO)(3)(THF)][PF(6)] precursor. Both ligand and complex structures were fully characterized by a variety of techniques including X-ray crystallography. The complexes did not exhibit the expected triplet mixed metal-ligand-to-ligand charge transfer (MLLCT) emission, because of its deactivation by the non-emissive triplet excited state of fulvene. The absorption profile shows that the MLLCT is overshadowed by the fulvene centered π-π* transition of higher molar absorptivity as shown by time dependent density functional theory (TD-DFT) calculations. The position of the fulvene on the pyridyl ring has a large effect on this transition, the para position displaying a much higher absorption coefficient (21.3 × 10(3) M(-1) cm(-1)) at lower energy (364 nm) than the meta position (331 nm, 16.0 × 10(3) M(-1) cm(-1)).

Nonclassical and semiclassical para-Bose states

NASA Astrophysics Data System (ADS)

Huerta Alderete, C.; Villanueva Vergara, Liliana; Rodríguez-Lara, B. M.

2017-04-01

Motivated by the proposal to simulate para-Bose oscillators in a trapped-ion setup [C. Huerta Alderete and B. M. Rodríguez-Lara, Phys. Rev. A 95, 013820 (2017), 10.1103/PhysRevA.95.013820], we introduce an overcomplete, nonorthogonal basis for para-Bose Hilbert spaces. The states spanning these bases can be experimentally realized in the trapped-ion simulation via time evolution. The para-Bose states show both nonclassical and semiclassical statistics on their Fock state distribution, asymmetric field quadrature variances, and do not minimize the uncertainty relation for the field quadratures. These properties are analytically controlled by the para-Bose order and the evolution time; both parameters might be feasible for fine tuning in the trapped-ion quantum simulation.

Microwave dielectric relaxation spectroscopy study of propylene glycol/ethanol binary mixtures: Temperature dependence

NASA Astrophysics Data System (ADS)

Vishwam, T.; Shihab, Suriya; Murthy, V. R. K.; Tiong, Ha Sie; Sreehari Sastry, S.

2017-05-01

Complex dielectric permittivity measurements of propylene glycol (PG) in ethanol at various mole fractions were measured by using open-ended coaxial probe technique at different temperatures in the frequency range 0.02 < ν/GHz < 20. The dipole moment (μ), excess dipole moment (Δμ),excess permittivity (εE), excess inverse relaxation time(1/τ)E, Bruggeman parameter (fB), excess Helmholtz energy (ΔFE) are determined using experimental data. From the minimum energy based geometry optimization, dipole moments of individual monomers of propylene glycol and ethanol and their binary system have been evaluated theoretically at gaseous state as well as alcoholic medium by using PCM and IEFPCM solvation models from the Hatree-Fock (HF) and Density Functional Theory (DFT-B3LYP) methods with 6-311G* and 6-311G** basis sets. The obtained results have been interpreted in terms of the short and long range ordering of the dipoles, Kirkwood correlation factor (geff), thermodynamic parameters, mean molecular polarizability (αM) and interaction in the mixture through hydrogen bonding. Dielectric relaxation study of propylene glycol in ethanol medium Determination of excess dielectric and thermodynamic parameters Comparison of experimental dipole moment with theoretical calculations Interpretation of the molecular interactions in the liquid through H-bonding Correlation between the evaluated dielectric parameters and theoretical results

Influence of Molecular Oxygen on Ortho-Para Conversion of Water Molecules

NASA Astrophysics Data System (ADS)

Valiev, R. R.; Minaev, B. F.

2017-07-01

The mechanism of influence of molecular oxygen on the probability of ortho-para conversion of water molecules and its relation to water magnetization are considered within the framework of the concept of paramagnetic spin catalysis. Matrix elements of the hyperfine ortho-para interaction via the Fermi contact mechanism are calculated, as well as the Maliken spin densities on water protons in H2O and O2 collisional complexes. The mechanism of penetration of the electron spin density into the water molecule due to partial spin transfer from paramagnetic oxygen is considered. The probability of ortho-para conversion of the water molecules is estimated by the quantum chemistry methods. The results obtained show that effective ortho-para conversion of the water molecules is possible during the existence of water-oxygen dimers. An external magnetic field affects the ortho-para conversion rate given that the wave functions of nuclear spin sublevels of the water protons are mixed in the complex with oxygen.

Solution of the Skyrme-Hartree-Fock-Bogolyubov equations in the Cartesian deformed harmonic-oscillator basis.. (VI) HFODD (v2.40h): A new version of the program

NASA Astrophysics Data System (ADS)

Dobaczewski, J.; Satuła, W.; Carlsson, B. G.; Engel, J.; Olbratowski, P.; Powałowski, P.; Sadziak, M.; Sarich, J.; Schunck, N.; Staszczak, A.; Stoitsov, M.; Zalewski, M.; Zduńczuk, H.

2009-11-01

We describe the new version (v2.40h) of the code HFODD which solves the nuclear Skyrme-Hartree-Fock or Skyrme-Hartree-Fock-Bogolyubov problem by using the Cartesian deformed harmonic-oscillator basis. In the new version, we have implemented: (i) projection on good angular momentum (for the Hartree-Fock states), (ii) calculation of the GCM kernels, (iii) calculation of matrix elements of the Yukawa interaction, (iv) the BCS solutions for state-dependent pairing gaps, (v) the HFB solutions for broken simplex symmetry, (vi) calculation of Bohr deformation parameters, (vii) constraints on the Schiff moments and scalar multipole moments, (viii) the DT2h transformations and rotations of wave functions, (ix) quasiparticle blocking for the HFB solutions in odd and odd-odd nuclei, (x) the Broyden method to accelerate the convergence, (xi) the Lipkin-Nogami method to treat pairing correlations, (xii) the exact Coulomb exchange term, (xiii) several utility options, and we have corrected three insignificant errors. New version program summaryProgram title: HFODD (v2.40h) Catalogue identifier: ADFL_v2_2 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/ADFL_v2_2.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 79 618 No. of bytes in distributed program, including test data, etc.: 372 548 Distribution format: tar.gz Programming language: FORTRAN-77 and Fortran-90 Computer: Pentium-III, AMD-Athlon, AMD-Opteron Operating system: UNIX, LINUX, Windows XP Has the code been vectorised or parallelized?: Yes, vectorised RAM: 10 Mwords Word size: The code is written in single-precision for use on a 64-bit processor. The compiler option -r8 or +autodblpad (or equivalent) has to be used to promote all real and complex single-precision floating-point items to double precision when the code is used on a 32-bit machine. Classification: 17.22 Catalogue identifier of previous version: ADFL_v2_1 Journal reference of previous version: Comput. Phys. Commun. 167 (2005) 214 External routines: Lapack (http://www.netlib.org/lapack/), Blas (http://www.netlib.org), linpack (http://www.netlib/linpack/) Does the new version supersede the previous version?: Yes Nature of problem: The nuclear mean-field and an analysis of its symmetries in realistic cases are the main ingredients of a description of nuclear states. Within the Local Density Approximation, or for a zero-range velocity-dependent Skyrme interaction, the nuclear mean-field is local and velocity dependent. The locality allows for an effective and fast solution of the self-consistent Hartree-Fock equations, even for heavy nuclei, and for various nucleonic (n-particle n-hole) configurations, deformations, excitation energies, or angular momenta. Similar Local Density Approximation in the particle-particle channel, which is equivalent to using a zero-range interaction, allows for a simple implementation of pairing effects within the Hartree-Fock-Bogolyubov method. Solution method: The program uses the Cartesian harmonic oscillator basis to expand single-particle or single-quasiparticle wave functions of neutrons and protons interacting by means of the Skyrme effective interaction and zero-range pairing interaction. The expansion coefficients are determined by the iterative diagonalization of the mean field Hamiltonians or Routhians which depend non-linearly on the local neutron and proton densities. Suitable constraints are used to obtain states corresponding to a given configuration, deformation or angular momentum. The method of solution has been presented in [1]. Summary of revisions: Projection on good angular momentum (for the Hartree-Fock states) has been implemented. Calculation of the GCM kernels has been implemented. Calculation of matrix elements of the Yukawa interaction has been implemented. The BCS solutions for state-dependent pairing gaps have been implemented. The HFB solutions for broken simplex symmetry have been implemented. Calculation of Bohr deformation parameters has been implemented. Constraints on the Schiff moments and scalar multipole moments have been implemented. The DT2h transformations and rotations of wave functions have been implemented. The quasiparticle blocking for the HFB solutions in odd and odd-odd nuclei has been implemented. The Broyden method to accelerate the convergence has been implemented. The Lipkin-Nogami method to treat pairing correlations has been implemented. The exact Coulomb exchange term has been implemented. Several utility options have been implemented. Three insignificant errors have been corrected. Restrictions: The main restriction is the CPU time required for calculations of heavy deformed nuclei and for a given precision required. Unusual features: The user must have access to an implementation of the BLAS (Basic Linear Algebra Subroutines), the NAGLIB subroutine F02AXE, or LAPACK subroutines ZHPEV, ZHPEVX, or ZHEEVR, which diagonalize complex Hermitian matrices, and the LINPACK subroutines ZGEDI and ZGECO, which invert arbitrary complex matrices and calculate determinants or provide another set of subroutines that can perform such a tasks. The LAPACK and LINPACK subroutines and an unoptimized version of the BLAS can be obtained from the Netlib Repository at the University of Tennessee, Knoxville: http://www.netlib.org/. Running time: One Hartree-Fock iteration for the superdeformed, rotating, parity conserving state of 15266Dy86 takes about six seconds on the AMD-Athlon 1600+ processor. Starting from the Woods-Saxon wave functions, about fifty iterations are required to obtain the energy converged within the precision of about 0.1 keV. In the case where every value of the angular velocity is converged separately, the complete superdeformed band with precisely determined dynamical moments J (2) can be obtained in forty minutes of CPU time on the AMD-Athlon 1600+ processor. This time can be often reduced by a factor of three when a self-consistent solution for a given rotational frequency is used as a starting point for a neighboring rotational frequency. References: J. Dobaczewski, J. Dudek, Comput. Phys. Commun. 102 (1997) 166.

First time-dependent study of H{sub 2} and H{sub 3}{sup +} ortho-para chemistry in the diffuse interstellar medium: Observations meet theoretical predictions

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

Albertsson, T.; Semenov, D.; Henning, Th.

The chemistry in the diffuse interstellar medium (ISM) initiates the gradual increase of molecular complexity during the life cycle of matter. A key molecule that enables build-up of new molecular bonds and new molecules via proton donation is H{sub 3}{sup +}. Its evolution is tightly related to molecular hydrogen and thought to be well understood. However, recent observations of ortho and para lines of H{sub 2} and H{sub 3}{sup +} in the diffuse ISM showed a puzzling discrepancy in nuclear spin excitation temperatures and populations between these two key species. H{sub 3}{sup +}, unlike H{sub 2}, seems to be outmore » of thermal equilibrium, contrary to the predictions of modern astrochemical models. We conduct the first time-dependent modeling of the para-fractions of H{sub 2} and H{sub 3}{sup +} in the diffuse ISM and compare our results to a set of line-of-sight observations, including new measurements presented in this study. We isolate a set of key reactions for H{sub 3}{sup +} and find that the destruction of the lowest rotational states of H{sub 3}{sup +} by dissociative recombination largely controls its ortho/para ratio. A plausible agreement with observations cannot be achieved unless a ratio larger than 1:5 for the destruction of (1, 1)- and (1, 0)-states of H{sub 3}{sup +} is assumed. Additionally, an increased cosmic-ray ionization rate to 10{sup –15} s{sup –1} further improves the fit whereas variations of other individual physical parameters, such as density and chemical age, have only a minor effect on the predicted ortho/para ratios. Thus, our study calls for new laboratory measurements of the dissociative recombination rate and branching ratio of the key ion H{sub 3}{sup +} under interstellar conditions.« less

First Time-dependent Study of H2 and H_3^+ Ortho-Para Chemistry in the Diffuse Interstellar Medium: Observations Meet Theoretical Predictions

NASA Astrophysics Data System (ADS)

Albertsson, T.; Indriolo, N.; Kreckel, H.; Semenov, D.; Crabtree, K. N.; Henning, Th.

2014-05-01

The chemistry in the diffuse interstellar medium (ISM) initiates the gradual increase of molecular complexity during the life cycle of matter. A key molecule that enables build-up of new molecular bonds and new molecules via proton donation is H_3^+. Its evolution is tightly related to molecular hydrogen and thought to be well understood. However, recent observations of ortho and para lines of H2 and H_3^+ in the diffuse ISM showed a puzzling discrepancy in nuclear spin excitation temperatures and populations between these two key species. H_3^+, unlike H2, seems to be out of thermal equilibrium, contrary to the predictions of modern astrochemical models. We conduct the first time-dependent modeling of the para-fractions of H2 and H_3^+ in the diffuse ISM and compare our results to a set of line-of-sight observations, including new measurements presented in this study. We isolate a set of key reactions for H_3^+ and find that the destruction of the lowest rotational states of H_3^+ by dissociative recombination largely controls its ortho/para ratio. A plausible agreement with observations cannot be achieved unless a ratio larger than 1:5 for the destruction of (1, 1)- and (1, 0)-states of H_3^+ is assumed. Additionally, an increased cosmic-ray ionization rate to 10-15 s-1 further improves the fit whereas variations of other individual physical parameters, such as density and chemical age, have only a minor effect on the predicted ortho/para ratios. Thus, our study calls for new laboratory measurements of the dissociative recombination rate and branching ratio of the key ion H_{3}^{+} under interstellar conditions. Partly based on observations collected at the European Organization for Astronomical Research in the Southern Hemisphere, Chile, as part of program 088.C-0351.

Spectral and thermal studies with anti-fungal aspects of some organotin(IV) complexes with nitrogen and sulphur donor ligands derived from 2-phenylethylamine

NASA Astrophysics Data System (ADS)

Singh, Rajeev; Kaushik, N. K.

2008-11-01

Some complexes of 2-phenylethyl dithiocarbamate, thiohydrazides and thiodiamines with dibenzyltin(IV) chloride, tribenzyltin(IV) chloride and di( para-chlorobenzyl)tin(IV) dichloride have been synthesized and investigated in 1:2 and 1:1 molar ratio. The dithiocarbamate ligand act as monoanionic bidentate and thiohydrazide, thiodiamines act as neutral bidentate ligand. The synthesized complexes have been characterized by elemental analysis and molecular weight determination studies and their bonding pattern suggested on the basis of electronic, infrared, 1H and 13C NMR spectroscopy. Using thermogravimetric (TG) and differential thermal analysis (DTA) various thermodynamic and kinetic parameters viz. reaction order ( n), apparent activation energy ( Ea), apparent activation entropy ( S#) and heat of reaction (Δ H) have been calculated and correlated with the structural aspects for solid-state decomposition of complexes. The ligands and their tin complexes have also been screened for their fungitoxicity activity against Rhizoctonia solanii and Sclerotium rolfsii and their ED 50 values calculated.

Spectral and thermal studies with anti-fungal aspects of some organotin(IV) complexes with nitrogen and sulphur donor ligands derived from 2-phenylethylamine.

PubMed

Singh, Rajeev; Kaushik, N K

2008-11-15

Some complexes of 2-phenylethyl dithiocarbamate, thiohydrazides and thiodiamines with dibenzyltin(IV) chloride, tribenzyltin(IV) chloride and di(para-chlorobenzyl)tin(IV) dichloride have been synthesized and investigated in 1:2 and 1:1 molar ratio. The dithiocarbamate ligand act as monoanionic bidentate and thiohydrazide, thiodiamines act as neutral bidentate ligand. The synthesized complexes have been characterized by elemental analysis and molecular weight determination studies and their bonding pattern suggested on the basis of electronic, infrared, 1H and 13C NMR spectroscopy. Using thermogravimetric (TG) and differential thermal analysis (DTA) various thermodynamic and kinetic parameters viz. reaction order (n), apparent activation energy (Ea), apparent activation entropy (S#) and heat of reaction (DeltaH) have been calculated and correlated with the structural aspects for solid-state decomposition of complexes. The ligands and their tin complexes have also been screened for their fungitoxicity activity against Rhizoctonia solanii and Sclerotium rolfsii and their ED50 values calculated.

Molecular structure, magnetic properties, cyclic voltammetry of the low-spin iron(III) Bis(4-ethylaniline) complex with the para-chloro substituted meso-tetraphenylporphyrin

NASA Astrophysics Data System (ADS)

Dhifaoui, Selma; Mchiri, Chadlia; Quatremare, Pierre; Marvaud, Valérie; Bujacz, Anna; Nasri, Habib

2018-02-01

In this study, the preparation of a new iron(III) hexacoordinated metalloporphyrin namely the bis(4-ethylaniline){meso-tetra(para-chlorophenyl)porphyrinato}iron(III) triflate hemi-4-ethylaniline monohydrate with the formula [FeIII(TClPP)(PhEtNH2)2]SO3CF3•1/2PhEtNH2•H2O (I) was reported. This is the first example of an iron(III) metalloporphyrin bis(primary amine) with an aryl group adjacent to the amino group. This species was characterized by elemental, spectroscopic analysis including UV-visible and IR data, cyclic voltammetry, SQUID measurements and X-ray molecular structure. The mean equatorial distance between the iron(III) and the nitrogens of the porphyrin is appropriate for a low-spin (S = 1/2) iron(III) porphyrin complex. The magnetic data confirm the low-spin state of our ferric derivative while the cyclic voltammetry indicates a shift of the half potential E1/2[Fe(III)/Fe(II)] of complex (I) toward more negative value. In the crystal of (I), the [FeIII(TClPP)(PhEtNH2)2]+ ions, the triflate counterions and the water molecules are involved in a number of O__H⋯O, N__H⋯O, C-H⋯O and C__H⋯π intermolecular interactions forming a three-dimension network.

Evidence for disequilibrium of ortho and para hydrogen on Jupiter from Voyager IRIS measurements

NASA Technical Reports Server (NTRS)

Conrath, B. J.; Gierasch, P. J.

1983-01-01

Preliminary results of an analysis of the ortho state/para state ratio (parallel/antiparallel) for molecular H2 in the Jovian atmosphere using Voyager IR spectrometer (IRIS) data are reported. The study was undertaken to expand the understanding of the thermodynamics of a predominantly H2 atmosphere, which takes about 100 million sec to reach equilibrium. IRIS data provided 4.3/cm resolution in the 300-700/cm spectral range dominated by H2 lines. Approximately 600 spectra were examined to detect any disequilibrium between the hydrogen species. The results indicate that the ortho-para ratio is not in an equilibrium state in the upper Jovian troposphere. A thorough mapping of the para-state molecules in the upper atmosphere could therefore aid in mapping the atmospheric flowfield.

Pre-symplectic algebroids and their applications

NASA Astrophysics Data System (ADS)

Liu, Jiefeng; Sheng, Yunhe; Bai, Chengming

2018-03-01

In this paper, we introduce the notion of a pre-symplectic algebroid and show that there is a one-to-one correspondence between pre-symplectic algebroids and symplectic Lie algebroids. This result is the geometric generalization of the relation between left-symmetric algebras and symplectic (Frobenius) Lie algebras. Although pre-symplectic algebroids are not left-symmetric algebroids, they still can be viewed as the underlying structures of symplectic Lie algebroids. Then we study exact pre-symplectic algebroids and show that they are classified by the third cohomology group of a left-symmetric algebroid. Finally, we study para-complex pre-symplectic algebroids. Associated with a para-complex pre-symplectic algebroid, there is a pseudo-Riemannian Lie algebroid. The multiplication in a para-complex pre-symplectic algebroid characterizes the restriction to the Lagrangian subalgebroids of the Levi-Civita connection in the corresponding pseudo-Riemannian Lie algebroid.

Steric effects in the design of Co-Schiff base complexes for the catalytic oxidation of lignin models to para-benzoquinones

Treesearch

Berenger Biannic; Joseph J. Bozell; Thomas Elder

2014-01-01

New Co-Schiff base complexes that incorporate a sterically hindered ligand and an intramolecular bulky piperazine base in close proximity to the Co center are synthesized. Their utility as catalysts for the oxidation of para-substituted lignin model phenols with molecular oxygen is examined. Syringyl and guaiacyl alcohol, as models of S and G units in lignin, are...

Sub-Doppler Electronic Spectrum of the BENZENE-D2 Complex

NASA Astrophysics Data System (ADS)

Hayashi, Masato; Ohshima, Yasuhiro

2014-06-01

Excitation spectrum of the benzene-D2 van der Waals (vdW) complex in the vicinity of the S1 ← S0 601 vibronic transition of the monomer was recorded by utilizing mass-selective two-color resonance-enhanced two-photon ionization. Extensive adiabatic cooling with the rotational temperature of ěrb|<| 0.5 K was conducted by the high-pressure pulsed expansion, and sub-Doppler resolution yielding the line width of 250 MHz was realized in a collimated molecular beam by employing Fourier-transform-limited ultraviolet pulses for the excitation. In contrast to our previous study on the benzene-H2 complex, weaker binding ortho nuclear-spin isomer, correlating to the j = 0 state of a freely rotating D2, was observed in addition to the stronger binding para isomer (with j = 1), by using a gas sample of normal D2. Three and two vibronic bands involving vdW-mode excitation were observed for the para and ortho isomers, respectively. By comparing the present results with those of the benzene-H2 complex, we made unambiguous assignments on the vdW modes involved in each observed band, and obtained complete sets of vibrational frequencies of all the three vdW modes for the both H2 and D2 isotopomers in the S1 61 manifold. One of the vdW frequency correlates to the splitting between the m = 0 and ± 1 sublevels in the j = 1 state of a freely rotating H2/D2 molecule, and the potential barrier for the hindered internal rotation has been evaluated to be ca. 60 cm-1 from the values. Ratio of the vdW frequencies between the H2 and D2 species deviate significantly from the value for the harmonic vibration (i.e., √{2} ≈ 1.4), indicating substantial anharmonic character of the vdW modes in the complex. M. Hayashi and Y. Ohshima, Chem. Phys. 419, 131-137 (2013). M. Hayashi and Y. Ohshima, J. Phys. Chem. A 117, 9819-9830 (2013).

Control of exciton confinement in quantum dot-organic complexes through energetic alignment of interfacial orbitals.

PubMed

Frederick, Matthew T; Amin, Victor A; Swenson, Nathaniel K; Ho, Andrew Y; Weiss, Emily A

2013-01-09

This paper describes a method to control the quantum confinement, and therefore the energy, of excitonic holes in CdSe QDs through adsorption of the hole-delocalizing ligand phenyldithiocarbamate, PTC, and para substitutions of the phenyl ring of this ligand with electron-donating or -withdrawing groups. These substitutions control hole delocalization in the QDs through the energetic alignment of the highest occupied orbitals of PTC with the highest density-of-states region of the CdSe valence band, to which PTC couples selectively.

The Ratio of Ortho- to Para-H2 in Photodissociation Regions

NASA Technical Reports Server (NTRS)

Sternberg, Amiel; Neufeld, David A.

1999-01-01

We discuss the ratio of ortho- to para-H2 in photodissociation regions (PDRs). We draw attention to an apparent confusion in the literature between the ortho-to-para ratio of molecules in FUV-pumped vibrationally excited states and the total H2 ortho-to-para abundance ratio. These ratios are not the same because the process of FUV pumping of fluorescent H2 emission in PDRs occurs via optically thick absorption lines. Thus gas with an equilibrium ratio of ortho- to para-H2 equal to 3 will yield FUV-pumped vibrationally excited ortho-to-para ratios smaller than 3, because the ortho-H2 pumping rates are preferentially reduced by optical depth effects. Indeed, if the ortho and para pumping lines are on the "square root" part of the curve of growth, then the expected ratio of ortho and para vibrational line strengths is 3(sup 1/2) approximately 1.7, close to the typically observed value. Thus, contrary to what has sometimes been stated in the literature, most previous measurements of the ratio of ortho- to para-H2 in vibrationally excited states are entirely consistent with a total ortho-to-para ratio of 3, the equilibrium value for temperatures greater than 200 K. We present an analysis and several detailed models that illustrate the relationship between the total ratios of ortho- to para-H2 and the vibrationally excited ortho-to-para ratios in PDRs. Recent Infrared Space Observatory measurements of pure rotational and vibrational H2 emissions from the PDR in the star-forming region S140 provide strong observational support for our conclusions.

Generating para-water from para-hydrogen: A Gedankenexperiment.

PubMed

Ivanov, Konstantin L; Bodenhausen, Geoffrey

2018-07-01

A novel conceptual approach is described that is based on the transfer of hyperpolarization from para-hydrogen in view of generating a population imbalance between the two spin isomers of H 2 O. The approach is analogous to SABRE (Signal Amplification By Reversible Exchange) and makes use of the transfer of spin order from para-hydrogen to H 2 O in a hypothetical organometallic complex. The spin order transfer is expected to be most efficient at avoided level crossings. The highest achievable enrichment levels of para- and ortho-water are discussed. Copyright © 2018 Elsevier Inc. All rights reserved.

Capture techniques' use of Caranguejo-uçá crabs (Ucides cordatus) in Paraíba state (northeastern Brazil) and its socio-environmental implications.

PubMed

Nascimento, Douglas M; Ferreira, Emmanoela N; Bezerra, Dandara M M S Q; Rocha, Pollyana D; Alves, Rômulo R N; Mourão, José S

2012-12-01

The present study was undertaken in two traditional communities that are located on the margins of the estuary and mangrove complex of the Mamanguape River, Paraíba state (PB), Brazil. This work describes the crabs capture techniques tapamento and redinha, and identifies the negative socio-environmental impacts of redinha, using qualitative methods (open and semi-structured interviews, guided tours, direct observation and the administration of questionnaires). Results indicate that currently only two principle techniques are used to capture Ucides cordatus: redinha and tapamento. Tapamento has a low impact in relation to redinha. Redinha was pointed out by interviewees as a system that has social impact (social conflicts, breaking of traditions, substitution and extinction of techniques) and environmental impact (less selective captures and high productivity, mangrove pollution, death of crabs caught in traps, cutting of the roots of Rhizophora mangle, micro-habitat loss resulting from galleries destroyed and polluted). Knowledge of crab harvesting carried out using these two techniques and the possible social and environmental impacts caused by redinha, can lead to more effective planning and actions towards the conservation of the species.

Para Sport Athletic Identity from Competition to Retirement: A Brief Review and Future Research Directions.

PubMed

Guerrero, Michelle; Martin, Jeffrey

2018-05-01

The primary purpose of this article is to review the literature on para sport athletic identity and provide avenues for future research direction. First, the authors briefly describe the existing quantitative and qualitative research on para sport athletic identity and, thereby, illustrate the complexities para sport athletes experience regarding the way they describe their participation in competitive sport. Next, the authors describe how para sport athletes with acquired permanent disabilities and congenital disabilities face similar, yet unique, identity-related challenges. Finally, the authors argue that future researchers should consider examining para sport athletes' identity through narrative identity. Copyright © 2018 Elsevier Inc. All rights reserved.

Bimetallic lanthanide amido complexes as highly active initiators for the ring-opening polymerization of lactides.

PubMed

Sun, Song; Nie, Kun; Tan, Yufang; Zhao, Bei; Zhang, Yong; Shen, Qi; Yao, Yingming

2013-02-28

A series of neutral bimetallic lanthanide amido complexes supported by rigid phenylene bridged bis(β-diketiminate) ligands were synthesized, and their catalytic behavior for the polymerization of L-lactide and rac-lactide was explored. The amine elimination reaction of Ln[N(TMS)(2)](3)(μ-Cl)Li(THF)(3) with PARA-H(2), [PARA-H(2) = 2[2,6-(i)Pr(2)C(6)H(3)NHC(Me)C(H)C(Me)N]-(para-phenylene)] in a 2:1 molar ratio in THF at 25 °C afforded the corresponding bimetallic lanthanide amido complexes PARA-{Ln[N(SiMe(3))(2)](2)}(2) [Ln = Nd(1), Sm(2), Y(3)] in high isolated yields. Similar reaction of Nd[N(TMS)(2)](3)(μ-Cl)Li(THF)(3) with META-H(2), [META-H(2) = 2[2,6-(i)Pr(2)C(6)H(3)NHC(Me)C(H)C(Me)N]-(meta-phenylene)] at 90 °C in toluene for about 48 h gave META-{Nd[N(SiMe(3))(2)](2)}(2) (4). Complexes 1-4 were well characterized by elemental analysis, IR spectroscopy, and their definitive structures were confirmed by an X-ray crystal structure analysis. The coordination environment and coordination geometry around the metal atoms are similar in these complexes. Each of the metal atoms is four-coordinated with two nitrogen atoms from the N,N-chelating β-diketiminate unit, and two nitrogen atoms from two (Me(3)Si)(2)N- groups to form a distorted tetrahedron. These complexes can serve as highly active initiators for L-lactide polymerization in toluene. In addition, they also showed high activity towards rac-lactide polymerization in THF at room temperature, giving heterotactic-enriched polymers (P(r) ≈ 0.70), and complex 4 displays obviously higher activity in comparison with complex 1.

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

Keefer, Donald A.; Shaffer, Eric G.; Storsved, Brynne

A free software application, RVA, has been developed as a plugin to the US DOE-funded ParaView visualization package, to provide support in the visualization and analysis of complex reservoirs being managed using multi-fluid EOR techniques. RVA, for Reservoir Visualization and Analysis, was developed as an open-source plugin to the 64 bit Windows version of ParaView 3.14. RVA was developed at the University of Illinois at Urbana-Champaign, with contributions from the Illinois State Geological Survey, Department of Computer Science and National Center for Supercomputing Applications. RVA was designed to utilize and enhance the state-of-the-art visualization capabilities within ParaView, readily allowing jointmore » visualization of geologic framework and reservoir fluid simulation model results. Particular emphasis was placed on enabling visualization and analysis of simulation results highlighting multiple fluid phases, multiple properties for each fluid phase (including flow lines), multiple geologic models and multiple time steps. Additional advanced functionality was provided through the development of custom code to implement data mining capabilities. The built-in functionality of ParaView provides the capacity to process and visualize data sets ranging from small models on local desktop systems to extremely large models created and stored on remote supercomputers. The RVA plugin that we developed and the associated User Manual provide improved functionality through new software tools, and instruction in the use of ParaView-RVA, targeted to petroleum engineers and geologists in industry and research. The RVA web site (http://rva.cs.illinois.edu) provides an overview of functions, and the development web site (https://github.com/shaffer1/RVA) provides ready access to the source code, compiled binaries, user manual, and a suite of demonstration data sets. Key functionality has been included to support a range of reservoirs visualization and analysis needs, including: sophisticated connectivity analysis, cross sections through simulation results between selected wells, simplified volumetric calculations, global vertical exaggeration adjustments, ingestion of UTChem simulation results, ingestion of Isatis geostatistical framework models, interrogation of joint geologic and reservoir modeling results, joint visualization and analysis of well history files, location-targeted visualization, advanced correlation analysis, visualization of flow paths, and creation of static images and animations highlighting targeted reservoir features.« less

RVA: A Plugin for ParaView 3.14

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

2015-09-04

RVA is a plugin developed for the 64-bit Windows version of the ParaView 3.14 visualization package. RVA is designed to provide support in the visualization and analysis of complex reservoirs being managed using multi-fluid EOR techniques. RVA, for Reservoir Visualization and Analysis, was developed at the University of Illinois at Urbana-Champaign, with contributions from the Illinois State Geological Survey, Department of Computer Science and National Center for Supercomputing Applications. RVA was designed to utilize and enhance the state-of-the-art visualization capabilities within ParaView, readily allowing joint visualization of geologic framework and reservoir fluid simulation model results. Particular emphasis was placed onmore » enabling visualization and analysis of simulation results highlighting multiple fluid phases, multiple properties for each fluid phase (including flow lines), multiple geologic models and multiple time steps. Additional advanced functionality was provided through the development of custom code to implement data mining capabilities. The built-in functionality of ParaView provides the capacity to process and visualize data sets ranging from small models on local desktop systems to extremely large models created and stored on remote supercomputers. The RVA plugin that we developed and the associated User Manual provide improved functionality through new software tools, and instruction in the use of ParaView-RVA, targeted to petroleum engineers and geologists in industry and research. The RVA web site (http://rva.cs.illinois.edu) provides an overview of functions, and the development web site (https://github.com/shaffer1/RVA) provides ready access to the source code, compiled binaries, user manual, and a suite of demonstration data sets. Key functionality has been included to support a range of reservoirs visualization and analysis needs, including: sophisticated connectivity analysis, cross sections through simulation results between selected wells, simplified volumetric calculations, global vertical exaggeration adjustments, ingestion of UTChem simulation results, ingestion of Isatis geostatistical framework models, interrogation of joint geologic and reservoir modeling results, joint visualization and analysis of well history files, location-targeted visualization, advanced correlation analysis, visualization of flow paths, and creation of static images and animations highlighting targeted reservoir features.« less

Near-resonant rotational energy transfer in HCl–H{sub 2} inelastic collisions

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

Lanza, Mathieu; Lique, François, E-mail: francois.lique@univ-lehavre.fr; Kalugina, Yulia

2014-02-14

We present a new four-dimensional (4D) potential energy surface for the HCl–H{sub 2} van der Waals system. Both molecules were treated as rigid rotors. Potential energy surface was obtained from electronic structure calculations using a coupled cluster with single, double, and perturbative triple excitations method. The four atoms were described using the augmented correlation-consistent quadruple zeta basis set and bond functions were placed at mid-distance between the HCl and H{sub 2} centers of mass for a better description of the van der Waals interaction. The global minimum is characterized by the well depth of 213.38 cm{sup −1} corresponding to themore » T-shape structure with H{sub 2} molecule on the H side of the HCl molecule. The dissociation energies D{sub 0} are 34.7 cm{sup −1} and 42.3 cm{sup −1} for the complex with para- and ortho-H{sub 2}, respectively. These theoretical results obtained using our new PES are in good agreement with experimental values [D. T. Anderson, M. Schuder, and D. J. Nesbitt, Chem. Phys. 239, 253 (1998)]. Close coupling calculations of the inelastic integral rotational cross sections of HCl in collisions with para-H{sub 2} and ortho-H{sub 2} were performed at low and intermediate collisional energies. Significant differences exist between para- and ortho-H{sub 2} results. The strongest collision-induced rotational HCl transitions are the transitions with Δj = 1 for collisions with both para-H{sub 2} and ortho-H{sub 2}. Rotational relaxation of HCl in collision with para-H{sub 2} in the rotationally excited states j = 2 is dominated by near-resonant energy transfer.« less

Quantum epistemology from subquantum ontology: Quantum mechanics from theory of classical random fields

NASA Astrophysics Data System (ADS)

Khrennikov, Andrei

2017-02-01

The scientific methodology based on two descriptive levels, ontic (reality as it is) and epistemic (observational), is briefly presented. Following Schrödinger, we point to the possible gap between these two descriptions. Our main aim is to show that, although ontic entities may be unaccessible for observations, they can be useful for clarification of the physical nature of operational epistemic entities. We illustrate this thesis by the concrete example: starting with the concrete ontic model preceding quantum mechanics (the latter is treated as an epistemic model), namely, prequantum classical statistical field theory (PCSFT), we propose the natural physical interpretation for the basic quantum mechanical entity-the quantum state ("wave function"). The correspondence PCSFT ↦ QM is not straightforward, it couples the covariance operators of classical (prequantum) random fields with the quantum density operators. We use this correspondence to clarify the physical meaning of the pure quantum state and the superposition principle-by using the formalism of classical field correlations. In classical mechanics the phase space description can be considered as the ontic description, here states are given by points λ =(x , p) of phase space. The dynamics of the ontic state is given by the system of Hamiltonian equations.We can also consider probability distributions on the phase space (or equivalently random variables valued in it). We call them probabilistic ontic states. Dynamics of probabilistic ontic states is given by the Liouville equation.In classical physics we can (at least in principle) measure both the coordinate and momentum and hence ontic states can be treated as epistemic states as well (or it is better to say that here epistemic states can be treated as ontic states). Probabilistic ontic states represent probabilities for outcomes of joint measurement of position and momentum.However, this was a very special, although very important, example of description of physical phenomena. In general there are no reasons to expect that properties of ontic states are approachable through our measurements. There is a gap between ontic and epistemic descriptions, cf. also with 't Hooft [49,50] and G G. Groessing et al. [51]. In general the presence of such a gap also implies unapproachability of the probabilistic ontic states, i.e., probability distributions on the space of ontic states. De Broglie [28] called such probability distributions hidden probabilities and distinguished them sharply from probability distributions of measurements outcomes, see also Lochak [29]. (The latter distributions are described by the quantum formalism.)This ontic-epistemic approach based on the combination of two descriptive levels for natural phenomena is closely related to the old Bild conception which was originated in the works of Hertz. Later it was heavily explored by Schrödinger in the quantum domain, see, e.g., [8,11] for detailed analysis. According to Hertz one cannot expect to construct a complete theoretical model based explicitly on observable quantities. The complete theoretical model can contain quantities which are unapproachable for external measurement inspection. For example, Hertz by trying to create a mechanical model for Maxwell's electromagnetism invented hidden masses. The main distinguishing property of a theoretical model (in contrast to an observational model) is the continuity of description, i.e., the absence of gaps in description. From this viewpoint, the quantum mechanical description is not continuous: there is a gap between premeasurement dynamics and the measurement outcome. QM cannot say anything what happens in the process of measurement, this is the well known measurement problem of QM [32], cf. [52,53]. Continuity of description is closely related to causality. However, here we cannot go in more detail, see [8,11].The important question is about interrelation between two levels of description, ontic-epistemic (or theoretical-observational). In the introduction we have already cited Schrödinger who emphasized the possible complexity of this interrelation. In particular, in general there is no reason to expect a straightforward coupling of the form, cf. [9,10]:

Investigating the role of chain and linker length on the catalytic activity of an H 2 production catalyst containing a β-hairpin peptide

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

Reback, Matthew L.; Ginovska, Bojana; Buchko, Garry W.

Building on our recent report of an active H2 production catalyst [Ni(PPh2NProp-peptide)2]2+ (Prop=para-phenylpropionic acid, peptide (R10)=WIpPRWTGPR-NH2, p=D-proline, and P2N=1-aza-3,6-diphosphacycloheptane) that contains structured -hairpin peptides, here we investigate how H2 production is effected by: (1) the length of the hairpin (eight or ten residues) and (2) limiting the flexibility between the peptide and the core complex by altering the length of the linker: para-phenylpropionic acid (three carbons) or para-benzoic acid (one carbon). Reduction of the peptide chain length from ten to eight residues increases or maintains the catalytic current for H2 production for all complexes, suggesting a non-productive steric interaction atmore » longer peptide lengths. While the structure of the hairpin appears largely intact for the complexes, NMR data are consistent with differences in dynamic behavior which may contribute to the observed differences in catalytic activity. Molecular dynamics simulations demonstrate that complexes with a one-carbon linker have the desired effect of restricting the motion of the hairpin relative to the complex; however, the catalytic currents are significantly reduced compared to complexes containing a three-carbon linker as a result of the electron withdrawing nature of the -COOH group. These results demonstrate the complexity and interrelated nature of the outer coordination sphere on catalysis.« less

Spectroscopic and structural studies of a new para-iodo-N-benzyl amide of salinomycin

NASA Astrophysics Data System (ADS)

Antoszczak, Michał; Janczak, Jan; Rutkowski, Jacek; Brzezinski, Bogumił; Huczyński, Adam

2017-11-01

A new para-iodo-N-benzyl amide of salinomycin was synthesized and characterized by NMR, FT-IR, DFT, single crystal X-ray diffraction and theoretical methods. The results obtained for the crystal, in solution and in gas phase provided evidence of pseudo-cyclic structure of this compound stabilized by intramolecular hydrogen bonds. It was shown that the compound studied forms stable 1:1 complexes with monovalent (Li+, Na+, K+, Rb+ and Cs+) and divalent (Mg2+, Ca2+, Sr2+ and Ba2+) cations demonstrating that the chemical modification of salinomycin carboxyl group considerably changes the ionophoretic properties of this antibiotic. For the first time, the ESI MS fragmentations of the complex of para-iodo-N-benzyl amide of salinomycin with Na+ are also discussed in details.

Para-hydrogen induced polarization of Si-29 NMR resonances as a potentially useful tool for analytical applications.

PubMed

Ellena, Silvano; Viale, Alessandra; Gobetto, Roberto; Aime, Silvio

2012-08-01

Para-hydrogen-induced polarization effects have been observed in the (29)Si NMR spectra of trimethylsilyl para-hydrogenated molecules. The high signal enhancements and the long T(1) values observed for the (29)Si hyperpolarized resonances point toward the possibility of using (29)Si for hyperpolarization applications. A method for the discrimination of multiple compounds and/or complex mixtures of hydroxylic compounds (such as steroids), consisting of the silylization of alcoholic functionalities with an unsaturated silylalkyl moiety and subsequent reaction with para-H(2), is proposed. Copyright © 2012 John Wiley & Sons, Ltd.

Structure of Mandelate Racemase with Bound Intermediate Analogues Benzohydroxamate and Cupferron†

PubMed Central

Lietzan, Adam D.; Nagar, Mitesh; Pellmann, Elise A.; Bourque, Jennifer R.; Bearne, Stephen L.; St Maurice, Martin

2012-01-01

Mandelate racemase (MR, EC 5.1.2.2) from Pseudomonas putida catalyzes the Mg2+-dependent interconversion of the enantiomers of mandelate, stabilizing the altered substrate in the transition state by 26 kcal/mol relative to the substrate in the ground state. To understand the origins of this binding discrimination, we solved the X-ray crystal structures of wild-type MR complexed with two analogues of the putative aci-carboxylate intermediate, benzohydroxamate and cupferron, to 2.2-Å resolution. Benzohydroxamate is shown to be a reasonable mimic of the transition state/intermediate since its binding affinity to 21 MR variants correlates well with changes in the free energy of transition state stabilization afforded by these variants. Both benzohydroxamate and cupferron chelate the active site divalent metal ion and are bound in a conformation with the phenyl ring coplanar with the hydroxamate and diazeniumdiolate moieties, respectively. Structural overlays of MR complexed with benzohydroxamate, cupferron, and the ground state analogue (S)-atrolacatate reveal that the para-carbon of the substrate phenyl ring moves by 0.8–1.2 Å between the ground state and intermediate state, consistent with the proposal that the phenyl ring moves during MR catalysis while the polar groups remain relatively fixed. Although the overall protein structure of MR with bound intermediate analogues is very similar to MR with bound (S)-atrolactate, the intermediate-Mg2+ distance shortens, suggesting a tighter complex with the catalytic Mg2+. In addition, Tyr 54 moves nearer to the phenyl ring of the bound intermediate analogues, contributing to an overall constriction of the active site cavity. However, site-directed mutagenesis experiments revealed that the role of Tyr 54 in MR catalysis is relatively minor, suggesting that alterations in enzyme structure that contribute to discrimination between the altered substrate in the transition state and the ground state by this proficient enzyme are extremely subtle. PMID:22264153

Near infrared overtone (vOH = 2 ← 0) spectroscopy of Ne-H2O clusters

NASA Astrophysics Data System (ADS)

Ziemkiewicz, Michael P.; Pluetzer, Christian; Wojcik, Michael; Loreau, Jérôme; van der Avoird, Ad; Nesbitt, David J.

2017-03-01

Vibrationally state selective overtone spectroscopy and dynamics of weakly bound Ne-H2O complexes (D0(para) = 31.67 cm-1, D0(ortho) = 34.66 cm-1) are reported for the first time, based on near infrared excitation of van der Waals cluster bands correlating with vOH = 2 ← 0 overtone transitions (|02-⟩←|00+⟩ and |02+⟩ ←|00+⟩ ) out of the ortho (101) and para (000) internal rotor states of the H2O moiety. Quantum theoretical calculations for nuclear motion on a high level ab initio potential energy surface (CCSD(T)/VnZ-f12 (n = 3,4), corrected for basis set superposition error and extrapolated to the complete basis set limit) are employed for assignment of Σ ←Σ ,Π ←Σ , and Σ ←Π infrared bands in the overtone spectra, where Σ ( K = 0) and Π (K = 1) represent approximate projections (K) of the body angular momentum along the Ne-H2O internuclear axis. End-over-end tumbling of the ortho Ne-H2O cluster is evident via rotational band contours observed, with band origins and rotational progressions in excellent agreement with ab initio frequency and intensity predictions. A clear Q branch in the corresponding |02+⟩fΠ (111) ←eΣ (000) para Ne-H2O spectrum provides evidence for a novel e/f parity-dependent metastability in these weakly bound clusters, in agreement with ab initio bound state calculations and attributable to the symmetry blocking of an energetically allowed channel for internal rotor predissociation. Finally, Boltzmann analysis of the rotational spectra reveals anomalously low jet temperatures (Trot ≈ 4(1) K), which are attributed to "evaporative cooling" of weakly bound Ne-H2O clusters and provide support for similar cooling dynamics in rare gas-tagging studies.

Detection of the MW Transition Between Ortho and Para States

NASA Astrophysics Data System (ADS)

Kanamori, Hideto; Dehghani, Zeinab Tafti; Mizoguchi, Asao; Endo, Yasuki

2017-06-01

Thorough the detailed analysis of the hyperfine resolved rotational transitions, we have been pointed out that there exists not a little interaction between ortho and para states in the molecular Hamiltonian of S_2Cl_2. Using the ortho-para mixed molecular wavefunctions derived from the Hamiltonian, we calculated the transition moment and frequency of the ortho-para forbidden transitions in the cm- and mm-wave region, and picked up some promising candidate transitions for the spectroscopic detection. In the experiment, the S_2Cl_2 vapor with Ar buffer gas in a supersonic jet condition was used with FTMW spectrometer at National Chiao Tung University. As a result, seven hyperfine resolved rotational transitions in the cm-wave region were detected as the ortho-para transition at the predicted frequency within the experimental error range. The observed intensity was 10^{-3} smaller than that of an allowed transition, which is also consistent with the prediction. This is the first time the electric dipole transition between ortho and para states has been detected in a free isolated molecule. A. Mizoguchi, S. Ota, H. Kanamori, Y. Sumiyoshi, and Y. Endo, J. Mol. Spectrosc, 250, 86 (2008) Z. T. Dehghani, S. Ota, A. Mizoguchi and H. Kanamori, J. Phys. Chem. A, 117(39), 10041, (2013)

Histological Pattern Of Endometrial Samples In Postmenopausal Women With Abnormal Uterine Bleeding.

PubMed

Deeba, Farhat; Shaista; Khan, Bushra

2016-01-01

Abnormal uterine bleeding is one of the most common clinical problems in gynaecological practice and is an indicator of various underlying disorders. An endometrial biopsy should be done in all women over 35 years with AUB to rule out endometrial cancer or pre-malignant lesion and to initiate treatment. However, wide range of histological patterns on endometrial biopsy offer a diagnostic challenge to practicing pathologists. The objective of this study was to determine histological patterns of endometrium in postmenopausal women with abnormal uterine bleeding. This cross-sectional study was conducted in the department of obstetrics and gynaecology, Benazir Bhutto Shaheed women and children teaching hospital, Abbottabad from 15/11/2014 to 14/05/2015. This study involved 110 postmenopausal women presenting with abnormal uterine bleeding. A written informed consent was obtained from every patient. The mean age of the patients was 61.60±6.17 years and the mean duration of AUB was 5.20±2.80 years. Most of the patients were para 6 (28.2%) and para 5 (28.2%) followed by para 4 (18.2%) and para 3 (17.3%) while only 8.2% were para 1. The most common histological pattern observed was complex hyperplasia without atypia (30.9%) followed by atrophic endometrium (24.5%), simple hyperplasia (23.6%), malignancy (12.7%), complex hyperplasia with atypia (4.5%) and benign endometrial polyp (3.6%). When stratified the data, there was no significant difference of histological patterns across various age groups (p=.673), duration of AUB (p=.064) and parity (p=.242). The most common histological pattern observed in postmenopausal women with AUB was complex hyperplasia without atypia (30.9%) followed by atrophic endometrium (24.5%), simple hyperplasia (23.6%), malignancy (12.7%), complex hyperplasia with atypia (4.5%) and benign endometrial polyp (3.6%).

A new ab initio potential energy surface for the collisional excitation of HCN by para- and ortho-H2

NASA Astrophysics Data System (ADS)

Denis-Alpizar, Otoniel; Kalugina, Yulia; Stoecklin, Thierry; Vera, Mario Hernández; Lique, François

2013-12-01

We present a new four-dimensional potential energy surface for the collisional excitation of HCN by H2. Ab initio calculations of the HCN-H2 van der Waals complex, considering both molecules as rigid rotors, were carried out at the explicitly correlated coupled cluster with single, double, and perturbative triple excitations [CCSD(T)-F12a] level of theory using an augmented correlation-consistent triple zeta (aVTZ) basis set. The equilibrium structure is linear HCN-H2 with the nitrogen pointing towards H2 at an intermolecular separation of 7.20 a0. The corresponding well depth is -195.20 cm-1. A secondary minimum of -183.59 cm-1 was found for a T-shape configuration with the H of HCN pointing to the center of mass of H2. We also determine the rovibrational energy levels of the HCN-para-H2 and HCN-ortho-H2 complexes. The calculated dissociation energies for the para and ortho complexes are 37.79 cm-1 and 60.26 cm-1, respectively. The calculated ro-vibrational transitions in the HCN-H2 complex are found to agree by more than 0.5% with the available experimental data, confirming the accuracy of the potential energy surface.

Experimental and theoretical investigations of H2O-Ar

NASA Astrophysics Data System (ADS)

Vanfleteren, Thomas; Földes, Tomas; Herman, Michel; Liévin, Jacques; Loreau, Jérôme; Coudert, Laurent H.

2017-07-01

We have used continuous-wave cavity ring-down spectroscopy to record the spectrum of H2O A r in the 2OH excitation range of H2O . 24 sub-bands have been observed. Their rotational structure (Trot = 12 K) is analyzed and the lines are fitted separately for ortho and para species together with microwave and far infrared data from the literature, with a unitless standard deviation σ =0.98 and 1.31, respectively. Their vibrational analysis is supported by a theoretical input based on an intramolecular potential energy surface obtained through ab initio calculations and computation of the rotational energy of sub-states of the complex with the water monomer in excited vibrational states up to the first hexad. For the ground and (010) vibrational states, the theoretical results agree well with experimental energies and rotational constants in the literature. For the excited vibrational states of the first hexad, they guided the assignment of the observed sub-bands. The upper state vibrational predissociation lifetime is estimated to be 3 ns from observed spectral linewidths.

Parent's Guide to Special Education in Washington State, 1985-86 [and] Guia para Padres: Para Educacion Especial en el Estado de Washington.

ERIC Educational Resources Information Center

Washington Office of the State Superintendent of Public Instruction, Olympia.

This pamphlet guides parents of children with disabilities through the procedures for acquiring special education services in the state of Washington. Following an overview of special education, the pamphlet presents information on notice and consent procedures, confidentiality of records, individualized education programs (IEP), the placement…

MARVEL analysis of the measured high-resolution rovibrational spectra of C2H2

NASA Astrophysics Data System (ADS)

Chubb, Katy L.; Joseph, Megan; Franklin, Jack; Choudhury, Naail; Furtenbacher, Tibor; Császár, Attila G.; Gaspard, Glenda; Oguoko, Patari; Kelly, Adam; Yurchenko, Sergei N.; Tennyson, Jonathan; Sousa-Silva, Clara

2018-01-01

Rotation-vibration energy levels are determined for the electronic ground state of the acetylene molecule, 12C2H2, using the Measured Active Rotational-Vibrational Energy Levels (MARVEL) technique. 37,813 measured transitions from 61 publications are considered. The distinct components of the spectroscopic network linking ortho and para states of the molecule are considered separately. The 20,717 ortho and 17,096 para transitions measured experimentally are used to determine 6013 ortho and 5200 para energy levels. The MARVEL results are compared with alternative compilations based on the use of effective Hamiltonians.

Rotational state modification and fast ortho-para conversion of H2 trapped within the highly anisotropic potential of Pd(210)

NASA Astrophysics Data System (ADS)

Ohno, S.; Ivanov, D.; Ogura, S.; Wilde, M.; Arguelles, E. F.; Diño, W. A.; Kasai, H.; Fukutani, K.

2018-02-01

The rotational state and ortho-para conversion of H2 on a Pd(210) surface is investigated with rotational-state-selective temperature-programmed desorption (RS-TPD) and theoretical calculations. The isotope dependence of TPD shows a higher desorption energy for D2 than that for H2, which is ascribed to the rotational and zero-point vibrational energies. The RS-TPD data show that the desorption energy of H2(J =1 ) (J : rotational quantum number) is higher than that of H2(J =0 ). This is due to the orientationally anisotropic potential confining the adsorbed H2, which is in agreement with theoretical calculations. Furthermore, the H2 desorption intensity ratio in J =1 and J =0 indicates fast ortho-para conversion in the adsorption state, which we estimate to be of the order of 1 s.

High temperature ethylene polymerization catalyzed by titanium(IV) complexes with tetradentate aminophenolate ligands in cis-O, N, N chelating mode.

PubMed

Zhao, Ruiguo; Liu, Taotao; Wang, Liying; Ma, Haiyan

2014-09-07

A series of titanium trichloride complexes , ligated with claw-type tetradentate aminophenolate ligands were synthesized from the direct reaction of TiCl4(THF)2 with 1 equiv. of the corresponding aminophenol in the presence of triethylamine. For comparison purposes, titanium isopropoxide complexes were also synthesized via the reaction of Ti(O(i)Pr)4 and 1 equiv. of the proligand. Similar reactions of ZrCl4(THF)2 with the corresponding aminophenol ligands in the presence of triethylamine only allowed the isolation of zirconium complex . The X-ray diffraction studies reveal that titanium trichloride complexes , and titanium triisopropoxide complex all possess a distorted octahedral geometry with the tetradentate aminophenolate ligand in cis-O, N, N chelating mode, where the methoxy group of the aryl unit does not coordinate with the metal center in the solid state. Upon activation with MMAO, these titanium and zirconium(iv) complexes exhibited moderate to high catalytic activities for ethylene polymerization at 30-120 °C, producing high-molecular-weight polyethylenes with broad distributions (Mw/Mn = 10.2-34.8). The activities of titanium trichloride complexes are significantly higher than those of titanium isopropoxide and zirconium trichloride complexes at high temperatures. The highest activity of 15 456 kg (mol-Ti h)(-1) could be achieved by titanium trichloride complex with bromo groups on both ortho- and para-positions of the phenolate ring of the ligand at 120 °C.

The Reaction Kinetics of 3-Hydroxybenzoate 6-Hydroxylase from Rhodococcus jostii RHA1 Provide an Understanding of the para-Hydroxylation Enzyme Catalytic Cycle*

PubMed Central

Sucharitakul, Jeerus; Tongsook, Chanakan; Pakotiprapha, Danaya; van Berkel, Willem J. H.; Chaiyen, Pimchai

2013-01-01

3-Hydroxybenzoate 6-hydroxylase (3HB6H) from Rhodococcus jostii RHA1 is an NADH-specific flavoprotein monooxygenase that catalyzes the para-hydroxylation of 3-hydroxybenzoate (3HB) to form 2,5-dihydroxybenzoate (2,5-DHB). Based on results from stopped-flow spectrophotometry, the reduced enzyme-3HB complex reacts with oxygen to form a C4a-peroxy flavin with a rate constant of 1.13 ± 0.01 × 106 m−1 s−1 (pH 8.0, 4 °C). This intermediate is subsequently protonated to form a C4a-hydroperoxyflavin with a rate constant of 96 ± 3 s−1. This step shows a solvent kinetic isotope effect of 1.7. Based on rapid-quench measurements, the hydroxylation occurs with a rate constant of 36 ± 2 s−1. 3HB6H does not exhibit substrate inhibition on the flavin oxidation step, a common characteristic found in most ortho-hydroxylation enzymes. The apparent kcat at saturating concentrations of 3HB, NADH, and oxygen is 6.49 ± 0.02 s−1. Pre-steady state and steady-state kinetic data were used to construct the catalytic cycle of the reaction. The data indicate that the steps of product release (11.7 s−1) and hydroxylation (36 ± 2 s−1) partially control the overall turnover. PMID:24129570

A full-dimensional potential energy surface and quantum dynamics of inelastic collision process for H2-HF

NASA Astrophysics Data System (ADS)

Yang, Dongzheng; Huang, Jing; Zuo, Junxiang; Hu, Xixi; Xie, Daiqian

2018-05-01

A full-dimensional ab initio potential energy surface for the H2-HF van der Waals complex was constructed by employing the coupled-cluster singles and doubles with noniterative inclusion of connected triples with augmented correlation-consistent polarised valence quadruple-zeta basis set plus bond functions. Using the improved coupled-states approximation including the nearest neighbor Coriolis couplings, we calculated the state-to-state scattering dynamics for pure rotational and ro-vibrational energy transfer processes. For pure rotational energy transfer, our results showed a different dynamical behavior for para-H2 and ortho-H2 in collision with hydrogen fluoride (HF), which is consistent with the previous study. Interestingly, some strong resonant peaks were presented in the cross sections for ro-vibrational energy transfer. In addition, the calculated vibrational-resolved rate constant is in agreement with the experimental results reported by Bott et al. These dynamics data can be further applied to the numerical simulation of HF chemical lasers.

Interrupting Commemoration: Thinking with Art, Thinking through the Strictures of Argentina's "Espacio para la memoria"

ERIC Educational Resources Information Center

Paolantonio, Mario Di

2011-01-01

Recently, a few buildings within the "Espacio para la memoria" in Buenos Aires have been designated as a UNESCO Centre where, amongst other educational activities, evidentiary materials of the past repression are to be stored and displayed. Another building in the complex houses a Community Centre operated by the Mothers of the Plaza de…

Separating para and ortho water.

PubMed

Horke, Daniel A; Chang, Yuan-Pin; Długołęcki, Karol; Küpper, Jochen

2014-10-27

Water exists as two nuclear-spin isomers, para and ortho, determined by the overall spin of its two hydrogen nuclei. For isolated water molecules, the conversion between these isomers is forbidden and they act as different molecular species. Yet, these species are not readily separated, and no pure para sample has been produced. Accordingly, little is known about their specific physical and chemical properties, conversion mechanisms, or interactions. The production of isolated samples of both spin isomers is demonstrated in pure beams of para and ortho water in their respective absolute ground state. These single-quantum-state samples are ideal targets for unraveling spin-conversion mechanisms, for precision spectroscopy and fundamental symmetry-breaking studies, and for spin-enhanced applications, for example laboratory astrophysics and astrochemistry or hypersensitized NMR experiments. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Environmental Security: What Environmental Issues Impact Regional Stability and Affect United States Foreign Policy with Mexico?

DTIC Science & Technology

1997-03-01

extraregional sponsor of Alianza para el Desarrollo Sostenible (Sustainable Development Alliance - ALIDES), along with United States and Canada. ALIDES is...more stable the government the better the country will be able to solve its environmental problems. 42 Glossary ALIDES Alianza para el Desarrollo ... Sostenible (Sustainable Development Alliance) C Centigrade CFCs Chlorofluorocarbons BECC Border Environment Cooperation Commission BNC Binational

Interrelations between the mesomeric and electronegativity effects in para-substituted derivatives of phenol/phenolate and aniline/anilide H-bonded complexes: a DFT-based computational study.

PubMed

Szatyłowicz, Halina; Krygowski, Tadeusz M; Jezierska, Aneta; Panek, Jarosław J

2009-05-14

We were able to test the Bent-Walsh rule by examining geometric parameters in the vicinity of the ipso-carbon atom of H-bonded complexes of para-substituted phenol/phenolate and aniline/anilide derivatives for the three cases (i) a versus alpha, (ii) alpha versus d(CO) or d(CN), and (iii) a versus d(CO) or d(CN), where alpha is the ring valence angle at the ipso-carbon atom (C1 substituted by OH or O(-) or NH(2) or NH(-)) and a is the arithmetic mean of the two C(ipso)-C(ortho) bond lengths. The data for nonequilibrium H-bonded complexes of unsubstituted phenol/phenolate and aniline/anilide with the respective bases F(-) and CN(-) and acids HF and HCN showed the same dependence of a on d(CX) (X = O, N) as the data for equilibrium complexes of para-Y-substituted phenol/phenolate and aniline/anilide derivatives (Y = NO, NO(2), CHO, COMe, CONH(2), Cl, F, H, Me, OMe, OH) with the same bases and acids. The slope of these dependencies was negative, as expected. In the remaining cases (a versus alpha and alpha versus d(CO) or d(CN)), the slopes for simulated complexes followed the Bent-Walsh rule. Finally, for the equilibrium complexes in which the substituent effect was included, the slopes of the trend lines for the substituted systems were opposite. This is because in the a versus alpha relationships, electonegativity and the resonance effect act in the same direction, whereas for the other two cases, these effects are opposite, and the resonance effect dominates.

Potential of silver against human colon cancer: (synthesis, characterization and crystal structures of xylyl (Ortho, meta, &Para) linked bis-benzimidazolium salts and Ag(I)-NHC complexes: In vitro anticancer studies)

PubMed Central

2013-01-01

Background Since the first successful synthesis of Ag(I)-N-heterocyclic carbene complex in 1993, this class of compounds has been extensively used for transmetallation reactions where the direct synthesis using other metal ions was either difficult or impossible. Initially, silver(I)-NHC complexes were tested for their catalytic potential but could not get fame because of lower potential compare to other competent compounds in this field; however, these compounds proved to have vital antimicrobial activities. These encouraging biomedical applications further convinced researchers to test these compounds against cancer. The current work has been carried out with this aim. Results N-ipropylbenzimidazole was synthesized by reaction of benzimidazole with ipropyl bromide. The subsequent treatment of the resulting N-alkylbenzimidazole with ortho/meta/para-(bromomethylene) benzene afforded corresponding bis-benzimidazolium bromides (5-7). The counter anion (Br-) of each salt was replaced by hexaflourophosphate (PF6-) for the ease of handling and further purification (8-10). Each salt (Ligand), in halide form, was further allowed to react with Ag2O with stirring at room temperature for a period of two days to synthesize dinuclear Ag(I)-NHC complexes (11-13). All synthesized compounds were characterized by spectroscopic techniques and microanalysis. Molecular structures of compounds 5, 9 &10 were established through single crystal x-ray diffraction technique. All the compounds were assessed for their anti-proliferation test on human colorectal cancer cell line (HCT 116). Results showed that the ligands (5-10) showed mild to negligible cytotoxicity on HCT 116 cells whereas respective silver complexes (11-13) exhibited dose dependent cytotoxicity towards the colon cancer cells with IC50 ranges between 9.7 to 44.5 μM. Interestingly, the complex 13 having para-xylyl spacer was found the most active (IC50 9.7 μM) that verifies our previously reported results. Conclusions All the bis-benzimidazolium salts (8-10) were found inactive whereas after bonding with silver cations, the Ag(I)-NHC complexes (11-13) showed a dose dependent cytotoxic activity. This proved that silver practice an important role in death of cancer cells. Also, the N-alkyl/aryl substitutions and ortho/metal/para xylyl units regulate the cytotoxicity. PMID:23391345

Torsional, Vibrational and Vibration-Torsional Levels in the S_{1} and Ground Cationic D_{0}^{+} States of Para-Xylene

NASA Astrophysics Data System (ADS)

Gardner, Adrian M.; Tuttle, William Duncan; Groner, Peter; Wright, Timothy G.

2017-06-01

Insight gained from examining the "pure" torsional, vibrational and vibration-torsional (vibtor) levels of the single rotor molecules: toluene (methylbenzene) and para-fluorotoluene (pFT), is applied to the double rotor para-xylene (p-dimethylbenzene) molecule . Resonance-enhanced multiphoton ionization (REMPI) spectroscopy and zero-kinetic-energy (ZEKE) spectroscopy are employed in order to investigate the S_{1} and ground cationic states of para-xylene. Observed transitions are assigned in the full molecular symmetry group (G_{72}) for the first time. J. R. Gascooke, E. A. Virgo, and W. D. Lawrance, J. Chem. Phys., 143, 044313 (2015). A. M. Gardner, W. D. Tuttle, L. Whalley, A. Claydon, J. H. Carter and T. G. Wright, J. Chem. Phys., 145, 124307 (2016). A. M. Gardner, W. D. Tuttle, P. Groner and T. G. Wright, J. Chem. Phys., (2017, in press).

Long-lived 1H singlet spin states originating from para-hydrogen in Cs-symmetric molecules stored for minutes in high magnetic fields.

PubMed

Franzoni, María Belén; Buljubasich, Lisandro; Spiess, Hans W; Münnemann, Kerstin

2012-06-27

Nuclear magnetic resonance (NMR) is a very powerful tool in physics, chemistry, and life sciences, although limited by low sensitivity. This problem can be overcome by hyperpolarization techniques dramatically enhancing the NMR signal. However, this approach is restricted to relatively short time scales depending on the nuclear spin-lattice relaxation time T(1) in the range of seconds. This makes long-lived singlet states very useful as a way to extend the hyperpolarization lifetimes. Para-hydrogen induced polarization (PHIP) is particularly suitable, because para-H(2) possesses singlet symmetry. Most PHIP experiments, however, are performed on asymmetric molecules, and the initial singlet state is directly converted to a NMR observable triplet state decaying with T(1), in the order of seconds. We demonstrate that in symmetric molecules, a long-lived singlet state created by PHIP can be stored for several minutes on protons in high magnetic fields. Subsequently, it is converted into observable high nonthermal magnetization by controlled singlet-triplet conversion via level anticrossing.

Vibration and Vibration-Torsion Levels of the S_{1} and Ground Cationic D_{0}^{+} States of Para-Fluorotoluene and Para-Xylene Below 1000 \\wn

NASA Astrophysics Data System (ADS)

Tuttle, William Duncan; Gardner, Adrian M.; Whalley, Laura E.; Wright, Timothy G.

2017-06-01

We have employed resonance-enhanced multiphoton ionisation (REMPI) spectroscopy and zero-kinetic-energy (ZEKE) spectroscopy to investigate the first excited electronic singlet (S_{1}) state and the cationic ground state (D_{0}^{+}) of para-fluorotoluene (pFT) and para-xylene (pXyl). Spectra have been recorded via a large number of selected intermediate levels, to support assignment of the vibration and vibration-torsion levels in these molecules and to investigate possible couplings. The study of levels in this region builds upon previous work on the lower energy regions of pFT and pXyl and here we are interested in how vibration-torsion (vibtor) levels might combine and interact with vibrational ones, and so we consider the possible couplings which occur. Comparisons between the spectra of the two molecules show a close correspondence, and the influence of the second methyl rotor in para-xylene on the onset of intramolecular vibrational redistribution (IVR) in the S_{1} state is a point of interest. This has bearing on future work which will need to consider the role of both more flexible side chains of substituted benzene molecules, and multiple side chains. A. M. Gardner, W. D. Tuttle, L. Whalley, A. Claydon, J. H. Carter and T. G. Wright, J. Chem. Phys., 145, 124307 (2016). A. M. Gardner, W. D. Tuttle, P. Groner and T. G. Wright, J. Chem. Phys., (2017, in press). W. D. Tuttle, A. M. Gardner, K. O'Regan, W. Malewicz and T. G. Wright, J. Chem. Phys., (2017, in press).

National Workshop on Astrobiology: The Life Science Involvement of AAS I Laben

NASA Astrophysics Data System (ADS)

Adami, Giorgio

2006-12-01

The search for traces of past and present life is a complex and multidisciplinary research activity involving several scientific heritages and a specific industrial ability for planetary exploration. Laben was established in 1958 to design and manufacture electronic instruments for research in nuclear physics. In the mid 2004 the company was merged with Alenia Spazio. It is now part of Alcatel Alenia Space, a French Italian joint venture. Alcatel Alenia Space Italia SpA is a Finmeccanica Company. Currently the plant of Vimodrone provides a wide heritage in life science oriented to space application. The experience in Space Life Science is consolidated in the following research areas: (1) Physiology: Mouse models related to studies on human physiology Human neuroscience research and dosimetry (2) Animal Adaptation and Behaviour: mice behaviour related to stabling stress (3) Developmental Biology: aquatic microorganisms cultivation (4) Cell culture & Biotechnology: Protein crystal growth General purpose Multiwell Next Biotechnology studies and development: Bio reactor, mainly oriented to tissue engineering Microsensor for tissue control (organ replacement) Multiwell for adherent cell culture or for automated biosensor based on cell culture Experiment Container for organic systems Experiment Container for small animals Instrumentation based on fluorescent Biosensors Sensors for Life science experiments for Biopan capsule and Space Vehicle Ray Shielding Materials Random Positioning Machine specialisation (Support ground equipment) The biological features of this heritage is at disposal for the exobiology multi science. The involvement of industries, from the beginning of the exobiology projects, allows a cost effective technologies closed loop development between Research Centres, Principal Investigators and industry.

Differential regulation of ParaHox genes by retinoic acid in the invertebrate chordate amphioxus (Branchiostoma floridae).

PubMed

Osborne, Peter W; Benoit, Gérard; Laudet, Vincent; Schubert, Michael; Ferrier, David E K

2009-03-01

The ParaHox cluster is the evolutionary sister to the Hox cluster. Like the Hox cluster, the ParaHox cluster displays spatial and temporal regulation of the component genes along the anterior/posterior axis in a manner that correlates with the gene positions within the cluster (a feature called collinearity). The ParaHox cluster is however a simpler system to study because it is composed of only three genes. We provide a detailed analysis of the amphioxus ParaHox cluster and, for the first time in a single species, examine the regulation of the cluster in response to a single developmental signalling molecule, retinoic acid (RA). Embryos treated with either RA or RA antagonist display altered ParaHox gene expression: AmphiGsx expression shifts in the neural tube, and the endodermal boundary between AmphiXlox and AmphiCdx shifts its anterior/posterior position. We identified several putative retinoic acid response elements and in vitro assays suggest some may participate in RA regulation of the ParaHox genes. By comparison to vertebrate ParaHox gene regulation we explore the evolutionary implications. This work highlights how insights into the regulation and evolution of more complex vertebrate arrangements can be obtained through studies of a simpler, unduplicated amphioxus gene cluster.

ParA and ParB coordinate chromosome segregation with cell elongation and division during Streptomyces sporulation

PubMed Central

Donczew, Magdalena; Mackiewicz, Paweł; Wróbel, Agnieszka; Flärdh, Klas; Zakrzewska-Czerwińska, Jolanta

2016-01-01

In unicellular bacteria, the ParA and ParB proteins segregate chromosomes and coordinate this process with cell division and chromosome replication. During sporulation of mycelial Streptomyces, ParA and ParB uniformly distribute multiple chromosomes along the filamentous sporogenic hyphal compartment, which then differentiates into a chain of unigenomic spores. However, chromosome segregation must be coordinated with cell elongation and multiple divisions. Here, we addressed the question of whether ParA and ParB are involved in the synchronization of cell-cycle processes during sporulation in Streptomyces. To answer this question, we used time-lapse microscopy, which allows the monitoring of growth and division of single sporogenic hyphae. We showed that sporogenic hyphae stop extending at the time of ParA accumulation and Z-ring formation. We demonstrated that both ParA and ParB affect the rate of hyphal extension. Additionally, we showed that ParA promotes the formation of massive nucleoprotein complexes by ParB. We also showed that FtsZ ring assembly is affected by the ParB protein and/or unsegregated DNA. Our results indicate the existence of a checkpoint between the extension and septation of sporogenic hyphae that involves the ParA and ParB proteins. PMID:27248800

A new ab initio potential energy surface for the collisional excitation of HCN by para- and ortho-H{sub 2}

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

Denis-Alpizar, Otoniel, E-mail: otonieldenisalpizar@gmail.com; Departamento de Física, Universidad de Matanzas, Matanzas 40100; Kalugina, Yulia

We present a new four-dimensional potential energy surface for the collisional excitation of HCN by H{sub 2}. Ab initio calculations of the HCN–H{sub 2} van der Waals complex, considering both molecules as rigid rotors, were carried out at the explicitly correlated coupled cluster with single, double, and perturbative triple excitations [CCSD(T)-F12a] level of theory using an augmented correlation-consistent triple zeta (aVTZ) basis set. The equilibrium structure is linear HCN–H{sub 2} with the nitrogen pointing towards H{sub 2} at an intermolecular separation of 7.20 a{sub 0}. The corresponding well depth is −195.20 cm{sup −1}. A secondary minimum of −183.59 cm{sup −1}more » was found for a T-shape configuration with the H of HCN pointing to the center of mass of H{sub 2}. We also determine the rovibrational energy levels of the HCN–para-H{sub 2} and HCN–ortho-H{sub 2} complexes. The calculated dissociation energies for the para and ortho complexes are 37.79 cm{sup −1} and 60.26 cm{sup −1}, respectively. The calculated ro-vibrational transitions in the HCN–H{sub 2} complex are found to agree by more than 0.5% with the available experimental data, confirming the accuracy of the potential energy surface.« less

Jet-Cooled Infrared Laser Spectroscopy in the Umbrella νb{2} Vibration Region of NH_3: Improving the Potential Energy Surface Model of the NH_3-Ar Van Der Waals Complex

NASA Astrophysics Data System (ADS)

Asselin, Pierre; Jabri, Atef; Potapov, Alexey; Loreau, Jérome; van der Avoird, Ad

2017-06-01

Taking advantage of our sensitive laser spectrometer coupled to a pulsed slit jet, we recorded near the νb{2} vibration a series of rovibrational transitions of the NH_3-Ar van der Waals (vdW) complex. These transitions involve in the ground vibrational state several internal rotor states corresponding to the ortho{NH_3} and para{NH_3} spin modifications of the complex. They are labeled by Σ_{a}(j,k), Σ_{s}(j,k), Π_{a}(j,k) and Π_{s}(j,k) where Σ(K=0) and Π(K=1) indicate the projection K of the total rotational angular momentum J on the vdW axis, the superscripts s and a designate a symmetric or antisymmetric NH_3 inversion wave function, and j, k quantum numbers indicate the correlation between the internal-rotor state of the complex and the j, k rotational state of the free NH_3 monomer. Five bands have been identified, only one of which was partly observed before. They include transitions starting from the Σ_{a}(j=0 or j=1) state without any internal angular momentum, consequently they can be assigned from the band contour of a linear-molecule-like K=0, ΔJ=1 transition. The energies and splittings of the rovibrational levels of the νb{2}=1←0 spectrum derived from the analysis of the Π_{s}, Σ_{s}(j=1)← Σ_{a}(j=0), k=0 bands and mostly of the Σ_{s}, Π_{s} and Σ_{a}(j=1)←Σ_{a}(j=1), k=1 bands bring relevant information about the νb{2} dependence of the NH_3-Ar interaction, the rovibrational dynamics of the NH_3-Ar complex and provide a sensitive test of a recently developed 4D potential energy surface that includes explicitly its dependence on the umbrella motion. P. Asselin, Y. Berger, T. R. Huet, R. Motiyenko, L. Margulès, R. J. Hendricks, M. R. Tarbutt, S. Tokunaga, B. Darquié, PCCP 19, 4576 (2017), G. T. Fraser, A.S. Pine and W. A. Kreiner, J. Chem. Phys. 94, 7061 (1991). J. Loreau, J. Liévin, Y. Scribano and A. van der Avoird, J. Chem. Phys. 141, 224303 (2014).

SABRE-Relay: A Versatile Route to Hyperpolarization.

PubMed

Roy, Soumya S; Appleby, Kate M; Fear, Elizabeth J; Duckett, Simon B

2018-03-01

Signal Amplification by Reversible Exchange (SABRE) is used to switch on the latent singlet spin order of para-hydrogen (p-H 2 ) so that it can hyperpolarize a substrate (sub = nicotinamide, nicotinate, niacin, pyrimidine, and pyrazine). The substrate then reacts reversibly with [Pt(OTf) 2 (bis-diphenylphosphinopropane)] by displacing OTf - to form [Pt(OTf)(sub)(bis-diphenylphosphinopropane)]OTf. The 31 P NMR signals of these metal complexes prove to be enhanced when the substrate possesses an accessible singlet state or long-lived Zeeman polarization. In the case of pyrazine, the corresponding 31 P signal was 105 ± 8 times larger than expected, which equated to an 8 h reduction in total scan time for an equivalent signal-to-noise ratio under normal acquisition conditions. Hence, p-H 2 derived spin order is successfully relayed into a second metal complex via a suitable polarization carrier (sub). When fully developed, we expect this route involving a second catalyst to successfully hyperpolarize many classes of substrates that are not amenable to the original SABRE method.

SABRE-Relay: A Versatile Route to Hyperpolarization

PubMed Central

2018-01-01

Signal Amplification by Reversible Exchange (SABRE) is used to switch on the latent singlet spin order of para-hydrogen (p-H2) so that it can hyperpolarize a substrate (sub = nicotinamide, nicotinate, niacin, pyrimidine, and pyrazine). The substrate then reacts reversibly with [Pt(OTf)2(bis-diphenylphosphinopropane)] by displacing OTf– to form [Pt(OTf)(sub)(bis-diphenylphosphinopropane)]OTf. The 31P NMR signals of these metal complexes prove to be enhanced when the substrate possesses an accessible singlet state or long-lived Zeeman polarization. In the case of pyrazine, the corresponding 31P signal was 105 ± 8 times larger than expected, which equated to an 8 h reduction in total scan time for an equivalent signal-to-noise ratio under normal acquisition conditions. Hence, p-H2 derived spin order is successfully relayed into a second metal complex via a suitable polarization carrier (sub). When fully developed, we expect this route involving a second catalyst to successfully hyperpolarize many classes of substrates that are not amenable to the original SABRE method. PMID:29432020

Liquid-state carbon-13 hyperpolarization generated in an MRI system for fast imaging

PubMed Central

Schmidt, A. B.; Berner, S.; Schimpf, W.; Müller, C.; Lickert, T.; Schwaderlapp, N.; Knecht, S.; Skinner, J. G.; Dost, A.; Rovedo, P.; Hennig, J.; von Elverfeldt, D.; Hövener, J. -B.

2017-01-01

Hyperpolarized (HP) tracers dramatically increase the sensitivity of magnetic resonance imaging (MRI) to monitor metabolism non-invasively and in vivo. Their production, however, requires an extra polarizing device (polarizer) whose complexity, operation and cost can exceed that of an MRI system itself. Furthermore, the lifetime of HP tracers is short and some of the enhancement is lost during transfer to the application site. Here, we present the production of HP tracers in water without an external polarizer: by Synthesis Amid the Magnet Bore, A Dramatically Enhanced Nuclear Alignment (SAMBADENA) is achieved within seconds, corresponding to a hyperpolarization of ∼20%. As transfer of the tracer is no longer required, SAMBADENA may permit a higher polarization at the time of detection at a fraction of the cost and complexity of external polarizers. This development is particularly promising in light of the recently extended portfolio of biomedically relevant para-hydrogen-tracers and may lead to new diagnostic applications. PMID:28262691

Challenges in preparing, preserving and detecting para-water in bulk: overcoming proton exchange and other hurdles.

PubMed

Mammoli, Daniele; Salvi, Nicola; Milani, Jonas; Buratto, Roberto; Bornet, Aurélien; Sehgal, Akansha Ashvani; Canet, Estel; Pelupessy, Philippe; Carnevale, Diego; Jannin, Sami; Bodenhausen, Geoffrey

2015-10-28

Para-water is an analogue of para-hydrogen, where the two proton spins are in a quantum state that is antisymmetric under permutation, also known as singlet state. The populations of the nuclear spin states in para-water are believed to have long lifetimes just like other Long-Lived States (LLSs). This hypothesis can be verified by measuring the relaxation of an excess or a deficiency of para-water, also known as a "Triplet-Singlet Imbalance" (TSI), i.e., a difference between the average population of the three triplet states T (that are symmetric under permutation) and the population of the singlet state S. In analogy with our recent findings on ethanol and fumarate, we propose to adapt the procedure for Dissolution Dynamic Nuclear Polarization (D-DNP) to prepare such a TSI in frozen water at very low temperatures in the vicinity of 1.2 K. After rapid heating and dissolution using an aprotic solvent, the TSI should be largely preserved. To assess this hypothesis, we studied the lifetime of water as a molecular entity when diluted in various solvents. In neat liquid H2O, proton exchange rates have been characterized by spin-echo experiments on oxygen-17 in natural abundance, with and without proton decoupling. One-dimensional exchange spectroscopy (EXSY) has been used to study proton exchange rates in H2O, HDO and D2O mixtures diluted in various aprotic solvents. In the case of 50 mM H2O in dioxane-d8, the proton exchange lifetime is about 20 s. After dissolving, one can observe this TSI by monitoring intensities in oxygen-17 spectra of H2O (if necessary using isotopically enriched samples) where the AX2 system comprising a "spy" oxygen A and two protons X2 gives rise to binomial multiplets only if the TSI vanishes. Alternatively, fast chemical addition to a suitable substrate (such as an activated aldehyde or ketone) can provide AX2 systems where a carbon-13 acts as a spy nucleus. Proton signals that relax to equilibrium with two distinct time constants can be considered as a hallmark of a TSI. We optimized several experimental procedures designed to preserve and reveal dilute para-water in bulk.

Constraining the physical state by symmetries

NASA Astrophysics Data System (ADS)

Fatibene, L.; Ferraris, M.; Magnano, G.

2017-03-01

After reviewing the hole argument and its relations with initial value problem and general covariance, we shall discuss how much freedom one has to define the physical state in a generally covariant field theory (with or without internal gauge symmetries). Our analysis relies on Cauchy problems, thus it is restricted to globally hyperbolic spacetimes. We shall show that in generally covariant theories on a compact space (as well as for internal gauge symmetries on any spacetime) one has no freedom and one is forced to declare as physically equivalent two configurations which differ by a global spacetime diffeomorphism (or by an internal gauge transformation) as it is usually prescribed. On the contrary, when space is not compact, the result does not hold true and one may have different options to define physically equivalent configurations, still preserving determinism. For this scenario to be effective, the group G of formal transformations needs to be a subgroup of dynamical symmetries (otherwise field equations, which are written in terms of configurations would not induce equations for the physical state classes) and it must contain the group D generated by Cauchy transformations (otherwise the equations induced on physical state classes would not be well posed, either). We argue that it is exactly because of this double inclusion that the hole argument in its initial problem formulation is more powerful than in its boundary formulation. In the boundary formulation of the hole argument one still has that the group G of formal transformations is a subgroup of dynamical symmetries, but there is no evidence for it to contain a particular non-trivial subgroup.In this paper we shall show that this scenario is exactly implemented in generally covariant theories. In the last section we shall show it to be implemented in gauge theories as well.Norton also argued (see [1]) that the definition of physical state is something to be discussed in physics and it is not something which can be settled by a purely mathematical argument. This position is certainly plausible and agreeable. However, we shall here argue that some constraints to the definition of physical state can be in fact put on a mathematical stance (the ones which go back to Einstein-Hilbert about well-posedness of Cauchy problems).A physical state is hence defined as an equivalence class of configurations, for which dynamics is well-posed, i.e. its evolution is deterministically singled out by initial conditions. It also defines what the physical observables are, i.e., by definition, the quantities which depend on the equivalence classes, but not on the specific representative configurations. Equivalently, physical observables are defined as quantities which are invariant with respect to formal transformations.A detailed analysis of these issues shows an unexpected structure of cases which is not clarified in general, yet. What is clear is that assuming, as usually done, that the physical state of a generally covariant theory is to be identified with equivalence classes of configurations modulo spacetime diffeomorphisms is a fair assumption, still a choice which is sometimes forced by mathematics (in particular by determinism in the form of Cauchy theorem on globally hyperbolic spacetimes with a compact space) but sometimes it is one of many possible choices which, in those cases, we agree should be addressed from a physical stance.We shall argue that sometimes one can find subclasses of diffeomorphisms (i.e. the group generated by Cauchy-compatible transformations, below denoted by D →) which play a distinctive role in the discussion and which, to the best of our knowledge, has not properly been taken into account in standard frameworks.Let us start, for the sake of simplicity, by restricting to generally covariant theories. Gauge theories will be briefly discussed in the conclusions since most of what we shall do easily applies to those cases, as well; see [20] for general framework and notation.In a generally covariant theory one has a huge group of symmetries S containing the (lift to the configuration bundle of the) spacetime diffeomorphisms. The group of spacetime diffeomorphisms will be denoted by Diff(M) . In particular, the subgroup of spacetime diffeomorphisms which can be connected by a flow with the identity idM will be denoted by Diffe(M) . Any element Φ ∈Diffe(M) can be obtained by evaluating a 1-parameter subgroup Φs at s = 1, i.e. Φ =Φ1. The 1-parameter subgroup Φs is also called a flow of diffeomorphisms.The standard attitude is to assume that in a generally covariant theory any two configurations of fields differing by any spacetime diffeomorphism represent the same physical state. In other words, if σ is a section of the configuration bundle and Φ∗ σ =σ‧ is its image through a diffeomorphism (in Diffe(M) or in Diff(M) depending on the case) then both σ and σ‧ represent the same physical state of the system.Let us call formal transformations the group G of transformations which fix the physical state, or, equivalently, define the physical states of the orbits of the group G. As a matter of fact defining the group of formal transformations is equivalent to defining the physical state. Either one defines the physical state as the orbits of the action of formal transformations or defines formal transformations as the transformations acting on configurations by mapping one representative of the physical state into another representative of the same physical state, i.e. fixing the physical states.In order for this to make sense one needs a formal transformation Φ to be a symmetry of the system (as it is in generally covariant theories) since if σ is a solution, of course also σ‧ must be a solution as well. In other words any formal transformation (acting on configurations but leaving the physical state unchanged) must be a symmetry and the symmetry group is an upper bound to the group of formal transformations, i.e. one must have G ⊂ S.We shall show that there is a lower bound (which will be denoted by D → and which is generated by Cauchy transformations) for the group G of formal transformations as well, i.e. one must have D → ⊂ G ⊂ S.We shall argue that when D → ⊊ S =Diffe(M) one has a certain freedom in setting G between its lower and upper bounds. In these cases one has different options to set the group D → ⊂ G ⊂ S and each different assumption about what G is, in fact defines a different theory with the same dynamics but different interpretation of what is the physical state and what can be in principle observed; see [21]. We shall also discuss topological conditions on M for which this freedom is nullified and one is forced to set G =Diffe(M) as usually done in the literature. On the other hand, we can discuss the motion of particles in spacetime on a physical stance and show that it is reasonable to assume that the physical state is described by worldline trajectories and parameterisations are irrelevant. The two viewpoints come (quite independently) to the same conclusion, which is a good thing. We shall also show a counter example, showing a globally hyperbolic spacetime M = R × R with a non-compact space Σ ≡ R in which the situation is different from the compact space case. As a consequence, the usual assumption of identifying configurations which differ by a diffeomorphism is a legitimate though in general unmotivated choice. When describing a system one should be aware of which assumptions come from mathematical constraints and which assumptions are done on a physical stance.When setting up a general covariant theory one should first study whether the group D → is a strict subgroup of Diffe(M) . If it is, one should characterise possible subgroups D → ⊂ G ⊂ S. Then one should declare which one of such groups G is elected as the group of formal transformations. Different choices lead to different theories with an equivalent dynamics but different observables.

Standards for Advisement, Invocation, and Waiver of Counsel in Military Intelligence Interrogations

DTIC Science & Technology

2004-04-01

appointed counsel experienced 288 Id para. 86.1 289 Direccion Nacional contra el Terrorismo . 290 Id para. 86.2. 291 See id. (citing Decree-Law 25,744, art...60 (1st Cir. 2000) ( en banc); United States v. Zabenah, 837 F.2d 1249, 1261 (5th Cir. 1988); Goldstar v. United States, 967 F.2d 965, 968 (4th Cir...Jimenez-Nava, 243 F.3d at 195-98. 135 Jimenez-Nava, 243 F.3d at 198. See also United States v. Lombera-Camorlinga, 206 F.3d 882, 885 (9th Cir. 2000) ( en

Un Nuevo Convenio para el Aprendizaje: Una Sociedad para Mejorar los Resultados Educativos en el Estado de Nueva York (A New Compact for Learning: A Partnership To Improve Educational Results in New York State).

ERIC Educational Resources Information Center

New York State Education Dept., Albany. Office of Elementary, Middle and Secondary Education.

This Spanish translation of the abridged version of "A New Compact for Learning" acknowledges the current U.S. education system's inadequacy to educate U.S. citizenry and introduces New York State's New Compact for Learning, intended as a plan to reorganize New York's own system. The compact's fundamental principles are: (1) recognizing…

Vibrational dynamics of glass forming: 2-phenylbutan-1-ol (BEP), 2-(trifluoromethyl)phenethyl alcohol (2TFMP) and 4-(trifluoromethyl)phenethyl alcohol (4TFMP) in their thermodynamic phases

NASA Astrophysics Data System (ADS)

Juszyńska-Gałązka, Ewa; Zając, Wojciech; Saito, Kazuya; Yamamura, Yasuhisa; Juruś, Natalia

2018-02-01

The complex polymorphism and vibrational dynamics of three glass-forming single-phenyl-ring alcohols (with and without fluorine atoms) have been studied by complementary methods. Glass of isotropic liquid phase and cold crystallization of metastable supercooled liquid state were detected. Temperature investigations of vibrational motions show important role of hydrogen bonds in interactions between molecules. Theoretical calculations for isolated molecule, as well as dimer- and tetramer-type aggregates of non-covalently bound molecules, allow for a good description of experimental spectra. Intermolecular interactions of molecules with ortho and para positions of CF3 group in phenyl ring have a similar influence on the spectra observed.

Field performance of malaria rapid diagnostic test for the detection of Plasmodium falciparum infection in Odisha State, India.

PubMed

Sahu, S S; Gunasekaran, K; Jambulingam, P

2015-12-01

Rapid diagnostic tests (RDTs) have become an essential surveillance tool in the malaria control programme in India. The current study aimed to assess the performance of ParaHIT-f, a rapid test in diagnosis of Plasmodium falciparum infection through detecting its specific antigen, histidine rich protein 2 (PfHRP-2), in Odisha State, India. The study was undertaken in eight falciparum malaria endemic southern districts of Odisha State. Febrile patients included through active case detection, were diagnosed by Accredited Social Health Activists (ASHAs) for P. falciparum infection using the RDT, ParaHIT-f. The performance of ParaHIT-f was evaluated using microscopy as the gold standard. A total of 1030 febrile patients were screened by both microscopy and the RDT for P. falciparum infection. The sensitivity of ParaHIT-f was 63.6% (95% CI: 56.0-70.6) and specificity was 98.9% (95% CI: 97.9-99.5), with positive and negative predictive values (PPV and NPV) of 92.6% (95% CI: 86.0-96.3) and 93.0% (95% CI: 91.0-94.5), respectively. When related to parasitaemia, the RDT sensitivity was 47.8% at the low parasitaemia of 4 to 40 parasites/µl of blood. The results showed that the performance of the RDT, ParaHIT-f, was not as sensitive as microscopy in detecting true falciparum infections; a high specificity presented a low frequency of false-positive RDT results. t0 he sensitivity of ParaHIT-f was around 60 per cent. It is, therefore, essential to improve the efficiency (sensitivity) of the kit so that the true falciparum infections will not be missed especially in areas where P. falciparum has been the predominant species causing cerebral malaria.

Photoelectron Spectroscopy Study of Quinonimides

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

Hossain, Ekram; Deng, Shihu M.; Gozem, Samer

Structures and energetics of o-, m- and p-quinonimide anions (OC6H4N) and quinoniminyl radicals have been investigated by using negative ion photoelectron spectroscopy. Modeling of the photoelectron spectrum of the ortho isomer shows that the ground state of the anion is a triplet, while the quinoniminyl radical has a doublet ground state with a doublet-quartet splitting of 35.5 kcal/mol. The para radical has doublet ground state, but a band for a quartet state is missing from the photoelectron spectrum indicating that the anion has a singlet ground state, in contrast to previously reported calculations. The theoretical modeling is revisited here, andmore » it is shown that accurate predictions for the electronic structure of the para quinonimide anion require both an accurate account of electron correlation and a sufficiently diffuse basis set. Electron affinities of o- and p-quinoniminyl radicals are measured to be 1.715 ± 0.010 and 1.675 ± 0.010 eV, respectively. The photoelectron spectrum of the m-quinonimide anion shows that the ion undergoes several different rearrangements, including a rearrangement to the energetically favorable para isomer. Such rearrangements preclude a meaningful analysis of the experimental spectrum.« less

Copper(II) hexaaza macrocyclic binuclear complexes obtained from the reaction of their copper(I) derivates and molecular dioxygen.

PubMed

Costas, Miquel; Ribas, Xavi; Poater, Albert; López Valbuena, Josep Maria; Xifra, Raül; Company, Anna; Duran, Miquel; Solà, Miquel; Llobet, Antoni; Corbella, Montserrat; Usón, Miguel Angel; Mahía, José; Solans, Xavier; Shan, Xiaopeng; Benet-Buchholz, Jordi

2006-05-01

Density functional theory (DFT) calculations have been carried out for a series of Cu(I) complexes bearing N-hexadentate macrocyclic dinucleating ligands and for their corresponding peroxo species (1c-8c) generated by their interaction with molecular O2. For complexes 1c-7c, it has been found that the side-on peroxodicopper(II) is the favored structure with regard to the bis(mu-oxo)dicopper(III). For those complexes, the singlet state has also been shown to be more stable than the triplet state. In the case of 8c, the most favored structure is the trans-1,2-peroxodicopper(II) because of the para substitution and the steric encumbrance produced by the methylation of the N atoms. Cu(II) complexes 4e, 5e, and 8e have been obtained by O2 oxidation of their corresponding Cu(I) complexes and structurally and magnetically characterized. X-ray single-crystal structures for those complexes have been solved, and they show three completely different types of Cu(II)2 structures: (a) For 4e, the Cu(II) centers are bridged by a phenolate group and an external hydroxide ligand. The phenolate group is generated from the evolution of 4c via intramolecular arene hydroxylation. (b) For 5e, the two Cu(II) centers are bridged by two hydroxide ligands. (c) For the 8e case, the Cu(II) centers are ligated to terminally bound hydroxide ligands, rare because of its tendency to bridge. The evolution of complexes 1c-8c toward their oxidized species has also been rationalized by DFT calculations based mainly on their structure and electrophilicity. The structural diversity of the oxidized species is also responsible for a variety of magnetic behavior: (a) strong antiferromagnetic (AF) coupling with J = -482.0 cm(-1) (g = 2.30; rho = 0.032; R = 5.6 x 10(-3)) for 4e; (b) AF coupling with J = -286.3 cm(-1) (g = 2.07; rho = 0.064; R = 2.6 x 10(-3)) for 5e; (c) an uncoupled Cu(II)2 complex for 8e.

Infrared and Microwave Spectra of Ne-WATER Complex

NASA Astrophysics Data System (ADS)

Liu, Xunchen; Thomas, Javix; Xu, Yunjie; Hou, Dan; Li, Hui

2016-06-01

The binary complex of rare gas atom and water is an ideal model to study the anisotropic potential energy surface of van der Waals interaction and the large amplitude motion. Although Xe-H_2O, Kr-H_2O, Ar-H_2O, Ar-D_2O and even Ne-D_2O complexes were studied by microwave or high resolution infrared spectroscopy, the lighter Ne-H_2O complex has remained unidentified. In this talk, we will present the theoretical and experimental investigation of the Ne-H_2O complex. A four-dimension PES for H_2O-Ne which only depended on the intramolecular (Q2) normal-mode coordinate of H2O monomer was calculated in this work to determine the rovibrational energy levels and mid-infrared transitions. Aided with the calculated transitions, we were able to assigned the high resolution mid-infrared spectra of both 20Ne-H_2O and 22Ne-H_2O complexes that are generated with a pulsed supersonic molecular beam in a multipass direct absorption spectrometer equiped with an external cavity quantum cascade laser at 6 μm. Several bands of both para and ortho Ne-H2O were assigned and fitted using the Hamiltonian with strong Coriolis and angular-radical coupling terms. The predicted groud state energy levels are then confirmed by the J=1-0 and J=2-1 transitions measurement using a cavity based Fourier transform microwave spectrometer.

Para hydrogen equilibration in the atmospheres of the outer planets

NASA Technical Reports Server (NTRS)

Conrath, Barney J.

1986-01-01

The thermodynamic behavior of the atmospheres of the Jovian planets is strongly dependent on the extent to which local thermal equilibration of the ortho and para states of molecular hydrogen is achieved. Voyager IRIS data from Jupiter imply substantial departures of the para hydrogen fraction from equilibrium in the upper troposphere at low latitudes, but with values approaching equilibrium at higher latitudes. Data from Saturn are less sensitive to the orth-para ratio, but suggest para hydrogen fractions near the equilibrium value. Above approximately the 200 K temperature level, para hydrogen conversion can enhance the efficiency of convection, resulting in a substantial increase in overturning times on all of the outer planets. Currently available data cannot definitively establish the ortho-para ratios in the atmospheres of Uranus and Neptune, but suggest values closer to local equilibrium than to the 3.1 normal ratio. Modeling of sub-millimeter wavelength measurements of these planets suggest thermal structures with frozen equilibrium lapse rates in their convective regions.

Breaking the Barrier to Slow Water Exchange Rates for Optimal Magnetic Resonance Detection of paraCEST Agents.

PubMed

Fernando, W Shirangi; Martins, André F; Zhao, Piyu; Wu, Yunkou; Kiefer, Garry E; Platas-Iglesias, Carlos; Sherry, A Dean

2016-03-21

EuDOTA-tetraamide complexes as paraCEST agents offer an attractive platform for designing biological sensors and responsive agents. The early versions of these agents showed low sensitivity at temperature and power levels suitable for in vivo applications partly due to non-optimal water exchange rates. Here we report two new EuDOTA derivatives having glutamyl-phosphonate side arms that display the slowest water exchange rates of any other paraCEST agent reported so far. The advantages of such systems are demonstrated experimentally both in vitro and in vivo and DFT calculations were performed to help understand the physical-chemical reasons for this interesting behavior.

Rapid Catalyst Capture Enables Metal-Free para-Hydrogen-Based Hyperpolarized Contrast Agents.

PubMed

Barskiy, Danila A; Ke, Lucia A; Li, Xingyang; Stevenson, Vincent; Widarman, Nevin; Zhang, Hao; Truxal, Ashley; Pines, Alexander

2018-05-10

Hyperpolarization techniques based on the use of para-hydrogen provide orders of magnitude signal enhancement for magnetic resonance spectroscopy and imaging. The main drawback limiting widespread applicability of para-hydrogen-based techniques in biomedicine is the presence of organometallic compounds (the polarization transfer catalysts) in solution with hyperpolarized contrast agents. These catalysts are typically complexes of platinum-group metals, and their administration in vivo should be avoided. Herein, we show how extraction of a hyperpolarized compound from an organic phase to an aqueous phase combined with a rapid (less than 10 s) Ir-based catalyst capture by metal scavenging agents can produce pure para-hydrogen-based hyperpolarized contrast agents, as demonstrated by high-resolution nuclear magnetic resonance (NMR) spectroscopy and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The presented methodology enables fast and efficient means of producing pure hyperpolarized aqueous solutions for biomedical and other uses.

Quantum rotation of ortho and para-water encapsulated in a fullerene cage

PubMed Central

Beduz, Carlo; Carravetta, Marina; Chen, Judy Y.-C.; Concistrè, Maria; Denning, Mark; Frunzi, Michael; Horsewill, Anthony J.; Johannessen, Ole G.; Lawler, Ronald; Lei, Xuegong; Levitt, Malcolm H.; Li, Yongjun; Mamone, Salvatore; Murata, Yasujiro; Nagel, Urmas; Nishida, Tomoko; Ollivier, Jacques; Rols, Stéphane; Rõõm, Toomas; Sarkar, Riddhiman; Turro, Nicholas J.; Yang, Yifeng

2012-01-01

Inelastic neutron scattering, far-infrared spectroscopy, and cryogenic nuclear magnetic resonance are used to investigate the quantized rotation and ortho–para conversion of single water molecules trapped inside closed fullerene cages. The existence of metastable ortho-water molecules is demonstrated, and the interconversion of ortho-and para-water spin isomers is tracked in real time. Our investigation reveals that the ground state of encapsulated ortho water has a lifted degeneracy, associated with symmetry-breaking of the water environment. PMID:22837402

Structure, internal mobility, and spectrum of the ammonia dimer: Calculation of the vibration-rotation-tunneling states

NASA Astrophysics Data System (ADS)

Olthof, E. H. T.; van der Avoird, A.; Wormer, P. E. S.

1994-11-01

We have obtained a potential for (NH3)2 by calculating the six-dimensional vibra- tion-rotation-tunneling (VRT) states from a model potential with some variable parameters, and adjusting some calculated transition frequencies to the observed far-infrared spectrum. The equilibrium geometry is strongly bent away from a linear hydrogen bonded structure. Equivalent minima with the proton donor and acceptor interchanged are separated by a barrier of only 7 cm-1. The barriers to rotation of the monomers about their C3 axes are much higher. The VRT levels from this potential agree to about 0.25 cm-1 with all far-infrared frequencies of (NH3)2 observed for K=0, ‖K‖=1, and ‖K‖=2 and for all the symmetry species: Ai=ortho-ortho, Ei=para-para, and G=ortho-para. Moreover, the dipole moments and the nuclear quadrupole splittings agree well with the values that are observed for the G states. The potential has been explicitly transformed to the center-of-mass coordinates of (ND3)2 and used to study the effects of the deuteration on the VRT states. The observed decrease of the dipole moment and the (small) changes in the nuclear quadrupole splittings are well reproduced. It follows from our calculations that the ammonia dimer is highly nonrigid and that vibrational averaging effects are essential. Seemingly contradictory effects of this averaging on its properties are the consequence of the different hindered rotor behavior of ortho and para monomers.

Observation of nuclear spin species conversion inside the 1593 cm -1 structure of H 2O trapped in argon matrices: Nitrogen impurities and the H 2O:N 2 complex

NASA Astrophysics Data System (ADS)

Pardanaud, Cédric; Vasserot, Anne-Marie; Michaut, Xavier; Abouaf-Marguin, L.

2008-02-01

We have investigated, at high resolution (0.03 cm -1), the 1593 cm -1 structure observed in the IR absorption spectrum of water trapped in solid argon doped with nitrogen. It exhibits a doublet at 1592.59 ± 0.05 and 1593.08 ± 0.05 cm -1 and a line centered at 1592.93 ± 0.05 cm -1. The central component, which increases irreversibly upon annealing and when the concentration is increased, is due to the proton acceptor submolecule of the H 2O dimer, as mentioned in the literature. The doublet is assigned to the H 2O:N 2 complex. After a fast cooling of the sample from 20 to 4 K, the low frequency line of the doublet decreases with time and the high frequency one increases, the total integrated absorption increasing slightly. The ratio of the integrated intensities between the low frequency component and the high frequency one reaches a constant limit of 0.5 ± 0.1 at infinite time. This time behavior, perfectly exponential with a time constant τ of about 680 min, is reproducible. As the nitrogen molecule cannot rotate in an argon substitutional site, and as the H 2O submolecule seems to preserve somewhat its identity, this is interpreted as nuclear spin species conversion between ortho and para states of the H 2O submolecule within the complex. The order of magnitude of the energy difference between the ortho and para lowest levels, about 5 cm -1, is too weak to imply any, even very hindered, rotational motion of H 2O, but it could be the energy range of a tunneling effect. When the temperature is increased, the two components coalesce at 25 K into a single symmetrical line pointing at 1593.3 cm -1 and the conversion time shortens dramatically. An Arrhenius plot leads to a weak activation energy of the conversion process (about 30 cm -1). A possible geometry of the complex in solid argon, different from the gas phase one, is proposed.

Securing Tyrants or Fostering Reform? U.S. Internal Security Assistance to Repressive and Transitioning Regimes

DTIC Science & Technology

2006-01-01

los Derechos Humanos , “Informe de Labores, Junio 1997–Mayo 1998,” San Salvador, 1998, pp. 230–238. Also see Call, “Democratisation, War and State...countries in the region: Costa Rica, Guatemala, Haiti, Mexico, and Panama. Based on 57 Procuraduría para la Defensa de los Derechos Humanos , pp. 230–238...www.state.gov/p/sa/rls/rm/26277.htm. Procuraduría para la Defensa de los Derechos Humanos , “Informe de Labores, Junio 1997–Mayo 1998,” San Salvador, 1998

The Hammett relationship and reactions in the excited electronic state: hemithioindigo Z/E-photoisomerization.

PubMed

Cordes, Thorben; Schadendorf, Torsten; Priewisch, Beate; Rück-Braun, Karola; Zinth, Wolfgang

2008-01-31

The photochemical reaction dynamics of a set of photochromic compounds based on thioindigo and stilbene molecular parts (hemithioindigos, HTI) are presented. Photochemical Z/E isomerization around the central double bond occurs with time constants of 216 ps (Z --> E) and 10 ps (E --> Z) for a 5-methyl-hemithioindigo. Chemical substitution on the stilbene moiety causes unusually strong changes in the reaction rate. Electron-donating substituents in the position para to the central double bond (e.g., para-methoxy) strongly accelerate the reaction, while the reaction is drastically slowed by electron-withdrawing groups in this position (e.g., para-nitrile). We correlate the experimental data of seven HTI-compounds in a quantitative manner using the Hammett equation and present a qualitative explanation for the application of ground-state Hammett constants to describe the photoisomerization reaction.

Electron-impact electronic-state excitation of para-benzoquinone

NASA Astrophysics Data System (ADS)

Jones, D. B.; da Costa, R. F.; Kossoski, F.; Varella, M. T. do N.; Bettega, M. H. F.; Ferreira da Silva, F.; Limão-Vieira, P.; García, G.; Lima, M. A. P.; White, R. D.; Brunger, M. J.

2018-03-01

Angle resolved electron energy loss spectra (EELS) for para-benzoquinone (C6H4O2) have been recorded for incident electron energies of 20, 30, and 40 eV. Measured differential cross sections (DCSs) for electronic band features, composed of a combination of energetically unresolved electronic states, are subsequently derived from those EELS. Where possible, the obtained DCSs are compared with those calculated using the Schwinger multichannel method with pseudopotentials. These calculations were performed using a minimum orbital basis single configuration interaction framework at the static exchange plus polarisation level. Here, quite reasonable agreement between the experimental cross sections and the theoretical cross sections for the summation of unresolved states was observed.

Preparation of ortho-para ratio controlled D2 gas for muon-catalyzed fusion.

PubMed

Imao, H; Ishida, K; Kawamura, N; Matsuzaki, T; Matsuda, Y; Toyoda, A; Strasser, P; Iwasaki, M; Nagamine, K

2008-05-01

A negative muon in hydrogen targets, e.g., D2 or D-T mixture, can catalyze nuclear fusions following a series of atomic processes involving muonic hydrogen molecular formation (muon-catalyzed fusion, muCF). The ortho-para state of D2 is a crucial parameter not only for enhancing the fusion rate but also to precisely investigate various muonic atom processes. We have developed a system for controlling and measuring the ortho-para ratio of D2 gas for muCF experiments. We successfully collected para-enriched D2 without using liquid-hydrogen coolant. Ortho-enriched D2 was also obtained by using a catalytic conversion method with a mixture of chromium oxide and alumina. The ortho-para ratio of D2 gas was measured with a compact Raman spectroscopy system. We produced large volume (5-30 l at STP), high-purity (less than ppm high-Z contaminant) D2 targets with a wide range of ortho-para ratios (ortho 20%-99%). By using the ortho-para controlled D2 in muCF experiments, we observed the dependence of muCF phenomena on the ortho-para ratio.

Preparation of ortho-para ratio controlled D{sub 2} gas for muon-catalyzed fusion

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

Imao, H.; Ishida, K.; Matsuzaki, T.

2008-05-15

A negative muon in hydrogen targets, e.g., D{sub 2} or D-T mixture, can catalyze nuclear fusions following a series of atomic processes involving muonic hydrogen molecular formation (muon-catalyzed fusion, {mu}CF). The ortho-para state of D{sub 2} is a crucial parameter not only for enhancing the fusion rate but also to precisely investigate various muonic atom processes. We have developed a system for controlling and measuring the ortho-para ratio of D{sub 2} gas for {mu}CF experiments. We successfully collected para-enriched D{sub 2} without using liquid-hydrogen coolant. Ortho-enriched D{sub 2} was also obtained by using a catalytic conversion method with a mixturemore » of chromium oxide and alumina. The ortho-para ratio of D{sub 2} gas was measured with a compact Raman spectroscopy system. We produced large volume (5-30 l at STP), high-purity (less than ppm high-Z contaminant) D{sub 2} targets with a wide range of ortho-para ratios (ortho 20%-99%). By using the ortho-para controlled D{sub 2} in {mu}CF experiments, we observed the dependence of {mu}CF phenomena on the ortho-para ratio.« less

The influence of an arduous military training program on immune function and upper respiratory tract infection incidence.

PubMed

Whitham, Martin; Laing, Stewart J; Dorrington, Melanie; Walters, Robert; Dunklin, Steve; Bland, Duncan; Bilzon, James L J; Walsh, Neil P

2006-08-01

The effects of the first 19 weeks of U.K. Parachute Regiment (PARA) training on upper respiratory tract infection (URTI) incidence and immune function (circulating leukocyte counts, lymphocyte subsets, lipopolysaccharide-stimulated neutrophil degranulation, and salivary immunoglobulin A concentrations) were investigated for 14 PARA recruits and 12 control subjects. No significant differences were reported between groups for the number or duration of URTIs, lymphocyte subsets, or salivary immunoglobulin A concentrations during training. URTI incidence was greater in the PARA group at weeks 2 and 3 (p < 0.05), coinciding with a decrease in circulating leukocyte and lymphocyte counts (p < 0.05). Neutrophil degranulation was similar in the PARA and control groups at weeks 0 and 19. Decreases in saliva flow rate occurred in the PARA group at week 15 and weeks 18 to 20 (p < 0.05). These results show a limited effect of PARA training on URTI incidence and immune function. The progressive decrease in saliva flow rate during PARA training may indicate an ensuing state of hypohydration.

Experimental and theoretical study on the excited-state dynamics of ortho-, meta-, and para-methoxy methylcinnamate.

PubMed

Miyazaki, Yasunori; Yamamoto, Kanji; Aoki, Jun; Ikeda, Toshiaki; Inokuchi, Yoshiya; Ehara, Masahiro; Ebata, Takayuki

2014-12-28

The S1 state dynamics of methoxy methylcinnamate (MMC) has been investigated under supersonic jet-cooled conditions. The vibrationally resolved S1-S0 absorption spectrum was recorded by laser induced fluorescence and mass-resolved resonant two-photon ionization spectroscopy and separated into conformers by UV-UV hole-burning (UV-UV HB) spectroscopy. The S1 lifetime measurements revealed different dynamics of para-methoxy methylcinnamate from ortho-methoxy methylcinnamate and meta-methoxy methylcinnamate (hereafter, abbreviated as p-, o-, and m-MMCs, respectively). The lifetimes of o-MMC and m-MMC are on the nanosecond time scale and exhibit little tendency of excess energy dependence. On the other hand, p-MMC decays much faster and its lifetime is conformer and excess energy dependent. In addition, the p-MMC-H2O complex was studied to explore the effect of hydration on the S1 state dynamics of p-MMC, and it was found that the hydration significantly accelerates the nonradiative decay. Quantum chemical calculation was employed to search the major decay route from S1(ππ(∗)) for three MMCs and p-MMC-H2O in terms of (i) trans → cis isomerization and (ii) internal conversion to the (1)nπ(∗) state. In o-MMC and m-MMC, the large energy barrier is created for the nonradiative decay along (i) the double-bond twisting coordinate (∼1000 cm(-1)) in S1 as well as (ii) the linear interpolating internal coordinate (∼1000 cm(-1)) from S1 to (1)nπ(∗) states. The calculation on p-MMC decay dynamics suggests that both (i) and (ii) are available due to small energy barrier, i.e., 160 cm(-1) by the double-bond twisting and 390 cm(-1) by the potential energy crossing. The hydration of p-MMC raises the energy barrier of the IC route to the S1/(1)nπ(∗) conical intersection, convincing that the direct isomerization is more likely to occur.

Preparation of a Cobalt(II) Cage: An Undergraduate Laboratory Experiment That Produces a ParaSHIFT Agent for Magnetic Resonance Spectroscopy

ERIC Educational Resources Information Center

Burns, Patrick J.; Tsitovich, Pavel B.; Morrow, Janet R.

2016-01-01

Laboratory experiments that demonstrate the effect of paramagnetic complexes on chemical shifts and relaxation times of protons are a useful way to introduce magnetic resonance spectroscopy (MRS) probes or magnetic resonance imaging (MRI) contrast agents. In this undergraduate inorganic chemistry experiment, a paramagnetic Co(II) cage complex is…

Bilateral Agreement for Military Assistance between the Government of Honduras and the Government of the United States

DTIC Science & Technology

2013-06-13

en especial al Instituto para la Cooperación de la Seguridad Hemisférica (WHINSEC) por haberme brindado la gran oportunidad de participar en este...contra cualquiera de los países de América como un sistema de seguridad colectivo, dicho pacto fue suscrito en la Conferencia Interamericana para el...Mantenimiento de la Paz y la Seguridad del Continente, esto en Rio de Janeiro del 15 de agosto al 2 de septiembre de 1947, consecuentemente para

Mechanistic Studies of ε-Caprolactone Polymerization by (salen)AlOR Complexes and a Predictive Model for Cyclic Ester Polymerizations

PubMed Central

2016-01-01

Aluminum alkoxide complexes (2) of salen ligands with a three-carbon linker and para substituents having variable electron-withdrawing capabilities (X = NO2, Br, OMe) were prepared, and the kinetics of their ring-opening polymerization (ROP) of ε-caprolactone (CL) were investigated as a function of temperature, with the aim of drawing comparisons to similar systems with two-carbon linkers investigated previously (1). While 1 and 2 exhibit saturation kinetics and similar dependences of their ROP rates on substituents X (invariant Keq, similar Hammett ρ = +1.4(1) and 1.2(1) for k2, respectively), ROP by 2 was significantly faster than for 1. Theoretical calculations confirm that, while the reactant structures differ, the transition state geometries are quite similar, and by analyzing the energetics of the involved distortions accompanying the structural changes, a significant contribution to the basis for the rate differences was identified. Using this knowledge, a simplified computational method for evaluating ligand structural influences on cyclic ester ROP rates is proposed that may have utility for future catalyst design. PMID:26900488

Alkali metal cation complexation by 1,3-alternate, mono-ionisable calix[4]arene-benzocrown-6 compounds

DOE PAGES

Surowiec, Malgorzata A.; Custelcean, Radu; Surowiec, Kazimierz; ...

2014-04-23

Alkali metal cation extraction behavior for two series of 1,3-alternate, mono-ionizable calix[4]arene-benzocrown-6 compounds is examined. In Series 1, the proton-ionizable group is a substituent on the benzo group of the polyether ring that directs it away from the crown ether cavity. In Series 2, the proton-ionizable group is attached to one para position in the calixarene framework, thus positioning it over the crown ether ring. Competitive solvent extraction of alkali metal cations from aqueous solutions into chloroform shows high Cs+ efficiency and selectivity. Single-species extraction pH profiles of Cs+ for Series 1 and 2 ligands with the same proton-ionizable groupmore » are very similar. Thus, association of Cs+ with the calixcrown ring is more important than the the proton-ionizable group’s position in relation to the crown ether cavity. Solid-state structures are presented for two unionized ligands from Series 2, as is a crystal containing two different ionized ligand–Cs+ complexes.« less

Conformational explosion: Understanding the complexity of short chain para-dialkylbenzene potential energy surfaces

NASA Astrophysics Data System (ADS)

Mishra, Piyush; Hewett, Daniel M.; Zwier, Timothy S.

2018-05-01

The single-conformation ultraviolet and infrared spectroscopy of three short-chain para-dialkylbenzenes (para-diethylbenzene, para-dipropylbenzene, and para-dibutylbenzene) is reported for the jet-cooled, isolated molecules. The present study builds off previous work on single-chain n-alkylbenzenes, where an anharmonic local mode Hamiltonian method was developed to account for stretch-bend Fermi resonance in the alkyl CH stretch region [D. P. Tabor et al., J. Chem. Phys. 144, 224310 (2016)]. The jet-cooled molecules are interrogated using laser-induced fluorescence (LIF) excitation, fluorescence dip infrared spectroscopy, and dispersed fluorescence. The LIF spectra in the S1 ← S0 origin region show a dramatic increase in the number of resolved transitions with increasing length of the alkyl chains, reflecting an explosion in the number of unique low-energy conformations formed when two independent alkyl chains are present. Since the barriers to isomerization of the alkyl chain are similar in size, this results in an "egg carton" shaped potential energy surface. A combination of electronic frequency shift and alkyl CH stretch infrared spectra is used to generate a consistent set of conformational assignments. Using these experimental techniques in conjunction with computational methods, subsets of origin transitions in the LIF excitation spectrum can be classified into different conformational families. Two conformations are resolved in para-diethylbenzene, seven in para-dipropylbenzene, and about nineteen in para-dibutylbenzene. These chains are largely independent of each other as there are no new single-chain conformations induced by the presence of a second chain. A cursory LIF excitation scan of para-dioctylbenzene shows a broad congested spectrum at frequencies consistent with interactions of alkyl chains with the phenyl π cloud.

Conformational explosion: Understanding the complexity of short chain para-dialkylbenzene potential energy surfaces.

PubMed

Mishra, Piyush; Hewett, Daniel M; Zwier, Timothy S

2018-05-14

The single-conformation ultraviolet and infrared spectroscopy of three short-chain para-dialkylbenzenes (para-diethylbenzene, para-dipropylbenzene, and para-dibutylbenzene) is reported for the jet-cooled, isolated molecules. The present study builds off previous work on single-chain n-alkylbenzenes, where an anharmonic local mode Hamiltonian method was developed to account for stretch-bend Fermi resonance in the alkyl CH stretch region [D. P. Tabor et al., J. Chem. Phys. 144, 224310 (2016)]. The jet-cooled molecules are interrogated using laser-induced fluorescence (LIF) excitation, fluorescence dip infrared spectroscopy, and dispersed fluorescence. The LIF spectra in the S 1 ← S 0 origin region show a dramatic increase in the number of resolved transitions with increasing length of the alkyl chains, reflecting an explosion in the number of unique low-energy conformations formed when two independent alkyl chains are present. Since the barriers to isomerization of the alkyl chain are similar in size, this results in an "egg carton" shaped potential energy surface. A combination of electronic frequency shift and alkyl CH stretch infrared spectra is used to generate a consistent set of conformational assignments. Using these experimental techniques in conjunction with computational methods, subsets of origin transitions in the LIF excitation spectrum can be classified into different conformational families. Two conformations are resolved in para-diethylbenzene, seven in para-dipropylbenzene, and about nineteen in para-dibutylbenzene. These chains are largely independent of each other as there are no new single-chain conformations induced by the presence of a second chain. A cursory LIF excitation scan of para-dioctylbenzene shows a broad congested spectrum at frequencies consistent with interactions of alkyl chains with the phenyl π cloud.

Integrating Visualization Applications, such as ParaView, into HEP Software Frameworks for In-situ Event Displays

NASA Astrophysics Data System (ADS)

Lyon, A. L.; Kowalkowski, J. B.; Jones, C. D.

2017-10-01

ParaView is a high performance visualization application not widely used in High Energy Physics (HEP). It is a long standing open source project led by Kitware and involves several Department of Energy (DOE) and Department of Defense (DOD) laboratories. Futhermore, it has been adopted by many DOE supercomputing centers and other sites. ParaView is unique in speed and efficiency by using state-of-the-art techniques developed by the academic visualization community that are often not found in applications written by the HEP community. In-situ visualization of events, where event details are visualized during processing/analysis, is a common task for experiment software frameworks. Kitware supplies Catalyst, a library that enables scientific software to serve visualization objects to client ParaView viewers yielding a real-time event display. Connecting ParaView to the Fermilab art framework will be described and the capabilities it brings discussed.

Communications: Development and characterization of a source of rotationally cold, enriched para-H3+.

PubMed

Tom, Brian A; Mills, Andrew A; Wiczer, Michael B; Crabtree, Kyle N; McCall, Benjamin J

2010-02-28

In an effort to develop a source of H(3)(+) that is almost entirely in a single quantum state (J=K=1), we have successfully generated a plasma that is enriched to approximately 83% in para-H(3)(+) at a rotational temperature of 80 K. This enrichment is a result of the nuclear spin selection rules at work in hydrogenic plasmas, which dictate that only para-H(3)(+) will form from para-H(2), and that para-H(3)(+) can be converted to ortho-H(3)(+) by subsequent reaction with H(2). This is the first experimental study in which the H(2) and H(3) (+) nuclear spin selection rules have been observed at cold temperatures. The ions were produced from a pulsed solenoid valve source, cooled by supersonic expansion, and interrogated via continuous-wave cavity ringdown spectroscopy.

Derechos Educacionales de los Padres: Una Explicacion de los Procedimientos de Seguridad para los Padres de Ninos con Discapacidades. Bajo la Clausula del Acta de Educacion para Individuos con Discapacidades (IDEA) y las Reglas para la Administracion del Acta de Educacion para Ninos Excepcionales (Educational Rights of Parents: An Explanation of Procedural Safeguards Available to Parents of Children with Disabilities. Under Provisions of the Individuals with Disabilities Education Act (IDEA) and the Rules for the Administration of the Exceptional Children's Educational Act [ECEA]).

ERIC Educational Resources Information Center

Mountain Plains Regional Resource Center, Des Moines, IA.

This pamphlet, in Spanish, describes Colorado parents' educational rights under federal and state special education rules and regulations. It addresses: (1) free appropriate public education and termination of services; (2) required prior notice to parents if there is a proposed change or refusal to change a child's special education program; (3)…

Ortho-para spin isomers of the protons in the methylene group--possible implications for protein structure.

PubMed

Shinitzky, Meir; Elitzur, Avshalom C

2006-09-01

The two hydrogen atoms attached to the carbon in the methylene group are of two different spin configurations, similar to those in the case of water: ortho, where the two proton spins are parallel to each other, and para, where they are antiparallel. The ortho configuration has three degenerate states, while the para configuration is singular, leading to a statistical ratio of these isomers 3:1 ortho/para. Such spin isomers are present in glycine and most chiral amino acids where they may induce broadening of structural zones, a possibility which remains to be assessed. The implications of this neglected possibility could be far-reaching, in particular with respect to protein structure and the origins of biochirality.

Longitudinal nuclear spin relaxation of ortho- and para-hydrogen dissolved in organic solvents.

PubMed

Aroulanda, Christie; Starovoytova, Larisa; Canet, Daniel

2007-10-25

The longitudinal relaxation time of ortho-hydrogen (the spin isomer directly observable by NMR) has been measured in various organic solvents as a function of temperature. Experimental data are perfectly interpreted by postulating two mechanisms, namely intramolecular dipolar interaction and spin-rotation, with activation energies specific to these two mechanisms and to the solvent in which hydrogen is dissolved. This permits a clear separation of the two contributions at any temperature. Contrary to the self-diffusion coefficients at a given temperature, the rotational correlation times extracted from the dipolar relaxation contribution do not exhibit any definite trend with respect to solvent viscosity. Likewise, the spin-rotation correlation time obeys Hubbard's relation only in the case of hydrogen dissolved in acetone-d6, yielding in that case a spin-rotation constant in agreement with literature data. Concerning para-hydrogen, which is NMR-silent, the only feasible approach is to dissolve para-enriched hydrogen in these solvents and to follow the back-conversion of the para-isomer into the ortho-isomer. Experimentally, this conversion has been observed to be exponential, with a time constant assumed to be the relaxation time of the singlet state (the spin state of the para-isomer). A theory, based on intermolecular dipolar interactions, has been worked out for explaining the very large values of these relaxation times which appear to be solvent-dependent.

Expedition54_Education_In-flight_Para_Los_Ninos_053_1755_621343_hires

NASA Image and Video Library

2018-02-22

SPACE STATION CREW MEMBER DISCUSSES LIFE IN SPACE WITH HISPANIC STUDENTS IN LOS ANGELES:::::::: Aboard the International Space Station, Expedition 54 Flight Engineer Joe Acaba of NASA discussed his mission on the complex and life and research in space with students at the Para Los Ninos School in Los Angeles during an in-flight educational event Feb. 22. Acaba, who has been in orbit since last September, is returning to Earth on a Russian Soyuz spacecraft on Feb. 27 (U.S. time) for a landing in south central Kazakhstan.

Conformational Explosion: Understanding the Complexity of the Para-Dialkylbenzene Potential Energy Surfaces

NASA Astrophysics Data System (ADS)

Mishra, Piyush; Hewett, Daniel M.; Zwier, Timothy S.

2017-06-01

This talk focuses on the single-conformation spectroscopy of small-chain para-dialkylbenzenes. This work builds on previous studies from our group on long-chain n-alkylbenzenes that identified the first folded structure in octylbenzene. The dialkylbenzenes are representative of a class of molecules that are common components of coal and aviation fuel and are known to be present in vehicle exhaust. We bring the molecules para-diethylbenzene, para-dipropylbenzene and para-dibutylbenzene into the gas phase and cool the molecules in a supersonic expansion. The jet-cooled molecules are then interrogated using laser-induced fluorescence excitation, fluorescence dip IR spectroscopy (FDIRS) and dispersed fluorescence. The LIF spectra in the S_{0}-S_{1} origin region show dramatic increases in the number of resolved transitions with increasing length of alkyl chains, reflecting an explosion in the number of unique low-energy conformations formed when two independent alkyl chains are present. Since the barriers to isomerization of the alkyl chain are similar in size, this results in an 'egg carton' shape to the potential energy surface. We use a combination of electronic frequency shift and alkyl CH stretch infrared spectra to generate a consistent set of conformational assignments.

Infrared identification of the σ-complex of Cl-C6H6 in the reaction of chlorine atom and benzene in solid para-hydrogen.

PubMed

Bahou, Mohammed; Witek, Henryk; Lee, Yuan-Pern

2013-02-21

The reaction of a chlorine atom with benzene (C6H6) is important in organic chemistry, especially in site-selective chlorination reactions, but its product has been a subject of debate for five decades. Previous experimental and theoretical studies provide no concrete conclusion on whether the product is a π- or σ-form of the Cl-C6H6 complex. We took advantage of the diminished cage effect of para-hydrogen (p-H2) to produce Cl in situ to react with C6H6 (or C6D6) upon photolysis of a Cl2/C6H6 (or C6D6)/p-H2 matrix at 3.2 K. The infrared spectrum, showing intense lines at 1430.5, 833.6, 719.8, 617.0, and 577.4 cm(−1), and several weaker ones for Cl-C6H6, and the deuterium shifts of observed new lines unambiguously indicate that the product is a 6-chlorocyclohexadienyl radical, i.e., the σ-complex of Cl-C6H6. Observation of the σ-complex rather than the π-complex indicates that the σ-complex is more stable in solid p-H2 at 3.2 K. The spectral information is crucial for further investigations of the Cl + C6H6 reaction either in the gaseous or solution phase.

The metallogenic role of east-west fracture zones in South America with regard to the motion of lithospheric plates (with an example from Brazil)

USGS Publications Warehouse

Kutina, J.; Carter, William D.; Lopez, F.X.

1978-01-01

The role of east-west fracture zones in South America is discussed with regard to global fracturing and the motion of lithospheric plates. A set of major NW-trending lineaments has been derived which show a tendency to be spaced equidistantly and may correspond to a set of east-west fractures in the "pre-drift" position of the South American plate. Statistical analysis of linears in the ERTS-mosaics shows that NW-fractures are also among the most important ones in the Andes region, suggesting that the above major lineaments extend into the basement of the Andes. Some of the old major fractures, trending east-west in the present orientation of South America, are discussed and their NE orientation in the pre-drift position of the plate is considered. An example of structural control of ore deposition in the Brazilian Shield is presented, using the maps of the RADAM Project. It is concluded that the small tin-bearing granitic bodies concentrated in the region of Sao Felix do Xingu in the state of Para represent upper parts of an unexposed granitoid massif which is controlled by the intersection of a major east-west fracture zone probably represents westward extension of the Patos Lineament of the easternmost part of Brazil, connected with the east-west fracture zone of the Para state through the basement of the Maranhao Basin (Sineclise do Maranhao-Piaui). It is expected that the proposed "Patos-Para Lineament" extends further westward and may similarly control, at intersections with fractures of other trends, some mineralization centers in the western part of the state of Para and in the state of Amazonas.

Investigating pyridazine and phthalazine exchange in a series of iridium complexes in order to define their role in the catalytic transfer of magnetisation from para-hydrogen.

PubMed

Appleby, Kate M; Mewis, Ryan E; Olaru, Alexandra M; Green, Gary G R; Fairlamb, Ian J S; Duckett, Simon B

2015-07-01

The reaction of [Ir(IMes)(COD)Cl], [IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, COD = 1,5-cyclooctadiene] with pyridazine (pdz) and phthalazine (phth) results in the formation of [Ir(COD)(IMes)(pdz)]Cl and [Ir(COD)(IMes)(phth)]Cl. These two complexes are shown by nuclear magnetic resonance (NMR) studies to undergo a haptotropic shift which interchanges pairs of protons within the bound ligands. When these complexes are exposed to hydrogen, they react to form [Ir(H) 2 (COD)(IMes)(pdz)]Cl and [Ir(H) 2 (COD)(IMes)(phth)]Cl, respectively, which ultimately convert to [Ir(H) 2 (IMes)(pdz) 3 ]Cl and [Ir(H) 2 (IMes)(phth) 3 ]Cl, as the COD is hydrogenated to form cyclooctane. These two dihydride complexes are shown, by NMR, to undergo both full N-heterocycle dissociation and a haptotropic shift, the rates of which are affected by both steric interactions and free ligand p K a values. The use of these complexes as catalysts in the transfer of polarisation from para -hydrogen to pyridazine and phthalazine via signal amplification by reversible exchange (SABRE) is explored. The possible future use of drugs which contain pyridazine and phthalazine motifs as in vivo or clinical magnetic resonance imaging probes is demonstrated; a range of NMR and phantom-based MRI measurements are reported.

Reaction Intermediates of Quinol Oxidation in a Photoactivatable System that Mimics Electron Transfer in the Cytochrome bc1 Complex

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

Cape, Jonathan L.; Bowman, Michael K.; Kramer, David M.

2005-03-30

Current competing models for the two-electron oxidation of quinol (QH{sub 2}) at the cytochrome bc{sub 1} complex and related complexes have different requirements for the reaction intermediate. At present, the intermediate species of the enzymatic oxidation process have not been observed or characterized, probably due to their transient nature. Here, we use a biomimetic oxidant, Ru(bpy){sub 2}(pbim)(PF6)2 (bpy = 2,2'-dipyridyl, pbim = 2-(2-benzimidazolate)pyridine) in an aprotic medium to probe the oxidation of the ubiquinol analogue, 2,3-dimethoxy-5-methyl-1,4-benzoquinol (UQH{sub 2}-0), an the plastoquinol analogue, trimethyl-1,4-benzoquinol (TMQH{sub 2}-0), using time-resolved and steady state spectroscopic techniques. This system qualitatively reproduces key features observed duringmore » ubiquinol oxidation by the mitochondrial cytochrome bc1 complex. Comparison of isotope dependent activation properties in the native and synthetic systems, as well as, analysis of the time-resolved direct-detection electron para magnetic resonance signals in the synthetic system allows us to conclude that: (1) the initial and rate-limiting step in quinol oxidation, both in the biological and biomimetic systems, involves electron and proton transfer, probably via a proton coupled electron transfer mechanism; (2) a neutral semiquinone intermediate is formed in the biomimetic system; and (3) oxidation of the QH*/QH{sub 2} couple for UQH{sub 2}-0, but not TMQH{sub 2}-0, exhibits a non-classical primary deuterium kinetic isotope effect on its Arrhenius activation energy ({Delta}G{sup TS}), where {Delta}G{sup TS} for the protiated form is larger than for the deuterated form. The same behavior is observed during steady state turnover of the cyt bc{sub 1} complex using ubiquinol, but not plastoquinol, as a substrate, leading to the conclusion that similar chemical pathways are involved in both systems. The synthetic system is an unambiguous n=1 electron acceptor and it is thus inferred that sequential oxidation of ubiquinol (by two sequential n=1 processes) is more rapid than a truly concerted (n=2) oxidation in the cyt bc{sub 1} complex.« less

Mosquito Bites

MedlinePlus

... spreading to the United States. One factor is climate change, which makes the conditions in some parts of ... United States. How can I prevent mosquito bites? Use an insect ... DEET, picaridin, IR3535, oil of lemon eucalyptus, or para-menthane-diol. It ...

Carnivorous diving beetles of the genus Desmopachria (Coleoptera: Dytiscidae) from Brazil: New species, new records, and a checklist

PubMed Central

Braga, Rafael Benzi; Ferreira, Nelson

2014-01-01

Abstract Eight new species of DesmopachriaBabington, 1841 are described and illustrated from Brazil: D. dicrophallica sp. nov. , D. disticta sp. nov. , D. grammosticta sp. nov. , D . grandinigra sp. nov. , D. itamontensis sp. nov. , D. leptophallica sp. nov. , D. stethothrix sp. nov. , and D. ukuki sp. nov. The species D. amyaeMiller, 2001 , D. cheiMiller, 1999 , D. margarita Young, 1990, and D. volatidiscaMiller, 2001 are recorded for the first time from Brazil. From species of the Desmopachria reported in Brazil, D. aldessaYoung, 1980 has a new record from Pará state and D. fossulataZimmermann, 1928, D. granoidesYoung, 1986 , and D. laevis Sharp, 1882 have new records from Rio de Janeiro State. A checklist of all Desmopachria recorded from Brazil is presented with notes about some of the localities. Resumo Oito espécies novas de DesmopachriaBabington, 1841 são descritas e ilustradas para o Brasil, D. dicrophallica sp. nov. , D. disticta sp. nov. , D. grammosticta sp. nov. , D . grandinigra sp. nov., D. itamontensis sp. nov., D. leptophallica sp. nov., D. stethothrix sp. nov. e D. ukuki sp. nov. As espécies D. amyaeMiller, 2001, D. cheiMiller, 1999 , D. margarita Young, 1990 e D. volatidiscaMiller, 2001 são registradas pela primeira vez para o Brasil. Das espécies de Desmopachria registradas para o Brasil D. aldessaYoung, 1980 tem um novo registro para o estado do Pará e D. fossulataZimmermann, 1928 , D. granoidesYoung, 1986 e D. laevis Sharp, 1882 têm novos registros para o estado do Rio de Janeiro. Uma listagem de todos os Desmopachria registrados para o Brasil é apresentada, com notas acerca de algumas localidades. PMID:25373202

Pressure-induced orientational glass phase in molecular para-hydrogen.

PubMed

Schelkacheva, T I; Tareyeva, E E; Chtchelkatchev, N M

2009-02-01

We propose a theoretical description of a possible orientational glass transition in solid molecular para-hydrogen and ortho-deuterium under pressure supposing that they are mixtures of J=0 and J=2 states of molecules. The theory uses the basic concepts and methods of standard spin-glass theory. We expect our orientational glass to correspond to the II' phase of the high-pressure hydrogen phase diagram.

Parallel Grand Canonical Monte Carlo (ParaGrandMC) Simulation Code

NASA Technical Reports Server (NTRS)

Yamakov, Vesselin I.

2016-01-01

This report provides an overview of the Parallel Grand Canonical Monte Carlo (ParaGrandMC) simulation code. This is a highly scalable parallel FORTRAN code for simulating the thermodynamic evolution of metal alloy systems at the atomic level, and predicting the thermodynamic state, phase diagram, chemical composition and mechanical properties. The code is designed to simulate multi-component alloy systems, predict solid-state phase transformations such as austenite-martensite transformations, precipitate formation, recrystallization, capillary effects at interfaces, surface absorption, etc., which can aid the design of novel metallic alloys. While the software is mainly tailored for modeling metal alloys, it can also be used for other types of solid-state systems, and to some degree for liquid or gaseous systems, including multiphase systems forming solid-liquid-gas interfaces.

A centroid molecular dynamics study of liquid para-hydrogen and ortho-deuterium.

PubMed

Hone, Tyler D; Voth, Gregory A

2004-10-01

Centroid molecular dynamics (CMD) is applied to the study of collective and single-particle dynamics in liquid para-hydrogen at two state points and liquid ortho-deuterium at one state point. The CMD results are compared with the results of classical molecular dynamics, quantum mode coupling theory, a maximum entropy analytic continuation approach, pair-product forward- backward semiclassical dynamics, and available experimental results. The self-diffusion constants are in excellent agreement with the experimental measurements for all systems studied. Furthermore, it is shown that the method is able to adequately describe both the single-particle and collective dynamics of quantum liquids. (c) 2004 American Institute of Physics

Inequalities in healthy life expectancy by Federated States.

PubMed

Szwarcwald, Célia Landmann; Montilla, Dália Elena Romero; Marques, Aline Pinto; Damacena, Giseli Nogueira; Almeida, Wanessa da Silva de; Malta, Deborah Carvalho

2017-06-01

To estimate the healthy life expectancy at 60 years by sex and Federated States and to investigate geographical inequalities by socioeconomic status. Healthy life expectancy was estimated by the Sullivan method, based on the information of the National Survey on Health, 2013. Three criteria were adopted for the definition of "unhealthy state": self-assessment of bad health, functionality for performing the activities of daily living, and the presence of noncommunicable disease with intense degree of limitation. The indicator of socioeconomic status was built based on the number of goods at household and educational level of the head of household. To analyze the geographical inequalities and socioeconomic level, inequality measures were calculated, such as the ratio, the difference, and the angular coefficient. Healthy life expectancy among men ranged from 13.8 (Alagoas) to 20.9 (Espírito Santo) for the self-assessment criterion of bad health. Among women, the corresponding estimates were always higher and ranged from 14.9 (Maranhão) to 22.2 (São Paulo). As to the ratio of inequality by Federated State, the medians were always higher for healthy life expectancy than for life expectancy, regardless of the definition adopted for healthy state. Regarding the differences per Federated State, the healthy life expectancy was seven years higher in one state than in another. By socioeconomic status, differences of three and four years were found, approximately, between the last and first fifth, for men and women, respectively. Despite the association of the mortality indicators with living conditions, the inequalities are even more pronounced when the welfare and the limitations in usual activities are considered, showing the necessity to promote actions and programs to reduce the socio-spatial gradient. Estimar a esperança de vida saudável aos 60 anos por sexo e Unidade da Federação e investigar as desigualdades geográficas e por nível socioeconômico. A esperança de vida saudável foi estimada pelo método de Sullivan, com base nas informações da Pesquisa Nacional de Saúde, 2013. Foram adotados três critérios para definição de estado "não saudável": autoavaliação de saúde ruim, funcionalidade para realização das atividades da vida diária, e presença de doença crônica não transmissível com grau intenso de limitação. O indicador de nível socioeconômico foi construído com base no número de bens no domicílio e grau de escolaridade do responsável. Para analisar as desigualdades geográficas e por nível socioeconômico, foram calculadas medidas de desigualdade, como a razão, a diferença e o coeficiente angular. A esperança de vida saudável entre os homens variou de 13,8 (Alagoas) a 20,9 (Espírito Santo) para o critério de autoavaliação de saúde ruim. Entre as mulheres, as estimativas correspondentes foram sempre mais altas e variaram de 14,9 (Maranhão) a 22,2 (São Paulo). Quanto à razão de desigualdades por Unidade da Federação, as medianas foram sempre maiores para a esperança de vida saudável do que para a esperança de vida, independentemente da definição adotada para estado saudável. Quanto às diferenças por Unidade da Federação, a esperança de vida saudável chegou a ser sete anos maior em um estado do que em outro. Por nível socioeconômico, foram encontradas diferenças de três e quatro anos, aproximadamente, entre os últimos e primeiro quintos, para homens e mulheres, respectivamente. Além de os indicadores de mortalidade estarem associados às condições de vida, as desigualdades são ainda mais pronunciadas quando o bem-estar e as limitações nas atividades habituais são levados em consideração, mostrando a necessidade de promover ações e programas para diminuir o gradiente socioespacial.

Integrating Visualization Applications, such as ParaView, into HEP Software Frameworks for In-situ Event Displays

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

Lyon, A. L.; Kowalkowski, J. B.; Jones, C. D.

ParaView is a high performance visualization application not widely used in High Energy Physics (HEP). It is a long standing open source project led by Kitware and involves several Department of Energy (DOE) and Department of Defense (DOD) laboratories. Futhermore, it has been adopted by many DOE supercomputing centers and other sites. ParaView is unique in speed and efficiency by using state-of-the-art techniques developed by the academic visualization community that are often not found in applications written by the HEP community. In-situ visualization of events, where event details are visualized during processing/analysis, is a common task for experiment software frameworks.more » Kitware supplies Catalyst, a library that enables scientific software to serve visualization objects to client ParaView viewers yielding a real-time event display. Connecting ParaView to the Fermilab art framework will be described and the capabilities it brings discussed.« less

Refinement of the experimental dynamic structure factor for liquid para-hydrogen and ortho-deuterium using semi-classical quantum simulation.

PubMed

Smith, Kyle K G; Poulsen, Jens Aage; Cunsolo, A; Rossky, Peter J

2014-01-21

The dynamic structure factor of liquid para-hydrogen and ortho-deuterium in corresponding thermodynamic states (T = 20.0 K, n = 21.24 nm(-3)) and (T = 23.0 K, n = 24.61 nm(-3)), respectively, has been computed by both the Feynman-Kleinert linearized path-integral (FK-LPI) and Ring-Polymer Molecular Dynamics (RPMD) methods and compared with Inelastic X Ray Scattering spectra. The combined use of computational and experimental methods enabled us to reduce experimental uncertainties in the determination of the true sample spectrum. Furthermore, the refined experimental spectrum of para-hydrogen and ortho-deuterium is consistently reproduced by both FK-LPI and RPMD results at momentum transfers lower than 12.8 nm(-1). At larger momentum transfers the FK-LPI results agree with experiment much better for ortho-deuterium than for para-hydrogen. More specifically we found that for k ∼ 20.0 nm(-1) para-hydrogen provides a test case for improved approximations to quantum dynamics.

Adiabatic Variational Theory for Cold Atom-Molecule Collisions: Application to a Metastable Helium Atom Colliding with ortho- and para-Hydrogen Molecules.

PubMed

Pawlak, Mariusz; Shagam, Yuval; Klein, Ayelet; Narevicius, Edvardas; Moiseyev, Nimrod

2017-03-16

We recently developed an adiabatic theory for cold molecular collision experiments. In our previous application of this theory ( Pawlak, M.; et al. J. Chem. Phys. 2015 , 143 , 074114 ), we assumed that during the experiment the collision of an atom with a diatom takes place when the diatom is in the ground rotational state and is located in a plane. In this paper, we present how the variational approach of the adiabatic theory for low-temperature collision experiments can be used for the study a 5D collision between the atom and the diatomic molecule with no limitations on its rotational quantum states and no plane restrictions. Moreover, we show here the dramatic differences in the measured reaction rates of He(2 3 S 1 ) + ortho/para-H 2 → He(1s 2 ) + ortho/para-H 2 + + e - resulting from the anisotropic long-range interactions in the reaction. In collisions of metastable helium with molecular hydrogen in the ground rotational state, the isotropic potential term dominates the dynamics. When the collision is with molecular hydrogen in the first excited rotational state, the nonisotropic interactions play an important role in the dynamics. The agreement of our results with the latest experimental findings ( Klein , A. ; et al. Nat. Phys. 2017 , 13 , 35 - 38 ) is very good.

The School of Posture as a postural training method for Paraíba Telecommunications Operators.

PubMed

Cardia, M C; Soares Màsculo, F

2001-01-01

This work proposes to show the experience of posture training accomplished in the Paraíba State Telecommunication Company, using the knowledge of the Back School. The sample was composed of 12 operators, employees of the company, representing 31% of this population. The model applied in TELPA (Paraíba Telecommunication Company, Brazil) was based on the models of Sherbrooke, Canada, and of the School of Posture of Paraìba Federal University. Fifty-eight point four percent of participants showed a reduction of column pain, 25% improved the quality of the rest and the received training was considered enough for the learning of correct postures at work in 75% of the cases. The whole population approved of the training, and 83.3% of the cases considered that this training influenced their lives very positively.

ParaView visualization of Abaqus output on the mechanical deformation of complex microstructures

NASA Astrophysics Data System (ADS)

Liu, Qingbin; Li, Jiang; Liu, Jie

2017-02-01

Abaqus® is a popular software suite for finite element analysis. It delivers linear and nonlinear analyses of mechanical and fluid dynamics, includes multi-body system and multi-physics coupling. However, the visualization capability of Abaqus using its CAE module is limited. Models from microtomography have extremely complicated structures, and datasets of Abaqus output are huge, requiring a visualization tool more powerful than Abaqus/CAE. We convert Abaqus output into the XML-based VTK format by developing a Python script and then using ParaView to visualize the results. Such capabilities as volume rendering, tensor glyphs, superior animation and other filters allow ParaView to offer excellent visualizing manifestations. ParaView's parallel visualization makes it possible to visualize very big data. To support full parallel visualization, the Python script achieves data partitioning by reorganizing all nodes, elements and the corresponding results on those nodes and elements. The data partition scheme minimizes data redundancy and works efficiently. Given its good readability and extendibility, the script can be extended to the processing of more different problems in Abaqus. We share the script with Abaqus users on GitHub.

Crystal growth and DFT insight on sodium para-nitrophenolate para-nitrophenol dihydrate single crystal for NLO applications

NASA Astrophysics Data System (ADS)

Selvakumar, S.; Boobalan, Maria Susai; Anthuvan Babu, S.; Ramalingam, S.; Leo Rajesh, A.

2016-12-01

Single crystals of sodium para-nitrophenolate para-nitrophenol dihydrate (SPPD) were grown by slow evaporation technique and its structure has been studied by FT-IR, FT-Raman and single crystal X-ray diffraction techniques. The optical and electrical properties were characterized by UV-Vis spectrum, and dielectric studies respectively. SPPD was thermally stable up to 128 °C as determined by TG-DTA curves. Using the Kurtz-Perry powder method, the second-harmonic generation efficiency was found to be five times to that of KDP. Third-order nonlinear response was studied using Z-scan technique with a He-Ne laser (632.8 nm) and NLO parameters such as intensity dependent refractive index, nonlinear absorption coefficient and third-order susceptibility were also estimated. The molecular geometry from X-ray experiment in the ground state has been compared using density functional theory (DFT) with appropriate basis set. The first-order hyperpolarizability also calculated using DFT approaches. Stability of the molecule arising from hyperconjugative interactions leading to its nonlinear optical activity and charge delocalization were analyzed using natural bond orbital technique. HOMO-LUMO energy gap value suggests the possibility of charge transfer within the molecule. Based on optimized ground state geometries, Natural bond orbital (NBO) analysis was performed to study donor-acceptor interactions.

Analysis of Cytochrome P450 CYP119 Ligand-dependent Conformational Dynamics by Two-dimensional NMR and X-ray Crystallography*

PubMed Central

Basudhar, Debashree; Madrona, Yarrow; Kandel, Sylvie; Lampe, Jed N.; Nishida, Clinton R.; de Montellano, Paul R. Ortiz

2015-01-01

Defining the conformational states of cytochrome P450 active sites is critical for the design of agents that minimize drug-drug interactions, the development of isoform-specific P450 inhibitors, and the engineering of novel oxidative catalysts. We used two-dimensional 1H,15N HSQC chemical shift perturbation mapping of 15N-labeled Phe residues and x-ray crystallography to examine the ligand-dependent conformational dynamics of CYP119. Active site Phe residues were most affected by the binding of azole inhibitors and fatty acid substrates, in agreement with active site localization of the conformational changes. This was supported by crystallography, which revealed movement of the F-G loop with various azoles. Nevertheless, the NMR chemical shift perturbations caused by azoles and substrates were distinguishable. The absence of significant chemical shift perturbations with several azoles revealed binding of ligands to an open conformation similar to that of the ligand-free state. In contrast, 4-phenylimidazole caused pronounced NMR changes involving Phe-87, Phe-144, and Phe-153 that support the closed conformation found in the crystal structure. The same closed conformation is observed by NMR and crystallography with a para-fluoro substituent on the 4-phenylimidazole, but a para-chloro or bromo substituent engendered a second closed conformation. An open conformation is thus favored in solution with many azole ligands, but para-substituted phenylimidazoles give rise to two closed conformations that depend on the size of the para-substituent. The results suggest that ligands selectively stabilize discrete cytochrome P450 conformational states. PMID:25670859

Assessment of the trophic status of four coastal lagoons and one estuarine delta, eastern Brazil.

PubMed

Cotovicz Junior, Luiz Carlos; Brandini, Nilva; Knoppers, Bastiaan Adriaan; Mizerkowski, Byanka Damian; Sterza, José Mauro; Ovalle, Alvaro Ramon Coelho; Medeiros, Paulo Ricardo Petter

2013-04-01

Anthropogenic eutrophication of aquatic ecosystems continues to be one of the major environmental issues worldwide and also of Brazil. Over the last five decades, several approaches have been proposed to discern the trophic state and the natural and cultural processes involved in eutrophication, including the multi-parameter Assessment of Estuarine Trophic Status (ASSETS) index model. This study applies ASSETS to four Brazilian lagoons (Mundaú, Manguaba, Guarapina, and Piratininga) and one estuarine delta (Paraíba do Sul River), set along the eastern Brazilian coast. The model combines three indices based on the pressure-state-response (PSR) approach to rank the trophic status and forecast the potential eutrophication of a system, to which a final ASSETS grade is established. The lagoons were classified as being eutrophic and highly susceptible to eutrophication, due primarily to their longer residence times but also their high nutrient input index. ASSETS classified the estuary of the Paraíba do Sul river with a low to moderate trophic state (e.g., largely mesotrophic) and low susceptibility to eutrophication. Its nutrient input index was high, but the natural high dilution and flushing potential driven by river flow mitigated the susceptibility to eutrophication. Eutrophication forecasting provided more favorable trends for the Mundaú and Manguaba lagoons and the Paraíba do Sul estuary, in view of the larger investments in wastewater treatment and remediation plans. The final ASSETS ranking system established the lagoons of Mundaú as "moderate," Manguaba as "bad," Guarapina as "poor," and Piratininga as "bad," whereas the Paraíba do Sul River Estuary was "good."

The nuclear quadrupole coupling constants and the structure of the para-para ammonia dimer

NASA Astrophysics Data System (ADS)

Heineking, N.; Stahl, W.; Olthof, E. H. T.; Wormer, P. E. S.; van der Avoird, A.; Havenith, M.

1995-06-01

Expressions are derived for the nuclear quadrupole splittings in the E3 and E4 (para-para) states of (NH3)2 and it is shown that these can be matched with the standard expressions for rigid rotors with two identical quadrupolar nuclei. The matching is exact only when the off-diagonal Coriolis coupling is neglected. However, the selection rules for rotational transitions are just opposite to those for the rigid rotor. Hyperfine splittings are measured for the J=2←1 transitions in the E3 and E4 states with ‖K‖=1; the quadrupole coupling constants χaa=0.1509(83) MHz and χbb-χcc=2.8365(83) MHz are extracted from these measurements by the use of the above mentioned correspondence with the rigid rotor expressions. The corresponding results are also calculated, with and without the Coriolis coupling, from the six-dimensional vibration-rotation-tunneling (VRT) wave functions of (NH3)2, which were previously obtained by Olthof et al. [E.H.T. Olthof, A. van der Avoird, and P.E.S. Wormer, J. Chem. Phys. 101, 8430 (1994)]. From the comparison of χaa with the measured value it follows that the semiempirical potential and the resulting VRT states of Olthof et al. are very accurate along the interchange (ϑA,ϑB) coordinate. From χbb-χcc it follows that this potential is probably too soft in the dihedral angle γ¯=γA-γB, which causes the torsional amplitude to be larger than derived from the experiment.

Architecture of the ParF*ParG protein complex involved in prokaryotic DNA segregation.

PubMed

Barillà, Daniela; Hayes, Finbarr

2003-07-01

The mechanism by which low copy number plasmids are segregated at cell division involves the concerted action of two plasmid-encoded proteins that assemble on a centromere-like site. This study explores the topology of the DNA segregation machinery specified by the parFG locus of TP228, a partition system which is phylogenetically distinct from more well-characterized archetypes. A variety of genetic, biochemical and biophysical strategies revealed that the ParG protein is dimeric. ParF, which is more closely related to the cell division regulator MinD than to the prototypical ParA partition protein of plasmid P1, is instead multimeric and its polymeric state appears to be modulated by ATP which correlates with the proposed ATP-binding activity of ParF. ParG interacts in a sequence-specific manner with the DNA region upstream of the parFG locus and this binding is modulated by ParF. Intriguingly, the ParF and ParG proteins form at least two types of discrete complex in the absence of this region suggesting that the assembly dynamics of these proteins onto DNA is intricate.

Torsional, Vibrational and Vibration-Torsional Levels in the S_{1} and Ground Cationic D_{0}^{+} States of Para-Fluorotoluene

NASA Astrophysics Data System (ADS)

Gardner, Adrian M.; Tuttle, William Duncan; Whalley, Laura E.; Claydon, Andrew; Carter, Joseph H.; Wright, Timothy G.

2017-06-01

The S_{1} electronic state and ground state of the cation of para-fluorotoluene (pFT) have been investigated using resonance-enhanced multiphoton ionization (REMPI) spectroscopy and zero-kinetic-energy (ZEKE) spectroscopy. Here we focus on the low wavenumber region where a number of "pure" torsional, fundamental vibrational and vibration-torsional levels are expected; assignments of observed transitions are discussed, which are compared to results of published work on toluene (methylbenzene) from the Lawrance group. The similarity in the activity observed in the excitation spectrum of the two molecules is striking. A. M. Gardner, W. D. Tuttle, L. Whalley, A. Claydon, J. H. Carter and T. G. Wright, J. Chem. Phys., 145, 124307 (2016). J. R. Gascooke, E. A. Virgo, and W. D. Lawrance J. Chem. Phys., 143, 044313 (2015).

A Xylenol Orange-Based Screening Assay for the Substrate Specificity of Flavin-Dependent para-Phenol Oxidases.

PubMed

Ewing, Tom A; van Noord, Aster; Paul, Caroline E; van Berkel, Willem J H

2018-01-14

Vanillyl alcohol oxidase (VAO) and eugenol oxidase (EUGO) are flavin-dependent enzymes that catalyse the oxidation of para -substituted phenols. This makes them potentially interesting biocatalysts for the conversion of lignin-derived aromatic monomers to value-added compounds. To facilitate their biocatalytic exploitation, it is important to develop methods by which variants of the enzymes can be rapidly screened for increased activity towards substrates of interest. Here, we present the development of a screening assay for the substrate specificity of para -phenol oxidases based on the detection of hydrogen peroxide using the ferric-xylenol orange complex method. The assay was used to screen the activity of VAO and EUGO towards a set of twenty-four potential substrates. This led to the identification of 4-cyclopentylphenol as a new substrate of VAO and EUGO and 4-cyclohexylphenol as a new substrate of VAO. Screening of a small library of VAO and EUGO active-site variants for alterations in their substrate specificity led to the identification of a VAO variant (T457Q) with increased activity towards vanillyl alcohol (4-hydroxy-3-methoxybenzyl alcohol) and a EUGO variant (V436I) with increased activity towards chavicol (4-allylphenol) and 4-cyclopentylphenol. This assay provides a quick and efficient method to screen the substrate specificity of para -phenol oxidases, facilitating the enzyme engineering of known para- phenol oxidases and the evaluation of the substrate specificity of novel para -phenol oxidases.

Experimental and theoretical study on the excited-state dynamics of ortho-, meta-, and para-methoxy methylcinnamate

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

Miyazaki, Yasunori; Yamamoto, Kanji; Aoki, Jun

The S{sub 1} state dynamics of methoxy methylcinnamate (MMC) has been investigated under supersonic jet-cooled conditions. The vibrationally resolved S{sub 1}-S{sub 0} absorption spectrum was recorded by laser induced fluorescence and mass-resolved resonant two-photon ionization spectroscopy and separated into conformers by UV-UV hole-burning (UV-UV HB) spectroscopy. The S{sub 1} lifetime measurements revealed different dynamics of para-methoxy methylcinnamate from ortho-methoxy methylcinnamate and meta-methoxy methylcinnamate (hereafter, abbreviated as p-, o-, and m-MMCs, respectively). The lifetimes of o-MMC and m-MMC are on the nanosecond time scale and exhibit little tendency of excess energy dependence. On the other hand, p-MMC decays much faster andmore » its lifetime is conformer and excess energy dependent. In addition, the p-MMC-H{sub 2}O complex was studied to explore the effect of hydration on the S{sub 1} state dynamics of p-MMC, and it was found that the hydration significantly accelerates the nonradiative decay. Quantum chemical calculation was employed to search the major decay route from S{sub 1}(ππ{sup ∗}) for three MMCs and p-MMC-H{sub 2}O in terms of (i) trans → cis isomerization and (ii) internal conversion to the {sup 1}nπ{sup ∗} state. In o-MMC and m-MMC, the large energy barrier is created for the nonradiative decay along (i) the double-bond twisting coordinate (∼1000 cm{sup −1}) in S{sub 1} as well as (ii) the linear interpolating internal coordinate (∼1000 cm{sup −1}) from S{sub 1} to {sup 1}nπ{sup ∗} states. The calculation on p-MMC decay dynamics suggests that both (i) and (ii) are available due to small energy barrier, i.e., 160 cm{sup −1} by the double-bond twisting and 390 cm{sup −1} by the potential energy crossing. The hydration of p-MMC raises the energy barrier of the IC route to the S{sub 1}/{sup 1}nπ{sup ∗} conical intersection, convincing that the direct isomerization is more likely to occur.« less

Dipolar induced para-hydrogen-induced polarization.

PubMed

Buntkowsky, Gerd; Gutmann, Torsten; Petrova, Marina V; Ivanov, Konstantin L; Bommerich, Ute; Plaumann, Markus; Bernarding, Johannes

2014-01-01

Analytical expressions for the signal enhancement in solid-state PHIP NMR spectroscopy mediated by homonuclear dipolar interactions and single pulse or spin-echo excitation are developed and simulated numerically. It is shown that an efficient enhancement of the proton NMR signal in solid-state NMR studies of chemisorbed hydrogen on surfaces is possible. Employing typical reaction efficacy, enhancement-factors of ca. 30-40 can be expected both under ALTADENA and under PASADENA conditions. This result has important consequences for the practical application of the method, since it potentially allows the design of an in-situ flow setup, where the para-hydrogen is adsorbed and desorbed from catalyst surfaces inside the NMR magnet. Copyright © 2014 Elsevier Inc. All rights reserved.

Petrology, thermobarometry and geochronology of Yelapa Complex: Implications in the tectonic history of the basement of Puerto Vallarta Batholith, Mexico

NASA Astrophysics Data System (ADS)

Gutiérrez Aguilar, F.; Schaaf, P. E. G.; Hernandez-Trevino, T.; Solis-Pichardo, G.; Vite-Sánchez, O.

2017-12-01

The Yelapa Complex (YC) is localizated in the north, central and western of Cabo Corrientes in Jalisco, México. Is constituted by metasedimentary, metaigneous and migmatites which are intruded by deformed plutons. The YC are part of the Puerto Vallarta Batholith a body of 9000 km2 exposed at the mid-western part of the Mexican Pacific margin. The para-gneis of YC in the region of Chimo, present a mineral assemblage of Sil + Bt + Pl ± Grt ± Fsp ± Ilm. The orto-gneis in the región of Cabo Corrientes are constituted by Pl + Amp ± Qz ± Ap ± Zrn. Phase equilibria modelling of two paragneis yield peak conditions of 7-8 kbar and 650-700ºC. The patterns of REE of the studied rocks suggest: 1) Enrichment of LREE and flat patterns in HREE with respect to chondrite and; 2) Negative Eu anomaly in all samples analyzed suggesting plagioclase fractionation. On the other hand, the study of individual zircons using LA-ICP-MS from 3 para-gneis and 1 orto-gneis yield following information: 1) A máximum depositional age of 223 Ma, which also show abundant zircón populations with ages between 241-273 Ma for para-gneis and 2) The protolith age crystallization of 127 Ma for orto-gneis. The results along with new Sr-Nd isotopic data from whole rock and Rb-Sr in micas, suggest a tectonic evolution for the Yelapa Complex as a transition from a passive continental margin regime ( 223-273 Ma) to a continental arc setting ( 127). Thus, regional metamorphism and multiple magmatic episodes were associated to the convergence of the Farallon and North America plates during the Middle Jurassic to the Late Cretaceous.

[Transport of dinitrosyl iron complexes into animal lungs].

PubMed

Mojokina, G N; Elistratova, N A; Mikoyan, V D; Vanin, A F

2015-01-01

Effective accumulation of binuclear dinitrosyl iron complexes with glutathione was shown after a subcutaneous para lymphatic injection of an aqueous solution of a dinitrosyl-iron complex into animal lung tissue at a single-dose of 2 micromoles per kilogram two times a day with a 2-h interval. Two hours later after the administration was repeated the concentration of these complexes was 16 micromoles per kilogram of tissue dropping down for the last two hours to 7 micromoles per kilogram of tissue. At one dose injection of binuclear dinitrosyl iron complexes with glutathione their concentration in 2 and 4 hours was two times lower than in the previous experiments. Presumably at the obtained concentration of dinitrosyl iron complexes a bactericidal effect in lungs can be observed against mycobacterium tuberculosis and rapidly proliferating lung tumors.

Un Manual para Padres y Madres Immigrantes. Proteja los Derechos de Educacion para Sus Hijos e Hijas (A Handbook for Immigrant Parents: Protect the Educational Rights of Your Children).

ERIC Educational Resources Information Center

Multicultural Education, Training and Advocacy (META), Inc., San Francisco, CA.

This handbook for Spanish-speaking immigrant parents outlines the legal rights of immigrant children to educational services. All children in the United States have a right to attend school. Schools may require proof of residency and vaccination before enrollment, but a signed sworn statement attesting to the child's age may be substituted for a…

Pick and Choose: A Videotape Series on Nutrition for Migrant Families (Coja y Escoja: Peliculas para Television Sobre la Nutricion para las Familias Migratorias).

ERIC Educational Resources Information Center

1979

One of the major problems faced by migrant workers throughout the United States is a lack of awareness of the relationship between proper diet and an individual's general health and well being. To help solve this problem was the major objective of the series "Pick and Choose." The three 15-minute programs in the series present…

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

Jones, J.

The Department of Energy of the United States of America works to guarantee provisions of safe energy, reliable and economically accessible to support to one developing economy and to protect the atmosphere. These suggestions and ideas to increase the energy efficiency in their house represent simple ways in which our citizens can contribute to preserve the atmosphere at world-wide level, to reduce the level of contamination of the air and to reserve our natural resources for future generations. [Spanish] El Departamento de Energa de los Estados Unidos de America trabaja para garantizar suministros de energa seguros, confiables y econmicamente accesiblesmore » para apoyar a una economa en desarrollo y proteger el medio ambiente. Estas sugerencias e ideas para aumentar la eficiencia energetica en su casa representan maneras sencillas en que nuestros ciudadanos pueden contribuir a preservar el medio ambiente a nivel mundial, a reducir el nivel de contaminacin del aire y a reservar nuestros recursos naturales para las generaciones futuras.« less

Para-hydrogenated glucose derivatives as potential 13C-hyperpolarized probes for magnetic resonance imaging.

PubMed

Reineri, Francesca; Santelia, Daniela; Viale, Alessandra; Cerutti, Erika; Poggi, Luisa; Tichy, Tomas; Premkumar, Samuel S D; Gobetto, Roberto; Aime, Silvio

2010-05-26

A set of molecules in which a glucose moiety is bound to a hydrogenable synthon has been synthesized and evaluated for hydrogenation reactions and for the corresponding para-hydrogen-induced polarization (PHIP) effects, in order to select suitable candidates for an in vivo magnetic resonance imaging (MRI) method for the assessment of glucose cellular uptake. It has been found that amidic derivatives do not yield any polarization enhancement, probably due to singlet-triplet state mixing along the reaction pathway. In contrast, ester derivatives are hydrogenated in high yield and afford enhanced (1)H and (13)C NMR spectra after para-hydrogenation. The obtained PHIP patterns are discussed and explained on the basis of the calculated spin level populations in the para-hydrogenated products. These molecules may find interesting applications in (13)C MRI as hyperpolarized probes for assessing the activity of glucose transporters in cells.

Paleoenvironmental evolution based on benthic foraminifera biofacies of the Paraíba do Sul Deltaic Complex, eastern Brazil

NASA Astrophysics Data System (ADS)

Gasparini, Sarah Pereira; Vilela, Claudia Gutterres

2017-12-01

The paleoecology and distribution of benthic foraminiferal assemblages were analyzed in the core 2-MU-1-RJ well, drilled in the Paraíba do Sul Deltaic Complex, Rio de Janeiro (Brazil). An abundant assemblage was found in the upper portion of the well core, inferred to be pleistocenic deposits. The coastal dynamic was recognized from five biofacies based on clusters, the Planktonic/Benthic (P/B) ratios and indicator species distribution in the core. Several biofacies were identified along the core depending on the species dominance. From the bottom to the top of the core, the biofacies succession represents the environmental changes in the coastal area associated to sea-level oscillations. The biofacies ABP dominated by Ammonia parkinsoniana and Bolivina spp. and Pararotalia cananeiaensis represents an inner shelf environment; biofacies QP dominated by shelf miliolids species; biofacies PGH, dominated by P. cananeiaensis, Gavelinopsis praegeri, and Hanzawaia nitidula, represents the estuary complex with middle or outer shelf influence; biofacies QL represents hypersaline waters dominated by lagoonal miliolids; and biofacies HP characterized by Haynesina germanica and P. cananeiaensis is associated with paralic environments. Marine ingressions are recorded and those biofacies show the pleistocenic coastal hydrodinamic in the deltaic complex. The foraminiferal biofacies contribute with detailed information to sedimentary facies previously characterized in the study area by the reconstruction of paleoenvironment succession.

One Language for the United States? (Un Idioma para Los Estados Unidos?) CSG Backgrounder.

ERIC Educational Resources Information Center

Ford, Mark L.

The United States has become increasingly multilingual in recent decades, and while English is the most commonly spoken language, almost 11 percent of Americans prefer to speak another language at home. Bilingualism is promoted by governmental units at the federal, state, and local levels through a variety of programs, particularly in education…

77 FR 35795 - Applications for New Awards; Teacher Incentive Fund

Federal Register 2010, 2011, 2012, 2013, 2014

2012-06-14

... personnel may include, for example, school counselors, media specialists, or para-educators. Performance... by the State as a priority school pursuant to the State's approved request for Elementary and... Incentive Fund AGENCY: Office of Elementary and Secondary Education, Department of Education. ACTION: Notice...

An improved coupled-states approximation including the nearest neighbor Coriolis couplings for diatom-diatom inelastic collision

NASA Astrophysics Data System (ADS)

Yang, Dongzheng; Hu, Xixi; Zhang, Dong H.; Xie, Daiqian

2018-02-01

Solving the time-independent close coupling equations of a diatom-diatom inelastic collision system by using the rigorous close-coupling approach is numerically difficult because of its expensive matrix manipulation. The coupled-states approximation decouples the centrifugal matrix by neglecting the important Coriolis couplings completely. In this work, a new approximation method based on the coupled-states approximation is presented and applied to time-independent quantum dynamic calculations. This approach only considers the most important Coriolis coupling with the nearest neighbors and ignores weaker Coriolis couplings with farther K channels. As a result, it reduces the computational costs without a significant loss of accuracy. Numerical tests for para-H2+ortho-H2 and para-H2+HD inelastic collision were carried out and the results showed that the improved method dramatically reduces the errors due to the neglect of the Coriolis couplings in the coupled-states approximation. This strategy should be useful in quantum dynamics of other systems.

Ultrafast above-threshold dynamics of the radical anion of a prototypical quinone electron-acceptor.

PubMed

Horke, Daniel A; Li, Quansong; Blancafort, Lluís; Verlet, Jan R R

2013-08-01

Quinones feature prominently as electron acceptors in nature. Their electron-transfer reactions are often highly exergonic, for which Marcus theory predicts reduced electron-transfer rates because of a free-energy barrier that occurs in the inverted region. However, the electron-transfer kinetics that involve quinones can appear barrierless. Here, we consider the intrinsic properties of the para-benzoquinone radical anion, which serves as the prototypical electron-transfer reaction product involving a quinone-based acceptor. Using time-resolved photoelectron spectroscopy and ab initio calculations, we show that excitation at 400 and 480 nm yields excited states that are unbound with respect to electron loss. These excited states are shown to decay on a sub-40 fs timescale through a series of conical intersections with lower-lying excited states, ultimately to form the ground anionic state and avoid autodetachment. From an isolated electron-acceptor perspective, this ultrafast stabilization mechanism accounts for the ability of para-benzoquinone to capture and retain electrons.

New investigations of technical rhodium and iridium catalysts in homogeneous phase employing para-hydrogen induced polarization.

PubMed

Gutmann, Torsten; Ratajczyk, Tomasz; Dillenberger, Sonja; Xu, Yeping; Grünberg, Anna; Breitzke, Hergen; Bommerich, Ute; Trantzschel, Thomas; Bernarding, Johannes; Buntkowsky, Gerd

2011-09-01

It is shown that the para-hydrogen induced polarization (PHIP) phenomenon in homogenous solution containing the substrate styrene is also observable employing simple inorganic systems of the form MCl(3)·xH(2)O (M=Rh, Ir) as catalyst. Such observation confirms that already very simple metal complexes enable the creation of PHIP signal enhancement in solution. This opens up new pathways to increase the sensitivity of NMR and MRT by PHIP enhancement using cost-effective catalysts and will be essential for further mechanistic studies of simple transition metal systems. Copyright © 2011 Elsevier Inc. All rights reserved.

Spectroscopic characterization and reactivity studies of a mononuclear nonheme Mn(III)-hydroperoxo complex.

PubMed

So, Hee; Park, Young Jun; Cho, Kyung-Bin; Lee, Yong-Min; Seo, Mi Sook; Cho, Jaeheung; Sarangi, Ritimukta; Nam, Wonwoo

2014-09-03

We report the first example of a mononuclear nonheme manganese(III)-hydroperoxo complex derived from protonation of an isolated manganese(III)-peroxo complex bearing an N-tetramethylated cyclam (TMC) ligand, [Mn(III)(TMC)(OOH)](2+). The Mn(III)-hydroperoxo intermediate is characterized with various spectroscopic methods as well as with density functional theory (DFT) calculations, showing the binding of a hydroperoxide ligand in an end-on fashion. The Mn(III)-hydroperoxo species is a competent oxidant in oxygen atom transfer (OAT) reactions, such as the oxidation of sulfides. The electrophilic character of the Mn(III)-hydroperoxo complex is demonstrated unambiguously in the sulfoxidation of para-substituted thioanisoles.

Refinement of the experimental dynamic structure factor for liquid para-hydrogen and ortho-deuterium using semi-classical quantum simulation

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

Smith, Kyle K. G., E-mail: kylesmith@utexas.edu; Rossky, Peter J., E-mail: peter.rossky@austin.utexas.edu; Poulsen, Jens Aage, E-mail: jens72@chem.gu.se

The dynamic structure factor of liquid para-hydrogen and ortho-deuterium in corresponding thermodynamic states (T = 20.0 K, n = 21.24 nm{sup −3}) and (T = 23.0 K, n = 24.61 nm{sup −3}), respectively, has been computed by both the Feynman-Kleinert linearized path-integral (FK-LPI) and Ring-Polymer Molecular Dynamics (RPMD) methods and compared with Inelastic X Ray Scattering spectra. The combined use of computational and experimental methods enabled us to reduce experimental uncertainties in the determination of the true sample spectrum. Furthermore, the refined experimental spectrum of para-hydrogen and ortho-deuterium is consistently reproduced by both FK-LPI and RPMD results at momentum transfers lower than 12.8 nm{sup −1}.more » At larger momentum transfers the FK-LPI results agree with experiment much better for ortho-deuterium than for para-hydrogen. More specifically we found that for k ∼ 20.0 nm{sup −1} para-hydrogen provides a test case for improved approximations to quantum dynamics.« less

Modification of medullary respiratory-related discharge patterns by behaviors and states of arousal.

PubMed

Chang, F C

1992-02-07

The modulatory influences of behaviors and states of arousal on bulbar respiratory-related unit (RRU) discharge patterns were studied in an unanesthetized, freely behaving guinea pig respiratory model system. When fully instrumented, this model system permits concurrent monitoring and recording of (i) single units from either Bötzinger complex or nucleus para-ambiguus; (ii) electrocorticogram; and, (iii) diaphragmatic EMG. In addition to being used in surveys of RRU discharge patterns in freely behaving states, the model system also offered a unique opportunity in investigating the effects of pentobarbital on RRU discharge patterns before, throughout the course of, and during recovery from anesthesia. In anesthetized preparations, a particular RRU discharge pattern (such as tonic, incrementing or decrementing) typically displayed little, if any notable variation. The most striking development following pentobarbital was a state of progressive bradypnea attributable to a significantly augmented RRU cycle duration, burst duration and an increase in the RRU spike frequencies during anesthesia. In freely behaving states, medullary RRU activities rarely adhered to a fixed, immutable discharge pattern. More specifically, the temporal organization (such as burst duration, cycle duration, and the extent of modulation of within-burst spike frequencies) of RRU discharge patterns regularly showed complex and striking variations, not only with states of arousal (sleep/wakefulness, anesthesia) but also with discrete alterations in electrocorticogram (ECoG) activities and a multitude of on-going behavioral repertoires such as volitional movement, postural modification, phonation, mastication, deglutition, sniffing/exploratory behavior, alerting/startle reflexes. Only during sleep, and on occasions when the animal assumed a motionless, resting posture, could burst patterns of relatively invariable periodicity and uniform temporal attributes be observed. RRU activities during sniffing reflex is worthy of further note in that, based on power spectrum analyses of concurrently recorded ECoG activities, this particular discharge pattern was clearly associated with the activation of a 6-10 Hz theta rhythm. These findings indicated that bulbar RRU activity patterns are subject to change by not only behaviors and sleep/wakefulness cycles, but also a variety of modulatory influences and feedback/feedforward biases from other central and peripheral physiological control mechanisms.

Measurement of the adsorption energy difference between ortho- and para-D2 on an amorphous ice surface.

PubMed

Amiaud, L; Momeni, A; Dulieu, F; Fillion, J H; Matar, E; Lemaire, J-L

2008-02-08

Molecular hydrogen interaction on water ice surfaces is a major process taking place in interstellar dense clouds. By coupling laser detection and classical thermal desorption spectroscopy, it is possible to study the effect of rotation of D(2) on adsorption on amorphous solid water ice surfaces. The desorption profiles of ortho- and para-D(2) are different. This difference is due to a shift in the adsorption energy distribution of the two lowest rotational states. Molecules in J''=1 rotational state are on average more strongly bound to the ice surface than those in J''=0 rotational state. This energy difference is estimated to be 1.4+/-0.3 meV. This value is in agreement with previous calculation and interpretation. The nonspherical wave function J'' =1 has an interaction with the asymmetric part of the adsorption potential and contributes positively in the binding energy.

Analysis of cytochrome P450 CYP119 ligand-dependent conformational dynamics by two-dimensional NMR and X-ray crystallography.

PubMed

Basudhar, Debashree; Madrona, Yarrow; Kandel, Sylvie; Lampe, Jed N; Nishida, Clinton R; de Montellano, Paul R Ortiz

2015-04-17

Defining the conformational states of cytochrome P450 active sites is critical for the design of agents that minimize drug-drug interactions, the development of isoform-specific P450 inhibitors, and the engineering of novel oxidative catalysts. We used two-dimensional (1)H,(15)N HSQC chemical shift perturbation mapping of (15)N-labeled Phe residues and x-ray crystallography to examine the ligand-dependent conformational dynamics of CYP119. Active site Phe residues were most affected by the binding of azole inhibitors and fatty acid substrates, in agreement with active site localization of the conformational changes. This was supported by crystallography, which revealed movement of the F-G loop with various azoles. Nevertheless, the NMR chemical shift perturbations caused by azoles and substrates were distinguishable. The absence of significant chemical shift perturbations with several azoles revealed binding of ligands to an open conformation similar to that of the ligand-free state. In contrast, 4-phenylimidazole caused pronounced NMR changes involving Phe-87, Phe-144, and Phe-153 that support the closed conformation found in the crystal structure. The same closed conformation is observed by NMR and crystallography with a para-fluoro substituent on the 4-phenylimidazole, but a para-chloro or bromo substituent engendered a second closed conformation. An open conformation is thus favored in solution with many azole ligands, but para-substituted phenylimidazoles give rise to two closed conformations that depend on the size of the para-substituent. The results suggest that ligands selectively stabilize discrete cytochrome P450 conformational states. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Analysis of Cytochrome P450 CYP119 Ligand-dependent Conformational Dynamics by Two-dimensional NMR and X-ray Crystallography

DOE PAGES

Basudhar, Debashree; Madrona, Yarrow; Kandel, Sylvie; ...

2015-02-10

Defining the conformational states of cytochrome P450 active sites is critical for the design of agents that minimize drug-drug interactions, the development of isoform-specific P450 inhibitors, and the engineering of novel oxidative catalysts. In this paper, we used two-dimensional 1H,15N HSQC chemical shift perturbation mapping of 15N-labeled Phe residues and x-ray crystallography to examine the ligand-dependent conformational dynamics of CYP119. Active site Phe residues were most affected by the binding of azole inhibitors and fatty acid substrates, in agreement with active site localization of the conformational changes. This was supported by crystallography, which revealed movement of the F-G loop withmore » various azoles. Nevertheless, the NMR chemical shift perturbations caused by azoles and substrates were distinguishable. The absence of significant chemical shift perturbations with several azoles revealed binding of ligands to an open conformation similar to that of the ligand-free state. In contrast, 4-phenylimidazole caused pronounced NMR changes involving Phe-87, Phe-144, and Phe-153 that support the closed conformation found in the crystal structure. The same closed conformation is observed by NMR and crystallography with a para-fluoro substituent on the 4-phenylimidazole, but a para-chloro or bromo substituent engendered a second closed conformation. An open conformation is thus favored in solution with many azole ligands, but para-substituted phenylimidazoles give rise to two closed conformations that depend on the size of the para-substituent. Finally, the results suggest that ligands selectively stabilize discrete cytochrome P450 conformational states.« less

Analysis of Cytochrome P450 CYP119 Ligand-dependent Conformational Dynamics by Two-dimensional NMR and X-ray Crystallography

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

Basudhar, Debashree; Madrona, Yarrow; Kandel, Sylvie

Defining the conformational states of cytochrome P450 active sites is critical for the design of agents that minimize drug-drug interactions, the development of isoform-specific P450 inhibitors, and the engineering of novel oxidative catalysts. In this paper, we used two-dimensional 1H,15N HSQC chemical shift perturbation mapping of 15N-labeled Phe residues and x-ray crystallography to examine the ligand-dependent conformational dynamics of CYP119. Active site Phe residues were most affected by the binding of azole inhibitors and fatty acid substrates, in agreement with active site localization of the conformational changes. This was supported by crystallography, which revealed movement of the F-G loop withmore » various azoles. Nevertheless, the NMR chemical shift perturbations caused by azoles and substrates were distinguishable. The absence of significant chemical shift perturbations with several azoles revealed binding of ligands to an open conformation similar to that of the ligand-free state. In contrast, 4-phenylimidazole caused pronounced NMR changes involving Phe-87, Phe-144, and Phe-153 that support the closed conformation found in the crystal structure. The same closed conformation is observed by NMR and crystallography with a para-fluoro substituent on the 4-phenylimidazole, but a para-chloro or bromo substituent engendered a second closed conformation. An open conformation is thus favored in solution with many azole ligands, but para-substituted phenylimidazoles give rise to two closed conformations that depend on the size of the para-substituent. Finally, the results suggest that ligands selectively stabilize discrete cytochrome P450 conformational states.« less

El Odio Se Cura: Un Programa Nacional para la Prevencion de los Crimenes de Odio para las Escuelas Intermedias (Healing the Hate: A National Crime Prevention Curriculum for Middle Schools).

ERIC Educational Resources Information Center

McLaughlin, Karen A.; Brilliant, Kelly J.

Designed for use in middle schools and youth organizations, this curriculum, in Spanish, deals with the extent of hate crime in the United States and presents strategies for reducing hate crimes among our youth. This flexible nine-unit curriculum is based on the principles that violence and prejudice are learned and therefore preventable, and that…

Improving Regional Security in Central America: Military Engagement Options for Nicaragua

DTIC Science & Technology

2002-12-01

Diálogo Centro-americano San José, Costa Rica No. 38 Marzo-Abril 1999 Ejércitos para preservar la paz y la democracia . Pedro Joaquín Chamorro...del Foro Civil Centroamericano para la Defensa y la Seguridad (FOCADES). (Declaration of Managua: Declaration of Managua: Constitution of the Central...State. Isacson, Adam 1998. Seguridad Cooperativa en Centroamérica. (Cooperative Security in Central America) Diálogo Centro-americano No. 35

Substitution effects on the absorption spectra of nitrophenolate isomers.

PubMed

Wanko, Marius; Houmøller, Jørgen; Støchkel, Kristian; Suhr Kirketerp, Maj-Britt; Petersen, Michael Åxman; Nielsen, Mogens Brøndsted; Nielsen, Steen Brøndsted; Rubio, Angel

2012-10-05

Charge-transfer excitations highly depend on the electronic coupling between the donor and acceptor groups. Nitrophenolates are simple examples of charge-transfer systems where the degree of coupling differs between ortho, meta and para isomers. Here we report the absorption spectra of the isolated anions in vacuo to avoid the complications of solvent effects. Gas-phase action spectroscopy was done with two different setups, an electrostatic ion storage ring and an accelerator mass spectrometer. The results are interpreted on the basis of CC2 quantum chemical calculations. We identified absorption maxima at 393, 532, and 399 nm for the para, meta, and ortho isomer, respectively, with the charge-transfer transition into the lowest excited singlet state. In the meta isomer, this π-π* transition is strongly redshifted and its oscillator strength reduced, which is related to the pronounced charge-transfer character, as a consequence of the topology of the conjugated π-system. Each isomer's different charge distribution in the ground state leads to a very different solvent shift, which in acetonitrile is bathochromic for the para and ortho, but hypsochromic for the meta isomer.

Rotationally inelastic scattering of PN by para-H2(j = 0) at low/moderate temperature

NASA Astrophysics Data System (ADS)

Najar, F.; Naouai, M.; Hanini, H. El; Jaidane, N.

2017-12-01

Calculation of the collisional rate coefficients with the most abundant species has been motivated by the desire to interpret observations of molecules in the interstellar medium. This paper will be concerned with rotational excitation of the phosphorus nitride (PN) molecule in its ground vibrational state by collisions with para-H2(j = 0). Ab intio potential energy surface for the PN-H2 van der Waals system, considering both molecules as rigid rotors, was computed via CCSD(T) method using the aug-cc-pVTZ basis sets, augmented by a bond functions placed at midway between the PN and H2 centres of mass. Cross-sections among the 40 first rotational levels of PN in collisions with para-H2(j = 0) were obtained using close coupling and coupled states calculations, for total energies up to 3000 cm- 1. Rate coefficients are presented for temperatures ranging from 5 to 300 K. A strong propensity favouring even Δj transitions is found. The comparison of the new PN-H2 rate coefficients with previously calculated PN-He rate coefficients shows that significant differences exist.

paraGSEA: a scalable approach for large-scale gene expression profiling

PubMed Central

Peng, Shaoliang; Yang, Shunyun

2017-01-01

Abstract More studies have been conducted using gene expression similarity to identify functional connections among genes, diseases and drugs. Gene Set Enrichment Analysis (GSEA) is a powerful analytical method for interpreting gene expression data. However, due to its enormous computational overhead in the estimation of significance level step and multiple hypothesis testing step, the computation scalability and efficiency are poor on large-scale datasets. We proposed paraGSEA for efficient large-scale transcriptome data analysis. By optimization, the overall time complexity of paraGSEA is reduced from O(mn) to O(m+n), where m is the length of the gene sets and n is the length of the gene expression profiles, which contributes more than 100-fold increase in performance compared with other popular GSEA implementations such as GSEA-P, SAM-GS and GSEA2. By further parallelization, a near-linear speed-up is gained on both workstations and clusters in an efficient manner with high scalability and performance on large-scale datasets. The analysis time of whole LINCS phase I dataset (GSE92742) was reduced to nearly half hour on a 1000 node cluster on Tianhe-2, or within 120 hours on a 96-core workstation. The source code of paraGSEA is licensed under the GPLv3 and available at http://github.com/ysycloud/paraGSEA. PMID:28973463

Infrared identification of the {sigma}-complex of Cl-C{sub 6}H{sub 6} in the reaction of chlorine atom and benzene in solid para-hydrogen

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

Bahou, Mohammed; Witek, Henryk; Lee, Yuan-Pern

2013-02-21

The reaction of a chlorine atom with benzene (C{sub 6}H{sub 6}) is important in organic chemistry, especially in site-selective chlorination reactions, but its product has been a subject of debate for five decades. Previous experimental and theoretical studies provide no concrete conclusion on whether the product is a {pi}- or {sigma}-form of the Cl-C{sub 6}H{sub 6} complex. We took advantage of the diminished cage effect of para-hydrogen (p-H{sub 2}) to produce Cl in situ to react with C{sub 6}H{sub 6} (or C{sub 6}D{sub 6}) upon photolysis of a Cl{sub 2}/C{sub 6}H{sub 6} (or C{sub 6}D{sub 6})/p-H{sub 2} matrix at 3.2more » K. The infrared spectrum, showing intense lines at 1430.5, 833.6, 719.8, 617.0, and 577.4 cm{sup -1}, and several weaker ones for Cl-C{sub 6}H{sub 6}, and the deuterium shifts of observed new lines unambiguously indicate that the product is a 6-chlorocyclohexadienyl radical, i.e., the {sigma}-complex of Cl-C{sub 6}H{sub 6}. Observation of the {sigma}-complex rather than the {pi}-complex indicates that the {sigma}-complex is more stable in solid p-H{sub 2} at 3.2 K. The spectral information is crucial for further investigations of the Cl + C{sub 6}H{sub 6} reaction either in the gaseous or solution phase.« less

Self-assembled squares and triangles by simultaneous hydrogen bonding and metal coordination.

PubMed

Marshall, Laura J; de Mendoza, Javier

2013-04-05

Through the combination of hydrogen bonding and metal-templated self-assembly, molecular squares and molecular triangles are observed in chloroform solution upon the complexation of hydrogen-bonded dimers of para-pyridyl-substituted 2-ureido-4-[1H]-pyrimidinone (UPy) and an appropriate cis-substituted palladium complex. Molecular modeling studies and NMR analysis confirmed the presence of two distinct structures in solution: the tubular structure of the molecular square and propeller-bowl structure of the molecular triangle.

MARVEL analysis of the measured high-resolution spectra of 14NH3

NASA Astrophysics Data System (ADS)

Al Derzi, Afaf R.; Furtenbacher, Tibor; Tennyson, Jonathan; Yurchenko, Sergei N.; Császár, Attila G.

2015-08-01

Accurate, experimental rotational-vibrational energy levels and line positions, with associated labels and uncertainties, are reported for the ground electronic state of the symmetric-top 14NH3 molecule. All levels and lines are based on critically reviewed and validated high-resolution experimental spectra taken from 56 literature sources. The transition data are in the 0.7-17 000 cm-1 region, with a large gap between 7000 and 15 000 cm-1. The MARVEL (Measured Active Rotational-Vibrational Energy Levels) algorithm is used to determine the energy levels. Out of the 29 450 measured transitions 10 041 and 18 947 belong to ortho- and para-14NH3, respectively. A careful analysis of the related experimental spectroscopic network (SN) allows 28 530 of the measured transitions to be validated, 18 178 of these are unique, while 462 transitions belong to floating components. Despite the large number of spectroscopic measurements published over the last 80 years, the transitions determine only 30 vibrational band origins of 14NH3, 8 for ortho- and 22 for para-14NH3. The highest J value, where J stands for the rotational quantum number, for which an energy level is validated is 31. The number of experimental-quality ortho- and para-14NH3 rovibrational energy levels is 1724 and 3237, respectively. The MARVEL energy levels are checked against ones in the BYTe first-principles database, determined previously. The lists of validated lines and levels for 14NH3 are deposited in the Supporting Information to this paper. Combination of the MARVEL energy levels with first-principles absorption intensities yields a huge number of experimental-quality rovibrational lines, which should prove to be useful for the understanding of future complex high-resolution spectroscopy on 14NH3; these lines are also deposited in the Supporting Information to this paper.

Photodissociation dynamics of the ortho- and para-xylyl radicals

NASA Astrophysics Data System (ADS)

Pachner, Kai; Steglich, Mathias; Hemberger, Patrick; Fischer, Ingo

2017-08-01

The photodissociation dynamics of the C8H9 isomers ortho- and para-xylyl are investigated in a free jet. The xylyl radicals are generated by flash pyrolysis from 2-(2-methylphenyl)- and 2-(4-methylphenyl) ethyl nitrite and are excited into the D3 state. REMPI- spectra show vibronic structure and the origin of the transition is identified at 32 291 cm-1 for the para- and at 32 132 cm-1 for the ortho-isomer. Photofragment H-atom action spectra show bands at the same energy and thus confirm H-atom loss from xylyl radicals. To gain further insight into the photodissociation dynamics, velocity map images of the hydrogen atom photofragments are recorded. Their angular distribution is isotropic and the translational energy release is in agreement with a dissociation to products in their electronic ground state. Photodissociation of para-xylyl leads to the formation of para-xylylene (C8H8), while the data for ortho-xylyl agree much better with the isomer benzocyclobutene as the dominant molecular fragment rather than ortho-xylylene. In computations we identified a new pathway for the reaction ortho-xylyl → benzocyclobutene + H with a barrier of 3.39 eV (27 340 cm-1), which becomes accessible at the employed excitation energy. It proceeds via a combination of scissoring and rotational motion of the -CH2 and -CH3 groups. However, the observed rate constants measured by delaying the excitation and ionization laser with respect to each other are significantly faster than computed ones, indicating intrinsic non-RRKM behaviour. A comparably high value of around 30% of the excess energy is released as translation of the H-atom photofragment.

Photodissociation dynamics of the ortho- and para-xylyl radicals.

PubMed

Pachner, Kai; Steglich, Mathias; Hemberger, Patrick; Fischer, Ingo

2017-08-28

The photodissociation dynamics of the C 8 H 9 isomers ortho- and para-xylyl are investigated in a free jet. The xylyl radicals are generated by flash pyrolysis from 2-(2-methylphenyl)- and 2-(4-methylphenyl) ethyl nitrite and are excited into the D 3 state. REMPI- spectra show vibronic structure and the origin of the transition is identified at 32 291 cm -1 for the para- and at 32 132 cm -1 for the ortho-isomer. Photofragment H-atom action spectra show bands at the same energy and thus confirm H-atom loss from xylyl radicals. To gain further insight into the photodissociation dynamics, velocity map images of the hydrogen atom photofragments are recorded. Their angular distribution is isotropic and the translational energy release is in agreement with a dissociation to products in their electronic ground state. Photodissociation of para-xylyl leads to the formation of para-xylylene (C 8 H 8 ), while the data for ortho-xylyl agree much better with the isomer benzocyclobutene as the dominant molecular fragment rather than ortho-xylylene. In computations we identified a new pathway for the reaction ortho-xylyl → benzocyclobutene + H with a barrier of 3.39 eV (27 340 cm -1 ), which becomes accessible at the employed excitation energy. It proceeds via a combination of scissoring and rotational motion of the -CH 2 and -CH 3 groups. However, the observed rate constants measured by delaying the excitation and ionization laser with respect to each other are significantly faster than computed ones, indicating intrinsic non-RRKM behaviour. A comparably high value of around 30% of the excess energy is released as translation of the H-atom photofragment.

A Transferencia do Controle da Educacao da Igreja para o Estado (The Transfer of Educational Control from the Church to the State).

ERIC Educational Resources Information Center

Silva, Marcos

2000-01-01

Analyzes the principal phases in the historical process of the occidental world that resulted in the transfer of educational control from the church to the state, demonstrating some of the consequences of this historic turn. (BT)

Rotation of molecular hydrogen in Si: unambiguous identification of ortho-H(2) and para-D(2).

PubMed

Chen, E Elinor; Stavola, Michael; Beall Fowler, W; Zhou, J Anna

2002-06-17

The 3618.4 and 2642.6 cm(-1) infrared absorption lines of interstitial H(2) and D(2) in silicon have been studied under applied uniaxial stresses. The resulting splittings and their small dependence on isotope establish that H(2) in Si is a nearly free rotor and that these lines arise from vibrational transitions between rovibrational states with rotational quantum number J = 1 (T(2) in T(d) symmetry) for ortho-H(2) and para-D(2).

State, Labor, Capital: Institutionalizing Democratic Class Compromise in the Southern Cone.

DTIC Science & Technology

1987-08-01

recent experiences) to which current unionists can hark back to. 89J. Samuel Valenzuela, "Movimientos Obreros y Sistemas Politicos: Un Analisis...O’Donnell, "Apuntes para una teoria de Estado," Documento CEDES/ G.E. CLASCO, N. 9 (1977); O’Donnell and 0. Oszlak, "Estado y Politicas Estatales en...Reflexiones a partir de algunas experiencias Latinoamericanas," Estudios CEDES, V. 3, N. 2 (1980); Oszlak, "Notas Criticas para una Teoria de la Burocracia

Sulfonamido tripods: tuning redox potentials via ligand modifications

PubMed Central

Lau, Nathanael; Ziller, Joseph W.

2014-01-01

A series of FeII–OH2 complexes were synthesized with ligands based on the tetradentate sulfonamido tripod N,N',N"-[2,2',2"-nitrilotris(ethane-2,1-diyl)]-tris-({R-Ph}-sulfonamido). These complexes differ by the substituent on the aryl rings and were fully characterized, including their molecular structures via X-ray diffraction methods. All the complexes were five-coordinate with trigonal bipyramidal geometry. A linear correlation was observed between the electronic effects of each ligand, given by the Hammett constants of the para-substituents, and the potential of the FeII/FeIII redox couple, which were determined using cyclic voltammetry. It was found that the range of redox potentials for the complexes spanned approximately 160 mV. PMID:25419035

Sulfonamido tripods: tuning redox potentials via ligand modifications.

PubMed

Lau, Nathanael; Ziller, Joseph W; Borovik, A S

2015-01-08

A series of Fe II -OH 2 complexes were synthesized with ligands based on the tetradentate sulfonamido tripod N , N ', N "-[2,2',2"-nitrilotris(ethane-2,1-diyl)]-tris-({R-Ph}-sulfonamido). These complexes differ by the substituent on the aryl rings and were fully characterized, including their molecular structures via X-ray diffraction methods. All the complexes were five-coordinate with trigonal bipyramidal geometry. A linear correlation was observed between the electronic effects of each ligand, given by the Hammett constants of the para -substituents, and the potential of the Fe II /Fe III redox couple, which were determined using cyclic voltammetry. It was found that the range of redox potentials for the complexes spanned approximately 160 mV.

Prevalence and risk factors associated with Tritrichomonas foetus infection in cattle in the state of Paraíba, Brazil.

PubMed

Filho, Ruy Brayner de Oliveira; Malta, Karla Campos; Borges, Jonas de Melo; Oliveira, Pollyanne Raysa Fernandes de; Filho, Givanildo Jacinto Dos Santos; Nascimento, Glaucia Grazielle; Mota, Rinaldo Aparecido; Júnior, José Wilton Pinheiro

2018-06-26

The objective of this study was to determine the prevalence of Tritrichomonas foetus infection and to evaluate risk factors associated with this infection among cattle in the state of Paraíba in northeastern Brazil. Samples of cervicovaginal mucus from 290 females and smegma from 59 males [beef, 31; mixed aptitude (beef and dairy), 10; and dairy, 18] from 31 farms were collected. Modified Diamond's medium and polymerase chain reaction (PCR) were used for the laboratory diagnosis of T. foetus infection. Univariate analysis and logistic regression were performed to test for potential risk factors in addition to prevalence mapping. No sample was positive for T. foetus in culture, and the prevalence of T. foetus infection using PCR was 3.7% (13/349) [confidence interval (CI) 95%, 2.1%-6.4%]. In total, 19.3% (6/31) of the farms had at least one animal positive for T. foetus. The contact of females with males from other farms [Odds ratio, 5.9; 95% CI, 1.5-22.4; p = 0.009] was identified as a risk factor for T. foetus infection. This study demonstrates that T. foetus infection is prevalent among dairy cows in the state of Paraíba, Brazil. Sexual resting, removal of positive females, and avoiding contact of females with males from other farms are recommended to reduce the risk of infection.

Tuning the reactivity of mononuclear nonheme manganese(iv)-oxo complexes by triflic acid

DOE PAGES

Chen, Junying; Yoon, Heejung; Lee, Yong -Min; ...

2015-04-14

Triflic acid (HOTf)-bound nonheme Mn( IV)-oxo complexes, [(L)Mn IV(O)] 2+–(HOTf) 2 (L = N4Py and Bn-TPEN; N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine and Bn-TPEN = N-benzyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine), were synthesized by adding HOTf to the solutions of the [(L)Mn IV(O)] 2+ complexes and were characterized by various spectroscopies. The one-electron reduction potentials of the Mn IV(O) complexes exhibited a significant positive shift upon binding of HOTf. The driving force dependences of electron transfer (ET) from electron donors to the Mn IV(O) and Mn IV(O)–(HOTf) 2 complexes were examined and evaluated in light of the Marcus theory of ET to determine the reorganization energies of ET.more » The smaller reorganization energies and much more positive reduction potentials of the [(L)Mn IV(O)] 2+–(HOTf) 2 complexes resulted in greatly enhanced oxidation capacity towards one-electron reductants and para-X-substituted-thioanisoles. The reactivities of the Mn(IV)-oxo complexes were markedly enhanced by binding of HOTf, such as a 6.4 × 10 5-fold increase in the oxygen atom transfer (OAT) reaction (i.e., sulfoxidation). Such a remarkable acceleration in the OAT reaction results from the enhancement of ET from para-X-substituted-thioanisoles to the MnIV(O) complexes as revealed by the unified ET driving force dependence of the rate constants of OAT and ET reactions of [(L)Mn IV(O)] 2+–(HOTf) 2. In contrast, deceleration was observed in the rate of H-atom transfer (HAT) reaction of [(L)Mn IV(O)] 2+–(HOTf) 2 complexes with 1,4-cyclohexadiene as compared with those of the [(L)Mn IV(O)] 2+ complexes. Thus, the binding of two HOTf molecules to the Mn IV(O) moiety resulted in remarkable acceleration of the ET rate when the ET is thermodynamically feasible. When the ET reaction is highly endergonic, the rate of the HAT reaction is decelerated due to the steric effect of the counter anion of HOTf.« less

Electrophilic and free radical nitration of benzene and toluene with various nitrating agents*

PubMed Central

Olah, George A.; Lin, Henry C.; Olah, Judith A.; Narang, Subhash C.

1978-01-01

Electrophilic nitration of toluene and benzene was studied under various conditions with several nitrating systems. It was found that high orthopara regioselectivity is prevalent in all reactions and is independent of the reactivity of the nitrating agent. The methyl group of toluene is predominantly ortho-para directing under all reaction conditions. Steric factors are considered to be important but not the sole reason for the variation in the ortho/para ratio. The results reinforce our earlier views that, in electrophilic aromatic nitrations with reactive nitrating agents, substrate and positional selectivities are determined in two separate steps. The first step involves a π-aromatic-NO2+ ion complex or encounter pair, whereas the subsequent step is of arenium ion nature (separate for the ortho, meta, and para positions). The former determines substrate selectivity, whereas the latter determines regioselectivity. Thermal free radical nitration of benzene and toluene with tetranitromethane in sharp contrast gave nearly statistical product distributions. PMID:16592503

Partition functions. I. Improved partition functions and thermodynamic quantities for normal, equilibrium, and ortho and para molecular hydrogen

NASA Astrophysics Data System (ADS)

Popovas, A.; Jørgensen, U. G.

2016-11-01

Context. Hydrogen is the most abundant molecule in the Universe. Its thermodynamic quantities dominate the physical conditions in molecular clouds, protoplanetary disks, etc. It is also of high interest in plasma physics. Therefore thermodynamic data for molecular hydrogen have to be as accurate as possible in a wide temperature range. Aims: We here rigorously show the shortcomings of various simplifications that are used to calculate the total internal partition function. These shortcomings can lead to errors of up to 40 percent or more in the estimated partition function. These errors carry on to calculations of thermodynamic quantities. Therefore a more complicated approach has to be taken. Methods: Seven possible simplifications of various complexity are described, together with advantages and disadvantages of direct summation of experimental values. These were compared to what we consider the most accurate and most complete treatment (case 8). Dunham coefficients were determined from experimental and theoretical energy levels of a number of electronically excited states of H2. Both equilibrium and normal hydrogen was taken into consideration. Results: Various shortcomings in existing calculations are demonstrated, and the reasons for them are explained. New partition functions for equilibrium, normal, and ortho and para hydrogen are calculated and thermodynamic quantities are reported for the temperature range 1-20 000 K. Our results are compared to previous estimates in the literature. The calculations are not limited to the ground electronic state, but include all bound and quasi-bound levels of excited electronic states. Dunham coefficients of these states of H2 are also reported. Conclusions: For most of the relevant astrophysical cases it is strongly advised to avoid using simplifications, such as a harmonic oscillator and rigid rotor or ad hoc summation limits of the eigenstates to estimate accurate partition functions and to be particularly careful when using polynomial fits to the computed values. Reported internal partition functions and thermodynamic quantities in the present work are shown to be more accurate than previously available data. The full datasets in 1 K temperature steps are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/595/A130

Electrical detection of ortho–para conversion in fullerene-encapsulated water

PubMed Central

Meier, Benno; Mamone, Salvatore; Concistrè, Maria; Alonso-Valdesueiro, Javier; Krachmalnicoff, Andrea; Whitby, Richard J.; Levitt, Malcolm H.

2015-01-01

Water exists in two spin isomers, ortho and para, that have different nuclear spin states. In bulk water, rapid proton exchange and hindered molecular rotation obscure the direct observation of two spin isomers. The supramolecular endofullerene H2O@C60 provides freely rotating, isolated water molecules even at cryogenic temperatures. Here we show that the bulk dielectric constant of this substance depends on the ortho/para ratio, and changes slowly in time after a sudden temperature jump, due to nuclear spin conversion. The attribution of the effect to ortho–para conversion is validated by comparison with nuclear magnetic resonance and quantum theory. The change in dielectric constant is consistent with an electric dipole moment of 0.51±0.05 Debye for an encapsulated water molecule, indicating the partial shielding of the water dipole by the encapsulating cage. The dependence of bulk dielectric constant on nuclear spin isomer composition appears to be a previously unreported physical phenomenon. PMID:26299447

First report of the protozoan parasite Perkinsus marinus in South America, infecting mangrove oysters Crassostrea rhizophorae from the Paraíba River (NE, Brazil).

PubMed

da Silva, Patricia Mirella; Vianna, Rogério Tubino; Guertler, Cristhiane; Ferreira, Liana Pinho; Santana, Lucas Nunes; Fernández-Boo, Sergio; Ramilo, Andrea; Cao, Asunción; Villalba, Antonio

2013-05-01

The present work aimed to study the infection by Perkinsus sp. in the mangrove oysters Crassostrea rhizophorae from the estuary of the Paraíba River (Paraíba State, Brazil). Perkinsosis was detected by incubation of oyster gill pieces in Ray's fluid thioglycollate medium. The monthly prevalence values were all above 70%, thus infection was not likely to be a transient event. Perkinsus sp. parasites isolated from eight oysters were propagated in vitro. PCR-RFLP analysis of in vitro cultured cells as well as the sequences of the rDNA ITS region allowed the identification of the in vitro propagated parasites as Perkinsus marinus. Phylogenetic analyses using rDNA ITS region sequences strongly supported the Perkinsus sp. from Paraíba in a monophyletic group with P. marinus. Thus, the results confirmed the species affiliation of Paraíba Perkinsus sp. as P. marinus. This is the first report of P. marinus in Brazil and South America and the first report of P. marinus naturally infecting C. rhizophorae. Copyright © 2013 Elsevier Inc. All rights reserved.

Homoleptic nickel(II) complexes of redox-tunable pincer-type ligands.

PubMed

Hewage, Jeewantha S; Wanniarachchi, Sarath; Morin, Tyler J; Liddle, Brendan J; Banaszynski, Megan; Lindeman, Sergey V; Bennett, Brian; Gardinier, James R

2014-10-06

Different synthetic methods have been developed to prepare eight new redox-active pincer-type ligands, H(X,Y), that have pyrazol-1-yl flanking donors attached to an ortho-position of each ring of a diarylamine anchor and that have different groups, X and Y, at the para-aryl positions. Together with four previously known H(X,Y) ligands, a series of 12 Ni(X,Y)2 complexes were prepared in high yields by a simple one-pot reaction. Six of the 12 derivatives were characterized by single-crystal X-ray diffraction, which showed tetragonally distorted hexacoordinate nickel(II) centers. The nickel(II) complexes exhibit two quasi-reversible one-electron oxidation waves in their cyclic voltammograms, with half-wave potentials that varied over a remarkable 700 mV range with the average of the Hammett σ(p) parameters of the para-aryl X, Y groups. The one- and two-electron oxidized derivatives [Ni(Me,Me)2](BF4)n (n = 1, 2) were prepared synthetically, were characterized by X-band EPR, electronic spectroscopy, and single-crystal X-ray diffraction (for n = 2), and were studied computationally by DFT methods. The dioxidized complex, [Ni(Me,Me)2](BF4)2, is an S = 2 species, with nickel(II) bound to two ligand radicals. The mono-oxidized complex [Ni(Me,Me)2](BF4), prepared by comproportionation, is best described as nickel(II) with one ligand centered radical. Neither the mono- nor the dioxidized derivative shows any substantial electronic coupling between the metal and their bound ligand radicals because of the orthogonal nature of their magnetic orbitals. On the other hand, weak electronic communication occurs between ligands in the mono-oxidized complex as evident from the intervalence charge transfer (IVCT) transition found in the near-IR absorption spectrum. Band shape analysis of the IVCT transition allowed comparisons of the strength of the electronic interaction with that in the related, previously known, Robin-Day class II mixed valence complex, [Ga(Me,Me)2](2+).

The effect of meta coupling on colour purity, quantum yield, and exciton utilizing efficiency in deep-blue emitters from phenanthroimidazole isomers.

PubMed

Wang, Zhiming; Li, Xueying; Zhang, Wanyu; Zhang, Shitong; Li, Hui; Yu, Zhenqiang; Chen, Yanming; Lu, Ping; Chen, Ping

2015-12-21

meta-Coupling isomers usually exhibit bluer emission than do the para-isomers, but the loss of efficiency with respect to photoluminescence (PL) and electroluminescence (EL) is an inevitable result in most cases, particularly for deep blue emitters. In this study, three blue emitting isomers, 4,4'-bis(1-phenyl-phenanthro[9,10-d]imidazol-2-yl)biphenyl (BPPI), 3,4'-bis(1-phenyl-phenanthro[9,10-d]-imidazol-2-yl)biphenyl (L-BPPI) and 3,3'-bis(1-phenyl-phenanthro[9,10-d]-imidazol-2-yl)biphenyl (Z-BPPI), were chosen as model compounds to investigate the essential reason behind the meta-coupling effect due to their different coupling forms, viz. para-para, para-meta, and meta-meta, respectively, in similar dimeric phenanthroimidazole frameworks. A combination of detailed photophysical data, device performance and DFT calculations for the excited state provided valuable information. In particular, the relationship between certain key parameters in calculations as well as PL or EL properties was confirmed, such as oscillator strength and quantum yield, among others, which could effectively reduce the issues related to synthesis and characterisation using prior computer simulations. Good agreement was observed in the results obtained from calculation and experiments, and it was concluded that meta-tuning barely realised improvement in EL, unless some special excited states formed or an exciton conversion channel appeared, as in the case of reverse intersystem crossing.

Simultaneous manipulation and observation of multiple ro-vibrational eigenstates in solid para-hydrogen.

PubMed

Katsuki, Hiroyuki; Ohmori, Kenji

2016-09-28

We have experimentally performed the coherent control of delocalized ro-vibrational wave packets (RVWs) of solid para-hydrogen (p-H 2 ) by the wave packet interferometry (WPI) combined with coherent anti-Stokes Raman scattering (CARS). RVWs of solid p-H 2 are delocalized in the crystal, and the wave function with wave vector k ∼ 0 is selectively excited via the stimulated Raman process. We have excited the RVW twice by a pair of femtosecond laser pulses with delay controlled by a stabilized Michelson interferometer. Using a broad-band laser pulse, multiple ro-vibrational states can be excited simultaneously. We have observed the time-dependent Ramsey fringe spectra as a function of the inter-pulse delay by a spectrally resolved CARS technique using a narrow-band probe pulse, resolving the different intermediate states. Due to the different fringe oscillation periods among those intermediate states, we can manipulate their amplitude ratio by tuning the inter-pulse delay on the sub-femtosecond time scale. The state-selective manipulation and detection of the CARS signal combined with the WPI is a general and efficient protocol for the control of the interference of multiple quantum states in various quantum systems.

Synthesis and characterization of para-pyridine linked NHC palladium complexes and their studies for the Heck-Mizoroki coupling reaction.

PubMed

Liu, Ya-Ming; Lin, Yi-Chun; Chen, Wen-Ching; Cheng, Jen-Hao; Chen, Yi-Lin; Yap, Glenn P A; Sun, Shih-Sheng; Ong, Tiow-Gan

2012-06-28

This paper describes the synthesis of 1-(pyridine-4-ylmethyl) NHC and their Pd(II) and Ag(I) complexes, which are fully characterized. Interestingly, we have also synthesized a Pd complex 3a-CO(3) using a more direct treatment of K(2)CO(3) with PdCl(2). 3a-CO(3) represents the first reported solid structure of a Pd η(2)-carbonato complex stabilized by an NHC framework. 3a-CO(3) can be easily converted to a PdCl(2) derivative by treating it with chloroform. We have found these palladium complexes mediate the Heck-Mizoroki coupling with a low catalyst loading. Furthermore, we also expand such catalytic manifold toward constructing fused polyaromatic substrates, a highly useful class of compounds in optoelectronic chemistry.

Ortho and parahydrogen in interstellar material

NASA Technical Reports Server (NTRS)

Reeves, R. R.; Harteck, P.

1979-01-01

The ortho/para molecular hydrogen ratio in the interstellar medium is considered. It is shown that the ortho/para ratio will be 3:1 in practically all chemical reactions, even at relatively low temperatures. Two examples of exothermic processes that will result in the formation of a 3:1 ortho:para ratio, corresponding to a high-temperature equilibrium, are examined: H2 formation via three-body or surface recombination and catalytic recombination involving electrons and H(-) ions. Gas-phase scrambling ion reactions are also discussed, and it is suggested that virtually all the H2 equilibrated via scrambling reactions involving H(+) and H3(+) ions should exist as parahydrogen in the J ? 0 quantum state. Arguments are given that deuterium cannot interfere with the long scrambling chain that results in parahydrogen formation.

Chemical mechanism of the Gram stain and synthesis of a new electron-opaque marker for electron microscopy which replaces the iodine mordant of the stain.

PubMed Central

Davies, J A; Anderson, G K; Beveridge, T J; Clark, H C

1983-01-01

Crystal violet (hexamethyl-para-rosaniline chloride) interacts with aqueous KI-I2 during the Gram stain via a simple metathetical anion exchange to produce a chemical precipitate. There is an apparent 1:1 stoichiometry between anion (I-) and cation (hexamethyl-para-rosaniline+) during the reaction and, since the small chloride anion is replaced by the bulkier iodide, the complex formed becomes insoluble in water. It is this same precipitate which forms in the cellular substance of bacteria (both gram-positive and gram-negative types) and which initiates the Gram reaction. Potassium trichloro(eta 2-ethylene)-platinum(II), as an electronopaque marker for electron microscopy, was chemically synthesized, and it produced an anion in aqueous solution which was compatible with crystal violet for the Gram stain. It interacted with crystal violet in a similar manner as iodide to produce an insoluble complex which was chemically and physically analogous to the dye-iodide precipitate. This platinum anion therefore allows the Gram staining mechanism to be followed by electron microscopy. Images PMID:6195147

New maser emission from nonmetastable ammonia in NGC 7538. IV. Coincident masers in adjacent states of para-ammonia

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

Hoffman, Ian M.; Joyce, Spenser A., E-mail: ihoffman@wittenberg.edu

We present the first detection of para-ammonia masers in NGC 7538: multiple epochs of observation of the {sup 14}NH{sub 3} (J, K) = (10, 8) and (9,8) lines. We detect both thermal absorption and nonthermal emission in the (10,8) and (9,8) transitions and the absence of a maser in the (11,8) transition. The (9,8) maser is observed to increase in intensity by 40% over six months. Using interferometric observations with a synthesized beam of 0.''25, we find that the (10,8) and (9,8) masers originate at the same sky position near IRS 1. With strong evidence that the (10,8) and (9,8)more » masers arise in the same volume, we discuss the application of pumping models for the simultaneous excitation of nonmetastable (J > K) para-ammonia states having the same value of K and consecutive values of J. We also present detections of thermal absorption in rotational states ranging in energy from E/k{sub B} ∼ 200 K to 2000 K, and several non-detections in higher-energy states. In particular, we describe the populations in eight adjacent rotational states with K = 6, including two maser transitions, along with the implications for ortho-ammonia pumping models. An existing torus model for molecular gas in the environment of IRS 1 has been applied to the masers; a variety of maser species are shown to agree with the model. Historical and new interferometric observations of {sup 15}NH{sub 3} (3,3) masers in the region indicate a precession of the rotating torus at a rate comparable to continuum-emission-based models of the region. We discuss the general necessity of interferometric observations for diagnosing the excitation state of the masers and for determining the geometry of the molecular environment.« less

Validated spectroscopic methods for determination of anti-histaminic drug azelastine in pure form: Analytical application for quality control of its pharmaceutical preparations

NASA Astrophysics Data System (ADS)

El-Masry, Amal A.; Hammouda, Mohammed E. A.; El-Wasseef, Dalia R.; El-Ashry, Saadia M.

2018-02-01

Two simple, sensitive, rapid, validated and cost effective spectroscopic methods were established for quantification of antihistaminic drug azelastine (AZL) in bulk powder as well as in pharmaceutical dosage forms. In the first method (A) the absorbance difference between acidic and basic solutions was measured at 228 nm, whereas in the second investigated method (B) the binary complex formed between AZL and Eosin Y in acetate buffer solution (pH 3) was measured at 550 nm. Different criteria that have critical influence on the intensity of absorption were deeply studied and optimized so as to achieve the highest absorption. The proposed methods obeyed Beer's low in the concentration range of (2.0-20.0 μg·mL- 1) and (0.5-15.0 μg·mL- 1) with % recovery ± S.D. of (99.84 ± 0.87), (100.02 ± 0.78) for methods (A) and (B), respectively. Furthermore, the proposed methods were easily applied for quality control of pharmaceutical preparations without any conflict with its co-formulated additives, and the analytical results were compatible with those obtained by the comparison one with no significant difference as insured by student's t-test and the variance ratio F-test. Validation of the proposed methods was performed according the ICH guidelines in terms of linearity, limit of quantification, limit of detection, accuracy, precision and specificity, where the analytical results were persuasive. The absorption spectrum of AZL (16 μg·mL- 1) in 0.1 M HCl. The absorption spectrum of AZL (16 μg·mL- 1) in 0.1 M NaOH. The difference absorption spectrum of AZL (16 μg·mL- 1) in 0.1 M NaOH vs 0.1 M HCl. The absorption spectrum of eosin binary complex with AZL (10 μg·mL- 1).

Quantum structural fluctuation in para-hydrogen clusters revealed by the variational path integral method

NASA Astrophysics Data System (ADS)

Miura, Shinichi

2018-03-01

In this paper, the ground state of para-hydrogen clusters for size regime N ≤ 40 has been studied by our variational path integral molecular dynamics method. Long molecular dynamics calculations have been performed to accurately evaluate ground state properties. The chemical potential of the hydrogen molecule is found to have a zigzag size dependence, indicating the magic number stability for the clusters of the size N = 13, 26, 29, 34, and 39. One-body density of the hydrogen molecule is demonstrated to have a structured profile, not a melted one. The observed magic number stability is examined using the inherent structure analysis. We also have developed a novel method combining our variational path integral hybrid Monte Carlo method with the replica exchange technique. We introduce replicas of the original system bridging from the structured to the melted cluster, which is realized by scaling the potential energy of the system. Using the enhanced sampling method, the clusters are demonstrated to have the structured density profile in the ground state.

Quantum structural fluctuation in para-hydrogen clusters revealed by the variational path integral method.

PubMed

Miura, Shinichi

2018-03-14

In this paper, the ground state of para-hydrogen clusters for size regime N ≤ 40 has been studied by our variational path integral molecular dynamics method. Long molecular dynamics calculations have been performed to accurately evaluate ground state properties. The chemical potential of the hydrogen molecule is found to have a zigzag size dependence, indicating the magic number stability for the clusters of the size N = 13, 26, 29, 34, and 39. One-body density of the hydrogen molecule is demonstrated to have a structured profile, not a melted one. The observed magic number stability is examined using the inherent structure analysis. We also have developed a novel method combining our variational path integral hybrid Monte Carlo method with the replica exchange technique. We introduce replicas of the original system bridging from the structured to the melted cluster, which is realized by scaling the potential energy of the system. Using the enhanced sampling method, the clusters are demonstrated to have the structured density profile in the ground state.

An NMR study of cobalt-catalyzed hydroformylation using para-hydrogen induced polarisation.

PubMed

Godard, Cyril; Duckett, Simon B; Polas, Stacey; Tooze, Robert; Whitwood, Adrian C

2009-04-14

The syntheses of Co(eta3-C3H5)(CO)2PR2R' (R, R' = Ph, Me; R, R' = Me, Ph; R = R' = Ph, Cy, CH2Ph) and Co(eta3-C3H5)(CO)(L) (L = dmpe and dppe) are described, and X-ray structures for Co(eta3-C3H5)(CO)(dppe) and the PPh2Me, PCy3 derivatives reported. The relative ability of Co(eta3-C3H5)(CO)2(PR2R') to exchange phosphine for CO follows the trend PMe2Ph < PPh2Me < PCy3 < P(CH2Ph)3 < PPh3. Reactions of the allyl complexes with para-hydrogen (p-H2) lead to the observation of para-hydrogen induced polarisation (PHIP) in both liberated propene and propane. Reaction of these complexes with both CO and H2 leads to the detection of linear acyl containing species Co(COCH2CH2CH3)(CO)3(PR2R') and branched acyl complexes Co(COCH(CH3)2)(CO)3(PR2R') via the PHIP effect. In the case of PPh2Me, additional signals for Co(COCH2CH2CH3)(CO)2(PPh2Me)(propene) and Co(COCH(CH3)2)(CO)2(PPh2Me)(propene) are also detected. When the reactions of H2 and diphenylacetylene are studied with the same precursor, Co(CO)3(PPh2Me)(CHPhCH2Ph) is seen. Studies on how the appearance and ratio, of the PHIP enhanced signals vary as a function of reaction temperature and H2 : CO ratio are reported. These profiles are used to learn about the mechanism of catalysis and reveal how the rates of key steps leading to linear and branched hydroformylation products vary with the phosphine. These data also reveal that the PMe2Ph and PPh2Me based systems yield the highest selectivity for linear hydroformylation products.

Arenium ions are not obligatory intermediates in electrophilic aromatic substitution

PubMed Central

Galabov, Boris; Koleva, Gergana; Simova, Svetlana; Hadjieva, Boriana; Schaefer, Henry F.; Schleyer, Paul von Ragué

2014-01-01

Our computational and experimental investigation of the reaction of anisole with Cl2 in nonpolar CCl4 solution challenges two fundamental tenets of the traditional SEAr (arenium ion) mechanism of aromatic electrophilic substitution. Instead of this direct substitution process, the alternative addition–elimination (AE) pathway is favored energetically. This AE mechanism rationalizes the preferred ortho and para substitution orientation of anisole easily. Moreover, neither the SEAr nor the AE mechanisms involve the formation of a σ-complex (Wheland-type) intermediate in the rate-controlling stage. Contrary to the conventional interpretations, the substitution (SEAr) mechanism proceeds concertedly via a single transition state. Experimental NMR investigations of the anisole chlorination reaction course at various temperatures reveal the formation of tetrachloro addition by-products and thus support the computed addition–elimination mechanism of anisole chlorination in nonpolar media. The important autocatalytic effect of the HCl reaction product was confirmed by spectroscopic (UV-visible) investigations and by HCl-augmented computational modeling. PMID:24972792

Excitation Localization/Delocalization Isomerism in a Strongly Coupled Covalent Dimer of 1,3-Diphenylisobenzofuran

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

Schrauben, Joel N.; Akdag, Akin; Wen, Jin

Two isomers of both the lowest excited singlet (S1) and triplet (T1) states of the directly para, para'-connected covalent dimer of the singlet-fission chromophore 1,3-diphenylisobenzofuran have been observed. In one isomer, excitation is delocalized over both halves of the dimer, and in the other, it is localized on one or the other half. For a covalent dimer in solution, such 'excitation isomerism' is extremely rare. The vibrationally relaxed isomers do not interconvert, and their photophysical properties, including singlet fission, differ significantly.

What Providers Should Know about Child Care Assistance for Families: A Targeted Effort to Reach Hispanic Families and Providers = Lo que Deben Saber los Proveedores Sobre el Programa de Ayuda de Cuidado Infantil para las Familias: Un Esfuerzo Especial para Alcanzar Familias y Proveedores Hispanos

ERIC Educational Resources Information Center

Child Care Bureau, 2004

2004-01-01

Federal and State governments can help families pay for child care. The families one serves may be eligible for this assistance, and one may receive this funding for services one provides, thus becoming a "participating provider." This paper provides answers to the following questions: (1) How can parents receive child care assistance?; (2) How do…

Numerical prediction of wall temperatures for near-critical para-hydrogen in turbulent upflow inside vertical tubes

NASA Technical Reports Server (NTRS)

Bellmore, C. P.; Reid, R. L.

1980-01-01

Presented herein is a method of including density fluctuations in the equations of turbulent transport. Results of a numerical analysis indicate that the method may be used to predict heat transfer for the case of near-critical para-hydrogen in turbulent upflow inside vertical tubes. Wall temperatures, heat transfer coefficients, and velocities obtained by coupling the equations of turbulent momentum and heat transfer with a perturbed equation of state show good agreement with experiment for inlet reduced pressures of 1.28-5.83.

Guide for Migrants in the State of Illinois = Guia para Migrantes en el Estado de Illinois.

ERIC Educational Resources Information Center

Langemach, Sharon; Koepplinger, Jessica

Prepared for migrant farmworkers traveling in the State of Illinois, the booklet, written in English and Spanish, provides basic information on (1) employment conditions--requirements of crew leaders and employers, deductions from wages, and laws regulating child labor; (2) housing--conditions of the camp grounds and of living units; (3)…

Rotationally inelastic cross sections, rates and cooling times for para-H2 +, ortho-D2 + and HD+ in cold helium gas

NASA Astrophysics Data System (ADS)

Vera, Mario Hernández; Schiller, Stephan; Wester, Roland; Gianturco, Francesco Antonio

2017-05-01

In the present work we discuss the dynamical processes guiding the relaxation of the internal rotational energy of three diatomic ions, the para-H2+, the ortho-D2+ and the HD+ in collision with He atoms. The state-changing cross sections and rates for these Molecular Hydrogen Ions (MHIs) are obtained from Close Coupling quantum dynamics calculations and the decay times into their respective ground states are computed by further solving the relevant time-evolution equations. The comparison of the results from the three molecules allows us to obtain a detailed understanding, and a deep insight, on the relative efficiencies of the relaxation processes considered. Contribution to the Topical Issue "Dynamics of Molecular Systems (MOLEC 2016)", edited by Alberto Garcia-Vela, Luis Banares and Maria Luisa Senent.

Prevalence and risk factors associated with goat gastrointestinal helminthiasis in the Sertão region of Paraíba State, Brazil.

PubMed

Vieira, Vanessa Diniz; Feitosa, Thais Ferreira; Vilela, Vinícius Longo Ribeiro; Azevedo, Sérgio Santos; de Almeida Neto, João Leite; de Morais, Dayana Firmino; Ribeiro, Ana Raquel Carneiro; Athayde, Ana Célia Rodrigues

2014-02-01

Gastrointestinal helminthiasis represents an obstacle to goat raising, causing severe damage to herds such as growth retardation, weight loss, and even death. In this study, we aimed to determine the prevalence and risk factors associated to goat gastrointestinal helminthiasis in the Sertão region of Paraíba State, Brazil. A total of 256 goats from 54 farms were systematically sampled. Blood and fecal samples were collected from each animal for egg per gram (EPG), larval culture, and packed cell volume (PCV) analyses. We found that 79.3% of the goats investigated were parasitized with gastrointestinal helminths. Significant correlation (p = 0.004) was observed between the EPG and PCV of the animals studied, and it was observed that the EPG increases as the PCV decreases. In the larval culture, the most prevalent helminth was Haemonchus sp. (83.2%). Age and sex were significant variables (p ≤ 0.20) for the development of gastrointestinal helminths: 86.8% of animals over 36 months of age and 81.7% of females were infected. The variable type of animal exploitation was also significant, with 90.3% (p ≤ 0.20) of the animals presenting double suitability (milk and meat). The Sertão region of Paraíba State presents high prevalence of gastrointestinal helminthiasis in goats, and age and type of animal exploitation are the most relevant risk factors to the development of these parasites.

Accidents caused by Bothrops and Bothropoides in the State of Paraiba: epidemiological and clinical aspects.

PubMed

Oliveira, Fagner Neves; Brito, Monalisa Taveira; Morais, Isabel Cristina Oliveira de; Fook, Sayonara Maria Lia; Albuquerque, Helder Neves de

2010-01-01

Bothrops and Bothropoides snakes cause 70% of the ophidic accidents in Brazil. The species that cause ophidic accidents in State of Paraíba are Bothropoides erythromelas, Bothrops leucurus and Bothropoides neuwiedi. This is a prospective and transverse study, following a quantitative approach of accidents involving Bothrops and Bothropoides admitted to the Toxicological Assistance and Information Centers of Campina Grande and João Pessoa (Ceatox-CG and Ceatox-JP), aimed at identifying the epidemiological and clinical profile of such accidents. All of the patients admitted had medical diagnoses and were monitored at Ceatox-CG or Ceatox-JP. The genera Bothrops and Bothropoides caused 91.7% of the ophidic accidents reported. Snake bites were frequent in men (75.1%), rural workers (65.1%), literate individuals (69%) between 11 and 20 years-old (21.7%), and toes the most common area attacked (52.7%). Most (86.6%) patients were admitted within 6 hours after the accident/bite, with a predominance of mild cases (64.6%). The annual occurrence in Paraíba was 5.5 accidents/100,000 inhabitants and lethality was 0.2%. Positive changes in the profiles of these accidents were verified, such as the non-application of inadequate solutions, including the use of tourniquet, coffee grounds, garlic, suction and/or cutting the bitten area. Moreover, the Itinerant Laboratory project, linked to Paraíba State University in partnership with Ceatox-CG, has contributed positively, providing several cities of the state with information regarding the prevention of accidents involving venomous animals. The local press has also contributed, reporting the educational work developed by the centers.

Consistent assignment of the vibrations of symmetric and asymmetric para-disubstituted benzene molecules

NASA Astrophysics Data System (ADS)

Andrejeva, Anna; Gardner, Adrian M.; Tuttle, William D.; Wright, Timothy G.

2016-03-01

We give a description of the phenyl-ring-localized vibrational modes of the ground states of the para-disubstituted benzene molecules including both symmetric and asymmetric cases. In line with others, we quickly conclude that the use of Wilson mode labels is misleading and ambiguous; we conclude the same regarding the related ones of Varsányi. Instead we label the modes consistently based upon the Mulliken (Herzberg) method for the modes of para-difluorobenzene (pDFB). Since we wish the labelling scheme to cover both symmetrically- and asymmetrically-substituted molecules, we apply the Mulliken labelling under C2v symmetry. By studying the variation of the vibrational wavenumbers with mass of the substituent, we are able to identify the corresponding modes across a wide range of molecules and hence provide consistent assignments. Particularly interesting are pairs of vibrations that evolve from in- and out-of-phase motions in pDFB to more localized modes in asymmetric molecules. We consider the para isomers of the following: the symmetric dihalobenzenes, xylene, hydroquinone, the asymmetric dihalobenzenes, halotoluenes, halophenols and cresol.

Cybersecurity threats to satellite communications: Towards a typology of state actor responses

NASA Astrophysics Data System (ADS)

Housen-Couriel, Deborah

2016-11-01

Cybersecurity threats to satellite communications are a relatively new phenomenon, yet have quickly come to the forefront of concern for the sustainability of satellite systems due to the vulnerabilities that such threats may exploit and negatively impact. These vulnerabilities are mission-critical: they include launch systems, communications, telemetry, tracking and command, and mission completion. They and other aspects of satellite communications depend heavily on secure and resilient cyber capabilities for all stages of the satellite's lifespan. Because of the inherently global nature of both satellite and cyberspace activities, these capabilities rely significantly on international cooperation for setting a baseline of agreed legal norms that protect satellites and satellite communications. This critical cooperation is relevant during all mission phases, from planning to final wrap-up. Under optimal circumstances, the norms and standards protecting satellites and satellite transmissions are developed and enforced by those nation-state actors that are committed to system operability and overall mission sustainability for those satellites launched under their aegis and responsibility. However, when breaches of international law do occur in the form of hostile cyber events that cause damage to satellite communications, a range of measures should be available to the victim state, provided by the appropriate legal regime or regimes. This article proposes that a comprehensive and integrative multi-stakeholder review be undertaken in the near future of the measures available under international law for responding to hostile acts directed at satellite systems and communications, in a manner that takes into account both existing regimes of international law reviewed herein, as well as considerations of cybersecurity. These measures will depend upon the characterization of hostile interference with satellite transmissions in accordance with a proposed typology of hostile events. At present, four key normative international law regimes influence the types of measures that may be undertaken by states: the UN Charter's collective security regime; space law (governing the launching of objects and their space activities, including liability for damages); global telecommunications law (governing data transmissions and protection of infrastructures); and the substantive law relating to transborder freedom of information. Moreover, the nascent normative framework that will eventually apply to state and non-state activities in cyberspace will also be relevant to satellite communications, although it has been largely excluded from analyses and studies. In summary, this article proposes a typology of hostile events, both kinetic and cyber-enabled, that are liable to disrupt satellite communications; and it reviews the four key relevant legal regimes and notes the challenges of nascent cybersecurity law on the international plane. The article concludes by advocating for the establishment of a framework for effective elucidation of appropriate legal remedies at the international level in responding to kinetic, virtual and hybrid threats and hostile disruptions to satellite communications. ASAT of various types, including hostile interference with satellite transmissions, has also been treated as a critical issue in the context of the increasing militarization of space, as addressed under the auspices of the United Nations' Office for Outer Space Affairs (UNOOSA) and Office for Disarmament Affairs (UNODA). For example, in the 2013 Report of the UN Group of Governmental Experts on Transparency and Confidence-Building Measures in Outer Space Activities (herein, "GGE") it was noted that the outer space environment is becoming "…increasingly congested, contested and competitive. In the context of international peace and security, there is growing concern that threats to vital space capabilities may increase during the next decade as a result of both natural and man-made hazards and the possible development of disruptive and destructive counterspace capabilities" [14].Ongoing work under the auspices of UN bodies and other intergovernmental organizations regarding the developing parameters of outer space governance has in recent years sharpened the understanding that a new, unified approach is needed [15]. The underlying assumption of this article is that international law has a key role to play in articulating these "rules of the road" for the activities of state actors relating to satellites, including the imposition of realistic and effective sanctions for those states that do not uphold and implement the applicable legal norms. Yet the additional and relatively unexplored issue of the application of international law to state activities in cyberspace is a relevant legal consideration that also needs to be weighed in evaluating the range of possible state responses to hostile disruption of satellite communications. This consideration is largely absent from existing intergovernmental initiatives regarding outer space governance [16]. Thus, the incorporation of cybersecurity considerations will be an important element of the analysis of harmful interference to satellite transmissions in light of the four regimes reviewed below. Thus, space law imposes upon states the responsibility for actions carried out by satellites under their jurisdiction and control, and duly attributable to them under international law. These actions may include physical damage caused by the creation of space debris that inflicts physical harm to other satellites.The full regime establishing responsibility and stipulating damages is set out in the Liability Convention, which elaborates on OST Article VII. The degree of liability incurred under particular circumstances is stipulated in the Liability Convention's Articles II through VI. For instance, Article II establishes absolute liability "for damage caused by [the launching state's] space object on the surface of the earth or to aircraft flight" [38]. This liability requires, for example, payment of compensation to the injured state when certain criteria have been met. In outer space, state liability must be established in accordance with the provisions of Liability Convention Articles II and IV. For these purposes, "damage" is defined as: "… [the] loss of life, personal injury or other impairment of health; or loss of or damage to property of States or of persons, natural or juridical, or property of international intergovernmental organizations" [39].There remains an open question of the applicability of the Liability Convention to satellite transmissions that are subject to hostile disruption through solely virtual means. A recent Draft Report of the Chair of the COPOUS Working Group on the Status and Application of the Five United Nations Treaties on Outer Space raised the question of expanding the scope of states' international responsibility and liability under this Convention [40]. The European Union's 2014 Draft Code of Conduct also formulates a broad approach, advocating "…the freedom for all States, in accordance with international law and obligations, to access, to explore, and to use outer space for peaceful purposes without harmful interference, fully respecting the security, safety and integrity of space objects…" [41]. It specifically endorses improving states' adherence to, and implementation of, ITU regulations addressing harmful radio-frequency interference [42].It is proposed here that a reasonable interpretation of Article VII might also include damage caused virtually by hostile disruption to satellite transmissions, whether by space debris or otherwise [43]. The Convention's concept of "loss or damage to property" would entail a determination that transmissions and the data they transmit constitute the "property" of a state or private entity the activity of which is attributable to a state. It is contended that this is not an unreasonable extension of the scope of the Convention, especially given the high commercial and financial value of many such transmissions. There is also precedent for such an approach, as in the application of the WIPO Convention to satellite transmissions, which it views as assets capable of bearing proprietary rights [44]. Moreover, commercial satellite operators and satellite consortia, such as International Maritime Satellite Organization (IMSO), are bound to provisions within their conventional regimes that require compensation when client transmissions are interrupted, distorted or otherwise damaged [45].In summary, the application of space law to the disruption of satellite transmissions may be characterized as follows. The determinative point of departure for space law is general international law, including the UN Charter and its regime of collective security. Although states may not claim sovereignty over particular territories in outer space, including the moon and other celestial bodies, satellites do remain under the sovereignty and the responsibility of the launching state or states. These legal principles are established in the OST, which also provides (together with the Liability Convention) for the liability of states for damage caused by satellites throughout the satellite's life span. In this author's view, the definition of "damage", crucial to the application of the Liability Convention, may be understood to include injuries caused by either kinetic or virtual means, including damage caused through and in cyberspace. More controversial is the question of whether satellite transmissions may be considered "property" under the Liability Convention, together with the applicable commercial satellite agreement, and are covered by its provisions. It is proposed that certain satellite transmissions are in fact subject to the Liability Convention as "property" and are protected by its provisions. Nonetheless, state practice regarding the issue is currently lacking, as it is, to a lesser degree, regarding liability for the clearer case of physical damage to satellites [46].

Human COQ9 Rescues a coq9 Yeast Mutant by Enhancing Coenzyme Q Biosynthesis from 4-Hydroxybenzoic Acid and Stabilizing the CoQ-Synthome

PubMed Central

He, Cuiwen H.; Black, Dylan S.; Allan, Christopher M.; Meunier, Brigitte; Rahman, Shamima; Clarke, Catherine F.

2017-01-01

Coq9 is required for the stability of a mitochondrial multi-subunit complex, termed the CoQ-synthome, and the deamination step of Q intermediates that derive from para-aminobenzoic acid (pABA) in yeast. In human, mutations in the COQ9 gene cause neonatal-onset primary Q10 deficiency. In this study, we determined whether expression of human COQ9 could complement yeast coq9 point or null mutants. We found that expression of human COQ9 rescues the growth of the temperature-sensitive yeast mutant, coq9-ts19, on a non-fermentable carbon source and increases the content of Q6, by enhancing Q biosynthesis from 4-hydroxybenzoic acid (4HB). To study the mechanism for the rescue by human COQ9, we determined the steady-state levels of yeast Coq polypeptides in the mitochondria of the temperature-sensitive yeast coq9 mutant expressing human COQ9. We show that the expression of human COQ9 significantly increased steady-state levels of yeast Coq4, Coq6, Coq7, and Coq9 at permissive temperature. Human COQ9 polypeptide levels persisted at non-permissive temperature. A small amount of the human COQ9 co-purified with tagged Coq6, Coq6-CNAP, indicating that human COQ9 interacts with the yeast Q-biosynthetic complex. These findings suggest that human COQ9 rescues the yeast coq9 temperature-sensitive mutant by stabilizing the CoQ-synthome and increasing Q biosynthesis from 4HB. This finding provides a powerful approach to studying the function of human COQ9 using yeast as a model. PMID:28736527

Level anti-crossings are a key factor for understanding para-hydrogen-induced hyperpolarization in SABRE experiments.

PubMed

Pravdivtsev, Andrey N; Yurkovskaya, Alexandra V; Vieth, Hans-Martin; Ivanov, Konstantin L; Kaptein, Robert

2013-10-07

Various hyperpolarization methods are able to enhance the sensitivity of nuclear magnetic resonance (NMR) spectroscopy and magnetic resonance imaging (MRI) by several orders of magnitude. Among these methods are para-hydrogen-induced polarization (PHIP) and signal amplification by reversible exchange (SABRE), which exploit the strong nuclear alignment of para-hydrogen. Several SABRE experiments have been reported but, so far, it has not been possible to account for the experimentally observed sign and magnetic-field dependence of substrate polarization. Herein, we present an analysis based on level anti-crossings (LACs), which provides a complete understanding of the SABRE effect. The field-dependence of both net and anti-phase polarization is measured for several ligands, which can be reproduced by the theory. The similar SABRE field-dependence for different ligands is also explained. In general, the LAC concept allows complex spin dynamics to be unraveled, and is crucial for optimizing the performance of novel hyperpolarization methods in NMR and MRI techniques. Copyright © 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.

Conservative nutrient use by big-leaf mahogany (Swietenia macrophylla King) planted under contrasting environmental conditions

Treesearch

E. Medina; E. Cuevas; A.E. Lugo; E. Terezo; J. Jimenez-Osornio; P.A. Macario-Mendoza; P. Montanez

2014-01-01

We analyzed the nutritional composition and isotope ratios (C and N) of big-leaf mahogany (Swietenia macrophylla King) leaves in plantations established on contrasting soils and climates in Central America (State of Quintana Roo, Yucatan, Mexico) and South America (State of Para, Brazil). The objective was to determine the adaptability of this species to large...

Molecular-level understanding of ground- and excited-state O-H...O hydrogen bonding involving the tyrosine side chain: a combined high-resolution laser spectroscopy and quantum chemistry study.

PubMed

Biswal, Himansu S; Bhattacharyya, Surjendu; Wategaonkar, Sanjay

2013-12-16

The present study combines both laser spectroscopy and ab initio calculations to investigate the intermolecular OH⋅⋅⋅O hydrogen bonding of complexes of the tyrosine side chain model chromophore compounds phenol (PH) and para-cresol (pCR) with H2 O, MeOH, PH and pCR in the ground (S0 ) state as well as in the electronic excited (S1 ) state. All the experimental and computational findings suggest that the H-bond strength increases in the S1 state and irrespective of the hydrogen bond acceptor used, the dispersion energy contribution to the total interaction energy is about 10-15 % higher in the S1 state compared to that in the S0 state. The alkyl-substituted (methyl; +I effect) H-bond acceptor forms a significantly stronger H bond both in the S0 and the S1 state compared to H2 O, whereas the aryl-substituted (phenyl; -R effect) H-bond donor shows a minute change in energy compared to H2 O. The theoretical study emphasizes the significant role of the dispersive interactions in the case of the pCR and PH dimers, in particular the CH⋅⋅⋅O and the CH⋅⋅⋅π interactions between the donor and acceptor subunits in controlling the structure and the energetics of the aromatic dimers. The aromatic dimers do not follow the acid-base formalism, which states that the stronger the base, the more red-shifted is the XH stretching frequency, and consequently the stronger is the H-bond strength. This is due to the significant contribution of the dispersion interaction to the total binding energy of these compounds. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Wild birds as pets in Campina Grande, Paraíba State, Brazil: an ethnozoological approach.

PubMed

Licarião, Morgana R; Bezerra, Dandara M M; Alves, Rômulo R N

2013-03-01

Birds are one of the animals most widely used by humans and are highly valued as pets. The present work reports the use of wild birds as pets in the city of Campina Grande, Paraíba State (PB), Brazil. The owners' choice and perceptions of the species ecology was assessed as well. The methodology employed included unstructured and semi-structured interviews, guided tours and direct observations. A total of 26 bird species distributed among ten families and four orders were identified. The most frequently encountered order was Passeriformes (76.9%), with a predominance of the family Emberizidae (34.6%). The specimens kept as pets were principally obtained in public markets or between the breeders themselves. The popularity of birds as pets, compounded by the inefficiency of official controls over the commerce of wild animals has stimulated the illegal capture and breeding of wild birds in Campina Grande.

Child Development: New Diagnoses for the NANDA International.

PubMed

Souza, Juliana Martins de; Cruz, Diná de Almeida Lopes Monteiro da; Veríssimo, Maria De La Ó Ramallo

2018-04-01

The paper proposes new diagnoses on child development (CD) for NANDA International. The study followed the recommended steps of Developmental Processes for NANDA International Nursing Diagnoses. It was a secondary analysis study on the findings of a concept analysis study on CD. A proposal of labels and components of three diagnoses: "Delayed child development," "Risk for delayed child development," and "Readiness for enhanced child development." The proposed diagnoses represent all the complexity of CD. The proposed diagnoses can support nurses in the development of a comprehensive care plan on the health of children. OBJETIVO: propor novos diagnósticos de enfermagem para a NANDA-International que abordem o desenvolvimento infantil. MÉTODO: Este estudo seguiu as etapas recomendadas para o desenvolvimento de diagnósticos de enfermagem da NANDA-International. Foi realizado a partir dos resultados da análise de conceito do termo desenvolvimento infantil. Propostos os títulos e os componentes de três diagnósticos: "Atraso no desenvolvimento infantil," "Risco de atraso no desenvolvimento infantil," e "Disposição para desenvolvimento infantil melhorado." CONCLUSÕES: Os diagnósticos propostos contemplam toda a complexidade do desenvolvimento infantil. IMPLICAÇÕES PARA A PRÁTICA DE ENFERMAGEM: Os novos diagnósticos podem subsidiar o enfermeiro na elaboração de um plano de cuidados integrais à saúde da criança. © 2016 NANDA International, Inc.

Putting Ourselves in the Big Picture: A Sustainable Approach to Project Management for e-Learning

ERIC Educational Resources Information Center

Buchan, Janet

2010-01-01

In a case study of a large Australian university the metaphor of panarchy is used as a means of describing and understanding the complex interrelationships of multi-scale institutional projects and the influences of a variety factors on the potential success of e-learning initiatives. The concept of para-analysis is introduced as a management…

JPRS Report, Science & Technology, Europe

DTIC Science & Technology

1992-02-06

also sunflower and corn oil); bioethanol is produced by fermenting sugars extracted from sugar beets and grains. Regulations limit its share of...Metal Complexes"] [Text] Frankfurt, 16 Oct—The fermentation technology research team of the University of Bielefeld’s School of Engineering is...Frequency of Continuous Operation in Fermentation and Product Recovery" first two para- graphs are VDI NACHRICHTEN introduction] [Text

Charge Transfer Directed Radical Substitution Enables para-Selective C–H Functionalization

PubMed Central

Boursalian, Gregory B.; Ham, Won Seok; Mazzotti, Anthony R.; Ritter, Tobias

2016-01-01

Efficient C–H functionalization requires selectivity for specific C–H bonds. Progress has been made for directed aromatic substitution reactions to achieve ortho- and meta- selectivity, but a general strategy for para-selective C–H functionalization has remained elusive. Herein, we introduce a previously unappreciated concept which enables nearly complete para selectivity. We propose that radicals with high electron affinity elicit areneto-radical charge transfer in the transition state of radical addition, which is the factor primarily responsible for high positional selectivity. We demonstrate that the selectivity is predictable by a simple theoretical tool and show the utility of the concept through a direct synthesis of aryl piperazines. Our results contradict the notion, widely held by organic chemists, that radical aromatic substitution reactions are inherently unselective. The concept of charge transfer directed radical substitution could serve as the basis for the development of new, highly selective C–H functionalization reactions. PMID:27442288

Anomalous heat transfer in two polymorphs of para-bromobenzophenone

NASA Astrophysics Data System (ADS)

Romantsova, O. O.; Horbatenko, Yu. V.; Krivchikov, A. I.; Korolyuk, O. A.; Vdovichenko, G. A.; Zloba, D. I.; Pyshkin, O. S.

2017-03-01

The thermal conductivity of a polycrystalline sample of monoclinic polymorph of para-bromobenzophenone in the T = 3-320 K temperature range was measured using steady-state linear heat flow. The temperature dependences of thermal conductivity are presented as the sum of two independent contributions: a contribution that corresponds to the thermal conductivity of an orientationally ordered crystal structure, and a new additional thermally activated contribution that manifests itself above 130 K. A comparison is made with the data on the thermal conductivity of a single crystal triclinic polymorph of para-bromobenzophenone. It is established that the contribution corresponding to the thermal conductivity of the orientationally ordered crystal structure depends on the molecular crystal packing, and the characteristic activation energy of the thermal activation contribution, which is caused by the intramolecular vibrations of the C-Br bond, does not depend on the grain size or on the structure of the sample.

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.

Charge-transfer-directed radical substitution enables para-selective C-H functionalization

NASA Astrophysics Data System (ADS)

Boursalian, Gregory B.; Ham, Won Seok; Mazzotti, Anthony R.; Ritter, Tobias

2016-08-01

Efficient C-H functionalization requires selectivity for specific C-H bonds. Progress has been made for directed aromatic substitution reactions to achieve ortho and meta selectivity, but a general strategy for para-selective C-H functionalization has remained elusive. Herein we introduce a previously unappreciated concept that enables nearly complete para selectivity. We propose that radicals with high electron affinity elicit arene-to-radical charge transfer in the transition state of radical addition, which is the factor primarily responsible for high positional selectivity. We demonstrate with a simple theoretical tool that the selectivity is predictable and show the utility of the concept through a direct synthesis of aryl piperazines. Our results contradict the notion, widely held by organic chemists, that radical aromatic substitution reactions are inherently unselective. The concept of radical substitution directed by charge transfer could serve as the basis for the development of new, highly selective C-H functionalization reactions.

Remediation of cadmium-contaminated soil by extraction with para-sulphonato-thiacalix[4]arene, a novel supramolecular receptor.

PubMed

Li, Yushuang; Hu, Xiaojun; Song, Xueying; Sun, Tieheng

2012-08-01

Batch extractions were conducted to evaluate the performance of para-sulphonato-thiacalix[4]arene (STC[4]A), a novel supramolecular receptor, for removing cadmium (Cd) from soil. The extraction mechanism was investigated by determination of the conditional stability constants (log K) of the STC[4]A-Cd complex. The influences of various variables were examined, including pH, contact time, and extractant concentration. The Cd extraction efficiency increased with increasing pH, reaching the maximum at pH 11 and then declining at higher pH values. This pH dependence was explained by the variation in the log K value of the STC[4]A-Cd complex along with pH change. When the STC[4]A dose was increased to an STC[4]A:Cd molar ratio of 2.5:1, Cd was exhaustively removed (up to 96.8%). The comparison experiment revealed that the Cd extraction performance of STC[4]A was almost equivalent to that of EDTA and significantly better than that of natural organic acids. STC[4]A extraction could efficiently prevent co-dissolution of soil minerals. Copyright © 2012 Elsevier Ltd. All rights reserved.

Iridium N-Heterocyclic Carbene Complexes as Efficient Catalysts for Magnetization Transfer from para-Hydrogen

PubMed Central

2011-01-01

While the characterization of materials by NMR is hugely important in the physical and biological sciences, it also plays a vital role in medical imaging. This success is all the more impressive because of the inherently low sensitivity of the method. We establish here that [Ir(H)2(IMes)(py)3]Cl undergoes both pyridine (py) loss as well as the reductive elimination of H2. These reversible processes bring para-H2 and py into contact in a magnetically coupled environment, delivering an 8100-fold increase in 1H NMR signal strength relative to non-hyperpolarized py at 3 T. An apparatus that facilitates signal averaging has been built to demonstrate that the efficiency of this process is controlled by the strength of the magnetic field experienced by the complex during the magnetization transfer step. Thermodynamic and kinetic data combined with DFT calculations reveal the involvement of [Ir(H)2(η2-H2)(IMes)(py)2]+, an unlikely yet key intermediate in the reaction. Deuterium labeling yields an additional 60% improvement in signal, an observation that offers insight into strategies for optimizing this approach. PMID:21469642

Iridium N-heterocyclic carbene complexes as efficient catalysts for magnetization transfer from para-hydrogen.

PubMed

Cowley, Michael J; Adams, Ralph W; Atkinson, Kevin D; Cockett, Martin C R; Duckett, Simon B; Green, Gary G R; Lohman, Joost A B; Kerssebaum, Rainer; Kilgour, David; Mewis, Ryan E

2011-04-27

While the characterization of materials by NMR is hugely important in the physical and biological sciences, it also plays a vital role in medical imaging. This success is all the more impressive because of the inherently low sensitivity of the method. We establish here that [Ir(H)(2)(IMes)(py)(3)]Cl undergoes both pyridine (py) loss as well as the reductive elimination of H(2). These reversible processes bring para-H(2) and py into contact in a magnetically coupled environment, delivering an 8100-fold increase in (1)H NMR signal strength relative to non-hyperpolarized py at 3 T. An apparatus that facilitates signal averaging has been built to demonstrate that the efficiency of this process is controlled by the strength of the magnetic field experienced by the complex during the magnetization transfer step. Thermodynamic and kinetic data combined with DFT calculations reveal the involvement of [Ir(H)(2)(η(2)-H(2))(IMes)(py)(2)](+), an unlikely yet key intermediate in the reaction. Deuterium labeling yields an additional 60% improvement in signal, an observation that offers insight into strategies for optimizing this approach.

Rovibrational transitions of H2 by collision with H+ at high temperature

NASA Astrophysics Data System (ADS)

González-Lezana, T.; Honvault, P.

2017-05-01

The H+ + H2 reaction is studied by means of both exact and statistical quantum methods. Integral cross-sections for processes initiated with rotationally excited H2(v, j = 1) to produce molecular hydrogen in its rotational ground state are reported up to a value of the collision energy of 3 eV. Rate constants for state-to-state transitions between different H2 rovibrational states are calculated up to 3000 K. Special emphasis is made on ortho/para conversion processes in which the parity j of the H2(j) states changes.

Molecular epidemiology of livestock rabies viruses isolated in the northeastern Brazilian states of Paraíba and Pernambuco from 2003 - 2009

PubMed Central

2012-01-01

Background Limited or no epidemiological information has been reported for rabies viruses (RABVs) isolated from livestock in the northeastern Brazilian states of Paraíba (PB) and Pernambuco (PE). The aim of this study was to clarify the molecular epidemiology of RABVs circulating in livestock, especially cattle, in these areas between 2003 and 2009. Findings Phylogenetic analysis based on 890 nt of the nucleoprotein (N) gene revealed that the 52 livestock-derived RABV isolates characterized here belonged to a single lineage. These isolates clustered with a vampire bat-related RABV lineage previously identified in other states in Brazil; within PB and PE, this lineage was divided between the previously characterized main lineage and a novel sub-lineage. Conclusions The occurrences of livestock rabies in PB and PE originated from vampire bat RABVs, and the causative RABV lineage has been circulating in this area of northeastern Brazil for at least 7 years. This distribution pattern may correlate to that of a vampire bat population isolated by geographic barriers. PMID:22243739

Records of Bat Flies (Diptera: Nycteribiidae and Streblidae) in the Semi-Arid Caatinga in the State of Paraíba, Northeastern Brazil.

PubMed

Barbier, E; Prado-Neto, J G; Bernard, E

2016-12-01

One of the largest gaps in the knowledge of ectoparasitic flies of the families Nycteribiidae and Streblidae in Brazil is the northeastern region, where most states do not have any record. Here, we present the first records of those two bat fly families for the state of Paraíba. We recorded a total of 10 species of five genera parasitizing eight bat species of four families. Trichobius diphyllae Wenzel (Streblidae) was the most abundant species, found parasitizing Diphylla ecaudata (Phyllostomidae), and T. dugesioides dugesioides Wenzel, the second, found on Trachops cirrhosus (Phyllostomidae). Three species were recorded for the first time in northeastern Brazil and seven species are new for the semi-arid Caatinga. We collected T. galei Wenzel and T. pallidus (Curran) on Natalus macrourus (Natalidae) and Furipterus horrens (Furipteridae), respectively, two endangered bat species, and the species-specific relationship with their hosts points out to some degree of vulnerability. In addition, we present information on host-parasite relationship, and data that extend the known geographic distribution of some species.

Complex educational and care (geron)technology for elderly individuals/families experiencing Alzheimer's disease.

PubMed

Ilha, Silomar; Santos, Silvana Sidney Costa; Backes, Dirce Stein; Barros, Edaiane Joana Lima; Pelzer, Marlene Teda; Costenaro, Regina Gema Santini

2017-01-01

To describe the contributions of the Integrated Multidisciplinary Care Group for Caregivers of Individuals with Alzheimer's Disease as an educational and care (geron)technology in the context of Alzheimer's disease in elderly individuals from the perspective of family members/caregivers. Exploratory, descriptive study with a qualitative approach conducted with 13 family members/caregivers of elderly people participating in the support group of a university institution of the state of Rio Grande do Sul, Brazil. Data collected between January and April 2016 through a semi-structured interview were submitted to discursive textual analysis. Family members/caregivers pointed out education and care as contributions of the group; education for care and for the future; exchange, socialization, and development of knowledge through the range of knowledge existing in the Group. The Group contributes as a (geron)technology of care and education for care in which knowledge is built and applied in practice, supporting the experienced disorders and improving the quality of care provided for elderly individuals with Alzheimer's disease. Descrever as contribuições do Grupo de Assistência Multidisciplinar Integrada aos Cuidadores de Pessoas com a Doença de Alzheimer como (geronto)tecnologia cuidativo-educacional no contexto da doença de Alzheimer em pessoas idosas, na perspectiva de familiares/cuidadores. Pesquisa exploratório-descritiva, qualitativa, realizada com 13 familiares/cuidadores de pessoas idosas, participantes do grupo de apoio de uma instituição universitária do Rio Grande do Sul, Brasil. Os dados coletados entre janeiro a abril/2016, com uma entrevista semiestruturada, foram submetidos à análise textual discursiva. Os familiares/cuidadores referiram como contribuições do Grupo a educação e o cuidado; a educação para o cuidado e para o futuro; a troca, socialização e construção do conhecimento por meio dos diversos saberes existentes no Grupo. O Grupo contribui como (geronto)tecnologia de cuidado e educação para o cuidado; nele, são construídos conhecimentos que, aplicados na prática, auxiliam nas desordens vivenciadas, melhorando o cuidado à pessoa idosa com doença de Alzheimer.

Charge and energy migration in molecular clusters: A stochastic Schrödinger equation approach.

PubMed

Plehn, Thomas; May, Volkhard

2017-01-21

The performance of stochastic Schrödinger equations for simulating dynamic phenomena in large scale open quantum systems is studied. Going beyond small system sizes, commonly used master equation approaches become inadequate. In this regime, wave function based methods profit from their inherent scaling benefit and present a promising tool to study, for example, exciton and charge carrier dynamics in huge and complex molecular structures. In the first part of this work, a strict analytic derivation is presented. It starts with the finite temperature reduced density operator expanded in coherent reservoir states and ends up with two linear stochastic Schrödinger equations. Both equations are valid in the weak and intermediate coupling limit and can be properly related to two existing approaches in literature. In the second part, we focus on the numerical solution of these equations. The main issue is the missing norm conservation of the wave function propagation which may lead to numerical discrepancies. To illustrate this, we simulate the exciton dynamics in the Fenna-Matthews-Olson complex in direct comparison with the data from literature. Subsequently a strategy for the proper computational handling of the linear stochastic Schrödinger equation is exposed particularly with regard to large systems. Here, we study charge carrier transfer kinetics in realistic hybrid organic/inorganic para-sexiphenyl/ZnO systems of different extension.

Charge and energy migration in molecular clusters: A stochastic Schrödinger equation approach

NASA Astrophysics Data System (ADS)

Plehn, Thomas; May, Volkhard

2017-01-01

The performance of stochastic Schrödinger equations for simulating dynamic phenomena in large scale open quantum systems is studied. Going beyond small system sizes, commonly used master equation approaches become inadequate. In this regime, wave function based methods profit from their inherent scaling benefit and present a promising tool to study, for example, exciton and charge carrier dynamics in huge and complex molecular structures. In the first part of this work, a strict analytic derivation is presented. It starts with the finite temperature reduced density operator expanded in coherent reservoir states and ends up with two linear stochastic Schrödinger equations. Both equations are valid in the weak and intermediate coupling limit and can be properly related to two existing approaches in literature. In the second part, we focus on the numerical solution of these equations. The main issue is the missing norm conservation of the wave function propagation which may lead to numerical discrepancies. To illustrate this, we simulate the exciton dynamics in the Fenna-Matthews-Olson complex in direct comparison with the data from literature. Subsequently a strategy for the proper computational handling of the linear stochastic Schrödinger equation is exposed particularly with regard to large systems. Here, we study charge carrier transfer kinetics in realistic hybrid organic/inorganic para-sexiphenyl/ZnO systems of different extension.

Gravimetric and magnetic fabric study of the Sintra Igneous complex: laccolith-plug emplacement in the Western Iberian passive margin

NASA Astrophysics Data System (ADS)

Terrinha, Pedro; Pueyo, Emilio L.; Aranguren, Aitor; Kullberg, José Carlos; Kullberg, Maria Carla; Casas-Sainz, Antonio; Azevedo, Maria do Rosário

2017-12-01

The geometry and emplacement of the 96 km2, Late Cretaceous Sintra Igneous complex (SIC, ca. 80 Ma) into the West Iberian passive margin is presented, based on structural data, gravimetric modeling, and magnetic fabrics. A granite laccolith ( 76 km2, < 1 km thick, according to gravimetric modeling) surrounds a suite of gabbro-diorite-syenite plugs ( 20 km2, 4 km deep) and is encircled by cone sheets and radial dykes. Anisotropy of Magnetic Susceptibility was interpreted from 54 sites showing fabrics of para- and ferro-magnetic origin. Most fabrics can be interpreted to have a magmatic origin, according to the scarcity of solid-state deformation in most part of the massif. Magnetic foliations are shallowly dipping in the granite laccolith and contain a sub-horizontal ENE-WSW lineation. The gabbro-syenite body displays concentric magnetic foliations having variable dips and steeply-plunging lineations. The SIC can be interpreted to be intruded along an NNW-SSE, 200 km-long fault, perpendicular to the magnetic lineation within the laccolith, and was preceded by the intrusion of basic sills and plugs. The SIC intruded the Mesozoic series of the Lusitanian Basin during the post-rift, passive margin stage, and its geometry was only slightly modified during the Paleogene inversion that resulted in thrusting of the northern border of the intrusion over the country rocks.

Bienvenido a los Estados Unidos. Una Guia para Refugiados (Welcome to the United States. A Guide for Refugees). First Edition.

ERIC Educational Resources Information Center

Economic and Social Research Council, Edinburgh (Scotland). Centre for Educational Sociology.

This guidebook provides Spanish-speaking refugees being resettled in the United States with general information about what they will encounter and the services they can receive in their first months in the country. This is the Spanish version, and is available in several other languages. The book is distributed to overseas processing agencies,…

El Estado de la Educacion para los Hispanos en los Estados Unidos (The Condition of Education for Hispanics in the United States).

ERIC Educational Resources Information Center

Brown, George H.; And Others

Organized into 4 chapters, the report provides tabular data portraying the educational condition for about 12 million Hispanic Americans in the United States, and shows how Hispanics compare with the majority population on various measures of educational participation and achievement. Providing an overview of Hispanic Americans in the U.S.,…

TOPOGRAPHIC VIEW THE STATE FORESTER'S COMPLEX, VIEW LOOKING SOUTH FROM ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

TOPOGRAPHIC VIEW THE STATE FORESTER'S COMPLEX, VIEW LOOKING SOUTH FROM STATE STREET, WITH THE NATIONAL REGISTER-LISTED OREGON STATE FORESTER'S OFFICE BUILDING TO THE LEFT OF VIEW. - Oregon State Forester's Office Complex, 2600 State Street, Salem, Marion, OR

Sheep gastrointestinal helminthiasis in the Sertão region of Paraíba State, Northeastern Brazil: prevalence and risk factors.

PubMed

Vieira, Vanessa Diniz; Vilela, Vinícius Longo Ribeiro; Feitosa, Thais Ferreira; Athayde, Ana Célia Rodrigues; Azevedo, Sérgio Santos; Souto, Diego Vagner de Oliveira; Silveira, Gian Libânio da; Melo, Lídio Ricardo Bezerra de

2014-01-01

In this study, we aimed to establish the prevalence and risk factors relating to gastrointestinal helminthiasis, and to characterize the sanitary management practiced among sheep herds in the Sertão region of the state of Paraíba, northeastern Brazil, based on factors that condition the ways of controlling these parasites in these herds. The research was carried out between April and July 2012. We visited 54 farms, where fecal and blood samples were individually collected from 465 animals. On each farm, a questionnaire was applied to gather information on variables relating to potential risk factors. The prevalence of sheep gastrointestinal helminthiasis in the region was 75.9%. At least one animal tested positive for this helminthiasis on 53 (98.1%) of the 54 farms evaluated. The eggs per gram of feces (EPG) analysis showed the following infection burdens: 51.8% with mild infection, 27.1% moderate infection, 9.9% heavy infection and 11.2% fatal infection. Among the sheep farms visited, anthelmintics were used on 81.5% (p <0.05). The most relevant risk factor in this study was the farm area, because it defines the area available for grazing animals. Properties with many animals and little pasture area, which are the most abundant type in the Sertão region of Paraíba, tend to have high prevalence of gastrointestinal helminthiasis, because the animals are more prone to reinfection. The Sertão region of Paraíba presents high prevalence of gastrointestinal helminthiasis among sheep, and the farm area is the most relevant risk factor for the development of these parasites.

Structural Analysis of Charge Discrimination in the Binding of Inhibitors to Human Carbonic Anhydrases I and II

PubMed Central

Srivastava, D. K.; Jude, Kevin M.; Banerjee, Abir L.; Haldar, Manas; Manokaran, Sumathra; Kooren, Joel; Mallik, Sanku; Christianson, David W.

2008-01-01

Despite the similarity in the active site pockets of carbonic anhydrase (CA) isozymes I and II, the binding affinities of benzenesulfonamide inhibitors are invariably higher with CA II as compared to CA I. To explore the structural basis of this molecular recognition phenomenon, we have designed and synthesized simple benzenesulfonamide inhibitors substituted at the para position with positively-charged, negatively-charged, and neutral functional groups, and we have determined the affinities and X-ray crystal structures of their enzyme complexes. The para-substituents are designed to bind in the midsection of the 15 Å deep active site cleft, where interactions with enzyme residues and solvent molecules are possible. We find that a para-substituted positively-charged amino group is more poorly tolerated in the active site of CA I compared with CA II. In contrast, a para-substituted negatively-charged carboxylate substituent is tolerated equally well in the active sites of both CA isozymes. Notably, enzyme-inhibitor affinity increases upon neutralization of inhibitor charged groups by amidation or esterification. These results inform the design of short molecular linkers connecting the benzenesulfonamide group and a para-substituted tail group in “two-prong” CA inhibitors: an optimal linker segment will be electronically neutral, yet capable of engaging in at least some hydrogen bond interactions with protein residues and/or solvent. Microcalorimetric data reveal that inhibitor binding to CA I is enthalpically less favorable and entropically more favorable than inhibitor binding to CA II. This contrasting behavior may arise in part from differences in active site desolvation and the conformational entropy of inhibitor binding to each isozyme active site. PMID:17407288

TOPOGRAPHIC VIEW OF THE STATE FORESTER'S COMPLEX, VIEW LOOKING SOUTHWEST ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

TOPOGRAPHIC VIEW OF THE STATE FORESTER'S COMPLEX, VIEW LOOKING SOUTHWEST FROM STATE STREET, WITH THE K.O.G BUILDING (KEEP OREGON GREEN) IN THE FOREGROUND. - Oregon State Forester's Office Complex, 2600 State Street, Salem, Marion, OR

Exploring the palladium- and platinum-bis(pyridine) complex motif by NMR spectroscopy, X-ray crystallography, (tandem) mass spectrometry, and isothermal titration calorimetry: do substituent effects follow chemical intuition?

PubMed

Weilandt, Torsten; Löw, Nora L; Schnakenburg, Gregor; Daniels, Jörg; Nieger, Martin; Schalley, Christoph A; Lützen, Arne

2012-12-21

A series of ten palladium-bis(pyridine) complexes, as well as their corresponding platinum complexes, have been synthesized. The pyridine ligands in each series carried different σ-donor and/or π-acceptor/donor substituents at the para-position of their pyridine rings. These complexes were analysed by NMR spectroscopy, X-ray crystallography, (tandem) MS, and isothermal titration calorimetry (ITC) to validate whether these methods allowed us to obtain a concise and systematic picture of the relative and absolute thermodynamic stabilities of the complexes, as determined by the electronic effects of the substituents. Interestingly, the NMR spectroscopic data hardly correlated with the expected substituent effects but the heteronuclear platinum-phosphorus coupling constants did. Crystallographic data were found to be blurred by packing effects. Instead, tandem MS and ITC data were in line with each other and followed the expected trends. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Husband-Wife Marital Privileges Under MRE 504: A Balancing of Public Policy Considerations

DTIC Science & Technology

1987-04-01

Lutwak v. United States, 344 U.S. 604 (1953)). I18.MCM, 1969, para. 151 b. 119. See e.g., supra notes 195-197, and accompanying text. 120. But cf. supra...accompanying text. 214. Mil. R. Evid. 504(c)(2)(A). 215. See Tinton, 23 M.J. 338. 216. Mil. R. Evid. 504(c)(2)(B). 217. See e.a. Lutwak v. United States, 344

Modelo Crosscultural de Pasantias para Lideres de la Educacion: Cooperacion entre Estados Unidos y Venezuela (Designing an Effective School Administrator Internship Program: United States and Venezuela Cooperation).

ERIC Educational Resources Information Center

Serafin, Ana Gil; Thompson, Eugene W.

A model was developed of an internship program designed to give valuable cross-cultural experience to school administrators in training at universities in the United States and Venezuela. A naturalistic approach was used to develop the model. Leading school administrators and educational leadership theorists in both countries were interviewed by…

Structure-Kinetics Correlations in Isostructural Crystals of α-(ortho-Tolyl)-acetophenones: Pinning Down Electronic Effects Using Laser-Flash Photolysis in the Solid State.

PubMed

Ayitou, Anoklase J-L; Flynn, Kristen; Jockusch, Steffen; Khan, Saeed I; Garcia-Garibay, Miguel A

2016-03-02

Aqueous suspensions of nanocrystals in the 200-500 nm size range of isostructural α-(ortho-tolyl)-acetophenone (1a) and α-(ortho-tolyl)-para-methylacetophenone (1b) displayed good absorption characteristics for flash photolysis experiments in a flow system, with transient spectra and decay kinetics with a quality that is similar to that recorded in solution. In contrast to solution measurements, reactions in the solid state were characterized by a rate limiting hydrogen transfer reaction from the triplet excited state and a very short-lived biradical intermediate, which does not accumulate. Notably, the rate for δ-hydrogen atom transfer of 1a (2.7 × 10(7) s(-1)) in the crystalline phase is 18-fold larger than that of 1b (1.5 × 10(6) s(-1)). With nearly identical molecular and crystal structures, this decrease in the rate of δ-hydrogen abstraction can be assigned unambiguously to an electronic effect by the para-methyl group in 1b, which increases the contribution of the (3)π,π* configuration relative to the reactive (3)n,π* configuration in the lowest triplet excited state. These results highlight the potential of relating single crystal X-ray structural data with absolute kinetics from laser flash photolysis.

Multivariate genetic determinants of EEG oscillations in schizophrenia and psychotic bipolar disorder from the BSNIP study

PubMed Central

Narayanan, B; Soh, P; Calhoun, V D; Ruaño, G; Kocherla, M; Windemuth, A; Clementz, B A; Tamminga, C A; Sweeney, J A; Keshavan, M S; Pearlson, G D

2015-01-01

Schizophrenia (SZ) and psychotic bipolar disorder (PBP) are disabling psychiatric illnesses with complex and unclear etiologies. Electroencephalogram (EEG) oscillatory abnormalities in SZ and PBP probands are heritable and expressed in their relatives, but the neurobiology and genetic factors mediating these abnormalities in the psychosis dimension of either disorder are less explored. We examined the polygenic architecture of eyes-open resting state EEG frequency activity (intrinsic frequency) from 64 channels in 105 SZ, 145 PBP probands and 56 healthy controls (HCs) from the multisite BSNIP (Bipolar-Schizophrenia Network on Intermediate Phenotypes) study. One million single-nucleotide polymorphisms (SNPs) were derived from DNA. We assessed eight data-driven EEG frequency activity derived from group-independent component analysis (ICA) in conjunction with a reduced subset of 10 422 SNPs through novel multivariate association using parallel ICA (para-ICA). Genes contributing to the association were examined collectively using pathway analysis tools. Para-ICA extracted five frequency and nine SNP components, of which theta and delta activities were significantly correlated with two different gene components, comprising genes participating extensively in brain development, neurogenesis and synaptogenesis. Delta and theta abnormality was present in both SZ and PBP, while theta differed between the two disorders. Theta abnormalities were also mediated by gene clusters involved in glutamic acid pathways, cadherin and synaptic contact-based cell adhesion processes. Our data suggest plausible multifactorial genetic networks, including novel and several previously identified (DISC1) candidate risk genes, mediating low frequency delta and theta abnormalities in psychoses. The gene clusters were enriched for biological properties affecting neural circuitry and involved in brain function and/or development. PMID:26101851

Nuclear spin hyperpolarization of the solvent using signal amplification by reversible exchange (SABRE).

PubMed

Moreno, Karlos X; Nasr, Khaled; Milne, Mark; Sherry, A Dean; Goux, Warren J

2015-08-01

Here we report the polarization of the solvent OH protons by SABRE using standard iridium-based catalysts under slightly acidic conditions. Solvent polarization was observed in the presence of a variety of structurally similar N-donor substrates while no solvent enhancement was observed in the absence of substrate or para-hydrogen (p-H2). Solvent polarization was sensitive to the polarizing field and catalyst:substrate ratio in a manner similar to that of substrate protons. SABRE experiments with pyridine-d5 suggest a mechanism where hyperpolarization is transferred from the free substrate to the solvent by chemical exchange while measured hyperpolarization decay times suggest a complimentary mechanism which occurs by direct coordination of the solvent to the catalytic complex. We found the solvent hyperpolarization to decay nearly 3 times more slowly than its characteristic spin-lattice relaxation time suggesting that the hyperpolarized state of the solvent may be sufficiently long lived (∼20s) to hyperpolarize biomolecules having exchangeable protons. This route may offer future opportunities for SABRE to impact metabolic imaging. Copyright © 2015 Elsevier Inc. All rights reserved.

Nuclear spin hyperpolarization of the solvent using signal amplification by reversible exchange (SABRE)

NASA Astrophysics Data System (ADS)

Moreno, Karlos X.; Nasr, Khaled; Milne, Mark; Sherry, A. Dean; Goux, Warren J.

2015-08-01

Here we report the polarization of the solvent OH protons by SABRE using standard iridium-based catalysts under slightly acidic conditions. Solvent polarization was observed in the presence of a variety of structurally similar N-donor substrates while no solvent enhancement was observed in the absence of substrate or para-hydrogen (p-H2). Solvent polarization was sensitive to the polarizing field and catalyst:substrate ratio in a manner similar to that of substrate protons. SABRE experiments with pyridine-d5 suggest a mechanism where hyperpolarization is transferred from the free substrate to the solvent by chemical exchange while measured hyperpolarization decay times suggest a complimentary mechanism which occurs by direct coordination of the solvent to the catalytic complex. We found the solvent hyperpolarization to decay nearly 3 times more slowly than its characteristic spin-lattice relaxation time suggesting that the hyperpolarized state of the solvent may be sufficiently long lived (∼20 s) to hyperpolarize biomolecules having exchangeable protons. This route may offer future opportunities for SABRE to impact metabolic imaging.

Nucleophilic substitution at centers other than carbon: reaction at the chlorine of N-chloroacetanilides with triethylamine as the nucleophile

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

Underwood, G.R.; Dietze, P.E.

1984-12-28

The reaction between triethylamine (TEA) and a series of para-substituted N-chloroacetanilides has been studied in aqueous solution buffered to pHs between 1 and 5. The exclusive product derived from the aromatic moiety is the corresponding acetanilide. The reaction occurs via two parallel pseudo-second-order paths, one acid catalyzed (the Orton-like mechanism), the other uncatalyzed. The uncatalyzed reaction is accelerated by the presence of electron-withdrawing substituents on the aromatic ring and can best be represented as nucleophilic displacement at chlorine. It therefore appears to be the prototype of a convenient class of reactions for the study of displacement reactions at chlorine. Themore » rho value for this reaction is 3.87, indicating substantial negative charge buildup in the aromatic ring during of the transition state. The acid-catalyzed reaction is more complex, presumable involving a protonation equilibrium for the N-chloroacetanilide prior to the rate-determining step similar to that in the Orton reaction. 15 references, 2 figures, 3 tables.« less

Upper limit for the D2H+ ortho-to-para ratio in the prestellar core 16293E (CHESS)

NASA Astrophysics Data System (ADS)

Vastel, C.; Caselli, P.; Ceccarelli, C.; Bacmann, A.; Lis, D. C.; Caux, E.; Codella, C.; Beckwith, J. A.; Ridley, T.

2012-11-01

The H_3^+ ion plays a key role in the chemistry of dense interstellar gas clouds where stars and planets are forming. The low temperatures and high extinctions of such clouds make direct observations of H_3^+ impossible, but lead to large abundances of H2D+ and D2H+, which are very useful probes of the early stages of star and planet formation. The ground-state rotational ortho-D2H+ 11,1-00,0 transition at 1476.6 GHz in the prestellar core 16293E has been searched for with the Herschel HIFI instrument, within the CHESS (Chemical HErschel Surveys of Star forming regions) Key Program. The line has not been detected at the 21 mK km s-1 level (3σ integrated line intensity). We used the ortho-H2D+ 11,0-11,1 transition and para-D2H+ 11,0-10,1 transition detected in this source to determine an upper limit on the ortho-to-para D2H+ ratio as well as the para-D2H+/ortho-H2D+ ratio from a non-local thermodynamic equilibrium analysis. The comparison between our chemical modeling and the observations suggests that the CO depletion must be high (larger than 100), with a density between 5 × 105 and 106 cm-3. Also the upper limit on the ortho-D2H+ line is consistent with a low gas temperature (~11 K) with a ortho-to-para ratio of 6 to 9, i.e. 2 to 3 times higher than the value estimated from the chemical modeling, making it impossible to detect this high frequency transition with the present state of the art receivers. The chemical network is only available at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/547/A33Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA.

Collisional excitation of sulfur dioxide by molecular hydrogen in warm molecular clouds

NASA Astrophysics Data System (ADS)

Balança, Christian; Spielfiedel, Annie; Feautrier, Nicole

2016-08-01

Interpretation of SO2 line emission in warm environments requires a detailed knowledge of collisional rate coefficients for a wide range of levels and temperatures. Using an accurate theoretical interaction potential for SO2-H2, rate coefficients for collisions of SO2 with para and ortho-H2 for the 31 first SO2, rotational levels are calculated for temperatures up to 500 K using the coupled states (CS) approximation. From a comparison with previously published close-coupling (CC) results, it was shown that the two sets of data agree within 20-30 per cent for both para- and ortho-H2 collisions. As previously found within the CC approach, the CS rate coefficients with ortho and para-H2 differ by a factor of 2 in average, the largest being mainly the rates for collisions with ortho-H2. For higher levels and temperatures, rate constants were computed within the infinite order sudden (IOS) approximation. Rate coefficients were obtained for the lowest 410 rotational levels of SO2 in the 100-1000 K temperature range. A comparison at 30, 100 and 300 K of the IOS data with the corresponding para-H2 CS results indicates that the IOS approximation systematically underestimates the CS results by a factor up to 2 at the lowest temperatures. As expected, IOS and CS rates are in a better agreement at higher temperatures. Considering that the IOS theory was developed for collisions with para-H2, this approach cannot describe with the same accuracy collisions with ortho-H2. So, our IOS data may be considered as quite reliable for collisions with para-H2 and less accurate for collisions with ortho-H2.

The Ortho-to-para Ratio of Water Molecules Desorbed from Ice Made from Para-water Monomers at 11 K

NASA Astrophysics Data System (ADS)

Hama, Tetsuya; Kouchi, Akira; Watanabe, Naoki

2018-04-01

Water has two nuclear-spin isomers: ortho- and para-H2O. Some observations of interstellar space and cometary comae have reported the existence of gaseous H2O molecules with anomalous ortho-to-para ratios (OPRs) less than the statistical value of three. This has been often used to estimate the formation temperature of ice on dust, which is inferred to be below 50 K. The relation between the nuclear-spin dynamics of H2O in ice at low temperatures and the OPR of gaseous H2O desorbed from the ice has yet to be explored in a laboratory. Consequently, the true meaning of the observed OPRs remains debated. We measure the OPR of H2O photodesorbed from ice made from para-H2O monomers at 11 K, which was prepared by the sublimation of Ne from a para-H2O/Ne matrix. The photodesorbed H2O molecules from the ice have the statistical OPR value of three, demonstrating the immediate nuclear-spin-state mixing of H2O toward the statistical value of ice even at 11 K. The OPR of H2O thermally desorbed from the ice also shows the expected statistical value. Our results indicate that the OPR of H2O desorbed from interstellar ice should be the statistical value regardless of the formation process of the ice, which cannot be used to deduce the ice-formation temperature. This study highlights the importance of interstellar gas-phase processes in understanding anomalous abundance ratios of nuclear-spin isomers of molecules in space.

On State Complexes and Special Cube Complexes

ERIC Educational Resources Information Center

Peterson, Valerie J.

2009-01-01

This thesis presents the first steps toward a classification of non-positively curved cube complexes called state complexes. A "state complex" is a configuration space for a "reconfigurable system," i.e., an abstract system in which local movements occur in some discrete manner. Reconfigurable systems can be used to describe, for example,…

Effect of the ortho-Hydroxyl Groups on a Bipyridine Ligand of Iridium Complexes for the High-Pressure Gas Generation from the Catalytic Decomposition of Formic Acid.

PubMed

Iguchi, Masayuki; Zhong, Heng; Himeda, Yuichiro; Kawanami, Hajime

2017-12-14

The hydroxyl groups of a 2,2'-bipyridine (bpy) ligand near the metal center activated the catalytic performance of the Ir complex for the dehydrogenation of formic acid at high pressure. The position of the hydroxyl groups on the ligand affected the catalytic durability for the high-pressure H 2 generation through the decomposition of formic acid. The Ir complex with a bipyridine ligand functionalized with para-hydroxyl groups shows a good durability with a constant catalytic activity during the reaction even under high-pressure conditions, whereas deactivation was observed for an Ir complex with a bipyridine ligand with ortho-hydroxyl groups (2). In the presence of high-pressure H 2 , complex 2 decomposed into the ligand and an Ir trihydride complex through the isomerization of the bpy ligand. This work provides the development of a durable catalyst for the high-pressure H 2 production from formic acid. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

On the positronium spin conversion reactions caused by some macrocyclic Co II complexes

NASA Astrophysics Data System (ADS)

Fantola-Lazzarini, Anna L.; Lazzarini, Ennio

2002-08-01

The rate constants, kCR, of ortho- into para-positronium ( o-Ps→ p-Ps) spin conversion reactions, CR, caused by the high-spin [Co IIsep] 2+, [Co IIdinosar] 2+ and [Co IIdiamsar] 2+ macrocyclic complexes and also by high-spin [Co II sen] 2+ tripod complex were measured at several temperatures. The delocalizations, β, of Co II unpaired electrons, promoted by the mentioned ligands, were determined by using the previously established correlations between kCR and the electron delocalization β of unpaired metal electrons. β is given by the ratio between the Racah inter-electronic repulsion parameters of complexes, B, and that of the free ions, B0. The β values are compared with those of the Co II complexes with en (1,2-ethanediamine), pn (1,2 propanediamine) and dien (2,2' diamino diethylamine) ligands. The kCR rate constants are also compared with those of the Ps oxidation reactions, OR, promoted by the corresponding Co III complexes. It is concluded that, unlike OR's, the CR's do not occur by formation of hepta-coordinate adducts with Ps atoms.

Anion photoelectron spectroscopy of deprotonated ortho-, meta-, and para-methylphenol

NASA Astrophysics Data System (ADS)

Nelson, Daniel J.; Gichuhi, Wilson K.; Miller, Elisa M.; Lehman, Julia H.; Lineberger, W. Carl

2017-02-01

The anion photoelectron spectra of ortho-, meta-, and para-methylphenoxide, as well as methyl deprotonated meta-methylphenol, were measured. Using the Slow Electron Velocity Map Imaging technique, the Electron Affinities (EAs) of the o-, m-, and p-methylphenoxyl radicals were measured as follows: 2.1991±0.0014, 2.2177±0.0014, and 2.1199±0.0014 eV, respectively. The EA of m-methylenephenol was also obtained, 1.024±0.008 eV. In all four cases, the dominant vibrational progressions observed are due to several ring distortion vibrational normal modes that were activated upon photodetachment, leading to vibrational progressions spaced by ˜500 cm-1. Using the methylphenol O-H bond dissociation energies reported by King et al. and revised by Karsili et al., a thermodynamic cycle was constructed and the acidities of the methylphenol isomers were determined as follows: Δa c i dH298K 0=348.39 ±0.25 , 348.82±0.25, 350.08±0.25, and 349.60±0.25 kcal/mol for cis-ortho-, trans-ortho-, m-, and p-methylphenol, respectively. The excitation energies for the ground doublet state to the lowest excited doublet state electronic transition in o-, m-, and p-methylphenoxyl were also measured as follows: 1.029±0.009, 0.962±0.002, and 1.029±0.009 eV, respectively. In the photoelectron spectra of the neutral excited states, C-O stretching modes were excited in addition to ring distortion modes. Electron autodetachment was observed in the cases of both m- and p-methylphenoxide, with the para isomer showing a lower photon energy onset for this phenomenon.

Optical and electrochemical properties of hydrogen-bonded phenol-pyrrolidino[60]fullerenes.

PubMed

Moore, Gary F; Megiatto, Jackson D; Hambourger, Michael; Gervaldo, Miguel; Kodis, Gerdenis; Moore, Thomas A; Gust, Devens; Moore, Ana L

2012-06-01

We report the photophysical and electrochemical properties of phenol-pyrrolidino[60]fullerenes 1 and 2, in which the phenol hydroxyl group is ortho and para to the pyrrolidino group, respectively, as well as those of a phenyl-pyrrolidino[60]fullerene model compound, 3. For the ortho analog 1, the presence of an intramolecular hydrogen bond is supported by (1)H NMR and FTIR characterization. The redox potential of the phenoxyl radical-phenol couple in this architecture is 240 mV lower than that observed in the associated para compound 2. Further, the C(60) excited-state lifetime of the hydrogen-bonded compound 1 in benzonitrile is 260 ps, while the corresponding lifetime for 2 is identical to that of the model compound 3 at 1.34 ns. Addition of excess organic acid to a benzonitrile solution of 1 gives rise to a new species, 4, with an excited-state lifetime of 1.40 ns. In nonpolar aprotic solvents such as toluene, all three compounds have a C(60) excited-state lifetime of ∼1 ns. These results suggest that the presence of an intramolecular H-bond in 1 poises the potential of phenoxyl radical-phenol redox couple at a value that it is thermodynamically capable of reducing the photoexcited fullerene. This is not the case for the para analog 2 nor is it the case for the protonated species 4. This work illustrates that in addition to being used as light activated electron acceptors, pyrrolidino fullerenes are also capable of acting as built-in proton-accepting units that influence the potential of an attached donor when organized in an appropriate molecular design.

Association between anemia and subclinical infection in children in Paraíba State, Brazil

PubMed Central

Sales, Márcia Cristina; de Queiroz, Everton Oliveira; Paiva, Adriana de Azevedo

2011-01-01

Background With subclinical infection, serum iron concentrations are reduced, altering the synthesis of hemoglobin, the main indicator of anemia. Objective To evaluate the association between subclinical infection and anemia in children of Paraíba State. Methods This is a cross-sectional study involving 1116 children aged 6 to 59 months from nine municipalities of Paraíba State. Demographic and socioeconomic data were collected by means of a specific questionnaire. The C-reactive protein and hemoglobin levels were determined by the latex agglutination technique and automated counter, respectively. C-reactive protein values ≥ 6 mg/L were used as indicative of subclinical infection, while the presence of anemia was determined by hemoglobin values < 11.0 g/dL. The data were analyzed using the Epi Info computer program, with significance being set at 5%. Results Data from this research showed that 80.1% of the children belonged to families that were below the bread line, with per capita income < ½ of the minimum wage at that time (R$ 350.00 approximately US$ 175.00). The prevalences of subclinical infection and anemia were 11.3% and 36.3%, respectively. Subclinical infection was significantly associated with anemia (p-value < 0.05). There were lower levels of hemoglobin in children with C-reactive protein ≥ 6 mg/L, with a mean hemoglobin level in children with subclinical infection of 10.93 g/dL (standard deviation - SD = 1.21 g/dL) and without infection of 11.26 g/dL (SD = 1.18 g/dL) (p-value < 0.05). Conclusion Anemia is associated with subclinical infection in this population, indicating that this is an important variable to be considered in studies of the prevalence of anemia in children. PMID:23284254

Massage and Reiki used to reduce stress and anxiety: Randomized Clinical Trial.

PubMed

Kurebayashi, Leonice Fumiko Sato; Turrini, Ruth Natalia Teresa; Souza, Talita Pavarini Borges de; Takiguchi, Raymond Sehiji; Kuba, Gisele; Nagumo, Marisa Toshi

2016-11-28

to evaluate the effectiveness of massage and reiki in the reduction of stress and anxiety in clients at the Institute for Integrated and Oriental Therapy in Sao Paulo (Brazil). clinical tests randomly done in parallel with an initial sample of 122 people divided into three groups: Massage + Rest (G1), Massage + Reiki (G2) and a Control group without intervention (G3). The Stress Systems list and the Trace State Anxiety Inventory were used to evaluate the groups at the start and after 8 sessions (1 month), during 2015. there were statistical differences (p = 0.000) according to the ANOVA (Analysis of Variance) for the stress amongst the groups 2 and 3 (p = 0.014) with a 33% reductions and a Cohen of 0.78. In relation to anxiety-state, there was a reduction in the intervention groups compared with the control group (p < 0.01) with a 21% reduction in group 2 (Cohen of 1.18) and a 16% reduction for group 1 (Cohen of 1.14). Massage + Reiki produced better results amongst the groups and the conclusion is for further studies to be done with the use of a placebo group to evaluate the impact of the technique separate from other techniques. RBR-42c8wp. avaliar a efetividade da Massagem e Reiki na redução de estresse e ansiedade em clientes do Instituto de Terapia Integrada e Oriental, em São Paulo (Brasil). ensaio clínico controlado randomizado paralelo com amostra inicial de 122 pessoas divididas em 3 grupos Massagem+Repouso (G1), Massagem+Reiki (G2) e Controle sem intervenção (G3). Foram avaliados pela Lista de Sintomas de Stress e pelo Inventário de Ansiedade Traço-Estado, no início e após 8 sessões (1 mês), durante o ano de 2015. houve diferença estatística (p = 0,000) segundo ANOVA para o estresse entre os grupos 2 e 3 (33% de redução e Cohen de 0,98) e entre os grupos 1 e 3 (p = 0,014), 24% de redução e Cohen de 0,78. Para a ansiedade-estado, houve redução nos grupos de intervenção comparados ao grupo Controle (p < 0,01), com 21% de redução para o Grupo 2 (Cohen de 1,18) e 16% de redução para o grupo 1 (Cohen de 1,14). a Massagem+Reiki conseguiu melhores resultados entre os grupos e se sugere outro estudo com uso de placebo para o Reiki, para avaliar o alcance da técnica em separado. RBR-42c8wp. evaluar la efectividad de Masaje y Reiki para reducción del estrés y ansiedad en clientes del Instituto de Terapia Integrada y Oriental, en Sao Paulo, Brasil. ensayo clínico controlado aleatorizado paralelo, con muestra inicial de 122 personas divididas en 3 grupos Masaje+Reposo (G1), Masaje+Reiki (G2) y Control sin intervención (G3). Los participantes fueron evaluados a través de la Lista de Síntomas de Stress y por el Inventario de Ansiedad Rasgo-Estado, en el inicio y después de 8 sesiones (1 mes), durante el año de 2015. hubo diferencia estadística (p = 0,000) según ANOVA para el estrés entre los grupos 2 y 3 (33% de reducción y Cohen de 0,98) y entre los grupos 1 y 3 (p = 0,014), 24% de reducción y Cohen de 0,78. Para la ansiedad-estado, hubo reducción en los grupos de intervención comparados al grupo Control (p < 0,01), con 21% de reducción para el Grupo 2 (Cohen de 1,18) y 16% de reducción para el grupo 1 (Cohen de 1,14). entre los grupos, el Masaje+Reiki consiguió mejores resultados; se sugiere realizar otro estudio con uso de placebo para el Reiki, para evaluar el alcance de la técnica de forma separada. RBR-42c8wp.

[A study of complexity and power spectrum of cortical EEG and hippocampal potential in rats under different behavioral states].

PubMed

Feng, Zhou-yan; Zheng, Xiao-xiang

2002-08-01

Objective. To study the complexity and the power spectrum of cortical EEG and hippocampal potential in rats under waking and sleep states. Method. Cortical EEG and hippocampal potential were collected by implanted electrodes in freely moving rats. Algorithmic complexity (Kc), approximate entropy (ApEn), power spectral density (PSD) and gravity frequency of PSD of the potential waves were calculated. Result. The complexity of hippocampal potential was higher than that of cortical EEG under every state. The complexity of cortical EEG was lowest under the state of non rapid eye movement (NREM) sleep. The complexity of hippocampal potential was highest under waking state. The total power of both potentials in 0.5- 30 Hz frequency band showed their highest values under NREM state. Conclusion. The values of Kc and ApEn are closely related to the distributions of PSD. When there are evident peaks in PSD, the complexities of signals will decrease. The complexities may be used to distinguish the difference between cortical EEG and hippocampal potential, or large differences between the same kind of potentials under different behavioral states.

Near-Ideal Xylene Selectivity in Adaptive Molecular Pillar[ n]arene Crystals.

PubMed

Jie, Kecheng; Liu, Ming; Zhou, Yujuan; Little, Marc A; Pulido, Angeles; Chong, Samantha Y; Stephenson, Andrew; Hughes, Ashlea R; Sakakibara, Fumiyasu; Ogoshi, Tomoki; Blanc, Frédéric; Day, Graeme M; Huang, Feihe; Cooper, Andrew I

2018-06-06

The energy-efficient separation of alkylaromatic compounds is a major industrial sustainability challenge. The use of selectively porous extended frameworks, such as zeolites or metal-organic frameworks, is one solution to this problem. Here, we studied a flexible molecular material, perethylated pillar[ n]arene crystals ( n = 5, 6), which can be used to separate C8 alkylaromatic compounds. Pillar[6]arene is shown to separate para-xylene from its structural isomers, meta-xylene and ortho-xylene, with 90% specificity in the solid state. Selectivity is an intrinsic property of the pillar[6]arene host, with the flexible pillar[6]arene cavities adapting during adsorption thus enabling preferential adsorption of para-xylene in the solid state. The flexibility of pillar[6]arene as a solid sorbent is rationalized using molecular conformer searches and crystal structure prediction (CSP) combined with comprehensive characterization by X-ray diffraction and 13 C solid-state NMR spectroscopy. The CSP study, which takes into account the structural variability of pillar[6]arene, breaks new ground in its own right and showcases the feasibility of applying CSP methods to understand and ultimately to predict the behavior of soft, adaptive molecular crystals.

Local evolution of pyrethroid resistance offsets gene flow among Aedes aegypti collections in Yucatan State, Mexico.

PubMed

Saavedra-Rodriguez, Karla; Beaty, Meaghan; Lozano-Fuentes, Saul; Denham, Steven; Garcia-Rejon, Julian; Reyes-Solis, Guadalupe; Machain-Williams, Carlos; Loroño-Pino, Maria Alba; Flores-Suarez, Adriana; Ponce-Garcia, Gustavo; Beaty, Barry; Eisen, Lars; Black, William C

2015-01-01

The mosquito Aedes aegypti is the major vector of the four serotypes of dengue virus (DENV1-4). Previous studies have shown that Ae. aegypti in Mexico have a high effective migration rate and that gene flow occurs among populations that are up to 150 km apart. Since 2000, pyrethroids have been widely used for suppression of Ae. aegypti in cities in Mexico. In Yucatan State in particular, pyrethroids have been applied in and around dengue case households creating an opportunity for local selection and evolution of resistance. Herein, we test for evidence of local adaptation by comparing patterns of variation among 27 Ae. aegypti collections at 13 single nucleotide polymorphisms (SNPs): two in the voltage-gated sodium channel gene para known to confer knockdown resistance, three in detoxification genes previously associated with pyrethroid resistance, and eight in putatively neutral loci. The SNPs in para varied greatly in frequency among collections, whereas SNPs at the remaining 11 loci showed little variation supporting previous evidence for extensive local gene flow. Among Ae. aegypti in Yucatan State, Mexico, local adaptation to pyrethroids appears to offset the homogenizing effects of gene flow. © The American Society of Tropical Medicine and Hygiene.

Curriculum Perspectives: Challenges for the Future. Proceedings of a Binational Symnposium = Perspectivas curriculares: Retos para el futuro. Actas del simposio binacional (Austin, Texas, November 9-10, 1994).

ERIC Educational Resources Information Center

Southwest Educational Development Lab., Austin, TX.

This proceedings, in English and Spanish, describes the first U.S./Mexico Curriculum Symposium, held in Austin, Texas, in November 1994. The symposium grew out of an ongoing exchange between educators in the Republic of Mexico and the United States and was attended by over 200 teachers, administrators, staff from state and regional education…

VizieR Online Data Catalog: Chemical reactions for a deuteration network (Vastel+, 2012)

NASA Astrophysics Data System (ADS)

Vastel, C.; Caselli, P.; Ceccarelli, C.; Bacmann, A.; Lis, D. C.; Caux, E.; Codella, C.; Beckwith, J. A.; Ridley, T.

2012-09-01

The ground-state rotational ortho-D2H+(1,1,1-0,0,0) transition at 1476.6GHz in the prestellar core 16293E has been searched for with the Herschel/HIFI instrument, within the CHESS (Chemical HErschel Surveys of Star forming regions) Key Program. The line has not been detected at the 21mK.km/s level (3 sigma integrated line intensity). We used the ortho-H2D+ 110-111 transition and para-D2H+ 110-101 transition detected in this source to determine an upper limit on the ortho-to-para D2H+ ratio as well as the para-D2H+/ortho-H2D+ ratio from a non-LTE analysis. We then compared our chemical modeling with the observations in order to estimate the CO depletion as well as the H2 density and kinetic temperature at the position observed. The chemical network is provided in the kida.dat file. (1 data file).

A nanoparticle catalyst for heterogeneous phase para-hydrogen-induced polarization in water.

PubMed

Glöggler, Stefan; Grunfeld, Alexander M; Ertas, Yavuz N; McCormick, Jeffrey; Wagner, Shawn; Schleker, P Philipp M; Bouchard, Louis-S

2015-02-16

Para-hydrogen-induced polarization (PHIP) is a technique capable of producing spin polarization at a magnitude far greater than state-of-the-art magnets. A significant application of PHIP is to generate contrast agents for biomedical imaging. Clinically viable and effective contrast agents not only require high levels of polarization but heterogeneous catalysts that can be used in water to eliminate the toxicity impact. Herein, we demonstrate the use of Pt nanoparticles capped with glutathione to induce heterogeneous PHIP in water. The ligand-inhibited surface diffusion on the nanoparticles resulted in a (1) H polarization of P=0.25% for hydroxyethyl propionate, a known contrast agent for magnetic resonance angiography. Transferring the (1) H polarization to a (13) C nucleus using a para-hydrogen polarizer yielded a polarization of 0.013%. The nuclear-spin polarizations achieved in these experiments are the first reported to date involving heterogeneous reactions in water. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Para-Krawtchouk polynomials on a bi-lattice and a quantum spin chain with perfect state transfer

NASA Astrophysics Data System (ADS)

Vinet, Luc; Zhedanov, Alexei

2012-07-01

Analogues of Krawtchouk polynomials defined on a bi-lattice are introduced. They are shown to provide a (novel) spin chain with perfect transfer. Their characterization, as well as their connection to the quadratic Hahn algebra, is given.

[Quantum differences of ortho/para H2O2 spin-isomers as a factor of the femtosecond charge separation kinetics modulation in reaction centers of purple bacteria].

PubMed

Pishchal'nikov, R Iu; Pershin, S M; Bunkin, A F

2012-01-01

We have proposed the mechanism of coherent modulations of the P* state in the transient absorption spectra of the reaction center isolated from purple bacteria. Two water molecules, located between special pair, Ba, Bb chlorophylls and histidine L173 and M202, are supposed to be ortho-H2O and para-H2O isomers with different magnetic properties. The distinctive modulation frequencies were labeling as rotational resonances of ortho-H2O. According to our assumption, the interaction of rotational modes of water isomers with the charge-transfer states is a reason of coherent modulations of kinetics. We have modified a Hamiltonian system in order to take into account the rotational modes of ortho-H2O. Evolution of the density matrix was calculated in Liouville space. The Redfield relaxation theory for molecular aggregates was used to model kinetics up to 3 ps.

Why are para-hydrogen clusters superfluid? A quantum theorem of corresponding states study.

PubMed

Sevryuk, Mikhail B; Toennies, J Peter; Ceperley, David M

2010-08-14

The quantum theorem of corresponding states is applied to N=13 and N=26 cold quantum fluid clusters to establish where para-hydrogen clusters lie in relation to more and less quantum delocalized systems. Path integral Monte Carlo calculations of the energies, densities, radial and pair distributions, and superfluid fractions are reported at T=0.5 K for a Lennard-Jones (LJ) (12,6) potential using six different de Boer parameters including the accepted value for hydrogen. The results indicate that the hydrogen clusters are on the borderline to being a nonsuperfluid solid but that the molecules are sufficiently delocalized to be superfluid. A general phase diagram for the total and kinetic energies of LJ (12,6) clusters encompassing all sizes from N=2 to N=infinity and for the entire range of de Boer parameters is presented. Finally the limiting de Boer parameters for quantum delocalization induced unbinding ("quantum unbinding") are estimated and the new results are found to agree with previous calculations for the bulk and smaller clusters.

Fruit Flies of the Genus Anastrepha (Diptera: Tephritidae) From Some Localities of Paraguay: New Records, Checklist, and Illustrated Key

PubMed Central

Arias, Osmar René; Fariña, Nelson Librado; Lopes, Gleidyane Novaes; Uramoto, Keiko; Zucchi, Roberto Antonio

2014-01-01

Abstract This study deals with fruit flies of the genus Anastrepha Schiner (Diptera: Tephritidae) collected in McPhail traps in the municipalities of Concepción, Belén, Horqueta, Loreto (state of Concepción) and Santa Rosa (state of Misiones), Paraguay. In total, 17 species were captured, 9 of which are new records for Paraguay. All morphological characters used for species identification are illustrated. RESUMEN. Se estudió las especies de moscas de las frutas del género Anastrepha Schiner (Diptera: Tephritidae), colectadas en trampas tipo McPhail en las localidades de Concepción, Belén, Horqueta (Departamento de Concepción) y Santa Rosa (Departamento de Misiones). En total fueron capturadas 17 especies, de las cuales nueve especies corresponden a nuevos registros para el Paraguay. Todos los caracteres morfológicos para la identificación de las especies fueron ilustrados. PMID:25525098

Earth Observation

NASA Image and Video Library

2014-08-19

ISS040-E-103496 (19 Aug. 2014) --- On an unusually cloud-free day at the height of the dry season in Amazonia, several fires were burning, giving rise to a broad smoke pall easily seen from the International Space Station, photographed by an Expedition 40 crew member. Parts of the space station appear along the margins of the image. Against the backdrop of the dark green rainforest, several fires follow the major highway BR 163 (lower center of the image to the top left). Fires are set to clear patches of forest for agriculture, a process that reveals red-brown soils. A long line of new cleared patches snakes east from BR 163 towards the remote valley of the Rio Crepori. Extensive deforested areas in Brazil?s state of Mato Grosso appear as tan areas across the top of the image. Fires show the advance of deforestation into the state of Para, the area shown in most of this view. Para is now second after Mato Grosso in terms of deforestation acreage.

Ex(2)Box: interdependent modes of binding in a two-nanometer-long synthetic receptor.

PubMed

Juríček, Michal; Barnes, Jonathan C; Dale, Edward J; Liu, Wei-Guang; Strutt, Nathan L; Bruns, Carson J; Vermeulen, Nicolaas A; Ghooray, Kala C; Sarjeant, Amy A; Stern, Charlotte L; Botros, Youssry Y; Goddard, William A; Stoddart, J Fraser

2013-08-28

Incorporation of two biphenylene-bridged 4,4'-bipyridinium extended viologen units into a para-phenylene-based cyclophane results in a synthetic receptor that is ~2 nm long and adopts a box-like geometry. This cyclophane, Ex(2)Box(4+), possesses the ability to form binary and ternary complexes with a myriad of guest molecules ranging from long π-electron-rich polycyclic aromatic hydrocarbons, such as tetracene, tetraphene, and chrysene, to π-electron-poor 2,6-dinitrotoluene, 1,2,4-trichlorobenzene, and both the 9,10- and 1,4-anthraquinone molecules. Moreover, Ex(2)Box(4+) is capable of forming one-to-one complexes with polyether macrocycles that consist of two π-electron-rich dioxynaphthalene units, namely, 1,5-dinaphtho[38]crown-10. This type of broad molecular recognition is possible because the electronic constitution of Ex(2)Box(4+) is such that the pyridinium rings located at the "ends" of the cyclophane are electron-poor and prefer to enter into donor-acceptor interactions with π-electron-rich guests, while the "middle" of the cyclophane, consisting of the biphenylene spacer, is more electron-rich and can interact with π-electron-poor guests. In some cases, these different modes of binding can act in concert to generate one-to-one complexes which possess high stability constants in organic media. The binding affinity of Ex(2)Box(4+) was investigated in the solid state by way of single-crystal X-ray diffraction and in solution by using UV-vis and NMR spectroscopy for 12 inclusion complexes consisting of the tetracationic cyclophane and the corresponding guests of different sizes, shapes, and electronic compositions. Additionally, density functional theory was carried out to elucidate the relative energetic differences between the different modes of binding of Ex(2)Box(4+) with anthracene, 9,10-anthraquinone, and 1,4-anthraquinone in order to understand the degree with which each mode of binding contributes to the overall encapsulation of each guest.

Chlorination of 2-phenoxypropanoic acid with NCP in aqueous acetic acid: using a novel ortho-para relationship and the para/meta ratio of substituent effects for mechanism elucidation.

PubMed

Segurado, Manuel A P; Reis, João Carlos R; de Oliveira, Jaime D Gomes; Kabilan, Senthamaraikannan; Shanthi, Manohar

2007-07-06

Rate constants were measured for the oxidative chlorodehydrogenation of (R,S)-2-phenoxypropanoic acid and nine ortho-, ten para- and five meta-substituted derivatives using (R,S)-1-chloro-3-methyl-2,6-diphenylpiperidin-4-one (NCP) as chlorinating agent. The kinetics was run in 50% (v/v) aqueous acetic acid acidified with perchloric acid under pseudo-first-order conditions with respect to NCP at temperature intervals of 5 K between 298 and 318 K, except at the highest temperature for the meta derivatives. The dependence of rate constants on temperature was analyzed in terms of the isokinetic relationship (IKR). For the 20 reactions studied at five different temperatures, the isokinetic temperature was estimated to be 382 K, which suggests the preferential involvement of water molecules in the rate-determining step. The dependence of rate constants on meta and para substitution was analyzed using the tetralinear extension of the Hammett equation. The parameter lambda for the para/meta ratio of polar substituent effects was estimated to be 0.926, and its electrostatic modeling suggests the formation of an activated complex bearing an electric charge near the oxygen atom belonging to the phenoxy group. A new approach is introduced for examining the effect of ortho substituents on reaction rates. Using IKR-determined values of activation enthalpies for a set of nine pairs of substrates with a given substituent, a linear correlation is found between activation enthalpies of ortho and para derivatives. The correlation is interpreted in terms of the selectivity of the reactant toward para- or ortho-monosubstituted substrates, the slope of which being related to the ortho effect. This slope is thought to be approximated by the ratio of polar substituent effects from ortho and para positions in benzene derivatives. Using the electrostatic theory of through-space interactions and a dipole length of 0.153 nm, this ratio was calculated at various positions of a charged reaction center along the benzene C1-C4 axis, being about 2.5 near the ring and decreasing steeply with increasing distance until reaching a minimum value of -0.565 at 1.3 nm beyond the aromatic ring. Activation enthalpies and entropies were estimated for substrates bearing the isoselective substituent in either ortho and para positions, being demonstrated that they are much different from the values for the parent substrate. The electrophilic attack on the phenolic oxygen atom by the protonated chlorinating agent is proposed as the rate-determining step, this step being followed by the fast rearrangement of the intermediate thus formed, leading to products containing chlorine in the aromatic ring.

Toward a Definition of Complexity for Quantum Field Theory States.

PubMed

Chapman, Shira; Heller, Michal P; Marrochio, Hugo; Pastawski, Fernando

2018-03-23

We investigate notions of complexity of states in continuous many-body quantum systems. We focus on Gaussian states which include ground states of free quantum field theories and their approximations encountered in the context of the continuous version of the multiscale entanglement renormalization ansatz. Our proposal for quantifying state complexity is based on the Fubini-Study metric. It leads to counting the number of applications of each gate (infinitesimal generator) in the transformation, subject to a state-dependent metric. We minimize the defined complexity with respect to momentum-preserving quadratic generators which form su(1,1) algebras. On the manifold of Gaussian states generated by these operations, the Fubini-Study metric factorizes into hyperbolic planes with minimal complexity circuits reducing to known geodesics. Despite working with quantum field theories far outside the regime where Einstein gravity duals exist, we find striking similarities between our results and those of holographic complexity proposals.

Toward a Definition of Complexity for Quantum Field Theory States

NASA Astrophysics Data System (ADS)

Chapman, Shira; Heller, Michal P.; Marrochio, Hugo; Pastawski, Fernando

2018-03-01

We investigate notions of complexity of states in continuous many-body quantum systems. We focus on Gaussian states which include ground states of free quantum field theories and their approximations encountered in the context of the continuous version of the multiscale entanglement renormalization ansatz. Our proposal for quantifying state complexity is based on the Fubini-Study metric. It leads to counting the number of applications of each gate (infinitesimal generator) in the transformation, subject to a state-dependent metric. We minimize the defined complexity with respect to momentum-preserving quadratic generators which form s u (1 ,1 ) algebras. On the manifold of Gaussian states generated by these operations, the Fubini-Study metric factorizes into hyperbolic planes with minimal complexity circuits reducing to known geodesics. Despite working with quantum field theories far outside the regime where Einstein gravity duals exist, we find striking similarities between our results and those of holographic complexity proposals.

Highly active, low-valence molybdenum- and tungsten-amide catalysts for bifunctional imine-hydrogenation reactions.

PubMed

Chakraborty, Subrata; Blacque, Olivier; Fox, Thomas; Berke, Heinz

2014-01-01

The reactions of [M(NO)(CO)4(ClAlCl3)] (M=Mo, W) with (iPr2PCH2CH2)2NH, (PN(H)P) at 90 °C afforded [M(NO)(CO)(PN(H)P)Cl] complexes (M=Mo, 1a; W, 1b). The treatment of compound 1a with KOtBu as a base at room temperature yielded the alkoxide complex [Mo(NO)(CO)(PN(H)P)(OtBu)] (2a). In contrast, with the amide base Na[N(SiMe3 )2 ], the PN(H) P ligand moieties in compounds 1a and 1b could be deprotonated at room temperature, thereby inducing dehydrochlorination into amido complexes [M(NO)(CO)(PNP)] (M=Mo, 3a; W, 3b; PNP=(iPr2PCH2CH2)2N)). Compounds 3a and 3b have pseudo-trigonal-bipyramidal geometries, in which the amido nitrogen atom is in the equatorial plane. At room temperature, compounds 3a and 3b were capable of adding dihydrogen, with heterolytic splitting, thereby forming pairs of isomeric amine-hydride complexes [Mo(NO)(CO)H(PN(H)P)] (4a(cis) and 4a(trans)) and [W(NO)(CO)H(PN(H)P)] (4b(cis) and 4b(trans); cis and trans correspond to the position of the H and NO groups). H2 approaches the Mo/W=N bond in compounds 3a,b from either the CO-ligand side or from the NO-ligand side. Compounds 4a(cis) and 4a(trans) were only found to be stable under a H2 atmosphere and could not be isolated. At 140 °C and 60 bar H2 , compounds 3a and 3b catalyzed the hydrogenation of imines, thereby showing maximum turnover frequencies (TOFs) of 2912 and 1120 h(-1), respectively, for the hydrogenation of N-(4-methoxybenzylidene)aniline. A Hammett plot for various para-substituted imines revealed linear correlations with a negative slope of -3.69 for para substitution on the benzylidene side and a positive slope of 0.68 for para substitution on the aniline side. Kinetics analysis revealed the initial rate of the hydrogenation reactions to be first order in c(cat.) and zeroth order in c(imine). Deuterium kinetic isotope effect (DKIE) experiments furnished a low kH /kD value (1.28), which supported a Noyori-type metal-ligand bifunctional mechanism with H2 addition as the rate-limiting step. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The calculation of transport properties in quantum liquids using the maximum entropy numerical analytic continuation method: Application to liquid para-hydrogen

PubMed Central

Rabani, Eran; Reichman, David R.; Krilov, Goran; Berne, Bruce J.

2002-01-01

We present a method based on augmenting an exact relation between a frequency-dependent diffusion constant and the imaginary time velocity autocorrelation function, combined with the maximum entropy numerical analytic continuation approach to study transport properties in quantum liquids. The method is applied to the case of liquid para-hydrogen at two thermodynamic state points: a liquid near the triple point and a high-temperature liquid. Good agreement for the self-diffusion constant and for the real-time velocity autocorrelation function is obtained in comparison to experimental measurements and other theoretical predictions. Improvement of the methodology and future applications are discussed. PMID:11830656

Partnership to Advance Alternative Fuel Vehicles; Ciudades Limpias: Alianza Para Promover El Uso De Vehiculos De Combustibles Alternativos (in Spanish)

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

LaRocque, T.

2001-10-01

This fact sheet provides a question and answer overview of the Clean Cities program including what it is, how it works, the program's accomplishments, and a map of Clean Cities throughout the United States.

Espanol para Hoteleria y Turismo = Spanish for Travel and Tourism.

ERIC Educational Resources Information Center

Montes, Yara G.

This beginning through advanced Spanish text includes grammar explanations, readings, and exercises with the emphasis on situations involving travel and tourism. The introductory lesson covers the Spanish language, the importance of Spanish in the United States, the Spanish alphabet, pronunciation, capitalization, punctuation, syllabication,…

Refractive index and solubility control of para-cymene solutions for index-matched fluid-structure interaction studies

NASA Astrophysics Data System (ADS)

Fort, Charles; Fu, Christopher D.; Weichselbaum, Noah A.; Bardet, Philippe M.

2015-12-01

To deploy optical diagnostics such as particle image velocimetry or planar laser-induced fluorescence (PLIF) in complex geometries, it is beneficial to use index-matched facilities. A binary mixture of para-cymene and cinnamaldehyde provides a viable option for matching the refractive index of acrylic, a common material for scaled models and test sections. This fluid is particularly appropriate for large-scale facilities and when a low-density and low-viscosity fluid is sought, such as in fluid-structure interaction studies. This binary solution has relatively low kinematic viscosity and density; its use enables the experimentalist to select operating temperature and to increase fluorescence signal in PLIF experiments. Measurements of spectral and temperature dependence of refractive index, density, and kinematic viscosity are reported. The effect of the binary mixture on solubility control of Rhodamine 6G is also characterized.

Army Transformaton: A View from the U.S. Army War College

DTIC Science & Technology

2001-07-01

military, see particularly Allan R. Millett, The General: Robert L . Bullard and Officership in the United States Army, 1881-1925, Westport, CT: Greenwood...Westport, CT: Greenwood, 1986, p. 182. 2. Captain Carl Reichman, “In Pace Para Bellum,” Infantry Journal, Vol. II, January 1906, p. 5, quoted in James L ...United States Army, enlarged edition, Bloomington: Indiana University Press, 1984, pp. 265-354; Allan R. Millett, The General: Robert L . Bullard and

Suits Against Terrorist States by Victims of Terrorism

DTIC Science & Technology

2008-05-01

Nat’l City Bank v. Banco Para El Comercio Exterior de Cuba, 462 U.S. 611 (1983) (“Bancec”) to judgments against designated terrorist States. Bancec held...to determine both whether an exception to the Cuban Government’s immunity from garnishment also applies to [ Empresa de Telecomunicaciones de Cuba, S.A...was eventually reversed on other grounds by the U.S. Court of Appeals for the Eleventh Circuit — Alejandre v. Telefonica Larga Distancia de Puerto Rico

Photoelectron Spectroscopy of Substituted Phenylnitrenes

NASA Astrophysics Data System (ADS)

Wijeratne, Neloni R.; Da Fonte, Maria; Wenthold, Paul G.

2009-06-01

Nitrenes are unusual molecular structures with unfilled electronic valences that are isoelectronic with carbenes. Although, both can be generated by either thermal or photochemical decomposition of appropriate precursors they usually exhibit different reactivities. In this work, we carry out spectroscopic studies of substituted phenylnitrene to determine how the introduction of substituents will affect the reactivity and its thermochemical properties. All studies were carried out by using the newly constructed time-of-flight negative ion photoelectron spectrometer (NIPES) at Purdue University. The 355 nm photoelectron spectra of the o-, m-, and p-chlorophenyl nitrene anions are fairly similar to that measured for phenylnitrene anion. All spectra show low energy triplet state and a high energy singlet state. The singlet state for the meta isomer is well-resolved, with a well defined origin and observable vibrational structure. Whereas the singlet states for the ortho and para isomers have lower energy onsets and no resolved structure. The isomeric dependence suggests that the geometry differences result from the resonance interaction between the nitrogen and the substituent. Quinoidal resonance structures are possible for the open-shell singlet states of the o- and p-chlorinated phenyl nitrenes. The advantages of this type of electronic structures for the open-shell singlet states is that the unpaired electrons can be more localized on separate atoms in the molecules, minimizing the repulsion between. Because the meta position is not in resonance with the nitrenes, substitution at that position should not affect the structure of the open-shell singlet state. The measured electron affinities (EA) of the triplet phenylnitrenes are in excellent agreement with the values predicted by electronic structure calculations. The largest EA, 1.82 eV is found for the meta isomer, with para being the smallest, 1.70 eV.

Verification of Disarmament or Limitation of Armaments: Instruments, Negotiations, Proposals

DTIC Science & Technology

1992-05-01

explosions and may complicate the process of detection. An even greater difficulty faced by seismologists is the ambient background of seismic "noise...suspected event would be a complex operation. It would consist of surveys of the area of the presumed nuclear explosion in order to measure ambient ...Draft Resolution to the OAS General Assembly, June 1991 and OAS Resolution "Cooperacion para la seguridad en el hemisferio. Limitacion de la

Simulation Technologies for C2IS Development & Training

DTIC Science & Technology

2008-02-01

break down complex goals or meta -reasoning events that the agent uses to decide which plans to implement. They are integral to the ongoing...controlled through various programming means, which may include the posting of a PlanChoice event. JACK agents are fully capable of meta -level...China [6] Jaillet, Christophe; Krajecki, Michael; and Fugere, Dr. Benoit Jean (2002). ParaZJeZisation en memoire partagee d’un moteur de simulation du

Characterization of surface complexes in enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Roy, D.; Furtak, T. E.

1984-11-01

An indicator molecule, para-nitrosodimethylanaline (p-NDMA), has been used to study the chemical nature of surface complexes involving the active site for SERS in the electrochemical environment. We present evidence for positively charged Ag atoms stabilized by coadsorbed Cl- ions as the primary sites which are produced during the oxidation reduction cycle treatment of an Ag electrode. Depending on the relative number of Cl- ions which influence the Ag site the active site demonstrates a greater or lesser electron accepting character toward p-NDMA. This character is influenced by the applied voltage and by the presence of Tl+ ions in the bulk of the solution near the surface. As in previously studied systems p-NDMA/Cl-/Ag complexes demonstrate charge transfer excitation which in this case is from the p-NDMA to the Ag site. These results further solidify the importance of complex formation in electrochemical SERS and suggest that caution should be applied when using SERS as a quantitative measure of surface coverage.

A Standardized, Evidence-Based Massage Therapy Program for Decentralized Elite Paracyclists: Creating the Model.

PubMed

Kennedy, Ann B; Trilk, Jennifer L

2015-09-01

Evidence suggests that para-athletes are injured more often than able-bodied athletes. The benefits of massage therapy for these disabled athletes are yet to be explored. This paper documents the process followed for creating a massage program for elite paracycling athletes with the goal to assess effects on recovery, rest, performance, and quality of life both on and off the bike. Massage therapists' private practices throughout the United States. A United States Paracycling team consisting of 9 elite athletes: 2 spinal cord injury, 2 lower limb amputation, 1 upper limb amputation, 1 transverse myelitis, 1 stroke, 1 traumatic brain injury, and 1 visually impaired. The process used to develop a massage therapy program for para-cyclists included meetings with athletes, coaching staff, team exercise physiologist, and sports massage therapists; peer-reviewed literature was also consulted to address specific health conditions of para-athletes. Team leadership and athletes identified needs for quicker recovery, better rest, and improved performance in elite paracyclists. This information was used to generate a conceptual model for massage protocols, and led to creation of the intake and exit questionnaires to assess patient health status and recovery. Forms also were created for a general health intake, therapist information, and a therapist's SOAAP notes. The conceptual model and questionnaires developed herein will help to operationalize an exploratory study investigating the feasibility of implementing a standardized massage therapy program for a decentralized elite paracycling team.

Lethality of firearms relative to other suicide methods: a population based study.

PubMed

Shenassa, E D; Catlin, S N; Buka, S L

2003-02-01

(1) To quantify lethality of firearms relative to other suicide methods, (2) to quantify the extent to which suicide mortality may be reduced by limiting access to firearms. Data on suicides and hospitalised para-suicides that occurred in the state of Illinois from 1990 to 1997 were combined. Total number of episodes for each suicide method was estimated as the sum of the number of suicides and the number of para-suicides for that method. Gender and suicide method were used as proxies for intention to die, and estimated lethality of suicide methods within method-gender groups (for example, male firearm users). Logistic regression was used to quantify the lethality of firearms relative to other suicide methods. Excess mortality associated with the use of firearms was estimated by conservatively assuming that in the absence of firearms the next most lethal suicide method would be used. From January 1990 to December 1997, among individuals 10 years or older in the state of Illinois, there were 37,352 hospital admissions for para-suicide and 10,287 completed suicides. Firearms are the most lethal suicide method. Episodes involving firearms are 2.6 times (95% CI 2.1 to 3.1) more lethal than those involving suffocation-the second most lethal suicide method. Preventing access to firearms can reduce the proportion of fatal firearms related suicides by 32% among minors, and 6.5% among adults. Limiting access to firearms is a potentially effective means of reducing suicide mortality.

Quantum mechanical study of the proton exchange in the ortho-para H2 conversion reaction at low temperature.

PubMed

Honvault, P; Jorfi, M; González-Lezana, T; Faure, A; Pagani, L

2011-11-14

Ortho-para H(2) conversion reactions mediated by the exchange of a H(+) proton have been investigated at very low energy for the first time by means of a time independent quantum mechanical (TIQM) approach. State-to-state probabilities and cross sections for H(+) + H(2) (v = 0, j = 0,1) processes have been calculated for a collision energy, E(c), ranging between 10(-6) eV and 0.1 eV. Differential cross sections (DCSs) for H(+) + H(2) (v = 0, j = 1) → H(+) + H(2) (v' = 0, j' = 0) for very low energies only start to develop a proper global minimum around the sideways scattering direction (θ≈ 90°) at E(c) = 10(-3) eV. Rate coefficients, a crucial information required for astrophysical models, are provided between 10 K and 100 K. The relaxation ortho-para process j = 1 → j' = 0 is found to be more efficient than the j = 0 → j' = 1 conversion at low temperatures, in line with the extremely small ratio between the ortho and para species of molecular hydrogen predicted at the temperature of interstellar cold molecular clouds. The results obtained by means of a statistical quantum mechanical (SQM) model, which has previously proved to provide an adequate description of the dynamics of the title reactions at a higher collision energy regime, have been compared with the TIQM results. A reasonable good agreement has been found with the only exception of the DCSs for the H(+) + H(2) (v = 0, j = 1) → H(+) + H(2) (v' = 0, j' = 0) process at very low energy. SQM cross sections are also slightly below the quantum results. Estimates for the rate coefficients, in good accord with the TIQM values, are a clear improvement with respect to pioneering statistical studies on the reaction.

Theoretical study on the influence of different para-substituents on 13C NMR of the single carbonyl curcumin analogues

NASA Astrophysics Data System (ADS)

Jia, Fei-yun; Ran, Ming; Zhang, Bo

2015-12-01

The structure of eight kinds of different para-substituents curcumin analogues has been optimized at the level of B3LYP/6-31G( d, p), under which the stability has been verified by means of vibration analysis. Moreover, NMR spectra of curcumin analogues compounds have been studied at the level of B3LYP/6-311G( d, p) by GIAO method. The results show that the structure of eight compounds, a larger conjugated system, has good planarity. The effect of ortho-substituents on bond lengths and bond angles is greater than para and meta. Different substituents and different positions of substituents all have different influence on NMR of the single carbonyl curcumin analogues. In general, after the hydrogen atom on the benzene ring is substituted by other groups, the δ value of α-C changes significantly, the δ value of ortho-carbon atom may also have great change, but the δ value change of meta-carbon atoms is not too obvious. The effect of substituent electronegativity on α-C atoms presents obvious regularity, while the influence of conjugate effect on carbon atoms of benzene ring is more complex. Finally, the bigger substituted alkyl is, the more the δ value of α-C increases.

Social-ecological resilience and geomorphic systems

NASA Astrophysics Data System (ADS)

Chaffin, Brian C.; Scown, Murray

2018-03-01

Governance of coupled social-ecological systems (SESs) and the underlying geomorphic processes that structure and alter Earth's surface is a key challenge for global sustainability amid the increasing uncertainty and change that defines the Anthropocene. Social-ecological resilience as a concept of scientific inquiry has contributed to new understandings of the dynamics of change in SESs, increasing our ability to contextualize and implement governance in these systems. Often, however, the importance of geomorphic change and geomorphological knowledge is somewhat missing from processes employed to inform SES governance. In this contribution, we argue that geomorphology and social-ecological resilience research should be integrated to improve governance toward sustainability. We first provide definitions of engineering, ecological, community, and social-ecological resilience and then explore the use of these concepts within and alongside geomorphology in the literature. While ecological studies often consider geomorphology as an important factor influencing the resilience of ecosystems and geomorphological studies often consider the engineering resilience of geomorphic systems of interest, very few studies define and employ a social-ecological resilience framing and explicitly link the concept to geomorphic systems. We present five key concepts-scale, feedbacks, state or regime, thresholds and regime shifts, and humans as part of the system-which we believe can help explicitly link important aspects of social-ecological resilience inquiry and geomorphological inquiry in order to strengthen the impact of both lines of research. Finally, we discuss how these five concepts might be used to integrate social-ecological resilience and geomorphology to better understand change in, and inform governance of, SESs. To compound these dynamics of resilience, complex systems are nested and cross-scale interactions from smaller and larger scales relative to the system of interest can play formative roles during periods of collapse and reorganization. Large- and small-scale disturbances as well as large-scale system memory/capacity and small-scale innovation can have significant impacts on the trajectory of a reorganizing system (Gunderson and Holling, 2002; Chaffin and Gunderson, 2016). Attempts to measure the property of ecological resilience across complex systems amounts to attempts to measure the persistence of system-controlling variables, including processes, parameters, and important feedbacks, when the system is exposed to varying degrees of disturbance (Folke, 2016).

VizieR Online Data Catalog: Thermodynamic quantities of molecular hydrogen (Popovas+, 2016)

NASA Astrophysics Data System (ADS)

Popovas, A.; Jorgensen, U. G.

2016-07-01

New partition functions for equilibrium, normal, and ortho and para hydrogen are calculated and thermodynamic quantities are reported for the temperature range 1-20000K. Our results are compared to previous estimates in the literature. The calculations are not limited to the ground electronic state, but include all bound and quasi-bound levels of excited electronic states. Dunham coefficients of these states of H2 are also reported. Reported internal partition functions and thermodynamic quantities in the present work are shown to be more accurate than previously available data. (4 data files).

Multivariate analysis applied to monthly rainfall over Rio de Janeiro state, Brazil

NASA Astrophysics Data System (ADS)

Brito, Thábata T.; Oliveira-Júnior, José F.; Lyra, Gustavo B.; Gois, Givanildo; Zeri, Marcelo

2017-10-01

Spatial and temporal patterns of rainfall were identified over the state of Rio de Janeiro, southeast Brazil. The proximity to the coast and the complex topography create great diversity of rainfall over space and time. The dataset consisted of time series (1967-2013) of monthly rainfall over 100 meteorological stations. Clustering analysis made it possible to divide the stations into six groups (G1, G2, G3, G4, G5 and G6) with similar rainfall spatio-temporal patterns. A linear regression model was applied to a time series and a reference. The reference series was calculated from the average rainfall within a group, using nearby stations with higher correlation (Pearson). Based on t-test ( p < 0.05) all stations had a linear spatiotemporal trend. According to the clustering analysis, the first group (G1) contains stations located over the coastal lowlands and also over the ocean facing area of Serra do Mar (Sea ridge), a 1500 km long mountain range over the coastal Southeastern Brazil. The second group (G2) contains stations over all the state, from Serra da Mantiqueira (Mantiqueira Mountains) and Costa Verde (Green coast), to the south, up to stations in the Northern parts of the state. Group 3 (G3) contains stations in the highlands over the state (Serrana region), while group 4 (G4) has stations over the northern areas and the continent-facing side of Serra do Mar. The last two groups were formed with stations around Paraíba River (G5) and the metropolitan area of the city of Rio de Janeiro (G6). The driest months in all regions were June, July and August, while November, December and January were the rainiest months. Sharp transitions occurred when considering monthly accumulated rainfall: from January to February, and from February to March, likely associated with episodes of "veranicos", i.e., periods of 4-15 days of duration with no rainfall.

Organometallic benzylidene anilines: donor-acceptor features in NCN-pincer Pt(ii) complexes with a 4-(E)-[(4-R-phenyl)imino]methyl substituent.

PubMed

Batema, Guido D; Lutz, Martin; Spek, Anthony L; van Walree, Cornelis A; van Klink, Gerard P M; van Koten, Gerard

2014-08-28

A series of organometallic 4,4'-substituted benzylidene aniline complexes 4-ClPt-3,5-(CH2NMe2)2C6H2CH[double bond, length as m-dash]NC6H4R'-4', abbreviated as PtCl[NCN(CH[double bond, length as m-dash]NC6H4R'-4')-4], with R' = NMe2, Me, H, Cl, CN (, respectively), was synthesized via a Schiff-base condensation reaction involving reaction of PtCl[NCN(CH[double bond, length as m-dash]O)-4] () with the appropriate 4-R'-substituted aniline derivative () in toluene. The resulting arylplatinum(ii) products were obtained in 75-88% yield. Notably, product was also obtained in 68% yield from a reaction in the solid state by grinding solid with aniline . The structures of , , and in the solid state (single crystal X-ray diffraction) showed a non-planar geometry, in particular for compound . The electronic interaction between the donor benzylidene fragment PtCl(NCN-CH) and the para-R' aniline substituent through the azomethine bridge was studied with NMR and UV/Vis spectroscopy. Linear correlations were found between the azomethine (1)H, the (195)Pt NMR and various (13)C NMR chemical shifts, and the substituent parameters σF and σR of R' at the aniline site. In common with organic benzylidene anilines, the azomethine (1)H NMR chemical shift showed anomalous substituent behavior. The (195)Pt NMR chemical shift of the platinum center can be used as a probe for the electronic properties of the delocalized π-system of the benzylidene aniline framework, to which it is connected. The dual substituent parameter treatment of the azomethine (13)C NMR shift gave important insight into the unique behaviour of the Pt-pincer group as a substituent. Inductively, it is a very strong electron-withdrawing group, whereas mesomerically it behaves like a very strong electron donating group.

Evolution of complexity following a global quench

NASA Astrophysics Data System (ADS)

Moosa, Mudassir

2018-03-01

The rate of complexification of a quantum state is conjectured to be bounded from above by the average energy of the state. A different conjecture relates the complexity of a holographic CFT state to the on-shell gravitational action of a certain bulk region. We use `complexity equals action' conjecture to study the time evolution of the complexity of the CFT state after a global quench. We find that the rate of growth of complexity is not only consistent with the conjectured bound, but it also saturates the bound soon after the system has achieved local equilibrium.

Spin polarization transfer mechanisms of SABRE: A magnetic field dependent study.

PubMed

Pravdivtsev, Andrey N; Ivanov, Konstantin L; Yurkovskaya, Alexandra V; Petrov, Pavel A; Limbach, Hans-Heinrich; Kaptein, Robert; Vieth, Hans-Martin

2015-12-01

We have investigated the magnetic field dependence of Signal Amplification By Reversible Exchange (SABRE) arising from binding of para-hydrogen (p-H2) and a substrate to a suitable transition metal complex. The magnetic field dependence of the amplification of the (1)H Nuclear Magnetic Resonance (NMR) signals of the released substrates and dihydrogen, and the transient transition metal dihydride species shows characteristic patterns, which is explained using the theory presented here. The generation of SABRE is most efficient at low magnetic fields due to coherent spin mixing at nuclear spin Level Anti-Crossings (LACs) in the SABRE complexes. We studied two Ir-complexes and have shown that the presence of a (31)P atom in the SABRE complex doubles the number of LACs and, consequently, the number of peaks in the SABRE field dependence. Interestingly, the polarization of SABRE substrates is always accompanied by the para-to-ortho conversion in dihydride species that results in enhancement of the NMR signal of free (H2) and catalyst-bound H2 (Ir-HH). The field dependences of hyperpolarized H2 and Ir-HH by means of SABRE are studied here, for the first time, in detail. The field dependences depend on the chemical shifts and coupling constants of Ir-HH, in which the polarization transfer takes place. A negative coupling constant of -7Hz between the two chemically equivalent but magnetically inequivalent hydride nuclei is determined, which indicates that Ir-HH is a dihydride with an HH distance larger than 2Å. Finally, the field dependence of SABRE at high fields as found earlier has been investigated and attributed to polarization transfer to the substrate by cross-relaxation. The present study provides further evidence for the key role of LACs in the formation of SABRE-derived polarization. Understanding the spin dynamics behind the SABRE method opens the way to optimizing its performance and overcoming the main limitation of NMR, its notoriously low sensitivity. Copyright © 2015 Elsevier Inc. All rights reserved.

Spin polarization transfer mechanisms of SABRE: A magnetic field dependent study

NASA Astrophysics Data System (ADS)

Pravdivtsev, Andrey N.; Ivanov, Konstantin L.; Yurkovskaya, Alexandra V.; Petrov, Pavel A.; Limbach, Hans-Heinrich; Kaptein, Robert; Vieth, Hans-Martin

2015-12-01

We have investigated the magnetic field dependence of Signal Amplification By Reversible Exchange (SABRE) arising from binding of para-hydrogen (p-H2) and a substrate to a suitable transition metal complex. The magnetic field dependence of the amplification of the 1H Nuclear Magnetic Resonance (NMR) signals of the released substrates and dihydrogen, and the transient transition metal dihydride species shows characteristic patterns, which is explained using the theory presented here. The generation of SABRE is most efficient at low magnetic fields due to coherent spin mixing at nuclear spin Level Anti-Crossings (LACs) in the SABRE complexes. We studied two Ir-complexes and have shown that the presence of a 31P atom in the SABRE complex doubles the number of LACs and, consequently, the number of peaks in the SABRE field dependence. Interestingly, the polarization of SABRE substrates is always accompanied by the para-to-ortho conversion in dihydride species that results in enhancement of the NMR signal of free (H2) and catalyst-bound H2 (Ir-HH). The field dependences of hyperpolarized H2 and Ir-HH by means of SABRE are studied here, for the first time, in detail. The field dependences depend on the chemical shifts and coupling constants of Ir-HH, in which the polarization transfer takes place. A negative coupling constant of -7 Hz between the two chemically equivalent but magnetically inequivalent hydride nuclei is determined, which indicates that Ir-HH is a dihydride with an HH distance larger than 2 Å. Finally, the field dependence of SABRE at high fields as found earlier has been investigated and attributed to polarization transfer to the substrate by cross-relaxation. The present study provides further evidence for the key role of LACs in the formation of SABRE-derived polarization. Understanding the spin dynamics behind the SABRE method opens the way to optimizing its performance and overcoming the main limitation of NMR, its notoriously low sensitivity.

Time-dependent density functional theory study of the luminescence properties of gold phosphine thiolate complexes.

PubMed

Guidez, Emilie B; Aikens, Christine M

2015-04-09

The origin of the emission of the gold phosphine thiolate complex (TPA)AuSCH(CH3)2 (TPA = 1,3,5-triaza-7-phosphaadamantanetriylphosphine) is investigated using time-dependent density functional theory (TDDFT). This system absorbs light at 3.6 eV, which corresponds mostly to a ligand-to-metal transition with some interligand character. The P-Au-S angle decreases upon relaxation in the S1 and T1 states. Our calculations show that these two states are strongly spin-orbit coupled at the ground state geometry. Ligand effects on the optical properties of this complex are also discussed by looking at the simple AuP(CH3)3SCH3 complex. The excitation energies differ by several tenths of an electronvolt. Excited state optimizations show that the excited singlet and triplet of the (TPA)AuSCH(CH3)2 complex are bent. On the other hand, the Au-S bond breaks in the excited state for the simple complex, and TDDFT is no longer an adequate method. The excited state energy landscape of gold phosphine thiolate systems is very complex, with several state crossings. This study also shows that the formation of the [(TPA)AuSCH(CH3)2]2 dimer is favorable in the ground state. The inclusion of dispersion interactions in the calculations affects the optimized geometries of both ground and excited states. Upon excitation, the formation of a Au-Au bond occurs, which results in an increase in energy of the low energy excited states in comparison to the monomer. The experimentally observed emission of the (TPA)AuSCH(CH3)2 complex at 1.86 eV cannot be unambiguously assigned and may originate from several excited states.

Toward nanomolar detection by NMR through SABRE hyperpolarization.

PubMed

Eshuis, Nan; Hermkens, Niels; van Weerdenburg, Bram J A; Feiters, Martin C; Rutjes, Floris P J T; Wijmenga, Sybren S; Tessari, Marco

2014-02-19

SABRE is a nuclear spin hyperpolarization technique based on the reversible association of a substrate molecule and para-hydrogen (p-H2) to a metal complex. During the lifetime of such a complex, generally fractions of a second, the spin order of p-H2 is transferred to the nuclear spins of the substrate molecule via a transient scalar coupling network, resulting in strongly enhanced NMR signals. This technique is generally applied at relatively high concentrations (mM), in large excess of substrate with respect to metal complex. Dilution of substrate ligands below stoichiometry results in progressive decrease of signal enhancement, which precludes the direct application of SABRE to the NMR analysis of low concentration (μM) solutions. Here, we show that the efficiency of SABRE at low substrate concentrations can be restored by addition of a suitable coordinating ligand to the solution. The proposed method allowed NMR detection below 1 μM in a single scan.

El Derecho de su Hijo(a) a Una Educacion: Una guia para los Padres de Ninos Impedidos en el Estado de Nueva York (Your Child's Right to an Education: A Guide for Parents of Children with Handicapping Conditions in New York State).

ERIC Educational Resources Information Center

New York State Education Dept. Albany. Office for the Education of Children with Handicapping Conditions.

Intended for parents of handicapped students, the guide (available in English, Spanish, or Chinese) sets forth the New York State policies for speical education. The following topics are among those considered: eligibility for special education, program types, alternative placements (such as residential settings), referral, evaluation,…

A multi-state approach to black-tailed prairie dog conservation and management in the United States (Enfoque multi-estatal para la Conservacion y manejo del perro llanero de cola negra en los Estados Unidos)

Treesearch

Robert J. Luce

2006-01-01

The black-tailed prairie dog (Cynomys ludovicianus) is unusual among species proposed for Endangered Species Act (ESA) listing in that several million individuals currently exist across a large area in the wild. The National Wildlife Federation's 1998 listing petition estimated the current area occupied by the species at 283,500-324,000 ha. Although widespread,...

Posture Statement of General Douglas M. Fraser, United States Air Force Commander, United States Southern Command, Before the 112th Congress House Armed Services Committee

DTIC Science & Technology

2012-03-06

1 Aravena, F. Confianza: base para la gobernabilidad y la convivencia democrática en América...Latinoamericano de Ciencias Sociales (FLACSO). 3 Joint Interagency Task Force South (JIATF South), our key component in detection and monitoring of illicit...Central America’s north, the government of Mexico has fully committed to reducing the power and impunity of transnational organized crime and drug

Distinction of nuclear spin states with the scanning tunneling microscope.

PubMed

Natterer, Fabian Donat; Patthey, François; Brune, Harald

2013-10-25

We demonstrate rotational excitation spectroscopy with the scanning tunneling microscope for physisorbed H(2) and its isotopes HD and D(2). The observed excitation energies are very close to the gas phase values and show the expected scaling with the moment of inertia. Since these energies are characteristic for the molecular nuclear spin states we are able to identify the para and ortho species of hydrogen and deuterium, respectively. We thereby demonstrate nuclear spin sensitivity with unprecedented spatial resolution.

Financiamiento público y privado para la investigación forestal en el sur de Estados Unidos durante el período 1920-2000

Treesearch

John A. Stanturf; Robert Kellison; F.S. Broerman; Stephen Jones; Alan Lucier

2002-01-01

Public and Private Funding of Forestry Research in the Southern United States, 1929-2999. Forest management in the southern United States intensified over the last 80 years and the pine forests of the Coastal Plain can be regarded as in the early stage of crop domestication. In 1997, 57 % of the softwood and 52 % of the hardwood timber produced in the country came from...

A Comparison of United States, Colombian and Peruvian Domestic Law on Terrorism. Are We Becoming More Like Our Neighbors to the South?

DTIC Science & Technology

2005-08-18

fisica 0 su salud mental 0 danen la propiedad publica 0 privada, 0 cuando de cualquier otra manera se pueda generar grave peligro para la poblaci6n. [The...the U.S. Government. estatal, sera reprimido con pena privativa de la libertad no...menor de diez alios. [Whoever provokes, creates, or maintains a state of distress, alarm or terror in the population or in a segment thereof, carrying

Mood states modulate complexity in heartbeat dynamics: A multiscale entropy analysis

NASA Astrophysics Data System (ADS)

Valenza, G.; Nardelli, M.; Bertschy, G.; Lanata, A.; Scilingo, E. P.

2014-07-01

This paper demonstrates that heartbeat complex dynamics is modulated by different pathological mental states. Multiscale entropy analysis was performed on R-R interval series gathered from the electrocardiogram of eight bipolar patients who exhibited mood states among depression, hypomania, and euthymia, i.e., good affective balance. Three different methodologies for the choice of the sample entropy radius value were also compared. We show that the complexity level can be used as a marker of mental states being able to discriminate among the three pathological mood states, suggesting to use heartbeat complexity as a more objective clinical biomarker for mental disorders.

The nature and role of trap states in a dendrimer-based organic field-effect transistor explosive sensor

NASA Astrophysics Data System (ADS)

Tang, Guoqiang; Chen, Simon S. Y.; Lee, Kwan H.; Pivrikas, Almantas; Aljada, Muhsen; Burn, Paul L.; Meredith, Paul; Shaw, Paul E.

2013-06-01

We report the fabrication and charge transport characterization of carbazole dendrimer-based organic field-effect transistors (OFETs) for the sensing of explosive vapors. After exposure to para-nitrotoluene (pNT) vapor, the OFET channel carrier mobility decreases due to trapping induced by the absorbed pNT. The influence of trap states on transport in devices before and after exposure to pNT vapor has been determined using temperature-dependent measurements of the field-effect mobility. These data clearly show that the absorption of pNT vapor into the dendrimer active layer results in the formation of additional trap states. Such states inhibit charge transport by decreasing the density of conducting states.

Computational Fluid Dynamics (CFD) simulations of a Heisenberg Vortex Tube

NASA Astrophysics Data System (ADS)

Bunge, Carl; Sitaraman, Hariswaran; Leachman, Jake

2017-11-01

A 3D Computational Fluid Dynamics (CFD) simulation of a Heisenberg Vortex Tube (HVT) is performed to estimate cooling potential with cryogenic hydrogen. The main mechanism driving operation of the vortex tube is the use of fluid power for enthalpy streaming in a highly turbulent swirl in a dual-outlet tube. This enthalpy streaming creates a temperature separation between the outer and inner regions of the flow. Use of a catalyst on the peripheral wall of the centrifuge enables endothermic conversion of para-ortho hydrogen to aid primary cooling. A κ- ɛ turbulence model is used with a cryogenic, non-ideal equation of state, and para-orthohydrogen species evolution. The simulations are validated with experiments and strategies for parametric optimization of this device are presented.

Determination of the Si-conducting polymer interfacial properties using A-C impedance techniques

NASA Technical Reports Server (NTRS)

Nagasubramanian, G.; Di Stefano, Salvador; Moacanin, Jovan

1985-01-01

A study was made of the interfacial properties of poly(pyrrole) (PP) deposited electrochemically onto single crystal p-Si surfaces. The interfacial properties are dependent upon the counterions. The formation of 'quasi-ohmic' and 'nonohmic' contacts, respectively, of PP(ClO4) and PP films doped with other counterions (BF4 and para-toluene sulfonate) with p-Si, are explained in terms of the conductivity of these films and the flat band potential, V(fb), of PP relative to that of p-Si. The PP film seems to passivate or block intrinsic surface states present on the p-Si surface. The differences in the impedance behavior of para-toluene sulfonate doped and ClO4 doped PP are compared.

New rate coefficients of CS in collision with para- and ortho-H2 and astrophysical implications

NASA Astrophysics Data System (ADS)

Denis-Alpizar, Otoniel; Stoecklin, Thierry; Guilloteau, Stéphane; Dutrey, Anne

2018-05-01

Astronomers use the CS molecule as a gas mass tracer in dense regions of the interstellar medium, either to measure the gas density through multi-line observations or the level of turbulence. This necessarily requires the knowledge of the rates coefficients with the most common colliders in the interstellar medium, He and H2. In the present work, the close coupling collisional rates are computed for the first thirty rotational states of CS in collision with para- and ortho-H2 using a recent rigid rotor potential energy surface. Some radiative transfer calculations, using typical astrophysical conditions, are also performed to test this new set of data and to compare with the existing ones.

Restricted Complexity Framework for Nonlinear Adaptive Control in Complex Systems

NASA Astrophysics Data System (ADS)

Williams, Rube B.

2004-02-01

Control law adaptation that includes implicit or explicit adaptive state estimation, can be a fundamental underpinning for the success of intelligent control in complex systems, particularly during subsystem failures, where vital system states and parameters can be impractical or impossible to measure directly. A practical algorithm is proposed for adaptive state filtering and control in nonlinear dynamic systems when the state equations are unknown or are too complex to model analytically. The state equations and inverse plant model are approximated by using neural networks. A framework for a neural network based nonlinear dynamic inversion control law is proposed, as an extrapolation of prior developed restricted complexity methodology used to formulate the adaptive state filter. Examples of adaptive filter performance are presented for an SSME simulation with high pressure turbine failure to support extrapolations to adaptive control problems.

Quantifying reactivity for electrophilic aromatic substitution reactions with Hirshfeld charge.

PubMed

Liu, Shubin

2015-03-26

An electrophilic aromatic substitution is a process where one atom or group on an aromatic ring is replaced by an incoming electrophile. The reactivity and regioselectivity of this category of reactions is significantly impacted by the group that is already attached to the aromatic ring. Groups promoting substitution at the ortho/para and meta position are called ortho/para and meta directing groups, respectively. Earlier, we have shown that regioselectivity of the electrophilic aromatic substitution is dictated by the nucleophilicity of the substituted aromatic ring, which is proportional to the Hirshfeld charge on the regioselective site. Ortho/para directing groups have the largest negative charge values at the ortho/para positions, whereas meta directing groups often have the largest negative charge value at the meta position. The electron donation or acceptance feature of a substitution group is irrelevant to the regioselectivity. In this contribution, we extend our previous study by quantifying the reactivity for this kind of reactions. To that end, we examine the transition-state structure and activation energy of an identity reaction for a series of monosubstituted-benzene molecules reacting with hydrogen fluoride using BF3 as the catalyst in the gas phase. A total of 18 substitution groups will be considered, nine of which are ortho/para directing and the other nine groups meta directing. From this study, we found that the barrier height of these reactions strongly correlates with the Hirshfeld charge on the regioselective site for both ortho/para and meta directing groups, with the correlation coefficient R(2) both better than 0.96. We also discovered a less accurate correlation between the barrier height and HOMO energy. These results reconfirm the validity and effectiveness of employing the Hirshfeld charge as a reliable descriptor of both reactivity and regioselectivity for this vastly important category of chemical transformations.

Substituent Effects on the [N-I-N](+) Halogen Bond.

PubMed

Carlsson, Anna-Carin C; Mehmeti, Krenare; Uhrbom, Martin; Karim, Alavi; Bedin, Michele; Puttreddy, Rakesh; Kleinmaier, Roland; Neverov, Alexei A; Nekoueishahraki, Bijan; Gräfenstein, Jürgen; Rissanen, Kari; Erdélyi, Máté

2016-08-10

We have investigated the influence of electron density on the three-center [N-I-N](+) halogen bond. A series of [bis(pyridine)iodine](+) and [1,2-bis((pyridine-2-ylethynyl)benzene)iodine](+) BF4(-) complexes substituted with electron withdrawing and donating functionalities in the para-position of their pyridine nitrogen were synthesized and studied by spectroscopic and computational methods. The systematic change of electron density of the pyridine nitrogens upon alteration of the para-substituent (NO2, CF3, H, F, Me, OMe, NMe2) was confirmed by (15)N NMR and by computation of the natural atomic population and the π electron population of the nitrogen atoms. Formation of the [N-I-N](+) halogen bond resulted in >100 ppm (15)N NMR coordination shifts. Substituent effects on the (15)N NMR chemical shift are governed by the π population rather than the total electron population at the nitrogens. Isotopic perturbation of equilibrium NMR studies along with computation on the DFT level indicate that all studied systems possess static, symmetric [N-I-N](+) halogen bonds, independent of their electron density. This was further confirmed by single crystal X-ray diffraction data of 4-substituted [bis(pyridine)iodine](+) complexes. An increased electron density of the halogen bond acceptor stabilizes the [N···I···N](+) bond, whereas electron deficiency reduces the stability of the complexes, as demonstrated by UV-kinetics and computation. In contrast, the N-I bond length is virtually unaffected by changes of the electron density. The understanding of electronic effects on the [N-X-N](+) halogen bond is expected to provide a useful handle for the modulation of the reactivity of [bis(pyridine)halogen](+)-type synthetic reagents.

Substituent Effects on the [N–I–N]+ Halogen Bond

PubMed Central

2016-01-01

We have investigated the influence of electron density on the three-center [N–I–N]+ halogen bond. A series of [bis(pyridine)iodine]+ and [1,2-bis((pyridine-2-ylethynyl)benzene)iodine]+ BF4– complexes substituted with electron withdrawing and donating functionalities in the para-position of their pyridine nitrogen were synthesized and studied by spectroscopic and computational methods. The systematic change of electron density of the pyridine nitrogens upon alteration of the para-substituent (NO2, CF3, H, F, Me, OMe, NMe2) was confirmed by 15N NMR and by computation of the natural atomic population and the π electron population of the nitrogen atoms. Formation of the [N–I–N]+ halogen bond resulted in >100 ppm 15N NMR coordination shifts. Substituent effects on the 15N NMR chemical shift are governed by the π population rather than the total electron population at the nitrogens. Isotopic perturbation of equilibrium NMR studies along with computation on the DFT level indicate that all studied systems possess static, symmetric [N–I–N]+ halogen bonds, independent of their electron density. This was further confirmed by single crystal X-ray diffraction data of 4-substituted [bis(pyridine)iodine]+ complexes. An increased electron density of the halogen bond acceptor stabilizes the [N···I···N]+ bond, whereas electron deficiency reduces the stability of the complexes, as demonstrated by UV-kinetics and computation. In contrast, the N–I bond length is virtually unaffected by changes of the electron density. The understanding of electronic effects on the [N–X–N]+ halogen bond is expected to provide a useful handle for the modulation of the reactivity of [bis(pyridine)halogen]+-type synthetic reagents. PMID:27265247

Fixed Differences in the paralytic Gene Define Two Lineages within the Lutzomyia longipalpis Complex Producing Different Types of Courtship Songs

PubMed Central

Lins, Rachel M. M. A.; Souza, Nataly A.; Brazil, Reginaldo P.; Maingon, Rhayza D. C.; Peixoto, Alexandre A.

2012-01-01

The sand fly Lutzomyia longipalpis (Diptera: Psychodidae: Phlebotominae), the most important vector of American visceral leishmaniasis, is widely distributed in Latin America. There is currently a consensus that it represents a species complex, however, the number and distribution of the different siblings is still uncertain. Previous analyses have indicated that Brazilian populations of this vector can be divided into two main groups according to the type of courtship song (Burst vs. Pulse) males produce during copulation. Nevertheless, no diagnostic differences have been observed between these two groups with most molecular markers used to date. We analyzed the molecular divergence in a fragment of the paralytic (para) gene, a locus involved in the control of courtship songs in Drosophila, among a number of Lu. longipalpis populations from Brazil producing Burst and Pulse-type songs. Our results revealed a very high level of divergence and fixed differences between populations producing the two types of songs. We also compared Lu. longipalpis with a very closely related species, Lutzomyia cruzi, which produces Burst-type songs. The results indicated a higher number of fixed differences between Lu. cruzi and the Pulse-type populations of Lu. longipalpis than with those producing Burst-type songs. The data confirmed our previous assumptions that the presence of different sibling species of the Lu. longipalpis complex in Brazil can be divided into two main groups, one representing a single species and a second more heterogeneous group that probably represents a number of incipient species. We hypothesize that para might be one of the genes directly involved in the control of the courtship song differences between these two groups or that it is linked to other loci associated with reproductive isolation of the Brazilian species. PMID:22970200

Detection of platinum dihydride bisphosphine complexes and studies of their reactivity through para-hydrogen-enhanced NMR methods.

PubMed

Godard, Cyril; López-Serrano, Joaquín; Gálvez-López, María-Dolores; Roselló-Merino, Marta; Duckett, Simon B; Khazal, Iman; Lledós, Agustí; Whitwood, Adrian C

2008-01-01

In-situ NMR studies on the reactions of Pt{CH2 = CHSi(Me)2}2O)(PCy3) with phosphines, HSiEt3 and--hydrogen or Pt(L)(L')(Me)(2) alone enable the detection of cis-Pt(L)(L')(H)2 [L = PCy3 and L' = PCy2H, PPh3 or PCy3] which then undergo hydride site interchange and H2 reductive elimination on the NMR timescale.

Directrices de los Servicios de Salud para Estudiantes Migratorios (Guidelines for Health Services for Migrant Students).

ERIC Educational Resources Information Center

California State Dept. of Education, Sacramento. Bureau of Community Services and Migrant Education.

To promote uniformity and continuity, standards have been established for planning, implementing, and evaluating student health programs provided by grade K-12 migrant education programs throughout California. In this Spanish language edition, state-mandated health requirements, the rationale for supplemental services, methods of providing…

Post 9/11 Gi Bill: A Proposal for Enhanced Services

ERIC Educational Resources Information Center

Bordley-Hughes, Shannon L.

2018-01-01

According to the Democratic Staff of the Joint Economic Committee, United States Congress (2017), "over 3.9 million soldiers have served in wartime, since September 11, 2001" ("Gulf War-era II Veterans," para. 1). The Post-9/11 Veterans Assistance Act of 2008 (GI Bill) "offers the 2 million Servicemembers who have served…

Ayuda economica: Guia para estudiantes, 2001-2002 (Financial Aid: Student Guide, 2001-2002).

ERIC Educational Resources Information Center

Office of Student Financial Assistance (ED), Washington, DC.

This guide, written in Spanish, describes federal student aid programs for postsecondary education and how to apply for them. It begins by outlining sources for learning about student aid, such as school financial aid administrators, state higher education agencies, foundations, organizations related to particular fields of interest and toll-free…

Civil Society Participation at CONFINTEA VI

ERIC Educational Resources Information Center

Haddad, Sergio

2012-01-01

This article analyzes the participation of civil society in the Sixth International Conference on Adult Education held in Belem do Para, Brazil, 1-4 December 2009. As a foundation, the discussion first illuminates the important role that civil society in general plays in democratic issues and the relation between the state and society followed by…

THE INTRARENAL DISTRIBUTION OF TRITIATED PARA-AMINOHIPPURIC ACID DETERMINED BY A MODIFIED TECHNIQUE OF SECTION FREEZE-DRY RADIOAUTOGRAPHY

PubMed Central

Bordier, Betrand; Ornstein, Leonard; Wedeen, Richard P.

1970-01-01

Section freeze-dry radioautography has been used to examine the intrarenal distribution of a water-soluble organic acid (para-aminohippuric acid (PAH-3H)) under constant-infusion, steady-state conditions in mouse and rat kidney in vivo. The technique described here has the following advantages: (a) Sectioning and freeze-drying are accomplished in a closed cryostat at temperatures below -40°C; (b) Handling of the section is facilitated by mounting of the section-to-be on adhesive-coated Saran Wrap prior to cutting; (c) Unembedded freeze-dried sections are attached to photographic film at ambient temperature in the dark room; (d) Fixation follows completion of radioautographic exposure and precedes photographic development; (e) Permanent close contact is maintained between tissue and film. Morphologic preservation compared favorably with that obtained by optimal fixation techniques, which, however, permit diffusion. Cellular accumulation of PAH-3H during secretion was demonstrated in the proximal tubule under steady-state conditions in vivo. The cellular concentration of PAH-3H was uniform throughout the length of the proximal tubule in mouse and rat kidney. PMID:4349130

[Ortho/para spin-isomers of H2O molecules as a factor responsible for formation of two structural motifs in water].

PubMed

Zakharov, S D

2013-01-01

According to the last results obtained by small-angle X-ray scattering and X-ray spectroscopy it was suggested that water within the nanometer scale represents a fluctuating mixture of clusters with tetrahedral structure and a subphase with partially broken hydrogen bonds whereas the nuclear configuration of the H20 molecule corresponds to single tetrahedral coordination. The basic reason of such structural partition is not clear until now. Here we show that it can be associated with the existence of two nuclear H2O spin-isomers which have different probability to be in one or another subphase. The para-molecule can transfer an excess of its rotational energy to the environment up to the complete stopping of rotation because its rotational quantum number J = 0 in the basic state. This property is favorable for the formation of clusters with closed H-bonds. Ortho-molecules with odd-numbered J states lack for this property and thus should be predominantly present in the surrounding with distorted bonds.

Two-dimensional H2 in Si: Raman scattering and modeling study

NASA Astrophysics Data System (ADS)

Melnikov, V. V.; Hiller, M.; Lavrov, E. V.

2018-03-01

Molecular hydrogen trapped within {111}-oriented platelets in silicon is studied by means of Raman scattering and first principles theory. The rotational transition S0(0 ) (J =0 →J =2 ) of para-H2 (nuclear spin I =0 ) at 353 cm-1 is used as a probe. We find that for temperatures below 100 K the S0(0 ) Raman line starts to broaden asymmetrically, which is interpreted as the onset of a phase transition from a state with a short-range order ("gaseous" or "liquid" phase) to a two-dimensional molecular crystal lying in the {111} plane of silicon. The shape of the S0(0 ) line at helium temperatures strongly depends on the relative content of ortho- (nuclear spin I =1 ) and para-H2 revealing the details of the intermolecular interaction. A comprehensive theoretical analysis based on ab initio calculations, molecular dynamics simulations, and rotational spectra modeling reveals that the phase transition to the crystalline state of the two-dimensional hydrogen does occur at temperatures substantially higher compared to those of bulk H2.

Branchiosyllis, Haplosyllis, Opisthosyllis and Trypanosyllis (Annelida: Syllidae) from Brazil, with the Description of Two New Species

PubMed Central

Paresque, Karla; Fukuda, Marcelo Veronesi; Nogueira, João Miguel de Matos

2016-01-01

Brazilian specimens of Branchiosyllis cf. exilis, B. tamandarensis sp. n., Haplosyllis lattigae sp. n., H. loboi, Opisthosyllis brunnea and O. viridis are described and illustrated herein, from recently collected material; also, the distributions of Haplosyllis amphimedonicola and H. rosenalessoae are expanded to other localities in the states of Paraíba and Pernambuco. Branchiosyllis tamandarensis sp. n. was found associated with sponges and is characterized by having a flattened, ribbon-like body, with longitudinal line of mid-dorsal papillae, peristomium dorsally inconspicuous, branchiae with up to six lobes, branchiae and ungulae on all parapodia, and falcigers absent. Haplosyllis lattigae sp. n. is characterized by having two kinds of chaetae with different sizes and shapes per parapodium, papillate dorsum from midbody, and midbody dorsal cirri alternating in length. Additionally, we provide keys to the Brazilian species of Branchiosyllis, Haplosyllis and Opisthosyllis, comparative tables of the new species described herein and selected similar congeners, and the first record for Trypanosyllis zebra in the states of Espírito Santo and Paraíba. PMID:27144528

FROM COMPLEX EVOLVING TO SIMPLE: CURRENT REVISIONAL AND ENDOSCOPIC PROCEDURES FOLLOWING BARIATRIC SURGERY.

PubMed

Zorron, Ricardo; Galvão-Neto, Manoel Passos; Campos, Josemberg; Branco, Alcides José; Sampaio, José; Junghans, Tido; Bothe, Claudia; Benzing, Christian; Krenzien, Felix

Roux-en-Y gastric bypass (RYGB) is a standard therapy in bariatric surgery. Sleeve gastrectomy and gastric banding, although with good results in the literature, are showing higher rates of treatment failure to reduce obesity-associated morbidity and body weight. Other problems after bariatric may occur, as band erosion, gastroesophageal reflux disease and might be refractory to medication. Therefore, a laparoscopic conversion to a RYGB can be an effective alternative, as long as specific indications for revision are fulfilled. The objective of this study was to analyse own and literature data on revisional bariatric procedures to evaluate best alternatives to current practice. Institutional experience and systematic review from the literature on revisional bariatric surgery. Endoscopic procedures are recently applied to ameliorate failure and complications of bariatric procedures. Therapy failure following RYGB occurs in up to 20%. Transoral outlet reduction is currently an alternative method to reduce the gastrojejunal anastomosis. The diameter and volume of sleeve gastrectomy can enlarge as well, which can be reduced by endoscopic full-thickness sutures longitudinally. Dumping syndrome and severe hypoglycemic episodes (neuroglycopenia) can be present in patients following RYGB. The hypoglycemic episodes have to be evaluated and usually can be treated conventionally. To avoid partial pancreatectomy or conversion to normal anatomy, a new laparoscopic approach with remnant gastric resection and jejunal interposition can be applied in non-responders alternatively. Hypoglycemic episodes are ameliorated while weight loss is sustained. Revisional and endoscopic procedures following bariatric surgery in patients with collateral symptomatic or treatment failure can be applied. Conventional non-surgical approaches should have been applied intensively before a revisional surgery will be indicated. Former complex surgical revisional procedures are evolving to less complicated endoscopic solutions. Bypass gástrico em Y-de-Roux (BGYR) é procedimento padrão em cirurgia bariátrica. Gastrectomia vertical e banda gástrica, embora com bons resultados na literatura, estão mostrando taxas mais elevadas de insucesso no tratamento para reduzir a morbidade associada à obesidade e peso corporal. Outros problemas pós-operatórios podem ocorrer, como a erosão da banda, e doença do refluxo gastroesofágico refratária à medicação. Portanto, conversão laparoscópica para BGYR pode ser alternativa eficaz, desde que indicações específicas para a revisão sejam cumpridas. Analisar os nossos dados e os da literatura sobre procedimentos bariátricos revisionais para avaliar melhores alternativas para a prática atual. Foram efetuados experiência institucional e revisão sistemática da literatura sobre cirurgia bariátrica revisional. Procedimentos endoscópicos estão sendo aplicados recentemente para melhorar a falha e complicações de procedimentos bariátricos. Falha terapêutica após BGYR ocorre em até 20%. A redução transoral é atualmente um método alternativo para reduzir a anastomose gastrojejunal. A gastrectomia vertical pode apresentar aumento de volume e do diâmetro do pouch , o qual podem ser reduzidos por meio de sutura total endoscópica longitudinal. Síndrome de dumping e episódios de hipoglicemia grave (neuroglicopenia) podem estar presentes nos pacientes com BGYR. Os episódios hipoglicêmicos devem ser avaliados e geralmente podem ser tratados convencionalmente. Para evitar pancreatectomia parcial ou conversão à anatomia normal, uma nova abordagem laparoscópica com ressecção do remanescente gástrico e interposição de jejuno, pode ser aplicada como alternativa em não-respondedores. Episódios de hipoglicemia melhoram, enquanto a perda de peso é mantida. Procedimentos revisionais endoscópicos podem ser aplicados após cirurgia bariátrica em pacientes com sintomas colaterais ou na falha do tratamento. Abordagens convencionais não-cirúrgicas devem ser aplicadas intensivamente antes que uma operação revisional seja indicada. Antigos procedimentos cirúrgicos revisionais complexos estão evoluindo para soluções endoscópicas menos complicadas.

Theoretical study of photoacidity of HCN: the effect of complexation with water.

PubMed

Muchová, Eva; Spirko, Vladimir; Hobza, Pavel; Nachtigallová, Dana

2006-11-14

The character of the hydrogen bonding and the excited state proton transfer (ESPT) in the model system HCN...H(2)O is investigated. The PES of the two lowest excited states of the H(2)O...HCN complex was calculated using the CASPT2 method. The nonadiabatic coupling of the two states of the (pi-->pi*) and (pi-->sigma*) character is responsible for the excited state proton/hydrogen transfer. Compared to the ground state, the barrier for this process is significantly smaller. An increased number of water molecules in the complex with cyclic hydrogen-bonded network causes a large blue shift of the state of the (pi-->sigma*) character. The question of the dissociation of the complex in its excited state is also addressed.

Square-antiprismatic eight-coordinate complexes of divalent first-row transition metal cations: a density functional theory exploration of the electronic-structural landscape.

PubMed

Conradie, Jeanet; Patra, Ashis K; Harrop, Todd C; Ghosh, Abhik

2015-02-16

Density functional theory (in the form of the PW91, BP86, OLYP, and B3LYP exchange-correlation functionals) has been used to map out the low-energy states of a series of eight-coordinate square-antiprismatic (D2d) first-row transition metal complexes, involving Mn(II), Fe(II), Co(II), Ni(II), and Cu(II), along with a pair of tetradentate N4 ligands. Of the five complexes, the Mn(II) and Fe(II) complexes have been synthesized and characterized structurally and spectroscopically, whereas the other three are as yet unknown. Each N4 ligand consists of a pair of terminal imidazole units linked by an o-phenylenediimine unit. The imidazole units are the strongest ligands in these complexes and dictate the spatial disposition of the metal three-dimensional orbitals. Thus, the dx(2)-y(2) orbital, whose lobes point directly at the coordinating imidazole nitrogens, has the highest orbital energy among the five d orbitals, whereas the dxy orbital has the lowest orbital energy. In general, the following orbital ordering (in order of increasing orbital energy) was found to be operative: dxy < dxz = dyz ≤ dz(2) < dx(2)-y(2). The square-antiprism geometry does not lead to large energy gaps between the d orbitals, which leads to an S = 2 ground state for the Fe(II) complex. Nevertheless, the dxy orbital has significantly lower energy relative to that of the dxz and dyz orbitals. Accordingly, the ground state of the Fe(II) complex corresponds unambiguously to a dxy(2)dxz(1)dyz(1)dz(2)(1)dx(2)-y(2)(1) electronic configuration. Unsurprisingly, the Mn(II) complex has an S = 5/2 ground state and no low-energy d-d excited states within 1.0 eV of the ground state. The Co(II) complex, on the other hand, has both a low-lying S = 1/2 state and multiple low-energy S = 3/2 states. Very long metal-nitrogen bonds are predicted for the Ni(II) and Cu(II) complexes; these bonds may be too fragile to survive in solution or in the solid state, and the complexes may therefore not be isolable. Overall, the different exchange-correlation functionals provided a qualitatively consistent and plausible picture of the low-energy d-d excited states of the complexes.

Fuzzy model to estimate the number of hospitalizations for asthma and pneumonia under the effects of air pollution.

PubMed

Chaves, Luciano Eustáquio; Nascimento, Luiz Fernando Costa; Rizol, Paloma Maria Silva Rocha

2017-06-22

Predict the number of hospitalizations for asthma and pneumonia associated with exposure to air pollutants in the city of São José dos Campos, São Paulo State. This is a computational model using fuzzy logic based on Mamdani's inference method. For the fuzzification of the input variables of particulate matter, ozone, sulfur dioxide and apparent temperature, we considered two relevancy functions for each variable with the linguistic approach: good and bad. For the output variable number of hospitalizations for asthma and pneumonia, we considered five relevancy functions: very low, low, medium, high and very high. DATASUS was our source for the number of hospitalizations in the year 2007 and the result provided by the model was correlated with the actual data of hospitalization with lag from zero to two days. The accuracy of the model was estimated by the ROC curve for each pollutant and in those lags. In the year of 2007, 1,710 hospitalizations by pneumonia and asthma were recorded in São José dos Campos, State of São Paulo, with a daily average of 4.9 hospitalizations (SD = 2.9). The model output data showed positive and significant correlation (r = 0.38) with the actual data; the accuracies evaluated for the model were higher for sulfur dioxide in lag 0 and 2 and for particulate matter in lag 1. Fuzzy modeling proved accurate for the pollutant exposure effects and hospitalization for pneumonia and asthma approach. Prever o número de internações por asma e pneumonia associadas à exposição a poluentes do ar no município em São José dos Campos, estado de São Paulo. Trata-se de um modelo computacional que utiliza a lógica fuzzy baseado na técnica de inferência de Mamdani. Para a fuzzificação das variáveis de entrada material particulado, ozônio, dióxido de enxofre e temperatura aparente foram consideradas duas funções de pertinência para cada variável com abordagem linguísticas: bom e ruim. Para a variável de saída número internações por asma e pneumonia, foram consideradas cinco funções de pertinências: muito baixo, baixo, médio, alto e muito alto. O número de internações no ano de 2007 foi obtido do Datasus e o resultado fornecido pelo modelo foi correlacionado com os dados reais de internação com defasagem (lag) de zero a dois dias. A acurácia do modelo foi estimada pela curva ROC para cada poluente e nestas defasagens. No ano de 2007 foram registradas 1.710 internações por pneumonia e asma em São José dos Campos, SP, com média diária de 4,9 internações (dp = 2,9). Os dados de saída do modelo mostraram correlação positiva e significativa (r = 0,38) com os dados reais; as acurácias avaliadas para o modelo foram maiores para o dióxido de enxofre nos lag 0 e 2 e para o material particulado no lag 1. Modelagem fuzzy se mostrou acurada para a abordagem de efeitos da exposição aos poluentes e internação por pneumonia e asma.

The economic burden of lung cancer and mesothelioma due to occupational and para-occupational asbestos exposure.

PubMed

Tompa, Emile; Kalcevich, Christina; McLeod, Chris; Lebeau, Martin; Song, Chaojie; McLeod, Kim; Kim, Joanne; Demers, Paul A

2017-11-01

To estimate the economic burden of lung cancer and mesothelioma due to occupational and para-occupational asbestos exposure in Canada. We estimate the lifetime cost of newly diagnosed lung cancer and mesothelioma cases associated with occupational and para-occupational asbestos exposure for calendar year 2011 based on the societal perspective. The key cost components considered are healthcare costs, productivity and output costs, and quality of life costs. There were 427 cases of newly diagnosed mesothelioma cases and 1904 lung cancer cases attributable to asbestos exposure in 2011 for a total of 2331 cases. Our estimate of the economic burden is $C831 million in direct and indirect costs for newly identified cases of mesothelioma and lung cancer and $C1.5 billion in quality of life costs based on a value of $C100 000 per quality-adjusted life year. This amounts to $C356 429 and $C652 369 per case, respectively. The economic burden of lung cancer and mesothelioma associated with occupational and para-occupational asbestos exposure is substantial. The estimate identified is for 2331 newly diagnosed, occupational and para-occupational exposure cases in 2011, so it is only a portion of the burden of existing cases in that year. Our findings provide important information for policy decision makers for priority setting, in particular the merits of banning the mining of asbestos and use of products containing asbestos in countries where they are still allowed and also the merits of asbestos removal in older buildings with asbestos insulation. © Article author(s) (or their employer(s) unless otherwise stated in the text of the article) 2017. All rights reserved. No commercial use is permitted unless otherwise expressly granted.

Development policy for the Brazilian health industry and qualification of national public laboratories.

PubMed

Viana, Ana Luiza d'Ávila; Silva, Hudson Pacifico da; Ibañez, Nelson; Iozzi, Fabíola Lana

2016-11-03

Technological innovations play a decisive role in societies' development by contributing to economic growth and the population's welfare. The state has a key role in this process by inducing innovative behavior, strategies, and decisions. This study addresses Brazil's current policy for development of the health industry and its effects on qualification of national public laboratories by contextualizing different cycles of interaction between health policy and the industrial base, discussing the government's development strategy and the transfer and absorption of health technology (through Industrial Development Partnerships), and presenting two current partnerships involving public laboratories in the production of medicines and vaccines. Resumo: As inovações tecnológicas jogam papel decisivo no processo de desenvolvimento das sociedades, visto que contribuem para gerar crescimento econômico e bem-estar da população. O Estado possui grande importância e centralidade nesse processo, pois pode induzir fortemente o comportamento, as estratégias e as decisões relativas à inovação. O presente artigo tem por objetivo investigar a atual política de desenvolvimento produtivo em saúde no Brasil e seus reflexos sobre a capacitação dos laboratórios públicos nacionais. Para essa finalidade, contextualiza os diferentes ciclos de interação entre a política de saúde e a sua base produtiva, discute a estratégia do governo brasileiro para o desenvolvimento, a transferência e a absorção de tecnologia na área da saúde (as parcerias para o desenvolvimento produtivo) e apresenta duas parcerias vigentes envolvendo laboratórios públicos para a produção de medicamentos e vacinas.

Socioeconomic Collapse of Rural Areas, Atlantic Forest Transition and Sustainability

NASA Astrophysics Data System (ADS)

Silva, R. F. B. D.; Batistella, M.; Moran, E. F.

2017-12-01

Centuries of human pressure over the Atlantic Forest has led the biome to encompass only 11.7 percent of forest remnants. On the other hand, natural regeneration has explained forest cover increase in specific regions since the 1960s as an outcome of land use policies, environmental legislation, agricultural modernization, economic development, and landscape biophysical conditions. We analyze Forest Transition (FT) pathways for the Paraíba Valley region, São Paulo State, Brazil looking for more sustainable relationships between land use and natural land cover. During the 18th and 19th centuries, the Valley's farms were responsible for providing the largest portion of the state's wealth. Nowadays, the Valley contributes with only 6% to the state's gross product and the share of rural activities is now insignificant. Between 1962 and 2011, forest cover area increased from 225 to 446 thousand hectares. Rural household survey was conducted in three municipalities (n=90, thirty in each municipality). To select the municipalities among the thirty-four present in the Paraíba Valley, we applied the modified Thompson Tau technique to detect outlier values for three selected variables: natural forest cover, eucalyptus plantation cover, and municipal revenue. The outliers were discharged and the municipality with the best performance (maximum value) for each variable was selected. Based on the rural household surveys and GIS analysis of satellite imagery classifications, topography and hydrology variables, we conclude that the diminished land use pressure in the Paraíba Valley is allowing the regeneration of forest cover. Over the observed period, the FT was strongly influenced by the unsuitable topography for agriculture (steep slopes) and the economic urban development since the 1960s. However, more recently (2000s), FT is more affected by the vicinity of eucalyptus plantations, the active role of local communities denouncing illegal environmental threats (e.g., deforestation), and voluntary afforestation practices, which we call the collective action pathways.

ISOLATION OF NOVEL PARA-PENTYL PHENYL BENZOATE FROM MONDIA WHITEI. (HOOK.F.) SKEELS (PERIPLOCACEAE), ITS STRUCTURE, SYNTHESIS AND NEUROPHARMACOLOGICAL EVALUATION.

PubMed

Bamigboye J, Taiwo; Josephine Y, Osasan; Olujide O, Olubiyi; A, Oyemitan Idris; Shakir A M, Atoyebi; Mark R J, Elsegood; Raymond C F, Jones

2017-01-01

Mondia whitei L. (Hook. F.) Skeels (Periplocaceae) is a medicinal plant used locally in managing pain, fever, loss of appetite and as aphrodiasc in the South-Western states of Nigeria. However, the fruit is consumed habitually in the South-Eastern states of Nigeria, leading to speculation that it may possess some central nervous system effect but which has not been scientifically investigated, hence this study. Fresh fruits of Mondia whitei were collected and identified by a taxonomist. They were chopped into small pieces and extracted with absolute ethanol. The crude extract was subjected to various chromatographic techniques to isolate a novel compound whose structure was elucidated from the analysis of the crystal data and by extensive use of spectroscopy. The structure was confirmed by synthesis. The compound was subjected to anxiolytic and sedative activity assay. Computational analysis of the receptor binding event of isolated compound at the gamma amino butyric acid A receptor was also evaluated. The structure of the compound was elucidated as para pentyl phenyl benzoate. The neuropharmacological evaluation of the compound indicated significant (p<0.05) depression of the central nervous system. The binding characteristics of the compound to gamma amino butyric acid A receptors appears to be more favorable than those obtained for gamma amino butyric acid, chlorpromazine, benzamidine, and is comparable with the affinity obtained for pentobarbitone and diazepam. These present data provide evidence for the role of para pentyl phenyl benzoate in the habitual consumption of the fruit as well as its central nervous system activities.

Functional analogue reaction systems of the DMSO reductase isoenzyme family: probable mechanism of S-oxide reduction in oxo transfer reactions mediated by bis(dithiolene)-tungsten(IV,VI) complexes.

PubMed

Sung, Kie-Moon; Holm, R H

2002-04-24

The recent development of structural and functional analogues of the DMSO reductase family of isoenzymes allows mechanistic examination of the minimal oxygen atom transfer paradigm M(IV) + QO M(VI) O + Q with the biological metals M = Mo and W. Systematic variation of the electronic environment at the WIV center of desoxo bis(dithiolene) complexes is enabled by introduction of para-substituted phenyl groups in the equatorial (eq) dithiolene ligand and the axial (ax) phenolate ligand. The compounds [W(CO)2(S2C2(C6H4-p-X)2)2] (54-60%) have been prepared by ligand transfer from [Ni(S2C2(C6H4-p-X)2)2] to [W(CO)3(MeCN)3]. A series of 25 complexes [W(IV)(OC6H4-p-X')(S2C2(C6H4-p-X)2)2]1- ([X4,X'], X = Br, F, H, Me, OMe; X' = CN, Br, H, Me, NH2; 41-53%) has been obtained by ligand substitution of five dicarbonyl complexes with five phenolate ligands. Linear free energy relationships between E1/2 and Hammett constant p for the electron-transfer series [Ni(S2C2(C6H4-p-X)2)2]0,1-,2- and [W(CO)2(S2C2(C6H4-p-X)2)2]0,1-,2- demonstrate a substituent influence on electron density distribution at the metal center. The reactions [WIV(OC6H4-p-X')(S2C2(C6H4-p-X)2)2]1- + (CH2)4SO [W(VI)O(OC6H4-p-X')(S2C2(C6H4-p-X)2)2]1- + (CH2)4S with constant substrate are second order with large negative activation entropies indicative of an associative transition state. Rate constants at 298 K adhere to the Hammett equations log(k([X4,X']/k[X4,H]) = rho(ax)sigma(p) and log(k[X4,X']/k([H4,X']) = 4rho(eq)sigma(p). Electron-withdrawing groups (EWG) and electron-donating groups (EDG) have opposite effects on the rate such that k(EWG) > k(EDG). The effects of X' on reactivity are found to be approximately 5 times greater than that of X (rho(ax) = 2.1, rho(eq) = 0.44) in the Hammett equation. Using these and other findings, a stepwise oxo transfer reaction pathway is proposed in which an early transition state, of primary W(IV)-O(substrate) bond-making character, is rate-limiting. This is followed by a six-coordinate substrate complex and a second transition state proposed to involve atom and electron transfer leading to the development of the W(VI)=O group. This work is the most detailed mechanistic investigation of oxo transfer mediated by a biological metal.

Synthesis, spectral characterization, structural investigation and antimicrobial studies of mononuclear Cu(II), Ni(II), Co(II), Zn(II) and Cd(II) complexes of a new potentially hexadentate N2O4 Schiff base ligand derived from salicylaldehyde

NASA Astrophysics Data System (ADS)

Keypour, Hassan; Shayesteh, Maryam; Rezaeivala, Majid; Chalabian, Firoozeh; Elerman, Yalcin; Buyukgungor, Orhan

2013-01-01

A new potentially hexadentate N2O4 Schiff base ligand, H2L derived from condensation reaction of an aromatic diamine and salicylaldehyde, and its metal complexes were characterized by elemental analyses, IR, UV-Vis, EI-MS, 1H and 13C NMR spectra, as well as conductance measurements. It has been originated that the Schiff base ligand with Cu(II), Ni(II), Co(II), Cd(II) and Zn(II) ions form mononuclear complexes on 1:1 (metal:ligand) stoichiometry. The conductivity data confirm the non-electrolytic nature of the complexes. Also the crystal structures of the complexes [ZnL] and [CoL] have also been determined by using X-ray crystallographic technique. The Zn(II) and Co(II) complexes show a tetrahedral configuration. Electronic absorption spectra of the Cu(II) and Ni(II) complexes suggest a square-planar geometry around the central metal ion. The synthesized compounds have antibacterial activity against the three Gram-positive bacteria: Bacillus cereus, Enterococcus faecalis and Listeria monocytogenes and also against the three Gram-negative bacteria: Salmonella paraB, Citrobacter freundii and Enterobacter aerogenes. The results showed that in some cases the antibacterial activity of complexes were more than nalidixic acid and amoxicillin as standards.

Minimized state complexity of quantum-encoded cryptic processes

NASA Astrophysics Data System (ADS)

Riechers, Paul M.; Mahoney, John R.; Aghamohammadi, Cina; Crutchfield, James P.

2016-05-01

The predictive information required for proper trajectory sampling of a stochastic process can be more efficiently transmitted via a quantum channel than a classical one. This recent discovery allows quantum information processing to drastically reduce the memory necessary to simulate complex classical stochastic processes. It also points to a new perspective on the intrinsic complexity that nature must employ in generating the processes we observe. The quantum advantage increases with codeword length: the length of process sequences used in constructing the quantum communication scheme. In analogy with the classical complexity measure, statistical complexity, we use this reduced communication cost as an entropic measure of state complexity in the quantum representation. Previously difficult to compute, the quantum advantage is expressed here in closed form using spectral decomposition. This allows for efficient numerical computation of the quantum-reduced state complexity at all encoding lengths, including infinite. Additionally, it makes clear how finite-codeword reduction in state complexity is controlled by the classical process's cryptic order, and it allows asymptotic analysis of infinite-cryptic-order processes.

BIRD'S EYE VIEW OF THE COMPLEX, VIEW LOOKING NORTHWEST, WITH ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

BIRD'S EYE VIEW OF THE COMPLEX, VIEW LOOKING NORTHWEST, WITH THE FOREST PRACTICES BUILDING IN THE FOREGROUND, THE K.O.G. BUILDING TO THE RIGHT OF VIEW, AND THE BRIDGE AND THE OREGON STATE FORESTER'S OFFICE BUILDING IN THE BACKGROUND. - Oregon State Forester's Office Complex, 2600 State Street, Salem, Marion, OR

Substituent effects in infrared spectroscopy—VII. Meta and para substituted methanesulphonanilides

NASA Astrophysics Data System (ADS)

Laurence, C.; Berthelot, M.; Lucon, M.; Tsuno, Y.

Substituent effects on the NH frequencies of the conformers of methanesulphonanilides, their cyclic dimers and their hydrogen bonded complexes with acetonitrile have been analysed by means of the Hammet equation. An electron-withdrawing substituent may either increase or decrease ν(NH) in the XC 6H 4NHY series according to the electronic nature of the Y group. This can be explained by the non-monotonic dependence of the NH stretching frequency on the ionic character of the NH bond.

Synthesis and fluorescence properties of some difluoroboron β-diketonate complexes and composite containing PMMA

NASA Astrophysics Data System (ADS)

Xing, Dongye; Hou, Yanjun; Niu, Haijun

2018-03-01

A series of difluoroboron β-diketonate complexes, containing the indon-β-diketonate ligand carrying methyl or methoxyl substituents was synthesized. The crystal structures of the complexes were confirmed by single crystal X-ray diffraction studies. The fluorescence properties of compounds were studied in solution state, solid state and on PMMA polymer matrix. The photophysical data of compounds 2a-2d exhibited strong fluorescence and photostability under the ultraviolet light (Hg lamp). The complex 2b showed higher fluorescence intensity in solution state as compared to other complexes of the series. The complexes 2c and 2d showed higher fluorescence intensity in the solid state, which are ascribed to the stronger π-π interactions between ligands in the solid state. The introduction of methoxyl or methyl groups on the benzene rings enhanced the absorption intensity, emission intensity, quantum yields and fluorescence lifetimes due to their electron-donating nature. Furthermore, the complex 2b was doped into the PMMA to produce hybrid materials, where the PMMA matrix acted as sensitizer for the central boron ion to enhance the fluorescence emission intensity and quantum yields.

Steric hindrance inhibits excited-state relaxation and lowers the extent of intramolecular charge transfer in two-photon absorbing dyes.

PubMed

Stewart, David J; Dalton, Matthew J; Long, Stephanie L; Kannan, Ramamurthi; Yu, Zhenning; Cooper, Thomas M; Haley, Joy E; Tan, Loon-Seng

2016-02-21

The two-photon absorbing dye AF240 [1, (7-benzothiazol-2-yl-9,9-diethylfluoren-2-yl)diphenylamine] is modified by adding bulky alkyl groups to the diphenylamino moiety. Three new compounds are synthesized which have ethyl groups in both ortho positions of each phenyl ring (2), t-butyl groups in one ortho position of each phenyl ring (3), and t-butyl groups in the para position of each phenyl ring (4). The dyes are examined in several aprotic solvents with varying polarity to observe the effects of the sterically hindering bulky groups on the ground and excited-state photophysical properties. While the ground state shows minimal solvent dependence, there is significant dependence on the fluorescence quantum yield and lifetime, as well as the excited-state energy levels. This effect is caused by the formation of an intramolecular charge-transfer (ICT) state, which is observed in the solvents more polar than n-hexane and supported by TD-DFT calculations. Electronic effects of ortho or para alkyl substitution should be similar, yet drastic differences are observed. A red shift in the fluorescence maximum is observed in 4 relative to 1, yet a blue shift occurs in 2 and 3 because the substituents at the sterically sensitive ortho-positions inhibit excited-state geometric relaxation and result in less ICT character than 1. Coupled with theoretical calculations, the data support a planar ICT (PICT) excited state where the diphenylamino nitrogen in an sp(2)-like geometry is integral with the plane containing the fluorene and benzothiazole moieties. Ultrafast transient absorption experiments show that ICT occurs rapidly (<150 fs) followed by geometric and solvent relaxation in ∼ 1-4 ps to form the PICT or solvent-stabilized ICT (SSICT) state. This relaxation is not observed in non-polar n-hexane because the solvent dependent ICT state energy lies higher than the locally-excited (LE) state. Finally, formation of a triplet state (T1) is only efficiently observed in n-hexane for all four dyes.

A low-spin Fe(III) complex with 100-ps ligand-to-metal charge transfer photoluminescence

NASA Astrophysics Data System (ADS)

Chábera, Pavel; Liu, Yizhu; Prakash, Om; Thyrhaug, Erling; Nahhas, Amal El; Honarfar, Alireza; Essén, Sofia; Fredin, Lisa A.; Harlang, Tobias C. B.; Kjær, Kasper S.; Handrup, Karsten; Ericson, Fredric; Tatsuno, Hideyuki; Morgan, Kelsey; Schnadt, Joachim; Häggström, Lennart; Ericsson, Tore; Sobkowiak, Adam; Lidin, Sven; Huang, Ping; Styring, Stenbjörn; Uhlig, Jens; Bendix, Jesper; Lomoth, Reiner; Sundström, Villy; Persson, Petter; Wärnmark, Kenneth

2017-03-01

Transition-metal complexes are used as photosensitizers, in light-emitting diodes, for biosensing and in photocatalysis. A key feature in these applications is excitation from the ground state to a charge-transfer state; the long charge-transfer-state lifetimes typical for complexes of ruthenium and other precious metals are often essential to ensure high performance. There is much interest in replacing these scarce elements with Earth-abundant metals, with iron and copper being particularly attractive owing to their low cost and non-toxicity. But despite the exploration of innovative molecular designs, it remains a formidable scientific challenge to access Earth-abundant transition-metal complexes with long-lived charge-transfer excited states. No known iron complexes are considered photoluminescent at room temperature, and their rapid excited-state deactivation precludes their use as photosensitizers. Here we present the iron complex [Fe(btz)3]3+ (where btz is 3,3‧-dimethyl-1,1‧-bis(p-tolyl)-4,4‧-bis(1,2,3-triazol-5-ylidene)), and show that the superior σ-donor and π-acceptor electron properties of the ligand stabilize the excited state sufficiently to realize a long charge-transfer lifetime of 100 picoseconds (ps) and room-temperature photoluminescence. This species is a low-spin Fe(III) d5 complex, and emission occurs from a long-lived doublet ligand-to-metal charge-transfer (2LMCT) state that is rarely seen for transition-metal complexes. The absence of intersystem crossing, which often gives rise to large excited-state energy losses in transition-metal complexes, enables the observation of spin-allowed emission directly to the ground state and could be exploited as an increased driving force in photochemical reactions on surfaces. These findings suggest that appropriate design strategies can deliver new iron-based materials for use as light emitters and photosensitizers.

Revision of the genus Macrostomus Wiedemann (Diptera, Empididae, Empidinae). IV. The amazonensis species-group.

PubMed

Rafael, José Albertino; Cumming, Jeffrey M

2015-04-14

Six new species of Macrostomus Wiedemann are described, namely M. acreanus sp. nov. from Brazil (Acre state), M. amazonensis sp. nov. from Guyana and Brazil (Roraima, Amazonas, Pará, Rondônia, and Mato Grosso states), M. albicaudatus sp. nov. from Brazil (Roraima, Amazonas, and Pará states), M. paraiba sp. nov. from Brazil (Paraíba state), M. trombetensis sp. nov. from Brazil (Pará state) and M. xavieri sp. nov. from Guyana and Brazil (Amazonas state). The six species are all treated in the M. amazonensis species-group, which is defined on the basis of one pair of ocellar setae and no supra-alar postsutural setae in combination with characters of the male and female terminalia. A key to the included species is presented and the geographical distributions of the species are mapped.

The 'Magic Light': A Discussion on Laser Ethics.

PubMed

Stylianou, Andreas; Talias, Michael A

2015-08-01

Innovations in technology and science form novel fields that, although beneficial, introduce new bio-ethical issues. In their short history, lasers have greatly influenced our everyday lives, especially in medicine. This paper focuses particularly on medical and para-medical laser ethics and their origins, and presents the complex relationships within laser ethics through a three-dimensional matrix model. The term 'laser' and the myth of the 'magic light' can be identified as landmarks for laser related ethical issues. These ethical issues are divided into five major groups: (1) media, marketing, and advertising; (2) economic outcomes; (3) user training; (4) the user-patient/client relationship; and (5) other issues. In addition, issues arising from two of the most common applications of lasers, laser eye surgery and laser tattoo removal, are discussed. The aim of this paper is to demonstrate that the use of medical and para-medical lasers has so greatly influenced our lives that the scientific community must initiate an earnest discussion of medical laser ethics.

Improving Nonspecific Binding and Solubility: Bicycloalkyl Groups and Cubanes as para-Phenyl Bioisosteres.

PubMed

Auberson, Yves P; Brocklehurst, Cara; Furegati, Markus; Fessard, Thomas C; Koch, Guido; Decker, Andrea; La Vecchia, Luigi; Briard, Emmanuelle

2017-04-20

Bicycloalkyl groups have been previously described as phenyl group bioisosteres. This article describes the synthesis of new building blocks allowing their introduction into complex molecules, and explores their use as a means to modify the physicochemical properties of drug candidates and improve the quality of imaging agents. In particular, the replacement of an aromatic ring with a bicyclo[1.1.1]pentane-1,3-diyl (BCP) group improves aqueous solubility by at least 50-fold, and markedly decreases nonspecific binding (NSB) as measured by CHI(IAM), the chromatographic hydrophobicity index on immobilized artificial membranes. Structural variations with the bicyclo[2.2.2]octane-1,4-diyl group led to more lipophilic molecules and did not show the same benefits regarding NSB or solubility, whereas substitutions with cubane-1,4-diyl showed improvements for both parameters. These results confirm the potential advantages of both BCP and cubane motifs as bioisosteric replacements for optimizing para-phenyl-substituted molecules. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

How to design 13C para-hydrogen-induced polarization experiments for MRI applications.

PubMed

Reineri, Francesca; Viale, Alessandra; Dastrù, Walter; Gobetto, Roberto; Aime, Silvio

2011-01-01

The application of hyperpolarization techniques for MRI purposes is gathering increasing attention, especially for nuclei such as (13)C or (129)Xe. Among the different proposed methods, ParaHydrogen Induced Polarization requires relatively cheap equipment. The setup of an MRI experiment by means of parahydrogen requires the application of skills and methodologies that derive from different fields of knowledge. The basic theory and a practical insight of this method are presented here. Parahydrogenation of alkynes, having a labelled (13)CO group adjacent to the triple bond, catalyzed by Rh(I) complexes containing a chelating phosphine, represents the best choice for producing and maintaining high heteronuclear polarization effect. In order to transform anti-phase into in-phase (net) (13)C polarization for MRI application it is necessary to set up the described magnetic field cycle procedure. In vitro and in vivo images have been acquired using fast imaging sequences (RARE and trueFISP). Copyright © 2010 John Wiley & Sons, Ltd.

Kin cell lysis is a danger signal that activates antibacterial pathways of Pseudomonas aeruginosa

PubMed Central

LeRoux, Michele; Kirkpatrick, Robin L; Montauti, Elena I; Tran, Bao Q; Peterson, S Brook; Harding, Brittany N; Whitney, John C; Russell, Alistair B; Traxler, Beth; Goo, Young Ah; Goodlett, David R; Wiggins, Paul A; Mougous, Joseph D

2015-01-01

The perception and response to cellular death is an important aspect of multicellular eukaryotic life. For example, damage-associated molecular patterns activate an inflammatory cascade that leads to removal of cellular debris and promotion of healing. We demonstrate that lysis of Pseudomonas aeruginosa cells triggers a program in the remaining population that confers fitness in interspecies co-culture. We find that this program, termed P. aeruginosa response to antagonism (PARA), involves rapid deployment of antibacterial factors and is mediated by the Gac/Rsm global regulatory pathway. Type VI secretion, and, unexpectedly, conjugative type IV secretion within competing bacteria, induce P. aeruginosa lysis and activate PARA, thus providing a mechanism for the enhanced capacity of P. aeruginosa to target bacteria that elaborate these factors. Our finding that bacteria sense damaged kin and respond via a widely distributed pathway to mount a complex response raises the possibility that danger sensing is an evolutionarily conserved process. DOI: http://dx.doi.org/10.7554/eLife.05701.001 PMID:25643398

Free energy surfaces for the interaction of D-glucose with planar aromatic groups in aqueous solution

NASA Astrophysics Data System (ADS)

Wohlert, Jakob; Schnupf, Udo; Brady, John W.

2010-10-01

Multidimensional potentials of mean force for the interactions in aqueous solution of both anomers of D-glucopyranose with two planar aromatic molecules, indole and para-methyl-phenol, have been calculated using molecular dynamics simulations with umbrella sampling and were subsequently used to estimate binding free energies. Indole and para-methyl-phenol serve as models for the side chains of the amino acids tryptophan and tyrosine, respectively. In all cases, a weak affinity between the glucose molecules and the flat aromatic surfaces was found. The global minimum for these interactions was found to be for the case when the pseudoplanar face of β-D-glucopyranose is stacked against the planar surfaces of the aromatic residues. The calculated binding free energies are in good agreement with both experiment and previous simulations. The multidimensional free energy maps suggest a mechanism that could lend kinetic stability to the complexes formed by sugars bound to sugar-binding proteins.

Selective inhibition of deactivated mitochondrial complex I by biguanides.

PubMed

Matsuzaki, Satoshi; Humphries, Kenneth M

2015-03-24

Biguanides are widely used antihyperglycemic agents for diabetes mellitus and prediabetes treatment. Complex I is the rate-limiting step of the mitochondrial electron transport chain (ETC), a major source of mitochondrial free radical production, and a known target of biguanides. Complex I has two reversible conformational states, active and de-active. The deactivated state is promoted in the absence of substrates but is rapidly and fully reversed to the active state in the presence of NADH. The objective of this study was to determine the relative sensitivity of active/de-active complex I to biguanide-mediated inhibition and resulting superoxide radical (O₂(•⁻)) production. Using isolated rat heart mitochondria, we show that deactivation of complex I sensitizes it to metformin and phenformin (4- and 3-fold, respectively), but not to other known complex I inhibitors, such as rotenone. Mitochondrial O₂(•⁻) production by deactivated complex I was measured fluorescently by NADH-dependent 2-hydroxyethidium formation at alkaline pH to impede reactivation. Superoxide production was 260.4% higher than in active complex I at pH 9.4. However, phenformin treatment of de-active complex I decreased O₂(•⁻) production by 14.9%, while rotenone increased production by 42.9%. Mitochondria isolated from rat hearts subjected to cardiac ischemia, a condition known to induce complex I deactivation, were sensitized to phenformin-mediated complex I inhibition. This supports the idea that the effects of biguanides are likely to be influenced by the complex I state in vivo. These results demonstrate that the complex I active and de-active states are a determinant in biguanide-mediated inhibition.

Radiative charge transfer in He+ + H2 collisions in the milli- to nano-electron-volt range: A theoretical study within state-to-state and optical potential approaches

NASA Astrophysics Data System (ADS)

Mrugała, Felicja; Kraemer, Wolfgang P.

2013-03-01

The paper presents a theoretical study of the low-energy dynamics of the radiative charge transfer (RCT) reaction He+(^{2}S) + H2(X ^{1}Σ +g) rArr He(^{1}S) + H2+(X 2Σ +g)+hν extending our previous studies on radiative association of HeH2+ [F. Mrugała, V. Špirko, and W. P. Kraemer, J. Chem. Phys. 118, 10547 (2003), 10.1063/1.1573184; F. Mrugała and W. P. Kraemer, J. Chem. Phys. 122, 224321 (2005), 10.1063/1.1924453]. The calculations account for the vibrational and rotational motions of the H2/H_2^+ diatomics and for the atom-diatom complex formation in the reactant and the product channels of the RCT reaction. Continuum states of He+ + H2(v = 0, j = 0) in the collision energy range ˜10-7-18.6 meV and all quasi-bound states of the He+ - H2(para; v = 0) complex formed in this range are taken into account. Close-coupling calculations are performed to determine rates of radiative transitions from these states to the continuum and quasi-bound states of the He + H+2 system in the energy range extending up to ˜0.16 eV above the opening of the HeH+ + H arrangement channel. From the detailed state-to-state calculated characteristics global functions of the RCT reaction, such as cross-section σ(E), emission intensity I(ν, T), and rate constant k(T) are derived, and are presented together with their counterparts for the radiative association (RA) reaction He+(2S) + H_2(X ^{1}Σ +g) rArr HeH2+(X ^{2}A^' })+ hν. The rate constant kRCT is approximately 20 times larger than kRA at the considered temperatures, 0.1 μK-50 K. Formation of rotational Feshbach resonances in the reactant channel plays an important role in both reactions. Transitions mediated by these resonances contribute more than 70% to the respective rates. An extension of the one-dimensional optical potential model is developed to allow inclusion of all three vibrational modes in the atom-diatom system. This three-dimensional optical potential model is used to check to which extent the state-to-state RCT rate constant is influenced by the possibility to access ground state continuum levels well above the opening of the HeH++ H arrangement channel. The results indicate that these transitions contribute about 30% to the "true" rate constant kRCT whereas their impact on the populations of the vibration-rotational states of the product H2+ ion is only minor. Present theoretical rate constant functions kRCT(T) obtained at different approximation levels are compared to experimental data: 1-1.1 × 10-14 s-1 cm3 at T = 15-35 K and ˜7.5 × 10-15 s-1 cm3 at 40 K [M. M. Schauer, S. R. Jefferts, S. E. Barlow, and G. H. Dunn, J. Chem. Phys. 91, 4593 (1989), 10.1063/1.456748]. The most reliable theoretical values of kRCT, obtained by combining results from the state-to-state and the optical potential calculations, are between 2.5 and 3.5 times larger than these experimental numbers. Possible sources for discrepancies are discussed.

Rotational quenching of H2CO by molecular hydrogen: cross-sections, rates and pressure broadening

NASA Astrophysics Data System (ADS)

Wiesenfeld, L.; Faure, A.

2013-07-01

We compute the rotational quenching rates of the first 81 rotational levels of ortho- and para-H2CO in collision with ortho- and para-H2, for a temperature range of 10-300 K. We make use of the quantum close-coupling and coupled-state scattering methods combined with the high accuracy potential energy surface of Troscompt et al. Rates are significantly different from the scaled rates of H2CO in collision with He; consequently, critical densities are notably lower. We compare a full close-coupling computation of pressure broadening cross-sections with experimental data and show that our results are compatible with the low-temperature measurements of Mengel & De Lucia, for a spin temperature of H2 around 50 K.

Dendronized fullerene-porphyrin conjugates in ortho, meta, and para positions: a charge-transfer assay.

PubMed

Krokos, Evangelos; Schubert, Christina; Spänig, Fabian; Ruppert, Michaela; Hirsch, Andreas; Guldi, Dirk M

2012-06-01

The physicochemical characterization, that is, ground and excited state, of a new series of dendronized porphyrin/fullerene electron donor-acceptor conjugates in nonaqueous and aqueous environments is reported. In contrast to previous work, we detail the charge-separation and charge-recombination dynamics in zinc and copper metalloporphyrins as a function of first- and second-generation dendrons as well as a function of ortho, meta, and para substitution. Both have an appreciable impact on the microenvironments of the redox-active constituents, namely the porphyrins and the fullerenes. As a matter of fact, the resulting charge-transfer dynamics were considerably impacted by the interplay between the associated forces that reach from dendron-induced shielding to dipole-charge interactions. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Guia para su incorporacion a los Estados Unidos de America (A Guide to Resettlement in the United States. Spanish).

ERIC Educational Resources Information Center

Center for Applied Linguistics, Washington, DC. Refugee Service Center.

This resettlement guide, entirely in Spanish, describes the initial stage of resettlement and the processes that refugees undergo as new arrivals. Subjects covered in this guide include pre-arrival procedures, admissions criteria, immigrant's statement of understanding, travel costs and U.S. Customs; resettlement procedures, immigrants'…

Ideas Para Fortalecer Las Destrezas en Matematicas. Ideas for Strengthening Mathematics Skills. Spanish Edition.

ERIC Educational Resources Information Center

New York State Education Dept., Albany. Bureau of Bilingual Education.

Presented is an overview of some specific schemes that have been used successfully by teachers throughout New York State to strengthen basic mathematics skills. Components offer ideas that have been successful with primary, intermediate, and secondary students. The contents of this Spanish language edition are identical to the English language and…

Teorizando acerca del Conocimiento Productivo para Entender la Educacion Teorico Profesional (Theorizing about Productive Knowledge To Understand Professional Technical Education).

ERIC Educational Resources Information Center

Hidalgo, Abelardo Castro; Carrasco, Decler Martinez

2000-01-01

States that, internationally, Professional Technical Education emerges as a method of providing educational solutions for poor sectors of the population. Cites University of Chalmer (Sweden) and University of Bio-Bio (Chile) as institutions transformed into technological universities. Discusses what is productive knowledge and conditions under…

Trees of the Tapajós: a photographic field guide

Treesearch

John A. Parrotta; John K. Francis; Rionaldo R. de Almeida

1995-01-01

This book contains illustrations and descriptions, in English and Portuguese, of 172 tree species com­monly found in primary and secondary forests of the centrai Brazilian Amazon region, focussing on the Tapajos National Forest in western Para State. Photographic illustrations for each species include foliage (plus flowers and/or fruits for some species), seedling,...

Access to What? Access, Diversity and Participation in India's Schools. Research Monograph No. 32

ERIC Educational Resources Information Center

Juneja, Nalini

2010-01-01

India has witnessed substantial diversification of provision to basic education. Policy changes from 1980s onwards, has seen the creation of para-formal delivery systems and the inclusion in the system of non state providers. The Education Guarantee Scheme and the Alternate Initiatives in Education programmes have generated new pathways to access.…

Para Los Ninos -- For the Children: Improving Education for Mexican Americans.

ERIC Educational Resources Information Center

Sotomayor, Frank

The U.S. Commission on Civil Rights conducted the Mexican American Education Study between 1969 and 1974. Drawn from the published and unpublished findings of this study, this report discusses the education of Mexican Americans in the 5 Southwestern states of Arizona, California, Colorado, New Mexico, and Texas, where about 85 percent of all…

Multiple mutations in the para-sodium channel gene are associated with pyrethroid resistance in Rhipicephalus microplus from the United States and Mexico

USDA-ARS?s Scientific Manuscript database

Rhipicephalus microplus is an invasive tick vector that transmits the protozoan parasites Babesia bovis and B. bigemina, the causative agents of bovine babesiosis (cattle fever). Acaricide resistant R. microplus populations have become a major problem for many cattle producing areas of the world. Py...

H2 Ortho-to-para Conversion on Grains: A Route to Fast Deuterium Fractionation in Dense Cloud Cores?

NASA Astrophysics Data System (ADS)

Bovino, S.; Grassi, T.; Schleicher, D. R. G.; Caselli, P.

2017-11-01

Deuterium fractionation, I.e., the enhancement of deuterated species with respect to non-deuterated ones, is considered to be a reliable chemical clock of star-forming regions. This process is strongly affected by the ortho-to-para H2 ratio. In this Letter we explore the effect of the ortho-para (o-p) H2 conversion on grains on the deuteration timescale in fully-depleted dense cores, including the most relevant uncertainties that affect this complex process. We show that (I) the o-p H2 conversion on grains is not strongly influenced by the uncertainties on the conversion time and the sticking coefficient, and (II) that the process is controlled by the temperature and the residence time of ortho-H2 on the surface, I.e., by the binding energy. We find that for binding energies between 330 and 550 K, depending on the temperature, the o-p H2 conversion on grains can shorten the deuterium fractionation timescale by orders of magnitude, opening a new route for explaining the large observed deuteration fraction D frac in dense molecular cloud cores. Our results suggest that the star formation timescale, when estimated through the timescale to reach the observed deuteration fractions, might be shorter than previously proposed. However, more accurate measurements of the binding energy are needed in order to better assess the overall role of this process.

Weaving and neural complexity in symmetric quantum states

NASA Astrophysics Data System (ADS)

Susa, Cristian E.; Girolami, Davide

2018-04-01

We study the behaviour of two different measures of the complexity of multipartite correlation patterns, weaving and neural complexity, for symmetric quantum states. Weaving is the weighted sum of genuine multipartite correlations of any order, where the weights are proportional to the correlation order. The neural complexity, originally introduced to characterize correlation patterns in classical neural networks, is here extended to the quantum scenario. We derive closed formulas of the two quantities for GHZ states mixed with white noise.

Quantum-rotor-induced polarization.

PubMed

Meier, Benno

2018-07-01

Quantum-rotor-induced polarization is closely related to para-hydrogen-induced polarization. In both cases, the hyperpolarized spin order derives from rotational interaction and the Pauli principle by which the symmetry of the rotational ground state dictates the symmetry of the associated nuclear spin state. In quantum-rotor-induced polarization, there may be several spin states associated with the rotational ground state, and the hyperpolarization is typically generated by hetero-nuclear cross-relaxation. This review discusses preconditions for quantum-rotor-induced polarization for both the 1-dimensional methyl rotor and the asymmetric rotor H 2 17 O@C 60 , that is, a single water molecule encapsulated in fullerene C 60 . Experimental results are presented for both rotors. Copyright © 2018 John Wiley & Sons, Ltd.

Una Guia para Los Padres sobre La Educacion Especial: El Derecho de Su Hijo(a) a Adquirir una Educacion en el Estado de Nueva York (A Parent's Guide to Special Education: Your Child's Right to an Education in New York State).

ERIC Educational Resources Information Center

New York State Education Dept. Albany. Office for the Education of Children with Handicapping Conditions.

This guide provides information to help parents of special needs children in New York become active partners in the planning and implementation of special education programs. The first part of the guide provides in-depth information related to the special education process in New York State public schools. A historical view of children's rights to…

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

Megala, M.; Rajkumar, Beulah J. M., E-mail: beulah-rajkumar@yahoo.co.in

The electronic and optical transfer properties of Benzene, Benzoic Acid (BA), Nitrobenzene (NB) and Para Nitro Benzoic Acid (PNBA) at ground and first excited state has been investigated by the Density functional theory (DFT)and Time Dependent Density Functional Theory (TDDFT) using SVWN functional/3-21G basis set respectively. Possible intra-molecular charge transfer and n to π* transitions in the ground and the first excitation states have been predicted by the molecular orbitals and the Natural Bond Orbital (NBO) analysis. The simulated absorption spectra have been generated and the result compared with existing experimental results.

Action mechanism of tyrosinase on meta- and para-hydroxylated monophenols.

PubMed

Fenoll, L G; Rodríguez-López, J N; Varón, R; García-Ruiz, P A; García-Cánovas, F; Tudela, J

2000-04-01

The relationship between the structure and activity of meta- and para-hydroxylated monophenols was studied during their tyrosinase-catalysed hydroxylation and the rate-limiting steps of the reaction mechanism were identified. The para-hydroxylated substrates permit us to study the effect of a substituent (R) in the carbon-1 position (C-1) of the benzene ring on the nucleophilic attack step, while the meta group permits a similar study of the effect on the electrophilic attack step. Substrates with a -OCH3 group on C-1, as p-hydroxyanisol (4HA) and m-hydroxyanisol (3HA), or with a -CH2OH group, as p-hydroxybenzylalcohol (4HBA) and m-hydroxybenzylalcohol (3HBA), were used because the effect of the substituent (R) size was assumed to be similar. However, the electron-donating effect of the -OCH3 group means that the carbon-4 position (C-4) is favoured for nucleophilic attack (para-hydroxylated substrates) or for electrophilic attack (meta-hydroxylated substrates). The electron-attracting effect of the -CH2OH group has the opposite effect, hindering nucleophilic (para) or electrophilic (meta) attack of C-4. The experimental data point to differences between the maximum steady-state rate (V(M)Max) of the different substrates, the value of this parameter depends on the nucleophilic and electrophilic attack. However, differences are greatest in the Michaelis constants (K(M)m), with the meta-hydroxylated substrates having very large values. The catalytic efficiency k(M)cat/K(M)m is much greater for thepara-hydroxylated substrates although it varies greatly between one substrate and the other. However, it varies much less in the meta-hydroxylated substrates since this parameter describes the power of the nucleophilic attack, which is weaker in the meta OH. The large increase in the K(M)m of the meta-hydroxylated substrates might suggest that the phenolic OH takes part in substrate binding. Since this is a weaker nucleophil than the para-hydroxylated substrates, the binding constant decreases, leading to an increase in K(M)m. The catalytic efficiency of tyrosinase on a monophenol (para or meta) is directly related to the nucleophilic power of the oxygen of the phenolic OH. The oxidation step is not limiting since if this were the case, the para and meta substrates would have the same V(M)max. The small difference between the absolute values of V(M)max suggests that the rate constants of the nucleophilic and electrophilic attacks are on the same order of magnitude.

Undecidability and Irreducibility Conditions for Open-Ended Evolution and Emergence.

PubMed

Hernández-Orozco, Santiago; Hernández-Quiroz, Francisco; Zenil, Hector

2018-01-01

Is undecidability a requirement for open-ended evolution (OEE)? Using methods derived from algorithmic complexity theory, we propose robust computational definitions of open-ended evolution and the adaptability of computable dynamical systems. Within this framework, we show that decidability imposes absolute limits on the stable growth of complexity in computable dynamical systems. Conversely, systems that exhibit (strong) open-ended evolution must be undecidable, establishing undecidability as a requirement for such systems. Complexity is assessed in terms of three measures: sophistication, coarse sophistication, and busy beaver logical depth. These three complexity measures assign low complexity values to random (incompressible) objects. As time grows, the stated complexity measures allow for the existence of complex states during the evolution of a computable dynamical system. We show, however, that finding these states involves undecidable computations. We conjecture that for similar complexity measures that assign low complexity values, decidability imposes comparable limits on the stable growth of complexity, and that such behavior is necessary for nontrivial evolutionary systems. We show that the undecidability of adapted states imposes novel and unpredictable behavior on the individuals or populations being modeled. Such behavior is irreducible. Finally, we offer an example of a system, first proposed by Chaitin, that exhibits strong OEE.

High field hyperpolarization-EXSY experiment for fast determination of dissociation rates in SABRE complexes

NASA Astrophysics Data System (ADS)

Hermkens, Niels K. J.; Feiters, Martin C.; Rutjes, Floris P. J. T.; Wijmenga, Sybren S.; Tessari, Marco

2017-03-01

SABRE (Signal Amplification By Reversible Exchange) is a nuclear spin hyperpolarization technique based on the reversible concurrent binding of small molecules and para-hydrogen (p-H2) to an iridium metal complex in solution. At low magnetic field, spontaneous conversion of p-H2 spin order to enhanced longitudinal magnetization of the nuclear spins of the other ligands occurs. Subsequent complex dissociation results in hyperpolarized substrate molecules in solution. The lifetime of this complex plays a crucial role in attained SABRE NMR signal enhancements. Depending on the ligands, vastly different dissociation rates have been previously measured using EXSY or selective inversion experiments. However, both these approaches are generally time-consuming due to the long recycle delays (up to 2 min) necessary to reach thermal equilibrium for the nuclear spins of interest. In the cases of dilute solutions, signal averaging aggravates the problem, further extending the experimental time. Here, a new approach is proposed based on coherent hyperpolarization transfer to substrate protons in asymmetric complexes at high magnetic field. We have previously shown that such asymmetric complexes are important for application of SABRE to dilute substrates. Our results demonstrate that a series of high sensitivity EXSY spectra can be collected in a short experimental time thanks to the NMR signal enhancement and much shorter recycle delay.

GENERAL PERSPECTIVE VIEW OF THE COMPLEX, VIEW LOOKING NORTHWEST AT ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

GENERAL PERSPECTIVE VIEW OF THE COMPLEX, VIEW LOOKING NORTHWEST AT THE OREGON FORESTER'S OFFICE BUILDING, WITH MILL CREEK IN THE FOREGROUND. - Oregon State Forester's Office Complex, 2600 State Street, Salem, Marion, OR

GENERAL PERSPECTIVE VIEW OF THE COMPLEX, VIEW LOOKING WEST AT ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

GENERAL PERSPECTIVE VIEW OF THE COMPLEX, VIEW LOOKING WEST AT THE MOTORPOOL, AUTOMOTIVE SHOP AND FOREST PROTECTION BUILDING (FROM LEFT TO RIGHT). - Oregon State Forester's Office Complex, 2600 State Street, Salem, Marion, OR

Jahn-Teller distortion in the phosphorescent excited state of three-coordinate Au(I) phosphine complexes.

PubMed

Barakat, Khaldoon A; Cundari, Thomas R; Omary, Mohammad A

2003-11-26

DFT calculations were used to optimize the phosphorescent excited state of three-coordinate [Au(PR3)3]+ complexes. The results indicate that the complexes rearrange from their singlet ground-state trigonal planar geometry to a T-shape in the lowest triplet luminescent excited state. The optimized structure of the exciton contradicts the structure predicted based on the AuP bonding properties of the ground-state HOMO and LUMO. The rearrangement to T-shape is a Jahn-Teller distortion because an electron is taken from the degenerate e' (5dxy, 5dx2-y2) orbital upon photoexcitation of the ground-state D3h complex. The calculated UV absorption and visible emission energies are consistent with the experimental data and explain the large Stokes' shifts while such correlations are not possible in optimized models that constrained the exciton to the ground-state trigonal geometry.

Kinetics and mechanism of styrene epoxidation by chlorite: role of chlorine dioxide.

PubMed

Leigh, Jessica K; Rajput, Jonathan; Richardson, David E

2014-07-07

An investigation of the kinetics and mechanism for epoxidation of styrene and para-substituted styrenes by chlorite at 25 °C in the pH range of 5-6 is described. The proposed mechanism in water and water/acetonitrile includes seven oxidation states of chlorine (-I, 0, I, II, III, IV, and V) to account for the observed kinetics and product distributions. The model provides an unusually detailed quantitative mechanism for the complex reactions that occur in mixtures of chlorine species and organic substrates, particularly when the strong oxidant chlorite is employed. Kinetic control of the reaction is achieved by the addition of chlorine dioxide to the reaction mixture, thereby eliminating a substantial induction period observed when chlorite is used alone. The epoxidation agent is identified as chlorine dioxide, which is continually formed by the reaction of chlorite with hypochlorous acid that results from ClO produced by the epoxidation reaction. The overall stoichiometry is the result of two competing chain reactions in which the reactive intermediate ClO reacts with either chlorine dioxide or chlorite ion to produce hypochlorous acid and chlorate or chloride, respectively. At high chlorite ion concentrations, HOCl is rapidly eliminated by reaction with chlorite, minimizing side reactions between HOCl and Cl2 with the starting material. Epoxide selectivity (>90% under optimal conditions) is accurately predicted by the kinetic model. The model rate constant for direct reaction of styrene with ClO2(aq) to produce epoxide is (1.16 ± 0.07) × 10(-2) M(-1) s(-1) for 60:40 water/acetonitrile with 0.20 M acetate buffer. Rate constants for para substituted styrenes (R = -SO3(-), -OMe, -Me, -Cl, -H, and -NO2) with ClO2 were determined. The results support the radical addition/elimination mechanism originally proposed by Kolar and Lindgren to account for the formation of styrene oxide in the reaction of styrene with chlorine dioxide.

Innovation, development, and financing of institutions of Higher Education in health.

PubMed

Poz, Mario Roberto Dal; Couto, Maria Helena Costa; Franco, Thais de Andrade Vidaurre

2016-11-03

The article analyzes the configuration and trends in institutions of Higher Education and their relationship as components of the Health Economic-Industrial Complex (HEIC). The expansion of higher education is part of the transition from elite to mass systems, with tensions between quantitative and qualitative aspects. Such changes reflect different cultures and are related to international phenomena such as globalization, economic transformations, the development of new information and communication technologies, and the emergence of an international knowledge network. The scale and content of these changes vary according to the expansion and institutional reconfiguration of educational systems, as well as the link between state and society. Market expansion for private higher education stirs competition, shapes business clusters, modifies training processes, and raises new public policy challenges. Resumo: Este artigo analisa a configuração e as tendências das instituições de Ensino Superior de saúde no seu relacionamento enquanto componentes do Complexo Econômico Industrial da Saúde (CEIS). A expansão do Ensino Superior é parte da transição de sistemas de elite para sistemas de massa, com tensionamentos entre aspectos quantitativos e qualitativos. Essas mudanças refletem diferentes culturas e se relacionam com fenômenos de escopo mundial como globalização, transformações econômicas, desenvolvimento de novas tecnologias de comunicação e informação, e emergência de uma rede internacional de conhecimento. A escala e o conteúdo dessas mudanças variam com a ampliação dos sistemas de ensino e na reconfiguração institucional, bem como na articulação entre Estado e sociedade. A ampliação do mercado privado no ensino acirra a competitividade, conformando conglomerados empresariais, alterando processos de formação e forjando novos desafios para as políticas públicas.

Network complexity as a measure of information processing across resting-state networks: evidence from the Human Connectome Project

PubMed Central

McDonough, Ian M.; Nashiro, Kaoru

2014-01-01

An emerging field of research focused on fluctuations in brain signals has provided evidence that the complexity of those signals, as measured by entropy, conveys important information about network dynamics (e.g., local and distributed processing). While much research has focused on how neural complexity differs in populations with different age groups or clinical disorders, substantially less research has focused on the basic understanding of neural complexity in populations with young and healthy brain states. The present study used resting-state fMRI data from the Human Connectome Project (Van Essen et al., 2013) to test the extent that neural complexity in the BOLD signal, as measured by multiscale entropy (1) would differ from random noise, (2) would differ between four major resting-state networks previously associated with higher-order cognition, and (3) would be associated with the strength and extent of functional connectivity—a complementary method of estimating information processing. We found that complexity in the BOLD signal exhibited different patterns of complexity from white, pink, and red noise and that neural complexity was differentially expressed between resting-state networks, including the default mode, cingulo-opercular, left and right frontoparietal networks. Lastly, neural complexity across all networks was negatively associated with functional connectivity at fine scales, but was positively associated with functional connectivity at coarse scales. The present study is the first to characterize neural complexity in BOLD signals at a high temporal resolution and across different networks and might help clarify the inconsistencies between neural complexity and functional connectivity, thus informing the mechanisms underlying neural complexity. PMID:24959130

Electronic spectra and photophysics of platinum(II) complexes with alpha-diimine ligands - Solid-state effects. I - Monomers and ligand pi dimers

NASA Technical Reports Server (NTRS)

Miskowski, Vincent M.; Houlding, Virginia H.

1989-01-01

Two types of emission behavior for Pt(II) complexes containing alpha-diimine ligands have been observed in dilute solution. If the complex also has weak field ligands such as chloride, ligand field (d-d) excited states become the lowest energy excited states. If only strong field ligands are present, a diimine 3(pi-pi/asterisk/) state becomes the lowest. In none of the cases studied did metal-to-ligand charge transfer excited state lie lowest.

Dynamics of harpooning studied by transition state spectroscopy. II. LiṡṡFH

NASA Astrophysics Data System (ADS)

Hudson, A. J.; Oh, H. B.; Polanyi, J. C.; Piecuch, P.

2000-12-01

The van der Waals complex LiṡṡFH was formed in crossed beams and the transition state of the excited-state reaction, Li*(2p 2P)+HF→LiF+H, was accessed by photoexcitation of this complex. The dynamics of the excited-state reaction were probed by varying the excitation wavelength over the range 570-970 nm while recording the photodepletion of the complex. The findings were interpreted using high-level ab initio calculations of the ground and lowest excited-state potential-energy surfaces.

On the importance of excited state dynamic response electron correlation in polarizable embedding methods.

PubMed

Eriksen, Janus J; Sauer, Stephan P A; Mikkelsen, Kurt V; Jensen, Hans J Aa; Kongsted, Jacob

2012-09-30

We investigate the effect of including a dynamic reaction field at the lowest possible ab inito wave function level of theory, namely the Hartree-Fock (HF) self-consistent field level within the polarizable embedding (PE) formalism. We formulate HF based PE within the linear response theory picture leading to the PE-random-phase approximation (PE-RPA) and bridge the expressions to a second-order polarization propagator approximation (SOPPA) frame such that dynamic reaction field contributions are included at the RPA level in addition to the static response described at the SOPPA level but with HF induced dipole moments. We conduct calculations on para-nitro-aniline and para-nitro-phenolate using said model in addition to dynamic PE-RPA and PE-CAM-B3LYP. We compare the results to recently published PE-CCSD data and demonstrate how the cost effective SOPPA-based model successfully recovers a great portion of the inherent PE-RPA error when the observable is the solvatochromic shift. We furthermore demonstrate that whenever the change in density resulting from the ground state-excited state electronic transition in the solute is not associated with a significant change in the electric field, dynamic response contributions formulated at the HF level of theory manage to capture the majority of the system response originating from derivative densities. Copyright © 2012 Wiley Periodicals, Inc.

Dual fluorescence of excited state intra-molecular proton transfer of HBFO: mechanistic understanding, substituent and solvent effects.

PubMed

Yang, Wenjing; Chen, Xuebo

2014-03-07

A combined approach of the multiconfigurational perturbation theory with the Rice-Ramsperger-Kassel-Marcus methodology has been employed to calculate the minimum potential energy profiles and the rates of excited state intra-molecular proton transfer (ESIPT) for the WOLED material molecule of HBFO and its four meta- or para-substituted compounds in gas phase, acetonitrile and cyclohexane solvents. The kinetic control for these reactions is quantitatively determined and extensively studied on the basis of the accurate potential energy surfaces when the thermodynamic factor associated with the free energy change becomes negligible in the case of the existence of a significant barrier in the ESIPT process. These computational efforts contribute to a deep understanding of the ESIPT mechanism, dual emission characteristics, kinetic controlling factor, substituent and solvent effects for these material molecules. The white light emission is generated by the establishment of dynamic equilibrium between enol and keto forms in the charge transfer excited SCT((1)ππ*) state. The performance of white light emission is quantitatively demonstrated to be mainly sensitive to the molecular tailoring approach of the electronic properties of meta- or para- substituents by the modulation of the forward/backward ESIPT rate ratio. The quality of white light emission is slightly tunable through its surrounding solvent environment. These computational results will provide a useful strategy for the molecular design of OLED and WOLED materials.

Weaving and neural complexity in symmetric quantum states

DOE PAGES

Susa, Cristian E.; Girolami, Davide

2017-12-27

Here, we study the behaviour of two different measures of the complexity of multipartite correlation patterns, weaving and neural complexity, for symmetric quantum states. Weaving is the weighted sum of genuine multipartite correlations of any order, where the weights are proportional to the correlation order. The neural complexity, originally introduced to characterize correlation patterns in classical neural networks, is here extended to the quantum scenario. We derive closed formulas of the two quantities for GHZ states mixed with white noise.

Weaving and neural complexity in symmetric quantum states

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

Susa, Cristian E.; Girolami, Davide

Here, we study the behaviour of two different measures of the complexity of multipartite correlation patterns, weaving and neural complexity, for symmetric quantum states. Weaving is the weighted sum of genuine multipartite correlations of any order, where the weights are proportional to the correlation order. The neural complexity, originally introduced to characterize correlation patterns in classical neural networks, is here extended to the quantum scenario. We derive closed formulas of the two quantities for GHZ states mixed with white noise.

Excited-State Proton-Transfer-Induced Trapping Enhances the Fluorescence Emission of a Locked GFP Chromophore

PubMed Central

2016-01-01

The chemical locking of the central single bond in core chromophores of green fluorescent proteins (GFPs) influences their excited-state behavior in a distinct manner. Experimentally, it significantly enhances the fluorescence quantum yield of GFP chromophores with an ortho-hydroxyl group, while it has almost no effect on the photophysics of GFP chromophores with a para-hydroxyl group. To unravel the underlying physical reasons for this different behavior, we report static electronic structure calculations and nonadiabatic dynamics simulations on excited-state intramolecular proton transfer, cis–trans isomerization, and excited-state deactivation in a locked ortho-substituted GFP model chromophore (o-LHBI). On the basis of our previous and present results, we find that the S1 keto species is responsible for the fluorescence emission of the unlocked o-HBI and the locked o-LHBI species. Chemical locking does not change the parts of the S1 and S0 potential energy surfaces relevant to enol–keto tautomerization; hence, in both chromophores, there is an ultrafast excited-state intramolecular proton transfer that takes only 35 fs on average. However, the locking effectively hinders the S1 keto species from approaching the keto S1/S0 conical intersections so that most of trajectories are trapped in the S1 keto region for the entire 2 ps simulation time. Therefore, the fluorescence quantum yield of o-LHBI is enhanced compared with that of unlocked o-HBI, in which the S1 excited-state decay is efficient and ultrafast. In the case of the para-substituted GFP model chromophores p-HBI and p-LHBI, chemical locking hardly affects their efficient excited-state deactivation via cis–trans isomerization; thus, the fluorescence quantum yields in these chromophores remain very low. The insights gained from the present work may help to guide the design of new GFP chromophores with improved fluorescence emission and brightness. PMID:26744782

Evaluating the Nature of So-Called S*-State Feature in Transient Absorption of Carotenoids in Light-Harvesting Complex 2 (LH2) from Purple Photosynthetic Bacteria.

PubMed

Niedzwiedzki, Dariusz M; Hunter, C Neil; Blankenship, Robert E

2016-11-03

Carotenoids are a class of natural pigments present in all phototrophic organisms, mainly in their light-harvesting proteins in which they play roles of accessory light absorbers and photoprotectors. Extensive time-resolved spectroscopic studies of these pigments have revealed unexpectedly complex photophysical properties, particularly for carotenoids in light-harvesting LH2 complexes from purple bacteria. An ambiguous, optically forbidden electronic excited state designated as S* has been postulated to be involved in carotenoid excitation relaxation and in an alternative carotenoid-to-bacteriochlorophyll energy transfer pathway, as well as being a precursor of the carotenoid triplet state. However, no definitive and satisfactory origin of the carotenoid S* state in these complexes has been established, despite a wide-ranging series of studies. Here, we resolve the ambiguous origin of the carotenoid S* state in LH2 complex from Rba. sphaeroides by showing that the S* feature can be seen as a combination of ground state absorption bleaching of the carotenoid pool converted to cations and the Stark spectrum of neighbor neutral carotenoids, induced by temporal electric field brought by the carotenoid cation-bacteriochlorophyll anion pair. These findings remove the need to assign an S* state, and thereby significantly simplify the photochemistry of carotenoids in these photosynthetic antenna complexes.

Fine-Tuning of Saponification-Triggered Gelation by Strategic Modification of Peripheral Substituents: Gelation Regulators.

PubMed

Kumar, Ashish; Singh, Roop Shikha; Kumar, Amit; Ali, Afsar; Biswas, Arnab; Pandey, Daya Shankar

2016-09-19

A pioneering approach towards controlling the efficiency of saponification assisted gelation in ethyl ester based Zn II -complexes have been described. Using four new ester containing bis-salen Zn II complexes (C1-C4) involving different para-azo phenyl substituted ligands it has been clearly shown that gelation efficiency is greatly influenced by the electronic effects of the substituents (-H (C1), -CH 3 (C2), -NO 2 (C3), and -OCH 3 (C4)). Morphological, photophysical, and rheological investigations corroborated the experimental observations well and established that gelation efficiency was enhanced with electron-withdrawing characteristics of substituents (C4

GENERAL PERSPECTIVE VIEW OF THE COMPLEX, VIEW LOOKING EAST AT ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

GENERAL PERSPECTIVE VIEW OF THE COMPLEX, VIEW LOOKING EAST AT THE FOREST PROTECTION BUILDING, THE MOTORPOOL, AND THE AUTOMOTIVE SHOP (FROM LEFT TO RIGHT). - Oregon State Forester's Office Complex, 2600 State Street, Salem, Marion, OR

First principles molecular dynamics study of nitrogen vacancy complexes in boronitrene

NASA Astrophysics Data System (ADS)

Ukpong, A. M.; Chetty, N.

2012-07-01

We present the results of first principles molecular dynamics simulations of nitrogen vacancy complexes in monolayer hexagonal boron nitride. The threshold for local structure reconstruction is found to be sensitive to the presence of a substitutional carbon impurity. We show that activated nitrogen dynamics triggers the annihilation of defects in the layer through formation of Stone-Wales-type structures. The lowest energy state of nitrogen vacancy complexes is negatively charged and spin polarized. Using the divacancy complex, we show that their formation induces spontaneous magnetic moments, which is tunable by electron or hole injection. The Fermi level s-resonant defect state is identified as a unique signature of the ground state of the divacancy complex. Due to their ability to enhance structural cohesion, only the divacancy and the nitrogen vacancy carbon-antisite complexes are able to suppress the Fermi level resonant defect state to open a gap between the conduction and valence bands.

Phenol oxidation through its adduct formation with chromium complex of 1,4,8,11-tetrakis(2-pyridylmethyl)-1,4,8,11-tetraazacyclotetradecane: A theoretical study

NASA Astrophysics Data System (ADS)

Narayanan, Jayanthi; Guadalupe, Hernández J.; Thangarasu, Pandiyan

2017-04-01

Structural and electronic properties of [cis-[Cr(tmpcH)X2]n+ (n = 2 or 4; X = OH-, Cl-, Br- and H2O; tmpcH = 1,4,8,11-tetrakis(2-pyridylmethyl)-1,4,8,11-tetraazacyclotetradecane were analyzed by DFT and TD-DFT methods. The local reactivity active site of the ligand was determined by the condensed-to atom Fukui indexes (CAFI) f(r). In the study, the axial bond distance with metal ion undergoes a considerable change from shorter to longer as OH < Cl- < Br- < H2O, agreeing with the molecular orbital analysis where the dz2 energy is lowered for OH- compared to H2O at the axial position. After analyzing the geometrical data collected from literature for the complexes of Cr(II), Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn (II) with tmpcH, it was found that the bond distance decreases with increasing number of d-electrons in the 3d orbital, suggesting that the over-lapping of oribital (π) from Npy with the metal d-orbital is more effective than those from Ncyclam with metal d-orbital. Therefore, the change of different oxidation states for [cis-[Cr(tmpcH)X2]n+ influences significantly the geometrical and electronic parameters. For cis-[Cr(tmpcH)Cl2]2+ the calculated bands are red shifted except for the lower energy band (595 nm) which agrees qualitatively with the experimental one; in addition, the effect of solvent on the electronic transition was analyzed. Furthermore, we collected the electronic data for several chromium complexes from the literature, and compared with our results by plotting the data against number of chromium compounds. Finally, the phenol oxidation properties of the chromium complexes were studied, and phenol forms an adduct with [Cr(tmpcH)Cl]3+ to yield [Cr(tmpcH)Cl-OPh]2+ which could produce the phenol radical, which is enhanced by the presence of -OCH3 group at para- position in the phenolic ring.

Analysis of Pilot Feedback Regarding the Use of State Awareness Technologies During Complex Situations

NASA Technical Reports Server (NTRS)

Evans, Emory; Young, Steven D.; Daniels, Taumi; Santiago-Espada, Yamira; Etherington, Tim

2016-01-01

A flight simulation study was conducted at NASA Langley Research Center to evaluate flight deck systems that (1) predict aircraft energy state and/or autoflight configuration, (2) present the current state and expected future state of automated systems, and/or (3) show the state of flight-critical data systems in use by automated systems and primary flight instruments. Four new technology concepts were evaluated vis-à-vis current state-of-the-art flight deck systems and indicators. This human-in-the-loop study was conducted using commercial airline crews. Scenarios spanned a range of complex conditions and several emulated causal factors and complexity in recent accidents involving loss of state awareness by pilots (e.g. energy state, automation state, and/or system state). Data were collected via questionnaires administered after each flight, audio/video recordings, physiological data, head and eye tracking data, pilot control inputs, and researcher observations. This paper strictly focuses on findings derived from the questionnaire responses. It includes analysis of pilot subjective measures of complexity, decision making, workload, situation awareness, usability, and acceptability.

Selective Inhibition of Deactivated Mitochondrial Complex I by Biguanides †

PubMed Central

Matsuzaki, Satoshi; Humphries, Kenneth M.

2015-01-01

Biguanides are widely used antihyperglycemic agents for diabetes mellitus and prediabetes treatment. Complex I is the rate limiting step of the mitochondrial electron transport chain (ETC), a major source of mitochondrial free radical production, and a known target of biguanides. Complex I has two reversible conformational states, active and de-active. The deactivated state is promoted in the absence of substrates, but is rapidly and fully reversed to the active state in the presence of NADH. The objective of this study was to determine the relative sensitivity of active/de-active complex I to biguanide-mediated inhibition and resulting superoxide radical (O2•−) production. Using isolated rat heart mitochondria, we show that deactivation of complex I sensitizes it to metformin and phenformin (4- and 3-fold, respectively), but not to other known complex I inhibitors, such as rotenone. Mitochondrial O2•− production by deactivated complex I was measured fluorescently by the NADH-dependent 2-hydroxyethidium formation at alkaline pH to impede reactivation. Superoxide production was 260.4% higher than in active complex I at pH 9.4. However, phenformin treatment of de-active complex I decreased O2•− production by 14.9% while rotenone increased production by 42.9%. Mitochondria isolated from rat hearts subjected to cardiac ischemia, a condition known to induce complex I deactivation, were sensitized to phenformin:mediated complex I inhibition. This supports that the effects of biguanides are likely to be influenced by the complex I state in vivo. These results demonstrate that the complex I active/de-active states are a determinant in biguanide-mediated inhibition. PMID:25719498

Formation of solvate structures by the ortho-, meta-, and para-isomers of hydroxybenzoic acid in supercritical fluid

NASA Astrophysics Data System (ADS)

Antipova, M. L.; Gurina, D. L.; Odintsova, E. G.; Petrenko, V. E.

2017-04-01

The solvate structures formed by the ortho-, meta-, and para-isomers of hydroxybenzoic acid ( o-HBA, m-HBA, and p-HBA) with a polar co-solvent (methanol at a concentration of 0.030 and 0.035 mole fractions) in supercritical carbon dioxide at a constant density of 0.7 g/cm3 and temperatures of 318 and 328 K have been studied by the classic molecular dynamics. It has been determined that a stable hydrogen-bonded complex with the co-solvent forms via the hydrogen of the carboxyl group for all isomers. The probability of this complex existence is high at all temperatures and concentrations. In the o-HBA molecule, the other functional groups are engaged in the intramolecular hydrogen bond, but not involved in interactions with methanol. It has been found that m-HBA and p-HBA can be involved in hydrogen bonds with methanol via hydroxyl hydrogen and oxygen atoms; they are characterized by the presence of one more co-solvent molecule (rarely, two molecules) in their solvation shell and intermittent formations/breakages of hydrogen bonds via other functional groups. These bonds are far less stable, and their formation is sensitive to change of temperature and co-solvent concentration. It has been concluded that the degree of selective solvation of m-HBA and p-HBA by co-solvent molecules is approximately the same, but the rate of structural rearrangements in the nearest environment of m-HBA is higher than that of p-HBA.

Mechanistic aspects of hydrogen abstraction for phenolic antioxidants. Electronic structure and topological electron density analysis.

PubMed

Singh, Nakul; O'Malley, Patrick J; Popelier, Paul L A

2005-02-21

Density functional calculations using the B3LYP functional are used to provide insight into the hydrogen abstraction mechanism of phenolic antioxidants. The energy profiles for 13 ortho, meta, para and di-methyl substituted phenols with hydroperoxyl radical have been determined. An excellent correlation between the enthalpy (DeltaH) and activation energy (DeltaEa) was found, obeying the Evans-Polanyi rule. The effects of hydrogen bonding on DeltaEa are also discussed. Electron donating groups at the ortho and para positions are able to lower the activation energy for hydrogen abstraction. The highly electron withdrawing fluoro substituent increases the activation energies relative to phenol at the meta position but not at the para position. The electron density is studied using the atoms in molecules (AIM) approach. Atomic and bond properties are extracted to describe the hydrogen atom abstraction mechanism. It is found that on going from reactants to transition state, the hydrogen atom experiences a loss in volume, electronic population and dipole moment. These features suggest that the phenol hydroperoxyl reactions proceed according to a proton coupled electron transfer (PCET) as opposed to a hydrogen atom transfer (HAT) mechanism.

Concentration and emission sources of airborne metals in particulate matter in the industrial district of Médio Paraíba, state of Rio de Janeiro, Brazil.

PubMed

Loyola, Josiane; de Almeida, Pierre Batista; Quiterio, Simone Lorena; Sousa, Célia Regina; Arbilla, Graciela; Escaleira, Viviane; de Carvalho, Maria Isabel; dos Santos Amaral Gomes da Silva, Alzira

2006-11-01

Total suspended particles and 12 airborne metals were determined in 4 sampling sites in the industrial region of Médio Paraíba, Brazil. The geometrical means for the four sampling locals were (in units of microg/m3): 65.9 in Barra Mansa, 57.3 in Jardim Paraíba (Volta Redonda), 41.7 in Resende, and 48.9 in Volta Grande (Volta Redonda). These values are lower than levels previously determined in urban and industrial locals of the Metropolitan Area of Rio de Janeiro. For metals, the higher concentrations were obtained for Ca, Zn, Al, Fe, and Mg. Ca, Zn, and Al levels are higher than those determined in other industrial areas. These three metals are used in steel manufacturing, the main economical activity of the region. Enrichment factors for Zn, Cu, Cd, and Pb are higher than 10, suggesting an industrial input. Statistical analysis show a high correlation among Ca, Mg, Zn, Cr, Al, Mn, and Fe, all of them used as raw materials in steel manufacturing and/or accumulated as industrial blast furnace slag and steelworks slag.

Resonances in the reaction ortho- and para- D2 + H at temperatures below 10 K

NASA Astrophysics Data System (ADS)

Simbotin, I.; Côté, R.

2016-05-01

In a previous study we reported cross sections for the reaction H2 + D in the temperature regime 10-6 < T < 10 K, and found pronounced shape resonances, especially in the p and d partial waves. We found that the resonant structures were sensitive to the initial rovibrational state of H2; in particular, we showed that the effect of the nuclear-spin symmetry was very important, since ortho- and para- H2 gave significantly different results. We now investigate the reaction D2 + H for vibrationally excited ortho- and para- D2, and compare and contrast these results with those for H2 + D. We remark that this benchmark system is a prototypical example of reactions with a strong barrier, which have very small cross sections in the cold and ultracold regimes. However, shape resonances can enhance the reaction cross sections by orders of magnitude for temperatures around and below T = 1 K. Moreover, resonant features would provide stringent tests for quantum chemistry calculations of potential energy surfaces. Partial support from the US Army Research Office (Grant No. W911NF-13-1-0213).

Pyrrole multimers and pyrrole-acetylene hydrogen bonded complexes studied in N2 and para-H2 matrixes using matrix isolation infrared spectroscopy and ab initio computations

NASA Astrophysics Data System (ADS)

Sarkar, Shubhra; Ramanathan, N.; Gopi, R.; Sundararajan, K.

2017-12-01

Hydrogen bonded interaction of pyrrole multimer and acetylene-pyrrole complexes were studied in N2 and p-H2 matrixes. DFT computations showed T-shaped geometry for the pyrrole dimer and cyclic complex for the trimer and tetramer were the most stable structures, stabilized by Nsbnd H⋯π interactions. The experimental vibrational wavenumbers observed in N2 and p-H2 matrixes for the pyrrole multimers were correlated with the computed wavenumbers. Computations performed at MP2/aug-cc-pVDZ level of theory showed that C2H2 and C4H5N forms 1:1 hydrogen-bonded complexes stabilized by Csbnd H⋯π interaction (Complex A), Nsbnd H⋯π interaction (Complex B) and π⋯π interaction (Complex C), where the former complex is the global minimum and latter two complexes were the first and second local minima, respectively. Experimentally, 1:1 C2H2sbnd C4H5N complexes A (global minimum) and B (first local minimum) were identified from the shifts in the Nsbnd H stretching, Nsbnd H bending, Csbnd H bending region of pyrrole and Csbnd H asymmetric stretching and bending region of C2H2 in N2 and p-H2 matrixes. Computations were also performed for the higher complexes and found two minima corresponding to the 1:2 C2H2sbnd C4H5N and three minima for the 2:1 C2H2sbnd C4H5N complexes. Experimentally the global minimum 1:2 and 2:1 C2H2sbnd C4H5N complexes were identified in N2 and p-H2 matrixes.

Infrared spectroscopy of solid normal hydrogen doped with CH3F and O2 at 4.2 K: CH3F:O2 complex and CH3F migration

NASA Astrophysics Data System (ADS)

Abouaf-Marguin, L.; Vasserot, A.-M.

2011-04-01

Double doping of solid normal hydrogen with CH3F and O2 at about 4.2 K gives evidence of (ortho-H2)n:CH3F clusters and of O2:CH3F complex formation. FTIR analysis of the time evolution of the spectra in the region of the v3 C-F stretching mode indicates that these clusters behave very differently from (ortho-H2)n:H2O clusters. The main point is the observed migration of CH3F molecules in solid para-H2 at 4.2 K which differs from that of H2O under identical experimental conditions. This is confirmed by an increase over time of the integrated intensity of the CH3F:O2 complex with a rate constant K = 2.7(2) . 10-4 s-1.

California Master Plan for Migrant Education, 1976 Edition (Plan Maestro de California para Educacion Migrante, Edicion de 1976).

ERIC Educational Resources Information Center

California State Dept. of Education, Sacramento. Div. of Compensatory Education.

Based on the national migrant education plan, California's master plan aims to mobilize the necessary State and Federal resources, and to unify and assist the efforts of local educational agencies to end the migrant child's failure in school. The plan includes provisions for: instructional activities on a regular and extended year basis designed…

How Can We Provide Safe Playgrounds? = Como podemos proveer lugares con juegos infantiles que no sean peligrosos para los ninos?

ERIC Educational Resources Information Center

ACCESS ERIC, Rockville, MD.

Outdoor playgrounds can be exciting places where children explore their environment and develop motor and social skills; however, they can also pose serious safety hazards. With the exception of California, no mandatory state or federal standards currently exist regarding manufacture or installation of playground equipment or surfaces. The…

Ayuda para Ninos Especiales (Help for Special Children).

ERIC Educational Resources Information Center

Simon, Rosalyn

In large type and in very simple language, this pamphlet informs parents, in Spanish, about the provisions of Public Law 94-142. It states that children with handicaps can go to public school with other children, that the school must give the special help that children with handicaps need to learn in school, and that the special help is called…

Financial Aid for Students Workbook, 1994-95 School Year = Ayuda Financiera para Estudiantes, Libreta del Ano Escolar 1994-95.

ERIC Educational Resources Information Center

California Student Aid Commission, Sacramento.

Presented in both English and Spanish language formats, this workbook explains how California residents can qualify for and obtain student financial aid in the form of federal and state grants and loans, work-study programs, institutional grants, federal campus-based programs, and the Federal Family Education Loan Program loans. A calendar of…

Materiales en Marcha para el Esfuerzo Bilingue-Bicultural (Materials on the March for the Promotion of Bilingualism/Biculturalism).

ERIC Educational Resources Information Center

San Diego City Schools, CA.

This newsletter is designed for use by teachers, counselors, and administrators involved in bilingual-bicultural education. In the first article C. V. Perez describes bilingual education programs in New York State. J. N. Vieira writes in Portuguese about the Brown University bilingual program. In her article "Portuguese Happenings," J.…

Homework Tips for Parents = Consejos para los padres sobre la tarea escola.

ERIC Educational Resources Information Center

Department of Education, Washington, DC. Office of Intergovernmental and Interagency Affairs.

Homework has been a part of students' lives since the beginning of formal school in the United States; the push for increased homework has increased, fueled by rising academic standards. Noting that parents involved can have either a positive or a negative influence on the value of homework, this booklet, in both English and Spanish, offers…

Guia Legal para Ciudadanos Envejeciente: Leyes y Programas Afectando los Ciudadanos Envejeciente de Kansas. (Legal Guide for Senior Citizens: Laws and Programs Affecting Kansas Senior Citizens).

ERIC Educational Resources Information Center

Hollinger, Judith A.

This booklet, translated into Spanish, is intended to inform (not advise) older Kansans about eligibility requirements and benefits provided by state and federal programs. Financial assistance programs discussed are Social Security, railroad retirements, veterans' benefits, unrestricted general assistance, Employee Retirement Income Security Act,…

Una Guia de Consejos Practicos Sobre la Lectura para los Padres (A Guide to Reading Tips for Parents).

ERIC Educational Resources Information Center

Department of Education, Washington, DC.

The No Child Left Behind program changes the federal role in education by asking America's schools to describe their success in terms of what each student accomplishes. The information in this reading guide, presented in Spanish, was developed by the United States Department of Education to assist parents, caregivers, and teachers in understanding…

Dominican Republic: Political and Economic Conditions and Relations with the United States

DTIC Science & Technology

2005-03-08

Killed in Dominican Republic Prison Fire,” The New York Times, March 8, 2008. 8 See Gerardo Reyes, “Esclavos en Paraíso,”El Nuevo Herald, Jan. 9... Perez , “Widespread Blackouts Leave President Scrambling to Boost Power,” Agence France-Presse, Feb. 8, 2000. 13 Jose de Cordoba, “Caribbean Cloud,”Wall

Designing an Intervention to Promote Critical Thinking about Statistics in the General Public

ERIC Educational Resources Information Center

Velautham, Leela

2017-01-01

"One in five American households do not have a single member in the labor force." This was a statistic heralded by President-elect Donald Trump (Appelbaum, 2016, para. 2), in a speech during the election campaign, to illustrate the apparently huge number of unemployed Americans and, thus, to expose the perilous state of the American…

Tracking and Treating Mobile Populations. The TB Net System. Migrant Clinicians Network Monograph Series. = El Sistema de Red para la TB.

ERIC Educational Resources Information Center

Migrant Clinicians Network, Inc., Austin, TX.

A comprehensive tracking and referral network that helps provide continuity of care for mobile populations with active tuberculosis (TB) or TB infection is considered essential for effective treatment of TB. However, the interstate referral system that exists between state health departments has been highly inefficient for serving migrant…

Aflatoxin M₁ in raw milk from different regions of São Paulo state--Brazil.

PubMed

Santili, Ana Beatriz Nappi; de Camargo, Adriano Costa; Nunes, Raquel de Syllos Rosa; da Gloria, Eduardo Micotti; Machado, Paulo Fernando; Cassoli, Laerte Dagher; Dias, Carlos Tadeu dos Santos; Calori-Domingues, Maria Antonia

2015-01-01

A total of 635 raw milk samples from 45 dairy farms, from three regions of São Paulo state - Brazil, were evaluated during 15 months for aflatoxin M1 (AFM1). AFM1 was determined by high performance liquid chromatograph with fluorescence detection. AFM1 was detected (>0.003 µg kg(-1)) in 72.9%, 56.3% and 27.5% of the samples from Bauru, Araçatuba and Vale do Paraíba regions, respectively. The mean AFM1 contamination considering all the samples was 0.021 µg kg(-1). Furthermore, the concentration of AFM1 was quite different among Bauru (0.038 µg kg(-1)), Araçatuba (0.017 µg kg(-1)) and Vale do Paraíba (<0.01 µg kg(-1)) regions. Only three samples (0.5%) had higher contamination than the tolerated limit in Brazil (0.50 µg kg(-1)) and 64 samples (10.1%) had a higher contamination than the maximum limit as set by the European Union (0.050 µg kg(-1)). The estimated AFM1 daily intake was 0.358 and 0.120 ng kg(-1) body weight per day for children and adults, respectively.

Hyperfine excitation of C2H and C2D by para-H2

NASA Astrophysics Data System (ADS)

Dumouchel, Fabien; Lique, François; Spielfiedel, Annie; Feautrier, Nicole

2017-10-01

The [C2H]/[C2D] abundance ratio is a useful tool to explore the physical and chemical conditions of cold molecular clouds. Hence, an accurate determination of both the C2H and C2D abundances is of fundamental interest. Due to the low density of the interstellar medium, the population of the energy levels of the molecules is not at local thermodynamical equilibrium. Thus, the accurate modelling of the emission spectra requires the calculation of collisional rate coefficients with the most abundant interstellar species. Hence, we provide rate coefficients for the hyperfine excitation of C2H and C2D by para-H2(j=0), the most abundant collisional partner in cold molecular clouds. State-to-state rate coefficients between the lowest levels were computed for temperatures ranging from 5 to 80 K. For both isotopologues, the Δj = ΔF propensity rule is observed. The comparison between C2H and C2D rate coefficients shows that differences by up to a factor of two exist, mainly for Δj = ΔN = 1 transitions. The new rate coefficients will significantly help in the interpretation of recent observed spectra.

Salud para su Corazón: a community-based Latino cardiovascular disease prevention and outreach model.

PubMed

Alcalay, R; Alvarado, M; Balcazar, H; Newman, E; Huerta, E

1999-10-01

Cardiovascular disease (CVD) is the leading cause of death for Latinos living in the United States. This population is generally unaware of important lifestyle or behavioral changes that can prevent CVD. The National Heart, Lung, and Blood Institute (NHLBI) designed and implemented Salud para su Corazón (Health for Your Heart), a culturally appropriate, community-based, theory-driven intervention model. NHLBI's goals were: (1) to design an intervention model appropriate to Latino populations; (2) to pilot test the model in a specific community with the objectives of increasing awareness about heart disease, raising knowledge about CVD prevention, and promoting heart-healthy lifestyles; and (3) to disseminate the model and the materials developed to other communities with similar needs. An agency-community partnership, under the leadership of the Community Alliance for Heart Health, guided all stages of the community intervention project. The multimedia bilingual community intervention included television telenovela format public service announcements (PSAs), radio programs, brochures, recipe booklets, charlas, a promotores training manual, and motivational videos. An evaluation survey assessed the impact of the intervention. A pre-post intervention survey was conducted with more than 300 participants, and results showed that the respondents were substantially more aware of risk factors for CVD, and had greatly increased their knowledge of ways to prevent heart disease. Dissemination efforts have resulted in numerous requests by health organizations, universities, and health maintenance organizations (HMOs) for educational materials and communication strategies produced by Salud para su Corazón. In addition, Univision, the largest Spanish-language broadcast television network, is airing the initiative's PSAs. Also, training seminars for promotores are being conducted in different regions of the United States, and several locations are planning to replicate this study.

Time domain para hydrogen induced polarization.

PubMed

Ratajczyk, Tomasz; Gutmann, Torsten; Dillenberger, Sonja; Abdulhussaein, Safaa; Frydel, Jaroslaw; Breitzke, Hergen; Bommerich, Ute; Trantzschel, Thomas; Bernarding, Johannes; Magusin, Pieter C M M; Buntkowsky, Gerd

2012-01-01

Para hydrogen induced polarization (PHIP) is a powerful hyperpolarization technique, which increases the NMR sensitivity by several orders of magnitude. However the hyperpolarized signal is created as an anti-phase signal, which necessitates high magnetic field homogeneity and spectral resolution in the conventional PHIP schemes. This hampers the application of PHIP enhancement in many fields, as for example in food science, materials science or MRI, where low B(0)-fields or low B(0)-homogeneity do decrease spectral resolution, leading to potential extinction if in-phase and anti-phase hyperpolarization signals cannot be resolved. Herein, we demonstrate that the echo sequence (45°-τ-180°-τ) enables the acquisition of low resolution PHIP enhanced liquid state NMR signals of phenylpropiolic acid derivatives and phenylacetylene at a low cost low-resolution 0.54 T spectrometer. As low field TD-spectrometers are commonly used in industry or biomedicine for the relaxometry of oil-water mixtures, food, nano-particles, or other systems, we compare two variants of para-hydrogen induced polarization with data-evaluation in the time domain (TD-PHIP). In both TD-ALTADENA and the TD-PASADENA strong spin echoes could be detected under conditions when usually no anti-phase signals can be measured due to the lack of resolution. The results suggest that the time-domain detection of PHIP-enhanced signals opens up new application areas for low-field PHIP-hyperpolarization, such as non-invasive compound detection or new contrast agents and biomarkers in low-field Magnetic Resonance Imaging (MRI). Finally, solid-state NMR calculations are presented, which show that the solid echo (90y-τ-90x-τ) version of the TD-ALTADENA experiment is able to convert up to 10% of the PHIP signal into visible magnetization. Copyright © 2012 Elsevier Inc. All rights reserved.

PROGRAM-ORIENTED INFORMATION--A MANAGEMENT SYSTEMS COMPLEX FOR STATE EDUCATION AGENCIES. PART II, MANUAL OF ACCOUNTING AND RELATED FINANCIAL PROCEDURES.

ERIC Educational Resources Information Center

FRIEDMAN, BURTON DEAN; AND OTHERS

THIS DOCUMENT IS THE SECOND PART OF A REPORT, PROGRAM-ORIENTED INFORMATION--A MANAGEMENT SYSTEMS COMPLEX FOR STATE EDUCATION AGENCIES. PART 1, EA 001 170, SUBTITLED "ANALYSIS AND PROPOSALS," CONTAINS AN OUTLINE OF THE NEED FOR A MANAGEMENT SYSTEMS COMPLEX WITHIN EACH STATE EDUCATION AGENCY. THIS DOCUMENT IS A MANUAL PRESENTING THE…

STUDY OF TURBULENT ENERGY OVER COMPLEX TERRAIN: STATE, 1978

EPA Science Inventory

The complex structure of the earth's surface influenced atmospheric parameters pertinent to modeling the diffusion process during the 1978 'STATE' field study. The Information Theory approach of statistics proved useful for analyzing the complex structures observed in the radiome...

The Common Core State Standards' Quantitative Text Complexity Trajectory: Figuring out How Much Complexity Is Enough

ERIC Educational Resources Information Center

Williamson, Gary L.; Fitzgerald, Jill; Stenner, A. Jackson

2013-01-01

The Common Core State Standards (CCSS) set a controversial aspirational, quantitative trajectory for text complexity exposure for readers throughout the grades, aiming for all high school graduates to be able to independently read complex college and workplace texts. However, the trajectory standard is presented without reference to how the…

Clinical and mycological study of scalp white piedra in the State of Paraíba, Brazil.

PubMed

Pontes, Zélia Braz Vieira da Silva; Ramos, Adriano Lira; Lima, Edeltrudes de Oliveira; Guerra, Maria de Fátima de Lacerda; Oliveira, Neuza Maria Cavalcante; Santos, Jozemar Pereira dos

2002-07-01

White piedra is a superficial mycoses characterized by nodules on the hair shaft, caused by the basidiomycetous yeasts. In the present study, clinical and mycological findings of scalp white piedra caused by Trichosporon spp. are related. Twenty three cases of scalp white piedra were observed with a high incidence in women (87%) and preschool children from 2 to 6 (74%) years old. These groups presented a relationship of dependence with this infection. Despite the low socio-economic status, poor standards of hygiene, (48% of the patients) as well as the fact that 30.4% of the children shared the same nursery, these factors were not significant for the transmission of the mycosis. These were the first reports of scalp white piedra in João Pessoa city, Paraíba, Brazil.

Blood vitamin C levels of motorized tricycle drivers in Parañaque, Philippines.

PubMed

Sia Su, Glenn L; Kayali, Sara

2008-08-01

Vitamin C is an essential micronutrient maintaining the state of well being of individuals. This study examined factors affecting and the blood vitamin C levels of motorized tricycle drivers in Parañaque City, Philippines. Consenting drivers (N=49) were included in the study and were assessed through self-administered questionnaires, 24-h food recalls, and anthropometric measurements and on the analysis of their blood vitamin C levels. Factors related to the blood vitamin C levels of the motorized tricycle drivers were determined by correlation analysis. Majority (79.6%) of drivers had low blood vitamin C levels. Workplace and vitamin C supplementations (p<0.05) were significantly related to the blood vitamin C levels of the motorized tricycle drivers. Further studies are recommended to understand the problem and the determinants of vitamin C deficiency among the general population.

Para-hydrogen induced polarization of amino acids, peptides and deuterium-hydrogen gas.

PubMed

Glöggler, Stefan; Müller, Rafael; Colell, Johannes; Emondts, Meike; Dabrowski, Martin; Blümich, Bernhard; Appelt, Stephan

2011-08-14

Signal Amplification by Reversible-Exchange (SABRE) is a method of hyperpolarizing substrates by polarization transfer from para-hydrogen without hydrogenation. Here, we demonstrate that this method can be applied to hyperpolarize small amounts of all proteinogenic amino acids and some chosen peptides down to the nanomole regime and can be detected in a single scan in low-magnetic fields down to 0.25 mT (10 kHz proton frequency). An outstanding feature is that depending on the chemical state of the used catalyst and the investigated amino acid or peptide, hyperpolarized hydrogen-deuterium gas is formed, which was detected with (1)H and (2)H NMR spectroscopy at low magnetic fields of B(0) = 3.9 mT (166 kHz proton frequency) and 3.2 mT (20 kHz deuterium frequency).

Evaluating the Nature of So-Called S*-State Feature in Transient Absorption of Carotenoids in Light-Harvesting Complex 2 (LH2) from Purple Photosynthetic Bacteria

PubMed Central

2016-01-01

Carotenoids are a class of natural pigments present in all phototrophic organisms, mainly in their light-harvesting proteins in which they play roles of accessory light absorbers and photoprotectors. Extensive time-resolved spectroscopic studies of these pigments have revealed unexpectedly complex photophysical properties, particularly for carotenoids in light-harvesting LH2 complexes from purple bacteria. An ambiguous, optically forbidden electronic excited state designated as S* has been postulated to be involved in carotenoid excitation relaxation and in an alternative carotenoid-to-bacteriochlorophyll energy transfer pathway, as well as being a precursor of the carotenoid triplet state. However, no definitive and satisfactory origin of the carotenoid S* state in these complexes has been established, despite a wide-ranging series of studies. Here, we resolve the ambiguous origin of the carotenoid S* state in LH2 complex from Rba. sphaeroides by showing that the S* feature can be seen as a combination of ground state absorption bleaching of the carotenoid pool converted to cations and the Stark spectrum of neighbor neutral carotenoids, induced by temporal electric field brought by the carotenoid cation–bacteriochlorophyll anion pair. These findings remove the need to assign an S* state, and thereby significantly simplify the photochemistry of carotenoids in these photosynthetic antenna complexes. PMID:27726397

Evaluating the nature of so-called S*-State feature in transient absorption of carotenoids in light-harvesting complex 2 (LH2) from purple photosynthetic bacteria

DOE PAGES

Niedzwiedzki, Dariusz M.; Hunter, C. Neil; Blankenship, Robert E.

2016-10-11

Carotenoids are a class of natural pigments present in all phototrophic organisms, mainly in their light-harvesting proteins in which they play roles of accessory light absorbers and photoprotectors. Extensive time-resolved spectroscopic studies of these pigments have revealed unexpectedly complex photophysical properties, particularly for carotenoids in light-harvesting LH2 complexes from purple bacteria. An ambiguous, optically forbidden electronic excited state designated as S* has been postulated to be involved in carotenoid excitation relaxation and in an alternative carotenoid-to-bacteriochlorophyll energy transfer pathway, as well as being a precursor of the carotenoid triplet state. However, no definitive and satisfactory origin of the carotenoid S*more » state in these complexes has been established, despite a wide-ranging series of studies. Here, we resolve the ambiguous origin of the carotenoid S* state in LH2 complex from Rba. sphaeroides by showing that the S* feature can be seen as a combination of ground state absorption bleaching of the carotenoid pool converted to cations and the Stark spectrum of neighbor neutral carotenoids, induced by temporal electric field brought by the carotenoid cation- bacteriochlorophyll anion pair. Lastly, these findings remove the need to assign an S* state, and thereby significantly simplify the photochemistry of carotenoids in these photosynthetic antenna complexes.« less

Evaluating the nature of so-called S*-State feature in transient absorption of carotenoids in light-harvesting complex 2 (LH2) from purple photosynthetic bacteria

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

Niedzwiedzki, Dariusz M.; Hunter, C. Neil; Blankenship, Robert E.

Carotenoids are a class of natural pigments present in all phototrophic organisms, mainly in their light-harvesting proteins in which they play roles of accessory light absorbers and photoprotectors. Extensive time-resolved spectroscopic studies of these pigments have revealed unexpectedly complex photophysical properties, particularly for carotenoids in light-harvesting LH2 complexes from purple bacteria. An ambiguous, optically forbidden electronic excited state designated as S* has been postulated to be involved in carotenoid excitation relaxation and in an alternative carotenoid-to-bacteriochlorophyll energy transfer pathway, as well as being a precursor of the carotenoid triplet state. However, no definitive and satisfactory origin of the carotenoid S*more » state in these complexes has been established, despite a wide-ranging series of studies. Here, we resolve the ambiguous origin of the carotenoid S* state in LH2 complex from Rba. sphaeroides by showing that the S* feature can be seen as a combination of ground state absorption bleaching of the carotenoid pool converted to cations and the Stark spectrum of neighbor neutral carotenoids, induced by temporal electric field brought by the carotenoid cation- bacteriochlorophyll anion pair. Lastly, these findings remove the need to assign an S* state, and thereby significantly simplify the photochemistry of carotenoids in these photosynthetic antenna complexes.« less

The RNA polymerase clamp interconverts dynamically among three states and is stabilized in a partly closed state by ppGpp.

PubMed

Duchi, Diego; Mazumder, Abhishek; Malinen, Anssi M; Ebright, Richard H; Kapanidis, Achillefs N

2018-06-06

RNA polymerase (RNAP) contains a mobile structural module, the 'clamp,' that forms one wall of the RNAP active-center cleft and that has been linked to crucial aspects of the transcription cycle, including promoter melting, transcription elongation complex stability, transcription pausing, and transcription termination. Using single-molecule FRET on surface-immobilized RNAP molecules, we show that the clamp in RNAP holoenzyme populates three distinct conformational states and interconvert between these states on the 0.1-1 s time-scale. Similar studies confirm that the RNAP clamp is closed in open complex (RPO) and in initial transcribing complexes (RPITC), including paused initial transcribing complexes, and show that, in these complexes, the clamp does not exhibit dynamic behaviour. We also show that, the stringent-response alarmone ppGpp, which reprograms transcription during amino acid starvation stress, selectively stabilizes the partly-closed-clamp state and prevents clamp opening; these results raise the possibility that ppGpp controls promoter opening by modulating clamp dynamics.

System complexity as a measure of safe capacity for the emergency department.

PubMed

France, Daniel J; Levin, Scott

2006-11-01

System complexity is introduced as a new measure of system state for the emergency department (ED). In its original form, the measure quantifies the uncertainty of demands on system resources. For application in the ED, the measure is being modified to quantify both workload and uncertainty to produce a single integrated measure of system state. Complexity is quantified using an information-theoretic or entropic approach developed in manufacturing and operations research. In its original form, complexity is calculated on the basis of four system parameters: 1) the number of resources (clinicians and processing entities such as radiology and laboratory systems), 2) the number of possible work states for each resource, 3) the probability that a resource is in a particular work state, and 4) the probability of queue changes (i.e., where a queue is defined by the number of patients or patient orders being managed by a resource) during a specified time period. An example is presented to demonstrate how complexity is calculated and interpreted for a simple system composed of three resources (i.e., emergency physicians) managing varying patient loads. The example shows that variation in physician work states and patient queues produces different scores of complexity for each physician. It also illustrates how complexity and workload differ. System complexity is a viable and technically feasible measurement for monitoring and managing surge capacity in the ED.

Resolving the excited state equilibrium of peridinin in solution.

PubMed

Papagiannakis, Emmanouil; Larsen, Delmar S; van Stokkum, Ivo H M; Vengris, Mikas; Hiller, Roger G; van Grondelle, Rienk

2004-12-14

The carotenoid peridinin is abundant in the biosphere, as it is the main pigment bound by the light-harvesting complexes of dinoflagellates, where it collects blue and green sunlight and transfers energy to chlorophyll a with high efficiency. Its molecular structure is particularly complex, giving rise to an intricate excited state manifold, which includes a state with charge-transfer character. To disentangle the excited states of peridinin and understand their function in vivo, we applied dispersed pump-probe and pump-dump-probe spectroscopy. The preferential depletion of population from the intramolecular charge transfer state by the dump pulse demonstrates that the S(1) and this charge transfer state are distinct entities. The ensuing dump-induced dynamics illustrates the equilibration of the two states which occurs on the time scale of a few picoseconds. Additionally, the dump pulse populates a short-lived ground state intermediate, which is suggestive of a complex relaxation pathway, probably including structural reorientation or solvation of the ground state. These findings indicate that the unique intramolecular charge transfer state of peridinin is an efficient energy donor to chlorophyll a in the peridinin-chlorophyll-protein complex and thus plays a significant role in global light harvesting.

Constructing polyatomic potential energy surfaces by interpolating diabatic Hamiltonian matrices with demonstration on green fluorescent protein chromophore

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

Park, Jae Woo; Rhee, Young Min, E-mail: ymrhee@postech.ac.kr; Department of Chemistry, Pohang University of Science and Technology

2014-04-28

Simulating molecular dynamics directly on quantum chemically obtained potential energy surfaces is generally time consuming. The cost becomes overwhelming especially when excited state dynamics is aimed with multiple electronic states. The interpolated potential has been suggested as a remedy for the cost issue in various simulation settings ranging from fast gas phase reactions of small molecules to relatively slow condensed phase dynamics with complex surrounding. Here, we present a scheme for interpolating multiple electronic surfaces of a relatively large molecule, with an intention of applying it to studying nonadiabatic behaviors. The scheme starts with adiabatic potential information and its diabaticmore » transformation, both of which can be readily obtained, in principle, with quantum chemical calculations. The adiabatic energies and their derivatives on each interpolation center are combined with the derivative coupling vectors to generate the corresponding diabatic Hamiltonian and its derivatives, and they are subsequently adopted in producing a globally defined diabatic Hamiltonian function. As a demonstration, we employ the scheme to build an interpolated Hamiltonian of a relatively large chromophore, para-hydroxybenzylidene imidazolinone, in reference to its all-atom analytical surface model. We show that the interpolation is indeed reliable enough to reproduce important features of the reference surface model, such as its adiabatic energies and derivative couplings. In addition, nonadiabatic surface hopping simulations with interpolation yield population transfer dynamics that is well in accord with the result generated with the reference analytic surface. With these, we conclude by suggesting that the interpolation of diabatic Hamiltonians will be applicable for studying nonadiabatic behaviors of sizeable molecules.« less

Passivating the sulfur vacancy in monolayer MoS2

NASA Astrophysics Data System (ADS)

Lu, Haichang; Kummel, Andrew; Robertson, John

2018-06-01

Various methods to passivate the sulfur vacancy in 2D MoS2 are modeled using density functional theory (DFT) to understand the passivation mechanism at an atomic scale. First, the organic super acid, bis(trifluoromethane)sulfonimide (TFSI) is a strong protonating agent, and it is experimentally found to greatly increase the photoluminescence efficiency. DFT simulations find that the effectiveness of passivation depends critically on the charge state and number of hydrogens donated by TFSI since this determines the symmetry of the defect complex. A symmetrical complex is formed by three hydrogen atoms bonding to the defect in a -1 charge state, and this gives no bandgap states and a Fermi level in the midgap. However, a charge state of +1 gives a lower symmetry complex with one state in the gap. One or two hydrogens also give complexes with gap states. Second, passivation by O2 can provide partial passivation by forming a bridge bond across the S vacancy, but it leaves a defect state in the lower bandgap. On the other hand, substitutional additions do not shift the vacancy states out of the gap.

Rovibrational states of interstitial H2 in Si

NASA Astrophysics Data System (ADS)

Koch, S.; Lavrov, E. V.; Weber, J.

2011-06-01

Rovibrational Q(J) transitions of the interstitial H2 molecule in Si have been investigated by Raman scattering in the temperature range 90-388 K. In accordance with an earlier suggestion [M. Hiller, E. V. Lavrov, and J. Weber, Phys. Rev. BPRBMDO1098-012110.1103/PhysRevB.74.235214 74, 235214 (2006)], it is shown that the Q(2) transition of para hydrogen couples to the TAX phonon of Si and appears in the Raman spectra at temperatures above 200 K. The results presented also indicate that the rotational J=3 state of ortho hydrogen is resonantly coupled to the OΓ phonon.

A Guide for Parents and Families about What Your 10th Grader Should Be Learning in School This Year. Don't Fail Your Children = Una Guia para los Padres y Familias Acerca de Lo Que Su Hijo de Decimo Grado Debe Aprender en la Escuela Este Ano. No Le Falle a Sus Hijos.

ERIC Educational Resources Information Center

South Carolina State Education Oversight Committee, Columbia.

This guide, in English- and Spanish-language versions, shares with parents information about the South Carolina Curriculum Standards. The standards outline state requirements for children's learning and what students across the state should be able to do in certain subjects. The guide lists seven key reasons parents should be aware of the new…

A Guide for Parents and Families about What Your 5th Grader Should Be Learning in School This Year. Don't Fail Your Children = Una Guia para los Padres y Familias Acerca de Lo Que Su Hijo de 5to Grado Debe Aprender en la Escuela Este Ano. No Le Falle a Sus Hijos.

ERIC Educational Resources Information Center

South Carolina State Dept. of Education, Columbia.

This guide, in English- and Spanish-language versions, shares with parents information about the South Carolina Curriculum Standards. The standards outline state requirements for children's learning and what students across the state should be able to do in certain subjects. The guide lists seven key reasons parents should be aware of the new…

A Guide for Parents and Families about What Your Kindergartner Should Be Learning in School This Year. Don't Fail Your Children = Una Guia para los Padres y Familias Acerca de Lo Que Su Hijo de Jardin Infantil (Kindergarten) Debe Aprender en la Escuela Este Ano. No Le Falle a Sus Hijos.

ERIC Educational Resources Information Center

South Carolina State Dept. of Education, Columbia.

This guide, in English- and Spanish-language versions, shares with parents information about the South Carolina Curriculum Standards. The standards outline state requirements for children's learning and what students across the state should be able to do in certain subjects. The guide lists seven key reasons parents should be aware of the new…

A Guide for Parents and Families about What Your 6th Grader Should Be Learning in School This Year. Don't Fail Your Children = Una Guia para los Padres y Familias Acerca de Lo Que Su Hijo de 6to Grado Debe Aprender en la Escuela Este Ano. No Le Falle a Sus Hijos.

ERIC Educational Resources Information Center

South Carolina State Dept. of Education, Columbia.

This guide, in English- and Spanish-language versions, shares with parents information about the South Carolina Curriculum Standards. The standards outline state requirements for children's learning and what students across the state should be able to do in certain subjects. The guide lists seven key reasons parents should be aware of the new…

A Guide for Parents and Families about What Your 3rd Grader Should Be Learning in School This Year. Don't Fail Your Children = Una Guia para los Padres y Familias Acerca de Lo Que Su Hijo de 3er Grado Debe Aprender en la Escuela Este Ano. No Le Falle a Sus Hijos.

ERIC Educational Resources Information Center

South Carolina State Dept. of Education, Columbia.

This guide, in English- and Spanish-language versions, shares with parents information about the South Carolina Curriculum Standards. The standards outline state requirements for children's learning and what students across the state should be able to do in certain subjects. The guide lists seven key reasons parents should be aware of the new…

A Guide for Parents and Families about What Your 11th Grader Should Be Learning in School This Year. Don't Fail Your Children = Una Guia para los Padres y Familias Acerca de Lo Que Su Hijo de Grado 11 Debe Aprender en la Escuela Este Ano. No Le Falle a Sus Hijos.

ERIC Educational Resources Information Center

South Carolina State Dept. of Education, Columbia.

This guide, in English- and Spanish-language versions, shares with parents information about the South Carolina Curriculum Standards. The standards outline state requirements for children's learning and what students across the state should be able to do in certain subjects. The guide lists seven key reasons parents should be aware of the new…

A Guide for Parents and Families about What Your 9th Grader Should Be Learning in School This Year. Don't Fail Your Children = Una Guia para los Padres y Familias Acerca de Lo Que Su Hijo de Noveno Grado Debe Aprender en la Escuela Este Ano. No Le Falle a Sus Hijos.

ERIC Educational Resources Information Center

South Carolina State Dept. of Education, Columbia.

This guide, in English- and Spanish-language versions, shares with parents information about the South Carolina Curriculum Standards. The standards outline state requirements for children's learning and what students across the state should be able to do in certain subjects. The guide lists seven key reasons parents should be aware of the new…

A Guide for Parents and Families about What Your 7th Grader Should Be Learning in School This Year. Don't Fail Your Children = Una Guia para los Padres y Familias Acerca de Lo Que Su Hijo de Septimo Grado Debe Aprender en la Escuela Este Ano. No Le Falle a Sus Hijos.

ERIC Educational Resources Information Center

South Carolina State Dept. of Education, Columbia.

This guide, in English- and Spanish-language versions, shares with parents information about the South Carolina Curriculum Standards. The standards outline state requirements for children's learning and what students across the state should be able to do in certain subjects. The guide lists seven key reasons parents should be aware of the new…

A Guide for Parents and Families about What Your 1st Grader Should Be Learning in School This Year. Don't Fail Your Children = Una Guia para los Padres y Familias Acerca de Lo Que Su Hijo de 1er Grado Debe Aprender en la Escuela Este Ano. No Le Falle a Sus Hijos.

ERIC Educational Resources Information Center

South Carolina State Dept. of Education, Columbia.

This guide, in English- and Spanish-language versions, shares with parents information about the South Carolina Curriculum Standards. The standards outline state requirements for children's learning and what students across the state should be able to do in certain subjects. The guide lists seven key reasons parents should be aware of the new…

A Guide for Parents and Families about What Your 8th Grader Should Be Learning in School This Year. Don't Fail Your Children = Una Guia para los Padres y Familias Acerca de Lo Que Su Hijo de Octavo Grado Debe Aprender en la Escuela Este Ano. No Le Falle a Sus Hijos.

ERIC Educational Resources Information Center

South Carolina State Dept. of Education, Columbia.

This guide, in English- and Spanish-language versions, shares with parents information about the South Carolina Curriculum Standards. The standards outline state requirements for children's learning and what students across the state should be able to do in certain subjects. The guide lists seven key reasons parents should be aware of the new…

A Guide for Parents and Families about What Your 2nd Grader Should Be Learning in School This Year. Don't Fail Your Children = Una Guia para los Padres y Familias Acerca de Lo Que Su Hijo de 2do Grado Debe Aprender en la Escuela Este Ano. No Le Falle a Sus Hijos.

ERIC Educational Resources Information Center

South Carolina State Dept. of Education, Columbia.

This guide, in English- and Spanish-language versions, shares with parents information about the South Carolina Curriculum Standards. The standards outline state requirements for children's learning and what students across the state should be able to do in certain subjects. The guide lists seven key reasons parents should be aware of the new…

A Guide for Parents and Families about What Your 4th Grader Should Be Learning in School This Year. Don't Fail Your Children = Una Guia para los Padres y Familias Acerca de Lo Que Su Hijo de 4to Grado Debe Aprender en la Escuela Este Ano. No Le Falle a Sus Hijos.

ERIC Educational Resources Information Center

South Carolina State Dept. of Education, Columbia.

This guide, in English- and Spanish-language versions, shares with parents information about the South Carolina Curriculum Standards. The standards outline state requirements for children's learning and what students across the state should be able to do in certain subjects. The guide lists seven key reasons parents should be aware of the new…

H{sub 2} Ortho-to-para Conversion on Grains: A Route to Fast Deuterium Fractionation in Dense Cloud Cores?

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

Bovino, S.; Grassi, T.; Schleicher, D. R. G.

Deuterium fractionation, i.e., the enhancement of deuterated species with respect to non-deuterated ones, is considered to be a reliable chemical clock of star-forming regions. This process is strongly affected by the ortho-to-para H{sub 2} ratio. In this Letter we explore the effect of the ortho–para (o–p) H{sub 2} conversion on grains on the deuteration timescale in fully-depleted dense cores, including the most relevant uncertainties that affect this complex process. We show that (i) the o–p H{sub 2} conversion on grains is not strongly influenced by the uncertainties on the conversion time and the sticking coefficient, and (ii) that the processmore » is controlled by the temperature and the residence time of ortho-H{sub 2} on the surface, i.e., by the binding energy. We find that for binding energies between 330 and 550 K, depending on the temperature, the o–p H{sub 2} conversion on grains can shorten the deuterium fractionation timescale by orders of magnitude, opening a new route for explaining the large observed deuteration fraction D {sub frac} in dense molecular cloud cores. Our results suggest that the star formation timescale, when estimated through the timescale to reach the observed deuteration fractions, might be shorter than previously proposed. However, more accurate measurements of the binding energy are needed in order to better assess the overall role of this process.« less

Manual del McVCO 1999

USGS Publications Warehouse

McChesney, P.J.

1999-01-01

El McVCO es un generador de frecuencias basado en un microcontrolador que reemplaza al oscilador controlado por voltaje (VCO) utilizado en telemetría analógica de datos sísmicas. Acepta señales de baja potencia desde un sismómetro y produce una señal subportadora modulada en frecuencia adecuada para enlaces telefónicos o vía radio a un lugar remoto de recolección de datos. La frecuencia de la subportadora y la ganancia pueden ser seleccionadas mediante un interruptor. Tiene la opción de poder operar con dos canales para la observación con ganancia alta y baja. El McVCO fue diseñado con el propósito de mejorar la telemetría analógica de las señales dentro de la Pacific Northwest Seismograph Network (PNSN) (Red Sismográfica del Noroeste del Pacífico). Su desarrollo recibió el respaldo del Programa de Geofísica de la Universidad de Washington y del "Volcano Hazards and Earthquake Hazards programs of the United States Geological Survey (USGS) (Programa de Investigaciones de Riesgos Volcánicos y Programa de Investigaciones de Riesgos Sísmicos de los EEUU). Cientos de instrumentos se han construido e instalado. Además de utilizarlo el PNSN, el McVCO es usado por el Observatorio Vulcanológico de Alaska para monitorear los volcanes aleutianos y por el USGS Volcano Disaster Assistance Program (Programa de Ayuda en las Catástrofes Volcánicas del USGS) para responder a crisis volcánicas en otros países. Este manual cubre el funcionamiento del McVCO, es una referencia técnica para aquellos que necesitan saber con más detalle cómo funciona el McVCO, y cubre una serie de temas que requieren un trato explícito o que derivan del despliegue del instrumento.

Ultrafast photochemistry of polyatomic molecules containing labile halogen atoms in solution

NASA Astrophysics Data System (ADS)

Mereshchenko, Andrey S.

Because breaking and making of chemical bonds lies at the heart of chemistry, this thesis focuses on dynamic studies of labile molecules in solutions using ultrafast transient absorption spectroscopy. Specifically, my interest is two-fold: (i) novel reaction intermediates of polyhalogenated carbon, boron and phosphorus compounds; (ii) photophysics and photochemistry of labile copper(II) halide complexes. Excitation of CH2Br2, CHBr3, BBr 3, and PBr3 into n(Br)sigma*(X-Br) states, where X=C, B, or P, leads to direct photoisomerization with formation of isomers having Br-Br bonds as well as rupture of one of X-Br bonds with the formation of a Br atom and a polyatomic radical fragment, which subsequently recombine to form similar isomer products. Nonpolar solvation stabilizes the isomers, consistent with intrinsic reaction coordinate calculations of the isomer ground state potential energy surfaces at the density functional level of theory, and consequently, the involvement of these highly energetic species on chemically-relevant time scales needs to be taken into account. Monochlorocomplexes in methanol solutions promoted to the ligand-to-metal charge transfer (LMCT) excited state predominantly undergo internal conversion via back electron transfer, giving rise to vibrationally hot ground-state parent complexes. Copper-chloride homolitical bond dissociation yielding the solvated copper(I) and Cl- atom/solvent CT complexes constitutes a minor pathway. Insights into ligand substitution mechanisms were acquired by monitoring the recovery of monochloro complexes at the expense of two unexcited dichloro- and unsubstituted forms of Cu(II) complexes also present in the solution. Detailed description of ultrafast excited-state dynamics of CuCl 42- complexes in acetonitrile upon excitation into all possible Ligand Field (LF) excited states and two most intense LMCT transitions is reported. The LF states were found to be nonreactive with lifetimes remarkably longer than those for copper(II) complexes studied so far, in particular, copper blue proteins. The highest 2A1 and lowest 2E LF states relax directly to the ground electronic state whereas the intermediate 2B1 LF state relaxes stepwise through the 2E state. The LMCT excited states are short-lived undergoing either ionic dissociation (CuCl3- + Cl-) or cascading relaxation through the manifold of vibrationally hot LF states to the ground state.

Intramolecular addition of cysteine thiyl radical to phenylalanine and tyrosine in model peptides, Phe (CysS•) and Tyr(CysS•): a computational study

PubMed Central

Naumov, Sergej; Schöneich, Christian

2009-01-01

Density Functional Theory (DFT) and ab initio calculations were carried out to evaluate the potential for intramolecular addition of cysteine (Cys) thiyl radicals (CysS•) to aromatic amino acids (Phe and Tyr) in water. These calculations yielded stable cyclic conformations, in which π-complexes were more stable than cyclohexadienyl radicals in water. In these π-complexes, the C2-S distances were significantly shorter compared to the C1-S and C3-S distances. Comparable results on the relative stabilities were obtained for model calculations for the addition of HS•/CH3S• to toluene and para-hydroxytoluene. The adduct of thiyl radicals with Phe was more stable than that with Tyr, and the stabilization energies depended on the C-terminal substituents. PMID:19309133

Role of B800 in carotenoid-bacteriochlorophyll energy and electron transfer in LH2 complexes from the purple bacterium Rhodobacter sphaeroides.

PubMed

Polívka, Tomas; Niedzwiedzki, Dariusz; Fuciman, Marcel; Sundström, Villy; Frank, Harry A

2007-06-28

The role of the B800 in energy and electron transfer in LH2 complexes has been studied using femtosecond time-resolved transient absorption spectroscopy. The B800 site was perturbed by application of lithium dodecyl sulfate (LDS), and comparison of treated and untreated LH2 complexes from Rhodobacter sphaeroides incorporating carotenoids neurosporene, spheroidene, and spheroidenone was used to explore the role of B800 in carotenoid to bacteriochlorophyll-a (BChla) energy transfer and carotenoid radical formation. Efficiencies of the S1-mediated energy transfer in the LDS-treated complexes were 86, 61, and 57% in the LH2 complexes containing neurosporene, spheroidene, and spheroidenone, respectively. Analysis of the carotenoid S1 lifetimes in solution, LDS-treated, and untreated LH2 complexes allowed determination of B800/B850 branching ratio in the S1-mediated energy transfer. It is shown that B800 is a major acceptor, as approximately 60% of the energy from the carotenoid S1 state is accepted by B800. This value is nearly independent of conjugation length of the carotenoid. In addition to its role in energy transfer, the B800 BChla is the only electron acceptor in the event of charge separation between carotenoid and BChla in LH2 complexes, which is demonstrated by prevention of carotenoid radical formation in the LDS-treated LH2 complexes. In the untreated complexes containing neurosporene and spheroidene, the carotenoid radical is formed with a time constant of 300-400 fs. Application of different excitation wavelengths and intensity dependence of the carotenoid radical formation showed that the carotenoid radical can be formed only after excitation of the S2 state of carotenoid, although the S2 state itself is not a precursor of the charge-separated state. Instead, either a hot S1 state or a charge-transfer state lying between S2 and S1 states of the carotenoid are discussed as potential precursors of the charge-separated state.

Aromatic acids in an Arctic ice core from Svalbard: a proxy record of biomass burning

NASA Astrophysics Data System (ADS)

Grieman, Mackenzie M.; Aydin, Murat; Isaksson, Elisabeth; Schwikowski, Margit; Saltzman, Eric S.

2018-05-01

This study presents vanillic acid and para-hydroxybenzoic acid levels in an Arctic ice core from Lomonosovfonna, Svalbard covering the past 800 years. These aromatic acids are likely derived from lignin combustion in wildfires and long-range aerosol transport. Vanillic and para-hydroxybenzoic acid are present throughout the ice core, confirming that these compounds are preserved on millennial timescales. Vanillic and para-hydroxybenzoic acid concentrations in the Lomonosovfonna ice core ranged from below the limits of detection to 0.2 and 0.07 ppb, respectively (1 ppb = 1000 ng L-1). Vanillic acid levels are high (maximum of 0.1 ppb) from 1200 to 1400 CE, then gradually decline into the twentieth century. The largest peak in the vanillic acid in the record occurs from 2000 to 2008 CE. In the para-hydrobenzoic acid record, there are three centennial-scale peaks around 1300, 1550, and 1650 CE superimposed on a long-term decline in the baseline levels throughout the record. Ten-day air mass back trajectories for a decade of fire seasons (March-November, 2006-2015) indicate that Siberia and Europe are the principle modern source regions for wildfire emissions reaching the Lomonosovfonna site. The Lomonosovfonna data are similar to those from the Eurasian Arctic Akademii Nauk ice core during the early part of the record (1220-1400 CE), but the two ice cores diverge markedly after 1400 CE. This coincides with a shift in North Atlantic climate marked by a change of the North Atlantic Oscillation from a positive to a more negative state.

Synthesis, characterization and reactivity of trinuclear Cu(II) complexes derived from disalicylaldehyde malonoyldihydrazone

NASA Astrophysics Data System (ADS)

Koch, Angira; Kumar, Arvind; De, Arjun K.; Phukan, Arnab; Lal, Ram A.

2014-08-01

Three new homotrinuclear copper(II) complexes [Cu3(slmh)(μ-Cl)2(CH3OH)3]ṡ0.5CH3OH (1), [Cu3(slmh)(NO3)2(CH3OH)5]ṡ1.5CH3OH (2) and [Cu3(slmh)(μ-ClO4)2(CH3OH)3]ṡ2CH3OH (3) from disalicylaldehyde malonoyldihydrazone have been synthesized and characterized. The composition of the complexes has been established on the basis of data obtained from analytical and thermoanalytical data. The structure of the complexes has been discussed in the light of molar conductance, electronic, FT-IR and far-IR spectral data, magnetic moment and EPR spectral studies. The molar conductance values for the complexes in DMSO solution indicate that all of them are non-electrolyte. The magnetic moment values for the complexes suggest considerable metal-metal intramolecular interaction between metal ions in the structural unit of the complexes. The EPR spectral features reveal that at RT, the ground state for the complexes is a mixture of the quartet state (S = 3/2) and doublet state (S = ½). At lower temperature, the ground state for the complexes is dx2-y2 with considerable contribution from dz2 orbital. Dihydrazone ligand is present in enol form in all of the complexes. The complexes have distorted square pyramidal stereochemistry. The electron transfer reactions of the complexes have been investigated by cyclic voltammetry. Hydrogen peroxide mediated oxidation of benzyl alcohol catalyzed by complex 1 has been studied.

High field hyperpolarization-EXSY experiment for fast determination of dissociation rates in SABRE complexes.

PubMed

Hermkens, Niels K J; Feiters, Martin C; Rutjes, Floris P J T; Wijmenga, Sybren S; Tessari, Marco

2017-03-01

SABRE (Signal Amplification By Reversible Exchange) is a nuclear spin hyperpolarization technique based on the reversible concurrent binding of small molecules and para-hydrogen (p-H 2 ) to an iridium metal complex in solution. At low magnetic field, spontaneous conversion of p-H 2 spin order to enhanced longitudinal magnetization of the nuclear spins of the other ligands occurs. Subsequent complex dissociation results in hyperpolarized substrate molecules in solution. The lifetime of this complex plays a crucial role in attained SABRE NMR signal enhancements. Depending on the ligands, vastly different dissociation rates have been previously measured using EXSY or selective inversion experiments. However, both these approaches are generally time-consuming due to the long recycle delays (up to 2min) necessary to reach thermal equilibrium for the nuclear spins of interest. In the cases of dilute solutions, signal averaging aggravates the problem, further extending the experimental time. Here, a new approach is proposed based on coherent hyperpolarization transfer to substrate protons in asymmetric complexes at high magnetic field. We have previously shown that such asymmetric complexes are important for application of SABRE to dilute substrates. Our results demonstrate that a series of high sensitivity EXSY spectra can be collected in a short experimental time thanks to the NMR signal enhancement and much shorter recycle delay. Copyright © 2017 Elsevier Inc. All rights reserved.

Effect of the substituent and hydrogen bond on the geometry and electronic properties of OH and O(-) groups in para-substituted phenol and phenolate derivatives.

PubMed

Szatylowicz, Halina; Krygowski, Tadeusz M

2010-10-14

Interrelations between intra- and intermolecular interactions were analyzed by using computational modeling of the para-X-substituted derivatives of phenol and phenolate (where X = NO, NO(2), CHO, COMe, COOH, CONH(2), Cl, F, H, Me, OMe, and OH) and their equilibrium H-bonded complexes with HB and B(-) (where HB = HF and HCN and B(-) = F(-) and CN(-)). B3LYP/6-311++G** computation was applied. Both the substituent effect and H-bonding changed the electronic properties of the -O(-) and -OH groups and geometric parameters of phenol and phenolate derivatives and their H-bonded complexes. C-O bond lengths and aromaticity indices of the ring were found to depend linearly on σ(p)(-) of the substituents. In the first case the greatest sensitivity on the substituent effect was for 4-X-C(6)H(4)OH···CN(-) and 4-X-C(6)H(4)O(-)···HF complexes, whereas for 4-X-C(6)H(4)O(-)···HCN systems it was comparable with that for phenol derivatives and a little smaller than that for 4-X-C(6)H(4)O(-) derivatives. This means that the strength of H-bonding may considerably change the sensitivity of the C-O bond length to the substituent effect. The greatest sensitivity of the aromaticity indices, both HOMA and NICS(1)zz, to σ(p)(-) was found for phenolate and then for phenolate H-bonded complexes, followed by phenol complexes, and the lowest sensitivity was observed for phenol derivatives. The interatomic proton-acceptor distance, being a measure of the H-bond strength, was found to depend linearly on σ(p)(-) of the substituents with a positive slope for O···HB (HF or HCN) interactions and a negative slope for OH···B(-) interactions. NBO charges on the oxygen and hydrogen atoms also depend on σ(p)(-) of the substituents. In the latter case for strong H-bonded complexes (energy less than ∼-20 kcal/mol) the substituent effect works oppositely for 4-X-C(6)H(4)OH···B(-) in comparison with the 4-X-C(6)H(4)O(-)···HB systems. Moreover, following the Espinoza et al. [J. Chem. Phys. 2002, 117, 5529] and Grabowski et al. [J. Phys. Chem. B 2006, 110, 6444] classifications, the above and q(H) vs proton-acceptor distance relationships suggest a partially covalent character of the hydrogen bond for these complexes and the degree of its covalent nature depending on the substituent.

Dedos de Luna. Children's Literature in Spanish: Bilingual Edition. Guia para maestros en espanol e ingles. Elementary Literature Series, Part II.

ERIC Educational Resources Information Center

Walker, Dana; Huerta, Mario

This curriculum unit is designed to give primary school students foreign language experiences and also to support the cultural literacy strand of the California State History-Social Science Framework. The unit is part of an elementary literature series which utilizes quality primary source literature from various world regions and countries and…

La Educacion Especial para Ninos con Impedimentos Desde Recien Nacidos Hasta Cinco Anos de Edad = Special Education for Handicapped Children Birth to Five.

ERIC Educational Resources Information Center

New York State Education Dept. Albany. Office for the Education of Children with Handicapping Conditions.

The manual, in Spanish, describes programs and resources available for preschool handicapped children and their families in conjunction with the New York State Education Department. Section 1 on assistance in securing services, reviews the service provided by Early Childhood Direction Centers, and outlines the role of local Committees on the…

Nueva dieta artificial para la producción masiva de Phymastichus Coffea (Himenóptera: Eulophidae) parasitoide de la broca del café, Hypothenemus hampei (Coleoptera: Scolytidae).

USDA-ARS?s Scientific Manuscript database

Phymastichus coffea (La Salle), (Hymenoptera: Eulophydae) is a parasitic wasp that attacks the adult coffee berry borer, Hypothenemus hampei (Ferrari) when it is tunnel into the berry. In 2001 a small colony of this parasitoid was introduced from CENICAFE, Colombia into United States to develop an i...

Manual for Courts-Martial United States. 2002 Edition

DTIC Science & Technology

2002-01-01

are enlistment papers, physical exam- ination papers, outline-figure and fingerprint cards, forensic laboratory reports, chain of custody docu- ments...physical examination papers, outline figure and fin- gerprint cards, forensic laboratory reports, chain of custody documents, morning reports and...Para. 142 e of the 1969 Manual, “Polygraph tests and drug- induced or hypnosis -induced interviews,” has been deleted as a result of the adoption of

Manual for Courts-Martial United States 1998 Edition.

DTIC Science & Technology

1998-01-01

exam- ination papers, outline-figure and fingerprint cards, forensic laboratory reports, chain of custody docu- ments, morning reports and other...examination papers, outline figure and fin- gerprint cards, forensic laboratory reports, chain of custody documents, morning reports and other per...the 1969 Manual, "Polygraph tests and drug- induced or hypnosis -induced interviews," has been deleted as a result of the adoption of Rule 702. Para

Development of floristic diversity in 10-year-old restoration forests on a bauxite mined site in Amazonia.

Treesearch

J. A. Parrotta; O. H. Knowles; J.M. Wunderle Jr.

1997-01-01

Patterns of plant and animal diversity were studied in a 10-year-old native species reforestation area at a bauxite-mined site at porto Trombetas in western Para State, Brazil. Understorey and overstorey floristic composition and structure, understorey light conditions, forest floor development and soil properties were evaluated in a total of 38 78.5-m2

Amazonian forest restoration: an innovative system for native species selection based on phenological data and performance indices

Treesearch

Oliver H. Knowles; John A. Parrotta

1995-01-01

One hundred and sixty taxa of upland moist forest trees were studied with reference to their suitability for forest restoration on bauxite mined Iands in western Para State, Brazil. Over a 14-year period, field observations in native primary forests, nursery studies, and evaluations of over 600 ha of mixed-species reforestation areas were used to characterize fruiting...

Abriendo Caminos Para La Educacion: A Case Study of a Parent Outreach Initiative Building on the Knowledge, Skills, and Resources of the Latina/o Community

ERIC Educational Resources Information Center

Fernandez, Graciela

2010-01-01

Informed by research studies that demonstrate a positive relationship between parent engagement and student academic attainment, state and national parent outreach initiatives have aimed to bridge the gap between Latina/o parents and schools. Such was the case with the Latina/o Family, School and Community "Avanzando" Project, which…

Molluscs production associated to lunar-tide cycle: a case study in Paraíba State under ethnoecology viewpoint

PubMed Central

Nishida, Alberto K; Nordi, Nivaldo; Alves, Rômulo RN

2006-01-01

Molluscs have been for a long time a very important food resource for humans. Therefore, oysters, clams, and mussels are highly required at seafood markets. Like any commercial food, it is necessary that molluscs present good quality standards, concerning some criteria such as amount of meat and appearance. In bivalves, condition index or fattening index is considered a satisfactory method for estimating the amount of meat related to the shell cavity. Molluscs gatherers of Paraíba State coast, northeastern Brazil, state that molluscan meat production increases during spring tide (designated by them as maré de lançamento) in opposition to the meat decrease which happens during neap tide (maré de quebramento) (they are designated technically in Portuguese as maré de sizígia and maré de quadratura, respectively). Weperformed a survey on the production of unha-de-velho or 'oldman'snail' (Tagelus plebeius) caught by molluscs gatherers in the estuary of River Paraíba do Norte, by observing locally their work, applying questionnaires, searching for a possible scientific relation of that molluscs condition to the gatherers empirical statement. Thus, we estimatedthe molluscs condition index through the method of solids percentage determination. We studied their work and the molluscs condition index during a full lunar-tide cycle. Determinations were carried out between 2nd September and 20th October, 1998, through 20 catches performed to obtain condition index from 400 bivalves. We observed that several biotic and abiotic ecological factors, namely reproduction cycle, biochemical components variations, animal size, and even parasitism, may affect the animal condition index. Despite this aspect, our present results confirmed a high overlapping (80%) of the condition index curve with lunar-tide cycle, in agreement with the gatherers statement. Although we recognize the need for formulating and testing other hypotheses, we consider a priori that the gatherers empirical assertion a unha tá gorda de acordocom a maré ('the "oldman's nail" is fat according to the tide', roughly translating) is justified by the observations here performed when the condition index increased during spring tide and decreased during neap tide. PMID:16784528

Synthesis, characterization and solid state electrical properties of 1-D coordination polymer of the type [Cu{sub x}Ni{sub 1-x}(dadb){center_dot}yH{sub 2}O]{sub n}

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

Prasad, R.L., E-mail: rlpjc@yahoo.co.in; Kushwaha, A.; Shrivastava, O.N.

2012-12-15

New heterobimetallic complexes [Cu{sub x}Ni{sub 1-x}(dadb){center_dot}yH{sub 2}O]{sub n} {l_brace}where dadb=2,5-Diamino-3,6-dichloro-1,4-benzoquinone (1); x=1 (2), 0.5 (4), 0.25 (5), 0.125 (6), 0.0625 (7) and 0 (3); y=2; n=degree of polymerization{r_brace} were synthesized and characterized. Heterobimetallic complexes show normal magnetic moments, whereas, monometallic complexes exhibit magnetic moments less than the value due to spin only. Thermo-gravimetric analysis shows that degradation of the ligand dadb moiety is being controlled by the electronic environment of the Cu(II) ions in preference over Ni(II) in heterobimetallic complexes. Existence of the mixed valency/non-integral oxidation states of copper and nickel metal ions in the complex 4 has been attributedmore » from magnetic moment and ESR spectral results. Solid state dc electrical conductivity of all the complexes was investigated. Monometallic complexes were found to be semiconductors, whereas heterobimetallic coordination polymer 4 was found to exhibit metallic behaviour. Existence of mixed valency/ non-integral oxidation state of metal ions seems to be responsible for the metallic behaviour. - Graphical abstract: Contrast to the semiconductor monometallic complexes 2 and 3, the heterobimetallic complex 4 exhibits metallic behaviour attributed to the mixed valency/non-integral oxidation state of the metal ions concluded from magnetic and ESR spectral studies. Highlights: Black-Right-Pointing-Pointer 1-D coordination compounds of the type Cu{sub x}Ni{sub 1-x}(dadb){center_dot}yH{sub 2}O were synthesized and characterized. Black-Right-Pointing-Pointer Thermal degradation of the complexes provides an indication of long range electronic communication between metal to ligand. Black-Right-Pointing-Pointer On inclusion of Ni(II) into 1-D coordination polymer of Cu(II). (a) Cu(II) and Ni(II) ions exhibit non-integral oxidation state. (b) resulting heterobimetallic complex 4 exhibits metallic behaviour at all temperature range of the present study whereas monometallic complexes are semiconductor.« less

Exploiting the benefit of S0 → T1 excitation in triplet-triplet annihilation upconversion to attain large anti-stokes shifts: tuning the triplet state lifetime of a tris(2,2'-bipyridine) osmium(ii) complex.

PubMed

Liu, Dongyi; Zhao, Yingjie; Wang, Zhijia; Xu, Kejing; Zhao, Jianzhang

2018-03-07

Os(ii) complexes are particularly interesting for triplet-triplet annihilation (TTA) upconversion, due to the strong direct S 0 → T 1 photoexcitation, as in this way, energy loss is minimized and large anti-Stokes shift can be achieved for TTA upconversion. However, Os(bpy) 3 has an intrinsic short T 1 state lifetime (56 ns), which is detrimental for the intermolecular triplet-triplet energy transfer (TTET), one of the crucial steps in TTA upconversion. In order to prolong the triplet state lifetime, we prepared an Os(ii) tris(bpy) complex with a Bodipy moiety attached, so that an extended T 1 state lifetime is achieved by excited state electronic configuration mixing or triplet state equilibrium between the coordination center-localized state ( 3 MLCT state) and Bodipy ligand-localized state ( 3 IL state). With steady-state and time-resolved transient absorption/emission spectroscopy, we proved that the 3 MLCT is slightly above the 3 IL state (by 0.05 eV), and the triplet state lifetime was prolonged by 31-fold (from 56 ns to 1.73 μs). The TTA upconversion quantum yield was increased by 4-fold as compared to that of the unsubstituted Os(ii) complex.

Novel Br-DPQ blue light-emitting phosphors for OLED.

PubMed

Dahule, H K; Thejokalyani, N; Dhoble, S J

2015-06-01

A new series of blue light-emitting 2,4-diphenylquinoline (DPQ) substituted blue light-emitting organic phosphors namely, 2-(4-methoxy-phenyl)-4-phenyl-quinoline (OMe-DPQ), 2-(4-methyl-phenyl)-4-phenylquinoline (M-DPQ), and 2-(4-bromo-phenyl)-4-phenylquinoline (Br-DPQ) were synthesized by substituting methoxy, methyl and bromine at the 2-para position of DPQ, respectively by Friedländer condensation of 2-aminobenzophenone and corresponding acetophenone. The synthesized phosphors were characterized by different techniques, e.g., Fourier transform infra-red (FTIR), differential scanning calorimeter (DSC), UV-visible absorption and photoluminescence spectra. FTIR spectra confirms the presence of chemical groups such as C=O, NH, or OH in all the three synthesized chromophores. DSC studies show that these complexes have good thermal stability. Although they are low-molecular-weight organic compounds, they have the potential to improve the stability and operating lifetime of a device made out of these complexes. The synthesized polymeric compounds demonstrate a bright emission in the blue region in the wavelength range of 405-450 nm in solid state. Thus the attachment of methyl, methoxy and bromine substituents to the diphenyl quinoline ring in these phosphors results in colour tuning of the phosphorescence. An electroluminescence (EL) cell of Br-DPQ phosphor was made and its EL behaviour was studied. A brightness-voltage characteristics curve of Br-DPQ cell revealed that EL begins at 400 V and then the brightness increases exponentially with applied AC voltage, while current-voltage (I-V) characteristics revealed that the turn on voltage of the fabricated EL cell was 11 V. Hence this phosphor can be used as a promising blue light material for electroluminescent devices. Copyright © 2014 John Wiley & Sons, Ltd.

Computational (DFT) and Experimental (EXAFS) Study of the Interaction of [Ir(IMes)(H)2 (L)3 ] with Substrates and Co-substrates Relevant for SABRE in Dilute Systems.

PubMed

van Weerdenburg, Bram J A; Engwerda, Anthonius H J; Eshuis, Nan; Longo, Alessandro; Banerjee, Dipanjan; Tessari, Marco; Guerra, Célia Fonseca; Rutjes, Floris P J T; Bickelhaupt, F Matthias; Feiters, Martin C

2015-07-13

Signal amplification by reversible exchange (SABRE) is an emerging hyperpolarization method in NMR spectroscopy, in which hyperpolarization is transferred through the scalar coupling network of para-hydrogen derived hydrides in a metal complex to a reversibly bound substrate. Substrates can even be hyperpolarized at concentrations below that of the metal complex by addition of a suitable co-substrate. Here we investigate the catalytic system used for trace detection in NMR spectroscopy with [Ir(IMes)(H)2 (L)3 ](+) (IMes=1,3-dimesitylimidazol-2-ylidene) as catalyst, pyridine as a substrate and 1-methyl-1,2,3-triazole as co-substrate in great detail. With density functional theory (DFT), validated by extended X-ray absorption fine structure (EXAFS) experiments, we provide explanations for the relative abundance of the observed metal complexes, as well as their contribution to SABRE. We have established that the interaction between iridium and ligands cis to IMes is weaker than that with the trans ligand, and that in mixed complexes with pyridine and triazole, the latter preferentially takes up the trans position. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nonlinear optical properties and excited state dynamics of sandwich-type mixed (phthalocyaninato)(Schiff-base) triple-decker complexes: Effect of rare earth atom

NASA Astrophysics Data System (ADS)

Li, Zhongguo; Gao, Feng; Xiao, Zhengguo; Wu, Xingzhi; Zuo, Jinglin; Song, Yinglin

2018-07-01

The third-order nonlinear optical properties of two di-lanthanide (Ln = Tb and Dy) sandwich complexes with mixed phthalocyanine and Schiff-base ligands were studied using Z-scan technique at 532 nm with 20 ps and 4 ns pulses. Both complexes exhibit reverse saturable absorption and self-focusing effect in ps regime, while the second-order hyperpolarizability decreases from Dy to Tb. Interestingly, the Tb triple-decker complexes show larger nonlinear absorption than Dy complexes on ns timescale. The time-resolved pump-probe measurements demonstrate that the nonlinear optical response was caused by excited-state mechanism related to the five-level model, while the singlet state lifetime of Dy complexes is 3 times shorter than that of Tb complexes. Our results indicate the lanthanide ions play a critical role in the photo-physical properties of triple-decker phthalocyanine complexes for their application as optical limiting materials.

Hydrogen-bond formation between isoindolo[2,1-a]indol-6-one and aliphatic alcohols in n-hexane.

PubMed

Demeter, Attila; Bérces, Tibor

2005-03-17

The spectroscopic, kinetic, and equilibrium properties of isoindolo[2,1-a]indol-6-one (I) were studied in n-hexane in the presence and absence of alcohols (X). Hydrogen-bonded-complex formation was found to occur between the alcohol and the ground state as well as the excited state of the I molecule. The spectra of I and its singly complexed derivative (IX) are similar; however, that of IX is red shifted. The extent of red shift increases with the hydrogen-bonding ability of the alcohol. Equilibrium constant measurements were made to determine the hydrogen-bond basicity (beta(2)(H)) for I and the singlet excited (1)I. The beta(2)(H) value for (1)I is found to be about twice that of the ground-state I. Time-resolved fluorescence decay measurements indicate that the reaction of singlet excited I with fluorinated alcohols is diffusion controlled, while the rate of complexation with nonfluorinated (weaker hydrogen bonding) aliphatic alcohols depends on the Gibbs energy change in the complexation reaction. The quantitative correlation between the rate coefficient of complexation of (1)I with alcohols and the Gibbs energy change in the complexation process allowed us to estimate the rate coefficient for the complexation of the ground-state I with alcohols. The formation of the singlet excited hydrogen-bonded complex is irreversible; (1)IX disappears in a first order and an alcohol induced second order reaction. The first order decay is predominantly due to internal conversion to the ground state, the rate of which depends on the ionization energy of the complexing alcohol.

Blue-to-Green Emitting Neutral Ir(III) Complexes Bearing Pentafluorosulfanyl Groups: A Combined Experimental and Theoretical Study

PubMed Central

2017-01-01

A structure–property relationship study of neutral heteroleptic (1 and 2, [Ir(C∧N)2(L∧X)]) and homoleptic (3 and 4, fac-[Ir(C∧N)3]) Ir(III) complexes (where L∧X = anionic 2,2,6,6-tetramethylheptane-3,5-dionato-κO3,κO6 (thd) and C∧N = a cyclometalating ligand bearing a pentafluorosulfanyl (−SF5) electron-withdrawing group (EWG) at the C4 (HL1) and C3 (HL2) positions of the phenyl moiety) is presented. These complexes have been fully structurally characterized, including by single-crystal X-ray diffraction, and their electrochemical and optical properties have also been extensively studied. While complexes 1 ([Ir(L1)2(thd)]), 3 (Ir(L1)3), and 4 (Ir(L2)3) exhibit irreversible first reduction waves based on the pentafluorosulfanyl substituent in the range of −1.71 to −1.88 V (vs SCE), complex 2 ([Ir(L2)2(thd)]) exhibits a quasi-reversible pyridineC∧N-based first reduction wave that is anodically shifted at −1.38 V. The metal + C∧N ligand oxidation waves are all quasi-reversible in the range of 1.08–1.54 V (vs SCE). The optical gap, determined from the lowest energy absorption maxima, decreases from 4 to 2 to 3 to 1, and this trend is consistent with the Hammett behavior (σm/σp with respect to the metal–carbon bond) of the −SF5 EWG. In degassed acetonitrile, for complexes 2–4, introduction of the −SF5 group produced a blue-shifted emission (λem 484–506 nm) in comparison to reference complexes [Ir(ppy)2(acac)] (R1, where acac = acetylacetonato) (λem 528 nm in MeCN), [Ir(CF3-ppy) (acac)] (R3, where CF3-ppyH = 2-(4-(trifluoromethyl)phenyl)pyridine) (λem 522 nm in DCM), and [Ir(CF3-ppy)3] (R8) (λem 507 nm in MeCN). The emission of complex 1, in contrast, was modestly red shifted (λem 534 nm). Complexes 2 and 4, where the −SF5 EWG is substituted para to the Ir–CC∧N bond, are efficient phosphorescent emitters, with high photoluminescence quantum yields (ΦPL = 58–79% in degassed MeCN solution) and microsecond emission lifetimes (τε = 1.35–3.02 μs). Theoretical and experimental observations point toward excited states that are principally ligand centered (3LC) in nature, but with a minor metal-to-ligand charge-transfer (3MLCT) transition component, as a function of the regiochemistry of the pentafluorosulfanyl group. The 3LC character is predominant over the mixed 3CT character for complexes 1, 2, and 4, while in complex 3, there is exclusive 3LC character as demonstrated by unrestricted density functional theory (DFT) calculations. The short emission lifetimes and reasonable ΦPL values in doped thin film (5 wt % in PMMA), particularly for 4, suggest that these neutral complexes would be attractive candidate emitters in organic light-emitting diodes. PMID:28613074

A spectroscopic study of the molecular interactions of harmane with pyrimidine and other diazines.

PubMed

Muñoz, M A; Guardado, P; Galán, M; Carmona, C; Balón, M

2000-01-17

FTIR, UV-vis, steady state and time-resolved fluorescence measurements show that harmane (1-methyl-9H-pyrido/3,4-b/indole) interacts with pyrimidine and its isomers pyrazine and pyridazine in its ground and lowest singlet states. The mechanisms of interaction are dependent on both the structure of the diazine and the nature of the solvent. Thus, in a low polar solvent such as toluene, harmane forms ground state 1:1 hydrogen-bonded complexes with all the diazines. These complexes quench the fluorescence of harmane and diminish its fluorescence lifetime. Conversely, in buffered (pH 8.7) aqueous solutions, pyrimidine behaves differently from the other diazines. Thus, whereas pyrimidine only interacts with harmane in its ground state, pyrazine and pyridazine also interact in the excited state. The harmane-pyrimidine ground state interaction is an entropic controlled process. Therefore, we propose the formation of pi-pi stacked 1:1 complexes between these substrates. Association constants for the different types of complexes and quenching parameters are reported.

Geochemical and isotopic constraints on the tectonic setting of Serra dos Carajas belt, eastern Para, Brazil

NASA Technical Reports Server (NTRS)

Olszewski, W. J., Jr.; Gibbs, A. K.; Wirth, K. R.

1986-01-01

The lower part of the Serra dos Carajas belt is the metavolcanic and metasedimentary Grao para Group (GPG). The GPG is thought to unconformably overlie the older (but undated) Xingu Complex, composed of medium and high-grade gneisses and amphibolite and greenstone belts. The geochemical data indicate that the GPG has many features in common with ancient and modern volcanic suites erupted through continental crust. The mafic rocks clearly differ from those of most Archean greenstone belts, and modern MORB, IAB, and hot-spot basalts. The geological, geochemical, and isotopic data are all consistent with deposition on continental crust, presumably in a marine basin formed by crustal extension. The isotopic data also suggest the existence of depleted mantle as a source for the parent magmas of the GPG. The overall results suggest a tectonic environment, igneous sources, and petrogenesis similar to many modern continental extensional basins, in contrast to most Archean greenstone belts. The Hammersley basin in Australia and the circum-Superior belts in Canada may be suitable Archean and Proterozoic analogues, respectively.

[H2O ortho-para spin conversion in aqueous solutions as a quantum factor of Konovalov paradox].

PubMed

Pershin, S M

2014-01-01

Recently academician Konovalov and co-workers observed an increase in electroconductivity and biological activity simultaneously with diffusion slowing (or nanoobject diameter increasing) and extremes of other parameters (ζ-potential, surface tension, pH, optical activity) in low concentration aqueous solutions. This phenomenon completely disappeared when samples were shielded against external electromagnetic fields by a Faraday cage. A conventional theory of water and water solutions couldn't explain "Konovalov paradox" observed in numerous experiments (representative sampling about 60 samples and 7 parameters). The new approach was suggested to describe the physics of water and explain "Konovalov paradox". The proposed concept takes into account the quantum differences of ortho-para spin isomers of H2O in bulk water (rotational spin-selectivity upon hydration and spontaneous formation of ice-like structures, quantum beats and spin conversion induced in the presence of a resonant electromagnetic radiation). A size-dependent self-assembly of amorphous complexes of H2O molecules more than 275 leading to the ice Ih structure observed in the previous experiments supports this concept.

Mechanism of nuclear spin initiated para-H2 to ortho-H2 conversion.

PubMed

Buntkowsky, G; Walaszek, B; Adamczyk, A; Xu, Y; Limbach, H-H; Chaudret, B

2006-04-28

In this paper a quantitative explanation for a diamagnetic ortho/para H2 conversion is given. The description is based on the quantum-mechanical density matrix formalism originally developed by Alexander and Binsch for studies of exchange processes in NMR spectra. Only the nuclear spin system is treated quantum-mechanically. Employing the model of a three spin system, the reactions of the hydrogen gas with the catalysts are treated as a phenomenological rate process, described by a rate constant. Numerical calculations reveal that for nearly all possible geometrical arrangements of the three spin system an efficient spin conversion is obtained. Only in the chemically improbable case of a linear group H-X-H no spin conversion is obtained. The efficiency of the spin conversion depends strongly on the lifetime of the H-X-H complex and on the presence of exchange interactions between the two hydrogens. Even moderate exchange couplings cause a quench of the spin conversion. Thus a sufficiently strong binding of the dihydrogen to the S spin is necessary to render the quenching by the exchange interaction ineffective.

N(2)O in small para-hydrogen clusters: Structures and energetics.

PubMed

Zhu, Hua; Xie, Daiqian

2009-04-30

We present the minimum-energy structures and energetics of clusters of the linear N(2)O molecule with small numbers of para-hydrogen molecules with pairwise additive potentials. Interaction energies of (p-H(2))-N(2)O and (p-H(2))-(p-H(2)) complexes were calculated by averaging the corresponding full-dimensional potentials over the H(2) angular coordinates. The averaged (p-H(2))-N(2)O potential has three minima corresponding to the T-shaped and the linear (p-H(2))-ONN and (p-H(2))-NNO structures. Optimization of the minimum-energy structures was performed using a Genetic Algorithm. It was found that p-H(2) molecules fill three solvation rings around the N(2)O axis, each of them containing up to five p-H(2) molecules, followed by accumulation of two p-H(2) molecules at the oxygen and nitrogen ends. The first solvation shell is completed at N = 17. The calculated chemical potential oscillates with cluster size up to the completed first solvation shell. These results are consistent with the available experimental measurements. (c) 2009 Wiley Periodicals, Inc.

Mechanism of the photochemical ligand substitution reactions of fac-[Re(bpy)(CO)(3)(PR(3))](+) complexes and the properties of their triplet ligand-field excited states.

PubMed

Koike, Kazuhide; Okoshi, Nobuaki; Hori, Hisao; Takeuchi, Koji; Ishitani, Osamu; Tsubaki, Hideaki; Clark, Ian P; George, Michael W; Johnson, Frank P A; Turner, James J

2002-09-25

We report herein the mechanism of the photochemical ligand substitution reactions of a series of fac-[Re(X(2)bpy)(CO)(3)(PR(3))](+) complexes (1) and the properties of their triplet ligand-field ((3)LF) excited states. The reason for the photostability of the rhenium complexes [Re(X(2)bpy)(CO)(3)(py)](+) (3) and [Re(X(2)bpy)(CO)(3)Cl] (4) was also investigated. Irradiation of an acetonitrile solution of 1 selectively gave the biscarbonyl complexes cis,trans-[Re(X(2)bpy)(CO)(2)(PR(3))(CH(3)CN)](+) (2). Isotope experiments clearly showed that the CO ligand trans to the PR(3) ligand was selectively substituted. The photochemical reactions proceeded via a dissociative mechanism from the (3)LF excited state. The thermodynamical data for the (3)LF excited states of complexes 1 and the corrective nonradiative decay rate constants for the triplet metal-to-ligand charge-transfer ((3)MLCT) states were obtained from temperature-dependence data for the emission lifetimes and for the quantum yields of the photochemical reactions and the emission. Comparison of 1 with [Re(X(2)bpy)(CO)(3)(py)](+) (3) and [Re(X(2)bpy)(CO)(3)Cl] (4) indicated that the (3)LF states of some 3- and 4-type complexes are probably accessible from the (3)MLCT state even at ambient temperature, but these complexes were stable to irradiation at 365 nm. The photostability of 3 and 4, in contrast to 1, can be explained by differences in the trans effects of the PR(3), py, and Cl(-) ligands.

Synthesis, characterization, structure and properties of heterobimetallic complexes [CuNi(μ-OAc) (μ-OH) (μ-OH2) (bpy)2] (BF4)2 and [CuNi(bz)3(bpy)2] ClO4 from 2,2‧ bipyridine

NASA Astrophysics Data System (ADS)

Kurbah, Sunshine D.; Kumar, A.; Syiemlieh, I.; Dey, A. K.; Lal, R. A.

2018-02-01

Heterobimetallic complexes of the composition [CuNi(bpy)2 (μ-OAc) (μ-OH) (μ-OH2)](BF4)2 (1) and [CuNi(bz)3 (bpy)2]ClO4 (2) were synthesized in moderate yield through solid state reaction and have been characterized by elemental analyses, molar conductance, mass spectra, magnetic moment, EPR, UV-Vis, IR spectroscopies and cyclic voltammetry. The ground state in complex (1) is doublet while that in complex (2), the ground state is a mixture of doublet and quartet, respectively. The structure of the complexes has been established by X-ray crystallography. The electron transfer reactions of the complexes have been investigated by cyclic voltammetry.

Redescription of the advertisement call of Physalaemus albifrons (Spix, 1824) (Amphibia, Anura, Leptodactylidae).

PubMed

Pederassi, Jonas; Lima, Mauro Sérgio Cruz Souza; Caramaschi, Ulisses; Souza, Patrícia Dos Santos; Santos, Mayra Caroliny De Oliveira; Silva, Islaíane Costa

2015-08-03

The genus Physalaemus Fitzinger, 1826 is composed by 46 species occurring from north to southern South America, east of the Andes (Frost 2015). Physalaemus albifrons is morphologically differentiated from the other species mainly due to the presence of a second tarsal tubercle located nearly the tibio-tarsal articulation (Bokermann 1966). Physalaemus albifrons occurs in Brazil from north of the State of Maranhão through the states of Piauí, Ceará, Bahia, Paraíba, Pernambuco, and Alagoas, being its more austral occurrence in the State of Minas Gerais (Frost 2015). The advertisement call of P. albifrons was described by Bokermann (1966); however, the description needs improvement by applying new technologies, which we provide herein.

The spectrum of darkonium in the Sun

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

Kouvaris, Chris; Langæble, Kasper; Nielsen, Niklas Grønlund

Dark matter that gets captured in the Sun may form positronium-like bound states if it self-interacts via light dark photons. In this case, dark matter can either annihilate to dark photons or recombine in bound states which subsequently also decay to dark photons. The fraction of the dark photons that leave the Sun without decaying to Standard Model particles have a characteristic energy spectrum which is a mixture of the direct annihilation process, the decays of ortho- and para- bound states and the recombination process. The ultimate decay of these dark photons to positron-electron pairs (via kinetic mixing) outside themore » Sun creates a distinct signal that can either identify or set strict constraints on dark photon models.« less

Electrically active induced energy levels and metastability of B and N vacancy-complexes in 4H–SiC

NASA Astrophysics Data System (ADS)

Igumbor, E.; Olaniyan, O.; Mapasha, R. E.; Danga, H. T.; Omotoso, E.; Meyer, W. E.

2018-05-01

Electrically active induced energy levels in semiconductor devices could be beneficial to the discovery of an enhanced p or n-type semiconductor. Nitrogen (N) implanted into 4H–SiC is a high energy process that produced high defect concentrations which could be removed during dopant activation annealing. On the other hand, boron (B) substituted for silicon in SiC causes a reduction in the number of defects. This scenario leads to a decrease in the dielectric properties and induced deep donor and shallow acceptor levels. Complexes formed by the N, such as the nitrogen-vacancy centre, have been reported to play a significant role in the application of quantum bits. In this paper, results of charge states thermodynamic transition level of the N and B vacancy-complexes in 4H–SiC are presented. We explore complexes where substitutional N/N or B/B sits near a Si (V) or C (V) vacancy to form vacancy-complexes (NV, NV, NV, NV, BV, BV, BV and BV). The energies of formation of the N related vacancy-complexes showed the NV to be energetically stable close to the valence band maximum in its double positive charge state. The NV is more energetically stable in the double negative charge state close to the conduction band minimum. The NV on the other hand, induced double donor level and the NV induced a double acceptor level. For B related complexes, the BV and BV were energetically stable in their single positive charge state close to the valence band maximum. As the Fermi energy is varied across the band gap, the neutral and single negative charge states of the BV become more stable at different energy levels. B and N related complexes exhibited charge state controlled metastability behaviour.

Diagnosis of compliance of health care product processing in Primary Health Care.

PubMed

Roseira, Camila Eugenia; Silva, Darlyani Mariano da; Passos, Isis Pienta Batista Dias; Orlandi, Fabiana Souza; Padoveze, Maria Clara; Figueiredo, Rosely Moralez de

2016-11-21

identify the compliance of health care product processing in Primary Health Care and assess possible differences in the compliance among the services characterized as Primary Health Care Service and Family Health Service. quantitative, observational, descriptive and inferential study with the application of structure, process and outcome indicators of the health care product processing at ten services in an interior city of the State of São Paulo - Brazil. for all indicators, the compliance indices were inferior to the ideal levels. No statistically significant difference was found in the indicators between the two types of services investigated. The health care product cleaning indicators obtained the lowest compliance index, while the indicator technical-operational resources for the preparation, conditioning, disinfection/sterilization, storage and distribution of health care products obtained the best index. the diagnosis of compliance of health care product processing at the services assessed indicates that the quality of the process is jeopardized, as no results close to ideal levels were obtained at any service. In addition, no statistically significant difference in these indicators was found between the two types of services studied. identificar a conformidade do processamento de produtos para saúde na Atenção Primária à Saúde e avaliar possível diferença na conformidade entre as unidades caracterizadas como Unidade Básica de Saúde e Unidade Saúde da Família. estudo quantitativo, observacional, descritivo e inferencial, com a aplicação de indicadores de estrutura, processo e resultado referentes ao processamento de produtos para a saúde em dez unidades, de um município do interior de São Paulo - Brasil. todos os indicadores obtiveram índice de conformidade inferior ao ideal. Não houve diferença estatisticamente significante nos indicadores entre os dois tipos de unidades investigadas, sendo o indicador de limpeza de produtos para saúde o de menor índice de conformidade, enquanto indicador de recursos técnico-operacionais para preparo, acondicionamento, desinfecção/esterilização, guarda e distribuição de produtos para saúde, o de melhor índice. o diagnóstico de conformidade do processamento de produtos para saúde nas unidades avaliadas indica comprometimento da qualidade do processo, uma vez que não foram obtidos resultados próximos ao valor ideal em nenhuma unidade. Além disso, não houve diferença estatisticamente significante desses indicadores entre os dois tipos de unidades estudadas. identificar la conformidad del procesamiento de productos para la salud en la Atención Primaria a la Salud y evaluar una posible diferencia en la conformidad entre las unidades caracterizadas: Unidad Básica de Salud y Unidad Salud de la Familia. estudio cuantitativo, observacional, descriptivo e inferencial; se aplicaron indicadores de estructura, proceso y resultado, referentes al procesamiento de productos para la salud en diez unidades de un municipio del interior de Sao Paulo, Brasil. todos los indicadores obtuvieron índice de conformidad inferior a lo ideal. No hubo diferencia estadísticamente significativa de los indicadores entre los dos tipos de unidades investigadas, siendo el indicador de limpieza de productos para la salud el de menor índice de conformidad; por otro lado, como indicador de recursos técnico-operacionales para preparación, acondicionamiento, desinfección/esterilización, almacenamiento y distribución de productos para la salud, fue el de mejor índice. el diagnóstico de conformidad del procesamiento de productos para la salud en las unidades evaluadas indica que está comprometida la calidad del proceso, ya que no fueron obtenidos resultados próximos al valor ideal en ninguna unidad. Además de eso, no hubo diferencia estadísticamente significativa de esos indicadores entre los dos tipos de unidades estudiadas.

Accuracy of probabilistic and deterministic record linkage: the case of tuberculosis.

PubMed

Oliveira, Gisele Pinto de; Bierrenbach, Ana Luiza de Souza; Camargo, Kenneth Rochel de; Coeli, Cláudia Medina; Pinheiro, Rejane Sobrino

2016-08-22

To analyze the accuracy of deterministic and probabilistic record linkage to identify TB duplicate records, as well as the characteristics of discordant pairs. The study analyzed all TB records from 2009 to 2011 in the state of Rio de Janeiro. A deterministic record linkage algorithm was developed using a set of 70 rules, based on the combination of fragments of the key variables with or without modification (Soundex or substring). Each rule was formed by three or more fragments. The probabilistic approach required a cutoff point for the score, above which the links would be automatically classified as belonging to the same individual. The cutoff point was obtained by linkage of the Notifiable Diseases Information System - Tuberculosis database with itself, subsequent manual review and ROC curves and precision-recall. Sensitivity and specificity for accurate analysis were calculated. Accuracy ranged from 87.2% to 95.2% for sensitivity and 99.8% to 99.9% for specificity for probabilistic and deterministic record linkage, respectively. The occurrence of missing values for the key variables and the low percentage of similarity measure for name and date of birth were mainly responsible for the failure to identify records of the same individual with the techniques used. The two techniques showed a high level of correlation for pair classification. Although deterministic linkage identified more duplicate records than probabilistic linkage, the latter retrieved records not identified by the former. User need and experience should be considered when choosing the best technique to be used. Analisar a acurácia das técnicas determinística e probabilística para identificação de registros duplicados de tuberculose, assim como as características dos pares discordantes. Foram analisados todos os registros de tuberculose no período de 2009 a 2011 do estado do Rio de Janeiro. Foi desenvolvido algoritmo para relacionamento determinístico, usando conjunto de 70 regras, a partir da combinação de fragmentos das variáveis-chave com ou sem modificações (Soundex ou substring). Cada regra era formada por três ou mais fragmentos. Para a abordagem probabilística, foi necessário estabelecer ponto de corte para o escore, acima do qual os links seriam classificados automaticamente como pertencentes ao mesmo indivíduo. O ponto de corte foi obtido por meio do relacionamento da base de dados Sistema de Informação de Agravos de Notificação - Tuberculose com ela mesma, posterior revisão manual e curvas ROC e precision-recall. Foram calculadas a sensibilidade e especificidade para análise de acurácia. A acurácia variou de 87,2% a 95,2% para sensibilidade e 99,8% a 99,9% para especificidade para as técnicas probabilística e determinística, respectivamente. A presença de valores faltantes para as variáveis-chave e o baixo percentual da medida de similaridade para o nome e data de nascimento foram os principais responsáveis pela não identificação dos registros do mesmo indivíduo pelas técnicas utilizadas. As duas técnicas apresentam alta concordância para a classificação como par. Apesar de a técnica determinística ter identificado mais registros duplicados que a probabilística, a segunda recuperou registros não identificados pela primeira. A necessidade e a experiência do usuário devem ser consideradas para a escolha da técnica a ser utilizada.

Calculation of the vibration-rotational transition intensities of water molecules trapped in an argon matrix: stretching O-H vibrations spectral region

NASA Astrophysics Data System (ADS)

Pitsevich, George; Shalamberidze, Elena; Malevich, Alex; Sablinskas, Valdas; Balevicius, Vytautas; Pettersson, Lars G. M.

2017-10-01

The frequencies and intensities of vibration-rotational transitions of water molecules in an argon matrix were calculated for temperatures of 6 and 30 K. The rigid asymmetric top approximation was used with available literature values of the effective rotational constants in the ground and excited vibrational states. The calculations were carried out by taking into account the existence of a non-equilibrium population distribution between the rotational levels of ortho- and para-water isomers. It was assumed that the temperature relaxation of the population of rotational levels is independent of the ortho- and para-isomers. Comparison of the results of the theoretical calculations with experimental literature data shows good agreement for the majority of the rotational structure lines for symmetric and antisymmetric stretching vibrations both in the frequency values and in the values of the relative intensities.

Pluton emplacement in a releasing bend in a transpressive regime: the arrozal granite in the Paraíba do Sul shear belt, Rio de Janeiro.

PubMed

Nummer, Alexis R; Machado, Rômulo; Dehler, Nolan M

2007-06-01

The Arrozal Granite, situated in the southwestern region of the State of Rio de Janeiro, has a granitic to granodioritic composition. It contains a strong mylonitic foliation along its border, passing gradually to a well-developed magmatic foliation towards its center. Structural analysis indicates that the Arrozal Granite was emplaced along the Além-Paraíba Shear Zone in a dextral transpressive tectonic regime. A regional shift of the trend along this shear zone from NE-SW to E-W, observed in the area, is interpreted to be casually related to the creation of space for the emplacement of the granite. Our data indicate that releasing bends may have played an important role for space generation during the emplacement of the Arrozal Granite and other plutons.

The effects of detergents DDM and beta-OG on the singlet excited state lifetime of the chlorophyll a in cytochrome b6f complex from spinach chloroplasts.

PubMed

Chen, XiaoBo; Zhao, XiaoHui; Zhang, JianPing; Li, LiangBi; Kuang, TingYun

2007-08-01

The singlet excited state lifetime of the chlorophyll a (Chl a) in cytochrome b(6)f (Cyt b(6)f) complex was reported to be shorter than that of free Chl a in methanol, but the value was different for Cyt b(6)f complexes from different sources ( approximately 200 and approximately 600 ps are the two measured results). The present study demonstrated that the singlet excited state lifetime is associated with the detergents n-dodecyl-beta-D-maltoside (DDM) and n-octyl-beta-D-glucopyranoside (beta-OG), but has nothing to do with the different sources of Cyt b(6)f complexes. Compared with the Cyt b(6)f dissolved in beta-OG, the Cyt b(6)f in DDM had a lower fluorescence yield, a lower photodegradation rate of Chl a, and a shorter lifetime of Chl a excited state. In short, the singlet excited state lifetime, approximately 200 ps, of the Chl a in Cyt b(6)f complex in DDM is closer to the true in vivo.

Dithia[3.3]paracyclophane-based monometal ruthenium acetylide complexes: synthesis, characterization and substituent effects.

PubMed

Zhu, Xingxun; Ou, Yaping; Zhang, Jing; Xia, Jian-Long; Yin, Jun; Yu, Guang-Ao; Liu, Sheng Hua

2013-05-21

A series of dithia[3.3]metaparacyclophane-based monometal ruthenium acetylide complexes have been synthesized. All of the complexes have been fully characterised by NMR spectrometry, X-ray crystallography and elemental analyses. At the same time, their basic optical properties, such as UV/Vis absorption spectra, and electrochemical properties have been determined. (1)H NMR and X-ray crystal structure studies reveal that there are intramolecular C-H···π interactions in these ruthenium complexes, in both solution and solid states. Electrochemical studies reveal that the substituted groups on the dithia[3.3]paracyclophane ring can clearly affect the oxidation activities of the ruthenium center by way of the intramolecular C-H···π interaction. In addition, electron-donating groups facilitate the oxidation of the ruthenium center compared with electron-deficient groups. UV/Vis absorption and IR spectra of some complexes in neutral and oxidized states also have been studied. IR spectra studies indicated that the substituents in the cyclophane have some effects on the ν(C≡C) bands of these complexes in the neutral state and little effect on ν(C≡C) of these complexes in the oxidized state.

Synthesis, characterization and solid state electrical properties of 1-D coordination polymer of the type [CuxNi1-x(dadb)·yH2O]n

NASA Astrophysics Data System (ADS)

Prasad, R. L.; Kushwaha, A.; Shrivastava, O. N.

2012-12-01

New heterobimetallic complexes [CuxNi1-x(dadb)·yH2O]n {where dadb=2,5-Diamino-3,6-dichloro-1,4-benzoquinone (1); x=1 (2), 0.5 (4), 0.25 (5), 0.125 (6), 0.0625 (7) and 0 (3); y=2; n=degree of polymerization} were synthesized and characterized. Heterobimetallic complexes show normal magnetic moments, whereas, monometallic complexes exhibit magnetic moments less than the value due to spin only. Thermo-gravimetric analysis shows that degradation of the ligand dadb moiety is being controlled by the electronic environment of the Cu(II) ions in preference over Ni(II) in heterobimetallic complexes. Existence of the mixed valency/non-integral oxidation states of copper and nickel metal ions in the complex 4 has been attributed from magnetic moment and ESR spectral results. Solid state dc electrical conductivity of all the complexes was investigated. Monometallic complexes were found to be semiconductors, whereas heterobimetallic coordination polymer 4 was found to exhibit metallic behaviour. Existence of mixed valency/ non-integral oxidation state of metal ions seems to be responsible for the metallic behaviour.

A Statistical Physics Characterization of the Complex Systems Dynamics: Quantifying Complexity from Spatio-Temporal Interactions

PubMed Central

Koorehdavoudi, Hana; Bogdan, Paul

2016-01-01

Biological systems are frequently categorized as complex systems due to their capabilities of generating spatio-temporal structures from apparent random decisions. In spite of research on analyzing biological systems, we lack a quantifiable framework for measuring their complexity. To fill this gap, in this paper, we develop a new paradigm to study a collective group of N agents moving and interacting in a three-dimensional space. Our paradigm helps to identify the spatio-temporal states of the motion of the group and their associated transition probabilities. This framework enables the estimation of the free energy landscape corresponding to the identified states. Based on the energy landscape, we quantify missing information, emergence, self-organization and complexity for a collective motion. We show that the collective motion of the group of agents evolves to reach the most probable state with relatively lowest energy level and lowest missing information compared to other possible states. Our analysis demonstrates that the natural group of animals exhibit a higher degree of emergence, self-organization and complexity over time. Consequently, this algorithm can be integrated into new frameworks to engineer collective motions to achieve certain degrees of emergence, self-organization and complexity. PMID:27297496

A Statistical Physics Characterization of the Complex Systems Dynamics: Quantifying Complexity from Spatio-Temporal Interactions

NASA Astrophysics Data System (ADS)

Koorehdavoudi, Hana; Bogdan, Paul

2016-06-01

Biological systems are frequently categorized as complex systems due to their capabilities of generating spatio-temporal structures from apparent random decisions. In spite of research on analyzing biological systems, we lack a quantifiable framework for measuring their complexity. To fill this gap, in this paper, we develop a new paradigm to study a collective group of N agents moving and interacting in a three-dimensional space. Our paradigm helps to identify the spatio-temporal states of the motion of the group and their associated transition probabilities. This framework enables the estimation of the free energy landscape corresponding to the identified states. Based on the energy landscape, we quantify missing information, emergence, self-organization and complexity for a collective motion. We show that the collective motion of the group of agents evolves to reach the most probable state with relatively lowest energy level and lowest missing information compared to other possible states. Our analysis demonstrates that the natural group of animals exhibit a higher degree of emergence, self-organization and complexity over time. Consequently, this algorithm can be integrated into new frameworks to engineer collective motions to achieve certain degrees of emergence, self-organization and complexity.

pH imaging of mouse kidneys in vivo using a frequency-dependent paraCEST agent

PubMed Central

Wu, Yunkou; Zhang, Shanrong; Soesbe, Todd C.; Yu, Jing; Vinogradov, Elena; Lenkinski, Robert E.; Sherry, A. Dean

2015-01-01

Purpose This study explored the feasibility of using a pH responsive paraCEST agent to image the pH gradient in kidneys of healthy mice. Methods CEST signals were acquired on an Agilent 9.4 T small animal MRI system using a steady-state gradient echo pulse sequence after a bolus injection of agent. The magnetic field inhomogeneity across each kidney was corrected using the WASSR method and pH maps were calculated by measuring the frequency of water exchange signal arising from the agent. Results Dynamic CEST studies demonstrated that the agent was readily detectable in kidneys only between 4 to 12 min post-injection. The CEST images showed a higher signal intensity in the pelvis and calyx regions and lower signal intensity in the medulla and cortex regions. The pH maps reflected tissue pH values spanning from 6.0 to 7.5 in kidneys of healthy mice. Conclusion This study demonstrated that pH maps of the kidney can be imaged in vivo by measuring the pH-dependent chemical shift of a single water exchange CEST peak without prior knowledge of the agent concentration in vivo. The results demonstrate the potential of using a simple frequency-dependent paraCEST agent for mapping tissue pH in vivo. PMID:26173637

High resolution quantum cascade laser studies of the ν3 band of methyl fluoride in solid para-hydrogen.

PubMed

McKellar, A R W; Mizoguchi, Asao; Kanamori, Hideto

2011-09-28

Spectra of solid para-H(2) doped with CH(3)F at 1.8 K are studied in the ν(3) region (~1040 cm(-1)) using a quantum cascade laser source. As shown previously, residual ortho-H(2) in the sample (~1000 ppm) gives rise to distinct spectral features due to clusters of the form CH(3)F-(ortho-H(2))(N), with N = 0, 1, 2, 3, etc. Brief annealing at 7 K is found to give narrower spectral lines (≥0.006 cm(-1)) than conventional (5 K) annealing, and causes the N = 3 and 4 lines to fragment into two or more components. The N = 3 line is observed to be particularly stable and persistent. The N = 0 line (no ortho-H(2) neighbors) is resolved into two closely spaced (≈0.007 cm(-1)) components which are assigned to the K = 0 and 1 states of CH(3)F rotating around its C(3v) symmetry axis (ortho- and para-CH(3)F, respectively). Similar K-structure is also evident for other lines. Weak but persistent features ("N = 1/2 lines") are observed mid way between N = 0 and 1. © 2011 American Institute of Physics

Identification of the Phenol Functionality in Deprotonated Monomeric and Dimeric Lignin Degradation Products via Tandem Mass Spectrometry Based on Ion-Molecule Reactions with Diethylmethoxyborane

NASA Astrophysics Data System (ADS)

Zhu, Hanyu; Max, Joann P.; Marcum, Christopher L.; Luo, Hao; Abu-Omar, Mahdi M.; Kenttämaa, Hilkka I.

2016-11-01

Conversion of lignin into smaller molecules provides a promising alternate and sustainable source for the valuable chemicals currently derived from crude oil. Better understanding of the chemical composition of the resulting product mixtures is essential for the optimization of such conversion processes. However, these mixtures are complex and contain isomeric molecules with a wide variety of functionalities, which makes their characterization challenging. Tandem mass spectrometry based on ion-molecule reactions has proven to be a powerful tool in functional group identification and isomer differentiation for previously unknown compounds. This study demonstrates that the identification of the phenol functionality, the most commonly observed functionality in lignin degradation products, can be achieved via ion-molecule reactions between diethylmethoxyborane (DEMB) and the deprotonated analyte in the absence of strongly electron-withdrawing substituents in the ortho- and para-positions. Either a stable DEMB adduct or an adduct that has lost a methanol molecule (DEMB adduct-MeOH) is formed for these ions. Deprotonated phenols with an adjacent phenol or hydroxymethyl functionality or a conjugated carboxylic acid functionality can be identified based on the formation of DEMB adduct-MeOH. Deprotonated compounds not containing the phenol functionality and phenols containing an electron-withdrawing ortho- or para-substituent were found to be unreactive toward diethylmethoxyborane. Hence, certain deprotonated isomeric compounds with phenol and carboxylic acid, aldehyde, carboxylic acid ester, or nitro functionalities can be differentiated via these reactions. The above mass spectrometry method was successfully coupled with high-performance liquid chromatography for the analysis of a complex biomass degradation mixture.

THE ABUNDANCE, ORTHO/PARA RATIO, AND DEUTERATION OF WATER IN THE HIGH-MASS STAR-FORMING REGION NGC 6334 I

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

Emprechtinger, M.; Lis, D. C.; Monje, R. R.

2013-03-01

We present Herschel/HIFI observations of 30 transitions of water isotopologues toward the high-mass star-forming region NGC 6334 I. The line profiles of H{sup 16} {sub 2}O, H{sup 17} {sub 2}O, H{sup 18} {sub 2}O, and HDO show a complex pattern of emission and absorption components associated with the embedded hot cores, a lower-density envelope, two outflow components, and several foreground clouds, some associated with the NGC 6334 complex, others seen in projection against the strong continuum background of the source. Our analysis reveals an H{sub 2}O ortho/para ratio of 3 {+-} 0.5 in the foreground clouds, as well as themore » outflow. The water abundance varies from {approx}10{sup -8} in the foreground clouds and the outer envelope to {approx}10{sup -6} in the hot core. The hot core abundance is two orders of magnitude below the chemical model predictions for dense, warm gas, but within the range of values found in other Herschel/HIFI studies of hot cores and hot corinos. This may be related to the relatively low gas and dust temperature ({approx}100 K), or time-dependent effects, resulting in a significant fraction of water molecules still locked up in dust grain mantles. The HDO/H{sub 2}O ratio in NGC 6334 I, {approx}2 Multiplication-Sign 10{sup -4}, is also relatively low, but within the range found in other high-mass star-forming regions.« less

Multiple hydrogen bonding in excited states of aminopyrazine in methanol solution: time-dependent density functional theory study.

PubMed

Chai, Shuo; Yu, Jie; Han, Yong-Chang; Cong, Shu-Lin

2013-11-01

Aminopyrazine (AP) and AP-methanol complexes have been theoretically studied by using density functional theory (DFT) and time-dependent density functional theory (TDDFT). The excited-state hydrogen bonds are discussed in detail. In the ground state the intermolecular multiple hydrogen bonds can be formed between AP molecule and protic solvents. The AP monomer and hydrogen-bonded complex of AP with one methanol are photoexcited initially to the S2 state, and then transferred to the S1 state via internal conversion. However the complex of AP with two methanol molecules is directly excited to the S1 state. From the calculated electronic excited energies and simulated absorption spectra, we find that the intermolecular hydrogen bonds are strengthened in the electronic excited states. The strengthening is confirmed by the optimized excited-state geometries. The photochemical processes in the electronic excited states are significantly influenced by the excited-state hydrogen bond strengthening. Copyright © 2013 Elsevier B.V. All rights reserved.

GENERAL PERSPECTIVE VIEW OF THE EAST SIDE OF THE COMPLEX, ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

GENERAL PERSPECTIVE VIEW OF THE EAST SIDE OF THE COMPLEX, VIEW LOOKING SOUTH WITH THE FIRE CACHE BUILDING, COMMUNICATIONS BUILDING, GRAPHICS BUILDING, FOREST PRACTICES BUILDING, AND THE K.O.G. (KEEP OREGON GREEN) BUILDING VISIBLE FROM LEFT TO RIGHT. - Oregon State Forester's Office Complex, 2600 State Street, Salem, Marion, OR

Complex sample survey estimation in static state-space

Treesearch

Raymond L. Czaplewski

2010-01-01

Increased use of remotely sensed data is a key strategy adopted by the Forest Inventory and Analysis Program. However, multiple sensor technologies require complex sampling units and sampling designs. The Recursive Restriction Estimator (RRE) accommodates this complexity. It is a design-consistent Empirical Best Linear Unbiased Prediction for the state-vector, which...

Joint Analysis of Band-Specific Functional Connectivity and Signal Complexity in Autism

ERIC Educational Resources Information Center

Ghanbari, Yasser; Bloy, Luke; Edgar, J. Christopher; Blaskey, Lisa; Verma, Ragini; Roberts, Timothy P. L.

2015-01-01

Examination of resting state brain activity using electrophysiological measures like complexity as well as functional connectivity is of growing interest in the study of autism spectrum disorders (ASD). The present paper jointly examined complexity and connectivity to obtain a more detailed characterization of resting state brain activity in ASD.…

Teaching Literature in an Age of Text Complexity

ERIC Educational Resources Information Center

Alsup, Janet

2013-01-01

The recently released Common Core State Standards increase classroom emphasis on informational texts in high school and recommend a three-part measurement for text complexity when selecting texts for classroom use. In this commentary I argue that fictional narratives can not only meet these stated criteria for complex texts and result in critical…

Fe N-Heterocyclic Carbene Complexes as Promising Photosensitizers.

PubMed

Liu, Yizhu; Persson, Petter; Sundström, Villy; Wärnmark, Kenneth

2016-08-16

The photophysics and photochemistry of transition metal complexes (TMCs) has long been a hot field of interdisciplinary research. Rich metal-based redox processes, together with a high variety in electronic configurations and excited-state dynamics, have rendered TMCs excellent candidates for interconversion between light, chemical, and electrical energies in intramolecular, supramolecular, and interfacial arrangements. In specific applications such as photocatalytic organic synthesis, photoelectrochemical cells, and light-driven supramolecular motors, light absorption by a TMC-based photosensitizer and subsequent excited-state energy or electron transfer constitute essential steps. In this context, TMCs based on rare and expensive metals, such as ruthenium and iridium, are frequently employed as photosensitizers, which is obviously not ideal for large-scale implementation. In the search for abundant and environmentally benign solutions, six-coordinate Fe(II) complexes (Fe(II)L6) have been widely considered as highly desirable alternatives. However, not much success has been achieved due to the extremely short-lived triplet metal-to-ligand charge transfer ((3)MLCT) excited state that is deactivated by low-lying metal-centered (MC) states on a 100 fs time scale. A fundamental strategy to design useful Fe-based photosensitizers is thus to destabilize the MC states relative to the (3)MLCT state by increasing the ligand field strength, with special focus on making eg σ* orbitals on the Fe center energetically less accessible. Previous efforts to directly transplant successful strategies from Ru(II)L6 complexes unfortunately met with limited success in this regard, despite their close chemical kinship. In this Account, we summarize recent promising results from our and other groups in utilizing strongly σ-donating N-heterocyclic carbene (NHC) ligands to make strong-field Fe(II)L6 complexes with significantly extended (3)MLCT lifetimes. Already some of the first homoleptic bis(tridentate) complexes incorporating (CNHC^Npyridine^CNHC)-type ligands gratifyingly resulted in extension of the (3)MLCT lifetime by more than 2 orders of magnitude compared to the parental [Fe(tpy)2](2+) (tpy = 2,2':6',2″-terpyridine) complex. Quantum chemical (QC) studies also revealed that the (3)MC instead of the (5)MC state likely dictates the deactivation of the (3)MLCT state, a behavior distinct from traditional Fe(II)L6 complexes but rather resembling Ru analogues. A heteroleptic Fe(II) NHC complex featuring mesoionic bis(1,2,3-triazol-5-ylidene) (btz) ligands also delivered a 100-fold elongation of the (3)MLCT lifetime relative to its parental [Fe(bpy)3](2+) (bpy = 2,2'-bipyridine) complex. Again, a Ru-like deactivation mechanism of the (3)MLCT state was indicated by QC studies. With a COOH-functionalized homoleptic complex, a record (3)MLCT lifetime of 37 ps was recently observed on an Al2O3 nanofilm. As a proof of concept, it was further demonstrated that the significant improvement in the (3)MLCT lifetime indeed benefits efficient light harvesting with Fe(II) NHC complexes. For the first time, close-to-unity electron injection from the lowest-energy (3)MLCT state to a TiO2 nanofilm was achieved by a stable Fe(II) complex. This is in complete contrast to conventional Fe(II)L6-derived photosensitizers that could only make use of high-energy photons. These exciting results significantly broaden the understanding of the fundamental photophysics and photochemistry of d(6) Fe(II) complexes. They also open up new possibilities to develop solar energy-converting materials based on this abundant, inexpensive, and intrinsically nontoxic element.

Lambda Red-mediated mutagenesis and efficient large scale affinity purification of the Escherichia coli NADH:ubiquinone oxidoreductase (complex I).

PubMed

Pohl, Thomas; Uhlmann, Mareike; Kaufenstein, Miriam; Friedrich, Thorsten

2007-09-18

The proton-pumping NADH:ubiquinone oxidoreductase, the respiratory complex I, couples the transfer of electrons from NADH to ubiquinone with the translocation of protons across the membrane. The Escherichia coli complex I consists of 13 different subunits named NuoA-N (from NADH:ubiquinone oxidoreductase), that are coded by the genes of the nuo-operon. Genetic manipulation of the operon is difficult due to its enormous size. The enzymatic activity of variants is obscured by an alternative NADH dehydrogenase, and purification of the variants is hampered by their instability. To overcome these problems the entire E. coli nuo-operon was cloned and placed under control of the l-arabinose inducible promoter ParaBAD. The exposed N-terminus of subunit NuoF was chosen for engineering the complex with a hexahistidine-tag by lambda-Red-mediated recombineering. Overproduction of the complex from this construct in a strain which is devoid of any membrane-bound NADH dehydrogenase led to the assembly of a catalytically active complex causing the entire NADH oxidase activity of the cytoplasmic membranes. After solubilization with dodecyl maltoside the engineered complex binds to a Ni2+-iminodiacetic acid matrix allowing the purification of approximately 11 mg of complex I from 25 g of cells. The preparation is pure and monodisperse and comprises all known subunits and cofactors. It contains more lipids than earlier preparations due to the gentle and fast purification procedure. After reconstitution in proteoliposomes it couples the electron transfer with proton translocation in an inhibitor sensitive manner, thus meeting all prerequisites for structural and functional studies.

Noble Gas-Uranium Coordination and Intersystem Crossing for the CUO(Ne)x(Ng)n (Ng = Ar, Kr, Xe) Complexes in Solid Neon

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

Andrews, Lester; Liang, Binyong; Li, Jun

2004-02-15

Atomic uranium excited by laser ablation reacts with CO in excess neon to produce the novel CUO molecule, which forms weak complexes CUO(Ne)m with neon and stronger complexes CUO(Ne)x(Ng)n (Ng = Ar, Kr, Xe) when the heavier noble gas atoms are present. The heavier CUO(Ne)m-1(Ng) complexes are identified through the effects of CO isotopic and Ng substitution on the neon matrix infrared spectra and by comparison to DFT frequency calculations on model complexes CUO(Ng) (Ng = Ne, Ar, Kr, Xe). The U-C and U-O stretching frequencies of CUO(Ne)m-1(Ng) complexes are slightly red shifted from 1047 and 872 cm-1 frequencies formore » the 1Sigma+ CUO ground state neon complex, which identifies singlet ground state CUO(Ne)m-1(Ng) complexes in solid neon. The next singlet CUO(Ne)x(Ng)2 complexes in excess neon follow in like manner. However, stretching modes and the isotopic shifts of the higher CUO(Ne)x(Ng)n complex approach those of the pure argon matrix CUO(Ar)n complex, which characterizes triple t ground state complexes by comparison to DFT frequency calculations.« less

pH-Dependent spin state population and 19F NMR chemical shift via remote ligand protonation in an iron(ii) complex.

PubMed

Gaudette, Alexandra I; Thorarinsdottir, Agnes E; Harris, T David

2017-11-30

An Fe II complex that features a pH-dependent spin state population, by virtue of a variable ligand protonation state, is described. This behavior leads to a highly pH-dependent 19 F NMR chemical shift with a sensitivity of 13.9(5) ppm per pH unit at 37 °C, thereby demonstrating the potential utility of the complex as a 19 F chemical shift-based pH sensor.

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

Meng, Jiang Ping; Yan, Zhi Shuo; Long, Ji Ying

By using a rigid dicarboxylate ligand, 4,5-di(4′-carboxylphenyl)benzene (H{sub 2}L), two complexes formulated as SrL(DMF)(H{sub 2}O)·(CH{sub 3}CN) (DMF=N,N′-dimethylformamide) (1) and BaL(H{sub 2}O){sub 2} (2) were solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Complexes 1 and 2 display two-dimensional (2D) layer structures. The two complexes exhibit different electrochemical and photoelectrochemical properties. Their thermal stabilities, cyclic voltammograms, UV–vis absorption and diffuse reflectance spectra and photoluminescence properties have been investigated. The band structures, the total density of states (TDOS) and partial density of states (PDOS) of the two complexes were calculated by CASTEP program. Complex 2 exhibits much higher photocurrent density thanmore » complex 1. The Mott–Schottky plots reveal that complexes 1 and 2 both are p-type semiconductors, which are in agreement with their band structure calculations. - Graphical abstract: Two alkaline earth metal(II) complexes with 2D layer structures are p-type semiconductors, they possess different band structures and density of states. And the Ba(II) complex 2 exhibits much higher photocurrent density than the Sr(II) complex 1.« less

A biogeochemical and isotopic view of Nitrogen and Carbon in rivers of the Alto Paraíba do Sul basin, São Paulo State, Brazil

NASA Astrophysics Data System (ADS)

Ravagnani, E. D. C.; Coletta, L. D.; Lins, S. R. M.; Antonio, J.; Mazzi, E. A.; Rossete, A. L. M.; Andrade, T. M. B.; Martinelli, L. A.

2014-12-01

The magnitude of potential flows of elements in tropical ecosystems is not well represented in the literature, even being very important. The Paraíba do Sul River drains the three more economically developed states in Brazil: São Paulo, Minas Gerais and Rio de Janeiro and its basin is considered extremely altered. Despite its economic and social importance (~ 5.3 mi inhabitants), we don't know much about carbon and nitrogen transport into its rivers and how these are affected by soil use changes. This work aimed to investigate these nutrients, using an isotopic and a biogeochemical approach, at some third order (Paraibuna, Paraitinga and Paraíba do Sul), second and first order rivers, all inserted at the Alto Paraíba do Sul Basin. In general, the low dissolved organic carbon, dissolved inorganic carbon, total dissolved nitrogen and inorganic N concentrations found in the first order rivers, showed the lower variation, despite changes in the soil use. Forested rivers presented higher DOC (3.3 mg.L-1) and TDN (14.2 mM) concentrations than the pasture rivers (2.6 mg.L-1 and 13.8 mM), while these presented higher DIC concentrations than those ones (90.2 mM and 71.2 mM). In third order rivers, the concentrations were also very low. Both carbon and nitrogen contents at the fine and coarse fractions of the suspended particulate material (SPM) were lower at Paraitinga and Paraiba do Sul Rivers. At the Paraibuna River, the fine fraction of SPM presented 25% of C concentration. The concentrations found at the coarse fraction were also higher at this river. The N concentrations were higher at the fine fraction and, consequently, this fraction presented higher C:N ratio. These observations allow us to say that the coarse fraction might be related to plant material, while the fine fraction is probably related to the soils. The δ13C in the SPM was lower in the Paraibuna River, probably due to the predominance of forest, while in the other ones pasture was the main soil use. The Paraibuna River presented the lower δ15N in the SPM results, similar to the results found at the Montane Forest, predominant at this basin, but are lower than the δ15N results found in the soils of the region. The higher results found in the Paraíba do Sul and Paraitinga Rivers may be explained by the highest N losses that occur in pasture grasses and soils.

The orbital ground state of the azide-substrate complex of human heme oxygenase is an indicator of distal H-bonding: implications for the enzyme mechanism.

PubMed

Ogura, Hiroshi; Evans, John P; Peng, Dungeng; Satterlee, James D; Ortiz de Montellano, Paul R; La Mar, Gerd N

2009-04-14

The active site electronic structure of the azide complex of substrate-bound human heme oxygenase 1 (hHO) has been investigated by (1)H NMR spectroscopy to shed light on the orbital/spin ground state as an indicator of the unique distal pocket environment of the enzyme. Two-dimensional (1)H NMR assignments of the substrate and substrate-contact residue signals reveal a pattern of substrate methyl contact shifts that places the lone iron pi-spin in the d(xz) orbital, rather than the d(yz) orbital found in the cyanide complex. Comparison of iron spin relaxivity, magnetic anisotropy, and magnetic susceptibilities argues for a low-spin, (d(xy))(2)(d(yz),d(xz))(3), ground state in both azide and cyanide complexes. The switch from singly occupied d(yz) for the cyanide to d(xz) for the azide complex of hHO is shown to be consistent with the orbital hole determined by the azide pi-plane in the latter complex, which is approximately 90 degrees in-plane rotated from that of the imidazole pi-plane. The induction of the altered orbital ground state in the azide relative to the cyanide hHO complex, as well as the mean low-field bias of methyl hyperfine shifts and their paramagnetic relaxivity relative to those in globins, indicates that azide exerts a stronger ligand field in hHO than in the globins, or that the distal H-bonding to azide is weaker in hHO than in globins. The Asp140 --> Ala hHO mutant that abolishes activity retains the unusual WT azide complex spin/orbital ground state. The relevance of our findings for other HO complexes and the HO mechanism is discussed.

The orbital ground state of the azide-substrate complex of human heme oxygenase is an indicator of distal H-bonding: Implications for the enzyme mechanism‡

PubMed Central

Ogura, Hiroshi; Evans, John P.; Peng, Dungeng; Satterlee, James D.; de Montellano, Paul R. Ortiz; Mar, Gerd N. La

2009-01-01

The active site electronic structure of the azide complex of substrate-bound human heme oxygenase-1, (hHO) has been investigated by 1H NMR spectroscopy to shed light on the orbital/spin ground state as an indicator of the unique distal pocket environment of the enzyme. 2D 1H NMR assignments of the substrate and substrate-contact residue signals reveal a pattern of substrate methyl contact shifts, that places the lone iron π-spin in the dxz orbital, rather than the dyz orbital found in the cyanide complex. Comparison of iron spin relaxivity, magnetic anisotropy and magnetic susceptibilities argues for a low-spin, (dxy)2(dyz,dxz)3, ground state in both azide and cyanide complexes. The switch from singly-occupied dyz for the cyanide to dxz for the azide complex of hHO is shown to be consistent with the orbital hole determined by the azide π-plane in the latter complex, which is ∼90° in-plane rotated from that of the imidazole π-plane. The induction of the altered orbital ground state in the azide relative to the cyanide hHO complex, as well as the mean low-field bias of methyl hyperfine shifts and their paramagnetic relaxivity relative to those in globins, indicate that azide exerts a stronger ligand field in hHO than in the globins, or that the distal H-bonding to azide is weaker in hHO than in globins. The Asp140 → Ala hHO mutant that abolishes activity retains the unusual WT azide complex spin/orbital ground state. The relevance of our findings for other HO complexes and the HO mechanism is discussed. PMID:19243105

Seleccionando materiales adecuados cultural y linguisticamente: Sugerencias para los proveedores de servicios (Selecting Culturally and Linguistically Appropriate Materials: Suggestions for Service Providers). ERIC Digest.

ERIC Educational Resources Information Center

Santos, Rosa Milagros; Reese, Debbie

The population of the United States is growing more culturally diverse each year, and this diversity is clearly evident among families with young children; however, individuals who work in early childhood programs are not as diverse as those they serve. Moreover, many early childhood professionals have little preparation for working with families…

Demonstration, Developmental and Research Project for Programs, Materials, Facilities and Educational Technology for Undereducated Adults. Counselor Aides; Virginia State Module. Final Report Series.

ERIC Educational Resources Information Center

Morehead State Univ., KY. Appalachian Adult Basic Education Demonstration Center.

The Counselor-Aide Program is implemented by para-professionals working cooperatively with a certified counselor, in an effort to raise the economic level of the adults in Carroll County, through an improvement in the educational level of achievement. The counselor aides feel that they have been reasonably successful in meeting the objectives as…

Supplement for Curriculum Guide for Mathematics: Spanish-Speaking Students, Grades 4-6 = Supplemento de la guia didactica de matematicas para los estudiantes de habla hispana, cuatro-sexto grados. Field Test.

ERIC Educational Resources Information Center

Chicago Board of Education, IL.

This supplementary math curriculum guide for use with Spanish-speaking, fouth through sixth grade students in Chicago public schools employs a contrastive analysis approach. Lessons are presented for objectives for which the instructional strategies used in the United States differ from those used in Spanish-speaking countries. (Objectives for…

A Handbook for Title I Migrant Parent Advisory Councils: Understanding the System=Un Folleto Para los Concilios de Padres Titulo I Migrante: Entendiendo el Sistema.

ERIC Educational Resources Information Center

Arredondo, C.; And Others

A bilingual handbook for Title I migrant Parent Advisory Councils (PACs) was designed to be used by administrators, teachers, consultants and parents in organizing and training PACs at local, district, and state levels. All information is duplicated in separate English and Spanish sections. The first part discusses the Texas migrant program,…

Manual sobre la Educacion en California para Padres de Idiomas Minoritarios (A Handbook on California Education for Language Minority Parents). Revised Edition. Spanish/English Edition.

ERIC Educational Resources Information Center

California State Dept. of Education, Sacramento. Office of Bilingual Bicultural Education.

The handbook, an update of the 1986 handbook, is designed for Spanish-speaking parents of California public school students, and answers commonly-asked questions about the state public education system and its services, particularly those of interest to this population. Information is presented in both Spanish-and English-language sections, in a…

Manual sobre la Educacion en California para Padres de Idiomas Minoritarios = A Handbook on California Education for Language Minority Parents--Spanish/English Edition.

ERIC Educational Resources Information Center

California State Dept. of Education, Sacramento. Bilingual Education Office.

This bilingual handbook, presented in both Spanish and English, is designed to assist parents of language minority students who are residing in California. The book is part of the technical assistance effort of the State Department of Education to clarify the operations of the California schools to language minority parents so they can better…

Naval Ships Acquisition Strategy for the Venezuelan Navy.

DTIC Science & Technology

1982-06-01

Contract LAdministration Manual (SAC), Washington, D.C., 198 16. Congreso de Venezuela, Constitucion de la Republica de Venezuela X- Disposiciones ...Directiva D-MA-CGM-0030-A, Estado Mayor General de la Armada, Caracas, Venezuela, June 29, 1981. 23. Congress of the United States of America, Public...Fundamentos Estrategicos para la Escuadra Venezolana en eI Futuro, Armada- de -Venezuela, Escuela Superior de Guerra Naval, XI Curso de Comando y Estado

Proyecto para la participacion de los padres de los estudiantes con competencia limitada en ingles (LEP) (Limited English Proficient (LEP) Parent Involvement Project).

ERIC Educational Resources Information Center

Pecoraro, Diane; Phommasouvanh, Bounlieng

The Limited English Proficient (LEP) Parent Involvement Project, a collaborative project between two state agencies, aims to help refugee and immigrant parents to be effective in their new American culture. Materials are provided that were developed for use in various adult education settings such as English-as-a-Second-Language (ESL) classes,…

Latino Families in the United States. A Resourcebook for Family Life Education = Las Familias Latinas en los Estados Unidos. Recursos para la Capacitacion Familiar.

ERIC Educational Resources Information Center

Andrade, Sally J., Ed.

The primary objectives of this resource book are to increase family life educators' knowledge and understanding of Latinos and to encourage advocacy by Latinos for appropriate family life programs in their communities. English and Spanish versions of the same text are included. There are six chapters. Chapter 1 outlines the book's objectives and…

FAMACHA(©) method as an auxiliary strategy in the control of gastrointestinal helminthiasis of dairy goats under semiarid conditions of Northeastern Brazil.

PubMed

Vilela, Vinícius Longo Ribeiro; Feitosa, Thais Ferreira; Linhares, Emanuel Figueiredo; Athayde, Ana Célia Rodrigues; Molento, Marcelo Beltrão; Azevedo, Sérgio Santos

2012-11-23

This study aimed to evaluate the utilization of FAMACHA(©) method as an auxiliary strategy to use the individual identification for the selective control of gastrointestinal helminthiasis in naturally infected dairy goats. The experiment was conducted on 63 farms in the towns of Passagem, Quixabá and Cacimba de Areia, semiarid region of the Paraíba state, Brazil. Fifty animals were used on each farm, being visited tree farms per month, totaling 1800 animals, between May 2009 and April 2010. The animals received no anthelmintic treatment for at least four months prior to the farm visits. All animals were subjected to parasitological faecal collection, blood sampling for packed cell volume and the visual/selective exam of the eye colour through the FAMACHA(©) method. Larvae culture was performed in every assessment on each farm. Haemonchus sp. was the most prevalent helminth (80.1%) on larval cultures. The use of this method allowed a reduction of 79.2% on anthelmintic application in dairy goats. The FAMACHA(©) method proved to be a viable auxiliary strategy to control gastrointestinal helminthiasis of dairy goats from a resource-poor area in the semiarid region of the Paraíba state, Northeastern Brazil. Copyright © 2012 Elsevier B.V. All rights reserved.

Redox-dependent substrate-cofactor interactions in the Michaelis-complex of a flavin-dependent oxidoreductase

NASA Astrophysics Data System (ADS)

Werther, Tobias; Wahlefeld, Stefan; Salewski, Johannes; Kuhlmann, Uwe; Zebger, Ingo; Hildebrandt, Peter; Dobbek, Holger

2017-07-01

How an enzyme activates its substrate for turnover is fundamental for catalysis but incompletely understood on a structural level. With redox enzymes one typically analyses structures of enzyme-substrate complexes in the unreactive oxidation state of the cofactor, assuming that the interaction between enzyme and substrate is independent of the cofactors oxidation state. Here, we investigate the Michaelis complex of the flavoenzyme xenobiotic reductase A with the reactive reduced cofactor bound to its substrates by X-ray crystallography and resonance Raman spectroscopy and compare it to the non-reactive oxidized Michaelis complex mimics. We find that substrates bind in different orientations to the oxidized and reduced flavin, in both cases flattening its structure. But only authentic Michaelis complexes display an unexpected rich vibrational band pattern uncovering a strong donor-acceptor complex between reduced flavin and substrate. This interaction likely activates the catalytic ground state of the reduced flavin, accelerating the reaction within a compressed cofactor-substrate complex.

Redox-dependent substrate-cofactor interactions in the Michaelis-complex of a flavin-dependent oxidoreductase

PubMed Central

Werther, Tobias; Wahlefeld, Stefan; Salewski, Johannes; Kuhlmann, Uwe; Zebger, Ingo; Hildebrandt, Peter; Dobbek, Holger

2017-01-01

How an enzyme activates its substrate for turnover is fundamental for catalysis but incompletely understood on a structural level. With redox enzymes one typically analyses structures of enzyme–substrate complexes in the unreactive oxidation state of the cofactor, assuming that the interaction between enzyme and substrate is independent of the cofactors oxidation state. Here, we investigate the Michaelis complex of the flavoenzyme xenobiotic reductase A with the reactive reduced cofactor bound to its substrates by X-ray crystallography and resonance Raman spectroscopy and compare it to the non-reactive oxidized Michaelis complex mimics. We find that substrates bind in different orientations to the oxidized and reduced flavin, in both cases flattening its structure. But only authentic Michaelis complexes display an unexpected rich vibrational band pattern uncovering a strong donor–acceptor complex between reduced flavin and substrate. This interaction likely activates the catalytic ground state of the reduced flavin, accelerating the reaction within a compressed cofactor–substrate complex.

Heartbeat Complexity Modulation in Bipolar Disorder during Daytime and Nighttime.

PubMed

Nardelli, Mimma; Lanata, Antonio; Bertschy, Gilles; Scilingo, Enzo Pasquale; Valenza, Gaetano

2017-12-20

This study reports on the complexity modulation of heartbeat dynamics in patients affected by bipolar disorder. In particular, a multiscale entropy analysis was applied to the R-R interval series, that were derived from electrocardiographic (ECG) signals for a group of nineteen subjects comprised of eight patients and eleven healthy control subjects. They were monitored using a textile-based sensorized t-shirt during the day and overnight for a total of 47 diurnal and 27 nocturnal recordings. Patients showed three different mood states: depression, hypomania and euthymia. Results show a clear loss of complexity during depressive and hypomanic states as compared to euthymic and healthy control states. In addition, we observed that a more significant complexity modulation among healthy and pathological mood states occurs during the night. These findings suggest that bipolar disorder is associated with an enhanced sleep-related dysregulation of the Autonomic Nervous System (ANS) activity, and that heartbeat complex dynamics may serve as a viable marker of pathological conditions in mental health.

Hydrogen exchange differences between chemoreceptor signaling complexes localize to functionally important subdomains.

PubMed

Koshy, Seena S; Li, Xuni; Eyles, Stephen J; Weis, Robert M; Thompson, Lynmarie K

2014-12-16

The goal of understanding mechanisms of transmembrane signaling, one of many key life processes mediated by membrane proteins, has motivated numerous studies of bacterial chemotaxis receptors. Ligand binding to the receptor causes a piston motion of an α helix in the periplasmic and transmembrane domains, but it is unclear how the signal is then propagated through the cytoplasmic domain to control the activity of the associated kinase CheA. Recent proposals suggest that signaling in the cytoplasmic domain involves opposing changes in dynamics in different subdomains. However, it has been difficult to measure dynamics within the functional system, consisting of extended arrays of receptor complexes with two other proteins, CheA and CheW. We have combined hydrogen exchange mass spectrometry with vesicle template assembly of functional complexes of the receptor cytoplasmic domain to reveal that there are significant signaling-associated changes in exchange, and these changes localize to key regions of the receptor involved in the excitation and adaptation responses. The methylation subdomain exhibits complex changes that include slower hydrogen exchange in complexes in a kinase-activating state, which may be partially consistent with proposals that this subdomain is stabilized in this state. The signaling subdomain exhibits significant protection from hydrogen exchange in complexes in a kinase-activating state, suggesting a tighter and/or larger interaction interface with CheA and CheW in this state. These first measurements of the stability of protein subdomains within functional signaling complexes demonstrate the promise of this approach for measuring functionally important protein dynamics within the various physiologically relevant states of multiprotein complexes.

Hydrogen Exchange Differences between Chemoreceptor Signaling Complexes Localize to Functionally Important Subdomains

PubMed Central

2015-01-01

The goal of understanding mechanisms of transmembrane signaling, one of many key life processes mediated by membrane proteins, has motivated numerous studies of bacterial chemotaxis receptors. Ligand binding to the receptor causes a piston motion of an α helix in the periplasmic and transmembrane domains, but it is unclear how the signal is then propagated through the cytoplasmic domain to control the activity of the associated kinase CheA. Recent proposals suggest that signaling in the cytoplasmic domain involves opposing changes in dynamics in different subdomains. However, it has been difficult to measure dynamics within the functional system, consisting of extended arrays of receptor complexes with two other proteins, CheA and CheW. We have combined hydrogen exchange mass spectrometry with vesicle template assembly of functional complexes of the receptor cytoplasmic domain to reveal that there are significant signaling-associated changes in exchange, and these changes localize to key regions of the receptor involved in the excitation and adaptation responses. The methylation subdomain exhibits complex changes that include slower hydrogen exchange in complexes in a kinase-activating state, which may be partially consistent with proposals that this subdomain is stabilized in this state. The signaling subdomain exhibits significant protection from hydrogen exchange in complexes in a kinase-activating state, suggesting a tighter and/or larger interaction interface with CheA and CheW in this state. These first measurements of the stability of protein subdomains within functional signaling complexes demonstrate the promise of this approach for measuring functionally important protein dynamics within the various physiologically relevant states of multiprotein complexes. PMID:25420045

Molecular Remodeling of Photosystem II during State Transitions in Chlamydomonas reinhardtii[W

PubMed Central

Iwai, Masakazu; Takahashi, Yuichiro; Minagawa, Jun

2008-01-01

State transitions, or the redistribution of light-harvesting complex II (LHCII) proteins between photosystem I (PSI) and photosystem II (PSII), balance the light-harvesting capacity of the two photosystems to optimize the efficiency of photosynthesis. Studies on the migration of LHCII proteins have focused primarily on their reassociation with PSI, but the molecular details on their dissociation from PSII have not been clear. Here, we compare the polypeptide composition, supramolecular organization, and phosphorylation of PSII complexes under PSI- and PSII-favoring conditions (State 1 and State 2, respectively). Three PSII fractions, a PSII core complex, a PSII supercomplex, and a multimer of PSII supercomplex or PSII megacomplex, were obtained from a transformant of the green alga Chlamydomonas reinhardtii carrying a His-tagged CP47. Gel filtration and single particles on electron micrographs showed that the megacomplex was predominant in State 1, whereas the core complex was predominant in State 2, indicating that LHCIIs are dissociated from PSII upon state transition. Moreover, in State 2, strongly phosphorylated LHCII type I was found in the supercomplex but not in the megacomplex. Phosphorylated minor LHCIIs (CP26 and CP29) were found only in the unbound form. The PSII subunits were most phosphorylated in the core complex. Based on these observations, we propose a model for PSII remodeling during state transitions, which involves division of the megacomplex into supercomplexes, triggered by phosphorylation of LHCII type I, followed by LHCII undocking from the supercomplex, triggered by phosphorylation of minor LHCIIs and PSII core subunits. PMID:18757554

Genetic types of oils in the petroliferous basins of Cuba

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

Maksimov, S.P.; Botneva, T.A.; Pankina, R.G.

Two oil- and gas basins, the North Cuban and the Central Cuban, have been discovered in Cuba and the nearby offshore areas. The North Cuban basin developed as a result of a complete cycle of inter-plate geodynamic evolution (divergence-convergence-isostatic adjustment of the plates), and the South Cuban basin formed during the phase of convergence and isostatic adjustment of the plates. The hydrocarbon deposits discovered in the North Cuban basin are marked by their exceptional variety, and include deposits of light and heavy oils, and even asphalt. The geological conditions of their occurrence are also varied. In this paper the authorsmore » present the results of a study of the oils and a discussion of their association with the source beds. For Cuba the solution of these problems is of special importance owing to the complexity of its geological structure and, in particular, the presence of oil deposits of varied composition in the overthrust complexes of the eugeosynclinal and miogeosynclinal allochthon and para-autochthon, as well as in the sediments of the autochthonous complex. 4 references.« less

"Long, Boring, and Tedious": Youths' Experiences with Complex, Religious Texts

ERIC Educational Resources Information Center

Rackley, Eric D.; Kwok, Michelle

2016-01-01

Growing out of the renewed attention to text complexity in the United States and the large population of youth who are deeply committed to reading scripture, this study explores 16 Latter-day Saint and Methodist youths' experiences with complex, religious texts. The study took place in the Midwestern United States. Data consisted of an academic…

Evaluating fuel complexes for fire hazard mitigation planning in the southeastern United States

Treesearch

Anne G. Andreu; Dan Shea; Bernard R. Parresol; Roger D. Ottmar

2012-01-01

Fire hazard mitigation planning requires an accurate accounting of fuel complexes to predict potential fire behavior and effects of treatment alternatives. In the southeastern United States, rapid vegetation growth coupled with complex land use history and forest management options requires a dynamic approach to fuel characterization. In this study we assessed...

Current correlations for the transport of interacting electrons through parallel quantum dots in a photon cavity

NASA Astrophysics Data System (ADS)

Gudmundsson, Vidar; Abdullah, Nzar Rauf; Sitek, Anna; Goan, Hsi-Sheng; Tang, Chi-Shung; Manolescu, Andrei

2018-06-01

We calculate the current correlations for the steady-state electron transport through multi-level parallel quantum dots embedded in a short quantum wire, that is placed in a non-perfect photon cavity. We account for the electron-electron Coulomb interaction, and the para- and diamagnetic electron-photon interactions with a stepwise scheme of configuration interactions and truncation of the many-body Fock spaces. In the spectral density of the temporal current-current correlations we identify all the transitions, radiative and non-radiative, active in the system in order to maintain the steady state. We observe strong signs of two types of Rabi oscillations.

Resonances at very low temperature for the reaction D2 + H

NASA Astrophysics Data System (ADS)

Simbotin, I.; Côté, R.

2017-05-01

We present numerical results for rate coefficients of reaction and vibrational quenching in the collision of H with {{{D}}}2(v,j) at cold and ultracold temperatures. We explore both ortho-D{}2(j=0) and para-D{}2(j=1) for several initial vibrational states (v≤slant 5), and find resonant structures in the energy range 0.01-10 K, which are sensitive to the initial rovibrational state (v, j). We compare the reaction rates for D2 + H with our previously obtained results for the isotopologue reaction H2 + D, and discuss the implications of our detailed study of this benchmark system for ultracold chemistry.

Photochemistry of copper(II) complexes with macrocyclic amine ligands

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

Muralidharan, S.; Ferraudi, G.

1981-07-01

The photochemical properties of Cu(dl-Me/sub 6/(14)aneN/sub 4/)/sup 2 +/ and Cu(rac-Me/sub 6/(14)aneN/sub 4/)/sup 2 +/ in the presence and absence of axially coordinated ligands have been investigated by continuous and flash irradiations. Flash photolysis of the complexes in deaerated aqueous solutions revealed the presence of copper-ligand radical complexes with closed- and open-cycle ligands. Flash photolysis of methanolic solutions of the complexes, in the presence of halides and pseudohalides, shows Cu(III) macrocyclic intermediates. The experimental observations can be explained in terms of two primary photoprocesses with origins in distinctive charge transfer to metal states. These states have been assigned as aminomore » to copper(II) charge-transfer state and acido to copper(II) charge-transfer state.« less