Stark widths and shifts for spectral lines of Sn IV

NASA Astrophysics Data System (ADS)

de Andrés-García, I.; Alonso-Medina, A.; Colón, C.

2016-01-01

In this paper, we present theoretical Stark widths and shifts calculated corresponding to 66 spectral lines of Sn IV. We use the Griem semi-empirical approach and the COWAN computer code. For the intermediate coupling calculations, the standard method of least-squares fitting from experimental energy levels was used. Data are presented for an electron density of 1017 cm-3 and temperatures T = 1.1-5.0 (104 K). The matrix elements used in these calculations have been determined from 34 configurations of Sn IV: 4d10ns(n = 5-10), 4d10nd(n = 5-8), 4d95s2, 4d95p2, 4d95s5d, 4d85s5p2 and 4d105g for even parity and 4d10np(n = 5-8), 4d10nf (n = 4-6), 4d95snp(n = 5-8), 4d85s25p and 4d95snf (n = 4-10) for odd parity. Also, in order to test the matrix elements used in our calculations, we present calculated values of radiative lifetimes of 14 levels of Sn IV. There is good agreement between our calculations and the experimental radiative lifetimes obtained from the bibliography. The spectral lines of Sn IV are observed in UV spectra of HD 149499 B obtained with the Far Ultraviolet Spectroscopic Explorer, the Goddard High Resolution Spectrograph and the International Ultraviolet Explorer. Theoretical trends of the Stark broadening parameter versus the temperature for relevant lines are presented. Also our values of Stark broadening parameters have been compared with the data available in the bibliography.

Synthesis, characterization, computational studies and biological evaluation of S-benzyl-β-N-[3-(4-hydroxy-3-methoxy-phenylallylidene)]dithiocarbazate

NASA Astrophysics Data System (ADS)

Bhat, Rayees A.; Kumar, D.; Malla, Manzoor A.; Bhat, Sami U.; Khan, Md Shahzad; Manzoor, Ovais; Srivastava, Anurag; Naikoo, Rawoof A.; Mohsin, Mohd; Mir, Muzzaffar A.

2018-03-01

S-Benzyl-β-N-[3-(4-hydroxy-3-methoxy-phenylallylidene)]dithiocarbazate (HL1), Schiff base of S-benzyl dithiocarbazate, was synthesized by 1:1 condensation between S-benzyl dithiocarbazate and 4-hydroxy-3-methoxy cinnamaldehyde. The nitrogen-sulfur Schiff base (HL1) was characterized by Mass, FT-IR, H1-NMR, Raman, and UV-VIS spectroscopic techniques. Theoretical quantum chemical calculations were performed using DFT in combination with B3LYP exchange correlation functional and 6-311++ G (d, p) basis sets level. The calculated values of chemical potential (μ), HOMO-LUMO energy gap, chemical hardness, softness (S), ionization energy (IE), electron affinity (EA), dipole moment (D) and relative stabilization energy of the compound were 0.14881 eV, 0.12542 eV, 0.06271 eV, 3.37299 eV, -0.21152 eV, -0.08610 eV, 4.4090 Debye and -1753.350 eV respectively. Theoretically calculated parameters like H1-NMR, FT-IR, UV-VIS, Raman, electrostatic potential and HOMO-LUMO energy gap are in good agreement with experimental results. Also, in-vitro cytotoxicity studies were done against two habitually infection causing bacteria strains including gram-positive (S. aureus) and gram-negative (E. coli) for antibacterial activity. The results showed appreciable biological activity and the activity increased with increase in dose.

Feeding frequency, but not dietary water content, affects voluntary physical activity in young lean adult female cats.

PubMed

de Godoy, M R C; Ochi, K; de Oliveira Mateus, L F; de Justino, A C C; Swanson, K S

2015-05-01

The objective of this study was to investigate whether increased dietary water content and feeding frequency increased voluntary physical activity of young, lean adult female cats. A replicated 4 × 4 Latin square design with a 2 × 2 factorial treatment arrangement (feeding frequency and water content) was used. The 4 treatments consisted of 1 meal daily dry pet food without added water (1D; 12% moisture as is), 1 meal daily dry pet food with added water (1W; 70% total water content), 4 meals daily dry pet food without added water (4D; 12% moisture as is), and 4 meals daily dry pet food with added water (4W; 70% total water content). Eight healthy adult, lean, intact, young, female domestic shorthair cats were used in this experiment. Voluntary physical activity was evaluated using Actical activity monitors placed on collars and worn around the cats' necks for the last 7 d of each experimental period of 14 d. Food anticipatory activity (FAA) was calculated based on 2 h prior to feeding periods and expressed as a percentage of total daily voluntary physical activity. Increased feeding frequency (4 vs. 1 meal daily) resulted in greater average daily activity (P = 0.0147), activity during the light period (P = 0.0023), and light:dark activity ratio (P = 0.0002). In contrast, physical activity during the dark period was not altered by feeding frequency (P > 0.05). Cats fed 4 meals daily had increased afternoon FAA (P= 0.0029) compared with cats fed once daily. Dietary water content did not affect any measure of voluntary physical activity. Increased feeding frequency is an effective strategy to increase the voluntary physical activity of cats. Thus, it may assist in the prevention and management of obesity.

Synthesis, structural characterization, antimicrobial activities and theoretical investigations of some 4-(4-aminophenylsulfonyl) phenylimino) methyl)-4-(aryldiazenyl) phenol

NASA Astrophysics Data System (ADS)

Ghasemian, Motaleb; Kakanejadifard, Ali; Karami, Tahereh

2016-11-01

The azo-azomethine dyes with a different substitution have been designed from the reaction of 4,4‧-diaminodiphenyl sulfone with 2-hydroxy-5-(aryldiazenyl)benzaldehyde. The compounds have been characterized by elemental analysis, Mass, IR, UV-Vis, TGA-DTA and NMR spectroscopy. The solvatochromism behaviors, effects of substitution and pH on the electronic absorption spectra of dyes were evaluated. The in vitro antimicrobial activities were also screened for their potential for antibiotic activities by broth micro dilution method. Also, the optimum molecular geometries, molecular electrostatic potential (MEP), nucleus-independent chemical shift (NICS) and frontier molecular orbitals (FMO), vibrational spectra (IR) and electronic absorption (UV-Vis) spectra of the title compounds have been investigated with the help of DFT and TDDFT methods with 6-311 ++G(d,p) basis sets and PCM calculations. The results of the calculations show excellent agreement with the experimental value.

Aerodynamic Heating Computations for Projectiles. Volume 2. Swept Wing Calculations Using the Planar Version of the ABRES Shape Change Code (PLNRASCC)

DTIC Science & Technology

1984-06-01

Mt n o ro " g < - OD-O)C 0N v : _grI40N40 O I0 eeg gr, Wn *, c.M b-C N Z ý VN dN N C4 C4 C4 e"Ř!02AWVý 00 0 P- 1( or . . . . . . . . . i...the ABRES Shape Change Code (ASCC)," Acurex Report TM -80-31/AS, July 1980. 3. M. J. Abbett, "Finite Difference Solution of the Subsonic/Supersonic...Development Command US Army AMCCOM Technical Support Activity ATTN: DRSMC- TDC (D) ATTN: DELSD-L DRSMC-TSS (D) Fort Monmouth, NJ 07703 DRSMC-LCA-F (D) Mr. 0

Correlation between oxygen adsorption energy and electronic structure of transition metal macrocyclic complexes.

PubMed

Liu, Kexi; Lei, Yinkai; Wang, Guofeng

2013-11-28

Oxygen adsorption energy is directly relevant to the catalytic activity of electrocatalysts for oxygen reduction reaction (ORR). In this study, we established the correlation between the O2 adsorption energy and the electronic structure of transition metal macrocyclic complexes which exhibit activity for ORR. To this end, we have predicted the molecular and electronic structures of a series of transition metal macrocyclic complexes with planar N4 chelation, as well as the molecular and electronic structures for the O2 adsorption on these macrocyclic molecules, using the density functional theory calculation method. We found that the calculated adsorption energy of O2 on the transition metal macrocyclic complexes was linearly related to the average position (relative to the lowest unoccupied molecular orbital of the macrocyclic complexes) of the non-bonding d orbitals (d(z(2)), d(xy), d(xz), and d(yz)) which belong to the central transition metal atom. Importantly, our results suggest that varying the energy level of the non-bonding d orbitals through changing the central transition metal atom and/or peripheral ligand groups could be an effective way to tuning their O2 adsorption energy for enhancing the ORR activity of transition metal macrocyclic complex catalysts.

TU-F-17A-08: The Relative Accuracy of 4D Dose Accumulation for Lung Radiotherapy Using Rigid Dose Projection Versus Dose Recalculation On Every Breathing Phase

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

Lamb, J; Lee, C; Tee, S

2014-06-15

Purpose: To investigate the accuracy of 4D dose accumulation using projection of dose calculated on the end-exhalation, mid-ventilation, or average intensity breathing phase CT scan, versus dose accumulation performed using full Monte Carlo dose recalculation on every breathing phase. Methods: Radiotherapy plans were analyzed for 10 patients with stage I-II lung cancer planned using 4D-CT. SBRT plans were optimized using the dose calculated by a commercially-available Monte Carlo algorithm on the end-exhalation 4D-CT phase. 4D dose accumulations using deformable registration were performed with a commercially available tool that projected the planned dose onto every breathing phase without recalculation, as wellmore » as with a Monte Carlo recalculation of the dose on all breathing phases. The 3D planned dose (3D-EX), the 3D dose calculated on the average intensity image (3D-AVE), and the 4D accumulations of the dose calculated on the end-exhalation phase CT (4D-PR-EX), the mid-ventilation phase CT (4D-PR-MID), and the average intensity image (4D-PR-AVE), respectively, were compared against the accumulation of the Monte Carlo dose recalculated on every phase. Plan evaluation metrics relating to target volumes and critical structures relevant for lung SBRT were analyzed. Results: Plan evaluation metrics tabulated using 4D-PR-EX, 4D-PR-MID, and 4D-PR-AVE differed from those tabulated using Monte Carlo recalculation on every phase by an average of 0.14±0.70 Gy, - 0.11±0.51 Gy, and 0.00±0.62 Gy, respectively. Deviations of between 8 and 13 Gy were observed between the 4D-MC calculations and both 3D methods for the proximal bronchial trees of 3 patients. Conclusions: 4D dose accumulation using projection without re-calculation may be sufficiently accurate compared to 4D dose accumulated from Monte Carlo recalculation on every phase, depending on institutional protocols. Use of 4D dose accumulation should be considered when evaluating normal tissue complication probabilities as well as in clinical situations where target volumes are directly inferior to mobile critical structures.« less

Cytotoxic activity of erypogein d from erythrina poeppigiana (leguminosae) against cervical cancer (HeLa), breast cancer (MCF-7) and ovarian cancer (SKOV-3) cells

NASA Astrophysics Data System (ADS)

Herlina, T.; Gaffar, S.; Widowati, W.

2018-05-01

Cancer is the uncontrolled growth of abnormal cells and continues to divide rapidly in the body. Current anticancer treatment usually causes many side effects. Natural products are then explored to be new alternatives for cancer treatment. Flavonoids have been known to possess medicinal properties, including anticancer. This study was performed to observe the cytotoxic activity of isoflavanone compound, erypogein D from Erythrina poeppigiana, toward cervical cancer (HeLa), breast cancer (MCF-7) and ovarian cancer (SKOV-3) cells. The cytotoxic activity of erypogein D was tested using MTS (3-(4,5-dimethylthiazol-2-yl)-5-(3- carboxyme-thoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium) assay. The percentage of cell mortality was calculated and the IC50 was analyzed using probit analysis. The result showed that cytotoxic activity of the erypogein D against HeLa, SKOV-3, and MCF-7 cells had an IC50 value 225, 70.74, and 30.12 μM, respectively. Based on IC50 value can be concluded that erypogein D is the most cytotoxic to breast cancer MCF-7 cell. However the cytotoxic activity of erypogein D toward MCF7 is moderate.

Increasing dietary EPA and DHA influence estimated fatty acid desaturase activity in systemic organs which is reflected in the red blood cell in mice.

PubMed

Davidson, Emily A; Pickens, C Austin; Fenton, Jenifer I

2018-03-01

Delta-5 (D5D) and delta-6 (D6D) desaturase are key enzymes in fatty acid (FA) metabolism. Dietary eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) may alter tissue FA composition via D5D and D6D. The purpose was to determine the relationship between dietary EPA + DHA, estimated desaturase activities of various tissues and the reflection of desaturase activity in the red blood cell (RBC). Mice were fed diets with increasing percent of energy from EPA + DHA. Phospholipid FA composition of heart, muscle, spleen, lung, adipose tissues and RBC were analysed. D5D and D6D enzyme activity estimates (EAE) were calculated as the ratio of 20:4/20:3 and 20:3/18:2, respectively. D5D EAE decreased in all tissues, except muscle, with increasing dietary EPA + DHA. RBC D5D EAE positively correlated with D5D EAE in all tissues. RBC D6D EAE positively correlated with muscle and inversely correlated with adipose D6D EAE. Our findings suggest differential influence of dietary EPA + DHA upon tissue desaturase activities.

Kinetics and Mechanism of the Oxidation of Cyclic Methylsiloxanes by Hydroxyl Radical in the Gas Phase: An Experimental and Theoretical Study.

PubMed

Xiao, Ruiyang; Zammit, Ian; Wei, Zongsu; Hu, Wei-Ping; MacLeod, Matthew; Spinney, Richard

2015-11-17

The ubiquitous presence of cyclic volatile methylsiloxanes (cVMS) in the global atmosphere has recently raised environmental concern. In order to assess the persistence and long-range transport potential of cVMS, their second-order rate constants (k) for reactions with hydroxyl radical ((•)OH) in the gas phase are needed. We experimentally and theoretically investigated the kinetics and mechanism of (•)OH oxidation of a series of cVMS, hexamethylcyclotrisiloxane (D3), octamethycyclotetrasiloxane (D4), and decamethycyclopentasiloxane (D5). Experimentally, we measured k values for D3, D4, and D5 with (•)OH in a gas-phase reaction chamber. The Arrhenius activation energies for these reactions in the temperature range from 313 to 353 K were small (-2.92 to 0.79 kcal·mol(-1)), indicating a weak temperature dependence. We also calculated the thermodynamic and kinetic behaviors for reactions at the M06-2X/6-311++G**//M06-2X/6-31+G** level of theory over a wider temperature range of 238-358 K that encompasses temperatures in the troposphere. The calculated Arrhenius activation energies range from -2.71 to -1.64 kcal·mol(-1), also exhibiting weak temperature dependence. The measured k values were approximately an order of magnitude higher than the theoretical values but have the same trend with increasing size of the siloxane ring. The calculated energy barriers for H-atom abstraction at different positions were similar, which provides theoretical support for extrapolating k for other cyclic siloxanes from the number of abstractable hydrogens.

Elevation of D4 dopamine receptor mRNA in postmortem schizophrenic brain.

PubMed

Stefanis, N C; Bresnick, J N; Kerwin, R W; Schofield, W N; McAllister, G

1998-01-01

The D4 dopamine (DA) receptor has been proposed to be a target for the development of a novel antipsychotic drug based on its pharmacological and distribution profile. There is much interest in whether D4 DA receptor levels are altered in schizophrenia, but the lack of an available receptor subtype-specific radioligand made this difficult to quantitate. In this study, we examined whether D4 mRNA levels are altered in different brain regions of schizophrenics compared to controls. Ribonuclease protection assays were carried out on total RNA samples isolated postmortem from frontal cortex and caudate brain regions of schizophrenics and matched controls. 32P-labelled RNA probes to the D4 DA receptor and to the housekeeping gene, glyceraldehyde-3-phosphate dehydrogenase (G3PDH), were hybridised with the RNA samples, digested with ribonucleases to remove unhybridised probe, and separated on 6% sequencing gels. Densitometer analysis on the subsequent autoradiogams was used to calculate the relative optical density of D4 mRNA compared to G3PDH mRNA. Statistical analysis of the data revealed a 3-fold higher level (P<0.011) of D4 mRNA in the frontal cortex of schizophrenics compared to controls. No increase was seen in caudate. D4 receptors could play a role in mediating dopaminergic activity in frontal cortex, an activity which may be malfunctioning in schizophrenia.

Chemistry and Selective Tumor Cell Growth Inhibitory Activity of Polyketides from the South China Sea Sponge Plakortis sp.

PubMed

Li, Jiao; Li, Cui; Riccio, Raffaele; Lauro, Gianluigi; Bifulco, Giuseppe; Li, Tie-Jun; Tang, Hua; Zhuang, Chun-Lin; Ma, Hao; Sun, Peng; Zhang, Wen

2017-05-03

Simplextone E ( 1 ), a new metabolite of polyketide origin, was isolated with eight known analogues ( 2 - 9 ) from the South China Sea sponge Plakortis sp. The relative configuration of the new compound was elucidated by a detailed analysis of the spectroscopic data and quantum mechanical calculation of NMR chemical shifts, aided by the newly reported DP4+ approach. Its absolute configuration was determined by the TDDFT/ECD calculation. Simplextone E ( 1 ) is proven to be one of the isomers of simplextone D. The absolute configuration at C-8 in alkyl chain of plakortone Q ( 2 ) was also assigned based on the NMR calculation. In the preliminary in vitro bioassay, compounds 6 and 7 showed a selective growth inhibitory activity against HCT-116 human colon cancer cells with IC 50 values of 8.3 ± 2.4 and 8.4 ± 2.3 μM, corresponding to that of the positive control, adriamycin (IC 50 4.1 μM). The two compounds also showed selective activities towards MCF-7 human breast cancer and K562 human erythroleukemia cells while compound 3 only displayed weak activity against K562 cells.

Experimental and theoretical studies on vibrational spectra of 4-(2-furanylmethyleneamino)antipyrine, 4-benzylideneaminoantipyrine and 4-cinnamilideneaminoantipyrine

NASA Astrophysics Data System (ADS)

Sun, Yu-Xi; Hao, Qing-Li; Yu, Zong-Xue; Jiang, Wen-Jun; Lu, Lu-De; Wang, Xin

2009-09-01

This work deals with the IR and Raman spectroscopy of 4-(2-furanylmethyleneamino) antipyrine (FAP), 4-benzylideneaminoantipyrine (BAP) and 4-cinnamilideneaminoantipyrine (CAP) by means of experimental and quantum chemical calculations. The equilibrium geometries, harmonic frequencies, infrared intensities and Raman scattering activities were calculated by density functional B3LYP method with the 6-31G(d) basis set. The comparisons between the calculated and experimental results covering molecular structures, assignments of fundamental vibrational modes and thermodynamic properties were investigated. The optimized molecular geometries have been compared with the experimental data obtained from XRD data, which indicates that the theoretical results agree well with the corresponding experimental values. For the three compounds, comparisons and assignments of the vibrational frequencies indicate that the calculated frequencies are close to the experimental data, and the IR spectra are comparable with some slight differences, whereas the Raman spectra are different clearly and the strongest Raman scattering actives are relative tightly to the molecular conjugative moieties linked through their Schiff base imines. The thermodynamic properties (heat capacities, entropies and enthalpy changes) and their correlations with temperatures were also obtained from the harmonic frequencies of the optimized strucutres.

Revisiting Geschwind's hypothesis on brain lateralisation: a functional MRI study of digit ratio (2D:4D) and sex interaction effects on spatial working memory.

PubMed

Kalmady, Sunil Vasu; Agarwal, Sri Mahavir; Shivakumar, Venkataram; Jose, Dania; Venkatasubramanian, Ganesan; Reddy, Y C Janardhan

2013-01-01

The Geschwind-Behan-Galaburda (GBG) hypothesis links cerebral lateralisation with prenatal testosterone exposure. Digit ratio measures in adults have been established as potential markers of foetal sex hormonal milieu. The aim of the study was to evaluate the sex-dependent interaction of digit ratio measures and cerebral lateralization as well as their neurohemodynamic correlates using functional MRI (fMRI). Digit ratio measures-ratio of index finger (2D) length to ring finger (4D) length (2D:4D) and difference between 2D:4D of two hands, i.e., right minus left (DR-L)-were calculated using high resolution digital images in 70 right-handed participants (42 men) based on reliable and valid method. fMRI was acquired during the performance of a spatial working memory task in a subset of 25 individuals (14 men), and analysed using Statistical Parametric Mapping 8 (SPM8) and the Laterality Index toolbox for SPM8. Men had significantly less bilateral 2D:4D than women. There was a significant negative correlation between right 2D:4D and 2-Back task accuracy (2BACC) in women. A significant sex-by-right 2D:4D interaction was observed in left parahippocampal gyrus activation. Additionally, sex-by-DR-L interaction was observed in left IPL activation. DR-L showed a significant positive correlation with the whole brain Laterality Index (LI), and LI, in turn, demonstrated a significant negative correlation with 2BACC. Our study observations suggest several novel sex-differential relationships between 2D:4D measures and fMRI activation during spatial working memory task performance. Given the pre-existing background data supporting digit ratio measures as putative indicator of prenatal sex hormonal milieu, our study findings add support to the Geschwind-Behan-Galaburda (GBG) hypothesis.

Comparative Study on Various Geometrical Core Design of 300 MWth Gas Cooled Fast Reactor with UN-PuN Fuel Longlife without Refuelling

NASA Astrophysics Data System (ADS)

Dewi Syarifah, Ratna; Su'ud, Zaki; Basar, Khairul; Irwanto, Dwi

2017-07-01

Nuclear power has progressive improvement in the operating performance of exiting reactors and ensuring economic competitiveness of nuclear electricity around the world. The GFR use gas coolant and fast neutron spectrum. This research use helium coolant which has low neutron moderation, chemical inert and single phase. Comparative study on various geometrical core design for modular GFR with UN-PuN fuel long life without refuelling has been done. The calculation use SRAC2006 code both PIJ calculation and CITATION calculation. The data libraries use JENDL 4.0. The variation of fuel fraction is 40% until 65%. In this research, we varied the geometry of core reactor to find the optimum geometry design. The variation of the geometry design is balance cylinder; it means that the diameter active core (D) same with height active core (H). Second, pancake cylinder (D>H) and third, tall cylinder (D

Estimating the onset of cambial activity in Scots pine in northern Finland by means of the heat-sum approach.

PubMed

Seo, Jeong-Wook; Eckstein, Dieter; Jalkanen, Risto; Rickebusch, Sophie; Schmitt, Uwe

2008-01-01

We estimated the date of onset (Date(est)) of cambial activity by the pinning method in Scots pine (Pinus sylvestris L.) trees at Vanttauskoski (Site 1) and Laanila (Site 2) near the latitudinal limit of Scots pine in northern Finland. In each year and at each site, observations were made on a different set of five trees. The estimated dates of onset of cambial activity were compared with the corresponding heat sums, calculated in degree-days according to two models. Within years, Date(est) varied among trees by up to 15 days at Site 1 and up to 13 days at Site 2. Among years, mean Date(est) varied by 15.3 days at Site 1 and 12.0 days at Site 2. The overall mean Date(est) differed between sites by 6 days (June 5 at Site 1 and June 11 at Site 2). Among all trees in all years, the mean number of degree days (d.d.) calculated from mean daily temperature above a threshold of 5 degrees C before Date(est) ranged from 68.7 to 135 d.d. at Site 1 and from 37.4 to 154.7 d.d. at Site 2. Among years, the mean heat sum before Date(est )ranged from 94 to 112.5 d.d. at Site 1 and from 61.4 to 136 d.d. at Site 2. Variation among years in heat sum before Date(est) at Site 2 was highly significant, indicating that one or more factors other than, or in addition to, heat sum determines the onset of cambial activity in Scots pine. Similar results were obtained when heat sum was computed from the area between the sine wave generated by daily maximum and minimum temperature and the threshold temperature.

The new Schiff base 4-[(4-Hydroxy-3-fluoro-5-methoxy-benzylidene)amino]-1,5-dimethyl-2-phenyl-1,2-dihydro-pyrazol-3-one: Experimental, DFT calculational studies and in vitro antimicrobial activity

NASA Astrophysics Data System (ADS)

İskeleli, Nazan Ocak; Alpaslan, Yelda Bingöl; Direkel, Şahin; Ertürk, Aliye Gediz; Süleymanoğlu, Nevin; Ustabaş, Reşat

2015-03-01

The synthesized Schiff base, 4-[(4-Hydroxy-3-fluoro-5-methoxy-benzylidene)amino]-1,5-dimethyl-2-phenyl-1,2-dihydro-pyrazol-3-one (I), has been characterized by 13C NMR, 1H NMR, 2D NMR (1H-1H COSY and 13C APT), FT-IR, UV-vis and X-ray single-crystal techniques. Molecular geometry of the compound I in the ground state, vibrational frequencies and chemical shift values have been calculated by using the density functional method (DFT) with 6-311++G(d,p) basis set. The obtained results indicate that optimized geometry can well reflect the crystal structural parameters. The differences between experimental and calculated results of FT-IR and NMR have supported the existence of intermolecular (O-H⋯O type) and intramolecular (C-H⋯O type) hydrogen bonds in the crystal structure. Molecular electrostatic potential (MEP), frontier molecular orbital analysis (HOMO-LUMO) and electronic absorption spectra were carried out at B3LYP/6-311G++(d,p). HOMO-LUMO electronic transition of 3.92 eV is due to contribution of the bands the n → π∗. The antimicrobial activity of the compound I was determined against the selected 11 bacteria and 8 fungi by microdilution broth assay with Alamar Blue. In vitro studies showed that the compound I has no antifungal effect for selected fungal isolates. However, the compound I shows remarkable antibacterial effect for the bacteria; Streptococcus pneumoniae, Haemophilus influenzae and Enterococcus faecalis.

Theoretical Studies of Routes to Synthesis of Tetrahedral N4

NASA Technical Reports Server (NTRS)

Lee, Timothy J.; Dateo, Christopher E.

2007-01-01

A paper [Chem. Phys. Lett. 345, 295 (2001)] describes theoretical studies of excited electronic states of nitrogen molecules, with a view toward utilizing those states in synthesizing tetrahedral N4, or Td N4 a metastable substance under consideration as a high-energy-density rocket fuel. Several ab initio theoretical approaches were followed in these studies, including complete active space self-consistent field (CASSCF), state-averaged CASSCF (SA-CASSCF), singles configuration interaction (CIS), CIS with second-order and third-order correlation corrections [CIS(D) and CIS(3)], and linear response singles and doubles coupled-cluster (LRCCSD). Standard double zeta polarized and triple zeta double polarized one-particle basis sets were used. The CASSCF calculations overestimated the excitation energies, while SACASSCF calculations partly corrected these overestimates. The accuracy of the CIS calculations varied, depending on the particular state, while the CIS(D), CIS(3), and LRCCSD results were in generally good agreement. The energies of the lowest six excited singlet states of Td N4 as calculated by the LRCCSD were compared with the energies of possible excited states of N2 + N2 fragments, leading to the conclusion that the most likely route for synthesis of Td N4 would involve a combination of two bound quintet states of N2.

Molecular dynamic simulations of selective self-diffusion of CH4/CO2/H2O/N2 in coal

NASA Astrophysics Data System (ADS)

Song, Y.; Jiang, B.; Li, F. L.

2017-06-01

The self-diffusion coefficients (D) of CH4/CO2/H2O/N2 at a relatively broad range of temperatures(298.15∼ 458.15K)and pressures (1∼6MPa) under the NPT, NPH, NVE, and NVT ensembles were obtained after the calculations of molecular mechanics(MM), annealing kinetics(AK), giant canonical Monte Carlo(GCMC), and molecular dynamics (MD) based on Wiser bituminous coal model (WM). The Ds of the adsorbates at the saturated adsorption configurations are D CH4418K. The average swelling ratios manifest as H2O (14.7∼35.18%)>CO2 (13.38∼32.25%)>CH4 (15.35∼23.71%)> N2 (11.47∼22.14%) (NPH, 1∼6MPa). There exits differences in D, swelling ratios and E among various ensembles, indicating that the selection of ensembles has an important influence on the MD calculations for self-diffusion coefficients.

Biological Insights of the Dopaminergic Stabilizer ACR16 at the Binding Pocket of Dopamine D2 Receptor.

PubMed

Ekhteiari Salmas, Ramin; Seeman, Philip; Aksoydan, Busecan; Stein, Matthias; Yurtsever, Mine; Durdagi, Serdar

2017-04-19

The dopamine D2 receptor (D2R) plays an important part in the human central nervous system and it is considered to be a focal target of antipsychotic agents. It is structurally modeled in active and inactive states, in which homodimerization reaction of the D2R monomers is also applied. The ASP2314 (also known as ACR16) ligand, a D2R stabilizer, is used in tests to evaluate how dimerization and conformational changes may alter the ligand binding space and to provide information on alterations in inhibitory mechanisms upon activation. The administration of the D2R agonist ligand ACR16 [ 3 H](+)-4-propyl-3,4,4a,5,6,10b-hexahydro-2H-naphtho[1,2-b][1,4]oxazin-9-ol ((+)PHNO) revealed K i values of 32 nM for the D2 high R and 52 μM for the D2 low R. The calculated binding affinities of ACR16 with post processing molecular dynamics (MD) simulations analyses using MM/PBSA for the monomeric and homodimeric forms of the D2 high R were -9.46 and -8.39 kcal/mol, respectively. The data suggests that the dimerization of the D2R leads negative cooperativity for ACR16 binding. The dimerization reaction of the D2 high R is energetically favorable by -22.95 kcal/mol. The dimerization reaction structurally and thermodynamically stabilizes the D2 high R conformation, which may be due to the intermolecular forces formed between the TM4 of each monomer, and the result strongly demonstrates dimerization essential for activation of the D2R.

Active Oxygen Vacancy Site for Methanol Synthesis from CO2 Hydrogenation on In2O3(110): A DFT Study

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

Ye, Jingyun; Liu, Changjun; Mei, Donghai

2013-06-03

Methanol synthesis from CO2 hydrogenation on the defective In2O3(110) surface with surface oxygen vacancies has been investigated using periodic density functional theory calculations. The relative stabilities of six possible surface oxygen vacancies numbered from Ov1 to Ov6 on the perfect In2O3(110) surface were examined. The calculated oxygen vacancy formation energies show that the D1 surface with the Ov1 defective site is the most thermodynamically favorable while the D4 surface with the Ov4 defective site is the least stable. Two different methanol synthesis routes from CO2 hydrogenation over both D1 and D4 surfaces were studied and the D4 surface was foundmore » to be more favorable for CO2 activation and hydrogenation. On the D4 surface, one of the O atoms of the CO2 molecule fills in the Ov4 site upon adsorption. Hydrogenation of CO2 to HCOO on the D4 surface is both thermodynamically and kinetically favorable. Further hydrogenation of HCOO involves both forming the C-H bond and breaking the C-O bond, resulting in H2CO and hydroxyl. The HCOO hydrogenation is slightly endothermic with an activation barrier of 0.57 eV. A high barrier of 1.14 eV for the hydrogenation of H2CO to H3CO indicates that this step is the rate-limiting step in the methanol synthesis on the defective In2O3(110) surface. We gratefully acknowledge the supports from the National Natural Science Foundation of China (#20990223) and from US Department of Energy, Basic Energy Science program (DE-FG02-05ER46231). D. Mei was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. The computations were performed in part using the Molecular Science Computing Facility in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), which is a U.S. Department of Energy national scientific user facility located at Pacific Northwest National Laboratory in Richland, Washington. PNNL is a multiprogram national laboratory operated for DOE by Battelle.« less

Empirical molecular-dynamics study of diffusion in liquid semiconductors

NASA Astrophysics Data System (ADS)

Yu, W.; Wang, Z. Q.; Stroud, D.

1996-11-01

We report the results of an extensive molecular-dynamics study of diffusion in liquid Si and Ge (l-Si and l-Ge) and of impurities in l-Ge, using empirical Stillinger-Weber (SW) potentials with several choices of parameters. We use a numerical algorithm in which the three-body part of the SW potential is decomposed into products of two-body potentials, thereby permitting the study of large systems. One choice of SW parameters agrees very well with the observed l-Ge structure factors. The diffusion coefficients D(T) at melting are found to be approximately 6.4×10-5 cm2/s for l-Si, in good agreement with previous calculations, and about 4.2×10-5 and 4.6×10-5 cm2/s for two models of l-Ge. In all cases, D(T) can be fitted to an activated temperature dependence, with activation energies Ed of about 0.42 eV for l-Si, and 0.32 or 0.26 eV for two models of l-Ge, as calculated from either the Einstein relation or from a Green-Kubo-type integration of the velocity autocorrelation function. D(T) for Si impurities in l-Ge is found to be very similar to the self-diffusion coefficient of l-Ge. We briefly discuss possible reasons why the SW potentials give D(T)'s substantially lower than ab initio predictions.

Excitation functions for (d,x) reactions on (133)Cs up to Ed=40MeV.

PubMed

Tárkányi, F; Ditrói, F; Takács, S; Hermanne, A; Baba, M; Ignatyuk, A V

2016-04-01

In the frame of a systematic study of excitation functions of deuteron induced reactions the excitation functions of the (133)Cs(d,x)(133m,133mg,131mg)Ba,(134,)(132)Cs and (12)(9m)Xe nuclear reactions were measured up to 40MeV deuteron energies by using the stacked foil irradiation technique and γ-ray spectroscopy of activated samples. The results were compared with calculations performed with the theoretical nuclear reaction codes ALICE-IPPE-D, EMPIRE II-D and TALYS calculation listed in the TENDL-2014 library. A moderate agreement was obtained. Based on the integral yields deduced from our measured cross sections, production of (131)Cs via the (133)Cs(d,4n)(131)Ba→(131)Cs reaction and (133)Ba via (133)Cs(d,2n) reactions is discussed in comparison with other charged particle production routes. Copyright © 2016 Elsevier Ltd. All rights reserved.

DFT simulation, quantum chemical electronic structure, spectroscopic and structure-activity investigations of 4-acetylpyridine

NASA Astrophysics Data System (ADS)

Atilgan, A.; Yurdakul, Ş.; Erdogdu, Y.; Güllüoğlu, M. T.

2018-06-01

The spectroscopic (UV-Vis and infrared), structural and some electronic property observations of the 4-acetylpyridine (4-AP) were reported, which are investigated by using some spectral methods and DFT calculations. FT-IR spectra were obtained for 4-AP at room temperature in the region 4000 cm-1- 400 cm-1. In the DFT calculations, the B3LYP functional with 6-311G++G(d,p) basis set was applied to carry out the quantum mechanical calculations. The Fourier Transform Infrared (FT-IR) and FT-Raman spectra were interpreted by using of normal coordinate analysis based on scaled quantum mechanical force field. The present work expands our understanding of the both the vibrational and structural properties as well as some electronic properties of the 4-AP by means of the theoretical and experimental methods.

Conformation and tautomerism of methoxy-substituted 4-phenyl-4-thiazoline-2-thiones: a combined crystallographic and ab initio investigation.

PubMed

Balti, Monaem; Norberg, Bernadette; Efrit, Mohamed Lotfi; Lanners, Steve; Wouters, Johan

2016-05-01

4-Phenyl-4-thiazoline-2-thiol is an active pharmaceutical compound, one of whose activities is as a human indolenamine dioxygenase inhibitor. It has been shown recently that in both the solid state and the gas phase, the thiazolinethione tautomer should be preferred. As part of both research on this lead compound and a medicinal chemistry program, a series of substituted arylthiazolinethiones have been synthesized. The molecular conformations and tautomerism of 4-(2-methoxyphenyl)-4-thiazoline-2-thione and 4-(4-methoxyphenyl)-4-thiazoline-2-thione, both C10H9NOS2, are reported and compared with the geometry deduced from ab initio calculations [PBE/6-311G(d,p)]. Both the crystal structure analyses and the calculations establish the thione tautomer for the two substituted arylthiazolinethiones. In the crystal structure of the 2-methoxyphenyl regioisomer, the thiazolinethione unit was disordered over two conformations. Both isomers exhibit similar hydrogen-bond patterns [R2(2)(8) motif] and form dimers. The crystal packing is further reinforced by short S...S interactions in the 2-methoxyphenyl isomer. The conformations of the two regioisomers correspond to stable geometries calculated from an ab initio energy-relaxed scan.

Superactive amidated COOH-terminal glucagon analogues with no methionine or tryptophan.

PubMed

Murphy, W A; Coy, D H; Lance, V A

1986-01-01

The functions of the Trp-25 and Met-27 residues and the free carboxy terminus of glucagon have been debated for many years. Despite some semi-synthetic data to the contrary, comparison of the glucagon sequence with the other 5 members of this family of peptides, all of them amides and particularly growth hormone-releasing factor(1-29) amide and its recently described analogues, suggests that alterations to these positions should be quite well tolerated in terms of biological activity. To test this prediction, [Phe-25,Leu-27]-glucagon amide was synthesized in high yield and was found to actually have superior glycogenolytic activity (196%) to glucagon in the rat. Replacement of Gly-4 by D-Phe, which has been shown to give much enhanced glycogenolytic activity than glucagon itself, also increased the activity of [D-Phe-4,Phe-25,Leu-27]-glucagon amide (518%). The L-Phe-4-analogue, [Phe-4,25,Leu-27]-glucagon amide, in contrast, was 20 times less active (30%), strongly suggesting the presence of a beta-bend in this N-terminal region of glucagon. This was supported by Chou-Fasman structural predictions which indicate extensive folding in the 1-15 region. Indeed, additional conformational restriction by substitution of D-Ser in position 2 of glucagon also increased activity to 226%. [D-Gln-3]-glucagon was slightly less active (74%) than glucagon. Chou-Fasman calculations on glucagon were compared to similar treatments of the VIP, secretin, PHI, and GRF(1-29) sequences.

Synthesis, spectroscopic characterization, theoretical study and anti-hepatic cancer activity study of 4-(1E,3Z,6E)-3-hydroxy-7-(4-hydroxy-3-methoxyphenyl)-5-oxohepta-1,3,6-trien-1-yl)-2-methoxyphenyl 4-nitrobenzoate, a novel curcumin congener

NASA Astrophysics Data System (ADS)

Srivastava, Sangeeta; Gupta, Preeti; Singh, Ranvijay Pratap; Jafri, Asif; Arshad, M.; Banerjee, Monisha

2017-08-01

In the present work 4-(1E,3Z,6E)-3-hydroxy-7-(4-hydroxy-3-methoxyphenyl)-5-oxohepta-1,3,6-trien-1-yl)-2-methoxyphenyl 4-nitrobenzoate (2), a novel curcumin ester was synthesized. The molecular structure and spectroscopic analysis were performed using experimental techniques like FT-IR, 1H,13C NMR, mass and UV-visible as well as theoretical calculations. The theoretical calculations were done by DFT level of theory using B3LYP/6-31G (d,p) basis set. The vibrational wavenumbers were calculated using DFT method and assigned with the help of potential energy distribution (PED). The electronic properties such as frontier orbitals and band gap energies have been calculated using time dependent density functional theory (TD-DFT). The strength and nature of weak intramolecular interactions have been studied by AIM approach. Global and local reactivity descriptors have been computed to predict reactivity and reactive sites in the molecule. First hyperpolarizability values have been calculated to describe the nonlinear optical (NLO) property of the synthesized compounds. Molecular electrostatic potential (MEP) analysis has also been carried out. The anti-hepatic cancer activity of compound 2 was also carried out.

Excitation energies, oscillator strengths and lifetimes in Mg-like vanadium

NASA Astrophysics Data System (ADS)

Gupta, G. P.; Msezane, A. Z.

2013-08-01

Excitation energies from the ground state for 86 fine-structure levels as well as oscillator strengths and radiative decay rates for all fine-structure transitions among the levels of the terms (1s22s22p6)3s2(1S), 3s3p(1,3Po), 3s3d(1,3D), 3s4s(1,3S), 3s4p(1,3Po), 3s4d(1,3D), 3s4f(1,3Fo), 3p2(1S, 3P, 1D), 3p3d(1,3Po, 1,3Do, 1,3Fo), 3p4s(1,3Po), 3p4p(1,3S, 1,3P, 1,3D), 3p4d(1,3Po, 1,3Do, 1,3Fo), 3p4f(1,3D, 1,3F, 1,3G) and 3d2(1S, 3P, 1D,3F,1G) of V XII are calculated using extensive configuration-interaction wave functions obtained with the configuration-interaction version 3 computer code of Hibbert. The important relativistic effects in intermediate coupling are included through the Breit-Pauli approximation. In order to keep our calculated energy splittings as close as possible to the corresponding experimental values, we have made small adjustments to the diagonal elements of the Hamiltonian matrices. The mixing among several fine-structure levels is found to be very strong. Our fine-tuned excitation energies, including their ordering, are in excellent agreement (better than 0.25%) with the available experimental results. From our calculated radiative decay rates, we have also calculated the radiative lifetimes of fine-structure levels. Generally, our calculated data for the excitation energies and radiative decay rates are found to agree reasonably well with other available calculations. However, significant differences between our calculated lifetimes and those from the calculation of Froese Fischer et al (2006 At. Data Nucl. Data Tables 92 607) for a few fine-structure levels, mainly those belonging to the 3p4d configuration, are noted and discussed. Also, our calculated lifetime for the longer-lived level 3s3p(3P1) is found to be in excellent agreement with the corresponding value of Curtis (1991 Phys. Scr. 43 137). ) for all 1108 transitions in V XII are available with the first author ().

[Protective effects of five different types of Dendrobium on CCl4-induced liver injury in mice].

PubMed

Wang, Kai; Sui, Dan-Juan; Wang, Chang-Suo; Yang, Li; Ouyang, Zhen; Chen, Nai-Fu; Han, Bang-Xing; Wei, Yuan

2017-05-01

This study aims to investigate the protective effect of Dendrobium huoshanense, D.officinale(Huoshan), D.officinale(Yunnan), D.moniliforme and D. henanense on CCl4-induced hepatic damage in mice. C57BL/6 mice were randomly divided into control group, model group, high-dose(7.5 g•kg⁻¹) and low-dose (1.25 g•kg⁻¹) groups of the five Dendrobium. Each group was intragastrically administered with drugs for 2 weeks. The control group was intraperitoneally injected with Olive oil solution, while the other groups were intraperitoneally given 0.5%CCl4combined with Olive oil solution 2 h later after the last administration. Subsequently, ALT and AST activities in serum, SOD activities and MDA contents in liver tissues were determined in all groups 16 h later after administration. The liver index was calculated, and hepatic histopathological examination was performed. The mRNA expressions of IL-1β, IL-6 and TNF-α were analyzed by Real-time PCR. Compared with the CCl4 model group, the activities of ALT and AST in serum decreased significantly in the five different Dendrobium groups. Meanwhile, in liver tissues, the levels of MDA reduced obviously, while the SOD activities markedly increased. Furthermore, liver tissue damage induced by CCl4 was ameliorated according to the histopathological examination. IL-1β, IL-6 and TNF-α mRNA expressions in D.huoshanense-treated liver tissues were significantly decreased. In conclusion, the five different Dendrobium groups showed hepatoprotective effects on CCl4-induced acute liver injury in mice. However, there were differences among Dendrobium of different types and origins. The protect effect of D.huoshanense is the most obvious, and the order of the protective effect of the other Dendrobium from high to low is D.officinale(Yunnan), D. officinale(Huoshan), D.henanense and D.moniliforme. The differences between the different types of Dendrobium might be related to their chemical components. Copyright© by the Chinese Pharmaceutical Association.

A single membrane-bound enzyme catalyzes the conversion of 2,5-diketo-d-gluconate to 4-keto-d-arabonate in d-glucose oxidative fermentation by Gluconobacter oxydans NBRC 3292.

PubMed

Tazoe, Masaaki; Oishi, Hiromi; Kobayashi, Setsuko; Hoshino, Tatsuo

2016-08-01

4-Keto-d-arabonate synthase (4KAS), which converts 2,5-diketo-d-gluconate (DKGA) to 4-keto-d-arabonate (4KA) in d-glucose oxidative fermentation by some acetic acid bacteria, was solubilized from the Gluconobacter oxydans NBRC 3292 cytoplasmic membrane, and purified in an electrophoretically homogenous state. A single membrane-bound enzyme was found to catalyze the conversion from DKGA to 4KA. The 92-kDa 4KAS was a homodimeric protein not requiring O2 or a cofactor for the conversion, but was stimulated by Mn(2+). N-terminal amino acid sequencing of 4KAS, followed by gene homology search indicated a 1,197-bp open reading frame (ORF), corresponding to the GLS_c04240 locus, GenBank accession No. CP004373, encoding a 398-amino acid protein with a calculated molecular weight of 42,818 Da. An Escherichia coli transformant with the 4kas plasmid exhibited 4KAS activity. Furthermore, overexpressed recombinant 4KAS was purified in an electrophoretically homogenous state and had the same molecular size as the natural enzyme.

WE-D-BRA-03: Four-Dimensional Dose Reconstruction Through Retrospective Phase Determination Using Cine Images of Electronic Portal Imaging Device

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

Yoon, J; Jung, J; Yi, B

2015-06-15

Purpose: To test a method to reconstruct a four-dimensional (4D) dose distribution using the correlation of pre-calculated 4D electronic portal imaging device (EPID) images and measured cine-EPID images. Methods: 1. A phantom designed to simulate a tumor in lung (a polystyrene block with 3.0 cm diameter embedded in cork) was placed on a sinusoidally moving platform with 2 cm amplitude and 4 sec/cycle. Ten-phase 4D CT images were acquired for treatment planning and dose reconstruction. A 6MV photon beam was irradiated on the phantom with static (field size=5×8.5 cm{sup 2}) and dynamic fields (sliding windows, 10×10 cm{sup 2}, X1 MLCmore » closing in parallel with the tumor movement). 2. 4D and 3D doses were calculated forwardly on PTV (1 cm margin). 3. Dose images on EPID under the fields were calculated for 10 phases. 4. Cine EPID images were acquired during irradiation. 5. Their acquisition times were correlated to the phases of the phantom at which irradiation occurred by inter-comparing calculated “reference” EPID images with measured images (2D gamma comparison). For the dynamic beam, the tumor was hidden under MLCs during a portion of irradiation time; the correlation performed when the tumor was visible was extrapolated. 6. Dose for each phase was reconstructed on the 4D CT images and summed over all phases. The summation was compared with forwardly calculated 4D and 3D dose distributions. Monte Carlo methods were used for all calculations. Results: For the open and dynamic beams, the 4D reconstructed doses showed the pass rates of 92.7 % and 100 %, respectively, at the isocenter plane given 3% / 3 mm criteria. The better agreement of the dynamic beam was from its dose gradient which blurred the otherwise sharp difference between forward and reconstructed doses. This also contributed slightly better agreement in DVH of PTV. Conclusion: The feasibility of 4D reconstruction was demonstrated.« less

Molecular structure, vibrational spectroscopic (FT-IR, FT-Raman), UV-vis spectra, first order hyperpolarizability, NBO analysis, HOMO and LUMO analysis, thermodynamic properties of benzophenone 2,4-dicarboxylic acid by ab initio HF and density functional method

NASA Astrophysics Data System (ADS)

Chaitanya, K.

2012-02-01

The FT-IR (4000-450 cm -1) and FT-Raman spectra (3500-100 cm -1) of benzophenone 2,4-dicarboxylic acid (2,4-BDA) have been recorded in the condensed state. Density functional theory calculation with B3LYP/6-31G(d,p) basis set have been used to determine ground state molecular geometries (bond lengths and bond angles), harmonic vibrational frequencies, infrared intensities, Raman activities and bonding features of the title compounds. The assignments of the vibrational spectra have been carried out with the help of normal co-ordinate analysis (NCA) following the scaled quantum mechanical force field (SQMFF) methodology. The first order hyperpolarizability ( β0) and related properties ( β, α0 and Δ α) of 2,4-BDA is calculated using HF/6-31G(d,p) method on the finite-field approach. The stability of molecule has been analyzed by using NBO analysis. The calculated first hyperpolarizability shows that the molecule is an attractive molecule for future applications in non-linear optics. The calculated HOMO and LUMO energies show that charge transfer occurs within these molecules. Mulliken population analysis on atomic charges is also calculated. Because of vibrational analyses, the thermodynamic properties of the title compound at different temperatures have been calculated. Finally, the UV-vis spectra and electronic absorption properties were explained and illustrated from the frontier molecular orbitals.

Oxidation of CO on a carbon-based material composed of nickel hydroxide and hydroxyl graphene oxide, (Ni4(OH)3-hGO)--a first-principles calculation.

PubMed

Yeh, Chen-Hao; Ho, Jia-Jen

2015-03-21

Nickel or nickel hydroxide clusters and graphene oxide (GO) composites are novel nanomaterials in the application of electrochemical catalysts. In this work, we calculated the energy of Ni4 adsorbed onto saturated hydroxyl graphene oxide (hGO), which forms a Ni4(OH)3 cluster on the hydroxyl graphene oxide (Ni4(OH)3-hGO) and releases 4.47 eV (5.22 eV with DFT-D3 correction). We subsequently studied the oxidation of CO on the Ni4(OH)3-hGO system via three mechanisms - LH, ER and carbonated mechanisms. Our results show that the activation energy for oxidation of the first CO molecule according to the ER mechanism is 0.14 eV (0.12 eV with DFT-D3 correction), much smaller than that with LH (Ea = 0.65 eV, 0.61 eV with DFT-D3 correction) and with carbonated (Ea = 1.28 eV, 1.20 eV with DFT-D3 correction) mechanisms. The barrier to oxidation of the second CO molecule to CO2 with the ER mechanism increases to 0.43 eV (0.37 eV with DFT-D3 correction), but still less than that via LH (Ea = 1.09 eV, 1.07 eV with DFT-D3 correction), indicating that CO could be effectively oxidized through the ER mechanism on the Ni4(OH)3/hGO catalyst.

Ab initio identification of the Li-rich phase in LiFePO4.

PubMed

Zeng, Hua; Gu, Yue; Teng, Gaofeng; Liu, Yimeng; Zheng, Jiaxin; Pan, Feng

2018-06-27

A recent discovery of anionic redox activity in Li-rich layered compounds opens a new direction for the design of high-capacity cathode materials for lithium-ion batteries. Here using extensive ab initio calculations, the thermodynamic existence of the Li-rich phase in LiFePO4 to form Li1+xFe1-xPO4 with x not exceeding 12.5% has been proved. Anionic redox activity and structural stability during delithiation are further investigated. Interestingly, it is found that Li1+xFe1-xPO4 cannot be delithiated completely and thus cannot achieve extra capacity by anionic redox activity, because the local oxygen-ion redox will cause the fracture of the rigid framework formed by phosphate tetrahedral polyanions. Although an extra capacity cannot be realized, the excess Li-ions at Fe sites can enhance the Li-ion diffusivity along the adjacent [010] channel and contribute to the shift from 1D to 2D/3D diffusion. This study provides a fresh perspective on olivine-type LiFePO4 and offers some important clues on designing Li-rich cathode materials with high energy density.

Large scale CIV3 calculations of fine-structure energy levels, oscillator strengths, and lifetimes in Fe XIV and Ni XVI

NASA Astrophysics Data System (ADS)

Gupta, G. P.; Msezane, A. Z.

2005-01-01

We have performed large scale CIV3 calculations of excitation energies from ground states for 109 fine-structure levels as well as of oscillator strengths and radiative decay rates for all electric-dipole-allowed and intercombination transitions among the (1s 22s 22p 6)3s 23p( 2P 0), 3s3p 2( 2S, 2P, 2D, 4P), 3s 23d( 2D), 3p 3( 4S 0, 2P 0, 2D 0), 3s3p( 3P 0)3d( 2P 0, 2D 0, 2F 0, 4P 0, 4D 0, 4F 0), 3s3p( 1P 0)3d( 2P 0, 2D 0, 2F 0), 3p 2( 1S)3d( 2D), 3p 2( 1D)3d( 2S, 2P, 2D), 3p 2( 3P)3d( 2P, 2D, 4P), 3s3d 2( 2S, 2P, 2D, 4P), 3p3d 2( 1S)( 2P 0), 3p3d 2( 1D)( 2P 0, 2D 0, 2F 0), 3p3d 2( 1G)( 2F 0), 3p3d 2( 3P)( 2P 0, 2D 0, 4S 0, 4P 0, 4D 0), 3p3d 2( 3F)( 2D 0, 2F 0, 4D 0, 4F 0), 3s 24s( 2S), 3s 24p( 2P 0), 3s 24d( 2D), 3s 24f( 2F 0), 3s3p( 3P 0)4s( 2P 0, 4P 0), and 3s3p( 1P 0)4s( 2P 0) states of Fe XIV and Ni XVI. These states are represented by very extensive configuration-interaction (CI) wavefunctions obtained using the CIV3 computer code of Hibbert. The relativistic effects in intermediate coupling are incorporated by means of the Breit-Pauli Hamiltonian which consists of the nonrelativistic term plus the one-body mass correction, Darwin term, and spin-orbit, spin-other-orbit, and spin-spin operators. The errors which often occur with sophisticated ab initio atomic structure calculations are reduced. Our calculated excitation energies, including their ordering, are in excellent agreement with the available experimental results for both of the ions studied. From our transition probabilities, we have also calculated radiative lifetimes of the lowest 37 fine-structure levels in Fe XIV and Ni XVI and compared them with available theoretical and experimental results. The mixing among several fine-structure levels is found to be so strong that the correct identification of these levels becomes very difficult. We predict new data for several levels where no other theoretical and/or experimental results are available. We hope that our extensive calculations will be useful to experimentalists in identifying the fine-structure levels in their future work.

Neutron Deep Penetration Calculations in Light Water with Monte Carlo TRIPOLI-4® Variance Reduction Techniques

NASA Astrophysics Data System (ADS)

Lee, Yi-Kang

2017-09-01

Nuclear decommissioning takes place in several stages due to the radioactivity in the reactor structure materials. A good estimation of the neutron activation products distributed in the reactor structure materials impacts obviously on the decommissioning planning and the low-level radioactive waste management. Continuous energy Monte-Carlo radiation transport code TRIPOLI-4 has been applied on radiation protection and shielding analyses. To enhance the TRIPOLI-4 application in nuclear decommissioning activities, both experimental and computational benchmarks are being performed. To calculate the neutron activation of the shielding and structure materials of nuclear facilities, the knowledge of 3D neutron flux map and energy spectra must be first investigated. To perform this type of neutron deep penetration calculations with the Monte Carlo transport code, variance reduction techniques are necessary in order to reduce the uncertainty of the neutron activation estimation. In this study, variance reduction options of the TRIPOLI-4 code were used on the NAIADE 1 light water shielding benchmark. This benchmark document is available from the OECD/NEA SINBAD shielding benchmark database. From this benchmark database, a simplified NAIADE 1 water shielding model was first proposed in this work in order to make the code validation easier. Determination of the fission neutron transport was performed in light water for penetration up to 50 cm for fast neutrons and up to about 180 cm for thermal neutrons. Measurement and calculation results were benchmarked. Variance reduction options and their performance were discussed and compared.

Synthesis, spectroscopic characterization, DFT studies and antifungal activity of (E)-4-amino-5-[N'-(2-nitro-benzylidene)-hydrazino]-2,4-dihydro-[1,2,4]triazole-3-thione

NASA Astrophysics Data System (ADS)

Joshi, Rachana; Pandey, Nidhi; Yadav, Swatantra Kumar; Tilak, Ragini; Mishra, Hirdyesh; Pokharia, Sandeep

2018-07-01

The hydrazino Schiff base (E)-4-amino-5-[N'-(2-nitro-benzylidene)-hydrazino]-2,4-dihydro-[1,2,4]triazole-3-thione was synthesized and structurally characterized by elemental analysis, FT-IR, Raman, 1H and 13C-NMR and UV-Vis studies. A density functional theory (DFT) based electronic structure calculations were accomplished at B3LYP/6-311++G(d,p) level of theory. A comparative analysis of calculated vibrational frequencies with experimental vibrational frequencies was carried out and significant bands were assigned. The results indicate a good correlation (R2 = 0.9974) between experimental and theoretical IR frequencies. The experimental 1H and 13C-NMR resonance signals were also compared to the calculated values. The theoretical UV-Vis spectral studies were carried out using time dependent-DFT method in gas phase and IEFPCM model in solvent field calculation. The geometrical parameters were calculated in the gas phase. Atomic charges at selected atoms were calculated by Mulliken population analysis (MPA), Hirshfeld population analysis (HPA) and Natural population analysis (NPA) schemes. The molecular electrostatic potential (MEP) map was calculated to assign reactive site on the surface of the molecule. The conceptual-DFT based global and local reactivity descriptors were calculated to obtain an insight into the reactivity behaviour. The frontier molecular orbital analysis was carried out to study the charge transfer within the molecule. The detailed natural bond orbital (NBO) analysis was performed to obtain an insight into the intramolecular conjugative electronic interactions. The titled compound was screened for in vitro antifungal activity against four fungal strains and the results obtained are explained through in silico molecular docking studies.

Polarization Dependent Bulk-sensitive Valence Band Photoemission Spectroscopy and Density Functional Theory Calculations: Part I. 3d Transition Metals

NASA Astrophysics Data System (ADS)

Ueda, Shigenori; Hamada, Ikutaro

2017-12-01

The X-ray polarization dependent valence band HAXPES spectra of 3d transition metals (TMs) of Ti-Zn were measured to investigate the orbital resolved electronic structures by utilizing that the fact the photoionization cross-section of the atomic orbitals strongly depends on the experimental geometry. We have calculated the HAXPES spectra, which correspond to the cross-section weighted densities of states (CSW-DOSs), where the DOSs were obtained by the density functional theory calculations, and we have determined the relative photoionization cross-sections of the 4s and 4p orbitals to the 3d orbital in the 3d TMs. The experimentally obtained bulk-sensitive 3d and 4s DOSs were good agreement with the calculated DOSs in Ti, V, Cr, and Cu. In contrast, the deviations between the experimental and calculated 3d DOSs for Mn, Fe, Co, Ni were found, suggesting that the electron correlation plays an important role in the electronic structures for these materials.

Molecular structure, quantum mechanical calculation and radical scavenging activities of (E)-4,6-dibromo-2-[(3,5-dimethylphenylimino)methyl]-3-methoxyphenol and (E)-4,6-dibromo-2-[(2,6-dimethylphenylimino)methyl]-3-methoxyphenol compounds.

PubMed

Alaşalvar, Can; Soylu, Mustafa Serkan; Güder, Aytaç; Albayrak, Çiğdem; Apaydın, Gökhan; Dilek, Nefise

2014-09-15

In this study, (E)-4,6-dibromo-2-[(3,5-dimethylphenylimino)methyl]-3-methoxyphenol and (E)-4,6-dibromo-2-[(2,6-dimethylphenylimino)methyl]-3-methoxyphenol compounds have been synthesized and characterized by using X-ray crystallographic method, FT-IR and Density functional method. The molecular geometry, vibrational frequencies of the title compounds in the ground state have been calculated by using B3LYP with the 6-31G(d,p) basis set. The tautomeric form of the compounds has been demonstrated by using single crystal X-ray method, FT-IR spectrometer and DFT method. In addition, HOMO-LUMO energy gap, molecular electrostatic potential map and NBO analysis of the compounds are performed at B3LYP/6-31G(d,p) level. It may be remarked that the free radical scavenging activities of the title compounds were assessed using DPPH, DMPD+, and ABTS+ assays. The obtained results show that especially compound 2 has effective DPPH (SC50 1.52±0.14 μg/mL), DMPD+ (SC50 1.22±0.21 μg/mL), and ABTS+ (SC50 3.32±0.17 μg/mL) scavenging activities compared with standards (BHA, rutin, and trolox). Copyright © 2014 Elsevier B.V. All rights reserved.

Evidence for anionic redox activity in a tridimensional-ordered Li-rich positive electrode β-Li2IrO3.

PubMed

Pearce, Paul E; Perez, Arnaud J; Rousse, Gwenaelle; Saubanère, Mathieu; Batuk, Dmitry; Foix, Dominique; McCalla, Eric; Abakumov, Artem M; Van Tendeloo, Gustaaf; Doublet, Marie-Liesse; Tarascon, Jean-Marie

2017-05-01

Lithium-ion battery cathode materials have relied on cationic redox reactions until the recent discovery of anionic redox activity in Li-rich layered compounds which enables capacities as high as 300 mAh g -1 . In the quest for new high-capacity electrodes with anionic redox, a still unanswered question was remaining regarding the importance of the structural dimensionality. The present manuscript provides an answer. We herein report on a β-Li 2 IrO 3 phase which, in spite of having the Ir arranged in a tridimensional (3D) framework instead of the typical two-dimensional (2D) layers seen in other Li-rich oxides, can reversibly exchange 2.5 e - per Ir, the highest value ever reported for any insertion reaction involving d-metals. We show that such a large activity results from joint reversible cationic (M n+ ) and anionic (O 2 ) n- redox processes, the latter being visualized via complementary transmission electron microscopy and neutron diffraction experiments, and confirmed by density functional theory calculations. Moreover, β-Li 2 IrO 3 presents a good cycling behaviour while showing neither cationic migration nor shearing of atomic layers as seen in 2D-layered Li-rich materials. Remarkably, the anionic redox process occurs jointly with the oxidation of Ir 4+ at potentials as low as 3.4 V versus Li + /Li 0 , as equivalently observed in the layered α-Li 2 IrO 3 polymorph. Theoretical calculations elucidate the electrochemical similarities and differences of the 3D versus 2D polymorphs in terms of structural, electronic and mechanical descriptors. Our findings free the structural dimensionality constraint and broaden the possibilities in designing high-energy-density electrodes for the next generation of Li-ion batteries.

Evidence for anionic redox activity in a tridimensional-ordered Li-rich positive electrode β-Li2IrO3

NASA Astrophysics Data System (ADS)

Pearce, Paul E.; Perez, Arnaud J.; Rousse, Gwenaelle; Saubanère, Mathieu; Batuk, Dmitry; Foix, Dominique; McCalla, Eric; Abakumov, Artem M.; van Tendeloo, Gustaaf; Doublet, Marie-Liesse; Tarascon, Jean-Marie

2017-05-01

Lithium-ion battery cathode materials have relied on cationic redox reactions until the recent discovery of anionic redox activity in Li-rich layered compounds which enables capacities as high as 300 mAh g-1. In the quest for new high-capacity electrodes with anionic redox, a still unanswered question was remaining regarding the importance of the structural dimensionality. The present manuscript provides an answer. We herein report on a β-Li2IrO3 phase which, in spite of having the Ir arranged in a tridimensional (3D) framework instead of the typical two-dimensional (2D) layers seen in other Li-rich oxides, can reversibly exchange 2.5 e- per Ir, the highest value ever reported for any insertion reaction involving d-metals. We show that such a large activity results from joint reversible cationic (Mn+) and anionic (O2)n- redox processes, the latter being visualized via complementary transmission electron microscopy and neutron diffraction experiments, and confirmed by density functional theory calculations. Moreover, β-Li2IrO3 presents a good cycling behaviour while showing neither cationic migration nor shearing of atomic layers as seen in 2D-layered Li-rich materials. Remarkably, the anionic redox process occurs jointly with the oxidation of Ir4+ at potentials as low as 3.4 V versus Li+/Li0, as equivalently observed in the layered α-Li2IrO3 polymorph. Theoretical calculations elucidate the electrochemical similarities and differences of the 3D versus 2D polymorphs in terms of structural, electronic and mechanical descriptors. Our findings free the structural dimensionality constraint and broaden the possibilities in designing high-energy-density electrodes for the next generation of Li-ion batteries.

Motion-robust intensity-modulated proton therapy for distal esophageal cancer.

PubMed

Yu, Jen; Zhang, Xiaodong; Liao, Li; Li, Heng; Zhu, Ronald; Park, Peter C; Sahoo, Narayan; Gillin, Michael; Li, Yupeng; Chang, Joe Y; Komaki, Ritsuko; Lin, Steven H

2016-03-01

To develop methods for evaluation and mitigation of dosimetric impact due to respiratory and diaphragmatic motion during free breathing in treatment of distal esophageal cancers using intensity-modulated proton therapy (IMPT). This was a retrospective study on 11 patients with distal esophageal cancer. For each patient, four-dimensional computed tomography (4D CT) data were acquired, and a nominal dose was calculated on the average phase of the 4D CT. The changes of water equivalent thickness (ΔWET) to cover the treatment volume from the peak of inspiration to the valley of expiration were calculated for a full range of beam angle rotation. Two IMPT plans were calculated: one at beam angles corresponding to small ΔWET and one at beam angles corresponding to large ΔWET. Four patients were selected for the calculation of 4D-robustness-optimized IMPT plans due to large motion-induced dose errors generated in conventional IMPT. To quantitatively evaluate motion-induced dose deviation, the authors calculated the lowest dose received by 95% (D95) of the internal clinical target volume for the nominal dose, the D95 calculated on the maximum inhale and exhale phases of 4D CT DCT0 andDCT50 , the 4D composite dose, and the 4D dynamic dose for a single fraction. The dose deviation increased with the average ΔWET of the implemented beams, ΔWETave. When ΔWETave was less than 5 mm, the dose error was less than 1 cobalt gray equivalent based on DCT0 and DCT50 . The dose deviation determined on the basis of DCT0 and DCT50 was proportionally larger than that determined on the basis of the 4D composite dose. The 4D-robustness-optimized IMPT plans notably reduced the overall dose deviation of multiple fractions and the dose deviation caused by the interplay effect in a single fraction. In IMPT for distal esophageal cancer, ΔWET analysis can be used to select the beam angles that are least affected by respiratory and diaphragmatic motion. To further reduce dose deviation, the 4D-robustness optimization can be implemented for IMPT planning. Calculation of DCT0 and DCT50 is a conservative method to estimate the motion-induced dose errors.

Prediction of p38 map kinase inhibitory activity of 3, 4-dihydropyrido [3, 2-d] pyrimidone derivatives using an expert system based on principal component analysis and least square support vector machine

PubMed Central

Shahlaei, M.; Saghaie, L.

2014-01-01

A quantitative structure–activity relationship (QSAR) study is suggested for the prediction of biological activity (pIC50) of 3, 4-dihydropyrido [3,2-d] pyrimidone derivatives as p38 inhibitors. Modeling of the biological activities of compounds of interest as a function of molecular structures was established by means of principal component analysis (PCA) and least square support vector machine (LS-SVM) methods. The results showed that the pIC50 values calculated by LS-SVM are in good agreement with the experimental data, and the performance of the LS-SVM regression model is superior to the PCA-based model. The developed LS-SVM model was applied for the prediction of the biological activities of pyrimidone derivatives, which were not in the modeling procedure. The resulted model showed high prediction ability with root mean square error of prediction of 0.460 for LS-SVM. The study provided a novel and effective approach for predicting biological activities of 3, 4-dihydropyrido [3,2-d] pyrimidone derivatives as p38 inhibitors and disclosed that LS-SVM can be used as a powerful chemometrics tool for QSAR studies. PMID:26339262

Patient-specific dosimetry based on quantitative SPECT imaging and 3D-DFT convolution

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

Akabani, G.; Hawkins, W.G.; Eckblade, M.B.

1999-01-01

The objective of this study was to validate the use of a 3-D discrete Fourier Transform (3D-DFT) convolution method to carry out the dosimetry for I-131 for soft tissues in radioimmunotherapy procedures. To validate this convolution method, mathematical and physical phantoms were used as a basis of comparison with Monte Carlo transport (MCT) calculations which were carried out using the EGS4 system code. The mathematical phantom consisted of a sphere containing uniform and nonuniform activity distributions. The physical phantom consisted of a cylinder containing uniform and nonuniform activity distributions. Quantitative SPECT reconstruction was carried out using the Circular Harmonic Transformmore » (CHT) algorithm.« less

Asphodosides A-E, anti-MRSA metabolites from Asphodelus microcarpus.

PubMed

Ghoneim, Mohammed M; Elokely, Khaled M; El-Hela, Atef A; Mohammad, Abd-Elsalam I; Jacob, Melissa; Radwan, Mohamed M; Doerksen, Robert J; Cutler, Stephen J; Ross, Samir A

2014-09-01

Bioassay guided fractionation of the ethanolic extract of Asphodelus microcarpus Salzm. et Viv. (Xanthorrhoeaceae or Asphodelaceae) resulted in isolation of five compounds identified as asphodosides A-E (1-5). Compounds 2-4 showed activity against methicillin resistant Staphylococcus aureus (MRSA) with IC50 values of 1.62, 7.0 and 9.0μg/mL, respectively. They also exhibited activity against Staphylococcus aureus (non-MRSA) with IC50 values of 1.0, 3.4 and 2.2μg/mL, respectively. The structure elucidation of isolated metabolites was carried out using spectroscopic data (1D and 2D NMR), optical rotation and both experimental and calculated electronic circular dichroism (ECD). Copyright © 2014 Elsevier Ltd. All rights reserved.

Gersemiols A-C and Eunicellol A, Diterpenoids from the Arctic Soft Coral Gersemia fruticosa.

PubMed

Angulo-Preckler, Carlos; Genta-Jouve, Grégory; Mahajan, Nipun; de la Cruz, Mercedes; de Pedro, Nuria; Reyes, Fernando; Iken, Katrin; Avila, Conxita; Thomas, Olivier P

2016-04-22

Three new diterpenes named gersemiols A-C (1-3) and a new eunicellane diterpene, eunicellol A (4), have been isolated together with the known sesquiterpene (+)-α-muurolene (5) from the Arctic soft coral Gersemia fruticosa. The name gersemiane was assigned to the rare and unnamed diterpene skeleton of compounds 1-3 corresponding to 4-isopropyl-1,5,8a-trimethyltetradecahydrophenanthrene. The chemical structures were elucidated on the basis of extensive spectroscopic analysis (HR-ESIMS, 1D and 2D NMR) as well as coupling constant calculations for the determination of the relative configurations. All compounds were tested for their antimicrobial activity against several bacteria and fungi and eunicellol A was found to exhibit moderate and selective antibacterial activity.

Electrochemical reduction of carbon fluorine bond in 4-fluorobenzonitrile Mechanistic analysis employing Marcus Hush quadratic activation-driving force relation

NASA Astrophysics Data System (ADS)

Muthukrishnan, A.; Sangaranarayanan, M. V.

2007-10-01

The reduction of carbon-fluorine bond in 4-fluorobenzonitrile in acetonitrile as the solvent, is analyzed using convolution potential sweep voltammetry and the dependence of the transfer coefficient on potential is investigated within the framework of Marcus-Hush quadratic activation-driving force theory. The validity of stepwise mechanism is inferred from solvent reorganization energy estimates as well as bond length calculations using B3LYP/6-31g(d) method. A novel method of estimating the standard reduction potential of the 4-fluorobenzonitrile in acetonitrile is proposed.

Construction and comparative evaluation of different activity detection methods in brain FDG-PET.

PubMed

Buchholz, Hans-Georg; Wenzel, Fabian; Gartenschläger, Martin; Thiele, Frank; Young, Stewart; Reuss, Stefan; Schreckenberger, Mathias

2015-08-18

We constructed and evaluated reference brain FDG-PET databases for usage by three software programs (Computer-aided diagnosis for dementia (CAD4D), Statistical Parametric Mapping (SPM) and NEUROSTAT), which allow a user-independent detection of dementia-related hypometabolism in patients' brain FDG-PET. Thirty-seven healthy volunteers were scanned in order to construct brain FDG reference databases, which reflect the normal, age-dependent glucose consumption in human brain, using either software. Databases were compared to each other to assess the impact of different stereotactic normalization algorithms used by either software package. In addition, performance of the new reference databases in the detection of altered glucose consumption in the brains of patients was evaluated by calculating statistical maps of regional hypometabolism in FDG-PET of 20 patients with confirmed Alzheimer's dementia (AD) and of 10 non-AD patients. Extent (hypometabolic volume referred to as cluster size) and magnitude (peak z-score) of detected hypometabolism was statistically analyzed. Differences between the reference databases built by CAD4D, SPM or NEUROSTAT were observed. Due to the different normalization methods, altered spatial FDG patterns were found. When analyzing patient data with the reference databases created using CAD4D, SPM or NEUROSTAT, similar characteristic clusters of hypometabolism in the same brain regions were found in the AD group with either software. However, larger z-scores were observed with CAD4D and NEUROSTAT than those reported by SPM. Better concordance with CAD4D and NEUROSTAT was achieved using the spatially normalized images of SPM and an independent z-score calculation. The three software packages identified the peak z-scores in the same brain region in 11 of 20 AD cases, and there was concordance between CAD4D and SPM in 16 AD subjects. The clinical evaluation of brain FDG-PET of 20 AD patients with either CAD4D-, SPM- or NEUROSTAT-generated databases from an identical reference dataset showed similar patterns of hypometabolism in the brain regions known to be involved in AD. The extent of hypometabolism and peak z-score appeared to be influenced by the calculation method used in each software package rather than by different spatial normalization parameters.

Theoretical study on the ground state of the polar alkali-metal-barium molecules: Potential energy curve and permanent dipole moment

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

Gou, Dezhi; Kuang, Xiaoyu, E-mail: scu-kuang@163.com; Gao, Yufeng

2015-01-21

In this paper, we systematically investigate the electronic structure for the {sup 2}Σ{sup +} ground state of the polar alkali-metal-alkaline-earth-metal molecules BaAlk (Alk = Li, Na, K, Rb, and Cs). Potential energy curves and permanent dipole moments (PDMs) are determined using power quantum chemistry complete active space self-consistent field and multi-reference configuration interaction methods. Basic spectroscopic constants are derived from ro-vibrational bound state calculation. From the calculations, it is shown that BaK, BaRb, and BaCs molecules have moderate values of PDM at the equilibrium bond distance (BaK:1.62 D, BaRb:3.32 D, and BaCs:4.02 D). Besides, the equilibrium bond length (4.93 Åmore » and 5.19 Å) and dissociation energy (0.1825 eV and 0.1817 eV) for the BaRb and BaCs are also obtained.« less

Fused heterocycles bearing bridgehead nitrogen as potent HIV-1 NNRTIs. Part 3: optimization of [1,2,4]triazolo[1,5-a]pyrimidine core via structure-based and physicochemical property-driven approaches.

PubMed

Huang, Boshi; Li, Cuicui; Chen, Wenmin; Liu, Tao; Yu, Mingyan; Fu, Lu; Sun, Yueyue; Liu, Huiqing; De Clercq, Erik; Pannecouque, Christophe; Balzarini, Jan; Zhan, Peng; Liu, Xinyong

2015-03-06

In our arduous efforts to develop new potent HIV-1 non-nucleoside reverse transcriptase (RT) inhibitors (NNRTIs), novel piperidine-linked [1,2,4]triazolo[1,5-a]pyrimidine derivatives were designed, synthesized and evaluated for their antiviral activities in MT-4 cell cultures. Biological results showed that all of the title compounds displayed moderate to excellent activities against wild-type (wt) HIV-1 strain (IIIB) with EC50 values ranging from 8.1 nM to 2284 nM in a cell-based assay. Among them, the most promising analog 7d possessed an EC50 value of 8.1 nM against wt HIV-1, which was much more potent than the reference drugs DDI, 3 TC, NVP and DLV. Additionally, 7d demonstrated weak activity against the double mutant HIV-1 strain (K103N + Y181C), and was more efficient than NVP in a RT inhibition assay. Besides, some measured and calculated physicochemical properties of 7d, like log P and water solubility, as well as the structure-activity relationships (SARs) analysis have been discussed in detail. Furthermore, the binding mode of the active compound 7d was rationalized by molecular simulation studies. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

Synthesis, crystal structure, theoretical calculations and antimicrobial properties of [Pt(tetramethylthiourea)4] [Pt(CN)4]·4H2O

NASA Astrophysics Data System (ADS)

Sadaf, Haseeba; Isab, Anvarhusein A.; Ahmad, Saeed; Espinosa, Arturo; Mas-Montoya, Míriam; Khan, Islam Ullah; Ejaz; Rehman, Seerat-ur; Ali, Muhammad Akhtar Javed; Saleem, Muhammad; Ruiz, José; Janiak, Christoph

2015-04-01

A new platinum(II) complex, [Pt(Tmtu)4][Pt(CN)4]·4H2O (1) was synthesized by reaction of K2[PtCl4], KCN and tetramethylthiourea (Tmtu). Its structure was determined by X-ray crystallography. The [Pt(CN)4]2- anion shows regular square planar geometry at platinum, while in the [Pt(Tmtu)4]2+ cation the geometry at platinum is somewhat distorted. Hydrogen bonding between water molecules and the cyanide nitrogen of [Pt(CN)4]2- ions stabilizes the structure and leads to a supramolecular 2D network. DFT calculations support the experimentally found dinuclear (homocoordinated) ion-pair structure 1 as the most stable in comparison to noncovalent dimer [Pt(CN)2(Tmtu)2]222 that could, in turn, be involved in the formation sequence of 1. Antimicrobial activities of the complex were evaluated by minimum inhibitory concentration and the results showed that the complex exhibited moderate activities against gram-negative bacteria (Escherichiacoli, Pseudomonas aeruginosa) and molds (Aspergillus niger,Penicilliumcitrinum).

Toward a W4-F12 approach: Can explicitly correlated and orbital-based ab initio CCSD(T) limits be reconciled?

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

Sylvetsky, Nitai, E-mail: gershom@weizmann.ac.il; Martin, Jan M. L., E-mail: gershom@weizmann.ac.il; Peterson, Kirk A., E-mail: kipeters@wsu.edu

2016-06-07

In the context of high-accuracy computational thermochemistry, the valence coupled cluster with all singles and doubles (CCSD) correlation component of molecular atomization energies presents the most severe basis set convergence problem, followed by the (T) component. In the present paper, we make a detailed comparison, for an expanded version of the W4-11 thermochemistry benchmark, between, on the one hand, orbital-based CCSD/AV{5,6}Z + d and CCSD/ACV{5,6}Z extrapolation, and on the other hand CCSD-F12b calculations with cc-pVQZ-F12 and cc-pV5Z-F12 basis sets. This latter basis set, now available for H–He, B–Ne, and Al–Ar, is shown to be very close to the basis setmore » limit. Apparent differences (which can reach 0.35 kcal/mol for systems like CCl{sub 4}) between orbital-based and CCSD-F12b basis set limits disappear if basis sets with additional radial flexibility, such as ACV{5,6}Z, are used for the orbital calculation. Counterpoise calculations reveal that, while total atomization energies with V5Z-F12 basis sets are nearly free of BSSE, orbital calculations have significant BSSE even with AV(6 + d)Z basis sets, leading to non-negligible differences between raw and counterpoise-corrected extrapolated limits. This latter problem is greatly reduced by switching to ACV{5,6}Z core-valence basis sets, or simply adding an additional zeta to just the valence orbitals. Previous reports that all-electron approaches like HEAT (high-accuracy extrapolated ab-initio thermochemistry) lead to different CCSD(T) limits than “valence limit + CV correction” approaches like Feller-Peterson-Dixon and Weizmann-4 (W4) theory can be rationalized in terms of the greater radial flexibility of core-valence basis sets. For (T) corrections, conventional CCSD(T)/AV{Q,5}Z + d calculations are found to be superior to scaled or extrapolated CCSD(T)-F12b calculations of similar cost. For a W4-F12 protocol, we recommend obtaining the Hartree-Fock and valence CCSD components from CCSD-F12b/cc-pV{Q,5}Z-F12 calculations, but the (T) component from conventional CCSD(T)/aug’-cc-pV{Q,5}Z + d calculations using Schwenke’s extrapolation; post-CCSD(T), core-valence, and relativistic corrections are to be obtained as in the original W4 theory. W4-F12 is found to agree slightly better than W4 with ATcT (active thermochemical tables) data, at a substantial saving in computation time and especially I/O overhead. A W4-F12 calculation on benzene is presented as a proof of concept.« less

Dose calculation with respiration-averaged CT processed from cine CT without a respiratory surrogate

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

Riegel, Adam C.; Ahmad, Moiz; Sun Xiaojun

2008-12-15

Dose calculation for thoracic radiotherapy is commonly performed on a free-breathing helical CT despite artifacts caused by respiratory motion. Four-dimensional computed tomography (4D-CT) is one method to incorporate motion information into the treatment planning process. Some centers now use the respiration-averaged CT (RACT), the pixel-by-pixel average of the ten phases of 4D-CT, for dose calculation. This method, while sparing the tedious task of 4D dose calculation, still requires 4D-CT technology. The authors have recently developed a means to reconstruct RACT directly from unsorted cine CT data from which 4D-CT is formed, bypassing the need for a respiratory surrogate. Using RACTmore » from cine CT for dose calculation may be a means to incorporate motion information into dose calculation without performing 4D-CT. The purpose of this study was to determine if RACT from cine CT can be substituted for RACT from 4D-CT for the purposes of dose calculation, and if increasing the cine duration can decrease differences between the dose distributions. Cine CT data and corresponding 4D-CT simulations for 23 patients with at least two breathing cycles per cine duration were retrieved. RACT was generated four ways: First from ten phases of 4D-CT, second, from 1 breathing cycle of images, third, from 1.5 breathing cycles of images, and fourth, from 2 breathing cycles of images. The clinical treatment plan was transferred to each RACT and dose was recalculated. Dose planes were exported at orthogonal planes through the isocenter (coronal, sagittal, and transverse orientations). The resulting dose distributions were compared using the gamma ({gamma}) index within the planning target volume (PTV). Failure criteria were set to 2%/1 mm. A follow-up study with 50 additional lung cancer patients was performed to increase sample size. The same dose recalculation and analysis was performed. In the primary patient group, 22 of 23 patients had 100% of points within the PTV pass {gamma} criteria. The average maximum and mean {gamma} indices were very low (well below 1), indicating good agreement between dose distributions. Increasing the cine duration generally increased the dose agreement. In the follow-up study, 49 of 50 patients had 100% of points within the PTV pass the {gamma} criteria. The average maximum and mean {gamma} indices were again well below 1, indicating good agreement. Dose calculation on RACT from cine CT is negligibly different from dose calculation on RACT from 4D-CT. Differences can be decreased further by increasing the cine duration of the cine CT scan.« less

Ferro and antiferro orbital ordering in Fe{sub 0.5}Mn{sub 0.5}V{sub 2}O{sub 4}

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

Dey, Dibyendu, E-mail: dibyendu@phy.iitkgp.ernet.in; Taraphder, A.; Maitra, T.

2016-05-23

Using density functional theory calculations, we have investigated the orbital ordering in Fe{sub 0.5}Mn{sub 0.5}V{sub 2}O{sub 4} where Fe and V sites are orbitally active. Our first principles study within GGA+U and GGA+U+SO shows ferro-orbital ordering of d{sub x2−y2} orbital at all Fe sites, whereas A-type antiferro-orbital ordering at V sites where one 3d electron occupies d{sub xy} orbital at every V site and another electron occupies either 1/√2 (d{sub xz} + d{sub yz}) or 1/√2 (d{sub xz} - d{sub yz}) orbital alternatively along c axis. Insulating nature and the orbital ordering of this compound are found to be correlationmore » driven while the effect of spin-orbit interaction on orbital ordering is not significant.« less

Aspartic cathepsin D endopeptidase contributes to extracellular digestion in clawed lobsters Homarus americanus and Homarus gammarus.

PubMed

Rojo, Liliana; Muhlia-Almazan, Adriana; Saborowski, Reinhard; García-Carreño, Fernando

2010-11-01

Acid digestive proteinases were studied in the gastric fluids of two species of clawed lobster (Homarus americanus and Homarus gammarus). An active protein was identified in both species as aspartic proteinase by specific inhibition with pepstatin A. It was confirmed as cathepsin D by mass mapping, N-terminal, and full-length cDNA sequencing. Both lobster species transcribed two cathepsin D mRNAs: cathepsin D1 and cathepsin D2. Cathepsin D1 mRNA was detected only in the midgut gland, suggesting its function as a digestive enzyme. Cathepsin D2 mRNA was found in the midgut gland, gonads, and muscle. The deduced amino acid sequence of cathepsin D1 and cathepsin D2 possesses two catalytic DTG active-site motifs, the hallmark of aspartic proteinases. The putatively active cathepsin D1 has a molecular mass of 36.4 kDa and a calculated pI of 4.14 and possesses three potential glycosylation sites. The sequences showed highest similarities with cathepsin D from insects but also with another crustacean cathepsin D. Cathepsin D1 transcripts were quantified during a starvation period using real-time qPCR. In H. americanus, 15 days of starvation did not cause significant changes, but subsequent feeding caused a 2.5-fold increase. In H. gammarus, starvation caused a 40% reduction in cathepsin D1 mRNA, and no effect was observed with subsequent feeding.

Similarity criteria in calculations of the energy characteristics of a cw oxygen - iodine laser

NASA Astrophysics Data System (ADS)

Mezhenin, A. V.; Azyazov, V. N.

2012-12-01

The calculated and experimental data on the energy efficiency of a cw oxygen - iodine laser (OIL) are analysed based on two similarity criteria, namely, on the ratio of the residence time of the gas mixture in the resonator to the characteristic time of extraction of the energy stored in singlet oxygen td and on the gain-to-loss ratio Π. It is shown that the simplified two-level laser model satisfactorily predicts the output characteristics of OILs with a stable resonator at τd <= 7. Efficient energy extraction from the OIL active medium is achieved in the case of τd = 5 - 7, Π = 4 - 8.

Scanned carbon beam irradiation of moving films: comparison of measured and calculated response

PubMed Central

2012-01-01

Background Treatment of moving target volumes with scanned particle beams benefits from treatment planning that includes the time domain (4D). Part of 4D treatment planning is calculation of the expected result. These calculation codes should be verified against suitable measurements. We performed simulations and measurements to validate calculation of the film response in the presence of target motion. Methods All calculations were performed with GSI's treatment planning system TRiP. Interplay patterns between scanned particle beams and moving film detectors are very sensitive to slight deviations of the assumed motion parameters and therefore ideally suited to validate 4D calculations. In total, 14 film motion parameter combinations with lateral motion amplitudes of 8, 15, and 20 mm and 4 combinations for lateral motion including range changes were used. Experimental and calculated film responses were compared by relative difference, mean deviation in two regions-of-interest, as well as line profiles. Results Irradiations of stationary films resulted in a mean relative difference of -1.52% ± 2.06% of measured and calculated responses. In comparison to this reference result, measurements with translational film motion resulted in a mean difference of -0.92% ± 1.30%. In case of irradiations incorporating range changes with a stack of 5 films as detector the deviations increased to -6.4 ± 2.6% (-10.3 ± 9.0% if film in distal fall-off is included) in comparison to -3.6% ± 2.5% (-13.5% ± 19.9% including the distal film) for the stationary irradiation. Furthermore, the comparison of line profiles of 4D calculations and experimental data showed only slight deviations at the borders of the irradiated area. The comparisons of pure lateral motion were used to determine the number of motion states that are required for 4D calculations depending on the motion amplitude. 6 motion states per 10 mm motion amplitude are sufficient to calculate the film response in the presence of motion. Conclusions By comparison to experimental data, the 4D extension of GSI's treatment planning system TRiP has been successfully validated for film response calculations in the presence of target motion within the accuracy limitation given by film-based dosimetry. PMID:22462523

Shielding Analysis of a Small Compact Space Nuclear Reactor

DTIC Science & Technology

1987-08-01

RESPONSE) =4, MAXWELLIAN FISSION SPECTRUM (ILNTEGRAL RESPONSE) =5, LOS ALAMOS FISSION SPECTRUM, 1982 (INTEGRAL RESPONSE) =6, VITAMIN C NEUTRON SPECTRUM...Appendices Appendix A: Calculations of Effective Radii.. A-1 Appendix B: Atom Density Calculations for FEMPlD and FEMP2D ................ B-I Appendix C ...FEMPID and FEM22D Data........... C -i Appendix D: Energy Group Definition .......... D-I Appendix E: Transport Equation, Legendr4 Polynomial

Organ-specific SPECT activity calibration using 3D printed phantoms for molecular radiotherapy dosimetry.

PubMed

Robinson, Andrew P; Tipping, Jill; Cullen, David M; Hamilton, David; Brown, Richard; Flynn, Alex; Oldfield, Christopher; Page, Emma; Price, Emlyn; Smith, Andrew; Snee, Richard

2016-12-01

Patient-specific absorbed dose calculations for molecular radiotherapy require accurate activity quantification. This is commonly derived from Single-Photon Emission Computed Tomography (SPECT) imaging using a calibration factor relating detected counts to known activity in a phantom insert. A series of phantom inserts, based on the mathematical models underlying many clinical dosimetry calculations, have been produced using 3D printing techniques. SPECT/CT data for the phantom inserts has been used to calculate new organ-specific calibration factors for (99m) Tc and (177)Lu. The measured calibration factors are compared to predicted values from calculations using a Gaussian kernel. Measured SPECT calibration factors for 3D printed organs display a clear dependence on organ shape for (99m) Tc and (177)Lu. The observed variation in calibration factor is reproduced using Gaussian kernel-based calculation over two orders of magnitude change in insert volume for (99m) Tc and (177)Lu. These new organ-specific calibration factors show a 24, 11 and 8 % reduction in absorbed dose for the liver, spleen and kidneys, respectively. Non-spherical calibration factors from 3D printed phantom inserts can significantly improve the accuracy of whole organ activity quantification for molecular radiotherapy, providing a crucial step towards individualised activity quantification and patient-specific dosimetry. 3D printed inserts are found to provide a cost effective and efficient way for clinical centres to access more realistic phantom data.

Synthesis, crystal structure, biological activity and theoretical calculations of novel isoxazole derivatives

NASA Astrophysics Data System (ADS)

Jin, R. Y.; Sun, X. H.; Liu, Y. F.; Long, W.; Chen, B.; Shen, S. Q.; Ma, H. X.

2016-01-01

Series of isoxazole derivatives were synthesized by substituted chalcones and 2-chloro-6-fluorobenzene formaldehyde oxime with 1,3-dipolar cycloaddition. The target compounds were determined by melting point, IR, 1H NMR, elemental analyses and HRMS. The crystal structure of compound 3a was detected by X-ray diffraction and it crystallizes in the triclinic space group p2(1)/c with z = 4. The molecular geometry of compound 3a was optimized using density functional theory (DFT/B3LYP) method with the 6-31G+(d,p) basis set in the ground state. From the optimized geometry of the molecule, FT-IR, FT-Raman, HOMO-LUMO and natural bond orbital (NBO) were calculated at B3LYP/6-31G+(d,p) level. Finally, the antifungal activity of the synthetic compounds were evaluated against Pythium solani, Gibberella nicotiancola, Fusarium oxysporium f.sp. niveum and Gibberella saubinetii.

Quantum chemical investigation of levofloxacin-boron complexes: A computational approach

NASA Astrophysics Data System (ADS)

Sayin, Koray; Karakaş, Duran

2018-04-01

Quantum chemical calculations are performed over some boron complexes with levofloxacin. Boron complex with fluorine atoms are optimized at three different methods (HF, B3LYP and M062X) with 6-31 + G(d) basis set. The best level is determined as M062X/6-31 + G(d) by comparison of experimental and calculated results of complex (1). The other complexes are optimized by using the best level. Structural properties, IR and NMR spectrum are examined in detail. Biological activities of mentioned complexes are investigated by some quantum chemical descriptors and molecular docking analyses. As a result, biological activities of complex (2) and (4) are close to each other and higher than those of other complexes. Additionally, NLO properties of mentioned complexes are investigated by some quantum chemical parameters. It is found that complex (3) is the best candidate for NLO applications.

New iron-based mixed-polyanion cathodes for lithium and sodium rechargeable batteries: combined first principles calculations and experimental study.

PubMed

Kim, Hyungsub; Park, Inchul; Seo, Dong-Hwa; Lee, Seongsu; Kim, Sung-Wook; Kwon, Woo Jun; Park, Young-Uk; Kim, Chul Sung; Jeon, Seokwoo; Kang, Kisuk

2012-06-27

New iron-based mixed-polyanion compounds Li(x)Na(4-x)Fe(3)(PO(4))(2)(P(2)O(7)) (x = 0-3) were synthesized, and their crystal structures were determined. The new compounds contained three-dimensional (3D)sodium/lithium paths supported by P(2)O(7) pillars in the crystal. First principles calculations identified the complex 3D paths with their activation barriers and revealed them as fast ionic conductors. The reversible electrode operation was found in both Li and Na cells with capacities of one-electron reaction per Fe atom, 140 and 129 mAh g(-1), respectively. The redox potential of each phase was ∼3.4 V (vs Li) for the Li-ion cell and ∼3.2 V (vs Na) for the Na-ion cell. The properties of high power, small volume change, and high thermal stability were also recognized, presenting this new compound as a potential competitor to other iron-based electrodes such as Li(2)FeP(2)O(7), Li(2)FePO(4)F, and LiFePO(4).

Synthesis, structure characterization, and anticancer activity of a novel oxygen-bridged tricyclic Biginelli adduct

NASA Astrophysics Data System (ADS)

Ibrahim, Mohamed M.; El-Sheshtawy, Hamdy S.; El-Kemary, Maged; Al-Juaid, Salih; Youssef, Mohamed; El-Azab, Islam H.

2017-06-01

Herein, we report the one-pot cyclization of Biginelli Adduct, ethyl 4-(2-hydroxyphenyl)-6-methyl-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate (I) to the oxygen-bridged adduct, ethyl 2-methyl-4-thioxo-3,4,5,6-tetrahydro-2H-2,6-methanobenzo[g] [1,3,5]oxadiazocine-11-carboxylate (II) in a high yield and purity under mild reaction condition using zinc(II) perchlorate hexahydrate as a highly efficient catalyst. The cyclic product (II) was characterized both in the solid state and in solution using FT-IR, 1H NMR, and UV-visible spectroscopy. Theoretical calculations using density functional theory with B3LYP/6-311++G(d,p) level were used to further investigate the structure properties. DFT calculations (gas phase) revealed the stability of cyclic compound II (3.45 kcal/mol) than compound I. In addition, the anticancer activity of II was investigated using MCF-7 human breast cell line. The results revealed a moderate activity with 223.55 μg/ml IC50 value.

Comparison of Newer IOL Power Calculation Methods for Eyes With Previous Radial Keratotomy

PubMed Central

Ma, Jack X.; Tang, Maolong; Wang, Li; Weikert, Mitchell P.; Huang, David; Koch, Douglas D.

2016-01-01

Purpose To evaluate the accuracy of the optical coherence tomography–based (OCT formula) and Barrett True K (True K) intraocular lens (IOL) calculation formulas in eyes with previous radial keratotomy (RK). Methods In 95 eyes of 65 patients, using the actual refraction following cataract surgery as target refraction, the predicted IOL power for each method was calculated. The IOL prediction error (PE) was obtained by subtracting the predicted IOL power from the implanted IOL power. The arithmetic IOL PE and median refractive PE were calculated and compared. Results All formulas except the True K produced hyperopic IOL PEs at 1 month, which decreased at ≥4 months (all P < 0.05). For the double-K Holladay 1, OCT formula, True K, and average of these three formulas (Average), the median absolute refractive PEs were, respectively, 0.78 diopters (D), 0.74 D, 0.60 D, and 0.59 D at 1 month; 0.69 D, 0.77 D, 0.77 D, and 0.61 D at 2 to 3 months; and 0.34 D, 0.65 D, 0.69 D, and 0.46 D at ≥4 months. The Average produced significantly smaller refractive PE than did the double-K Holladay 1 at 1 month (P < 0.05). There were no significant differences in refractive PEs among formulas at 4 months. Conclusions The OCT formula and True K were comparable to the double-K Holladay 1 method on the ASCRS (American Society of Cataract and Refractive Surgery) calculator. The Average IOL power on the ASCRS calculator may be considered when selecting the IOL power. Further improvements in the accuracy of IOL power calculation in RK eyes are desirable. PMID:27409468

New 1,3,4-thiadiazole compounds including pyrazine moiety: Synthesis, structural properties and antimicrobial features

NASA Astrophysics Data System (ADS)

Gür, Mahmut; Şener, Nesrin; Muğlu, Halit; Çavuş, M. Serdar; Özkan, Osman Emre; Kandemirli, Fatma; Şener, İzzet

2017-07-01

In the study, some new 1,3,4-thiadiazole compounds were synthesized and we have reported identification of the structures by using UV-Vis, FT-IR, 1H NMR, 13C NMR and Mass spectroscopic methods. Antimicrobial activities of the compounds against three microorganisms, namely, Candida albicans ATCC 26555, Staphylococcus aureus ATCC 9144, and Escherichia coli ATCC 25922 were investigated by using disk diffusion method. These thiadiazoles exhibited an antimicrobial activity against Staphylococcus aureus and Candida albicans. The experimental data was supported by the quantum chemical calculations. Density functional theory (DFT) calculations were carried out to obtain the ground state optimized geometries of the molecules using the B3LYP, M06 and PBE1PBE methods with 3-21 g, 4-31 g, 6-311++g(2d,2p), cc-pvtz and cc-pvqz basis sets in the different combinations. Frontier molecular orbitals (FMOs) energies, band gap energies and some chemical reactivity parameters were calculated by using the aforementioned methods and basis sets, and the results were also compared with the experimental UV-Vis data.

Infrared, Raman and NMR spectra, conformational stability, normal coordinate analysis and B3LYP calculations of 5-Amino-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde

NASA Astrophysics Data System (ADS)

Bahgat, Khaled; EL-Emary, Talaat

2013-02-01

FT Raman and IR spectra of the crystallized biologically active molecule, 5-Amino-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde (5-APHC, C11H11N3O) have been recorded and analyzed. The equilibrium geometry, bonding features and harmonic vibrational frequencies of 5-APHC have been investigated with the help of B3LYP density functional theory (DFT) method with 6-31G(d) and 6-311+G(d,p) as basis set. The calculated molecular geometry has been compared with the experimental data. The assignments of the vibrational spectra have been carried out with the help of normal coordinate analysis (NCA) following the scaled quantum mechanical force field (SQM) technique. The optimized geometry shows the co-planarity of the aldehyde group with pyrazole ring. Potential energy surface (PES) scan studies has also been carried out by ab initio calculations with B3LYP/6-311+G(d,p) basis set. The red shifting of NH2 stretching wavenumber indicates the formation of N-H⋯O hydrogen bonding. 1H and 13C NMR spectra were recorded and 1H and 13C nuclear magnetic resonance chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method. UV-Vis spectrum of the compound was recorded in the region 200-400 nm and the electronic properties HOMO and LUMO energies were calculated by time-dependent TD-DFT approach. Mulliken charges of the 5-APHC molecule was also calculated and interpreted.

Novel cocrystal of N-phthaloyl-β-alanine with 2,2-bipyridyl: Synthesis, computational and free radical scavenging activity studies

NASA Astrophysics Data System (ADS)

Chahkandi, Mohammad; Bhatti, Moazzam H.; Yunus, Uzma; Rehman, Naima; Nadeem, Muhammad; Tahir, Muhammad Nawaz; Zakria, Muhammad

2018-01-01

In the present work a novel cocrystal adduct of N-phthaloyl-β-alanine and 2,2-bipyridyl as compound 1 with molecular formula C16H13N3O4 was synthesized by slow evaporation process of the ethanoic solution containing these two moieties. In followings, the crystal structure and photophysical properties of 1 was characterized by single X-ray crystal analysis, FTIR, and UV-Vis spectra. The thermal behavior was analyzed by the Thermogravimetric/Differential Thermal Analyzer (TG-DTA). The cocrystal belong to monoclinic crystallographic system with space group P21/n, Z = 4. DPPH radical scavenging activity of the title cocrystal is slightly higher than coformer with lower IC50 value. Finally, using DFT calculations executed at hybrid B3LYP/6-311+G (d, p) level of theory the geometric and electronic structures of the crystalline network of C16H13N3O4 (1), studied. Inter-molecular conventional Osbnd H⋯N as well as the non-conventional Csbnd H⋯O hydrogen bonds (HBs) and Csbnd H···π and Csbnd O···π stacking interactions gathered the monomeric structures of 1 (1-mon) to create the 3D architecture of the network (1-net). The dispersion corrected density functional theory (DFT-D) calculations indicate that Osbnd H⋯N and Csbnd H⋯O HBs, govern the 1-net formation. The calculated UV-Vis spectrum in vacuo has agreement with the experimental one that shows five major bands in the range of 170-271 nm that could assigned to transitions between 2,2-bipyridyl and N-phthaloyl-β-alanine parts of 1 with n → π∗ and π → π* ligand-ligand-charge transfer (LLCT) character. The calculated electronic spectra in solvents (water, acetonitrile, methanol, and n-heptane) comparing with the vacuo one show broad bands with blue shifts.

Inhibitory Effect of 2,3,5,6-Tetrafluoro-4-[4-(aryl)-1H-1,2,3-triazol-1-yl]benzenesulfonamide Derivatives on HIV Reverse Transcriptase Associated RNase H Activities

PubMed Central

Pala, Nicolino; Esposito, Francesca; Rogolino, Dominga; Carcelli, Mauro; Sanna, Vanna; Palomba, Michele; Naesens, Lieve; Corona, Angela; Grandi, Nicole; Tramontano, Enzo; Sechi, Mario

2016-01-01

The HIV-1 ribonuclease H (RNase H) function of the reverse transcriptase (RT) enzyme catalyzes the selective hydrolysis of the RNA strand of the RNA:DNA heteroduplex replication intermediate, and represents a suitable target for drug development. A particularly attractive approach is constituted by the interference with the RNase H metal-dependent catalytic activity, which resides in the active site located at the C-terminus p66 subunit of RT. Herein, we report results of an in-house screening campaign that allowed us to identify 4-[4-(aryl)-1H-1,2,3-triazol-1-yl]benzenesulfonamides, prepared by the “click chemistry” approach, as novel potential HIV-1 RNase H inhibitors. Three compounds (9d, 10c, and 10d) demonstrated a selective inhibitory activity against the HIV-1 RNase H enzyme at micromolar concentrations. Drug-likeness, predicted by the calculation of a panel of physicochemical and ADME properties, putative binding modes for the active compounds, assessed by computational molecular docking, as well as a mechanistic hypothesis for this novel chemotype are reported. PMID:27556447

Synthesis, XRD crystal structure, spectroscopic characterization (FT-IR, 1H and 13C NMR), DFT studies, chemical reactivity and bond dissociation energy studies using molecular dynamics simulations and evaluation of antimicrobial and antioxidant activities of a novel chalcone derivative, (E)-1-(4-bromophenyl)-3-(4-iodophenyl)prop-2-en-1-one

NASA Astrophysics Data System (ADS)

Zainuri, D. Alwani; Arshad, Suhana; Khalib, N. Che; Razak, I. Abdul; Pillai, Renjith Raveendran; Sulaiman, S. Fariza; Hashim, N. Shafiqah; Ooi, K. Leong; Armaković, Stevan; Armaković, Sanja J.; Panicker, C. Yohannan; Van Alsenoy, C.

2017-01-01

In the present study, the title compound named as (E)-1-(4-bromophenyl)-3-(4-iodophenyl)prop-2-en-1-one was synthesized and structurally characterized by single-crystal X-ray diffraction. The compound crystallizes in the monoclinic system with P21/c space group with the unit cell parameters of a = 16.147 (2) Å, b = 14.270 (2) Å, c = 5.9058 (9) Å, β = 92.577 (3)° and Z = 4. The molecular geometry obtained from X-Ray structure determination was optimized by Density Functional Theory (DFT) using B3LYP/6-31G+(d, p)/Lanl2dz(f) method in the ground state. The IR spectrum was recorded and interpreted in details with the aid of Density Functional Theory (DFT) calculations and Potential Energy Distribution (PED) analysis. In order to investigate local reactivity properties of the title molecule, we have conducted DFT calculations of average local ionization energy surface and Fukui functions which were mapped to the electron density surface. In order to predict the open air stability and possible degradation properties, within DFT approach, we have also calculated bond dissociation energies. 1H and 13C NMR spectra were recorded and chemical shifts were calculated theoretically and compared with the experimental values. In addition, in vitro antimicrobial results show that the title compound has great potential of antibacterial activity against Staphylococcus aureus, Staphylococcus epidermidis and Micrococcus luteus bacteria and antifungal activity against Candida albicans in comparison to some reported chalcone derivatives. Antioxidant studies revealed the highest metal chelating activity of this compound.

Aphadilactones A-D, four diterpenoid dimers with DGAT inhibitory and antimalarial activities from a Meliaceae plant.

PubMed

Liu, Jia; He, Xiu-Feng; Wang, Gai-Hong; Merino, Emilio F; Yang, Sheng-Ping; Zhu, Rong-Xiu; Gan, Li-She; Zhang, Hua; Cassera, Maria B; Wang, He-Yao; Kingston, David G I; Yue, Jian-Min

2014-01-17

Aphadilactones A-D (1-4), four diastereoisomers possessing an unprecedented carbon skeleton, were isolated from the Meliaceae plant Aphanamixis grandifolia. Their challenging structures and absolute configurations were determined by a combination of spectroscopic data, chemical degradation, fragment synthesis, experimental CD spectra, and ECD calculations. Aphadilactone C (3) with the 5S,11S,5'S,11'S configuration showed potent and selective inhibition against the diacylglycerol O-acyltransferase-1 (DGAT-1) enzyme (IC50 = 0.46 ± 0.09 μM, selectivity index > 217) and is the strongest natural DGAT-1 inhibitor discovered to date. In addition, compounds 1-4 showed significant antimalarial activities with IC50 values of 190 ± 60, 1350 ± 150, 170 ± 10, and 120 ± 50 nM, respectively.

DFT calculations, spectroscopy and antioxidant activity studies on (E)-2-nitro-4-[(phenylimino)methyl]phenol

NASA Astrophysics Data System (ADS)

Temel, Ersin; Alaşalvar, Can; Gökçe, Halil; Güder, Aytaç; Albayrak, Çiğdem; Alpaslan, Yelda Bingöl; Alpaslan, Gökhan; Dilek, Nefise

2015-02-01

We have reported synthesis and characterization of (E)-2-nitro-4-[(phenylimino)methyl]phenol by using X-ray crystallographic method, FT-IR and UV-vis spectroscopies and density functional theory (DFT). Optimized geometry and vibrational frequencies of the title compound in the ground state have been computed by using B3LYP with the 6-311G+(d,p) basis set. HOMO-LUMO energy gap, Non-linear optical properties and NBO analysis of the compound are performed at B3LYP/6-311G+(d,p) level. Additionally, as remarkable properties, antioxidant activity of the title compound (CMPD) has been determined by using different antioxidant test methods i.e. ferric reducing antioxidant power (FRAP), hydrogen peroxide scavenging (HPSA), free radical scavenging (FRSA) and ferrous ion chelating activities (FICA). When compared with standards (BHA, BHT, and α-tocopherol), we have concluded that CPMD has effective FRAP, HPSA, FRSA and FICA.

Synthesis, crystal structures and theoretical calculations of new 1-[2-(5-chloro-2-benzoxazolinone-3-yl)acetyl]-3,5-diphenyl-4,5-dihydro-(1H)-pyrazoles

NASA Astrophysics Data System (ADS)

Gökşen, Umut Salgın; Alpaslan, Yelda Bingöl; Kelekçi, Nesrin Gökhan; Işık, Şamil; Ekizoğlu, Melike

2013-05-01

1-[2-(5-Chloro-2-benzoxazolinone-3-yl)acetyl]-3-phenyl-5-(3-methoxyphenyl)-4,5-dihydro-(1H)-pyrazole (5a), 1-[2-(5-chloro-2-benzoxazolinone-3-yl)acetyl]-3-phenyl-5-(3,4-dimethoxyphenyl)-4,5-dihydro-(1H)-pyrazole (5b) and 1-[2-(5-chloro-2-benzoxazolinone-3-yl)acetyl]-3-(4-methylphenyl)-5-(2,3-dimethoxyphenyl)-4,5-dihydro-(1H)-pyrazole (5c) were synthesized. The crystal and molecular structures of the compounds 5a, 5b and 5c were determined by elemental analyses, IR, 1H NMR, ESI-MS and single-crystal X-ray diffraction. DFT method with 6-31G(d,p) basis set was used to calculate the optimized geometrical parameters, vibrational frequencies and chemical shift values. The calculated vibrational frequencies and chemical shift values were compared with experimental IR and 1H NMR values. The results represented that there was a good agreement between experimental and calculated values of the compounds 5a-5c. In addition, DFT calculations of the compounds, molecular electrostatic potentials (MEPs) and frontier molecular orbitals were performed at B3LYP/6-31G(d,p) level of theory. Furthermore, compounds were tested against three Gram-positive bacteria: Staphylococcus aureus ATCC 29213 (American Type Culture Collection), methicillin resistant S. aureus (MRSA) ATCC 43300 and Enterococcus faecalis ATCC 29212; two Gram negative bacteria: Escherichia coli ATCC 25922 and Pseudomonas aeruginosa ATCC 27853; and three fungi: Candida albicans ATCC 90028, Candida krusei ATCC 6258 and Candida parapsilosis ATCC 90018. In general, all of the compounds were found to be slightly active against tested microorganisms.

Hybrid Density Functional Study of the Local Structures and Energy Levels of CaAl2O4:Ce3.

PubMed

Lou, Bibo; Jing, Weiguo; Lou, Liren; Zhang, Yongfan; Yin, Min; Duan, Chang-Kui

2018-05-03

First-principles calculations were carried out for the electronic structures of Ce 3+ in calcium aluminate phosphors, CaAl 2 O 4 , and their effects on luminescence properties. Hybrid density functional approaches were used to overcome the well-known underestimation of band gaps of conventional density functional approaches and to calculate the energy levels of Ce 3+ ions more accurately. The obtained 4f-5d excitation and emission energies show good consistency with measured values. A detailed energy diagram of all three sites is obtained, which explains qualitatively all of the luminescent phenomena. With the results of energy levels calculated by combining the hybrid functional of Heyd, Scuseria, and Ernzerhof (HSE06) and the constraint occupancy approach, we are able to construct a configurational coordinate diagram to analyze the processes of capture of a hole or an electron and luminescence. This approach can be applied for systematic high-throughput calculations in predicting Ce 3+ activated luminescent materials with a moderate computing requirement.

Holophyllane A: A Triterpenoid Possessing an Unprecedented B-nor-3,4-seco-17,14-friedo-lanostane Architecture from Abies holophylla

NASA Astrophysics Data System (ADS)

Kim, Chung Sub; Oh, Joonseok; Subedi, Lalita; Kim, Sun Yeou; Choi, Sang Un; Lee, Kang Ro

2017-03-01

A novel triterpenoid, holophyllane A (1), featuring a B-nor-3,4-seco-17,14-friedo-lanostane, along with its putative precursor, compound 2 were isolated from the methanol extract of the trunks of Abies holophylla. The 2D structure and relative configuration of 1 were initially determined via analysis of 1D and 2D NMR spectroscopic data and the assignment was confirmed by quantum mechanics-based NMR chemical shift calculations. The absolute configuration was established by comparison of the experimental and simulated ECD data generated at different theory levels. Compounds 1 and 2 exhibited moderate to weak cytotoxicity and significant inhibitory activity against nitric oxide (NO) production.

4f fine-structure levels as the dominant error in the electronic structures of binary lanthanide oxides.

PubMed

Huang, Bolong

2016-04-05

The ground-state 4f fine-structure levels in the intrinsic optical transition gaps between the 2p and 5d orbitals of lanthanide sesquioxides (Ln2 O3 , Ln = La…Lu) were calculated by a two-way crossover search for the U parameters for DFT + U calculations. The original 4f-shell potential perturbation in the linear response method were reformulated within the constraint volume of the given solids. The band structures were also calculated. This method yields nearly constant optical transition gaps between Ln-5d and O-2p orbitals, with magnitudes of 5.3 to 5.5 eV. This result verifies that the error in the band structure calculations for Ln2 O3 is dominated by the inaccuracies in the predicted 4f levels in the 2p-5d transition gaps, which strongly and non-linearly depend on the on-site Hubbard U. The relationship between the 4f occupancies and Hubbard U is non-monotonic and is entirely different from that for materials with 3d or 4d orbitals, such as transition metal oxides. This new linear response DFT + U method can provide a simpler understanding of the electronic structure of Ln2 O3 and enables a quick examination of the electronic structures of lanthanide solids before hybrid functional or GW calculations. © 2015 Wiley Periodicals, Inc.

Calculation of Spectra of Neutrons and Charged Particles Produced in a Target of a Neutron Generator

NASA Astrophysics Data System (ADS)

Gaganov, V. V.

2017-12-01

An algorithm for calculating the spectra of neutrons and associated charged particles produced in the target of a neutron generator is detailed. The products of four nuclear reactions 3H( d, n)4He, 2H( d, n)3He, 2H( d, p)3H, and 3He( d, p)4He are analyzed. The results of calculations are presented in the form of neutron spectra for several emission angles and spectra of associated charged particles emitted at an angle of 180° for a deuteron initial energy of 0.13 MeV.

Experimental validation of a deforming grid 4D dose calculation for PBS proton therapy.

PubMed

Krieger, Miriam; Klimpki, Grischa; Fattori, Giovanni; Hrbacek, Jan; Oxley, David; Safai, Sairos; Weber, Damien C; Lomax, Antony J; Zhang, Ye

2018-03-01

The aim of this study was to verify the temporal accuracy of the estimated dose distribution by a 4D dose calculation (4DDC) in comparison to measurements. A single-field plan (0.6 Gy), optimised for a liver patient case (CTV volume: 403cc), was delivered to a homogeneous PMMA phantom and measured by a high resolution scintillating-CCD system at two water equivalent depths. Various motion scenarios (no motion and motions with amplitude of 10 mm and two periods: 3.7 s and 4.4 s) were simulated using a 4D Quasar phantom and logged by an optical tracking system in real-time. Three motion mitigation approaches (single delivery, 6[Formula: see text] layered and volumetric rescanning) were applied, resulting in 10 individual measurements. 4D dose distributions were retrospectively calculated in water by taking into account the delivery log files (retrospective) containing information on the actually delivered spot positions, fluences, and time stamps. Moreover, in order to evaluate the sensitivity of the 4DDC inputs, the corresponding prospective 4DDCs were performed as a comparison, using the estimated time stamps of the spot delivery and repeated periodical motion patterns. 2D gamma analyses and dose-difference-histograms were used to quantify the agreement between measurements and calculations for all pixels with [Formula: see text]5% of the maximum calculated dose. The results show that a mean gamma score of 99.2% with standard deviation 1.0% can be achieved for 3%/3 mm criteria and all scenarios can reach a score of more than 95%. The average area with more than 5% dose difference was 6.2%. Deviations due to input uncertainties were obvious for single scan deliveries but could be smeared out once rescanning was applied. Thus, the deforming grid 4DDC has been demonstrated to be able to predict the complex patterns of 4D dose distributions for PBS proton therapy with high dosimetric and geometric accuracy, and it can be used as a valid clinical tool for 4D treatment planning, motion mitigation selection, and eventually 4D optimisation applications if the correct temporal information is available.

Experimental validation of a deforming grid 4D dose calculation for PBS proton therapy

NASA Astrophysics Data System (ADS)

Krieger, Miriam; Klimpki, Grischa; Fattori, Giovanni; Hrbacek, Jan; Oxley, David; Safai, Sairos; Weber, Damien C.; Lomax, Antony J.; Zhang, Ye

2018-03-01

The aim of this study was to verify the temporal accuracy of the estimated dose distribution by a 4D dose calculation (4DDC) in comparison to measurements. A single-field plan (0.6 Gy), optimised for a liver patient case (CTV volume: 403cc), was delivered to a homogeneous PMMA phantom and measured by a high resolution scintillating-CCD system at two water equivalent depths. Various motion scenarios (no motion and motions with amplitude of 10 mm and two periods: 3.7 s and 4.4 s) were simulated using a 4D Quasar phantom and logged by an optical tracking system in real-time. Three motion mitigation approaches (single delivery, 6× layered and volumetric rescanning) were applied, resulting in 10 individual measurements. 4D dose distributions were retrospectively calculated in water by taking into account the delivery log files (retrospective) containing information on the actually delivered spot positions, fluences, and time stamps. Moreover, in order to evaluate the sensitivity of the 4DDC inputs, the corresponding prospective 4DDCs were performed as a comparison, using the estimated time stamps of the spot delivery and repeated periodical motion patterns. 2D gamma analyses and dose-difference-histograms were used to quantify the agreement between measurements and calculations for all pixels with > 5% of the maximum calculated dose. The results show that a mean gamma score of 99.2% with standard deviation 1.0% can be achieved for 3%/3 mm criteria and all scenarios can reach a score of more than 95%. The average area with more than 5% dose difference was 6.2%. Deviations due to input uncertainties were obvious for single scan deliveries but could be smeared out once rescanning was applied. Thus, the deforming grid 4DDC has been demonstrated to be able to predict the complex patterns of 4D dose distributions for PBS proton therapy with high dosimetric and geometric accuracy, and it can be used as a valid clinical tool for 4D treatment planning, motion mitigation selection, and eventually 4D optimisation applications if the correct temporal information is available.

Computed potential energy surfaces for chemical reactions

NASA Technical Reports Server (NTRS)

Walch, Stephen P.

1988-01-01

The minimum energy path for the addition of a hydrogen atom to N2 is characterized in CASSCF/CCI calculations using the (4s3p2d1f/3s2p1d) basis set, with additional single point calculations at the stationary points of the potential energy surface using the (5s4p3d2f/4s3p2d) basis set. These calculations represent the most extensive set of ab initio calculations completed to date, yielding a zero point corrected barrier for HN2 dissociation of approx. 8.5 kcal mol/1. The lifetime of the HN2 species is estimated from the calculated geometries and energetics using both conventional Transition State Theory and a method which utilizes an Eckart barrier to compute one dimensional quantum mechanical tunneling effects. It is concluded that the lifetime of the HN2 species is very short, greatly limiting its role in both termolecular recombination reactions and combustion processes.

Molecular Modeling Studies of 11β-Hydroxysteroid Dehydrogenase Type 1 Inhibitors through Receptor-Based 3D-QSAR and Molecular Dynamics Simulations.

PubMed

Qian, Haiyan; Chen, Jiongjiong; Pan, Youlu; Chen, Jianzhong

2016-09-19

11β-Hydroxysteroid dehydrogenase type 1 (11β-HSD1) is a potential target for the treatment of numerous human disorders, such as diabetes, obesity, and metabolic syndrome. In this work, molecular modeling studies combining molecular docking, 3D-QSAR, MESP, MD simulations and free energy calculations were performed on pyridine amides and 1,2,4-triazolopyridines as 11β-HSD1 inhibitors to explore structure-activity relationships and structural requirement for the inhibitory activity. 3D-QSAR models, including CoMFA and CoMSIA, were developed from the conformations obtained by docking strategy. The derived pharmacophoric features were further supported by MESP and Mulliken charge analyses using density functional theory. In addition, MD simulations and free energy calculations were employed to determine the detailed binding process and to compare the binding modes of inhibitors with different bioactivities. The binding free energies calculated by MM/PBSA showed a good correlation with the experimental biological activities. Free energy analyses and per-residue energy decomposition indicated the van der Waals interaction would be the major driving force for the interactions between an inhibitor and 11β-HSD1. These unified results may provide that hydrogen bond interactions with Ser170 and Tyr183 are favorable for enhancing activity. Thr124, Ser170, Tyr177, Tyr183, Val227, and Val231 are the key amino acid residues in the binding pocket. The obtained results are expected to be valuable for the rational design of novel potent 11β-HSD1 inhibitors.

Asymmetric 3d Electronic Structure for Enhanced Oxygen Evolution Catalysis.

PubMed

Liu, Yang; Yin, Shibin; Shen, Pei Kang

2018-06-27

The oxygen evolution reaction (OER) is an essential process for renewable energy, and designing a bifunctional oxygen electrocatalyst with high catalytic performance plays a significant role. In this work, FeS, Ni 3 S 2 , Fe 5 Ni 4 S 8 , and N, O, S-doped meshy carbon base were successfully synthesized. The sample containing Fe 5 Ni 4 S 8 exhibited excellent OER performance. The density functional theory calculations indicate that the partial density of states for 3d electrons (3d-PDOS) of Fe and Ni atoms are changed from monometallic sulfide to bimetallic sulfide at the sulfur vacancy. The asymmetric 3d electronic structure optimizes the 3d-PDOS of Fe and Ni atoms, and leads to an enhanced OER activity. This work provides a new strategy to prepare a low-cost electrocatalyst for oxygen evolution with high-efficiency.

Crystal structures and thermodynamics/kinetics of Zn(II) coordination polymers with helical chains

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

He, Tian; Yue, Ke-Fen, E-mail: ykflyy@nwu.edu.cn; Zhao, Yi-xing

Solvothermal reactions of Zn(II) acetates and four V-shaped carboxylates ligands in the presence of 1,4-Bis(2-methyl-imidazol-1-yl)butane afforded four interesting Zn(II) coordination polymers with helical chains, namely, {[Zn(bib)(atibdc)]·2H_2O}{sub n} (1), {[Zn(bib)(atbip)]·H_2O}{sub n} (2), {[Zn(bib)(2,2′-tda)]}{sub n} (3) and {[Zn(bib)(5-tbipa)]·EtOH}{sub n} (4), (H{sub 2}atibdc=5-amino-2,4,6-triiodoisophthalic acid, H{sub 2}atbip=5-amino-2,4,6-tribromoisophthalic acid, 2,2′-H{sub 2}tad=2,2′-thiodiacetic acid, 5-H{sub 2}tbipa=5-tert-butyl-isophthalic acid). 1 reveals a 3D chiral framework with three kinds of helical chains along a, b and c axis. 2 shows a 2D step-type chiral framework with right-handed helical chains. 3 displays a wavelike 2D layer network possessing alternate left- and right-handed helical chains. 4 presents a four-connected 3D framework withmore » zigzag and meso-helical chains. The different spacers and substituent group of carboxylic acid ligands may lead to the diverse network structures of 1–4. The fluorescent properties of complexes 1−4 were studied. In addition, the thermal decompositions properties of 1–4 were investigated by simultaneous TG/DTG–DSC technique. The apparent activation energy E and the pre-exponential factor (A) of skeleton collapse for the complexes 1–4 are calculated by the integral Kissinger's method and Ozawa–Doyle's method. The activation energy E (E{sub 1}=209.658 kJ·mol{sup −1}, E{sub 2}=250.037 kJ mol{sup −1}, E{sub 3}=225.300 kJ mol{sup −1}, E{sub 4}=186.529 kJ·mol{sup −1}) demonstrates that the reaction rate of the melting decomposition is slow. The thermodynamic parameters (ΔH{sup ‡}, ΔG{sup ‡} and ΔS{sup ‡}) at the peak temperatures of the DTG curves were also calculated. ΔG{sup ‡}>0 indicates that the skeleton collapse is not spontaneous. ΔH{sub d}>0 suggests that the skeleton collapse is endothermic, corresponding to the intense endothermic peak of the DSC curve. The structural stability could be illustrated from the point of thermodynamics and kinetics. - Graphical abstract: Four new zinc coordination architectures constructed from the primary ligand bib, transition metal ions Zn(II) and four V-shaped carboxylate coligands. The different structural evolutions of complexes 1–4 have systematically illustrated that the carboxylate coligands play a critical role in the assemblies of the CPs. Their thermal decompositions properties of 1–4 were investigated by simultaneous TG/DTG–DSC technique. The apparent activation energy E and the pre-exponential factor (A) of skeleton collapse for the complexes 1−4 are calculated by the integral Kissinger’s method and Ozawa–Doyle’s method. The structural stability could be illustrated from the point of thermodynamics and kinetics. Display Omitted.« less

Energies and transition rates in Ge-like ions between In XVIII and Ce XXVII

NASA Astrophysics Data System (ADS)

Chen, Zhan-Bin; Wang, Kai

2017-03-01

The energy levels, wavelengths, oscillator strengths, and radiative electric dipole (E1), magnetic quadrupole (M2) transition probabilities for Ge-like ions (49 ≤ Z ≤ 58) among the lowest 88 fine-structure levels belonging to the ([Ar] 3d10)4s24p2, ([Ar] 3d10)4s24p4d, ([Ar] 3d10)4s4p3, ([Ar] 3d10)4s4p24d, ([Ar] 3d10)4s24d2, and ([Ar] 3d10)4p4 configurations are calculated using the fully relativistic multiconfiguration Dirac-Fock (MCDF) approach including the correlations within the n = 7 complex, Breit interaction (BI) and quantum electrodynamics (QED) effects. For comparison, an independent calculation using the many-body perturbation theory (MBPT) method is also carried out to confirm the present energy levels accuracy, taking Xe XXIII as an example. The present results are compared with available experimental and theoretical results and good agreement is obtained. These accurate theoretical data are useful for controlled thermonuclear fusion research, plasma physics, and astrophysical applications.

FTIR, FT-Raman, FT-NMR, UV-visible and quantum chemical investigations of 2-amino-4-methylbenzothiazole.

PubMed

Arjunan, V; Sakiladevi, S; Rani, T; Mythili, C V; Mohan, S

2012-03-01

The FT-IR (4000-400 cm(-1)) and FT-Raman (4000-100 cm(-1)) spectral measurements and complete assignments of the observed spectra of 2-amino-4-methylbenzothiazole (2A4MBT) have been proposed. Ab initio and DFT calculations have been performed and the structural parameters of the compound were determined from the optimised geometry with 6-31G(d,p), 6-311++G(d,p) and cc-pVDZ basis sets and giving energies, harmonic vibrational frequencies, depolarisation ratios, IR intensities and Raman activities. (1)H and (13)C NMR spectra were recorded and (1)H and (13)C nuclear magnetic resonance chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method. UV-visible spectrum of the compound was also recorded and the electronic properties, such as HOMO, LUMO and band gap energies were measured by time-dependent DFT (TD-DFT) approach. The geometric parameters, energies, harmonic vibrational frequencies, IR intensities, Raman activities chemical shifts and absorption wavelengths were compared with the available experimental data of the molecule. The influences of methyl and amino groups on the skeletal modes and on the proton chemical shifts have been investigated. Copyright © 2011 Elsevier B.V. All rights reserved.

Kinetic study of cytochrome P450 3A4 activity on warfarin by capillary electrophoresis with fluorescence detection.

PubMed

Zhang, Jie; Ha, Pham Thi Thanh; Lou, Yijia; Hoogmartens, Jos a; Van Schepdael, Ann

2005-08-05

The use of capillary electrophoresis (CE) for the determination of cytochrome P450 3A4 (CYP3A4) activity with R-warfarin as a substrate was investigated. CYP3A4 activity was determined by the quantitation of the product, 10-hydroxywarfarin, based on separation by CE. The separation conditions were as follows: capillary, 80.5 cm (75 microm i.d., 60 cm effective length); 50 mM sodium phosphate buffer (pH 6.5); 23 kV (90 microA) applied voltage; fluorescence detection, excitation wavelength, 310 nm, emission wavelength, 418 nm; capillary temperature, 37 degrees C. With the developed CYP3A4 activity assay and the Lineweaver-Burk equation, the Michaelis-Menten parameters Km and Vmax for formation of 10-hydroxywarfarin from R-warfarin in the presence of CYP3A4 were calculated to be 166 +/- 12 microM and 713 +/- 14 pmol/min/nmol (or 91.4 pmol/min/mg) CYP3A4, respectively.

The role of d-allo-isoleucine in the deposition of the anti-Leishmania peptide bombinin H4 as revealed by 31P solid-state NMR, VCD spectroscopy, and MD simulation.

PubMed

Mijiddorj, Batsaikhan; Kaneda, Shiho; Sato, Hisako; Kitahashi, Yuki; Javkhlantugs, Namsrai; Naito, Akira; Ueda, Kazuyoshi; Kawamura, Izuru

2018-07-01

Bombinin H4 is an antimicrobial peptide that was isolated from the toad Bombina variegata. Bombinin H family peptides are active against gram-positive, gram-negative bacteria, and fungi as well as the parasite Leishmania. Among them, bombinin H4 (H4), which contains d-allo-isoleucine (d-allo-Ile) as the second residue in its sequence, is the most active, and its l-isomer is bombinin H2 (H2). H4 has a significantly lower LC50 than H2 against Leishmania. However, the atomic-level mechanism of the membrane interaction and higher activity of H4 has not been clarified. In this work, we investigated the behavior of the conformations and interactions of H2 and H4 with the Leishmania membrane using 31 P solid-state nuclear magnetic resonance (NMR), vibrational circular dichroism (VCD) spectroscopy, and molecular dynamics (MD) simulations. The generation of isotropic 31 P NMR signals depending on the peptide concentration indicated the abilities of H2 and H4 to exert antimicrobial activity via membrane disruption. The VCD experiment and density functional theory calculation confirmed the different stability and conformations of the N-termini of H2 and H4. MD simulations revealed that the N-terminus of H4 is more stable than that of H2 in the membrane, in line with the VCD experiment data. VCD and MD analyses demonstrated that the first l-Ile and second d-allo-Ile of H4 tend to take a cis conformation. These residues function as an anchor and facilitate the easy winding of the helical conformation of H4 in the membrane. It may assist to quickly reach to the threshold concentration of H4 on the Leishmania membrane. This article is part of a Special Issue entitled: d-Amino acids: biology in the mirror, edited by Dr. Loredano Pollegioni, Dr. Jean-Pierre Mothet and Dr. Molla Gianluca. Copyright © 2018 Elsevier B.V. All rights reserved.

Design, synthesis and antimalarial screening of some hybrid 4-aminoquinoline-triazine derivatives against pf-DHFR-TS.

PubMed

Sahu, Supriya; Ghosh, Surajit Kumar; Kalita, Junmoni; Dutta, Mayurakhi; Bhat, Hans Raj

2016-04-01

Existing antifolate antimalarial drugs have shown resistance due to the mutations at some amino acid positions of Plasmodium falciparum DHFR-TS. In the present study, to overcome this resistance, a new series of hybrid 4-aminoquinoline-triazine derivatives were designed and docked into the active site of Pf-DHFR-TS (PDB i.d. 1J3K) using validated CDOCKER protocol. Binding energy was calculated by applying CHARMm forcefield. Binding energy and the pattern of interaction of the docked compounds were analysed. Fifteen compounds were selected for synthesis based on their binding energy values and docking poses. Synthesized compounds were characterised by FTIR, (1)H NMR, (13)C NMR, mass spectroscopy and were screened for antimalarial activity against 3D7 strain of Plasmodium falciparum. Copyright © 2016 Elsevier Inc. All rights reserved.

Investigation of the dynamic stereochemistry of dimesityl-2,4,6-trimethoxyphenylmethane by complete lineshape analysis and 2D EXSY NMR spectroscopy.

PubMed

Denkova, Pavletta; Vassilev, Nikolay; Van Lokeren, Luk; Willem, Rudolph

2008-04-01

The static and dynamic stereochemistry of dimesityl-2,4,6-trimethoxyphenylmethane in solution was investigated by lineshape analysis of 1D NMR spectra and cross-peak amplitude processing in 2D EXSY spectra, recorded at variable temperatures. Previous studies on this propeller-shaped chiral compound show that the stereomer threshold interconversion is associated with helicity reversal and occurs through [1,2]- and [1,3]-two ring flips of one mesityl and the 2,4,6-trimethoxyphenyl rings. In the present study, the experimental rate constants of the [1,2]- and [1,3]-two ring flips, which are identical, were determined at various temperatures by combining quantitative 2D EXSY spectra processing and complete lineshape analysis (CLSA) of 1D NMR spectra. The latter were subjected to reference deconvolution and linear prediction in order to eliminate the lineshape distortions due to magnetic field inhomogeneity. The activation parameters of these ring flips were determined by an Eyring equation analysis of the temperature dependence of the rate constant. The experimentally determined activation enthalpy and entropy for the two-ring flips, and those obtained from theoretical ab initio calculations at different levels of theory and basis sets, were found to be in good agreement. Copyright (c) 2008 John Wiley & Sons, Ltd.

Experimental results and model calculations of excitation functions relevant to the production of specific radioisotopes for metabolic radiotherapy and for pet

NASA Astrophysics Data System (ADS)

Menapace, E.; Birattari, C.; Bonardi, M. L.; Groppi, F.

2004-10-01

First results are given from the comparison of experimental values and model calculations on accelerator-produced high specific activity radionuclides in no-carrier-added (NCA) form. The relevant radioisotopes are: 64Cu, produced by natZn(d, αxn) and natZn(d,2p) reactions, for simultaneous positron/negatron metabolic radiotherapy and PET imaging; 66Ga high-energy positron emitter (4.2 MeV), produced by natZn(d, xn) reactions, for metabolic radiotherapy and for PET; 186gRe, produced by 186W(p,n) and 186W(d,2n) reactions, for negatron (1.1 MeV) metabolic radiotherapy; 211At/ 211Po, produced by 209Bi( α,2n) reaction (with spike of gamma emitter 210At produced by 209Bi( α,3n) reaction) and 225Ac/ 213Bi/ 213Po, produced by 226Ra(p,2n) reaction, both for high-LET radiotherapy.

Structure-activity relationship of the ionic cocrystal: 5-amino-2-naphthalene sulfonate·ammonium ions for pharmaceutical applications

NASA Astrophysics Data System (ADS)

Sangeetha, M.; Mathammal, R.

2018-02-01

The ionic cocrystals of 5-amino-2-naphthalene sulfonate · ammonium ions (ANSA-ṡNH4+) were grown under slow evaporation method and examined in detail for pharmaceutical applications. The crystal structure and intermolecular interactions were studied from the single X-ray diffraction analysis and the Hirshfeld surfaces. The 2D fingerprint plots displayed the inter-contacts possible in the ionic crystal. Computational DFT method was established to determine the structural, physical and chemical properties. The molecular geometries obtained from the X-ray studies were compared with the optimized geometrical parameters calculated using DFT/6-31 + G(d,p) method. The band gap energy calculated from the UV-Visible spectral analysis and the HOMO-LUMO energy gap are compared. The theoretical UV-Visible calculations helped in determining the type of electronic transition taking place in the title molecule. The maximum absorption bands and transitions involved in the molecule represented the drug reaction possible. Non-linear optical properties were characterized from SHG efficiency measurements experimentally and the NLO parameters are also calculated from the optimized structure. The reactive sites within the molecule are detailed from the MEP surface maps. The molecular docking studies evident the structure-activity of the ionic cocrystal for anti-cancer drug property.

Spectroscopic investigations (FT-IR, UV, 1H and 13C NMR) and DFT/TD-DFT calculations of potential analgesic drug 2-[2-(dimethylamino)ethyl]-6-methoxy-4-(pyridin-2-yl)-1(2H)-phthalazinone

NASA Astrophysics Data System (ADS)

Sroczyński, Dariusz; Malinowski, Zbigniew

2017-12-01

The theoretical molecular geometry and the IR, UV, 1H and 13C NMR spectroscopic properties of 2-[2-(dimethylamino)ethyl]-6-methoxy-4-(pyridin-2-yl)-1(2H)-phthalazinone with the previously demonstrated in vivo analgesic activity were characterized. The conformational analysis, performed using the molecular mechanics method with the General AMBER Force Field (GAFF) and the Density Functional Theory (DFT) approach with the B3LYP hybrid functional and the 6-31 + g(d) basis sets, allowed to determine the most stable rotamer. The theoretical molecular geometry of this conformer was then calculated at the B3LYP/6-311++g(d,p) level of theory, and its phthalazinone core was compared with the experimental geometry of 1(2H)-phthalazinone. The calculated vibrational frequencies and the potential energy distribution enabled to assign the theoretical vibrational modes to the experimental FT-IR bands. The UV spectrum calculated with the Time-Dependent Density Functional Theory (TD-DFT) method in methanol identified the main electronic transitions and their character. 1H and 13C NMR chemical shifts simulated by the Gauge-Independent Atomic Orbital (GIAO) method in chloroform confirmed the previous assignment of the experimental resonance signals. The stability of the molecule was considered taking into account the hyperconjugation and electron density delocalization effects evaluated by the Natural Bond Orbital (NBO) method. The calculated spatial distribution of molecular electrostatic potential made possible to estimate the regions with nucleophilic and electrophilic properties. The results of the potentiodynamic polarization measurements were also indicated the corrosion inhibition activity of the title compound on 100Cr6 bearing steel in 1 mol dm-3 HCl solution.

Density functional theory and Ab initio studies of vibrational spectroscopic (FT-IR, FT-Raman and UV) first order hyperpolarizabilities, NBO, HOMO-LUMO and TD-DFT analysis of the 1,2-Dihydropyrazolo (4,3-E) Pyrimidin-4-one

NASA Astrophysics Data System (ADS)

Ramachandran, G.; Muthu, S.; Uma Maheswari, J.

2013-02-01

Fourier transform Raman and Fourier transform infrared spectra of 1,2-Dihydropyrazolo (4,3-E) Pyrimidin-4-one were recorded in the regions 3500-100 cm-1 and 4000-400 cm-1 respectively in the solid phase. 1,2-Dihydropyrazolo (4, 3-E) Pyrimidin-4-one is used to treat hyperuricemia and its complication including chronic gout. The equilibrium geometry harmonic vibrational frequencies, infrared intensities and Raman intensities were calculated by Hartee Fock and density functional B3LYP methods with 6-31G (d, p) basis set, using Gaussian 03W program package on a Pentium IV/1.6 GHz personal computer. The thermodynamic functions of the title compound were also performed at the above methods and basis set. A detailed interpretation of the infrared and Raman spectra of 1,2-Dihydropyrazolo (4,3-E) Pyrimidin-4-one is reported. Stability of the molecule arising from hyper conjugative interactions, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. UV-vis of the compound was recorded. The calculated HOMO and LUMO energies show that chemical activity of the molecule. The first order hyperpolarizability (β) of this novel molecular system and related properties of 1,2-Dihydropyrazolo (4,3-E) Pyrimidin-4-one are calculated using HF/6-31G (d, p) method on the finite field approach. The experimental spectra also coincide satisfactorily with those of theoretically constructed spectra.

Tautomerization, molecular structure, transition state structure, and vibrational spectra of 2-aminopyridines: a combined computational and experimental study.

PubMed

Al-Otaibi, Jamelah S

2015-01-01

2-amino pyridine derivatives have attracted considerable interest because they are useful precursors for the synthesis of a variety of heterocyclic compounds possessing a medicinal value. In this work we aim to study both structural and electronic as well as high quality vibrational spectra for 2-amino-3-methylpyridine (2A3MP) and 2-amino-4-methylpyridine (2A4MP). Møller-Plesset perturbation theory (MP2/6-31G(d) and MP2/6-31++G(d,p) methods were used to investigate the structure and vibrational analysis of (2A3MP) and (2A4MP). Tautomerization of 2A4MP was investigated by Density Functional Theory (DFT/B3LYP) method in the gas phase. For the first time, all tautomers including NH → NH conversions as well as those usually omitted, NH → CH and CH → CH, were considered. The canonical structure (2A4MP1) is the most stable tautomer. It is 13.60 kcal/mole more stable than the next (2A4MP2). Transition state structures of pyramidal N inversion and proton transfer were computed at B3LYP/6-311++G(d,p). Barrier to transition state of hydrogen proton transfer is calculated as 44.81 kcal/mol. Transition state activation energy of pyramidal inversion at amino N is found to be 0.41 kcal/mol using the above method. Bond order and natural atomic charges were also calculated at the same level. The raman and FT-IR spectra of (2A3MP) and (2A4MP) were measured (4000-400 cm(-1)). The optimized molecular geometries, frequencies and vibrational bands intensity were calculated at ab initio (MP2) and DFT(B3LYP) levels of theory with 6-31G(d), 6-31++G(d,p) and 6-311++G(d,p) basis sets. The vibrational frequencies were compared with experimentally measured FT-IR and FT-Raman spectra. Reconsidering the vibrational analysis of (2A3MP) and (2A4MP) with more accurate FT-IR machine and highly accurate animation programs result in new improved vibrational assignments. Sophisticated quantum mechanics methods enable studying the transition state structure for different chemical systems.

Synthesis, characterization, quantum chemical calculations and evaluation of antioxidant properties of 1,3,4-thiadiazole derivatives including 2- and 3-methoxy cinnamic acids

NASA Astrophysics Data System (ADS)

Gür, Mahmut; Muğlu, Halit; Çavuş, M. Serdar; Güder, Aytaç; Sayıner, Hakan S.; Kandemirli, Fatma

2017-04-01

A series of 1,3,4-thiadiazole derivatives including 2- and 3-methoxy cinnamic acids were synthesized, and their structures were elucidated by the UV, IR, 1H NMR, 13C NMR spectroscopies and elemental analysis. The UV and IR calculations of the molecules were performed by using B3LYP, HF and MP2 methods with selected 6-311++G(2d,2p), 6-311++G(3df,3pd) and cc-pvtz basis sets. Dipole moment, polarizability, chemical hardness/softness and electronegativity were also calculated and analyzed. Experimental FT-IR spectra and UV-Vis spectrum of the compounds were compared with theoretical data. Furthermore, antioxidant activities of the compounds were practised via different test methods such as 2,2-diphenyl-1-picryl-hydrazyl (DPPHrad), N,N-dimethyl-p-phenylenediamine (DMPDrad +), and 2,2‧-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTSrad +) scavenging activity assays. When compared with standards (BHA-Butylated hydroxyanisole, RUT-Rutin, and TRO-Trolox), it was observed that especially XIII and XIV which include methoxy groups at the o- and m-positions, respectively, had effective activities.

Calculations of the thermal and fast neutron fluxes in the Syrian miniature neutron source reactor using the MCNP-4C code.

PubMed

Khattab, K; Sulieman, I

2009-04-01

The MCNP-4C code, based on the probabilistic approach, was used to model the 3D configuration of the core of the Syrian miniature neutron source reactor (MNSR). The continuous energy neutron cross sections from the ENDF/B-VI library were used to calculate the thermal and fast neutron fluxes in the inner and outer irradiation sites of MNSR. The thermal fluxes in the MNSR inner irradiation sites were also measured experimentally by the multiple foil activation method ((197)Au (n, gamma) (198)Au and (59)Co (n, gamma) (60)Co). The foils were irradiated simultaneously in each of the five MNSR inner irradiation sites to measure the thermal neutron flux and the epithermal index in each site. The calculated and measured results agree well.

Natural bond orbital analysis, electronic structure and vibrational spectral analysis of N-(4-hydroxyl phenyl) acetamide: A density functional theory

NASA Astrophysics Data System (ADS)

Govindasamy, P.; Gunasekaran, S.; Ramkumaar, G. R.

2014-09-01

The Fourier transform infrared (FT-IR) and FT-Raman spectra of N-(4-hydroxy phenyl) acetamide (N4HPA) of painkiller agent were recorded in the region 4000-450 cm-1 and 4000-50 cm-1 respectively. Density functional theory (DFT) has been used to calculate the optimized geometrical parameter, atomic charges, and vibrational wavenumbers and intensity of the vibrational bands. The computed vibrational wave numbers were compared with the FT-IR and FT-Raman experimental data. The computational calculations at DFT/B3LYP level with 6-31G(d,p), 6-31++G(d,p), 6-311G(d,p) and 6-311++G(d,p) basis sets. The complete vibrational assignments were performed on the basis of the potential energy distribution (PED) of the vibrational modes calculated using Vibrational energy distribution analysis (VEDA 4) program. The oscillator’s strength calculated by TD-DFT and N4HPA is approach complement with the experimental findings. The NMR chemical shifts 13C and 1H were recorded and calculated using the gauge independent atomic orbital (GIAO) method. The molecular electrostatic potential (MESP) and electron density surfaces of the molecule were constructed. The Natural charges and intermolecular contacts have been interpreted using Natural Bond orbital (NBO) analysis the HOMO-LUMO energy gap has been calculated. The thermodynamic properties like entropy, heat capacity and zero vibrational energy have been calculated.

Natural bond orbital analysis, electronic structure and vibrational spectral analysis of N-(4-hydroxyl phenyl) acetamide: a density functional theory.

PubMed

Govindasamy, P; Gunasekaran, S; Ramkumaar, G R

2014-09-15

The Fourier transform infrared (FT-IR) and FT-Raman spectra of N-(4-hydroxy phenyl) acetamide (N4HPA) of painkiller agent were recorded in the region 4000-450 cm(-1) and 4000-50 cm(-1) respectively. Density functional theory (DFT) has been used to calculate the optimized geometrical parameter, atomic charges, and vibrational wavenumbers and intensity of the vibrational bands. The computed vibrational wave numbers were compared with the FT-IR and FT-Raman experimental data. The computational calculations at DFT/B3LYP level with 6-31G(d,p), 6-31++G(d,p), 6-311G(d,p) and 6-311++G(d,p) basis sets. The complete vibrational assignments were performed on the basis of the potential energy distribution (PED) of the vibrational modes calculated using Vibrational energy distribution analysis (VEDA 4) program. The oscillator's strength calculated by TD-DFT and N4HPA is approach complement with the experimental findings. The NMR chemical shifts 13C and 1H were recorded and calculated using the gauge independent atomic orbital (GIAO) method. The molecular electrostatic potential (MESP) and electron density surfaces of the molecule were constructed. The Natural charges and intermolecular contacts have been interpreted using Natural Bond orbital (NBO) analysis the HOMO-LUMO energy gap has been calculated. The thermodynamic properties like entropy, heat capacity and zero vibrational energy have been calculated. Copyright © 2014 Elsevier B.V. All rights reserved.

Molecular-orbital models for the catalytic activity and selectivity of coordinatively unsaturated platinum surfaces and complexes

NASA Astrophysics Data System (ADS)

Balazs, A. C.; Johnson, K. H.

1982-01-01

Electronic structures have been calculated for 5-, 6-, and 10-atom Pt clusters, as well as for a Pt(PH 3) 4 coordination complex, using the self-consistent-field X-alpha scattered-wave (SCF-Xα-SW) molecular-orbital technique. The 10-atom cluster models the local geometry of a flat, unreconstructed Pt(100) surface, while the 5- and 6-atom clusters show features of a stepped Pt surface. Pt(PH 3) 4 resembles the chemically similar homogeneous catalyst Pt(PPh 3) 4. Common to all these coordinatively unsaturated complexes are orbitals lying near or coinciding with the highest occupied molecular orbital ("Fermi level") which show pronounced d lobes pointing directly into the vacuum. Under the hypothesis that these molecular orbitals are mainly responsible for the chemical activities of the above species, one can account for the relative similarities and differences in catalytic activity and selectivity displayed by unreconstructed Pt(100) surfaces, stepped Pt surfaces or particles, and isolated Pt(PPh 3) 4 coordination complexes. The relevance of these findings to catalyst-support interactions is also discussed. Finally, relativistic corrections to the electronic structures are calculated and their implications on catalytic properties discussed.

Activation of CH4 by Th(+) as studied by guided ion beam mass spectrometry and quantum chemistry.

PubMed

Cox, Richard M; Armentrout, P B; de Jong, Wibe A

2015-04-06

The reaction of atomic thorium cations with CH4 (CD4) and the collision-induced dissociation (CID) of ThCH4(+) with Xe are studied using guided ion beam tandem mass spectrometry. In the methane reactions at low energies, ThCH2(+) (ThCD2(+)) is the only product; however, the energy dependence of the cross-section is inconsistent with a barrierless exothermic reaction as previously assumed on the basis of ion cyclotron resonance mass spectrometry results. The dominant product at higher energies is ThH(+) (ThD(+)), with ThCH3(+) (ThCD3(+)) having a similar threshold energy. The latter product subsequently decomposes at still higher energies to ThCH(+) (ThCD(+)). CID of ThCH4(+) yields atomic Th(+) as the exclusive product. The cross-sections of all product ions are modeled to provide 0 K bond dissociation energies (in eV) of D0(Th(+)-H) ≥ 2.25 ± 0.18, D0(Th(+)-CH) = 6.19 ± 0.16, D0(Th(+)-CH2) ≥ 4.54 ± 0.09, D0(Th(+)-CH3) = 2.60 ± 0.30, and D0(Th(+)-CH4) = 0.47 ± 0.05. Quantum chemical calculations at several levels of theory are used to explore the potential energy surfaces for activation of methane by Th(+), and the effects of spin-orbit coupling are carefully considered. When spin-orbit coupling is explicitly considered, a barrier for C-H bond activation that is consistent with the threshold measured for ThCH2(+) formation (0.17 ± 0.02 eV) is found at all levels of theory, whereas this barrier is observed only at the BHLYP and CCSD(T) levels otherwise. The observation that the CID of the ThCH4(+) complex produces Th(+) as the only product with a threshold of 0.47 eV indicates that this species has a Th(+)(CH4) structure, which is also consistent with a barrier for C-H bond activation. This barrier is thought to exist as a result of the mixed ((4)F,(2)D) electronic character of the Th(+) J = (3)/2 ground level combined with extensive spin-orbit effects.

Enantioselectivity of debrisoquine 4-hydroxylation in Brazilian Caucasian hypertensive patients phenotyped as extensive metabolizers.

PubMed

Cerqueira, P M; Mateus, F H; Cesarino, E J; Bonato, P S; Lanchote, V L

2000-12-01

Debrisoquine (D), an antihypertensive drug metabolized to 4-hydroxydebrisoquine (4-OHD) by CYP2D6, is commonly used as an in vivo probe of CYP2D6 activity and can be used to phenotype individuals as either extensive (EMs) or poor metabolizers (PMs) of such drugs as beta-adrenergic blockers, tricyclic antidepressants, and class 1C antiarrhythmics. This report describes reversed-phase HPLC systems by which D and 4-OHD or S-(+) and R-(-)-4-OHD in urine are more selectively quantified without the need for derivatization techniques. We also studied the urinary excretion of R-(-)- and S-(+)-4-hydroxydebrisoquine in EM hypertensive patients in order to determine weather 4-OHD formation exhibits enantioselectivity. Twelve patients with mild to severe essential hypertension were admitted to the study. They received a single tablet of Declinax containing 10 mg debrisoquine sulfate. All the urine excreted during the following 8 h was collected. The debrisoquine metabolic ratio (DMR) was calculated as % of dose excreted as D/% of dose excreted as 4-OHD and the debrisoquine recovery ratio (DRR) was calculated as % of dose excreted as 4-OHD/% of dose excreted as D+4-OHD. Debrisoquine and its metabolite were determined in urine by HPLC using a reversed-phase Select B LiChrospher column, a mobile phase of 0.25 N acetate buffer, pH 5-acetonitrile (9:1, v/v) and a fluorescence detector. The limit of quantitation was determined to be 25.0 ng/ml for D and 18.75 ng/ml for 4-OHD. Intra- and inter-day relative standard deviations (RSDs) were less than 10%. All hypertensive patients studied showed a DMR of less than 12.6 or a DRR higher than 0.12 and were classified as EMs. Direct enantioselective separation on chiral stationary phase involved resolution of S-(+)-4-OHD and R-(-)-4-OHD on a Chiralcel OD-R column with a mobile phase of 0.125 N sodium perchlorate, pH 5-acetonitrile-methanol (85:12:3, v/v/v). The quantitation limit of each enantiomer was 3.75 ng/ml of urine. Intra- and inter-day RSDs were less than 10% for each enantiomer. A high degree of enantioselectivity in the 4-hydroxylation of D favouring the S-(+) enantiomer was observed, resulting in R-(-)-4-OHD not detected in the urine of the EM hypertensive patients studied.

Atomic-scale distortion of optically activated Sm dopants identified with site-selective X-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Ishii, Masashi; Crowe, Iain F.; Halsall, Matthew P.; Hamilton, Bruce; Hu, Yongfeng; Sham, Tsun-Kong; Harako, Susumu; Zhao, Xin-Wei; Komuro, Shuji

2013-10-01

The local structure of luminescent Sm dopants was investigated using an X-ray absorption fine-structure technique with X-ray-excited optical luminescence. Because this technique evaluates X-ray absorption from luminescence, only optically active sites are analyzed. The Sm L3 near-edge spectrum contains split 5d states and a shake-up transition that are specific to luminescent Sm. Theoretical calculations using cluster models identified an atomic-scale distortion that can reproduce the split 5d states. The model with C4v local symmetry and compressive bond length of Sm-O of a six-fold oxygen (SmO6) cluster is most consistent with the experimental results.

Reanalysis of tritium production in a sphere of /sup 6/LiD irradiated by 14-MeV neutrons

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

Fawcett, L.R. Jr.

1985-08-01

Tritium production and activation of radiochemical detector foils in a sphere of /sup 6/LiD irradiated by a central source of 14-MeV neutrons has been reanalyzed. The /sup 6/LiD sphere consisted of 10 solid hemispherical nested shells with ampules of /sup 6/LiH, /sup 7/LiH, and activation foils located 2.2, 5, 7.7, 12.6, 20, and 30 cm from the center. The Los Alamos Monte Carlo Neutron Photon Transport Code (MCNP) was used to calculate neutron transport through the /sup 6/LiD, tritium production in the ampules, and foil activation. The MCNP input model was three-dimensional and employed ENDF/B-V cross sections for transport, tritiummore » production, and (where available) foil activation. The reanalyzed experimentally observed-to-calculated values of tritium production were 1.053 +- 2.1% in /sup 6/LiH and 0.999 +- 2.1% in /sup 7/LiH. The recalculated foil activation observed-to-calculated ratios were not generally improved over those reported in the original analysis.« less

Graphene for batteries, supercapacitors and beyond

NASA Astrophysics Data System (ADS)

El-Kady, Maher F.; Shao, Yuanlong; Kaner, Richard B.

2016-07-01

Graphene has recently enabled the dramatic improvement of portable electronics and electric vehicles by providing better means for storing electricity. In this Review, we discuss the current status of graphene in energy storage and highlight ongoing research activities, with specific emphasis placed on the processing of graphene into electrodes, which is an essential step in the production of devices. We calculate the maximum energy density of graphene supercapacitors and outline ways for future improvements. We also discuss the synthesis and assembly of graphene into macrostructures, ranging from 0D quantum dots, 1D wires, 2D sheets and 3D frameworks, to potentially 4D self-folding materials that allow the design of batteries and supercapacitors with many new features that do not exist in current technology.

Analysis of the 3d(sup 6)4s((sup 6)D)4f-5g supermultiplet of Fe I in laboratory and solar infrared spectra

NASA Technical Reports Server (NTRS)

Johansson, S.; Nave, G.; Geller, M.; Sauval, A. J.; Grevesse, N.; Schoenfeld, W. G.; Change, E. S.; Farmer, C. B.

1994-01-01

The combined laboratory and solar analysis of the highly excited subconfigurations 3d(sup 6)4s((sup 6)D)4f and 3d(sup 6)4s((sup 6)D)5g of Fe I has allowed us to classify 87 lines of the 4f-5g supermultiplet in the spectral region 2545-2585 per cm. The level structure of these JK-coupled configurations is predicted by semiempirical calculations and the quardrupolic approximation. Semiempirical gf-values have been calculated and are compared to gf-values derived from the solar spectrum. The solar analysis has shown that these lines, which should be much less sensitive than lower excitation lines to departures from Local Thermal Equilibrium (LTE) and to temperature uncertanties, lead to a solar abundance of iron which is consistent with the meteoritic value (A(sub Fe) = 7.51).

Analysis of the track- and dose-averaged LET and LET spectra in proton therapy using the GEANT4 Monte Carlo code

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

Guan, Fada; Peeler, Christopher; Taleei, Reza

Purpose: The motivation of this study was to find and eliminate the cause of errors in dose-averaged linear energy transfer (LET) calculations from therapeutic protons in small targets, such as biological cell layers, calculated using the GEANT 4 Monte Carlo code. Furthermore, the purpose was also to provide a recommendation to select an appropriate LET quantity from GEANT 4 simulations to correlate with biological effectiveness of therapeutic protons. Methods: The authors developed a particle tracking step based strategy to calculate the average LET quantities (track-averaged LET, LET{sub t} and dose-averaged LET, LET{sub d}) using GEANT 4 for different tracking stepmore » size limits. A step size limit refers to the maximally allowable tracking step length. The authors investigated how the tracking step size limit influenced the calculated LET{sub t} and LET{sub d} of protons with six different step limits ranging from 1 to 500 μm in a water phantom irradiated by a 79.7-MeV clinical proton beam. In addition, the authors analyzed the detailed stochastic energy deposition information including fluence spectra and dose spectra of the energy-deposition-per-step of protons. As a reference, the authors also calculated the averaged LET and analyzed the LET spectra combining the Monte Carlo method and the deterministic method. Relative biological effectiveness (RBE) calculations were performed to illustrate the impact of different LET calculation methods on the RBE-weighted dose. Results: Simulation results showed that the step limit effect was small for LET{sub t} but significant for LET{sub d}. This resulted from differences in the energy-deposition-per-step between the fluence spectra and dose spectra at different depths in the phantom. Using the Monte Carlo particle tracking method in GEANT 4 can result in incorrect LET{sub d} calculation results in the dose plateau region for small step limits. The erroneous LET{sub d} results can be attributed to the algorithm to determine fluctuations in energy deposition along the tracking step in GEANT 4. The incorrect LET{sub d} values lead to substantial differences in the calculated RBE. Conclusions: When the GEANT 4 particle tracking method is used to calculate the average LET values within targets with a small step limit, such as smaller than 500 μm, the authors recommend the use of LET{sub t} in the dose plateau region and LET{sub d} around the Bragg peak. For a large step limit, i.e., 500 μm, LET{sub d} is recommended along the whole Bragg curve. The transition point depends on beam parameters and can be found by determining the location where the gradient of the ratio of LET{sub d} and LET{sub t} becomes positive.« less

Development of a four-dimensional Monte Carlo dose calculation system for real-time tumor-tracking irradiation with a gimbaled X-ray head.

PubMed

Ishihara, Yoshitomo; Nakamura, Mitsuhiro; Miyabe, Yuki; Mukumoto, Nobutaka; Matsuo, Yukinori; Sawada, Akira; Kokubo, Masaki; Mizowaki, Takashi; Hiraoka, Masahiro

2017-03-01

To develop a four-dimensional (4D) dose calculation system for real-time tumor tracking (RTTT) irradiation by the Vero4DRT. First, a 6-MV photon beam delivered by the Vero4DRT was simulated using EGSnrc. A moving phantom position was directly measured by a laser displacement gauge. The pan and tilt angles, monitor units, and the indexing time indicating the phantom position were also extracted from a log file. Next, phase space data at any angle were created from both the log file and particle data under the dynamic multileaf collimator. Irradiation both with and without RTTT, with the phantom moving, were simulated using several treatment field sizes. Each was compared with the corresponding measurement using films. Finally, dose calculation for each computed tomography dataset of 10 respiratory phases with the X-ray head rotated was performed to simulate the RTTT irradiation (4D plan) for lung, liver, and pancreatic cancer patients. Dose-volume histograms of the 4D plan were compared with those calculated on the single reference respiratory phase without the gimbal rotation [three-dimensional (3D) plan]. Differences between the simulated and measured doses were less than 3% for RTTT irradiation in most areas, except the high-dose gradient. For clinical cases, the target coverage in 4D plans was almost identical to that of the 3D plans. However, the doses to organs at risk in the 4D plans varied at intermediate- and low-dose levels. Our proposed system has acceptable accuracy for RTTT irradiation in the Vero4DRT and is capable of simulating clinical RTTT plans. Copyright © 2017 Associazione Italiana di Fisica Medica. Published by Elsevier Ltd. All rights reserved.

3 D Co3 (PO4 )2 -Reduced Graphene Oxide Flowers for Photocatalytic Water Splitting: A Type II Staggered Heterojunction System.

PubMed

Samal, Alaka; Swain, Smrutirekha; Satpati, Biswarup; Das, Dipti Prakasini; Mishra, Barada Kanta

2016-11-23

The design, synthesis, and photoelectrochemical characterization of Co 3 (PO 4 ) 2 , a hydrogen evolving catalyst modified with reduced graphene oxide (RGO), is reported. The 3 D flowerlike Co 3 (PO 4 ) 2 heterojunction system, consisting of 3 D flowerlike Co 3 (PO 4 ) 2 and RGO sheets, was synthesized by a one-pot in situ photoassisted method under visible-light irradiation, which was achieved without the addition of surfactant or a structure-directing reagent. For the first time, Co 3 (PO 4 ) 2 is demonstrated to act as a hydrogen evolving catalyst rather than being used as an oxygen evolving photoanode. In particular, 3 D flowerlike Co 3 (PO 4 ) 2 anchored to RGO nanosheets is shown to possess dramatically improved photocatalytic activity. This enhanced photoactivity is mainly due to the staggered type II heterojunction system, in which photoinduced electrons from 3 D flowerlike Co 3 (PO 4 ) 2 transfer to the RGO sheets and result in decreased charge recombination, as evidenced by photoluminescence spectroscopy. The band gap of Co 3 (PO 4 ) 2 was calculated to be 2.35 eV by the Kubelka-Munk method. Again, the Co 3 (PO 4 ) 2 semiconductor displays n-type behavior, as observed from Mott-Schottky measurements. These RGO-Co 3 (PO 4 ) 2 conjugates are active in the visible range of solar light for water splitting and textile dye degradation, and can be used towards the development of greener and cheaper photocatalysts by exploiting solar light. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spectrophotometric, voltammetric and cytotoxicity studies of 2-hydroxy-5-methoxyacetophenone thiosemicarbazone and its N(4)-substituted derivatives: A combined experimental-computational study

NASA Astrophysics Data System (ADS)

Akgemci, Emine Guler; Saf, Ahmet Ozgur; Tasdemir, Halil Ugur; Türkkan, Ercan; Bingol, Haluk; Turan, Suna Ozbas; Akkiprik, Mustafa

2015-02-01

In this study, 2-hydroxy-5-methoxyacetophenone thiosemicarbazone (HMAT) and its novel N(4) substituted derivatives were synthesized and characterized by different techniques. The optical band gap of the compounds and the energy of HOMO were experimentally examined by UV-vis spectra and cyclic voltammetry measurements, respectively. Furthermore, the conformational spaces of the compounds were scanned with molecular mechanics method. The geometry optimization, HOMO and LUMO energies, the energy gap of the HOMO-LUMO, dipole moment of the compounds were theoretically calculated by the density functional theory B3LYP/6-311++G(d,p) level. The minimal electronic excitation energy and maximum wavelength calculations of the compounds were also performed by TD-DFT//B3LYP/6-311++G(d,p) level of theory. Theoretically calculated values were compared with the related experimental values. The combined results exhibit that all compounds have good electron-donor properties which affect anti-proliferative activity. The cytotoxic effects of the compounds were also evaluated against HeLa (cervical carcinoma), MCF-7 (breast carcinoma) and PC-3 (prostatic carcinoma) cell lines using the standard MTT assay. All tested compounds showed antiproliferative effect having IC50 values in different range. In comparison with that of HMAT, it was obtained that while ethyl group on 4(N)-substituted position decreased in potent anti-proliferative effect, the phenyl group on the position increased in anti-proliferative effect for the tested cancer cell line. Considering the molecular energy parameters, the cytotoxicity activities of the compounds were discussed.

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

Katsuta, Y; Tohoku University Graduate School of Medicine, Sendal, Miyagi; Kadoya, N

Purpose: In this study, we developed a system to calculate three dimensional (3D) dose that reflects dosimetric error caused by leaf miscalibration for head and neck and prostate volumetric modulated arc therapy (VMAT) without additional treatment planning system calculation on real time. Methods: An original system called clarkson dose calculation based dosimetric error calculation to calculate dosimetric error caused by leaf miscalibration was developed by MATLAB (Math Works, Natick, MA). Our program, first, calculates point doses at isocenter for baseline and modified VMAT plan, which generated by inducing MLC errors that enlarged aperture size of 1.0 mm with clarkson dosemore » calculation. Second, error incuced 3D dose was generated with transforming TPS baseline 3D dose using calculated point doses. Results: Mean computing time was less than 5 seconds. For seven head and neck and prostate plans, between our method and TPS calculated error incuced 3D dose, the 3D gamma passing rates (0.5%/2 mm, global) are 97.6±0.6% and 98.0±0.4%. The dose percentage change with dose volume histogram parameter of mean dose on target volume were 0.1±0.5% and 0.4±0.3%, and with generalized equivalent uniform dose on target volume were −0.2±0.5% and 0.2±0.3%. Conclusion: The erroneous 3D dose calculated by our method is useful to check dosimetric error caused by leaf miscalibration before pre treatment patient QA dosimetry checks.« less

Quantification of the kV X-ray imaging dose during real-time tumor tracking and from three- and four-dimensional cone-beam computed tomography in lung cancer patients using a Monte Carlo simulation.

PubMed

Nakamura, Mitsuhiro; Ishihara, Yoshitomo; Matsuo, Yukinori; Iizuka, Yusuke; Ueki, Nami; Iramina, Hiraku; Hirashima, Hideaki; Mizowaki, Takashi

2018-03-01

Knowledge of the imaging doses delivered to patients and accurate dosimetry of the radiation to organs from various imaging procedures is becoming increasingly important for clinicians. The purposes of this study were to calculate imaging doses delivered to the organs of lung cancer patients during real-time tumor tracking (RTTT) with three-dimensional (3D), and four-dimensional (4D) cone-beam computed tomography (CBCT), using Monte Carlo techniques to simulate kV X-ray dose distributions delivered using the Vero4DRT. Imaging doses from RTTT, 3D-CBCT and 4D-CBCT were calculated with the planning CT images for nine lung cancer patients who underwent stereotactic body radiotherapy (SBRT) with RTTT. With RTTT, imaging doses from correlation modeling and from monitoring of imaging during beam delivery were calculated. With CBCT, doses from 3D-CBCT and 4D-CBCT were also simulated. The doses covering 2-cc volumes (D2cc) in correlation modeling were up to 9.3 cGy for soft tissues and 48.4 cGy for bone. The values from correlation modeling and monitoring were up to 11.0 cGy for soft tissues and 59.8 cGy for bone. Imaging doses in correlation modeling were larger with RTTT. On a single 4D-CBCT, the skin and bone D2cc values were in the ranges of 7.4-10.5 cGy and 33.5-58.1 cGy, respectively. The D2cc from 4D-CBCT was approximately double that from 3D-CBCT. Clinicians should Figure that the imaging dose increases the cumulative doses to organs.

Quantification of the kV X-ray imaging dose during real-time tumor tracking and from three- and four-dimensional cone-beam computed tomography in lung cancer patients using a Monte Carlo simulation

PubMed Central

Nakamura, Mitsuhiro; Ishihara, Yoshitomo; Matsuo, Yukinori; Iizuka, Yusuke; Ueki, Nami; Iramina, Hiraku; Hirashima, Hideaki; Mizowaki, Takashi

2018-01-01

Abstract Knowledge of the imaging doses delivered to patients and accurate dosimetry of the radiation to organs from various imaging procedures is becoming increasingly important for clinicians. The purposes of this study were to calculate imaging doses delivered to the organs of lung cancer patients during real-time tumor tracking (RTTT) with three-dimensional (3D), and four-dimensional (4D) cone-beam computed tomography (CBCT), using Monte Carlo techniques to simulate kV X-ray dose distributions delivered using the Vero4DRT. Imaging doses from RTTT, 3D-CBCT and 4D-CBCT were calculated with the planning CT images for nine lung cancer patients who underwent stereotactic body radiotherapy (SBRT) with RTTT. With RTTT, imaging doses from correlation modeling and from monitoring of imaging during beam delivery were calculated. With CBCT, doses from 3D-CBCT and 4D-CBCT were also simulated. The doses covering 2-cc volumes (D2cc) in correlation modeling were up to 9.3 cGy for soft tissues and 48.4 cGy for bone. The values from correlation modeling and monitoring were up to 11.0 cGy for soft tissues and 59.8 cGy for bone. Imaging doses in correlation modeling were larger with RTTT. On a single 4D-CBCT, the skin and bone D2cc values were in the ranges of 7.4–10.5 cGy and 33.5–58.1 cGy, respectively. The D2cc from 4D-CBCT was approximately double that from 3D-CBCT. Clinicians should Figure that the imaging dose increases the cumulative doses to organs. PMID:29385514

ECG-based 4D-dose reconstruction of cardiac arrhythmia ablation with carbon ion beams: application in a porcine model

NASA Astrophysics Data System (ADS)

Richter, Daniel; Immo Lehmann, H.; Eichhorn, Anna; Constantinescu, Anna M.; Kaderka, Robert; Prall, Matthias; Lugenbiel, Patrick; Takami, Mitsuru; Thomas, Dierk; Bert, Christoph; Durante, Marco; Packer, Douglas L.; Graeff, Christian

2017-09-01

Noninvasive ablation of cardiac arrhythmia by scanned particle radiotherapy is highly promising, but especially challenging due to cardiac and respiratory motion. Irradiations for catheter-free ablation in intact pigs were carried out at the GSI Helmholtz Center in Darmstadt using scanned carbon ions. Here, we present real-time electrocardiogram (ECG) data to estimate time-resolved (4D) delivered dose. For 11 animals, surface ECGs and temporal structure of beam delivery were acquired during irradiation. R waves were automatically detected from surface ECGs. Pre-treatment ECG-triggered 4D-CT phases were synchronized to the R-R interval. 4D-dose calculation was performed using GSI’s in-house 4D treatment planning system. Resulting dose distributions were assessed with respect to coverage (D95 and V95), heterogeneity (HI  =  D5-D95) and normal tissue exposure. Final results shown here were performed offline, but first calculations were started shortly after irradiation The D95 for TV and PTV was above 95% for 10 and 8 out of 11 animals, respectively. HI was reduced for PTV versus TV volumes, especially for some of the animals targeted at the atrioventricular junction, indicating residual interplay effects due to cardiac motion. Risk structure exposure was comparable to static and 4D treatment planning simulations. ECG-based 4D-dose reconstruction is technically feasible in a patient treatment-like setting. Further development of the presented approach, such as real-time dose calculation, may contribute to safe, successful treatments using scanned ion beams for cardiac arrhythmia ablation.

Phonon vibrational frequencies of all single-wall carbon nanotubes at the lambda point: reduced matrix calculations.

PubMed

Wang, Yufang; Wu, Yanzhao; Feng, Min; Wang, Hui; Jin, Qinghua; Ding, Datong; Cao, Xuewei

2008-12-01

With a simple method-the reduced matrix method, we simplified the calculation of the phonon vibrational frequencies according to SWNTs structure and their phonon symmetric property and got the dispersion properties of all SWNTs at Gamma point in Brillouin zone, whose diameters lie between 0.6 and 2.5 nm. The calculating time is shrunk about 2-4 orders. A series of the dependent relationships between the diameters of SWNTs and the frequencies of Raman and IR active modes are given. Several fine structures including "glazed tile" structures in omega approximately d figures are found, which might predict a certain macro-quantum phenomenon of the phonons in SWNTs.

Pyrazolo[3,4-d]pyrimidines as novel inhibitors of O-acetyl-L-serine sulfhydrylase of Entamoeba histolytica: an in silico study.

PubMed

Yadava, Umesh; Shukla, Bindesh Kumar; Roychoudhury, Mihir; Kumar, Devesh

2015-04-01

Amoebiasis, a worldwide explosive epidemic, caused by the gastrointestinal anaerobic protozoan parasite Entamoeba histolytica, infects the large intestine and, in advance stages, liver, kidney, brain and lung. Metronidazole (MNZ)-the first line medicament against amoebiasis-is potentially carcinogenic to humans and shows significant side-effects. Pyrazolo[3,4-d]pyrimidine compounds have been reported to demonstrate antiamoebic activity. In silico molecular docking simulations on nine pyrazolo[3,4-d]pyrimidine molecules without linkers (molecules 1-9) and nine pyrazolo[3,4-d]pyrimidine molecules with a trimethylene linker (molecules 10-18) along with the reference drug metronidazole (MNZ) were conducted using the modules of the programs Glide-SP, Glide-XP and Autodock with O-acetyl-L-serine sulfhydrylase (OASS) enzyme-a promising target for inhibiting the growth of Entamoeba histolytica. Docking simulations using Glide-SP demonstrate good agreement with reported biological activities of molecules 1-9 and indicate that molecules 2 and 4 may act as potential high affinity inhibitors. Trimethylene linker molecules show improved binding affinities among which molecules 15 and 16 supersede. MD simulations on the best docked poses of molecules 2, 4, 15, 16 and MNZ were carried out for 20 ns using DESMOND. It was observed that the docking complexes of molecules 4, 15 and MNZ remain stable in aqueous conditions and do not undergo noticeable fluctuations during the course of the dynamics. Relative binding free energy calculations of the ligands with the enzyme were executed on the best docked poses using the molecular mechanics generalized Born surface area (MM-GBSA) approach, which show good agreement with the reported biological activities.

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

Negahdar, M; Loo, B; Maxim, P

Purpose: Elasticity may distinguish malignant from benign pulmonary nodules. To compare determining of malignant pulmonary nodule (MPN) elasticity from four dimensional computed tomography (4D CT) images versus inhale/exhale breath-hold CT images. Methods: We analyzed phase 00 and 50 of 4D CT and deep inhale and natural exhale of breath-hold CT images of 30 MPN treated with stereotactic ablative radiotherapy (SABR). The radius of the smallest MPN was 0.3 cm while the biggest one was 2.1 cm. An intensity based deformable image registration (DIR) workflow was applied to the 4D CT and breath-hold images to determine the volumes of the MPNsmore » and a 1 cm ring of surrounding lung tissue (ring) in each state. Next, an elasticity parameter was derived by calculating the ratio of the volume changes of MPN (exhale:inhale or phase50:phase00) to that of a 1 cm ring of lung tissue surrounding the MPN. The proposed formulation of elasticity enables us to compare volume changes of two different MPN in two different locations of lung. Results: The calculated volume ratio of MPNs from 4D CT (phase50:phase00) and breath-hold images (exhale:inhale) was 1.00±0.23 and 0.95±0.11, respectively. It shows the stiffness of MPN and comparably bigger volume changes of MPN in breath-hold images because of the deeper degree of inhalation. The calculated elasticity of MPNs from 4D CT and breath-hold images was 1.12±0.22 and 1.23±0.26, respectively. For five patients who have had two MPN in their lung, calculated elasticity of tumor A and tumor B follows same trend in both 4D CT and breath-hold images. Conclusion: We showed that 4D CT and breath-hold images are comparable in the ability to calculate the elasticity of MPN. This study has been supported by Department of Defense LCRP 2011 #W81XWH-12-1-0286.« less

An unusual stable mononuclear Mn(III) bis-terpyridine complex exhibiting Jahn-Teller compression: electrochemical synthesis, physical characterisation and theoretical study.

PubMed

Romain, Sophie; Duboc, Carole; Neese, Frank; Rivière, Eric; Hanton, Lyall R; Blackman, Allan G; Philouze, Christian; Leprêtre, Jean-Claude; Deronzier, Alain; Collomb, Marie-Noëlle

2009-01-01

The mononuclear manganese bis-terpyridine complex [Mn(tolyl-terpy)(2)](X)(3) (1(X)(3); X=BF(4), ClO(4), PF(6); tolyl-terpy=4'-(4-methylphenyl)-2,2':6',2"-terpyridine), containing Mn in the unusual +III oxidation state, has been isolated and characterised. The 1(3+) ion is a rare example of a mononuclear Mn(III) complex stabilised solely by neutral N ligands. Complex 1(3+) is obtained by electrochemical oxidation of the corresponding Mn(II) compound 1(2+) in anhydrous acetonitrile. Under these conditions the cyclic voltammogram of 1(2+) exhibits not only the well-known Mn(II)/Mn(III) oxidation at E(1/2)=+0.91 V versus Ag/Ag(+) (+1.21 V vs. SCE) but also a second metal-based oxidation process corresponding to Mn(III)/Mn(IV) at E(1/2)=+1.63 V (+1.93 V vs. SCE). Single crystals of 1(PF(6))(3)2 CH(3)CN were obtained by an electrocrystallisation procedure. X-ray analysis unambiguously revealed its tetragonally compressed octahedral geometry and high-spin character. The electronic properties of 1(3+) were investigated in detail by magnetic measurements and theoretical calculations, from which a D value of +4.82 cm(-1) was precisely determined. Density functional and complete active space self consistent field ab initio calculations both correctly predict a positive sign of D, in agreement with the compressed tetragonal distortion observed in the X-ray structure of 1(PF(6))(3)2 CH(3)CN. The different contributions to D were calculated, and the results show that 1) the spin-orbit coupling part (+2.593 cm(-1)) is predominant compared to the spin-spin interaction (+1.075 cm(-1)) and 2) the excited triplet states make the dominant contribution to the total D value.

Symmetry adapted cluster-configuration interaction calculation of the photoelectron spectra of famous biological active steroids

NASA Astrophysics Data System (ADS)

Abyar, Fatemeh; Farrokhpour, Hossein

2014-11-01

The photoelectron spectra of some famous steroids, important in biology, were calculated in the gas phase. The selected steroids were 5α-androstane-3,11,17-trione, 4-androstane-3,11,17-trione, cortisol, cortisone, corticosterone, dexamethasone, estradiol and cholesterol. The calculations were performed employing symmetry-adapted cluster/configuration interaction (SAC-CI) method using the 6-311++G(2df,pd) basis set. The population ratios of conformers of each steroid were calculated and used for simulating the photoelectron spectrum of steroid. It was found that more than one conformer contribute to the photoelectron spectra of some steroids. To confirm the calculated photoelectron spectra, they compared with their corresponding experimental spectra. There were no experimental gas phase Hesbnd I photoelectron spectra for some of the steroids of this work in the literature and their calculated spectra can show a part of intrinsic characteristics of this molecules in the gas phase. The canonical molecular orbitals involved in the ionization of each steroid were calculated at the HF/6-311++g(d,p) level of theory. The spectral bands of each steroid were assigned by natural bonding orbital (NBO) calculations. Knowing the electronic structures of steroids helps us to understand their biological activities and find which sites of steroid become active when a modification is performing under a biological pathway.

Validation of a Pressed Pentolite Donor for the Large Scale Gap Test (LGST) at DSTO

DTIC Science & Technology

2013-03-01

20.5 a based on dent depth measurement and referenced to RT 60/40 3.1.3 Modelling Data The VoD and PCJ were calculated using CHEETAH 4.0...compositions as well as ideal explosives. It should be noted that CHEETAH assumes the charge is of infinite length as it can not model size effects. It can...calculated from CHEETAH 4.0 and Experimental data Donor Origin Density (g.cm-3) Calculated PCJ (GPa) Experimental P (GPa) Calculated VoD (m.s-1

DFT calculations, spectroscopy and antioxidant activity studies on (E)-2-nitro-4-[(phenylimino)methyl]phenol.

PubMed

Temel, Ersin; Alaşalvar, Can; Gökçe, Halil; Güder, Aytaç; Albayrak, Çiğdem; Alpaslan, Yelda Bingöl; Alpaslan, Gökhan; Dilek, Nefise

2015-02-05

We have reported synthesis and characterization of (E)-2-nitro-4-[(phenylimino)methyl]phenol by using X-ray crystallographic method, FT-IR and UV-vis spectroscopies and density functional theory (DFT). Optimized geometry and vibrational frequencies of the title compound in the ground state have been computed by using B3LYP with the 6-311G+(d,p) basis set. HOMO-LUMO energy gap, Non-linear optical properties and NBO analysis of the compound are performed at B3LYP/6-311G+(d,p) level. Additionally, as remarkable properties, antioxidant activity of the title compound (CMPD) has been determined by using different antioxidant test methods i.e. ferric reducing antioxidant power (FRAP), hydrogen peroxide scavenging (HPSA), free radical scavenging (FRSA) and ferrous ion chelating activities (FICA). When compared with standards (BHA, BHT, and α-tocopherol), we have concluded that CPMD has effective FRAP, HPSA, FRSA and FICA. Copyright © 2014 Elsevier B.V. All rights reserved.

Computational model for the acylation step of the β-lactam ring: Potential application for L,D-transpeptidase 2 in mycobacterium tuberculosis

NASA Astrophysics Data System (ADS)

Fakhar, Zeynab; Govender, Thavendran; Lamichhane, Gyanu; Maguire, Glenn E. M.; Kruger, Hendrik G.; Honarparvar, Bahareh

2017-01-01

Tuberculosis (TB) remains a major global health quandary. The peptidoglycan layer of mycobacterium tuberculosis (M.tb) consists of glycoproteins that are crosslinked by transpeptidases. Carbapenems are a subfamily of β-lactam antibiotics that inactivate the L,D-transpeptidase enzyme effectively (3 → 3 crosslinks). The mechanism of ring opening and thioester bond formation between the β-lactam core and the Cys354 active residue (for L,D-transpeptidase) during the acylation step is still the subject of considerable discussion. Herein, an acylation mechanism is proposed through four possible model transition states (TS), namely four membered-ring (TS-4, TS-4-His and TS-4-water) and six membered-ring (TS-6-water) transition states. The quantum chemical calculations for these TS models were performed with Density Functional Theory (DFT) using the B3LYP functional and the 6-31 + G(d) basis set. The calculated thermodynamic properties such as relative reaction energies (ΔEreaction), Gibbs free energies (ΔG), enthalpy energies (ΔH) and entropy contributions (ΔS) were reported at 298.15 K for the four considered pathways. The highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) were calculated to evaluate and compare the chemical reactivities of the considered TS models. Natural bond orbital (NBO) analysis was performed to determine the effective intermolecular orbital interactions E(2) derived by the second perturbation theory. The chemical hardness (η) and softness (S) and Fukui indices (fk+, fk-) of these TS models were compared to confirm the feasibility and preference of the considered pathways. The outcome of this study will pave the way for an improved understanding of the LDT/carbapenem acylation reaction at a molecular level.

Relativistic Atomic Data for Lines in Ge-Like Sm and Eu Ions

NASA Astrophysics Data System (ADS)

Nagy, O.; El Sayed, Fatma

2012-11-01

Energies, wavelengths, transition probabilities, and oscillator strengths have been calculated for the 4s24p2 - 4s4p3, 4s24p2 - 4s24p4d and 4s4p3 - 4p4 allowed transitions in heavy Ge-like Sm and Eu ions. The fully relativistic Multiconfiguration Dirac-Fock (MCDF) method taking into account both the correlations within the n = 4 complex and the quantum electrodynamic (QED) effects have been used in the calculations. MCDFGME code is used to calculate electron impact excitation cross sections for the 4s24p2 - 4s4p3, and 4s24p2 - 4s24p4d transitions with plane-wave Born approximation. The results of SmXXXI and Eu XXXII are compared with HFR method results.

Theoretical, spectroscopic and antioxidant activity studies on (E)-2-[(2-fluorophenylimino)methyl]-4-hydroxyphenol and (E)-2-[(3-fluorophenylimino)methyl]-4-hydroxyphenol compounds

NASA Astrophysics Data System (ADS)

Alaşalvar, Can; Güder, Aytaç; Gökçe, Halil; Albayrak Kaştaş, Çiğdem; Çatak Çelik, Raziye

2017-04-01

We studied synthesis and characterization of the title compounds by using X-ray crystallographic technique, FT-IR spectroscopy, UV-Vis spectroscopy and Density functional method. Optimized geometry, vibrational frequencies and UV-Vis parameters of the title compounds in the ground state have been calculated by using B3LYP with the 6-311G+ (d,p) basis set. HOMO - LUMO energy gap, Non-linear optical properties are performed at B3LYP/6-311G+(d,p) level. For determination of antioxidant properties of the title compounds (CMPD1 and CMPD2) have been investigated by using different methods, i.e. ferric reducing antioxidant power (FRAP), hydrogen peroxide scavenging (HPSA), free radical scavenging (FRSA) and ferrous ion chelating activities (FICA). In comparison with standard antioxidants (BHA, BHT, and α-tocopherol), CPMD1 and CMPD2 have influential FRAP, HPSA, FRSA and FICA.

[Isolation and characterization of active compounds from Aloe vera with a possible role in skin protection].

PubMed

Kostálová, D; Bezáková, L; Oblozinský, M; Kardosová, A

2004-09-01

Aloe vera is widely used in food supplements, beverages, pharmaceuticals, and cosmetics. It has been long recognized as an effective natural remedy for its wound-healing properties and its positive influence on other inflammatory skin disorders. Major proteins and mono- and polysaccharides were identified and analysed from Aloe vera commercial extract. Molecular weight of proteins calculated from the sets of molecular weight reference standards, ranged from 70 kDa for the largest to 14 kDa for the smallest ones. IR spectral analysis of the carbohydrate fraction shows that the main carbohydrate copound is acetylated (1 --> 4)-beta-D-mannan substituated with D-galactose and D-glucose. The results have shown that proteins and polysaccharides are a necessary component in the study of biological activity of Aloe vera leaf extract.

Dihydroisocoumarins from Radix Glycyrrhizae.

PubMed

Zhao, Songsong; Yan, Xinjia; Zhao, Ying; Wen, Jing; Zhao, Zhenzhen; Liu, Hongwei

2018-05-11

Radix Glycyrrhizae is the rhizome of Glycyrrhiza inflata Bat., Glycyrrhiza uralensis Fisch. or Glycyrrhiza glabra L. The present paper describes the isolation and the structural elucidation of three new dihydroisocoumarins obtained from the 70% EtOH extract of Radix Glycyrrhizae. And the cytotoxic activities of these new compounds were also evaluated using four cell lines, subsequently. A pair of new dihydroisocoumarin epimers ((3R,4S)-4,8-dihydroxy-3-methyl-1-oxoisochroman-5-yl)methyl acetate (1) and ((3R,4R)-4,8-dihydroxy-3-methyl-1-oxoisochroman-5-yl)methyl acetate (2) along with a new dihydroisocoumarin (3R,4R)-4,8-dihydroxy-3,5-dimethylisochroman-1-one (3) were isolated from Radix Glycyrrhizae. Their structures were elucidated on the basis of chemical and spectral analysis, including 1D, 2D NMR analyses, HR-ESI-MSand ECD calculation comparing with those of experimental CD spectra. Cytotoxic activities of the three compounds were evaluated using the HepG2, A549, LoVo and Hela cell lines, respectively. IC 50 values indicated compounds 1-3 exhibited moderate or less cytotoxic activity in vitro. Dihydroisocoumarin is not the common components in Radix Glycyrrhizae, a series of dihydroisocoumarin were obtained in this plant could be a supplement to the chemical study of this plant.

Structure, spectroscopic analyses (FT-IR and NMR), vibrational study, chemical reactivity and molecular docking study on 3,3'-((4-(trifluoromethyl)phenyl)methylene)bis(2-hydroxynaphthalene-1,4-dione), a promising anticancerous bis-lawsone derivative

NASA Astrophysics Data System (ADS)

Yadav, Krishna Kant; Kumar, Abhishek; Kumar, Amarendra; Misra, Neeraj; Brahmachari, Goutam

2018-02-01

Lawsone (2-hydroxy-1,4-naphthoquinone)has been evaluated to possess a wide range of biological and pharmacological activities. The interesting structural pattern of lawsone coupled with its so-called multifaceted pharmacological potential have made this scaffolds useful in certain chemical processes, particularly in synthesizing ligands for metal complexations, and also few of its derivatives have shown a number of biological activities. The equilibrium geometry of 3,3‧-((4-(trifluoromethyl)phenyl)methylene)bis(2-hydroxynaphthalene-1,4-dione) (1; TPMHD), a promising anticancerous lawsone derivative, has been determined and analyzed at DFT method employingB3LYP/6-311++G(d,p) level of theory. The reactivity descriptors such as Fukui functions and HOMO-LUMO gap are calculated and discussed. The infrared spectra of TPMHD(1) are calculated and compared with the experimentally observed ones. Moreover, 1H and 13C NMR spectra have been calculated by using the gauge independent atomic orbital method. The docking studies reveal that the TPMHD has strong binding affinity toward target protein 2SHP. Thus the compound has a possible use as a drug in cancer therapy. The study suggests further investigation on TPMHD for their in-depth biological and pharmaceutical importance.

Susceptibility-based functional brain mapping by 3D deconvolution of an MR-phase activation map.

PubMed

Chen, Zikuan; Liu, Jingyu; Calhoun, Vince D

2013-05-30

The underlying source of T2*-weighted magnetic resonance imaging (T2*MRI) for brain imaging is magnetic susceptibility (denoted by χ). T2*MRI outputs a complex-valued MR image consisting of magnitude and phase information. Recent research has shown that both the magnitude and the phase images are morphologically different from the source χ, primarily due to 3D convolution, and that the source χ can be reconstructed from complex MR images by computed inverse MRI (CIMRI). Thus, we can obtain a 4D χ dataset from a complex 4D MR dataset acquired from a brain functional MRI study by repeating CIMRI to reconstruct 3D χ volumes at each timepoint. Because the reconstructed χ is a more direct representation of neuronal activity than the MR image, we propose a method for χ-based functional brain mapping, which is numerically characterised by a temporal correlation map of χ responses to a stimulant task. Under the linear imaging conditions used for T2*MRI, we show that the χ activation map can be calculated from the MR phase map by CIMRI. We validate our approach using numerical simulations and Gd-phantom experiments. We also analyse real data from a finger-tapping visuomotor experiment and show that the χ-based functional mapping provides additional activation details (in the form of positive and negative correlation patterns) beyond those generated by conventional MR-magnitude-based mapping. Copyright © 2013 Elsevier B.V. All rights reserved.

Synthesis, molecular structure, spectral analysis, and biological activity of new malonamide derivatives as α-glucosidase inhibitors

NASA Astrophysics Data System (ADS)

Barakat, Assem; Islam, Mohammad Shahidul; Al-Majid, Abdullah Mohammed; Soliman, Saied M.; Ghabbour, Hazem A.; Yousuf, Sammer; Choudhary, M. Iqbal; Ul-Haq, Zaheer

2017-04-01

Two new malonamide derivatives were synthesized via the Michael addition of N1,N3-di(pyridin-2-yl)malonamide to α,β-unsaturated ketones using a 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) catalyst at room temperature. All reactions efficiently furnished the desired malonamide derivatives, which differed only in their substitution on one phenyl group, with one derivative bearing a bromine substituent and the other bearing a methyl group. The structures of newly synthesized compounds were then elucidated by single-crystal X-ray diffraction, infrared spectroscopy, NMR spectroscopy, mass spectrometry, and elemental analysis. In addition, the synthesized compounds were evaluated for their in vitro cytotoxicity against cancer cell lines and for α-glucosidase inhibition. The target compounds exhibited enhanced α-glucosidase inhibition activity (i.e., IC50 = 12.8 ± 0.1 and 28.4 ± 0.2 μM) compared to the common drug acarbose (IC50 = 840 ± 1.73 μM). Both compounds were found to be non-cytotoxic against H460 (lung carcinoma) and T3T (normal fibroblast) cell lines. In addition, the bromo-substituted derivative exhibited weak cytotoxic against cervical cancer HeLa (IC50 = 13.8 ± 0.4 μM) and breast cancer MCF-7 (IC50 = 21.11 ± 0.88 μM) cell lines, while the methyl-substituted derivative showed weak cytotoxicity against the MCF-7 cell line (IC50 = 47.9 ± 0.7 μM). Density functional theory (DFT) B3LYP/6-311G(d,p) calculations were employed to examine the molecular structures and electronic properties of the prepared compounds. As expected, the bromo-derivative (2.2377 D) exhibited a higher polarity than the methyl-derivative (1.9160 D). Furthermore, the HOMO and LUMO diagrams were constructed and the electronic spectra of both compounds were assigned using time-dependent (TD)-DFT calculations. Finally, the calculated NMR chemical shifts correlated well with the experimental data.

SU-F-303-13: Initial Evaluation of Four Dimensional Diffusion- Weighted MRI (4D-DWI) and Its Effect On Apparent Diffusion Coefficient (ADC) Measurement

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

Liu, Y; Yin, F; Czito, B

2015-06-15

Purpose: Diffusion-weighted imaging(DWI) has been shown to have superior tumor-to-tissue contrast for cancer detection.This study aims at developing and evaluating a four dimensional DWI(4D-DWI) technique using retrospective sorting method for imaging respiratory motion for radiotherapy planning,and evaluate its effect on Apparent Diffusion Coefficient(ADC) measurement. Materials/Methods: Image acquisition was performed by repeatedly imaging a volume of interest using a multi-slice single-shot 2D-DWI sequence in the axial planes and cine MRI(served as reference) using FIESTA sequence.Each 2D-DWI image were acquired in xyz-diffusion-directions with a high b-value(b=500s/mm2).The respiratory motion was simultaneously recorded using bellows.Retrospective sorting was applied in each direction to reconstruct 4D-DWI.Themore » technique was evaluated using a computer simulated 4D-digital human phantom(XCAT),a motion phantom and a healthy volunteer under an IRB-approved study.Motion trajectories of regions-of-interests(ROI) were extracted from 4D-DWI and compared with reference.The mean motion trajectory amplitude differences(D) between the two was calculated.To quantitatively analyze the motion artifacts,XCAT were controlled to simulate regular motion and the motions of 10 liver cancer patients.4D-DWI,free-breathing DWI(FB- DWI) were reconstructed.Tumor volume difference(VD) of each phase of 4D-DWI and FB-DWI from the input static tumor were calculated.Furthermore, ADC was measured for each phase of 4D-DWI and FB-DWI data,and mean tumor ADC values(M-ADC) were calculated.Mean M-ADC over all 4D-DWI phases was compared with M-ADC calculated from FB-DWI. Results: 4D-DWI of XCAT,the motion phantom and the healthy volunteer demonstrated the respiratory motion clearly.ROI D values were 1.9mm,1.7mm and 2.0mm,respectively.For motion artifacts analysis,XCAT 4D-DWI images show much less motion artifacts compare to FB-DWI.Mean VD for 4D-WDI and FB-DWI were 8.5±1.4% and 108±15%,respectively.Mean M-ADC for ADC measured from 4D-DWI and M-ADC measured from FB-DWI were (2.29±0.04)*0.001*mm2/s and (3.80±0.01)*0.001*mm2/s,respectively.ADC value ground-truth is 2.24*0.001*mm2/s from the input of the simulation. Conclusion: A respiratory correlated 4D-DWI technique has been initially evaluated in phantoms and a human subject.Comparing to free breathing DWI,4D-DWI can lead to more accurate measurement of ADC.« less

40 CFR Appendix I to Subpart B of... - Appendix I to Subpart B of Part 205

Code of Federal Regulations, 2011 CFR

2011-07-01

...: Acceleration Test: Deceleration Test: Acceleration Test Run No. 1 2 3 4 5 dBA Left Right Highest RPM attained in End Zone Calculated Sound Pressure dBA Deceleration Test with Exhaust Brake Applied dBA Left Right Calculated Sound Pressure dBA TEST Personnel: (Name) Recorded By: Date:......... (Signature) Supervisor...

40 CFR Appendix I to Subpart B of... - Appendix I to Subpart B of Part 205

Code of Federal Regulations, 2010 CFR

2010-07-01

...: Acceleration Test: Deceleration Test: Acceleration Test Run No. 1 2 3 4 5 dBA Left Right Highest RPM attained in End Zone Calculated Sound Pressure dBA Deceleration Test with Exhaust Brake Applied dBA Left Right Calculated Sound Pressure dBA TEST Personnel: (Name) Recorded By: Date:......... (Signature) Supervisor...

A density functional theory study on the acetylene cyclotrimerization on Pd-modified Au(111) surface

NASA Astrophysics Data System (ADS)

Ren, Bohua; Dong, Xiuqin; Yu, Yingzhe; Zhang, Minhua

2017-10-01

Calculations based on the first-principle density functional theory were carried out to study the possible acetylene cyclotrimerization reactions on Pd-Au(111) surface and to investigate the effect of Au atom alloying with Pd. The adsorption of C2H2, C4H4, C6H6 and the PDOS of 4d orbitals of surface Pd and Au atoms were studied. The comparison of d-band center of Pd and Au atom before and after C2H2 or C4H4 adsorption suggests that these molecules affect the activity of Pd-Au(111) surface to some degree due to the high binding energy of the adsorption. In our study, the second neighboring Pd ensembles on Pd-Au(111) surface can adsorb two acetylene molecules on parallel-bridge site of two Au atoms and one Pd atom, respectively. Csbnd C bonds are parallel to each other and two acetylenes are adsorbed face to face to produce four-membered ring C4H4 firstly. The geometric effect and electronic effect of Pd-Au(111) surface with the second neighboring Pd ensembles both help to reduce this activation barrier.

Household factors, family behavior patterns, and adherence to dietary and physical activity guidelines among children at risk for obesity.

PubMed

Kunin-Batson, Alicia S; Seburg, Elisabeth M; Crain, A Lauren; Jaka, Meghan M; Langer, Shelby L; Levy, Rona L; Sherwood, Nancy E

2015-01-01

To describe the proportion of children adhering to recommended physical activity and dietary guidelines, and examine demographic and household correlates of guideline adherence. Cross-sectional (pre-randomization) data from a behavioral intervention trial designed to prevent unhealthy weight gain in children. A total of 421 children (aged 5-10 years) at risk for obesity (body mass index percentile, 70-95). Physical activity (accelerometry), screen time (parent survey), and fruit and vegetable and sugar-sweetened beverage intake (24-hour dietary recall). Proportions meeting guidelines were calculated. Logistic regression examined associations between demographic and household factors and whether children met recommended guidelines for (1) physical activity (≥ 60 min/d), (2) screen time (≤ 2 h/d), (3) fruit and vegetable intake (≥ 5 servings/d), and (4) sugar-sweetened beverage avoidance. Few children met more than 1 guideline. Only 2% met all 4 recommended guidelines and 19% met none. Each guideline had unique sociodemographic and domain-specific household predictors (ie, availability of certain foods and beverages, media, and active play and exercise equipment). Families equipped to promote healthy child behavior patterns in 1 activity or dietary domain may not be in others. Results have implications for the development of interventions to affect children's weight-related behaviors and growth trajectories. Copyright © 2015 Society for Nutrition Education and Behavior. Published by Elsevier Inc. All rights reserved.

High power density supercapacitors based on the carbon dioxide activated D-glucose derived carbon electrodes and 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid

NASA Astrophysics Data System (ADS)

Tooming, T.; Thomberg, T.; Kurig, H.; Jänes, A.; Lust, E.

2015-04-01

The electrochemical impedance spectroscopy, cyclic voltammetry, constant current charge/discharge and the constant power discharge methods have been applied to establish the electrochemical characteristics of the electrical double-layer capacitor (EDLC) consisting of the 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4) ionic liquid and microporous carbon electrodes. Microporous carbon material used for preparation of electrodes (GDAC - glucose derived activated carbon), has been synthesised from D-(+)-glucose by the hydrothermal carbonization method, including subsequent pyrolysis, carbon dioxide activation and surface cleaning step with hydrogen. The Brunauer-Emmett-Teller specific surface area (SBET = 1540 m2 g-1), specific surface area calculated using the non-local density functional theory in conjunction with stable adsorption integral equation using splines (SAIEUS) model SSAIEUS = 1820 m2 g-1, micropore surface area (Smicro = 1535 m2 g-1), total pore volume (Vtot = 0.695 cm3 g-1) and the pore size distribution were obtained from the N2 sorption data. The SBET, Smicro and Vtot values have been correlated with the electrochemical characteristics strongly dependent on the carbon activation conditions applied for EDLCs. Wide region of ideal polarizability (ΔV ≤ 3.2 V), very short charging/discharging time constant (2.7 s), and high specific series capacitance (158 F g-1) have been calculated for the optimized carbon material GDAC-10h (activation of GDAC with CO2 during 10 h) in EMImBF4 demonstrating that this system can be used for completing the EDLC with high energy- and power densities.

One-Loop One-Point Functions in Gauge-Gravity Dualities with Defects.

PubMed

Buhl-Mortensen, Isak; de Leeuw, Marius; Ipsen, Asger C; Kristjansen, Charlotte; Wilhelm, Matthias

2016-12-02

We initiate the calculation of loop corrections to correlation functions in 4D defect conformal field theories (dCFTs). More precisely, we consider N=4 SYM theory with a codimension-one defect separating two regions of space, x_{3}>0 and x_{3}<0, where the gauge group is SU(N) and SU(N-k), respectively. This setup is made possible by some of the real scalar fields acquiring a nonvanishing and x_{3}-dependent vacuum expectation value for x_{3}>0. The holographic dual is the D3-D5 probe brane system where the D5-brane geometry is AdS_{4}×S^{2} and a background gauge field has k units of flux through the S^{2}. We diagonalize the mass matrix of the dCFT making use of fuzzy-sphere coordinates and we handle the x_{3} dependence of the mass terms in the 4D Minkowski space propagators by reformulating these as standard massive AdS_{4} propagators. Furthermore, we show that only two Feynman diagrams contribute to the one-loop correction to the one-point function of any single-trace operator and we explicitly calculate this correction in the planar limit for the simplest chiral primary. The result of this calculation is compared to an earlier string-theory computation in a certain double scaling limit and perfect agreement is found. Finally, we discuss how to generalize our calculation to any single-trace operator, to finite N, and to other types of observables such as Wilson loops.

Accuracy of Corneal Power Measurements for Intraocular Lens Power Calculation after Myopic Laser In situ Keratomileusis.

PubMed

Helaly, Hany A; El-Hifnawy, Mohammad A M; Shaheen, Mohamed Shafik; Abou El-Kheir, Amr F

2016-01-01

To evaluate the accuracy of corneal power measurements for intraocular lens (IOL) power calculation after myopic laser in situ keratomileusis (LASIK). The study evaluated 45 eyes with a history of myopic LASIK. Corneal power was measured using manual keratometry, automated keratometry, optical biometry, and Scheimflug tomography. Different hypothetical IOL power calculation formulas were performed for each case. The steepest mean K value was measured with manual keratometry (37.48 ± 2.86 D) followed by automated keratometry (37.31 ± 2.83 D) then optical biometry (37.06 ± 2.98 D) followed by Scheimflug tomography (36.55 ± 3.08). None of the K values generated by Scheimflug tomography were steeper than the measurements from the other 3 instruments. Using equivalent K reading (EKR) 4 mm with the Double-K SRK/T formula, the refractive outcome generated 97.8% of cases within ± 2 D, 80.0% of cases within ± 1 D, and 42.2% of cases within ± 0.5 D. The best combination of formulas was "Shammas-PL + Double-K SRK/T formula using EKR 4 mm." Scheimflug tomography imaging using the Holladay EKR 4 mm improved the accuracy of IOL power calculation in post-LASIK eyes. The best option is a combination of formulas. We recommended the use the combined "Shammas-PL ± Double-K SRK/T formula using EKR 4 mm"h for optical outcomes.

Embedded cluster calculations for hydrogen chemisorption on the (111) surfaces of fcc Co, Ni, Cu, Rh, Pd and Ag

NASA Astrophysics Data System (ADS)

Muscat, J. P.; Newns, D. M.

1980-10-01

We present a muffin tin based calculation on (TM) 3H, (TM) 7H and (TM) 19H clusters embedded at the surface of an effective jellium-like medium whose potential is treated in scattering length approximation. We consider the changes occurring when the d-like perturbation of the TM muffin tins is switched on. The broad chemisorption-induced resonance seen for H on the effective jellium surface is narrowed and shifted down in energy. Furthermore the occupation of this resonance is increased from about 1.1 electrons to about 1.4 (on 3d metals) or 1.8 (on 4d metals), due to d-like states dropping down from the d band to form a relatively welldefined "bonding state". An antibonding state containing about 0.4 electrons is formed at the top of the d band. The results are compared with other calculations and with photoemission data. Implications for the metal-hydrogen distance and (for Ni) the demagnetizing effect of hydrogen chemisorption are discussed. We use the change in total single particle energy when the d-like perturbation is switched on to estimate trends in chemisorption energy along the 3d and 4d series. In the 3d case experimental data is available on the difference in chemisorption energy between Ni and Cu which is in reasonable agreement with our estimate.

Preparation and characterization of Tb3+ ions doped zincborophosphate glasses for green emission

NASA Astrophysics Data System (ADS)

Bindu, S. Hima; Raju, D. Siva; Krishna, V. Vinay; Raju, Ch. Linga

2017-06-01

The present study reports the preparation of various concentrations of Tb3+ ions doped zincborophosphate glasses and analysis by XRD, FTIR, optical, emission and decay curve spectras. The effect of borate groups on the phosphate was evidenced by FTIR spectroscopy. The JO intensity parameters was calculated using Judd-Offlet theory. The fluroscence spectra of Tb3+ doped zincborophosphate glasses revealed the efficient blue and green emissions due to 5D3 and 5D4 excited levels to 7Fj ground state respectively. The decay curves exhibits single exponential curves for all the Tb3+ ion concentrations. Various radiative and fluorescence parameters are calculated using JO intensity parameters. Based on the results obtained in the present study, the Tb3+ ions doped zincborophosphate glasses behaves as a efficient laser active materials for highintensity emissions in the green region.

A new SO2 emissions budget for Anatahan volcano (Mariana Islands) based on ten years of satellite observations

NASA Astrophysics Data System (ADS)

McCormick, Brendan; Popp, Christoph; Andrews, Benjamin; Cottrell, Elizabeth

2015-04-01

Satellite remote sensing offers great potential for the study of sulphur dioxide (SO2) gas emissions from volcanoes worldwide. Anatahan is a remote volcano in the Mariana Islands, SW Pacific. Existing SO2 emissions data from Anatahan, from ground-based UV spectrometer measurements, place the volcano among the largest natural SO2 sources worldwide. However, these measurements are limited in number and only available from intervals of eruptive activity. Activity varies widely at Anatahan: over the past decade, records held in the Smithsonian Institution Global Volcanism Program Volcanoes of the World database describe the alternation of intense eruptions with long intervals of quiescence, where much lower intensity activity took place. We present ten years of satellite-based measurements of SO2 in the atmosphere over Anatahan, using data from the UV spectrometers OMI, GOME-2, and SCIAMACHY, and the IR spectrometer AIRS. We find Anatahan's emissions to be highly variable both within and between intervals of eruption and quiescence. We demonstrate a close agreement between trends in SO2 emission evident from our remote sensing data and records of activity compiled from a range of other sources and instruments, across daily to annual temporal scales. Mean eruptive SO2 emissions at Anatahan are ~6400 t/d, and range from <1000 to >18000 t/d. Quiescent emissions are below our instrument detection limits and are therefore unlikely to exceed 150-300 t/d. Overall, accounting for both eruptive and quiescent emissions, we calculate a revised decadal mean SO2 emission rate of 1060-1200 t/d. We further calculate a total decadal SO2 yield from Anatahan of 4-5 Mt, significantly lower than the 17-34 Mt calculated if ground-based campaign data are used in isolation. The use of isolated measurements to extrapolate longer term emissions budgets is subject to clear uncertainty, and we argue that our satellite observations, covering a longer interval of Anatahan's history, are better suited to such calculations, and do not require widespread extrapolation. We propose that the use of multi-year satellite datasets, ideally in conjunction with key ground-based data and longterm records of activity, can make major improvements to existing emissions budgets at Anatahan and other volcanoes worldwide.

Infrared spectra and anharmonic coupling of proton-bound nitrogen dimers N2-H+-N2, N2-D+-N2, and 15N2-H+-15N2 in solid para-hydrogen.

PubMed

Liao, Hsin-Yi; Tsuge, Masashi; Tan, Jake A; Kuo, Jer-Lai; Lee, Yuan-Pern

2017-08-09

The proton-bound nitrogen dimer, N 2 -H + -N 2 , and its isotopologues were investigated by means of vibrational spectroscopy. These species were produced upon electron bombardment of mixtures of N 2 (or 15 N 2 ) and para-hydrogen (p-H 2 ) or normal-D 2 (n-D 2 ) during deposition at 3.2 K. Reduced-dimension anharmonic vibrational Schrödinger equations were constructed to account for the strong anharmonic effects in these protonated species. The fundamental lines of proton motions in N 2 -H + -N 2 were observed at 715.0 (NH + N antisymmetric stretch, ν 4 ), 1129.6 (NH + N bend, ν 6 ), and 2352.7 (antisymmetric NN/NN stretch, ν 3 ) cm -1 , in agreement with values of 763, 1144, and 2423 cm -1 predicted with anharmonic calculations using the discrete-variable representation (DVR) method at the CCSD/aug-cc-pVDZ level. The lines at 1030.2 and 1395.5 cm -1 were assigned to combination bands involving nν 2 + ν 4 (n = 1 and 2) according to theoretical calculations; ν 2 is the N 2 N 2 stretching mode. For 15 N 2 -H + - 15 N 2 in solid p-H 2 , the corresponding major lines were observed at 710.0 (ν 4 ), 1016.7 (ν 2 + ν 4 ), 1124.3 (ν 6 ), 1384.8 (2ν 2 + ν 4 ), and 2274.9 (ν 3 ) cm -1 . For N 2 -D + -N 2 in solid n-D 2 , the corresponding major lines were observed at 494.0 (ν 4 ), 840.7 (ν 2 + ν 4 ), 825.5 (ν 6 ), and 2356.2 (ν 3 ) cm -1 . In addition, two lines at 762.0 (weak) and 808.3 cm -1 were tentatively assigned to be some modes of N 2 -H + -N 2 perturbed or activated by a third N 2 near the proton.

Lung Dosimetry for Radioiodine Treatment Planning in the Case of Diffuse Lung Metastases

PubMed Central

Song, Hong; He, Bin; Prideaux, Andrew; Du, Yong; Frey, Eric; Kasecamp, Wayne; Ladenson, Paul W.; Wahl, Richard L.; Sgouros, George

2010-01-01

The lungs are the most frequent sites of distant metastasis in differentiated thyroid carcinoma. Radioiodine treatment planning for these patients is usually performed following the Benua– Leeper method, which constrains the administered activity to 2.96 GBq (80 mCi) whole-body retention at 48 h after administration to prevent lung toxicity in the presence of iodine-avid lung metastases. This limit was derived from clinical experience, and a dosimetric analysis of lung and tumor absorbed dose would be useful to understand the implications of this limit on toxicity and tumor control. Because of highly nonuniform lung density and composition as well as the nonuniform activity distribution when the lungs contain tumor nodules, Monte Carlo dosimetry is required to estimate tumor and normal lung absorbed dose. Reassessment of this toxicity limit is also appropriate in light of the contemporary use of recombinant thyrotropin (thyroid-stimulating hormone) (rTSH) to prepare patients for radioiodine therapy. In this work we demonstrated the use of MCNP, a Monte Carlo electron and photon transport code, in a 3-dimensional (3D) imaging–based absorbed dose calculation for tumor and normal lungs. Methods A pediatric thyroid cancer patient with diffuse lung metastases was administered 37MBq of 131I after preparation with rTSH. SPECT/CT scans were performed over the chest at 27, 74, and 147 h after tracer administration. The time–activity curve for 131I in the lungs was derived from the whole-body planar imaging and compared with that obtained from the quantitative SPECT methods. Reconstructed and coregistered SPECT/CT images were converted into 3D density and activity probability maps suitable for MCNP4b input. Absorbed dose maps were calculated using electron and photon transport in MCNP4b. Administered activity was estimated on the basis of the maximum tolerated dose (MTD) of 27.25 Gy to the normal lungs. Computational efficiency of the MCNP4b code was studied with a simple segmentation approach. In addition, the Benua–Leeper method was used to estimate the recommended administered activity. The standard dosing plan was modified to account for the weight of this pediatric patient, where the 2.96-GBq (80 mCi) whole-body retention was scaled to 2.44 GBq (66 mCi) to give the same dose rate of 43.6 rad/h in the lungs at 48 h. Results Using the MCNP4b code, both the spatial dose distribution and a dose–volume histogram were obtained for the lungs. An administered activity of 1.72 GBq (46.4 mCi) delivered the putative MTD of 27.25 Gy to the lungs with a tumor absorbed dose of 63.7 Gy. Directly applying the Benua–Leeper method, an administered activity of 3.89 GBq (105.0 mCi) was obtained, resulting in tumor and lung absorbed doses of 144.2 and 61.6 Gy, respectively, when the MCNP-based dosimetry was applied. The voxel-by-voxel calculation time of 4,642.3 h for photon transport was reduced to 16.8 h when the activity maps were segmented into 20 regions. Conclusion MCNP4b–based, patient-specific 3D dosimetry is feasible and important in the dosimetry of thyroid cancer patients with avid lung metastases that exhibit prolonged retention in the lungs. PMID:17138741

On a boundary-localized Higgs boson in 5D theories.

PubMed

Barceló, Roberto; Mitra, Subhadip; Moreau, Grégory

In the context of a simple five-dimensional (5D) model with bulk matter coupled to a brane-localized Higgs boson, we point out a non-commutativity in the 4D calculation of the mass spectrum for excited fermion towers: the obtained expression depends on the choice in ordering the limits, [Formula: see text] (infinite Kaluza-Klein tower) and [Formula: see text] ([Formula: see text] being the parameter introduced for regularizing the Higgs Dirac peak). This introduces the question of which one is the correct order; we then show that the two possible orders of regularization (called I and II) are experimentally equivalent, as both can typically reproduce the measured observables, but that the one with less degrees of freedom (I) could be uniquely excluded by future experimental constraints. This conclusion is based on the exact matching between the 4D and 5D analytical calculations of the mass spectrum - via regularizations of type I and II. Beyond a deeper insight into the Higgs peak regularizations, this matching brings another confirmation of the validity of the 5D mixed formalism. All the conclusions, deduced from regularizing the Higgs peak through a brane shift or a smoothed square profile, are expected to remain similar in realistic models with a warped extra-dimension. The complementary result of the study is that the non-commutativity disappears, both in the 4D and the 5D calculations, in the presence of higher order derivative operators. For clarity, the 4D and 5D analytical calculations, matching with each other, are presented in the first part of the paper, while the second part is devoted to the interpretation of the results.

Impact of temporal probability in 4D dose calculation for lung tumors.

PubMed

Rouabhi, Ouided; Ma, Mingyu; Bayouth, John; Xia, Junyi

2015-11-08

The purpose of this study was to evaluate the dosimetric uncertainty in 4D dose calculation using three temporal probability distributions: uniform distribution, sinusoidal distribution, and patient-specific distribution derived from the patient respiratory trace. Temporal probability, defined as the fraction of time a patient spends in each respiratory amplitude, was evaluated in nine lung cancer patients. Four-dimensional computed tomography (4D CT), along with deformable image registration, was used to compute 4D dose incorporating the patient's respiratory motion. First, the dose of each of 10 phase CTs was computed using the same planning parameters as those used in 3D treatment planning based on the breath-hold CT. Next, deformable image registration was used to deform the dose of each phase CT to the breath-hold CT using the deformation map between the phase CT and the breath-hold CT. Finally, the 4D dose was computed by summing the deformed phase doses using their corresponding temporal probabilities. In this study, 4D dose calculated from the patient-specific temporal probability distribution was used as the ground truth. The dosimetric evaluation matrix included: 1) 3D gamma analysis, 2) mean tumor dose (MTD), 3) mean lung dose (MLD), and 4) lung V20. For seven out of nine patients, both uniform and sinusoidal temporal probability dose distributions were found to have an average gamma passing rate > 95% for both the lung and PTV regions. Compared with 4D dose calculated using the patient respiratory trace, doses using uniform and sinusoidal distribution showed a percentage difference on average of -0.1% ± 0.6% and -0.2% ± 0.4% in MTD, -0.2% ± 1.9% and -0.2% ± 1.3% in MLD, 0.09% ± 2.8% and -0.07% ± 1.8% in lung V20, -0.1% ± 2.0% and 0.08% ± 1.34% in lung V10, 0.47% ± 1.8% and 0.19% ± 1.3% in lung V5, respectively. We concluded that four-dimensional dose computed using either a uniform or sinusoidal temporal probability distribution can approximate four-dimensional dose computed using the patient-specific respiratory trace.

Calculation of levels, transition rates, and lifetimes for the arsenic isoelectronic sequence Sn XVIII-Ba XXIV, W XLII

NASA Astrophysics Data System (ADS)

Wang, K.; Chen, Z. B.; Chen, C. Y.; Yan, J.; Dang, W.; Zhao, X. H.; Yang, X.

2017-09-01

Multi-configuration Dirac-Fock (MCDF) calculations of energy levels, wavelengths, oscillator strengths, lifetimes, and electric dipole (E1), magnetic dipole (M1), electric quadrupole (E2), magnetic quadrupole (M2) transition rates are reported for the arsenic isoelectronic sequence Sn XVIII-Ba XXIV, W XLII. Results are presented among the 86 levels of the 4s2 4p3, 4 s 4p4, 4p5, 4s2 4p2 4 d, and 4 s 4p3 4 d configurations in each ion. The relativistic atomic structure package GRASP2K is adopted for the calculations, in which the contributions from the correlations within the n ≤ 7 complexes, Breit interaction (BI) and quantum electrodynamics (QED) effects are taking into account. The many-body perturbation theory (MBPT) method is also employed as an independent calculation for comparison purposes, taking W XLII as an example. Calculated results are compared with data from other calculations and the observed values from the Atomic Spectra Database (ASD) of the National Institute of Standards and Technology (NIST). Good agreements are obtained. i.e, the accuracy of our energy levels is assessed to be better than 0.6%. These accurate theoretical data should be useful for diagnostics of hot plasmas in fusion devices.

Validation of the WIMSD4M cross-section generation code with benchmark results

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

Deen, J.R.; Woodruff, W.L.; Leal, L.E.

1995-01-01

The WIMSD4 code has been adopted for cross-section generation in support of the Reduced Enrichment Research and Test Reactor (RERTR) program at Argonne National Laboratory (ANL). Subsequently, the code has undergone several updates, and significant improvements have been achieved. The capability of generating group-collapsed micro- or macroscopic cross sections from the ENDF/B-V library and the more recent evaluation, ENDF/B-VI, in the ISOTXS format makes the modified version of the WIMSD4 code, WIMSD4M, very attractive, not only for the RERTR program, but also for the reactor physics community. The intent of the present paper is to validate the WIMSD4M cross-section librariesmore » for reactor modeling of fresh water moderated cores. The results of calculations performed with multigroup cross-section data generated with the WIMSD4M code will be compared against experimental results. These results correspond to calculations carried out with thermal reactor benchmarks of the Oak Ridge National Laboratory (ORNL) unreflected HEU critical spheres, the TRX LEU critical experiments, and calculations of a modified Los Alamos HEU D{sub 2}O moderated benchmark critical system. The benchmark calculations were performed with the discrete-ordinates transport code, TWODANT, using WIMSD4M cross-section data. Transport calculations using the XSDRNPM module of the SCALE code system are also included. In addition to transport calculations, diffusion calculations with the DIF3D code were also carried out, since the DIF3D code is used in the RERTR program for reactor analysis and design. For completeness, Monte Carlo results of calculations performed with the VIM and MCNP codes are also presented.« less

Constructing and Validating 3D-pharmacophore Models to a Set of MMP-9 Inhibitors for Designing Novel Anti-melanoma Agents.

PubMed

Medeiros Turra, Kely; Pineda Rivelli, Diogo; Berlanga de Moraes Barros, Silvia; Mesquita Pasqualoto, Kerly Fernanda

2016-07-01

A receptor-independent (RI) four-dimensional structure-activity relationship (4D-QSAR) formalism was applied to a set of sixty-four β-N-biaryl ether sulfonamide hydroxamate derivatives, previously reported as potent inhibitors against matrix metalloproteinase subtype 9 (MMP-9). MMP-9 belongs to a group of enzymes related to the cleavage of several extracellular matrix components and has been associated to cancer invasiveness/metastasis. The best RI 4D-QSAR model was statistically significant (N=47; r(2) =0.91; q(2) =0.83; LSE=0.09; LOF=0.35; outliers=0). Leave-N-out (LNO) and y-randomization approaches indicated the QSAR model was robust and presented no chance correlation, respectively. Furthermore, it also had good external predictability (82 %) regarding the test set (N=17). In addition, the grid cell occupancy descriptors (GCOD) of the predicted bioactive conformation for the most potent inhibitor were successfully interpreted when docked into the MMP-9 active site. The 3D-pharmacophore findings were used to predict novel ligands and exploit the MMP-9 calculated binding affinity through molecular docking procedure. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Insights into stability, electronic properties, defect properties and Li ions migration of Na, Mg and Al-doped LiVPO4F for cathode materials of lithium ion batteries: A first-principles investigation

NASA Astrophysics Data System (ADS)

Lv, Xiaojun; Xu, Zhenming; Li, Jie; Chen, Jiangan; Liu, Qingsheng

2016-07-01

The effects of Na, Mg and Al doping on the structure, electronic property, defect property and Li ions migration of LiVPO4F were investigated by the first-principles method. Calculations show that the processes of forming Li0.875Na0.125VPO4F, α- and β-LiMg0.375V0.75PO4F, α- and β-LiAl0.125V0.875PO4F are all feasible. Na, Mg and Al doping significantly improve the electrical conductivity of LiVPO4F and simultaneously maintain their structural stability attributing to the reduction of band gaps through variations of V-3d spin up orbitals. Li vacancy defects of LiVPO4F are not ignorable, and vacancy defects with a lower activation energy for Li atom are far more likely to occur than Frenkel defects for Li and vacancy defects for other atoms. For pristine LiVPO4F, path D along [0.012 0 . 17 ̅ 0.572] direction is found to have the lowest activation energy of 0.418 eV, suggesting that anisotropic nature of Li ion conduction and LiVPO4F is a one-dimensional (1D)-ion conductor. The corresponding diffusion coefficient was estimated to be 2.82×10-9 cm2/s, which is in good agreement with those experimental values.

An energy balance of front crawl.

PubMed

Zamparo, P; Pendergast, D R; Mollendorf, J; Termin, A; Minetti, A E

2005-05-01

With the aim of computing a complete energy balance of front crawl, the energy cost per unit distance (C = Ev(-1), where E is the metabolic power and v is the speed) and the overall efficiency (eta(o) = W(tot)/C, where W(tot) is the mechanical work per unit distance) were calculated for subjects swimming with and without fins. In aquatic locomotion W(tot) is given by the sum of: (1) W(int), the internal work, which was calculated from video analysis, (2) W(d), the work to overcome hydrodynamic resistance, which was calculated from measures of active drag, and (3) W(k), calculated from measures of Froude efficiency (eta(F)). In turn, eta(F) = W(d)/(W(d) + W(k)) and was calculated by modelling the arm movement as that of a paddle wheel. When swimming at speeds from 1.0 to 1.4 m s(-1), eta(F) is about 0.5, power to overcome water resistance (active body drag x v) and power to give water kinetic energy increase from 50 to 100 W, and internal mechanical power from 10 to 30 W. In the same range of speeds E increases from 600 to 1,200 W and C from 600 to 800 J m(-1). The use of fins decreases total mechanical power and C by the same amount (10-15%) so that eta(o) (overall efficiency) is the same when swimming with or without fins [0.20 (0.03)]. The values of eta(o) are higher than previously reported for the front crawl, essentially because of the larger values of W(tot) calculated in this study. This is so because the contribution of W(int) to W(tot )was taken into account, and because eta(F) was computed by also taking into account the contribution of the legs to forward propulsion.

Structural, spectral and NBO analysis of 3-(1-(3-hydroxypropylamino)ethylidene)chroman-2,4-dione

NASA Astrophysics Data System (ADS)

Avdović, Edina H.; Milenković, Dejan; Dimitrić-Marković, Jasmina M.; Vuković, Nenad; Trifunović, Srećko R.; Marković, Zoran

2017-11-01

The structure of the newly synthesized coumarin derivative, 3-(1-(3-hydroxypropylamino)-ethylidene)-chroman-2,4-dione, was investigated experimentally and theoretically. FTIR, 1H and 13C NMR spectroscopic methods along with the density functional theory calculations, with B3LYP functional (and with empirical dispersion corrections D3BJ) in combination with the 6-311+G(d,p) basis set, are performed in order to characterize the molecular structure and spectroscopic behavior of the investigated coumarin derivative. Molecular docking analysis was carried out in order to identify the potency of inhibition of the title molecule against human C-reactive protein. The inhibition activity was obtained for ten conformations of ligand inside protein.

Ab Initio Crystal Field for Lanthanides.

PubMed

Ungur, Liviu; Chibotaru, Liviu F

2017-03-13

An ab initio methodology for the first-principle derivation of crystal-field (CF) parameters for lanthanides is described. The methodology is applied to the analysis of CF parameters in [Tb(Pc) 2 ] - (Pc=phthalocyanine) and Dy 4 K 2 ([Dy 4 K 2 O(OtBu) 12 ]) complexes, and compared with often used approximate and model descriptions. It is found that the application of geometry symmetrization, and the use of electrostatic point-charge and phenomenological CF models, lead to unacceptably large deviations from predictions based on ab initio calculations for experimental geometry. It is shown how the predictions of standard CASSCF (Complete Active Space Self-Consistent Field) calculations (with 4f orbitals in the active space) can be systematically improved by including effects of dynamical electronic correlation (CASPT2 step) and by admixing electronic configurations of the 5d shell. This is exemplified for the well-studied Er-trensal complex (H 3 trensal=2,2',2"-tris(salicylideneimido)trimethylamine). The electrostatic contributions to CF parameters in this complex, calculated with true charge distributions in the ligands, yield less than half of the total CF splitting, thus pointing to the dominant role of covalent effects. This analysis allows the conclusion that ab initio crystal field is an essential tool for the decent description of lanthanides. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Atomic data on inelastic processes in low-energy manganese-hydrogen collisions

NASA Astrophysics Data System (ADS)

Belyaev, Andrey K.; Voronov, Yaroslav V.

2017-10-01

Aims: The aim of this paper is to calculate cross sections and rate coefficients for inelastic processes in low-energy Mn + H and Mn+ + H- collisions, especially, for processes with high and moderate rate coefficients. These processes are required for non-local thermodynamic equilibrium (non-LTE) modeling of manganese spectra in cool stellar atmospheres, and in particular, for metal-poor stars. Methods: The calculations of the cross sections and the rate coefficients were performed by means of the quantum model approach within the framework of the Born-Oppenheimer formalism, that is, the asymptotic semi-empirical method for the electronic MnH molecular structure calculation followed by the nonadiabatic nuclear dynamical calculation by means of the multichannel analytic formulas. Results: The cross sections and the rate coefficients for low-energy inelastic processes in manganese-hydrogen collisions are calculated for all transitions between 21 low-lying covalent states and one ionic state. We show that the highest values of the cross sections and the rate coefficients correspond to the mutual neutralization processes into the final atomic states Mn(3d54s(7S)5s e 6S), Mn(3d54s(7S)5p y 8P°), Mn(3d54s(7S)5s e 8S), Mn(3d54s(7S)4d e 8D) [the first group], the processes with the rate coefficients (at temperature T = 6000 K) of the values 4.38 × 10-8, 2.72 × 10-8, 1.98 × 10-8, and 1.59 × 10-8 cm3/ s, respectively, that is, with the rate coefficients exceeding 10-8 cm3/ s. The processes with moderate rate coefficients, that is, with values between 10-10 and 10-8 cm3/ s include many excitation, de-excitation, mutual neutralization and ion-pair formation processes. In addition to other processes involving the atomic states from the first group, the processes from the second group include those involving the following atomic states: Mn(3d5(6S)4s4p (1P°) y 6P°), Mn(3d54s(7S)4d e 6D), Mn(3d54s(7S)5p w 6P°), Mn(3d5(4P)4s4p (3P°) y 6D°), Mn(3d5(4G)4s4p (3P°) y 6F°). The processes with the highest and moderate rate coefficients are expected to be important for non-LTE modeling of manganese spectra in stellar atmospheres. Rate coefficients Kif(T) for the excitation, de-excitation, mutual neutralization, and ion-pair formation processes in manganese-hydrogen collisions 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/606/A106

Sorption of biodegradation end products of nonylphenol polyethoxylates onto activated sludge.

PubMed

Hung, Nguyen Viet; Tateda, Masafumi; Ike, Michihiko; Fujita, Masanori; Tsunoi, Shinji; Tanaka, Minoru

2004-01-01

Nonylphenol(NP), nonylphenoxy acetic acid (NP1EC), nonylphenol monoethoxy acetic acid (NP2EC), nonylphenol monoethoxylate (NP1EO) and nonylphenol diethoxylate (NP2EO) are biodegradation end products (BEPs) of nonionic surfactant nonylphenolpolyethoxylates (NPnEO). In this research, sorption of these compounds onto model activated sludge was characterized. Sorption equilibrium experiments showed that NP, NP1EO and NP2EO reached equilibrium in about 12 h, while equilibrium of NP1EC and NP2EC were reached earlier, in about 4 h. In sorption isotherm experiments, obtained equilibrium data at 28 degrees C fitted well to Freundlich sorption model for all investigated compounds. For NP1EC, in addition to Freundlich, equilibrium data also fitted well to Langmuir model. Linear sorption model was also tried, and equilibrium data of all NP, NP1EO, NP2EO and NP2EC except NP1EC fitted well to this model. Calculated Freundlich coefficient (K(F)) and linear sorption coefficient (K(D)) showed that sorption capacity of the investigated compounds were in order NP > NP2EO > NP1EO > NP1EC approximately NP2EC. For NP, NP1EO and NP2EO, high values of calculated K(F) and K(D) indicated an easy uptake of these compounds from aqueous phase onto activated sludge. Whereas, NP1EC and NP2EC with low values of K(F) and K(D) absorbed weakly to activated sludge and tended to preferably remain in aqueous phase.

Pretest Predictions for Phase II Ventilation Tests

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

Yiming Sun

The objective of this calculation is to predict the temperatures of the ventilating air, waste package surface, and concrete pipe walls that will be developed during the Phase II ventilation tests involving various test conditions. The results will be used as inputs to validating numerical approach for modeling continuous ventilation, and be used to support the repository subsurface design. The scope of the calculation is to identify the physical mechanisms and parameters related to thermal response in the Phase II ventilation tests, and describe numerical methods that are used to calculate the effects of continuous ventilation. The calculation is limitedmore » to thermal effect only. This engineering work activity is conducted in accordance with the ''Technical Work Plan for: Subsurface Performance Testing for License Application (LA) for Fiscal Year 2001'' (CRWMS M&O 2000d). This technical work plan (TWP) includes an AP-2.21Q, ''Quality Determinations and Planning for Scientific, Engineering, and Regulatory Compliance Activities'', activity evaluation (CRWMS M&O 2000d, Addendum A) that has determined this activity is subject to the YMP quality assurance (QA) program. The calculation is developed in accordance with the AP-3.12Q procedure, ''Calculations''. Additional background information regarding this activity is contained in the ''Development Plan for Ventilation Pretest Predictive Calculation'' (DP) (CRWMS M&O 2000a).« less

Exploration geophysics calculator programs for use on Hewlett-Packard models 67 and 97 programmable calculators

USGS Publications Warehouse

Campbell, David L.; Watts, Raymond D.

1978-01-01

Program listing, instructions, and example problems are given for 12 programs for the interpretation of geophysical data, for use on Hewlett-Packard models 67 and 97 programmable hand-held calculators. These are (1) gravity anomaly over 2D prism with = 9 vertices--Talwani method; (2) magnetic anomaly (?T, ?V, or ?H) over 2D prism with = 8 vertices?Talwani method; (3) total-field magnetic anomaly profile over thick sheet/thin dike; (4) single dipping seismic refractor--interpretation and design; (5) = 4 dipping seismic refractors--interpretation; (6) = 4 dipping seismic refractors?design; (7) vertical electrical sounding over = 10 horizontal layers--Schlumberger or Wenner forward calculation; (8) vertical electric sounding: Dar Zarrouk calculations; (9) magnetotelluric planewave apparent conductivity and phase angle over = 9 horizontal layers--forward calculation; (10) petrophysics: a.c. electrical parameters; (11) petrophysics: elastic constants; (12) digital convolution with = 10-1ength filter.

Construction of reactive potential energy surfaces with Gaussian process regression: active data selection

NASA Astrophysics Data System (ADS)

Guan, Yafu; Yang, Shuo; Zhang, Dong H.

2018-04-01

Gaussian process regression (GPR) is an efficient non-parametric method for constructing multi-dimensional potential energy surfaces (PESs) for polyatomic molecules. Since not only the posterior mean but also the posterior variance can be easily calculated, GPR provides a well-established model for active learning, through which PESs can be constructed more efficiently and accurately. We propose a strategy of active data selection for the construction of PESs with emphasis on low energy regions. Through three-dimensional (3D) example of H3, the validity of this strategy is verified. The PESs for two prototypically reactive systems, namely, H + H2O ↔ H2 + OH reaction and H + CH4 ↔ H2 + CH3 reaction are reconstructed. Only 920 and 4000 points are assembled to reconstruct these two PESs respectively. The accuracy of the GP PESs is not only tested by energy errors but also validated by quantum scattering calculations.

Study on Thermal Deformation Behavior of TC4 – ELI Titanium Alloy

NASA Astrophysics Data System (ADS)

Song, Y.; Zhang, F. S.; Huang, T.; Song, K. X.

2018-05-01

The TC4-ELI titanium alloy was subjected to hot compression deformation test by the Gleeble-1500D thermal simulation test machine. The thermal deformation behavior of the TC4-ELI titanium alloy was studied under the condition of 850°C-1050°C, 0.001s-1-10s-1 strain rate and 50% deformation. The constitutive equation of TC4-ELI titanium alloy was established based on the hyperbolic sine model of Arrhenius equation. The results show that the flow stress of TC4-ELI titanium alloy decreases with the increase of temperature at high temperature. The calculated heat activation energy of TC4-ELI titanium alloy is 300367.5807J / mol.

Theoretical study on the antitumor properties of Ru(II) complexes containing 2-pyridyl, 2-pyridine-4-carboxylic acid ligands

NASA Astrophysics Data System (ADS)

Erkan kariper, Sultan; Sayin, Koray; Karakaş, Duran

2017-12-01

[Ru(bipy)2(CppH)]2+(1), [Ru(bipy)2(Cpp-NH-Hex-COOH)]2+(2), [Ru(dppz)2(CppH)]2+(3) and [Ru(dppz)2(Cpp-NH-Hex-COOH)]2+(4) were calculated by Hartree-Fock (HF), Density Functional Theory (DFT) hybrid B3LYP and Moller-Plesset Perturbation (MPn n = 2,3) theory method and CEP-4G, CEP-31G, CEP-121G, LANL2DZ, LANL2MB, SDD basic sets and a mixed basic set with the keyword GEN in gas phase and water. Structure parameters obtained from optimized structures were compared with experimental parameters. M062X/(6-31G(d))(CEP-4G) level was taken into account for the most appropriate calculation level. IR, UV-VIS and NMR spectrums were examined for structural characterization. The optimal structure was identified via structure parameters, IR, UV-VIS and NMR spectrums. For the most compatible structure, the highest molecular orbital energy (EHOMO) which one of the most effective chemical determiners on the antitumor activity of the complexes, the lowest molecular orbital energy (ELUMO), LUMO-HOMO energy gap, hardness (η), softness (σ), electronegativity (χ), chemical potential (μ), electrophilicity index (ω), molar volume (V), dipole moment (DM), total negative charge (TNC), enthalpy (H), entropy (S) and total energy (E) were calculated. The causes of anticancer activity of the complexes have been studied.

Synthesis of Wurtzite Cu2ZnSnS4 Nanosheets with Exposed High-Energy (002) Facets for Fabrication of Efficient Pt-Free Solar Cell Counter Electrodes.

PubMed

Zhang, Xiaoyan; Xu, You; Zhang, Junjie; Dong, Shuai; Shen, Liming; Gupta, Arunava; Bao, Ningzhong

2018-01-10

Two-dimensional (2D) semiconducting nanomaterials have generated much interest both because of fundamental scientific interest and technological applications arising from the unique properties in two dimensions. However, the colloidal synthesis of 2D quaternary chalcogenide nanomaterials remains a great challenge owing to the lack of intrinsic driving force for its anisotropic growth. 2D wurtzite Cu 2 ZnSnS 4 nanosheets (CZTS-NS) with high-energy (002) facets have been obtained for the first time via a simple one-pot thermal decomposition method. The CZTS-NS exhibits superior photoelectrochemical activity as compared to zero-dimensional CZTS nanospheres and comparable performance to Pt counter electrode for dye sensitized solar cells. The improved catalytic activity can be attributed to additional reactive catalytic sites and higher catalytic reactivity in high-energy (002) facets of 2D CZTS-NS. This is in accordance with the density functional theory (DFT) calculations, which indicates that the (002) facets of wurtzite CZTS-NS possess higher surface energy and exhibits remarkable reducibility for I 3 - ions. The developed synthetic method and findings will be helpful for the design and synthesis of 2D semiconducting nanomaterials, especially eco-friendly copper chalcogenide nanocrystals for energy harvesting and photoelectric applications.

Synthesis, crystal structures, computational studies and antimicrobial activity of new designed bis((5-aryl-1,3,4-oxadiazol-2-yl)thio)alkanes

NASA Astrophysics Data System (ADS)

Ahmed, Muhammad Naeem; Sadiq, Beenish; Al-Masoudi, Najim A.; Yasin, Khawaja Ansar; Hameed, Shahid; Mahmood, Tariq; Ayub, Khurshid; Tahir, Muhammad Nawaz

2018-03-01

A new series of bis((5-aryl-1,3,4-oxadiazol-2-yl)thio)alkanes 4-14 have been synthesized via nucleophilic substitution reaction of dihaloalkanes with respective 1,3,4-oxadiazole-2-thiols 3a-f, and characterized by spectroscopic techniques. The structures of 4 and 12 were unambiguously confirmed by single-crystal X-ray diffraction analysis. Density functional theory calculations at B3LYP/6-31 + G(d) level of theory were performed for comparison of X-ray geometric parameters, molecular electrostatic potential (MEP) and frontier molecular orbital analyses of synthesized compounds. MEP analysis revealed that these compounds are nucleophilic in nature. Frontier molecular orbitals (FMOs) analysis of 4-14 was performed for evaluation of kinetic stability. All synthesized compounds were screened in vitro for antimicrobial activity against three bacterial and three fungal strains and showed promising results.

Theoretical and vibrational study of N-(3-chloro-4-fluoro-phenyl)-7-methoxy-6-(3-morpholin-4-ylpropoxy)-quinazolin-4-amine (gefitinib)

NASA Astrophysics Data System (ADS)

Mıhçıokur, Özlem; Özpozan, Talat

2015-12-01

N-(3-chloro-4fluoro-phenyl)-7-methoxy-6-(3-morpholin-4ylpropoxy)-quinazolin-4-amine (GEF), a quinalizoline derivative used as new anti-cancer agent, designed to target activity of epidermal growth factor receptor (EGFR) promoting the growth, division and spread of cancer cells, was examined from the vibrational and theoretical point of view. All calculations have been carried out both in gaseous and aqueous phases. In the calculations of both phases, the molecule has been optimized through conformer analysis beginning with the x-ray data. The conformer analyses have been carried out in each phases and the geometrical differences between the most stable structures in gaseous and in aqueous phases have been discussed. The solvent effect for GEF in aqueous solution was simulated by using self-consistent reaction field (SCRF) calculations employing the integral equation formalism variant (IEFPCM) model. NBO analysis has been performed to indicate the presence of intramolecular charge transfer. The complete assignments of the vibrational spectra (IR&Raman) were made with the aid of calculated spectra both in gaseous and aqueous phases. The observed spectral data of the title compound were compared with the calculated spectra obtained by DFT/B3LYP and DFT/B3PW91 methods using 6-31G(d,p) basis set. The theoretical results were found to be in good agreement with the measured experimental data especially for the interpretation of intra molecular interactions.

Theoretical Investigation of Methane Hydroxylation over Isoelectronic [FeO]2+- and [MnO]+-Exchanged Zeolites Activated by N2O.

PubMed

Mahyuddin, M Haris; Shiota, Yoshihito; Staykov, Aleksandar; Yoshizawa, Kazunari

2017-09-05

While the most likely structure of the active site in iron-containing zeolites has been recently identified as [FeO] 2+ (Snyder et al. Nature 2016, 536, 317-321), the mechanism for the direct conversion of methane to methanol over this active species is still debatable between the direct-radical-rebound or nonradical (concerted) mechanism. Using density functional theory on periodic systems, we calculated the two reaction mechanisms over two d 4 isoelectronic systems, [FeO] 2+ and [MnO] + zeolites. We found that [FeO] 2+ zeolites favor the direct-radical-rebound mechanism with low CH 4 activation energies, while [MnO] + zeolites prefer the nonradical mechanism with higher CH 4 activation energies. These contrasts, despite their isoelectronic structures, are mainly due to the differences in the metal coordination number and O α (oxo) spin density. Moreover, molecular orbital analyses suggest that the zeolite steric hindrance further degrades the reactivity of [MnO] + zeolites toward methane. Two types of zeolite frameworks, i.e., medium-pore ZSM-5 (MFI framework) and small-pore SSZ-39 (AEI framework) zeolites, were evaluated, but no significant differences in the reactivity were found. The rate-determining reaction step is found to be methanol desorption instead of methane activation. Careful examination of the most stable sites hosting the active species and calculation for N 2 O decomposition over [Fe] 2+ -MFI and -AEI zeolites were also performed.

Potential dosimetric benefits of adaptive tumor tracking over the internal target volume concept for stereotactic body radiation therapy of pancreatic cancer.

PubMed

Karava, Konstantina; Ehrbar, Stefanie; Riesterer, Oliver; Roesch, Johannes; Glatz, Stefan; Klöck, Stephan; Guckenberger, Matthias; Tanadini-Lang, Stephanie

2017-11-09

Radiotherapy for pancreatic cancer has two major challenges: (I) the tumor is adjacent to several critical organs and, (II) the mobility of both, the tumor and its surrounding organs at risk (OARs). A treatment planning study simulating stereotactic body radiation therapy (SBRT) for pancreatic tumors with both the internal target volume (ITV) concept and the tumor tracking approach was performed. The two respiratory motion-management techniques were compared in terms of doses to the target volume and organs at risk. Two volumetric-modulated arc therapy (VMAT) treatment plans (5 × 5 Gy) were created for each of the 12 previously treated pancreatic cancer patients, one using the ITV concept and one the tumor tracking approach. To better evaluate the overall dose delivered to the moving tumor volume, 4D dose calculations were performed on four-dimensional computed tomography (4DCT) scans. The resulting planning target volume (PTV) size for each technique was analyzed. Target and OAR dose parameters were reported and analyzed for both 3D and 4D dose calculation. Tumor motion ranged from 1.3 to 11.2 mm. Tracking led to a reduction of PTV size (max. 39.2%) accompanied with significant better tumor coverage (p<0.05, paired Wilcoxon signed rank test) both in 3D and 4D dose calculations and improved organ at risk sparing. Especially for duodenum, stomach and liver, the mean dose was significantly reduced (p<0.05) with tracking for 3D and 4D dose calculations. By using an adaptive tumor tracking approach for respiratory-induced pancreatic motion management, a significant reduction in PTV size can be achieved, which subsequently facilitates treatment planning, and improves organ dose sparing. The dosimetric benefit of tumor tracking is organ and patient-specific.

Effect of foot type on knee valgus, ground reaction force, and hip muscle activation in female soccer players.

PubMed

Rath, Meghan E; Stearne, David J; Walker, Cameron R; Cox, Jaime C

2016-05-01

The purpose of this study was to determine the degree to which subtalar joint pronation resulting from a supple planus foot affects knee alignment, hip muscle activation and ground reaction force attenuation in female athletes during a broad jump-to-cut maneuver. Twelve National Collegiate Athletic Association (NCAA) Division II female soccer players (age=19.4±1.4 years, height=1.64±0.05 m, mass=64.10±4.8 kg) were identified as having either supple planus (SP) or rigid feet (RF). Participants completed three broad jump-to-cut trials onto a force plate while EMG and motion data were collected. Muscle activation levels (percentage of maximal voluntary contraction [%MVC]) in the gluteus maximus, gluteus medius, biceps femoris, and rectus femoris were calculated, and peak vertical and medial shear force, rate of loading, and valgus angle were collected for each trial. Mann-Whitney U tests revealed no statistical significance between foot-type groups, however, effect size statistics revealed practical significance for between-group %MVC biceps femoris (d=1.107), %MVC gluteus maximus (d=1.069), and vertical ground reaction force (d=1.061). Athletes with a SP foot type may experience decreased hip muscle activation associated with increased vertical ground reaction force during a broad jump-to-cut maneuver. This might result in reduced dynamic stability and neuromuscular control during deceleration, potentially increasing the risk of non-contact ACL injury in female soccer players.

Characterization and Thermal Decomposition of Nanometer 2,2', 4,4', 6,6'-Hexanitro-Stilbene and 1,3,5-Triamino-2,4,6-Trinitrobenzene Fabricated by a Mechanical Milling Method

NASA Astrophysics Data System (ADS)

Song, Xiaolan; Wang, Yi; Zhao, Shanshan; An, Chongwei; Wang, Jingyu; Zhang, Jinglin

2018-04-01

Nanometer 2,2', 4,4', 6,6'-hexanitro-stilbene (HNS) and 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) were fabricated on a high-energy ball mill. The particle sizes of nano-HNS and nano-TATB were 98.4 and 57.8 nm, respectively. An SEM analysis was employed to image the micron morphology of nano-explosives. The particle size distribution was calculated by measuring the size of 300 particles in SEM images. XRD, IR, and XPS analyses were used to confirm whether the crystal phase, molecule structure, and surface elements were changed by the milling process. Thermal decomposition of nano-HNS and nano-TATB was investigated by differential scanning calorimetry (DSC) and thermal-infrared spectrometry online (DSC-IR) analyses. Using DSC traces collected from different heating rates, the kinetic and thermodynamic parameters of thermolysis of raw and nano-explosives were calculated (activation energy (EK), pre-exponential factor (lnAK), rate constant (k), activation heat (ΔH≠), activation free energy (ΔG≠), activation entropy (ΔS≠), critical temperature of thermal explosion (Tb), and critical heating rate of thermal explosion (dT/dt)Tb). The results indicated that nano-explosives were of different kinetic and thermodynamic properties from starting explosives. In addition, the gas products for thermal decomposition of nano-HNS and nano-TATB were detected. Although HNS and TATB are both nitro explosives, the decomposition products of the two were different. A mechanism to explain the difference is proposed.

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

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

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

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

H→γγ as a Triangle Anomaly: Possible Implications for the Hierarchy Problem

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

de Gouvea, Andre; Kile, Jennifer; Vega-Morales, Roberto

2013-06-24

The Standard Model calculation of H→γγ has the curious feature of being finite but regulator-dependent. While dimensional regularization yields a result which respects the electromagnetic Ward identities, additional terms which violate gauge invariance arise if the calculation is done setting d = 4. This discrepancy between the d=4 – ϵ and d = 4 results is recognized as a true ambiguity which must be resolved using physics input; as dimensional regularization respects gauge invariance, the d = 4 – ϵ calculation is accepted as the correct SM result. However, here we point out another possibility; working in analogy with the gauge chiral anomaly, we note that it is possible that the individual diagrams do violate the electromagnetic Ward identities, but that the gauge-invariance-violating terms cancel when all contributions to H→γγ, both from the SM and from new physics, are included. We thus examine the consequences of the hypothesis that the d = 4 calculation is valid, but that such a cancellation occurs. We work in general renormalizable gauge, thus avoiding issues with momentum routing ambiguities. We point out that the gauge-invariance-violating terms in d = 4 arise not just for the diagram containing a SMmore » $$W^{\\pm}$$ boson, but also for general fermion and scalar loops, and relate these terms to a lack of shift invariance in Higgs tadpole diagrams. We then derive the analogue of "anomaly cancellation conditions", and find consequences for solutions to the hierarchy problem. In particular, we find that supersymmetry obeys these conditions, even if it is softly broken at an arbitrarily high scale.« less

Association of different biomarkers of renal function with D-dimer levels in patients with type 1 diabetes mellitus (renal biomarkers and D-dimer in diabetes).

PubMed

Domingueti, Caroline Pereira; Fóscolo, Rodrigo Bastos; Dusse, Luci Maria S; Reis, Janice Sepúlveda; Carvalho, Maria das Graças; Gomes, Karina Braga; Fernandes, Ana Paula

2018-02-01

Objective This study aimed to evaluate the association between different renal biomarkers with D-Dimer levels in diabetes mellitus (DM1) patients group classified as: low D-Dimer levels (< 318 ng/mL), which included first and second D-Dimer tertiles, and high D-Dimer levels (≥ 318 ng/mL), which included third D-Dimer tertile. Materials and methods D-Dimer and cystatin C were measured by ELISA. Creatinine and urea were determined by enzymatic method. Estimated glomerular filtration rate (eGFR) was calculated using CKD-EPI equation. Albuminuria was assessed by immunoturbidimetry. Presence of renal disease was evaluated using each renal biomarker: creatinine, urea, cystatin C, eGFR and albuminuria. Bivariate logistic regression analysis was performed to assess which renal biomarkers are associated with high D-Dimer levels and odds ratio was calculated. After, multivariate logistic regression analysis was performed to assess which renal biomarkers are associated with high D-Dimer levels (after adjusting for sex and age) and odds ratio was calculated. Results Cystatin C presented a better association [OR of 9.8 (3.8-25.5)] with high D-Dimer levels than albuminuria, creatinine, eGFR and urea [OR of 5.3 (2.2-12.9), 8.4 (2.5-25.4), 9.1 (2.6-31.4) and 3.5 (1.4-8.4), respectively] after adjusting for sex and age. All biomarkers showed a good association with D-Dimer levels, and consequently, with hypercoagulability status, and cystatin C showed the best association among them. Conclusion Therefore, cystatin C might be useful to detect patients with incipient diabetic kidney disease that present an increased risk of cardiovascular disease, contributing to an early adoption of reno and cardioprotective therapies.

Surface-enhanced Raman spectroscopy of hexabenzobenzene, C24H12, an analogue of a graphene nanostructure

NASA Astrophysics Data System (ADS)

Owens, Frank J.

2018-05-01

While large scale fabrication of graphene nanoribbons remains a challenge, there exist materials which can be fabricated in quantities such as hexabenzobenzene,HBZB, (C24H12) and which have a two-dimensional (2D) carbon structure similar to graphene nanostructures. Using a 632 nm laser, no Raman spectra could be obtained from the solid material because of a strong luminescence produced by the laser. However, surface-enhanced Raman spectroscopy enabled the measurement of some of the Raman active modes. The G and D modes, which are characteristic fingerprints of a 2D graphene structure, were observed at 1331 and 1600 cm-1, respectively. Density functional theory at the B3LYP/6-31G* level was used to calculate the minimum energy structure and the Raman active vibrational frequencies of HBZB. The calculated minimum energy structure was 2D having D6h symmetry in agreement with the experimental structure in the liquid phase. The calculated frequencies were in good agreement with the measured values.

Pharmacophore Modelling and 4D-QSAR Study of Ruthenium(II) Arene Complexes as Anticancer Agents (Inhibitors) by Electron Conformational- Genetic Algorithm Method.

PubMed

Yavuz, Sevtap Caglar; Sabanci, Nazmiye; Saripinar, Emin

2018-01-01

The EC-GA method was employed in this study as a 4D-QSAR method, for the identification of the pharmacophore (Pha) of ruthenium(II) arene complex derivatives and quantitative prediction of activity. The arrangement of the computed geometric and electronic parameters for atoms and bonds of each compound occurring in a matrix is known as the electron-conformational matrix of congruity (ECMC). It contains the data from HF/3-21G level calculations. Compounds were represented by a group of conformers for each compound rather than a single conformation, known as fourth dimension to generate the model. ECMCs were compared within a certain range of tolerance values by using the EMRE program and the responsible pharmacophore group for ruthenium(II) arene complex derivatives was found. For selecting the sub-parameter which had the most effect on activity in the series and the calculation of theoretical activity values, the non-linear least square method and genetic algorithm which are included in the EMRE program were used. In addition, compounds were classified as the training and test set and the accuracy of the models was tested by cross-validation statistically. The model for training and test sets attained by the optimum 10 parameters gave highly satisfactory results with R2 training= 0.817, q 2=0.718 and SEtraining=0.066, q2 ext1 = 0.867, q2 ext2 = 0.849, q2 ext3 =0.895, ccctr = 0.895, ccctest = 0.930 and cccall = 0.905. Since there is no 4D-QSAR research on metal based organic complexes in the literature, this study is original and gives a powerful tool to the design of novel and selective ruthenium(II) arene complexes. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Effects of doping on photocatalytic activity for water splitting of metal oxides and nitride

NASA Astrophysics Data System (ADS)

Arai, Naoki; Saito, Nobuo; Nishiyama, Hiroshi; Kadowaki, Haruhiko; Kobayashi, Hisayoshi; Sato, Kazunori; Inoue, Yasunobu

2007-09-01

The effects of metal-ion doping or replacement on the photocatalytic performance for water splitting of d 10 and d 0 metal oxides and d 10 metal nitride were studied. The photocatalysts examined were (1) α-Ga 2-2xIn 2xO 3 and ZnGa 2-2xIn 2xO 4 in which In 3+ was added to Ga IIO 3 and ZnGa IIO 4, respectively, (2) Y xIn 2-xO 3 being a solid solution of In IIO 3 and Y IIO 3, (3) metal ion doped CeO II, and (4) metal ion doped GaN. The photocatalytic activity of 1 wt % RuO II-loaded α-Ga 2-2xIn 2xO 3 increased sharply with increasing x, reached a maximum at around x=0.02, and considerably decreased with further increase in x. The DFT calculation showed that the band structures of α-Ga 2-2xIn 2xO 3 had the contribution of In 4d orbital to the valence band and of In5s orbital to the conduction band. Similar effects were observed for ZnGa 2-2xIn 2xO 4. RuO II-dispersed Y xIn 2-xO 3 had a capability of producing H II and O II in the range x=1.0-1.5 in which the highest activity was obtained at x=1.3. The structures of both InO 6 and YO 6 octahedra were deformed in the solid solution,, and the hybridization of In5s5p and Y4d orbitals in the conduction band was enhanced. Undoped CeO II was photocatalytically inactive, but metal ion-doped CeO II showed a considerable photocatalytic activity. The activation occurred in the case that metal ions doped had larger ion sizes than that of Ce 4+. The small amount doping of divalent metal ions (Zn 2+ and Mg 2+) converted photocatalytically inactive GaN to an efficient photocatalyst. The doping was shown to produce p-type GaN which had the large concentration and high mobility of holes. The roles of metal ion doping and replacement in the photocatalytic properties are discussed.

New spiro-oxindole constructed with pyrrolidine/thioxothiazolidin-4-one derivatives: Regioselective synthesis, X-ray crystal structures, Hirshfeld surface analysis, DFT, docking and antimicrobial studies

NASA Astrophysics Data System (ADS)

Barakat, Assem; Soliman, Saied M.; Al-Majid, Abdullah Mohammed; Ali, M.; Islam, Mohammad Shahidul; Elshaier, Yaseen A. M. M.; Ghabbour, Hazem A.

2018-01-01

In this work, polycyclic heterocycles containing spirooxindole, pyrrolidine, and thioxothiazolidin-4-one rings have been synthesized via the regioselective 1,3-dipolar cycloaddition of azomethine ylide, which is generated in situ by the condensation of the dicarbonyl compound isatin and the secondary amino acid (L-proline), with 5-arylidine-2-thioxothiazolidin-4-one as the dipolarophile. The structure of the synthesized compounds 4a and 4b were determined by using X-ray single crystal diffraction, and also, Hirshfeld surface analysis were reported. Their geometric parameters were calculated using density functional theory at the B3LYP/6-311G (d,p) level of theory. Both compounds showed antimicrobial and antifungal activity better than selected standards (ampicillin and gentamicin in case of antibacterial activity and Amphotericin A and fluconazole in case of antifungal activity). Molecular docking study of the synthesized compounds indicated that phenyl group plays an important role in determination of compound interaction inside the receptors.

Substance-P antagonists: effect on spontaneous and drug-induced locomotor activity in the rat.

PubMed

Elliott, P J; Iversen, S D

1987-05-01

The substance P (SP) antagonists (D-Pro4, D-Trp7,9, Leu11) SP(4-11), (D-Pro4, D-Trp7,9, Phe11)SP(4-11) and (D-Pro4, D-Trp7,9,10, Leu11) SP (4-11) were infused into the lateral ventricles (i.c.v.) and their effects on spontaneous and drug-induced locomotor activity were investigated. The drug DiMeC7, the stable substance P agonist, was used to stimulate locomotor activity because of its prolonged action. Only (D-Pro4, D-Trp7,9,10) SP (4-11) was found to attenuate the drug-induced increases in motor activity, indicating that it is a substance P antagonist with activity in the CNS.

Signature of chaos in the 4 f -core-excited states for highly-charged tungsten ions

NASA Astrophysics Data System (ADS)

Safronova, Ulyana; Safronova, Alla

2014-05-01

We evaluate radiative and autoionizing transition rates in highly charged W ions in search for the signature of chaos. In particularly, previously published results for Ag-like W27+, Tm-like W5+, and Yb-like W4+ ions as well as newly obtained for I-like W21+, Xe-like W20+, Cs-like W19+, and La-like W17+ ions (with ground configuration [Kr] 4d10 4fk with k = 7, 8, 9, and 11, respectively) are considered that were calculated using the multiconfiguration relativistic Hebrew University Lawrence Livermore Atomic Code (HULLAC code) and the Hartree-Fock-Relativistic method (COWAN code). The main emphasis was on verification of Gaussian statistics of rates as a function of transition energy. There was no evidence of such statistics for above mentioned previously published results as well as for the transitions between the excited and autoionizing states for newly calculated results. However, we did find the Gaussian profile for the transitions between excited states such as the [Kr] 4d10 4fk - [Kr] 4d10 4f k - 1 5 d transitions , for newly calculated W ions. This work is supported in part by DOE under NNSA Cooperative Agreement DE-NA0001984.

Molecular structure, FT-IR, vibrational assignments, HOMO-LUMO, MEP, NBO analysis and molecular docking study of ethyl-6-(4-chlorophenyl)-4-(4-fluorophenyl)-2-oxocyclohex-3-ene-1-carboxylate.

PubMed

Sheena Mary, Y; Yohannan Panicker, C; Sapnakumari, M; Narayana, B; Sarojini, B K; Al-Saadi, Abdulaziz A; Van Alsenoy, Christian; War, Javeed Ahmad

2015-03-05

The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments of ethyl-6-(4-chlorophenyl)-4-(4-fluoro-phenyl)-2-oxocyclohex-3-ene-1-carboxylate have been investigated experimentally and theoretically using Gaussian09 software. The title compound was optimized using the HF and DFT levels of theory. The geometrical parameters are in agreement with the XRD data. The stability of the molecule has been analyzed by NBO analysis. The HOMO and LUMO analysis is used to determine the charge transfer within the molecule. Molecular electrostatic potential was performed by the DFT method. As can be seen from the MEP map of the title compound, regions having the negative potential are over the electro negative atoms, the region having the positive potential are over the phenyl rings and the remaining species are surrounded by zero potential. First hyperpolarizability is calculated in order to find its role in non linear optics. The title compound binds at the active sites of both CypD and β-secretase and the molecular docking results draw the conclusion that the compound might exhibit β-secretase inhibitory activity which could be utilized for development of new anti-alzheimeric drugs with mild CypD inhibitory activity. Copyright © 2014 Elsevier B.V. All rights reserved.

Molecular structure, vibrational spectra, NBO analysis, first hyperpolarizability, and HOMO-LUMO studies of 2-amino-4-hydroxypyrimidine by density functional method

NASA Astrophysics Data System (ADS)

Jeyavijayan, S.

2015-04-01

This study is a comparative analysis of FTIR and FT-Raman spectra of 2-amino-4-hydroxypyrimidine. The total energies of different conformations have been obtained from DFT (B3LYP) method with 6-31+G(d,p) and 6-311++G(d,p) basis sets. The barrier of planarity between the most stable and planar form is also predicted. The molecular structure, vibrational wavenumbers, infrared intensities, Raman scattering activities were calculated for the molecule using the B3LYP density functional theory (DFT) method. The computed values of frequencies are scaled using multiple scaling factors to yield good coherence with the observed values. Reliable vibrational assignments were made on the basis of total energy distribution (TED) along with scaled quantum mechanical (SQM) method. The stability of the molecule arising from hyperconjugative interactions, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. Non-linear properties such as electric dipole moment (μ), polarizability (α), and hyperpolarizability (β) values of the investigated molecule have been computed using B3LYP quantum chemical calculation. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. Besides, molecular electrostatic potential (MEP), Mulliken's charges analysis, and several thermodynamic properties were performed by the DFT method.

A program to compute the two-step excitation of mesospheric sodium atoms for the Polychromatic Laser Guide Star Project

NASA Astrophysics Data System (ADS)

Bellanger, Véronique; Courcelle, Arnaud; Petit, Alain

2004-09-01

A program to compute the two-step excitation of sodium atoms ( 3S→3P→4D) using the density-matrix formalism is presented. The BEACON program calculates population evolution and the number of photons emitted by fluorescence from the 3P, 4D, 4P, 4S levels. Program summaryTitle of program: BEACON Catalogue identifier:ADSX Program Summary URL:http://cpc.cs.qub.ac.uk/cpc/summaries/ADSX Program obtainable from: CPC Program Library, Queen's University of Belfast, N. Ireland Licensing provisions: none Operating systems under which the program has been tested: Win; Unix Programming language used: FORTRAN 77 Memory required to execute with typical data: 1 Mw Number of bits in a word: 32 Number of processors used: 1 (a parallel version of this code is also available and can be obtained on request) Number of lines in distributed program, including test data, etc.: 29 287 Number of bytes in distributed program, including test data, etc.: 830 331 Distribution format: tar.gz CPC Program Library subprograms used: none Nature of physical problem: Resolution of the Bloch equations in the case of the two-step laser excitation of sodium atoms. Method of solution: The program BEACON calculates the evolution of level population versus time using the density-matrix formalism. The number of photons emitted from the 3P, 4D and 4P levels is calculated using the branching ratios and the level lifetimes. Restriction on the complexity of the problem: Since the backscatter emission is calculated after the excitation process, excitation with laser pulse duration longer than the 4D level lifetime cannot be rigorously treated. Particularly, cw laser excitation cannot be calculated with this code. Typical running time:12 h

Degradation of polymer electrolyte membrane fuel cell by siloxane in biogas

NASA Astrophysics Data System (ADS)

Seo, Ji-Sung; Kim, Da-Yeong; Hwang, Sun-Mi; Seo, Min Ho; Seo, Dong-Jun; Yang, Seung Yong; Han, Chan Hui; Jung, Yong-Min; Guim, Hwanuk; Nahm, Kee Suk; Yoon, Young-Gi; Kim, Tae-Young

2016-06-01

We studied the degradation and durability of polymer electrolyte membrane fuel cell (PEMFC) at membrane-electrode-assembly (MEA) level by injection of octamethylcyclotetrasiloxane (D4) as a representative siloxane, which has been found in many industrial and personal products. Specifically, i) GC/MS analysis demonstrated that the ring-opening polymerization of D4 could result in the formation of various linear and cyclic siloxanes in both electrodes of MEA; ii) post-test analysis revealed that the transformed siloxanes were transported from the anode to the cathode via free-volumes in the polymer membrane; iii) RDE measurement and DFT calculation revealed that D4 was not directly responsible for the electrocatalytic activity of Pt; iv) electrochemical analysis demonstrated that the residual methyl groups of siloxane and various siloxanes did not hinder the proton transport in the polymer membrane; and v) siloxanes accumulated in the primary and secondary pores with the exception of an external surface of carbon, causing an increase in the oxygen reactant's resistance and resulting in a decrease of the cell performance. In addition, we confirmed that injection of D4 did not affect the carbon corrosion adversely because the siloxane had little influence on water sorption in the catalyst layer.

The second to fourth digit ratio (2D:4D) in Saudi boys with autism: A potential screening tool.

PubMed

Al-Zaid, Felwah S; Alhader, AbdelFattah A; Al-Ayadhi, Laila Y

2015-07-01

Autism is a neurodevelopment disorder with a strikingly higher prevalence in boys than girls. There are many theories regarding this gender bias, and prenatal exposure to high levels of fetal testosterone (FT) may be a predisposing factor. The second to fourth digit ratio (2D:4D) is the only indirect measure that reflects this association postnatally. Thus, this study measured the lengths of the index finger (2D) and the ring finger (4D) and calculated the 2D:4D ratio. Subsequently, this ratio was used to indirectly determine the potential prenatal exposure to high levels of FT in autistic children. This case-control study was conducted with 60 male children with 31 individuals having classic-onset autism and 29 individuals serving as age-matched, healthy controls. The lengths of both the index (2D) and the ring (4D) fingers of the right hand of both autism and control groups were obtained using a scanner and the 2D:4D ratio was calculated. The 2D:4D ratio in the current study was significantly lower in boys with autism compared to the controls (p ≤ 0.001). This study demonstrates a significantly lower 2D:4D ratio in Saudi boys with autism, which indirectly suggests that these boys were exposed to high levels of prenatal FT. Accordingly, prenatal exposure to high levels of FT is a risk factor for the development of autism, and the postnatal measurement of the 2D:4D ratio could be a potential screening tool. Copyright © 2015. Published by Elsevier Ireland Ltd.

3D QSAR models built on structure-based alignments of Abl tyrosine kinase inhibitors.

PubMed

Falchi, Federico; Manetti, Fabrizio; Carraro, Fabio; Naldini, Antonella; Maga, Giovanni; Crespan, Emmanuele; Schenone, Silvia; Bruno, Olga; Brullo, Chiara; Botta, Maurizio

2009-06-01

Quality QSAR: A combination of docking calculations and a statistical approach toward Abl inhibitors resulted in a 3D QSAR model, the analysis of which led to the identification of ligand portions important for affinity. New compounds designed on the basis of the model were found to have very good affinity for the target, providing further validation of the model itself.The X-ray crystallographic coordinates of the Abl tyrosine kinase domain in its active, inactive, and Src-like inactive conformations were used as targets to simulate the binding mode of a large series of pyrazolo[3,4-d]pyrimidines (known Abl inhibitors) by means of GOLD software. Receptor-based alignments provided by molecular docking calculations were submitted to a GRID-GOLPE protocol to generate 3D QSAR models. Analysis of the results showed that the models based on the inactive and Src-like inactive conformations had very poor statistical parameters, whereas the sole model based on the active conformation of Abl was characterized by significant internal and external predictive ability. Subsequent analysis of GOLPE PLS pseudo-coefficient contour plots of this model gave us a better understanding of the relationships between structure and affinity, providing suggestions for the next optimization process. On the basis of these results, new compounds were designed according to the hydrophobic and hydrogen bond donor and acceptor contours, and were found to have improved enzymatic and cellular activity with respect to parent compounds. Additional biological assays confirmed the important role of the selected compounds as inhibitors of cell proliferation in leukemia cells.

High transport and excellent optical property of a two-dimensional single-layered hybrid perovskite (C4H9NH3)2PbBr4: a theoretical study.

PubMed

Lei, Jun-Hui; Zhao, Yu-Qing; Tang, Qiong; Lin, Jian-Guo; Cai, Meng-Qiu

2018-05-16

Organic-inorganic hybrid perovskites are developed to pursue high charge carrier mobility and light absorption coefficient. In this study, we present a detailed comparative research of the atomic and electronic structures of single-layered perovskites (C4H9NH3)2PbBr4 with two-dimensional/three-dimensional (2D/3D) spatial arrangement to predict the in plane charge carrier mobility along with the charge effective mass, elastic constant, and deformation potential. The calculated results reveal that the intrinsic in plane carrier mobilities of 2D single-layered hybrid perovskite (C4H9NH3)2PbBr4 along the 100 and 010 directions are superior to those of the 3D structure. Furthermore, the optical properties are calculated from the electronic structure; it is found that the light absorption spectrum of 2D single-layered perovskite (C4H9NH3)2PbBr4 with a high absorption coefficient is wider than that of the 3D phase. We speculate that the superior mobility and wider absorption spectrum of the 2D mono-layered perovskite are due to high charge density and ferroelectricity originating from structure distortion upon 3D-to-2D structure transformation. These results indicate that the 2D single-layered hybrid perovskite (C4H9NH3)2PbBr4 is a potential candidate for application in the optoelectronic and photovoltaic fields.

Association between obesity and depressive symptoms among U.S. Military active duty service personnel, 2002.

PubMed

Kress, Amii M; Peterson, Michael R; Hartzell, Michael C

2006-03-01

The association between obesity and depression remains equivocal. The purpose of this study was to describe the prevalence and association of obesity and depressive symptoms among military personnel. A cross-sectional analysis was performed using data (N=10,040) from the U.S. Department of Defense (DoD) Survey of Health-Related Behaviors. Prevalence odds ratios were calculated to describe the association between obesity and depressive symptoms. Approximately 10% of active duty men and 4% of active duty women were obese. The prevalence of depressive symptoms ranged from approximately 16% of overweight men to 49% of obese women. Obese men and women and underweight men had increased odds of depressive symptoms as compared with normal-weight individuals. The DoD should emphasize prevention and regular screening for obesity and depressive symptoms to improve readiness and reduce health care costs and disease burden in this cohort.

First principle study of AlX (X=3d, 4d, 5d elements and Lu) dimer.

PubMed

Ouyang, Yifang; Wang, Jianchuan; Hou, Yuhua; Zhong, Xiaping; Du, Yong; Feng, Yuanping

2008-02-21

The ground state equilibrium bond length, harmonic vibrational frequency, and dissociation energy of AlX (X=3d,4d,5d elements and Lu) dimers are investigated by density functional method B3LYP. The present results are in good agreement with the available experimental and other theoretical values except the dissociation energy of AlCr. The present calculations show that the late transition metal can combine strongly with aluminum compared with the former transition metal. The present calculation also indicates that it is more reasonable to replace La with Lu in the Periodic Table and that the bonding strengths of zinc, cadmium, and mercury with aluminum are very weak.

Energy Levels and Oscillator Strengths for Allowed Transitions in S III

NASA Technical Reports Server (NTRS)

Tayal, S. S.

1995-01-01

We have calculated energy levels and oscillator strengths for dipole-allowed transitions between the terms belonging to the 3s(sup 2)3p(sup 2), 3s3p(sup 3), 3S(sup 2)3p3d, 3S(sup 2)3p4s, 3S(sup 2)3p4p and 3s(sup 2)3p4d configurations of S iii in the LS-coupling scheme. We used flexible radial functions and included a large number of configurations in the configuration-interaction expansions to ensure convergence. The calculated energy levels are in close agreement with the recent laboratory measurement. The present oscillator strengths are compared with other calculations and experiments and most of the existing discrepancies between the available calculations are resolved.

SU-E-T-222: Computational Optimization of Monte Carlo Simulation On 4D Treatment Planning Using the Cloud Computing Technology

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

Chow, J

Purpose: This study evaluated the efficiency of 4D lung radiation treatment planning using Monte Carlo simulation on the cloud. The EGSnrc Monte Carlo code was used in dose calculation on the 4D-CT image set. Methods: 4D lung radiation treatment plan was created by the DOSCTP linked to the cloud, based on the Amazon elastic compute cloud platform. Dose calculation was carried out by Monte Carlo simulation on the 4D-CT image set on the cloud, and results were sent to the FFD4D image deformation program for dose reconstruction. The dependence of computing time for treatment plan on the number of computemore » node was optimized with variations of the number of CT image set in the breathing cycle and dose reconstruction time of the FFD4D. Results: It is found that the dependence of computing time on the number of compute node was affected by the diminishing return of the number of node used in Monte Carlo simulation. Moreover, the performance of the 4D treatment planning could be optimized by using smaller than 10 compute nodes on the cloud. The effects of the number of image set and dose reconstruction time on the dependence of computing time on the number of node were not significant, as more than 15 compute nodes were used in Monte Carlo simulations. Conclusion: The issue of long computing time in 4D treatment plan, requiring Monte Carlo dose calculations in all CT image sets in the breathing cycle, can be solved using the cloud computing technology. It is concluded that the optimized number of compute node selected in simulation should be between 5 and 15, as the dependence of computing time on the number of node is significant.« less

Structure and vibrational analysis of methyl 3-amino-2-butenoate.

PubMed

Berenji, Ali Reza; Tayyari, Sayyed Faramarz; Rahimizadeh, Mohammad; Eshghi, Hossein; Vakili, Mohammad; Shiri, Ali

2013-02-01

The molecular structure and vibrational spectra of methyl 3-(amino)-2-butenoate (MAB) and its deuterated analogous, D(3)MAB, were investigated using density functional theory (DFT) calculations. The geometrical parameters and harmonic vibrational wavenumbers of MAB and D(3)MAB were obtained at the B3LYP/6-311++G(d,p) level. The calculated vibrational wavenumbers were compared with the corresponding experimental results. The assignment of the IR and Raman spectra of MAB and D(3)MAB was facilitated by calculating the anharmonic wavenumbers at the B3LYP/6-311G(d,p) level as well as recording and calculating the MAB spectra in CCl(4) solution. The assigned normal modes were compared with a similar molecule, 4-amino-3-penten-2-one (APO). The theoretical results were in good agreement with the experimental data. All theoretical and experimental results indicate that substitution of a methyl group with a methoxy group considerably weakens the intramolecular hydrogen bond and reduces the π-electron delocalization in the chelated ring system. The IR spectra also indicate that in the solid state, MAB is not only engaged in an intramolecular hydrogen bond, but also forms an intermolecular hydrogen bond. However, the intermolecular hydrogen bond will be removed in dilute CCl(4) solution. Copyright © 2012 Elsevier B.V. All rights reserved.

Ab initio calculation of the $$np \\to d ³$$ radiative capture process

DOE PAGES

Beane, Silas R.; Chang, Emmanuel; Detmold, William; ...

2015-09-24

In this study, lattice QCD calculations of two-nucleon systems are used to isolate the short-distance two-body electromagnetic contributions to the radiative capture processmore » $$np \\to d\\gamma$$, and the photo-disintegration processes $$\\gamma^{(\\ast)} d \\to np$$. In nuclear potential models, such contributions are described by phenomenological meson-exchange currents, while in the present work, they are determined directly from the quark and gluon interactions of QCD. Calculations of neutron-proton energy levels in multiple background magnetic fields are performed at two values of the quark masses, corresponding to pion masses of $$m_\\pi \\sim 450$$ and 806 MeV, and are combined with pionless nuclear effective field theory to determine these low-energy inelastic processes. Extrapolating to the physical pion mass, a cross section of $$\\sigma^{lqcd}(np\\to d\\gamma)=332.4({\\tiny \\begin{array}{l}+5.4 \\\\ - 4.7\\end{array}})\\ mb$$ is obtained at an incident neutron speed of $$v=2,200\\ m/s$$, consistent with the experimental value of $$\\sigma^{expt}(np \\to d\\gamma) = 334.2(0.5)\\ mb$$.« less

THM and primordial nucleosynthesis: Results and perspectives

NASA Astrophysics Data System (ADS)

Pizzone, R. G.; Spartá, R.; Bertulani, C.; Spitaleri, C.; La Cognata, M.; Lamia, L.; Tumino, A.

2017-09-01

Big Bang Nucleosynthesis (BBN) requires several nuclear physics inputs and nuclear reaction rates. An up-to-date compilation of direct cross sections of d(d,p)t, d(d,n) 3 He and 3 He(d,p) 4 He reactions is given, being these ones among the most uncertain bare-nucleus cross sections. An intense experimental effort has been carried on in the last decade to apply the Trojan Horse Method (THM) to study reactions of relevance for the BBN and measure their astrophysical S( E) -factor. The reaction rates and the relative error for the four reactions of interest are then numerically calculated in the temperature ranges of relevance for BBN ( 0.01

Polyketides with α-Glucosidase Inhibitory Activity from a Mangrove Endophytic Fungus, Penicillium sp. HN29-3B1.

PubMed

Liu, Yayue; Yang, Qin; Xia, Guoping; Huang, Hongbo; Li, Hanxiang; Ma, Lin; Lu, Yongjun; He, Lei; Xia, Xuekui; She, Zhigang

2015-08-28

Five new compounds, pinazaphilones A and B (1, 2), two phenolic compounds (4, 5), and penicidone D (6), together with the known Sch 1385568 (3), (±)-penifupyrone (7), 3-O-methylfunicone (8), 5-methylbenzene-1,3-diol (9), and 2,4-dihydroxy-6-methylbenzoic acid (10) were obtained from the culture of the endophytic fungus Penicillium sp. HN29-3B1, which was isolated from a fresh branch of the mangrove plant Cerbera manghas collected from the South China Sea. Their structures were determined by analysis of 1D and 2D NMR and mass spectroscopic data. Structures of compounds 4 and 7 were further confirmed by a single-crystal X-ray diffraction experiment using Cu Kα radiation. The absolute configurations of compounds 1-3 were assigned by quantum chemical calculations of the electronic circular dichroic spectra. Compounds 2, 3, 5, and 7 inhibited α-glucosidase with IC50 values of 28.0, 16.6, 2.2, and 14.4 μM, respectively, and are thus more potent than the positive control, acarbose.

Laboratory derived constraints on electrical conductivity beneath Slave craton

NASA Astrophysics Data System (ADS)

Bagdassarov, Nikolai S.; Kopylova, Maya G.; Eichert, Sandrine

2007-04-01

The depth profile of the electrical conductivity, σ(d), beneath the Central Slave craton (Canada) has been reconstructed with the help of laboratory measurements carried out on peridotite xenoliths. σ(T) of xenoliths was determined in the piston-cylinder apparatus at 1 and 2 GPa and from 600 to 1150 °C. σ(T) of xenoliths follows the Arrhenius dependence with the activation energy, E, varying from 2.10 to 1.44 eV depending on temperature range and the Mg-number. The calculated xenolith geotherm and the suggested lithology beneath the Central Slave have been used to constrain σ(d) as follows: σ(d) in the crust varies between 0.5×10-5 and 10-3 S/m; the lithospheric σ(d) sharply decreases below the Moho at 39.4 km to 0.5×10-8 S/m, which corresponds to 460 °C, and then gradually increases with the depth d to 0.5×10-2 S/m. The modeled MT-response of the constrained σ(d) profile has been compared with MT-observations [Jones, A.G., Lezaeta, P., Ferguson, I.J., Chave, A.D., Evans, R.L., Garcia, X., Spratt J., 2003. The electrical structure of the Slave craton. Lithos, 71, 505-527]. The general trend of the calculated MT-response based on the σ(d) model mimics the MT-inversion of the field data from the Central Slave.

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

Venencia, C; Pino, M; Caussa, L

Purpose: The purpose of this work was to quantify the dosimetric impact of Monte Carlo (MC) dose calculation algorithm compared to Pencil Beam (PB) on Spine SBRT with HybridARC (HA) and sliding windows IMRT (dMLC) treatment modality. Methods: A 6MV beam (1000MU/min) produced by a Novalis TX (BrainLAB-Varian) equipped with HDMLC was used. HA uses 1 arc plus 8 IMRT beams (arc weight between 60–40%) and dIMRT 15 beams. Plans were calculated using iPlan v.4.5.3 (BrainLAB) and the treatment dose prescription was 27Gy in 3 fractions. Dose calculation was done by PB (4mm spatial resolution) with heterogeneity correction and MCmore » dose to water (4mm spatial resolution and 4% mean variance). PTV and spinal cord dose comparison were done. Study was done on 12 patients. IROC Spine Phantom was used to validate HA and quantify dose variation using PB and MC algorithm. Results: The difference between PB and MC for PTV D98%, D95%, Dmean, D2% were 2.6% [−5.1, 6.8], 0.1% [−4.2, 5.4], 0.9% [−1.5, 3.8] and 2.4% [−0.5, 8.3]. The difference between PB and MC for spinal cord Dmax, D1.2cc and D0.35cc were 5.3% [−6.4, 18.4], 9% [−7.0, 17.0] and 7.6% [−0.6, 14.8] respectively. IROC spine phantom shows PTV TLD dose variation of 0.98% for PB and 1.01% for MC. Axial and sagittal film plane gamma index (5%-3mm) was 95% and 97% for PB and 95% and 99% for MC. Conclusion: PB slightly underestimates the dose for the PTV. For the spinal cord PB underestimates the dose and dose differences could be as high as 18% which could have unexpected clinical impact. CI shows no variation between PB and MC for both treatment modalities Treatment modalities have no impact with the dose calculation algorithms used. Following the IROC pass-fail criteria, treatment acceptance requirement was fulfilled for PB and MC.« less

Evaluation and mitigation of the interplay effects of intensity modulated proton therapy for lung cancer in a clinical setting.

PubMed

Kardar, Laleh; Li, Yupeng; Li, Xiaoqiang; Li, Heng; Cao, Wenhua; Chang, Joe Y; Liao, Li; Zhu, Ronald X; Sahoo, Narayan; Gillin, Michael; Liao, Zhongxing; Komaki, Ritsuko; Cox, James D; Lim, Gino; Zhang, Xiaodong

2014-01-01

The primary aim of this study was to evaluate the impact of the interplay effects of intensity modulated proton therapy (IMPT) plans for lung cancer in the clinical setting. The secondary aim was to explore the technique of isolayered rescanning to mitigate these interplay effects. A single-fraction 4-dimensional (4D) dynamic dose without considering rescanning (1FX dynamic dose) was used as a metric to determine the magnitude of dosimetric degradation caused by 4D interplay effects. The 1FX dynamic dose was calculated by simulating the machine delivery processes of proton spot scanning on a moving patient, described by 4D computed tomography during IMPT delivery. The dose contributed from an individual spot was fully calculated on the respiratory phase that corresponded to the life span of that spot, and the final dose was accumulated to a reference computed tomography phase by use of deformable image registration. The 1FX dynamic dose was compared with the 4D composite dose. Seven patients with various tumor volumes and motions were selected for study. The clinical target volume (CTV) prescription coverage for the 7 patients was 95.04%, 95.38%, 95.39%, 95.24%, 95.65%, 95.90%, and 95.53% when calculated with the 4D composite dose and 89.30%, 94.70%, 85.47%, 94.09%, 79.69%, 91.20%, and 94.19% when calculated with the 1FX dynamic dose. For these 7 patients, the CTV coverage calculated by use of a single-fraction dynamic dose was 95.52%, 95.32%, 96.36%, 95.28%, 94.32%, 95.53%, and 95.78%, with a maximum monitor unit limit value of 0.005. In other words, by increasing the number of delivered spots in each fraction, the degradation of CTV coverage improved up to 14.6%. A single-fraction 4D dynamic dose without rescanning was validated as a surrogate to evaluate the interplay effects of IMPT for lung cancer in the clinical setting. The interplay effects potentially can be mitigated by increasing the amount of isolayered rescanning in each fraction delivery.

Hyperascyrones A-H, polyprenylated spirocyclic acylphloroglucinol derivatives from Hypericum ascyron Linn.

PubMed

Zhu, Hucheng; Chen, Chunmei; Liu, Junjun; Sun, Bin; Wei, Guangzheng; Li, Yan; Zhang, Jinwen; Yao, Guangmin; Luo, Zengwei; Xue, Yongbo; Zhang, Yonghui

2015-07-01

Eight polyprenylated spirocyclic acylphloroglucinol derivatives (PSAPs), hyperascyrones A-H, were isolated from the aerial parts of Hypericum ascyron Linn., together with six known analogs. Their structures were established by spectroscopic analyses including HRESIMS, 1D and 2D NMR, and their absolute configurations were determined by electronic circular dichroism calculations (ECD, Gaussian 09). Structures of previously reported tomoeones C, D, G, and H were revised. Hyperascyrones A-H were evaluated for their cytotoxic and anti-HIV-1 activities, with hyperascyrones C and G exhibiting significant cytotoxicities against HL-60 cell lines with IC50 values of 4.22 and 8.36 μM, respectively. In addition, the chemotaxonomic significance of these compounds was also discussed. Copyright © 2015 Elsevier Ltd. All rights reserved.

Full-dimensional quantum dynamics of rovibrationally inelastic scattering between CN and H2

NASA Astrophysics Data System (ADS)

Yang, Benhui; Wang, X. H.; Stancil, P. C.; Bowman, J. M.; Balakrishnan, N.; Forrey, R. C.

2016-12-01

We report six-dimensional (6D) potential energy surface (PES) and rovibrational scattering calculations for the CN-H2 collision system. The PES was computed using the high-level ab initio spin-restricted coupled-cluster with single, double, and perturbative triple excitations-F12B method and fitted to an analytic function using an invariant polynomial method in 6D. Quantum close-coupling calculations are reported for rotational transitions in CN by H2 and D2 collisions in 6D as well as four-dimensional (4D) within a rigid rotor model for collision energies of 1.0-1500 cm-1. Comparisons with experimental data and previous 4D calculations are presented for CN rotational levels j1 = 4 and 11. For the first time, rovibrational quenching cross sections and rate coefficients of CN (v1 = 1,j1 = 0) in collisions with para- and ortho-H2 are also reported in full-dimension. Agreement for pure rotational transitions is found to be good, but no experimental data on rovibrational collisional quenching for CN-H2 are available. Applications of the current rotational and rovibrational rate coefficients in astrophysical modeling are briefly discussed.

X-ray spectroscopic characterization of Co(IV) and metal–metal interactions in Co 4O 4: Electronic structure contributions to the formation of high-valent states relevant to the oxygen evolution reaction

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

Hadt, Ryan G.; Hayes, Dugan; Brodsky, Casey N.

2016-08-12

In this paper, the formation of high-valent states is a key factor in making highly active transition metal-based catalysts of the oxygen-evolving reaction (OER). These high oxidation states will be strongly influenced by the local geometric and electronic structures of the metal ion, which is difficult to study due to spectroscopically active and complex backgrounds, short lifetimes, and limited concentrations. Here, we use a wide range of complementary X-ray spectroscopies coupled to DFT calculations to study Co 4O 4 cubanes, which provide insight into the high-valent Co(IV) centers responsible for the activity of molecular and heterogeneous OER catalysts. The combinationmore » of X-ray absorption and 1s3p resonant inelastic X-ray scattering (Kβ RIXS) allow Co(IV) to be isolated and studied against a spectroscopically active Co(III) background. Co K- and L-edge X-ray absorption data allow for a detailed characterization of the 3d-manifold of effectively localized Co(IV) centers and provide a direct handle on the ligand field environment and covalency of the t 2g-based redox active molecular orbital. Kβ RIXS is also shown to provide a powerful probe of Co(IV), and specific spectral features are sensitive to the degree of oxo-mediated metal-metal coupling across Co 4O 4. Guided by the data, calculations show electron-hole delocalization can actually oppose Co(IV) formation. Computational extension of Co 4O 4 to CoM 3O 4 structures (M = redox-inactive metal) defines electronic structure contri-butions to Co(IV) formation. Redox activity is shown to be linearly related to covalency, and M(III) oxo inductive effects on Co(IV) oxo bonding can tune the covalency of high-valent sites over a large range and thereby tune E 0 over hundreds of mVs.« less

Arene-mercury complexes stabilized by gallium chloride: relative rates of H/D and arene exchange.

PubMed

Branch, Catherine S; Barron, Andrew R

2002-11-27

We have previously proposed that the Hg(arene)(2)(GaCl(4))(2) catalyzed H/D exchange reaction of C(6)D(6) with arenes occurs via an electrophilic aromatic substitution reaction in which the coordinated arene protonates the C(6)D(6). To investigate this mechanism, the kinetics of the Hg(C(6)H(5)Me)(2)(GaCl(4))(2) catalyzed H/D exchange reaction of C(6)D(6) with naphthalene has been studied. Separate second-order rate constants were determined for the 1- and 2-positions on naphthalene; that is, the initial rate of H/D exchange = k(1i)[Hg][C-H(1)] + k(2i)[Hg][C-H(2)]. The ratio of k(1i)/k(2i) ranges from 11 to 2.5 over the temperature range studied, commensurate with the proposed electrophilic aromatic substitution reaction. Observation of the reactions over an extended time period shows that the rates change with time, until they again reach a new and constant second-order kinetics regime. The overall form of the rate equation is unchanged: final rate = k(1f)[Hg][C-H(1)] + k(2f)[Hg][C-H(2)]. This change in the H/D exchange is accompanied by ligand exchange between Hg(C(6)D(6))(2)(GaCl(4))(2) and naphthalene to give Hg(C(10)H(8))(2)(GaCl(4))(2,) that has been characterized by (13)C CPMAS NMR and UV-visible spectroscopy. The activation parameters for the ligand exchange may be determined and are indicative of a dissociative reaction and are consistent with our previously calculated bond dissociation for Hg(C(6)H(6))(2)(AlCl(4))(2). The initial Hg(arene)(2)(GaCl(4))(2) catalyzed reaction of naphthalene with C(6)D(6) involves the deuteration of naphthalene by coordinated C(6)D(6); however, as ligand exchange progresses, the pathway for H/D exchange changes to where the protonation of C(6)D(6) by coordinated naphthalene dominates. The site selectivity for the H/D exchange is initially due to the electrophilic aromatic substitution of naphthalene. As ligand exchange occurs, this selectivity is controlled by the activation of the naphthalene C-H bonds by mercury.

Versatile fusion source integrator AFSI for fast ion and neutron studies in fusion devices

NASA Astrophysics Data System (ADS)

Sirén, Paula; Varje, Jari; Äkäslompolo, Simppa; Asunta, Otto; Giroud, Carine; Kurki-Suonio, Taina; Weisen, Henri; JET Contributors, The

2018-01-01

ASCOT Fusion Source Integrator AFSI, an efficient tool for calculating fusion reaction rates and characterizing the fusion products, based on arbitrary reactant distributions, has been developed and is reported in this paper. Calculation of reactor-relevant D-D, D-T and D-3He fusion reactions has been implemented based on the Bosch-Hale fusion cross sections. The reactions can be calculated between arbitrary particle populations, including Maxwellian thermal particles and minority energetic particles. Reaction rate profiles, energy spectra and full 4D phase space distributions can be calculated for the non-isotropic reaction products. The code is especially suitable for integrated modelling in self-consistent plasma physics simulations as well as in the Serpent neutronics calculation chain. Validation of the model has been performed for neutron measurements at the JET tokamak and the code has been applied to predictive simulations in ITER.

Advanced treatment planning using direct 4D optimisation for pencil-beam scanned particle therapy

NASA Astrophysics Data System (ADS)

Bernatowicz, Kinga; Zhang, Ye; Perrin, Rosalind; Weber, Damien C.; Lomax, Antony J.

2017-08-01

We report on development of a new four-dimensional (4D) optimisation approach for scanned proton beams, which incorporates both irregular motion patterns and the delivery dynamics of the treatment machine into the plan optimiser. Furthermore, we assess the effectiveness of this technique to reduce dose to critical structures in proximity to moving targets, while maintaining effective target dose homogeneity and coverage. The proposed approach has been tested using both a simulated phantom and a clinical liver cancer case, and allows for realistic 4D calculations and optimisation using irregular breathing patterns extracted from e.g. 4DCT-MRI (4D computed tomography-magnetic resonance imaging). 4D dose distributions resulting from our 4D optimisation can achieve almost the same quality as static plans, independent of the studied geometry/anatomy or selected motion (regular and irregular). Additionally, current implementation of the 4D optimisation approach requires less than 3 min to find the solution for a single field planned on 4DCT of a liver cancer patient. Although 4D optimisation allows for realistic calculations using irregular breathing patterns, it is very sensitive to variations from the planned motion. Based on a sensitivity analysis, target dose homogeneity comparable to static plans (D5-D95  <5%) has been found only for differences in amplitude of up to 1 mm, for changes in respiratory phase  <200 ms and for changes in the breathing period of  <20 ms in comparison to the motions used during optimisation. As such, methods to robustly deliver 4D optimised plans employing 4D intensity-modulated delivery are discussed.

Elevated aerosol layers modify the O2–O2 absorption measured by ground-based MAX-DOAS

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

Ortega, Ivan; Berg, Larry K.; Ferrare, Richard A.

2016-06-01

The oxygen collisional complex (O2-O2, or O4) is a greenhouse gas, and a calibration trace gas used to infer aerosol and cloud properties by Differential Optical Absorption Spectroscopy (DOAS). Recent reports suggest the need for an O4 correction factor (CFO4) when comparing simulated and measured O4 differential slant column densities (dSCD) by passive DOAS. We investigate the sensitivity of O4 dSCD simulations at ultraviolet (360 nm) and visible (477 nm) wavelengths towards separately measured aerosol extinction profiles. Measurements were conducted by the University of Colorado 2D-MAX-DOAS instrument and NASA’s multispectral High Spectral Resolution Lidar (HSRL-2) during the Two Column Aerosolmore » Project (TCAP) at Cape Cod, MA in July 2012. During two case study days with (1) high aerosol load (17 July, AOD ~ 0.35 at 477 nm), and (2) near molecular scattering conditions (22 July, AOD < 0.10 at 477 nm) the measured and calculated O4 dSCDs agreed within 6.4±0.4% (360 nm) and 4.7±0.6% (477 nm) if the HSRL-2 profiles were used as input to the calculations. However, if in the calculations the aerosol is confined to the surface layer (while keeping AOD constant) we find 0.53« less

Dissolved organic carbon--contaminant interaction descriptors found by 3D force field calculations.

PubMed

Govers, H A J; Krop, H B; Parsons, J R; Tambach, T; Kubicki, J D

2002-03-01

Enthalpies of transfer at 300 K of various partitioning processes were calculated in order to study the suitability of 3D force fields for the calculation of partitioning constants. A 3D fulvic acid (FA) model of dissolved organic carbon (DOC) was built in a MM+ force field using AMI atomic charges and geometrical optimization (GO). 3,5-Dichlorobiphenyl (PCB14), 4,4'-dichlorobiphenyl (PCB15), 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)-ethane (PPDDT) and 2-chloro-4-ethylamino-6-isopropylamino-s-triazine (Atrazine) were inserted into different sites and their interaction energies with FA were calculated. Energies of hydration were calculated and subtracted from FA-contaminant interactions of selected sites. The resulting values for the enthalpies of transfer from water to DOC were 2.8, -1.4, -6.4 and 0.0 kcal/mol for PCB 14, PCB15, PPDDT and Atrazine, respectively. The value of PPDDT compared favorably with the experimental value of -5.0 kcal/mol. Prior to this, the method was studied by the calculation of the enthalpies of vaporization and aqueous solution using various force fields. In the MM + force field GO predicted enthalpies of vaporization deviated by +0.7 (PCB14), +3.6 (PCB15) and -0.7 (PPDDT)kcal/mol from experimental data, whereas enthalpies of aqueous solution deviated by -3.6 (PCB14), +5.8 (PCB15) and +3.7 (PPDDT) kcal/mol. Only for PCB14 the wrong sign of this enthalpy value was predicted. Potential advantages and limitations of the approach were discussed.

Methylsulfonyl benzothiazoles (MSBT) derivatives: Search for new potential antimicrobial and anticancer agents.

PubMed

Lad, Nitin P; Manohar, Yogesh; Mascarenhas, Malcolm; Pandit, Yashwant B; Kulkarni, Mahesh R; Sharma, Rajiv; Salkar, Kavita; Suthar, Ashish; Pandit, Shivaji S

2017-03-01

A series of novel 4 and 5-substituted methylsulfonyl benzothiazole (MSBT) compounds having amide, alkoxy, sulfonamide, nitro and amine functionality were synthesized from sequential reactions on 5-ethoxy-2-(methylsulfonyl)benzo[d]thiazole such as nitration, reduction, sulfonation, dealkylation, etc. All synthesized compounds were screened against antimicrobial and selected screened for anticancer activity. Antimicrobial activities studies reveled that among all compounds screened, out of MSBT-07, MSBT-11, MSBT-12, MSBT-14, MSBT-19, and MSBT-27 were found to have promising antimicrobial activity at MIC range of 4-50μg/ml against selected bacterial as well as fungal species. Compounds having good antimicrobial activity were screened for cervical cancer (HeLA cell lines). Of these MSBT-07 and MSBT-12 significantly reduced the cell growth. Consequently their calculated GI 50 values were found to be 0.1 or <0.1μM. Copyright © 2016 Elsevier Ltd. All rights reserved.

Catalytic activity of Cu4-cluster to adsorb H2S gas: h-BN nanosheet

NASA Astrophysics Data System (ADS)

Kansara, Shivam; Gupta, Sanjeev K.; Sonvane, Yogesh

2018-05-01

We have investigated the electronic properties, adsorptions strength and charge transfer using first principles calculations using density functional theory (DFT). The hexagonal boron nitride (h-BN) substrate shows metallic behavior, which helps to enhance the absorption process. The adsorption of three different orientations (S, D and T) of the H2S gas molecules to analyze the maximum adsorption strength from them onto a copper cluster (Cu4) based on h-BN nanosheet. The maximum adsorption energy of the H2S gas molecule is -1.50 eV for the S orientation and for D and U, it is -0.71 eV and -0.78 eV, respectively. The results show that Cu4 cluster helps to capture H2S gas from the environment and results are useful for the cleaning environment from the toxic gases.

First Human Brain Imaging by the jPET-D4 Prototype With a Pre-Computed System Matrix

NASA Astrophysics Data System (ADS)

Yamaya, Taiga; Yoshida, Eiji; Obi, Takashi; Ito, Hiroshi; Yoshikawa, Kyosan; Murayama, Hideo

2008-10-01

The jPET-D4 is a novel brain PET scanner which aims to achieve not only high spatial resolution but also high scanner sensitivity by using 4-layer depth-of-interaction (DOI) information. The dimensions of a system matrix for the jPET-D4 are 3.3 billion (lines-of-response) times 5 million (image elements) when a standard field-of-view (FOV) of 25 cm diameter is sampled with a (1.5 mm)3 voxel . The size of the system matrix is estimated as 117 petabytes (PB) with the accuracy of 8 bytes per element. An on-the-fly calculation is usually used to deal with such a huge system matrix. However we cannot avoid extension of the calculation time when we improve the accuracy of system modeling. In this work, we implemented an alternative approach based on pre-calculation of the system matrix. A histogram-based 3D OS-EM algorithm was implemented on a desktop workstation with 32 GB memory installed. The 117 PB system matrix was compressed under the limited amount of computer memory by (1) eliminating zero elements, (2) applying the DOI compression (DOIC) method and (3) applying rotational symmetry and an axial shift property of the crystal arrangement. Spanning, which degrades axial resolution, was not applied. The system modeling and the DOIC method, which had been validated in 2D image reconstruction, were expanded into 3D implementation. In particular, a new system model including the DOIC transformation was introduced to suppress resolution loss caused by the DOIC method. Experimental results showed that the jPET-D4 has almost uniform spatial resolution of better than 3 mm over the FOV. Finally the first human brain images were obtained with the jPET-D4.

Soil extracellular enzyme activities, soil carbon and nitrogen storage under nitrogen fertilization: A meta-analysis

DOE PAGES

Jian, Siyang; Li, Jianwei; Chen, Ji; ...

2016-07-08

Nitrogen (N) fertilization affects the rate of soil organic carbon (SOC) decomposition by regulating extracellular enzyme activities (EEA). Extracellular enzymes have not been represented in global biogeochemical models. Understanding the relationships among EEA and SOC, soil N (TN), and soil microbial biomass carbon (MBC) under N fertilization would enable modeling of the influence of EEA on SOC decomposition. Based on 65 published studies, we synthesized the activities of α-1,4-glucosidase (AG), β-1,4-glucosidase (BG), β-d-cellobiosidase (CBH), β-1,4-xylosidase (BX), β-1,4-N-acetyl-glucosaminidase (NAG), leucine amino peptidase (LAP), urease (UREA), acid phosphatase (AP), phenol oxidase (PHO), and peroxidase (PEO) in response to N fertilization. Here, themore » proxy variables for hydrolytic C acquisition enzymes (C-acq), N acquisition (N-acq), and oxidative decomposition (OX) were calculated as the sum of AG, BG, CBH and BX; AG and LAP; PHO and PEO, respectively.« less

Experimentally-based ExB drifts in the DIII-D divertor and SOL calculated from integration of Ohm's law using Thomson scattering measurements of T e and n e

DOE PAGES

Stangeby, Peter C.; Elder, J. David; McLean, Adam G.; ...

2017-03-27

We calculated the 2D spatial distributions of cross field drift velocities from 2D Thomson scattering measurements of T e and n e in the divertor and SOL of DIII-D. In contrast with the method that has been used on DIII-D where the 2D distribution of plasma potential V plasma is obtained from measurements of the probe floating potential of reciprocating probes, the present method does not require insertion of a probe into the plasma and can therefore be used in high power discharges. Furthermore, the 2D spatial distribution of V plasma is calculated from Ohm’s Law for the parallel electricmore » field E || along each flux tube, E || s || = -1.71dT e/ds || - T e/n edn e/ds ||, where the Thomson scattering values of T e and n e are used. To within a constant of integration, V plasma is obtained by integrating E || along the flux-tubes (field lines); the constant is obtained for each flux tube using the sheath drop at the target calculated from the characteristic of Langmuir probes built into the divertor tiles. The 2D distributions of E./01/2 = -dV4/ds./01/2, E452510/2 = -dV4/ds452510/2, v789 452510/2 = E./01/2/B and v789 ./01/2 = E452510/2/B are then calculated as well as the particle drift flux densities Γ789 452510/2 = nv789 452510/2 and Γ789 ./01/2 = nv789 ./01/2 for electrons, fuel ions and impurity ions, using the appropriate values of particle density, n.« less

Experimentally-based ExB drifts in the DIII-D divertor and SOL calculated from integration of Ohm's law using Thomson scattering measurements of T e and n e

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

Stangeby, Peter C.; Elder, J. David; McLean, Adam G.

We calculated the 2D spatial distributions of cross field drift velocities from 2D Thomson scattering measurements of T e and n e in the divertor and SOL of DIII-D. In contrast with the method that has been used on DIII-D where the 2D distribution of plasma potential V plasma is obtained from measurements of the probe floating potential of reciprocating probes, the present method does not require insertion of a probe into the plasma and can therefore be used in high power discharges. Furthermore, the 2D spatial distribution of V plasma is calculated from Ohm’s Law for the parallel electricmore » field E || along each flux tube, E || s || = -1.71dT e/ds || - T e/n edn e/ds ||, where the Thomson scattering values of T e and n e are used. To within a constant of integration, V plasma is obtained by integrating E || along the flux-tubes (field lines); the constant is obtained for each flux tube using the sheath drop at the target calculated from the characteristic of Langmuir probes built into the divertor tiles. The 2D distributions of E./01/2 = -dV4/ds./01/2, E452510/2 = -dV4/ds452510/2, v789 452510/2 = E./01/2/B and v789 ./01/2 = E452510/2/B are then calculated as well as the particle drift flux densities Γ789 452510/2 = nv789 452510/2 and Γ789 ./01/2 = nv789 ./01/2 for electrons, fuel ions and impurity ions, using the appropriate values of particle density, n.« less

Improved accuracy of intraocular lens power calculation with the Zeiss IOLMaster.

PubMed

Olsen, Thomas

2007-02-01

This study aimed to demonstrate how the level of accuracy in intraocular lens (IOL) power calculation can be improved with optical biometry using partial optical coherence interferometry (PCI) (Zeiss IOLMaster) and current anterior chamber depth (ACD) prediction algorithms. Intraocular lens power in 461 consecutive cataract operations was calculated using both PCI and ultrasound and the accuracy of the results of each technique were compared. To illustrate the importance of ACD prediction per se, predictions were calculated using both a recently published 5-variable method and the Haigis 2-variable method and the results compared. All calculations were optimized in retrospect to account for systematic errors, including IOL constants and other off-set errors. The average absolute IOL prediction error (observed minus expected refraction) was 0.65 dioptres with ultrasound and 0.43 D with PCI using the 5-variable ACD prediction method (p < 0.00001). The number of predictions within +/- 0.5 D, +/- 1.0 D and +/- 2.0 D of the expected outcome was 62.5%, 92.4% and 99.9% with PCI, compared with 45.5%, 77.3% and 98.4% with ultrasound, respectively (p < 0.00001). The 2-variable ACD method resulted in an average error in PCI predictions of 0.46 D, which was significantly higher than the error in the 5-variable method (p < 0.001). The accuracy of IOL power calculation can be significantly improved using calibrated axial length readings obtained with PCI and modern IOL power calculation formulas incorporating the latest generation ACD prediction algorithms.

Evaluation of structure-reactivity descriptors and biological activity spectra of 4-(6-methoxy-2-naphthyl)-2-butanone using spectroscopic techniques

NASA Astrophysics Data System (ADS)

Agrawal, Megha; Deval, Vipin; Gupta, Archana; Sangala, Bagvanth Reddy; Prabhu, S. S.

2016-10-01

The structure and several spectroscopic features along with reactivity parameters of the compound 4-(6-methoxy-2-naphthyl)-2-butanone (Nabumetone) have been studied using experimental techniques and tools derived from quantum chemical calculations. Structure optimization is followed by force field calculations based on density functional theory (DFT) at the B3LYP/6-311++G(d,p) level of theory. The vibrational spectra have been interpreted with the aid of normal coordinate analysis. UV-visible spectrum and the effect of solvent have been discussed. The electronic properties such as HOMO and LUMO energies have been determined by TD-DFT approach. In order to understand various aspects of pharmacological sciences several new chemical reactivity descriptors - chemical potential, global hardness and electrophilicity have been evaluated. Local reactivity descriptors - Fukui functions and local softnesses have also been calculated to find out the reactive sites within molecule. Aqueous solubility and lipophilicity have been calculated which are crucial for estimating transport properties of organic molecules in drug development. Estimation of biological effects, toxic/side effects has been made on the basis of prediction of activity spectra for substances (PASS) prediction results and their analysis by Pharma Expert software. Using the THz-TDS technique, the frequency-dependent absorptions of NBM have been measured in the frequency range up to 3 THz.

Conformational stability, spectroscopic (FT-IR, FT-Raman and UV-Vis) analysis, NLO, NBO, FMO and Fukui function analysis of 4-hexylacetophenone by density functional theory.

PubMed

Saravanan, S; Balachandran, V

2015-03-05

The experimental and theoretical study on the structures and vibrations of 4-hexylacetophenone (abbreviated as 4HAP) are presented. The FT-IR and FT-Raman spectra of the title compound have been recorded in the region 4000-400cm(-1) and 3500-100cm(-1) respectively. The molecular structures, vibrational wavenumbers, infrared intensities and Raman activities were calculated using DFT (B3LYP and LSDA) method with 6-311++G(d,p) basis set. The most stable conformer of 4HAP is identified from the computational results. The assignments of the vibrational spectra have been carried out with the aid of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology (SQMEF). The linear polarizability (α) and the first hyperpolarizability (βtot) values of the investigated molecule have been computed using B3LYP and LSDA with 6-311++G(d,p) basis set. Stability of the molecule arising from hyper conjugative interaction and charge transfer delocalization has been analyzed using natural bond orbital (NBO) analysis. The molecule orbital contributions are studied by density of energy states (DOSs). UV-Vis spectrum and effects of solvents have been discussed effects of solvents have been discussed and the electronic properties such as HOMO and LUMO energies were determined by time-dependent TD-DFT approach. Fukui function and Mulliken analysis on atomic charges of the title compound have been calculated. Finally, electrophilic and nucleophilic descriptors of the title molecule have been calculated. Copyright © 2014 Elsevier B.V. All rights reserved.

3D delivered dose assessment using a 4DCT-based motion model

PubMed Central

Cai, Weixing; Hurwitz, Martina H.; Williams, Christopher L.; Dhou, Salam; Berbeco, Ross I.; Seco, Joao; Mishra, Pankaj; Lewis, John H.

2015-01-01

Purpose: The purpose of this work is to develop a clinically feasible method of calculating actual delivered dose distributions for patients who have significant respiratory motion during the course of stereotactic body radiation therapy (SBRT). Methods: A novel approach was proposed to calculate the actual delivered dose distribution for SBRT lung treatment. This approach can be specified in three steps. (1) At the treatment planning stage, a patient-specific motion model is created from planning 4DCT data. This model assumes that the displacement vector field (DVF) of any respiratory motion deformation can be described as a linear combination of some basis DVFs. (2) During the treatment procedure, 2D time-varying projection images (either kV or MV projections) are acquired, from which time-varying “fluoroscopic” 3D images of the patient are reconstructed using the motion model. The DVF of each timepoint in the time-varying reconstruction is an optimized linear combination of basis DVFs such that the 2D projection of the 3D volume at this timepoint matches the projection image. (3) 3D dose distribution is computed for each timepoint in the set of 3D reconstructed fluoroscopic images, from which the total effective 3D delivered dose is calculated by accumulating deformed dose distributions. This approach was first validated using two modified digital extended cardio-torso (XCAT) phantoms with lung tumors and different respiratory motions. The estimated doses were compared to the dose that would be calculated for routine 4DCT-based planning and to the actual delivered dose that was calculated using “ground truth” XCAT phantoms at all timepoints. The approach was also tested using one set of patient data, which demonstrated the application of our method in a clinical scenario. Results: For the first XCAT phantom that has a mostly regular breathing pattern, the errors in 95% volume dose (D95) are 0.11% and 0.83%, respectively for 3D fluoroscopic images reconstructed from kV and MV projections compared to the ground truth, which is clinically comparable to 4DCT (0.093%). For the second XCAT phantom that has an irregular breathing pattern, the errors are 0.81% and 1.75% for kV and MV reconstructions, both of which are better than that of 4DCT (4.01%). In the case of real patient, although it is impossible to obtain the actual delivered dose, the dose estimation is clinically reasonable and demonstrates differences between 4DCT and MV reconstruction-based dose estimates. Conclusions: With the availability of kV or MV projection images, the proposed approach is able to assess delivered doses for all respiratory phases during treatment. Compared to the planning dose based on 4DCT, the dose estimation using reconstructed 3D fluoroscopic images was as good as 4DCT for regular respiratory pattern and was a better dose estimation for the irregular respiratory pattern. PMID:26127043

3D delivered dose assessment using a 4DCT-based motion model

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

Cai, Weixing; Hurwitz, Martina H.; Williams, Christopher L.

Purpose: The purpose of this work is to develop a clinically feasible method of calculating actual delivered dose distributions for patients who have significant respiratory motion during the course of stereotactic body radiation therapy (SBRT). Methods: A novel approach was proposed to calculate the actual delivered dose distribution for SBRT lung treatment. This approach can be specified in three steps. (1) At the treatment planning stage, a patient-specific motion model is created from planning 4DCT data. This model assumes that the displacement vector field (DVF) of any respiratory motion deformation can be described as a linear combination of some basismore » DVFs. (2) During the treatment procedure, 2D time-varying projection images (either kV or MV projections) are acquired, from which time-varying “fluoroscopic” 3D images of the patient are reconstructed using the motion model. The DVF of each timepoint in the time-varying reconstruction is an optimized linear combination of basis DVFs such that the 2D projection of the 3D volume at this timepoint matches the projection image. (3) 3D dose distribution is computed for each timepoint in the set of 3D reconstructed fluoroscopic images, from which the total effective 3D delivered dose is calculated by accumulating deformed dose distributions. This approach was first validated using two modified digital extended cardio-torso (XCAT) phantoms with lung tumors and different respiratory motions. The estimated doses were compared to the dose that would be calculated for routine 4DCT-based planning and to the actual delivered dose that was calculated using “ground truth” XCAT phantoms at all timepoints. The approach was also tested using one set of patient data, which demonstrated the application of our method in a clinical scenario. Results: For the first XCAT phantom that has a mostly regular breathing pattern, the errors in 95% volume dose (D95) are 0.11% and 0.83%, respectively for 3D fluoroscopic images reconstructed from kV and MV projections compared to the ground truth, which is clinically comparable to 4DCT (0.093%). For the second XCAT phantom that has an irregular breathing pattern, the errors are 0.81% and 1.75% for kV and MV reconstructions, both of which are better than that of 4DCT (4.01%). In the case of real patient, although it is impossible to obtain the actual delivered dose, the dose estimation is clinically reasonable and demonstrates differences between 4DCT and MV reconstruction-based dose estimates. Conclusions: With the availability of kV or MV projection images, the proposed approach is able to assess delivered doses for all respiratory phases during treatment. Compared to the planning dose based on 4DCT, the dose estimation using reconstructed 3D fluoroscopic images was as good as 4DCT for regular respiratory pattern and was a better dose estimation for the irregular respiratory pattern.« less

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

Jian, Siyang; Li, Jianwei; Chen, Ji

Nitrogen (N) fertilization affects the rate of soil organic carbon (SOC) decomposition by regulating extracellular enzyme activities (EEA). Extracellular enzymes have not been represented in global biogeochemical models. Understanding the relationships among EEA and SOC, soil N (TN), and soil microbial biomass carbon (MBC) under N fertilization would enable modeling of the influence of EEA on SOC decomposition. Based on 65 published studies, we synthesized the activities of α-1,4-glucosidase (AG), β-1,4-glucosidase (BG), β-d-cellobiosidase (CBH), β-1,4-xylosidase (BX), β-1,4-N-acetyl-glucosaminidase (NAG), leucine amino peptidase (LAP), urease (UREA), acid phosphatase (AP), phenol oxidase (PHO), and peroxidase (PEO) in response to N fertilization. Here, themore » proxy variables for hydrolytic C acquisition enzymes (C-acq), N acquisition (N-acq), and oxidative decomposition (OX) were calculated as the sum of AG, BG, CBH and BX; AG and LAP; PHO and PEO, respectively.« less

Four-dimensional dose reconstruction through in vivo phase matching of cine images of electronic portal imaging device

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

Yoon, Jihyung; Jung, Jae Won, E-mail: jungj@ecu.ed

Purpose: A method is proposed to reconstruct a four-dimensional (4D) dose distribution using phase matching of measured cine images to precalculated images of electronic portal imaging device (EPID). Methods: (1) A phantom, designed to simulate a tumor in lung (a polystyrene block with a 3 cm diameter embedded in cork), was placed on a sinusoidally moving platform with an amplitude of 1 cm and a period of 4 s. Ten-phase 4D computed tomography (CT) images of the phantom were acquired. A planning target volume (PTV) was created by adding a margin of 1 cm around the internal target volume ofmore » the tumor. (2) Three beams were designed, which included a static beam, a theoretical dynamic beam, and a planning-optimized dynamic beam (PODB). While the theoretical beam was made by manually programming a simplistic sliding leaf motion, the planning-optimized beam was obtained from treatment planning. From the three beams, three-dimensional (3D) doses on the phantom were calculated; 4D dose was calculated by means of the ten phase images (integrated over phases afterward); serving as “reference” images, phase-specific EPID dose images under the lung phantom were also calculated for each of the ten phases. (3) Cine EPID images were acquired while the beams were irradiated to the moving phantom. (4) Each cine image was phase-matched to a phase-specific CT image at which common irradiation occurred by intercomparing the cine image with the reference images. (5) Each cine image was used to reconstruct dose in the phase-matched CT image, and the reconstructed doses were summed over all phases. (6) The summation was compared with forwardly calculated 4D and 3D dose distributions. Accounting for realistic situations, intratreatment breathing irregularity was simulated by assuming an amplitude of 0.5 cm for the phantom during a portion of breathing trace in which the phase matching could not be performed. Intertreatment breathing irregularity between the time of treatment and the time of planning CT was considered by utilizing the same reduced amplitude when the phantom was irradiated. To examine the phase matching in a humanoid environment, the matching was also performed in a digital phantom (4D XCAT phantom). Results: For the static, the theoretical, and the planning-optimized dynamic beams, the 4D reconstructed doses showed agreement with the forwardly calculated 4D doses within the gamma pass rates of 92.7%, 100%, and 98.1%, respectively, at the isocenter plane given by 3%/3 mm criteria. Excellent agreement in dose volume histogram of PTV and lung-PTV was also found between the two 4D doses, while substantial differences were found between the 3D and the 4D doses. The significant breathing irregularities modeled in this study were found not to be noticeably affecting the reconstructed dose. The phase matching was performed equally well in a digital phantom. Conclusions: The method of retrospective phase determination of a moving object under irradiation provided successful 4D dose reconstruction. This method will provide accurate quality assurance and facilitate adaptive therapy when distinguishable objects such as well-defined tumors, diaphragm, and organs with markers (pancreas and liver) are covered by treatment beam apertures.« less

Four-dimensional dose reconstruction through in vivo phase matching of cine images of electronic portal imaging device.

PubMed

Yoon, Jihyung; Jung, Jae Won; Kim, Jong Oh; Yi, Byong Yong; Yeo, Inhwan

2016-07-01

A method is proposed to reconstruct a four-dimensional (4D) dose distribution using phase matching of measured cine images to precalculated images of electronic portal imaging device (EPID). (1) A phantom, designed to simulate a tumor in lung (a polystyrene block with a 3 cm diameter embedded in cork), was placed on a sinusoidally moving platform with an amplitude of 1 cm and a period of 4 s. Ten-phase 4D computed tomography (CT) images of the phantom were acquired. A planning target volume (PTV) was created by adding a margin of 1 cm around the internal target volume of the tumor. (2) Three beams were designed, which included a static beam, a theoretical dynamic beam, and a planning-optimized dynamic beam (PODB). While the theoretical beam was made by manually programming a simplistic sliding leaf motion, the planning-optimized beam was obtained from treatment planning. From the three beams, three-dimensional (3D) doses on the phantom were calculated; 4D dose was calculated by means of the ten phase images (integrated over phases afterward); serving as "reference" images, phase-specific EPID dose images under the lung phantom were also calculated for each of the ten phases. (3) Cine EPID images were acquired while the beams were irradiated to the moving phantom. (4) Each cine image was phase-matched to a phase-specific CT image at which common irradiation occurred by intercomparing the cine image with the reference images. (5) Each cine image was used to reconstruct dose in the phase-matched CT image, and the reconstructed doses were summed over all phases. (6) The summation was compared with forwardly calculated 4D and 3D dose distributions. Accounting for realistic situations, intratreatment breathing irregularity was simulated by assuming an amplitude of 0.5 cm for the phantom during a portion of breathing trace in which the phase matching could not be performed. Intertreatment breathing irregularity between the time of treatment and the time of planning CT was considered by utilizing the same reduced amplitude when the phantom was irradiated. To examine the phase matching in a humanoid environment, the matching was also performed in a digital phantom (4D XCAT phantom). For the static, the theoretical, and the planning-optimized dynamic beams, the 4D reconstructed doses showed agreement with the forwardly calculated 4D doses within the gamma pass rates of 92.7%, 100%, and 98.1%, respectively, at the isocenter plane given by 3%/3 mm criteria. Excellent agreement in dose volume histogram of PTV and lung-PTV was also found between the two 4D doses, while substantial differences were found between the 3D and the 4D doses. The significant breathing irregularities modeled in this study were found not to be noticeably affecting the reconstructed dose. The phase matching was performed equally well in a digital phantom. The method of retrospective phase determination of a moving object under irradiation provided successful 4D dose reconstruction. This method will provide accurate quality assurance and facilitate adaptive therapy when distinguishable objects such as well-defined tumors, diaphragm, and organs with markers (pancreas and liver) are covered by treatment beam apertures.

Structural evolution of the methane cation in subfemtosecond photodynamics

NASA Astrophysics Data System (ADS)

Mondal, T.; Varandas, A. J. C.

2015-07-01

An ab initio quantum dynamics study has been performed to explore the structural rearrangement of ground state CH 4+ in subfemtosecond resolved photodynamics. The method utilizes time-dependent wave-packet propagation on the X ˜ 2 T 2 electronic manifold of the title cation in full dimensionality, including nonadiabatic coupling of the three electronic sheets. Good agreement is obtained with recent experiments [Baker et al., Science 312, 424 (2006)] which use high-order harmonic generation to probe the attosecond proton dynamics. The novel results provide direct theoretical support of the observations while unravelling the underlying details. With the geometrical changes obtained by calculating the expectation values of the nuclear coordinates as a function of time, the structural evolution is predicted to begin through activation of the totally symmetric a1 and doubly degenerate e modes. While the former retains the original Td symmetry of the cation, the Jahn-Teller active e mode conducts it to a D2d structure. At ˜1.85 fs, the intermediate D2d structure is further predicted to rearrange to local C2v minimum geometry via Jahn-Teller active bending vibrations of t2 symmetry.

Quantification of functional mitral regurgitation by real-time 3D echocardiography: comparison with 3D velocity-encoded cardiac magnetic resonance.

PubMed

Marsan, Nina Ajmone; Westenberg, Jos J M; Ypenburg, Claudia; Delgado, Victoria; van Bommel, Rutger J; Roes, Stijntje D; Nucifora, Gaetano; van der Geest, Rob J; de Roos, Albert; Reiber, Johan C; Schalij, Martin J; Bax, Jeroen J

2009-11-01

The aim of this study was to evaluate feasibility and accuracy of real-time 3-dimensional (3D) echocardiography for quantification of mitral regurgitation (MR), in a head-to-head comparison with velocity-encoded cardiac magnetic resonance (VE-CMR). Accurate grading of MR severity is crucial for appropriate patient management but remains challenging. VE-CMR with 3D three-directional acquisition has been recently proposed as the reference method. A total of 64 patients with functional MR were included. A VE-CMR acquisition was applied to quantify mitral regurgitant volume (Rvol). Color Doppler 3D echocardiography was applied for direct measurement, in "en face" view, of mitral effective regurgitant orifice area (EROA); Rvol was subsequently calculated as EROA multiplied by the velocity-time integral of the regurgitant jet on the continuous-wave Doppler. To assess the relative potential error of the conventional approach, color Doppler 2-dimensional (2D) echocardiography was performed: vena contracta width was measured in the 4-chamber view and EROA calculated as circular (EROA-4CH); EROA was also calculated as elliptical (EROA-elliptical), measuring vena contracta also in the 2-chamber view. From these 2D measurements of EROA, the Rvols were also calculated. The EROA measured by 3D echocardiography was significantly higher than EROA-4CH (p < 0.001) and EROA-elliptical (p < 0.001), with a significant bias between these measurements (0.10 cm(2) and 0.06 cm(2), respectively). Rvol measured by 3D echocardiography showed excellent correlation with Rvol measured by CMR (r = 0.94), without a significant difference between these techniques (mean difference = -0.08 ml/beat). Conversely, 2D echocardiographic approach from the 4-chamber view significantly underestimated Rvol (p = 0.006) as compared with CMR (mean difference = 2.9 ml/beat). The 2D elliptical approach demonstrated a better agreement with CMR (mean difference = -1.6 ml/beat, p = 0.04). Quantification of EROA and Rvol of functional MR with 3D echocardiography is feasible and accurate as compared with VE-CMR; the currently recommended 2D echocardiographic approach significantly underestimates both EROA and Rvol.

SU-F-T-142: An Analytical Model to Correct the Aperture Scattered Dose in Clinical Proton Beams

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

Sun, B; Liu, S; Zhang, T

2016-06-15

Purpose: Apertures or collimators are used to laterally shape proton beams in double scattering (DS) delivery and to sharpen the penumbra in pencil beam (PB) delivery. However, aperture-scattered dose is not included in the current dose calculations of treatment planning system (TPS). The purpose of this study is to provide a method to correct the aperture-scattered dose based on an analytical model. Methods: A DS beam with a non-divergent aperture was delivered using a single-room proton machine. Dose profiles were measured with an ion-chamber scanning in water and a 2-D ion chamber matrix with solid-water buildup at various depths. Themore » measured doses were considered as the sum of the non-contaminated dose and the aperture-scattered dose. The non-contaminated dose was calculated by TPS and subtracted from the measured dose. Aperture scattered-dose was modeled as a 1D Gaussian distribution. For 2-D fields, to calculate the scatter-dose from all the edges of aperture, a sum of weighted distance was used in the model based on the distance from calculation point to aperture edge. The gamma index was calculated between the measured and calculated dose with and without scatter correction. Results: For a beam with range of 23 cm and aperture size of 20 cm, the contribution of the scatter horn was ∼8% of the total dose at 4 cm depth and diminished to 0 at 15 cm depth. The amplitude of scatter-dose decreased linearly with the depth increase. The 1D gamma index (2%/2 mm) between the calculated and measured profiles increased from 63% to 98% for 4 cm depth and from 83% to 98% at 13 cm depth. The 2D gamma index (2%/2 mm) at 4 cm depth has improved from 78% to 94%. Conclusion: Using the simple analytical method the discrepancy between the measured and calculated dose has significantly improved.« less

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

Naseri, M; Rajabi, H; Wang, J

Purpose: Respiration causes lesion smearing, image blurring and quality degradation, affecting lesion contrast and the ability to define correct lesion size. The spatial resolution of current multi pinhole SPECT (MPHS) scanners is sub-millimeter. Therefore, the effect of motion is more noticeable in comparison to conventional SPECT scanner. Gated imaging aims to reduce motion artifacts. A major issue in gating is the lack of statistics and individual reconstructed frames are noisy. The increased noise in each frame, deteriorates the quantitative accuracy of the MPHS Images. The objective of this work, is to enhance the image quality in 4D-MPHS imaging, by 4Dmore » image reconstruction. Methods: The new algorithm requires deformation vector fields (DVFs) that are calculated by non-rigid Demons registration. The algorithm is based on the motion-incorporated version of ordered subset expectation maximization (OSEM) algorithm. This iterative algorithm is capable to make full use of all projections to reconstruct each individual frame. To evaluate the performance of the proposed algorithm a simulation study was conducted. A fast ray tracing method was used to generate MPHS projections of a 4D digital mouse phantom with a small tumor in liver in eight different respiratory phases. To evaluate the 4D-OSEM algorithm potential, tumor to liver activity ratio was compared with other image reconstruction methods including 3D-MPHS and post reconstruction registered with Demons-derived DVFs. Results: Image quality of 4D-MPHS is greatly improved by the 4D-OSEM algorithm. When all projections are used to reconstruct a 3D-MPHS, motion blurring artifacts are present, leading to overestimation of the tumor size and 24% tumor contrast underestimation. This error reduced to 16% and 10% for post reconstruction registration methods and 4D-OSEM respectively. Conclusion: 4D-OSEM method can be used for motion correction in 4D-MPHS. The statistics and quantification are improved since all projection data are combined together to update the image.« less

Atomic Data and Spectral Line Intensities for Ca IX

NASA Technical Reports Server (NTRS)

Landi, E.; Bhatia, A. K.

2012-01-01

Electron impact collision strengths, energy levels, oscillator strengths and spontaneous radiative decay rates are calculated for Ca IX. We include in the calculations the 33 lowest configurations in the n = 3, 4, 5 complexes, corresponding to 283 fine structure levels in the 3l3l ', 3l4l'' and 3l4l''' configurations, where l,l' = s, p, d, l '' = s, p, d, f and l''' = s, p, d, f, g. Collision strengths are calculated at five incident energies for all transitions: 5.8, 13.6, 24.2, 38.6 and 57.9 Ry above the threshold of each transition. An additional energy, very close to the transition threshold, has been added, whose value is between 0.0055 Ry and 0.23 Ry depending on the levels involved. Calculations have been carried out using the Flexible Atomic Code and the distorted wave approximation. Excitation rate coefficients are calculated as a function of electron temperature by assuming a Maxwellian electron velocity distribution. Using the excitation rate coefficients and the radiative transition rates calculated in the present work, statistical equilibrium equations for level populations are solved at electron densities covering the 10(exp 8)-10(exp 14)/cubic cm range and at an electron temperature of log T(sub e)(K)=5.8, corresponding to the maximum abundance of Ca IX. Spectral line intensities are calculated, and their diagnostic relevance is discussed.

CASSCF/CI calculations for first row transition metal hydrides - The TiH(4-phi), VH(5-delta), CrH(6-sigma-plus), MnH(7-sigma-plus), FeH(4,6-delta) and NiH(2-delta) states

NASA Technical Reports Server (NTRS)

Walch, S. P.; Bauschlicher, C. W., Jr.

1983-01-01

Calculations are performed for the predicted ground states of TiH(4-phi), VH(5-delta), CrH(6-sigma-plus), MnH(7-sigma-plus), Fett(4,6-delta) and NiH(2-delta). For FeH both the 6-delta and 4-delta states are studied, since both are likely candidates for the ground state. The ground state symmetries are predicted based on a combination of atomic coupling arguments and coupling of 4s(2)3d(n) and 4s(1)3d(n+1) terms in the molecular system. Electron correlation is included by a CASSCF/CI (SD) treatment. The CASSCF includes near-degeneracy effects, while correlation of the 3d electrons in included at the CI level.

Casscf/ci Calculations for First Row Transition Metal Hydrides - the TIH(4-PHI), VH(5-DELTA), CRH(6-SIGMA-PLUS), MNH(7-SIGMA-PLUS), FEH(4,6-DELTA) and NIH(2-DELTA) States

NASA Astrophysics Data System (ADS)

Walch, S. P.; Bauschlicher, C. W., Jr.

1983-04-01

Calculations are performed for the predicted ground states of TiH(4-phi), VH(5-delta), CrH(6-sigma-plus), MnH(7-sigma-plus), Fett(4,6-delta) and NiH(2-delta). For FeH both the 6-delta and 4-delta states are studied, since both are likely candidates for the ground state. The ground state symmetries are predicted based on a combination of atomic coupling arguments and coupling of 4s(2)3d(n) and 4s(1)3d(n+1) terms in the molecular system. Electron correlation is included by a CASSCF/CI (SD) treatment. The CASSCF includes near-degeneracy effects, while correlation of the 3d electrons in included at the CI level.

SU-E-T-129: Dosimetric Evaluation of the Impact of Density Correction On Dose Calculation of Breast Cancer Treatment: A Study Based On RTOG 1005 Cases

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

Li, J; Yu, Y

Purpose: RTOG 1005 requires density correction in the dose calculation of breast cancer radiation treatment. The aim of the study was to evaluate the impact of density correction on the dose calculation. Methods: Eight cases were studied, which were planned on an XiO treatment planning system with pixel-by-pixel density correction using a superposition algorithm, following RTOG 1005 protocol requirements. Four were protocol Arm 1 (standard whole breast irradiation with sequential boost) cases and four were Arm 2 (hypofractionated whole breast irradiation with concurrent boost) cases. The plans were recalculated with the same monitor units without density correction. Dose calculations withmore » and without density correction were compared. Results: Results of Arm 1 and Arm 2 cases showed similar trends in the comparison. The average differences between the calculations with and without density correction (difference = Without - With) among all the cases were: -0.82 Gy (range: -2.65∼−0.18 Gy) in breast PTV Eval D95, −0.75 Gy (range: −1.23∼0.26 Gy) in breast PTV Eval D90, −1.00 Gy (range: −2.46∼−0.29 Gy) in lumpectomy PTV Eval D95, −0.78 Gy (range: −1.30∼0.11 Gy) in lumpectomy PTV Eval D90, −0.43% (range: −0.95∼−0.14%) in ipsilateral lung V20, −0.81% (range: −1.62∼−0.26%) in V16, −1.95% (range: −4.13∼−0.84%) in V10, −2.64% (−5.55∼−1.04%) in V8, −4.19% (range: −6.92∼−1.81%) in V5, and −4.95% (range: −7.49∼−2.01%) in V4, respectively. The differences in other normal tissues were minimal. Conclusion: The effect of density correction was observed in breast target doses (an average increase of ∼1 Gy in D95 and D90, compared to the calculation without density correction) and exposed ipsilateral lung volumes in low dose region (average increases of ∼4% and ∼5% in V5 and V4, respectively)« less

Preeclampsia is associated with ACE I/D polymorphism, obesity and oxidative damage in Mexican women.

PubMed

González-Garrido, José A; García-Sánchez, José R; Tovar-Rodríguez, José M; Olivares-Corichi, Ivonne M

2017-10-01

This study sought to determine whether the angiotensin-converting enzyme insertion/deletion (ACE I/D) polymorphism, obesity and oxidative damage are risk factors for the development of preeclampsia in Mexican women. A total of 66 women with preeclampsia (PE) and 37 women with normal pregnancies (NP) were included in the study. DNA was extracted from whole blood, and the ACE I/D polymorphism was evaluated by polymerase chain reaction. ACE activity and oxidative damage were assessed in plasma. The intergroup comparisons were analyzed by an analysis of variance (ANOVA) with post hoc tests. Hardy-Weinberg equilibrium (HWE) was tested by x 2 analysis, odds ratios (OR) were calculated as a measure of the degree of relative risk of preeclampsia, and for correlations, we used Spearman's correlation coefficient. The frequency of the DD genotype was higher in PE (34.84%) than NP (10.82%). The OR of the DD genotype and D allele were associated with a 4.4-fold (CI=95% 2.24-14) and 3-fold (CI=95% 1.69-5.62) increased risk of developing PE, respectively. Major ACE activity in the DD genotype and obesity were features of the PE group; oxidative damage to proteins and a reduction in the activity of the antioxidant system showed a correlation with BMI (p<0.01). Our results suggest that ACE I/D polymorphism, high ACE activity, body mass index and oxidative damage may play key roles in the pathogenesis of PE in the Mexican population. Furthermore, these findings could be used as predictive factors of PE. Copyright © 2017 International Society for the Study of Hypertension in Pregnancy. Published by Elsevier B.V. All rights reserved.

[Study on the quantitative estimation method for VOCs emission from petrochemical storage tanks based on tanks 4.0.9d model].

PubMed

Li, Jing; Wang, Min-Yan; Zhang, Jian; He, Wan-Qing; Nie, Lei; Shao, Xia

2013-12-01

VOCs emission from petrochemical storage tanks is one of the important emission sources in the petrochemical industry. In order to find out the VOCs emission amount of petrochemical storage tanks, Tanks 4.0.9d model is utilized to calculate the VOCs emission from different kinds of storage tanks. VOCs emissions from a horizontal tank, a vertical fixed roof tank, an internal floating roof tank and an external floating roof tank were calculated as an example. The consideration of the site meteorological information, the sealing information, the tank content information and unit conversion by using Tanks 4.0.9d model in China was also discussed. Tanks 4.0.9d model can be used to estimate VOCs emissions from petrochemical storage tanks in China as a simple and highly accurate method.

Coupled s-p-d Exchange in Facet-Controlled Pd 3 Pb Tripods Enhances Oxygen Reduction Catalysis

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

Bu, Lingzheng; Shao, Qi; Pi, Yecan

Efficient oxygen reduction reaction (ORR) catalysts are the key in developing high-performance fuel cells. Palladium (Pd) is a promising catalyst system for ORR with its potential to replace platinum (Pt), however it usually exhibits lower activity than Pt. Herein, we report a class of ordered Pd3Pb tripods (TPs) with dominated {110} facets that show extremely high ORR performance in alkaline medium. Totally different from the well-known knowledge that excellent ORR activity of Pt catalyst is caused by its partially-filled d-orbital, our first principle calculations suggest that the strong charge exchange between Pd-4d and Pb-(sp) orbitals on Pd3Pb TPs {110} facetmore » results in the Pd-Pb local bonding unit with the orbital configuration similar to Pt. Consequently, the Pd3Pb TPs exhibit much higher ORR activities than commercial Pt/C and commercial Pd/C. The Pd3Pb TPs are rather endurable and sustain over 20,000 potential cycles with negligible structural and compositional changes.« less

Coupled s-p-d Exchange in Facet-Controlled Pd 3 Pb Tripods Enhances Oxygen Reduction Catalysis

DOE PAGES

Bu, Lingzheng; Shao, Qi; Pi, Yecan; ...

2018-02-01

Efficient oxygen reduction reaction (ORR) catalysts are the key in developing high-performance fuel cells. Palladium (Pd) is a promising catalyst system for ORR with its potential to replace platinum (Pt), however it usually exhibits lower activity than Pt. Herein, we report a class of ordered Pd3Pb tripods (TPs) with dominated {110} facets that show extremely high ORR performance in alkaline medium. Totally different from the well-known knowledge that excellent ORR activity of Pt catalyst is caused by its partially-filled d-orbital, our first principle calculations suggest that the strong charge exchange between Pd-4d and Pb-(sp) orbitals on Pd3Pb TPs {110} facetmore » results in the Pd-Pb local bonding unit with the orbital configuration similar to Pt. Consequently, the Pd3Pb TPs exhibit much higher ORR activities than commercial Pt/C and commercial Pd/C. The Pd3Pb TPs are rather endurable and sustain over 20,000 potential cycles with negligible structural and compositional changes.« less

A theoretical approach to the photochemical activation of matrix isolated aluminum atoms and their reaction with methane

NASA Astrophysics Data System (ADS)

Pacheco-Blas, M. A.; Novaro, O. A.; Pacheco-Sánchez, J. H.

2010-11-01

The photochemical activation of Al atoms in cryogenic matrices to induce their reaction with methane has been experimentally studied before. Here, a theoretical study of the nonadiabatic transition probabilities for the ground (P2:3s23p1) and the lowest excited states (S2:3s24s1 and D2:3s23d1) of an aluminum atom interacting with a methane molecule (CH4) was carried out through ab initio Hartree-Fock self-consistent field calculations. This was followed by a multiconfigurational study of the correlation energy obtained by extensive variational and perturbational configuration interaction analyses using the CIPSI program. The D2 state is readily inserted into a C-H bond, this being a prelude to a sequence of avoided crossings with the initially repulsive (to CH4) lower lying states P2 and S2. We then use a direct extension of the Landau-Zener theory to obtain transition probabilities at each avoided crossing, allowing the formation of an HAlCH3 intermediate that eventually leads to the final pair of products H+AlCH3 and HAl+CH3.

Spectroscopic characteristic (FT-IR, 1H, 13C NMR and UV-Vis) and theoretical calculations (MEP, DOS, HOMO-LUMO, PES, NBO analysis and keto-enol tautomerism) of new tetradentate N,N‧-bis(4-hydroxysalicylidene)-1,4-phenylenediamine ligand as chelating agent for the synthesis of dinuclear Co(II), Ni(II), Cu(II) and Zn(II) complexes

NASA Astrophysics Data System (ADS)

Rajaei, Iman; Mirsattari, Seyed Nezamoddin

2018-07-01

The synthesis and characterization of a novel symmetrical Schiff base ligand N,Nʹ-bis(4-hydroxysalicylidene)-1,4-phenylenediamine (BHSP) was presented in this study and characterized by FT-IR, NMR (1H and 13C) and UV-Vis spectroscopy experimentally and theoretically. Also a series of binuclear Co(II), Ni(II), Cu(II) and Zn(II) complexes of BHSP ligand have been synthesized by conventional sequential route in 1:1 equivalent of L:M ratio and characterized by routine physicochemical characterizations. The molecular geometry and vibrational frequencies of the BHSP in the ground state were calculated by using density functional theory (DFT) B3LYP method invoking 6-31G(d,p) and 6-31++G(d,p) basis sets. To study different conformations of the molecule, potential energy surface (PES) scan investigations were performed. The energetic behavior of the ligand compound (BHSP) in solvent media has been examined using B3LYP method with the 6-31G(d,p) and 6-31++G(d,p) basis sets by applying the polarized continuum model (PCM). In addition, DFT calculations of the BHSP ligand, molecular electrostatic potential (MEP), contour map, natural bond orbital (NBO) analysis, frontier molecular orbitals (FMO) analysis, NMR analysis and TD-DFT calculations were conducted. The calculated properties are in agreement with the available experimental data and closely related molecule BSP. The calculated results show that the optimized geometry can well reproduce the crystal structural parameters.

A Quantum Chemical and Statistical Study of Phenolic Schiff Bases with Antioxidant Activity against DPPH Free Radical

PubMed Central

Anouar, El Hassane

2014-01-01

Phenolic Schiff bases are known as powerful antioxidants. To select the electronic, 2D and 3D descriptors responsible for the free radical scavenging ability of a series of 30 phenolic Schiff bases, a set of molecular descriptors were calculated by using B3P86 (Becke’s three parameter hybrid functional with Perdew 86 correlation functional) combined with 6-31 + G(d,p) basis set (i.e., at the B3P86/6-31 + G(d,p) level of theory). The chemometric methods, simple and multiple linear regressions (SLR and MLR), principal component analysis (PCA) and hierarchical cluster analysis (HCA) were employed to reduce the dimensionality and to investigate the relationship between the calculated descriptors and the antioxidant activity. The results showed that the antioxidant activity mainly depends on the first and second bond dissociation enthalpies of phenolic hydroxyl groups, the dipole moment and the hydrophobicity descriptors. The antioxidant activity is inversely proportional to the main descriptors. The selected descriptors discriminate the Schiff bases into active and inactive antioxidants. PMID:26784873

Splay fault slip in a subduction margin, a new model of evolution

NASA Astrophysics Data System (ADS)

Conin, Marianne; Henry, Pierre; Godard, Vincent; Bourlange, Sylvain

2012-08-01

In subduction zones, major thrusts called splay faults are thought to slip coseismically during large earthquakes affecting the main plate interface. We propose an analytical condition for the activation of a splay fault based on force balance calculations and suggest thrusting along the splay fault is generally conditioned by the growth of the accretionary wedge, or by the erosion of the hanging wall. In theory, normal slip on the splay fault may occur when the décollement has a very low friction coefficient seaward. Such a low friction also implies an unstable extensional state within the outer wedge. Finite element elasto-plastic calculations with a geometry based on the Nankai Kumano section were performed and confirm that this analytical condition is a valid approximation. Furthermore, localized extension at a shallow level in the splay hanging wall is observed in models for a wide range of friction coefficients (from ∼0 to the value of internal friction coefficient of the rock, here equals to 0.4). The timing of slip established for the splay fault branch drilled on Nankai Kumano transect suggests a phase of concurrent splay and accretionary wedge growth ≈2 Ma to ≈1.5 Ma, followed by a locking of the splay ≈1.3 Ma. Active extension is observed in the hanging wall. This evolution can be explained by the activation of a deeper and weaker décollement, followed by an interruption of accretion. Activation of a splay as a normal fault, as hypothesized in the case of the Tohoku 2011 earthquake, can be achieved only if the friction coefficient on the décollement drops to near zero. We conclude that the tectonic stress state largely determines long-term variations of tightly related splay fault and outer décollement activity and thus influences where and how coseismic rupture ends, but that occurrence of normal slip on a splay fault requires coseismic friction reduction.

Antioxidant potential of curcumin-related compounds studied by chemiluminescence kinetics, chain-breaking efficiencies, scavenging activity (ORAC) and DFT calculations.

PubMed

Slavova-Kazakova, Adriana K; Angelova, Silvia E; Veprintsev, Timur L; Denev, Petko; Fabbri, Davide; Dettori, Maria Antonietta; Kratchanova, Maria; Naumov, Vladimir V; Trofimov, Aleksei V; Vasil'ev, Rostislav F; Delogu, Giovanna; Kancheva, Vessela D

2015-01-01

This study compares the ability to scavenge different peroxyl radicals and to act as chain-breaking antioxidants of monomers related to curcumin (1): dehydrozingerone (2), zingerone (3), (2Z,5E)-ethyl 2-hydroxy-6-(4-hydroxy-3-methoxyphenyl)-4-oxohexa-2,5-dienoate (4), ferulic acid (5) and their corresponding C 2-symmetric dimers 6-9. Four models were applied: model 1 - chemiluminescence (CL) of a hydrocarbon substrate used for determination of the rate constants (k A) of the reactions of the antioxidants with peroxyl radicals; model 2 - lipid autoxidation (lipidAO) used for assessing the chain-breaking antioxidant efficiency and reactivity; model 3 - oxygen radical absorbance capacity (ORAC), which yields the activity against peroxyl radicals generated by an azoinitiator; model 4 - density functional theory (DFT) calculations at UB3LYP/6-31+G(d,p) level, applied to explain the structure-activity relationship. Dimers showed 2-2.5-fold higher values of k A than their monomers. Model 2 gives information about the effects of the side chains and revealed much higher antioxidant activity for monomers and dimers with α,β-unsaturated side chains. Curcumin and 6 in fact are dimers of the same monomer 2. We conclude that the type of linkage between the two "halves" by which the molecule is made up does not exert influence on the antioxidant efficiency and reactivity of these two dimers. The dimers and the monomers demonstrated higher activity than Trolox (10) in aqueous medium (model 3). A comparison of the studied compounds with DL-α-tocopherol (11), Trolox and curcumin is made. All dimers are characterized through lower bond dissociation enthalpies (BDEs) than their monomers (model 4), which qualitatively supports the experimental results.

One-pot microwave assisted synthesis under green chemistry conditions, antioxidant screening, and cytotoxicity assessments of benzimidazole Schiff bases and pyrimido[1,2-a]benzimidazol-3(4H)-ones.

PubMed

Neochoritis, Constantinos G; Zarganes-Tzitzikas, Tryfon; Tsoleridis, Constantinos A; Stephanidou-Stephanatou, Julia; Kontogiorgis, Christos A; Hadjipavlou-Litina, Dimitra J; Choli-Papadopoulou, Theodora

2011-01-01

The synthesis of a number of benzimidazole Schiff bases 3 and 3-oxo-pyrimido[1,2-a]benzimidazoles 4 in excellent yields by a one-step sequence from the reaction of 2-aminobenzimidazole under green chemistry conditions is described. Structural assignments of the new compounds as well as complete assignment of (1)H and (13)C NMR signals have been unambiguously achieved based on the analysis of their (1)H and (13)C NMR (1D and 2D), IR, MS and elemental analysis data. To the synthesized Schiff bases the E-configuration was assigned on the basis of comparison of experimental and calculated (DFT) (13)C NMR chemical shifts. Compounds 3 and 4 were evaluated as inhibitors of lipoxygenase (LOX) and of lipid peroxidation (LPO). All the tested derivatives showed inhibition of lipid peroxidation, whereas most of them were found to have higher activation than the reference compound trolox; The Schiff bases 3e, 3h, and 3i, and the pyrimidobenzimidazoles 4a, 4e and 4f were found to be the most potent. The most potent LOX inhibitor within the subset of Schiff bases was found compound 3i, followed by 3f, whereas compounds 4a and 4g were found the most potent of the 3-oxo-pyrimido[1,2-a]benzimidazole group. Moreover, some cytotoxicity assessments were undertaken, whereupon it was found that Schiff base 3i and pyrimidobenzimidazoles 4e and 4f did not exhibit cytotoxicity at similar concentrations resembling thus the inhibitory activity of lipid peroxidation. The most cytotoxic Schiff base and pyrimidobenzimidazole were found to be 3d and 4c, respectively. Copyright © 2010 Elsevier Masson SAS. All rights reserved.

Four-dimensional dose evaluation using deformable image registration in radiotherapy for liver cancer

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

Hoon Jung, Sang; Min Yoon, Sang; Ho Park, Sung

2013-01-15

Purpose: In order to evaluate the dosimetric impact of respiratory motion on the dose delivered to the target volume and critical organs during free-breathing radiotherapy, a four-dimensional dose was evaluated using deformable image registration (DIR). Methods: Four-dimensional computed tomography (4DCT) images were acquired for 11 patients who were treated for liver cancer. Internal target volume-based treatment planning and dose calculation (3D dose) were performed using the end-exhalation phase images. The four-dimensional dose (4D dose) was calculated based on DIR of all phase images from 4DCT to the planned image. Dosimetric parameters from the 4D dose, were calculated and compared withmore » those from the 3D dose. Results: There was no significant change of the dosimetric parameters for gross tumor volume (p > 0.05). The increase D{sub mean} and generalized equivalent uniform dose (gEUD) for liver were by 3.1%{+-} 3.3% (p= 0.003) and 2.8%{+-} 3.3% (p= 0.008), respectively, and for duodenum, they were decreased by 15.7%{+-} 11.2% (p= 0.003) and 15.1%{+-} 11.0% (p= 0.003), respectively. The D{sub max} and gEUD for stomach was decreased by 5.3%{+-} 5.8% (p= 0.003) and 9.7%{+-} 8.7% (p= 0.003), respectively. The D{sub max} and gEUD for right kidney was decreased by 11.2%{+-} 16.2% (p= 0.003) and 14.9%{+-} 16.8% (p= 0.005), respectively. For left kidney, D{sub max} and gEUD were decreased by 11.4%{+-} 11.0% (p= 0.003) and 12.8%{+-} 12.1% (p= 0.005), respectively. The NTCP values for duodenum and stomach were decreased by 8.4%{+-} 5.8% (p= 0.003) and 17.2%{+-} 13.7% (p= 0.003), respectively. Conclusions: The four-dimensional dose with a more realistic dose calculation accounting for respiratory motion revealed no significant difference in target coverage and potentially significant change in the physical and biological dosimetric parameters in normal organs during free-breathing treatment.« less

Optimizing the calculation of DM,CO and VC via the single breath single oxygen tension DLCO/NO method.

PubMed

Coffman, Kirsten E; Taylor, Bryan J; Carlson, Alex R; Wentz, Robert J; Johnson, Bruce D

2016-01-15

Alveolar-capillary membrane conductance (D(M,CO)) and pulmonary-capillary blood volume (V(C)) are calculated via lung diffusing capacity for carbon monoxide (DL(CO)) and nitric oxide (DL(NO)) using the single breath, single oxygen tension (single-FiO2) method. However, two calculation parameters, the reaction rate of carbon monoxide with blood (θ(CO)) and the D(M,NO)/D(M,CO) ratio (α-ratio), are controversial. This study systematically determined optimal θ(CO) and α-ratio values to be used in the single-FiO2 method that yielded the most similar D(M,CO) and V(C) values compared to the 'gold-standard' multiple-FiO2 method. Eleven healthy subjects performed single breath DL(CO)/DL(NO) maneuvers at rest and during exercise. D(M,CO) and V(C) were calculated via the single-FiO2 and multiple-FiO2 methods by implementing seven θ(CO) equations and a range of previously reported α-ratios. The RP θ(CO) equation (Reeves, R.B., Park, H.K., 1992. Respiration Physiology 88 1-21) and an α-ratio of 4.0-4.4 yielded DM,CO and VC values that were most similar between methods. The RP θ(CO) equation and an experimental α-ratio should be used in future studies. Copyright © 2015 Elsevier B.V. All rights reserved.

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

Finnegan, D.L.; Miller, T.L.; Zoller, W.H.

Particle and gas samples were collected at Mauna Loa volcano during and after its eruption in March and April, 1984 and at Kilauea volcano in 1983, 1984, and 1985 during various phases of its ongoing activity. In the last two Kilauea sampling missions, samples were collected during eruptive activity. The samples were analyzed by INAA for over 40 elements. We have found Ir in samples collected at Kilauea and Mauna Loa during fountaining activity as well as after eruptive activity. Os was also seen in the Mauna Loa samples. Enrichment factors for Ir in the volcanic fumes range from 10/supmore » 4/ to 10/sup 5/ relative to BHVO. Flux calculations for Ir at Mauna Loa and Kilauea had ranges of 80 to 3000 and 10 to 315 g/d respectively. The percentage of Ir released from the magma into the fumes ranged from 1% to 12% for both volcanoes. Calculations assuming the Deccan as the source of Ir for the K/T boundary layer show that the concentration of Ir left in the basalts may be too low to account for all of the K/T Ir. It would require a very high fraction (> 30%) of the Ir to be purged from the basalt to account for all the Ir, which cannot be supported by the Hawaiian data. 26 refs., 1 fig., 4 tabs.« less

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

Sen, A

Purpose: Accuboost treatment planning uses dwell times from a nomogram designed with Monte Carlo calculations for round and D-shaped applicators. A quick dose calculation method has been developed for verification of the HDR Brachytherapy dose as a second check. Methods: Accuboost breast treatment uses several round and D-shaped applicators to be used non-invasively with an Ir-192 source from a HDR Brachytherapy afterloader after the breast is compressed in a mammographic unit for localization. The breast thickness, source activity, the prescription dose and the applicator size are entered into a nomogram spreadsheet which gives the dwell times to be manually enteredmore » into the delivery computer. Approximating the HDR Ir-192 as a point source, and knowing the geometry of the round and D-applicators, the distances from the source positions to the midpoint of the central plane are calculated. Using the exposure constant of Ir-192 and medium as human tissue, the dose at a point is calculated as: D(cGy) = 1.254 × A × t/R2, where A is the activity in Ci, t is the dwell time in sec and R is the distance in cm. The dose from each dwell position is added to get the total dose. Results: Each fraction is delivered in two compressions: cranio-caudally and medial-laterally. A typical APBI treatment in 10 fractions requires 20 compressions. For a patient treated with D45 applicators and an average of 5.22 cm thickness, this calculation was 1.63 % higher than the prescription. For another patient using D53 applicators in the CC direction and 7 cm SDO applicators in the ML direction, this calculation was 1.31 % lower than the prescription. Conclusion: This is a simple and quick method to double check the dose on the central plane for Accuboost treatment.« less

Eu(2+)-Activated Alkaline-Earth Halophosphates, M5(PO4)3X:Eu(2+) (M = Ca, Sr, Ba; X = F, Cl, Br) for NUV-LEDs: Site-Selective Crystal Field Effect.

PubMed

Kim, Donghyeon; Kim, Sung-Chul; Bae, Jong-Seong; Kim, Sungyun; Kim, Seung-Joo; Park, Jung-Chul

2016-09-06

Eu(2+)-activated M5(PO4)3X (M = Ca, Sr, Ba; X = F, Cl, Br) compounds providing different alkaline-earth metal and halide ions were successfully synthesized and characterized. The emission peak maxima of the M5(PO4)3Cl:Eu(2+) (M = Ca, Sr, Ba) compounds were blue-shifted from Ca to Ba (454 nm for Ca, 444 nm for Sr, and 434 nm for Ba), and those of the Sr5(PO4)3X:Eu(2+) (X = F, Cl, Br) compounds were red-shifted along the series of halides, F → Cl → Br (437 nm for F, 444 nm for Cl, and 448 nm for Br). The site selectivity and occupancy of the activator ions (Eu(2+)) in the M5(PO4)3X:Eu(2+) (M = Ca, Sr, Ba; X = F, Cl, Br) crystal lattices were estimated based on theoretical calculation of the 5d → 4f transition energies of Eu(2+) using LCAO. In combination with the photoluminescence measurements and theoretical calculation, it was elucidated that the Eu(2+) ions preferably enter the fully oxygen-coordinated sites in the M5(PO4)3X:Eu(2+) (M = Ca, Sr, Ba; X = F, Cl, Br) compounds. This trend can be well explained by "Pauling's rules". These compounds may provide a platform for modeling a new phosphor and application in the solid-state lighting field.

Calcitriol decreases TGF-β1 and angiotensin II production and protects against chlorhexide digluconate-induced liver peritoneal fibrosis in rats.

PubMed

Lee, Chung-Jen; Subeq, Yi-Maun; Lee, Ru-Ping; Liou, Hung-Hsiang; Hsu, Bang-Gee

2014-01-01

Peritoneal fibrosis is a major complication of peritoneal dialysis that can lead to ultrafiltration failure. This study investigates the protective effects of calcitriol on chlorhexidine digluconate-induced peritoneal fibrosis in rats. Peritoneal fibrosis was induced in Sprague-Dawley rats by daily administration of 0.5mL 0.1% chlorhexidine digluconate in normal saline via peritoneal dialysis for 1week. Rats received daily intravenous injections of calcitriol (low-dose, 10ng/kg; or high-dose, 100ng/kg) for 1week. After 7days, conventional 4.25% Dianeal (30mL) was administered via peritoneal dialysis over 4h. Peritoneal solute transport was calculated from the dialysate concentration relative to its concentration in the initial infused dialysis solution (D4/D0 glucose) for glucose, and the dialysate-to-plasma concentration ratio (D4/P4 urea) at 4h for urea. Rats were then sacrificed and the liver peritoneum was harvested for immunohistochemical analysis via microscopy. After dialysis, the D4/P4 Urea level was reduced; increases were observed in the D4/D0 glucose level and the levels of active transforming growth factor-β1 and angiotensin II in serum and dialysate; the liver peritoneum and muscle peritoneum was markedly thickened, and the expression of α-SMA, fibronectin, collagen, vascular endothelial growth factor, angiotensin II, transforming growth factor-β1, and phosphorylated Smad2/3 (P-Smad2/3)-positive cells in the liver peritoneum was elevated in the peritoneal fibrosis group compared with the vehicle group. Calcitriol decreased the serum and dialysate active transforming growth factor-β1 and angiotensin II level, decreased the thickness of the liver peritoneum and muscle peritoneum, and decreased the expression of α-SMA, fibronectin, collagen, vascular endothelial growth factor, angiotensin II, transforming growth factor-β1, and P-Smad2/3-positive cells in liver peritoneum cells. High-dose calcitriol exhibited better protective effects against peritoneal fibrosis than did the lower dose. Calcitriol protected against chlorhexidine digluconate-induced peritoneal fibrosis in rats by decreasing transforming growth factor-β1 and angiotensin II production. Copyright © 2013 Elsevier Ltd. All rights reserved.

The accuracy of a 2D and 3D dendritic tip scaling parameter in predicting the columnar to equiaxed transition (CET)

NASA Astrophysics Data System (ADS)

Seredyński, M.; Rebow, M.; Banaszek, J.

2016-09-01

The dendrite tip kinetics model accuracy relies on the reliability of the stability constant used, which is usually experimentally determined for 3D situations and applied to 2D models. The paper reports authors' attempts to cure the situation by deriving 2D dendritic tip scaling parameter for aluminium-based alloy: Al-4wt%Cu. The obtained parameter is then incorporated into the KGT dendritic growth model in order to compare it with the original 3D KGT counterpart and to derive two-dimensional and three-dimensional versions of the modified Hunt's analytical model for the columnar-to-equiaxed transition (CET). The conclusions drawn from the above analysis are further confirmed through numerical calculations of the two cases of Al-4wt%Cu metallic alloy solidification using the front tracking technique. Results, including the porous zone-under-cooled liquid front position, the calculated solutal under-cooling and a new predictor of the relative tendency to form an equiaxed zone, are shown, compared and discussed two numerical cases. The necessity to calculate sufficiently precise values of the tip scaling parameter in 2D and 3D is stressed.

2D Echocardiographic Evaluation of Right Ventricular Function Correlates With 3D Volumetric Models in Cardiac Surgery Patients.

PubMed

Magunia, Harry; Schmid, Eckhard; Hilberath, Jan N; Häberle, Leo; Grasshoff, Christian; Schlensak, Christian; Rosenberger, Peter; Nowak-Machen, Martina

2017-04-01

The early diagnosis and treatment of right ventricular (RV) dysfunction are of critical importance in cardiac surgery patients and impact clinical outcome. Two-dimensional (2D) transesophageal echocardiography (TEE) can be used to evaluate RV function using surrogate parameters due to complex RV geometry. The aim of this study was to evaluate whether the commonly used visual evaluation of RV function and size using 2D TEE correlated with the calculated three-dimensional (3D) volumetric models of RV function. Retrospective study, single center, University Hospital. Seventy complete datasets were studied consisting of 2D 4-chamber view loops (2-3 beats) and the corresponding 4-chamber view 3D full-volume loop of the right ventricle. RV function and RV size of the 2D loops then were assessed retrospectively purely qualitatively individually by 4 clinician echocardiographers certified in perioperative TEE. Corresponding 3D volumetric models calculating RV ejection fraction and RV end-diastolic volumes then were established and compared with the 2D assessments. 2D assessment of RV function correlated with 3D volumetric calculations (Spearman's rho -0.5; p<0.0001). No correlation could be established between 2D estimates of RV size and actual 3D volumetric end-diastolic volumes (Spearman's rho 0.15; p = 0.25). The 2D assessment of right ventricular function based on visual estimation as frequently used in clinical practice appeared to be a reliable method of RV functional evaluation. However, 2D assessment of RV size seemed unreliable and should be used with caution. Copyright © 2017 Elsevier Inc. All rights reserved.

15O PET Measurement of Blood Flow and Oxygen Consumption in Cold-Activated Human Brown Fat

PubMed Central

Muzik, Otto; Mangner, Thomas J.; Leonard, William R.; Kumar, Ajay; Janisse, James; Granneman, James G.

2013-01-01

Although it has been believed that brown adipose tissue (BAT) depots disappear shortly after the perinatal period in humans, PET imaging using the glucose analog 18F-FDG has shown unequivocally the existence of functional BAT in adult humans, suggesting that many humans retain some functional BAT past infancy. The objective of this study was to determine to what extent BAT thermogenesis is activated in adults during cold stress and to establish the relationship between BAT oxidative metabolism and 18F-FDG tracer uptake. Methods Twenty-five healthy adults (15 women and 10 men; mean age ± SD, 30 ± 7 y) underwent triple-oxygen scans (H215O, C15O, and 15O2) as well as measurements of daily energy expenditure (DEE; kcal/d) both at rest and after exposure to mild cold (15.5°C [60°F]) using indirect calorimetry. The subjects were divided into 2 groups (high BAT and low BAT) based on the presence or absence of 18F-FDG tracer uptake (standardized uptake value [SUV] > 2) in cervical–supraclavicular BAT. Blood flow and oxygen extraction fraction (OEF) were calculated from dynamic PET scans at the location of BAT, muscle, and white adipose tissue. Regional blood oxygen saturation was determined by near-infrared spectroscopy. The total energy expenditure during rest and mild cold stress was measured by indirect calorimetry. Tissue-level metabolic rate of oxygen (MRO2) in BAT was determined and used to calculate the contribution of activated BAT to DEE. Results The mass of activated BAT was 59.1 ± 17.5 g (range, 32–85 g) in the high-BAT group (8 women and 1 man; mean age, 29.6 ± 5.5 y) and 2.2 ± 3.6 g (range, 0–9.3 g) in the low-BAT group (9 men and 7 women; mean age, 31.4 ± 10 y). Corresponding maximal SUVs were significantly higher in the high-BAT group than in the low-BAT group (10.7 ± 3.9 vs. 2.1 ± 0.7, P = 0.01). Blood flow values were significantly higher in the high-BAT group than in the low-BAT group for BAT (12.9 ± 4.1 vs. 5.9 ± 2.2 mL/100 g/min, P = 0.03) and white adipose tissue (7.2 ± 3.4 vs. 5.7 ± 2.3 mL/100 g/min, P = 0.03) but were similar for muscle (4.4 ± 1.9 vs. 3.9 ± 1.7 mL/100 g/min). Moreover, OEF in BAT was similar in the 2 groups (0.51 ± 0.17 in high-BAT group vs. 0.47 ± 0.18 in low-BAT group, P = 0.39). During mild cold stress, calculated MRO2 values in BAT increased from 0.97 ± 0.53 to 1.42 ± 0.68 mL/100 g/min (P = 0.04) in the high-BAT group and were significantly higher than those determined in the low-BAT group (0.40 ± 0.28 vs. 0.51 ± 0.23, P = 0.67). The increase in DEE associated with BAT oxidative metabolism was highly variable in the high-BAT group, with an average of 3.2 ± 2.4 kcal/d (range, 1.9–4.6 kcal/d) at rest, and increased to 6.3 ± 3.5 kcal/d (range, 4.0–9.9 kcal/d) during exposure to mild cold. Although BAT accounted for only a small fraction of the cold-induced increase in DEE, such increases were not observed in subjects lacking BAT. Conclusion Mild cold-induced thermogenesis in BAT accounts for 15–25 kcal/d in subjects with relatively large BAT depots. Thus, although the presence of active BAT is correlated with cold-induced energy expenditure, direct measurement of MRO2 indicates that BAT is a minor source of thermogenesis in humans. PMID:23362317

SU-E-T-472: A Multi-Dimensional Measurements Comparison to Analyze a 3D Patient Specific QA Tool

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

Ashmeg, S; Jackson, J; Zhang, Y

Purpose: To quantitatively evaluate a 3D patient specific QA tool using 2D film and 3D Presage dosimetry. Methods: A brain IMRT case was delivered to Delta4, EBT2 film and Presage plastic dosimeter. The film was inserted in the solid water slabs at 7.5cm depth for measurement. The Presage dosimeter was inserted into a head phantom for 3D dose measurement. Delta4's Anatomy software was used to calculate the corresponding dose to the film in solid water slabs and to Presage in the head phantom. The results from Anatomy were compared to both calculated results from Eclipse and measured dose from filmmore » and Presage to evaluate its accuracy. Using RIT software, we compared the “Anatomy” dose to the EBT2 film measurement and the film measurement to ECLIPSE calculation. For 3D analysis, DICOM file of “Anatomy” was extracted and imported to CERR software, which was used to compare the Presage dose to both “Anatomy” calculation and ECLIPSE calculation. Gamma criteria of 3% - 3mm and 5% - 5mm was used for comparison. Results: Gamma passing rates of film vs “Anatomy”, “Anatomy” vs ECLIPSE and film vs ECLIPSE were 82.8%, 70.9% and 87.6% respectively when 3% - 3mm criteria is used. When the criteria is changed to 5% - 5mm, the passing rates became 87.8%, 76.3% and 90.8% respectively. For 3D analysis, Anatomy vs ECLIPSE showed gamma passing rate of 86.4% and 93.3% for 3% - 3mm and 5% - 5mm respectively. The rate is 77.0% for Presage vs ECLIPSE analysis. The Anatomy vs ECLIPSE were absolute dose comparison. However, film and Presage analysis were relative comparison Conclusion: The results show higher passing rate in 3D than 2D in “Anatomy” software. This could be due to the higher degrees of freedom in 3D than in 2D for gamma analysis.« less

Dose calculations accounting for breathing motion in stereotactic lung radiotherapy based on 4D-CT and the internal target volume.

PubMed

Admiraal, Marjan A; Schuring, Danny; Hurkmans, Coen W

2008-01-01

The purpose of this study was to determine the 4D accumulated dose delivered to the CTV in stereotactic radiotherapy of lung tumours, for treatments planned on an average CT using an ITV derived from the Maximum Intensity Projection (MIP) CT. For 10 stage I lung cancer patients, treatment plans were generated based on 4D-CT images. From the 4D-CT scan, 10 time-sorted breathing phases were derived, along with the average CT and the MIP. The ITV with a margin of 0mm was used as a PTV to study a worst case scenario in which the differences between 3D planning and 4D dose accumulation will be largest. Dose calculations were performed on the average CT. Dose prescription was 60Gy to 95% of the PTV, and at least 54Gy should be received by 99% of the PTV. Plans were generated using the inverse planning module of the Pinnacle(3) treatment planning system. The plans consisted of nine coplanar beams with two segments each. After optimisation, the treatment plan was transferred to all breathing phases and the delivered dose per phase was calculated using an elastic body spline model available in our research version of Pinnacle (8.1r). Then, the cumulative dose to the CTV over all breathing phases was calculated and compared to the dose distribution of the original treatment plan. Although location, tumour size and breathing-induced tumour movement varied widely between patients, the PTV planning criteria could always be achieved without compromising organs at risk criteria. After 4D dose calculations, only very small differences between the initial planned PTV coverage and resulting CTV coverage were observed. For all patients, the dose delivered to 99% of the CTV exceeded 54Gy. For nine out of 10 patients also the criterion was met that the volume of the CTV receiving at least the prescribed dose was more than 95%. When the target dose is prescribed to the ITV (PTV=ITV) and dose calculations are performed on the average CT, the cumulative CTV dose compares well to the planned dose to the ITV. Thus, the concept of treatment plan optimisation and evaluation based on the average CT and the ITV is a valid approach in stereotactic lung treatment. Even with a zero ITV to PTV margin, no significantly different dose coverage of the CTV arises from the breathing motion induced dose variation over time.

Widths of atomic 4s and 4p vacancy states, 46 less than or equal to Z less than or equal to 50

NASA Technical Reports Server (NTRS)

Hsiungchen, M.; Crasemann, B.; Yin, L. I.; Tsang, T.; Adler, I.

1975-01-01

Auger and X-ray photoelectron spectra involving N1, N2, and N3 vacancy states of Pd, Ag, Cd, In, and Sn were measured and compared with results of free atom calculations. As previously observed in Cu and Zn Auger spectra that involve 3d-band electrons, free-atom characteristics with regard to widths and structure were found in the Ag and Cd M4-N4,5N4,5 and M5-N4,5N4,5 Auger spectra that arise from transitions of 4d-band electrons. Theoretical N1 widths computed with calculated free-atom Auger energies agree well with measurements. Theory however predicts wider N2 than N3 vacancy states (as observed for Xe), while the measured N2 and N3 widths are nearly equal to each other and to the average of the calculated N2 and N3 widths. The calculations are made difficult by the exceedingly short lifetime of some 4p vacancies and by the extreme sensitivity of super-Coster-Kronig rates, which dominate the deexcitation, to the transition energy and to the fine details of the atomic potential.

Surface reaction of silicon chlorides during atomic layer deposition of silicon nitride

NASA Astrophysics Data System (ADS)

Yusup, Luchana L.; Park, Jae-Min; Mayangsari, Tirta R.; Kwon, Young-Kyun; Lee, Won-Jun

2018-02-01

The reaction of precursor with surface active site is the critical step in atomic layer deposition (ALD) process. We performed the density functional theory calculation with DFT-D correction to study the surface reaction of different silicon chloride precursors during the first half cycle of ALD process. SiCl4, SiH2Cl2, Si2Cl6 and Si3Cl8 were considered as the silicon precursors, and an NH/SiNH2*-terminated silicon nitride surface was constructed to model the thermal ALD processes using NH3 as well as the PEALD processes using NH3 plasma. The total energies of the system were calculated for the geometry-optimized structures of physisorption, chemisorption, and transition state. The order of silicon precursors in energy barrier, from lowest to highest, is Si3Cl8 (0.92 eV), Si2Cl6 (3.22 eV), SiH2Cl2 (3.93 eV) and SiCl4 (4.49 eV). Silicon precursor with lower energy barrier in DFT calculation showed lower saturation dose in literature for both thermal and plasma-enhanced ALD of silicon nitride. Therefore, DFT calculation is a promising tool in predicting the reactivity of precursor during ALD process.

Properties of Cerium Hydroxides from Matrix Infrared Spectra and Electronic Structure Calculations.

PubMed

Fang, Zongtang; Thanthiriwatte, K Sahan; Dixon, David A; Andrews, Lester; Wang, Xuefeng

2016-02-15

Reactions of laser ablated cerium atoms with hydrogen peroxide or hydrogen and oxygen mixtures diluted in argon and condensed at 4 K produced the Ce(OH)3 and Ce(OH)2 molecules and Ce(OH)2(+) cation as major products. Additional minor products were identified as the Ce(OH)4, HCeO, and OCeOH molecules. These new species were identified from their matrix infrared spectra with D2O2, D2, and (18)O2 isotopic substitution and correlating observed frequencies with values calculated by density functional theory. We find that the amounts of Ce(OH)3 and of the Ce(OH)2(+) cation increase on UV (λ > 220 nm) photolysis, while Ce(OH)2, Ce(OH)4, and HCeO are photosensitive. The observed major species for Ce are in the +III or +II oxidation state, and the minor product, Ce(OH)4, is in the +IV oxidation state. The calculations for the vibrational frequencies with the B3LYP functional agree well with the experiment. The NBO analysis shows significant backbonding to the metal 4f and 5d orbitals for the closed shell species. Most open shell species have the excess spin in the 4f with paired spin in the 5d due to backbonding. The heats of formation of the observed species were derived from the available data from experiment and the calculated reaction energies. The major products in this study are different from similar reactions for Th where the tetrahydroxide was the major species.

4-1BB regulates NKG2D costimulation in human cord blood CD8+ T cells.

PubMed

Kim, Young-June; Han, Myung-Kwan; Broxmeyer, Hal E

2008-02-01

Ligation of NKG2D, a potent costimulatory receptor, can be either beneficial or detrimental to CD8(+) cytotoxic T cell (CTL) responses. Factors for these diverse NKG2D effects remain elusive. In this study, we demonstrate that 4-1BB, another costimulatory receptor, is an essential regulator of NKG2D in CD8(+) T cells. Costimulation of NKG2D caused down-modulation of NKG2D, but induced 4-1BB expression on the cell surface, even in the presence of TGF-beta1, which inhibits 4-1BB expression. Resulting NKG2D(-)4-1BB(+) cells were activated but still in an immature state with low cytotoxic activity. However, subsequent 4-1BB costimulation induced cytotoxic activity and restored down-modulated NKG2D. The cytotoxic activity and NKG2D expression induced by 4-1BB on NKG2D(+)4-1BB(+) cells were refractory to TGF-beta1 down-modulation. Such 4-1BB effects were enhanced by IL-12. In contrast, in the presence of IL-4, 4-1BB effects were abolished because IL-4 down-modulated NKG2D and 4-1BB expression in cooperation with TGF-beta1, generating another CD8(+) T-cell type lacking both NKG2D and 4-1BB. These NKG2D(-)4-1BB(-) cells were inert and unable to gain cytotoxic activity. Our results suggest that 4-1BB plays a critical role in protecting NKG2D from TGF-beta1-mediated down-modulation. Co-expression of NKG2D and 4-1BB may represent an important biomarker for defining competency of tumor infiltrating CD8(+) T cells.

Thermal inactivation of H5N2 high-pathogenicity avian influenza virus in dried egg white with 7.5% moisture.

PubMed

Thomas, Colleen; Swayne, David E

2009-09-01

High-pathogenicity avian influenza viruses (HPAIV) cause severe systemic disease with high mortality in chickens. Isolation of HPAIV from the internal contents of chicken eggs has been reported, and this is cause for concern because HPAIV can be spread by movement of poultry products during marketing and trade activity. This study presents thermal inactivation data for the HPAIV strain A/chicken/PA/1370/83 (H5N2) (PA/83) in dried egg white with a moisture content (7.5%) similar to that found in commercially available spray-dried egg white products. The 95% upper confidence limits for D-values calculated from linear regression of the survival curves at 54.4, 60.0, 65.5, and 71.1 degrees C were 475.4, 192.2, 141.0, and 50.1 min, respectively. The line equation y = [0.05494 x degrees C] + 5.5693 (root mean square error = 0.0711) was obtained by linear regression of experimental D-values versus temperature. Conservative predictions based on the thermal inactivation data suggest that standard industry pasteurization protocols would be very effective for HPAIV inactivation in dried egg white. For example, these calculations predict that a 7-log reduction would take only 2.6 days at 54.4 degrees C.

Study of activity based costing implementation for palm oil production using value-added and non-value-added activity consideration in PT XYZ palm oil mill

NASA Astrophysics Data System (ADS)

Sembiring, M. T.; Wahyuni, D.; Sinaga, T. S.; Silaban, A.

2018-02-01

Cost allocation at manufacturing industry particularly in Palm Oil Mill still widely practiced based on estimation. It leads to cost distortion. Besides, processing time determined by company is not in accordance with actual processing time in work station. Hence, the purpose of this study is to eliminates non-value-added activities therefore processing time could be shortened and production cost could be reduced. Activity Based Costing Method is used in this research to calculate production cost with Value Added and Non-Value-Added Activities consideration. The result of this study is processing time decreasing for 35.75% at Weighting Bridge Station, 29.77% at Sorting Station, 5.05% at Loading Ramp Station, and 0.79% at Sterilizer Station. Cost of Manufactured for Crude Palm Oil are IDR 5.236,81/kg calculated by Traditional Method, IDR 4.583,37/kg calculated by Activity Based Costing Method before implementation of Activity Improvement and IDR 4.581,71/kg after implementation of Activity Improvement Meanwhile Cost of Manufactured for Palm Kernel are IDR 2.159,50/kg calculated by Traditional Method, IDR 4.584,63/kg calculated by Activity Based Costing Method before implementation of Activity Improvement and IDR 4.582,97/kg after implementation of Activity Improvement.

Comparative studies on molecular structure, vibrational spectra and hyperpolarizabilies of NLO chromophore Ethyl 4-Dimethylaminobenzoate

NASA Astrophysics Data System (ADS)

Amalanathan, M.; Jasmine, G. Femina; Roy, S. Dawn Dharma

2017-08-01

The molecular structure, vibrational spectra and polarizabilities of Ethyl 4-Dimethylaminobenzoate (EDAB) was investigated by density functional theory employing Becke's three parameter hybrid exchange functional with Lee-Yang-Parr (B3LYP) co-relational functional involving 6-311++G(d,p) basis set and compared with some other levels. A detailed interpretation of the IR and Raman spectra of EDBA have been reported and analyzed. Complete vibrational assignments of the vibrational modes have been done on the basis of the potential energy distribution (TED) using VEDA software. The molecular electrostatic potential mapped onto total density surface has been obtained. A study on the electronic properties, such as absorption wavelength, and frontier molecular orbitals energy, was performed using DFT approach. The stability of the molecule arising from hyper conjugative interactions and accompanying charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The natural and Mulliken charge also calculated and compared with different level of calculation. The dipole moment, polarizability and first, second order hyperpolarizabilities of the title molecule were calculated and compared with the experimental values. The energy gap between frontier orbitals has been used along with electric moments and first order hyperpolarizability, to understand the non linear optical (NLO) activity of the molecule. The NLO activity of molecule was confirmed by SHG analysis.

Synthesis, X-ray diffraction method, spectroscopic characterization (FT-IR, 1H and 13C NMR), antimicrobial activity, Hirshfeld surface analysis and DFT computations of novel sulfonamide derivatives

NASA Astrophysics Data System (ADS)

Demircioğlu, Zeynep; Özdemir, Fethi Ahmet; Dayan, Osman; Şerbetçi, Zafer; Özdemir, Namık

2018-06-01

Synthesized compounds of N-(2-aminophenyl)benzenesulfonamide 1 and (Z)-N-(2-((2-nitrobenzylidene)amino)phenyl)benzenesulfonamide 2 were characterized by antimicrobial activity, FT-IR, 1H and 13C NMR. Two new Schiff base ligands containing aromatic sulfonamide fragment of (Z)-N-(2-((3-nitrobenzylidene)amino)phenyl)benzenesulfonamide 3 and (Z)-N-(2-((4-nitrobenzylidene)amino)phenyl)benzenesulfonamide 4 were synthesized and investigated by spectroscopic techniques including 1H and 13C NMR, FT-IR, single crystal X-ray diffraction, Hirshfeld surface, theoretical method analyses and by antimicrobial activity. The molecular geometry obtained from the X-ray structure determination was optimized Density Functional Theory (DFT/B3LYP) method with the 6-311++G(d,p) basis set in ground state. From the optimized geometry of the molecules of 3 and 4, the geometric parameters, vibrational wavenumbers and chemical shifts were computed. The optimized geometry results, which were well represented the X-ray data, were shown that the chosen of DFT/B3LYP 6-311G++(d,p) was a successful choice. After a successful optimization, frontier molecular orbitals, chemical activity, non-linear optical properties (NLO), molecular electrostatic mep (MEP), Mulliken population method, natural population analysis (NPA) and natural bond orbital analysis (NBO), which cannot be obtained experimentally, were calculated and investigated.

Normalization of a collimated 14.7 MeV neutron source in a neutron spectrometry system for benchmark experiments

NASA Astrophysics Data System (ADS)

Ofek, R.; Tsechanski, A.; Shani, G.

1988-05-01

In the present study a method used to normalize a collimated 14.7 MeV neutron beam is introduced. It combined a measurement of the fast neutron scalar flux passing through the collimator, using a copper foil activation, with a neutron transport calculation of the foil activation per unit source neutron, carried out by the discrete-ordinates transport code DOT 4.2. The geometry of the collimated neutron beam is composed of a D-T neutron source positioned 30 cm in front of a 6 cm diameter collimator, through a 120 cm thick paraffin wall. The neutron flux emitted from the D-T source was counted by an NE-213 scintillator, simultaneously with the irradiation of the copper foil. Thus, the determination of the normalization factor of the D-T source is used for an absolute flux calibration of the NE-213 scintillator. The major contributions to the uncertainty in the determination of the normalization factor, and their origins, are discussed.

Seeking potential anticonvulsant agents that target GABAA receptors using experimental and theoretical procedures

NASA Astrophysics Data System (ADS)

Saavedra-Vélez, Margarita Virginia; Correa-Basurto, José; Matus, Myrna H.; Gasca-Pérez, Eloy; Bello, Martiniano; Cuevas-Hernández, Roberto; García-Rodríguez, Rosa Virginia; Trujillo-Ferrara, José; Ramos-Morales, Fernando Rafael

2014-12-01

The aim of this study was to identify compounds that possess anticonvulsant activity by using a pentylenetetrazol (PTZ)-induced seizure model. Theoretical studies of a set of ligands, explored the binding affinities of the ligands for the GABAA receptor (GABAAR), including some benzodiazepines. The ligands satisfy the Lipinski rules and contain a pharmacophore core that has been previously reported to be a GABAAR activator. To select the ligands with the best physicochemical properties, all of the compounds were analyzed by quantum mechanics and the energies of the highest occupied molecular orbital and lowest unoccupied molecular orbital were determined. Docking calculations between the ligands and the GABAAR were used to identify the complexes with the highest Gibbs binding energies. The identified compound D1 (dibenzo( b,f)(1,4)diazocine-6,11(5H,12H)-dione) was synthesized, experimentally tested, and the GABAAR-D1 complex was submitted to 12-ns-long molecular dynamics (MD) simulations to corroborate the binding conformation obtained by docking techniques. MD simulations were also used to analyze the decomposition of the Gibbs binding energy of the residues involved in the stabilization of the complex. To validate our theoretical results, molecular docking and MD simulations were also performed for three reference compounds that are currently in commercial use: clonazepam (CLZ), zolpidem and eszopiclone. The theoretical results show that the GABAAR-D1, and GABAAR-CLZ complexes bind to the benzodiazepine binding site, share a similar map of binding residues, and have similar Gibbs binding energies and entropic components. Experimental studies using a PTZ-induced seizure model showed that D1 possesses similar activity to CLZ, which corroborates the predicted binding free energy identified by theoretical calculations.

Purification, crystallization and preliminary X-ray structural studies of a 7.2 kDa cytotoxin isolated from the venom of Daboia russelli russelli of the Viperidae family

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

Roy Choudhury, Subhasree; Gomes, Aparna; Gomes, Antony

2006-03-01

A cytotoxin from Indian Russell’s viper (D. russelli russelli) venom having multifunctional activity has been crystallized in space group P4{sub 1}. Larger crystals diffracted to 1.5 Å but were found to be twinned; preliminary data were therefore collected (2.93 Å) from a smaller crystal. A cytotoxin (MW 7.2 kDa) from Indian Russell’s viper (Daboia russelli russelli) venom possessing antiproliferative activity, cardiotoxicity, neurotoxicity and myotoxicity has been purified, characterized and crystallized. The crystals belong to the tetragonal space group P4{sub 1}, with unit-cell parameters a = b = 47.94, c = 50.2 Å. Larger crystals, which diffracted to 1.5 Å, weremore » found to be twinned; diffraction data were therefore collected to 2.93 Å resolution using a smaller crystal. Molecular-replacement calculations identified two molecules of the protein in the asymmetric unit, which is in accordance with the calculated V{sub M} value.« less

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

Abou El-Maaref, A., E-mail: aahmh@hotmail.com; Allam, S.H.; El-Sherbini, Th.M.

The energy levels, oscillator strengths, line strengths, and transition probabilities for transitions among the terms belonging to the 3s{sup 2}3p{sup 2}, 3s3p{sup 3}, 3s{sup 2}3p3d, 3s{sup 2}3p4s, 3s{sup 2}3p4p and 3s{sup 2}3p4d configurations of silicon-like ions (Zn XVII, Ga XVIII, Ge XIX, and As XX) have been calculated using the configuration-interaction code CIV3. The calculations have been carried out in the intermediate coupling scheme using the Breit–Pauli Hamiltonian. The present calculations have been compared with the available experimental data and other theoretical calculations. Most of our calculations of energy levels and oscillator strengths (in length form) show good agreement withmore » both experimental and theoretical data. Lifetimes of the excited levels have also been calculated. -- Highlights: •We have calculated the fine-structure energy levels of Si-like Zn, Ga, Ge and As. •The calculations are performed using the configuration interaction method (CIV3). •We have calculated the oscillator strengths, line strengths and transition rates. •The wavelengths of the transitions are listed in this article. •We also have made comparisons between our data and other calculations.« less

Synthesis and conformational studies of carrabiose and its 4'-sulphate and 2,4'-disulphate.

PubMed

Parra, E; Caro, H N; Jiménez-Barbero, J; Martín-Lomas, M; Bernabé, M

1990-12-15

Methyl alpha-carrabioside (13), and its 4-sulphate (19) and 2,4-disulphate (20) have been synthesised via glycosylation of methyl 3,6-anhydro-2-O-benzyl-alpha-D-galactopyranoside with 2,3,6-tri-O-acetyl-4-O-benzyl-beta-D-galactopyranosyl bromide and subsequent partial or complete debenzylation, sulphation, and deprotection of the resulting disaccharide derivatives. Conformational studies have been carried out on 13, 19, and 20 on the basis of 1D and 2D 1H-n.m.r. spectroscopy and molecular mechanics calculations.

Effects of atorvastatin on biomarkers of immune activation, inflammation, and lipids in virologically suppressed, HIV-1 infected individuals with LDL cholesterol <130mg/dl (AIDS Clinical Trials Group Study A5275)

PubMed Central

NIXON, Daniel E.; BOSCH, Ronald J.; S.CHAN, Ellen; FUNDERBURG, Nicholas T.; HODDER, Sally; LAKE, Jordan E.; LEDERMAN, Michael M.; KLINGMAN, Karin L.; ABERG, Judith A.

2016-01-01

Background Persistent immune activation and inflammation in virologically suppressed HIV infection are linked to excess cardiovascular risk. Objective To evaluate atorvastatin as a strategy to reduce cardiovascular risk. Methods A5275 was a multicenter, prospective, randomized, double-blind, placebo-controlled, cross-over pilot study of atorvastatin (10mg/day for 4 weeks then 20mg/day for 16 weeks) with a planned enrollment of 97 HIV-infected participants ≥18 years old, receiving boosted protease inhibitor-based ART for ≥6 months, with plasma HIV-1 RNAs below limits of quantification ≥180 days, and fasting LDL-C ≥70 mg/dL and <130 mg/dL. Primary endpoints were differences of changes ([week 44 – week 24] - [week 20 - baseline]) in CD4+ and CD8+ T-lymphocyte activation (% CD38+/DR+) and plasma levels of IL-6 and D-dimer. Arms were compared using Wilcoxon rank sum tests and also summarized changes pre-to-post atorvastatin treatment. Analyses were as-treated. Results Ninety-eight participants were enrolled at 31 U.S. sites and 73 completed study treatment. Atorvastatin treatment did not decrease T-lymphocyte or monocyte activation, circulating biomarker levels (interleukin-6, D-dimer, soluble CD14, soluble CD163, monocyte chemoattractant protein-1, interferon-γ-induced protein-10, high sensitivity C-reactive protein, CD40L, P-selectin) or white blood cell Krüppel-like Factor 2/4 mRNA levels. Pre-to-post atorvastatin reductions in calculated LDL (−38%), oxidized-LDL (−33%), and lipoprotein-associated phospholipase A2 (−31%) were significant (p<0.01). Conclusion In virologically suppressed individuals with HIV infection, atorvastatin did not significantly decrease levels of soluble or cellular biomarkers of immune activation and inflammation, but resulted in robust reductions in LDL-C, oxLDL, and LpPLA2, biomarkers associated with cardiovascular risk. PMID:28391912

FTIR, FT-RAMAN, NMR, spectra, normal co-ordinate analysis, NBO, NLO and DFT calculation of N,N-diethyl-4-methylpiperazine-1-carboxamide molecule

NASA Astrophysics Data System (ADS)

Muthu, S.; Elamurugu Porchelvi, E.

2013-11-01

The Fourier Transform Infrared (FT-IR) and FT-Raman of N,N-diethyl-4-methylpiperazine-1-carboxamide (NND4MC) have been recorded and analyzed. The structure of the compound was optimized and the structural characteristics were determined by density functional theory (DFT) using B3LYP method with 6-31G(d,p) and 6-311G(d,p) basis sets. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. The theoretically predicted FT-IR and FT-Raman spectra of the title molecule have been constructed. The detailed interpretation of the vibrational spectra has been carried out with aid of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology. Stability of the molecule arising from hyperconjugative interactions and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The results show that electron density (ED) in the σ* and π* antibonding orbitals and second order delocalization energies (E2) confirm the occurrence of intramolecular charge transfer (ICT) within the molecule. The electronic dipole moment (μD) and the first hyperpolarizability (βtot) values of the investigated molecule were computed using Density Functional Theory (DFT/B3LYP) with 6-31G(d,p) and 6-311G(d,p) basis sets. The calculated results also show that the NND4MC molecule may have microscopy nonlinear optical (NLO) behavior with non zero values. Mulliken atomic charges of NND4MC were calculated. The 13C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results. The UV-Vis spectrum of the compound was recorded. The theoretical electronic absorption spectra have been calculated by using CIS, TD-DFT methods. A study on the electronic properties, such as HOMO and LUMO energies, molecular electrostatic potential (MEP) were also performed.

Electron Impact Exciation of Fe IX

NASA Astrophysics Data System (ADS)

Tayal, Swaraj; Zatsarinny, Oleg

2015-05-01

Transition probabilities and electron impact excitation collision strengths and rates for astrophysically important extreme ultraviolet lines of Fe IX are calculated. The 322 fine-structure levels of the 3s2 3p6 , 3s2 3p5 3 d , 3 s 3p6 3 d , 3s2 3p5 4 s , and 3s2 3p4 3d2 configurations are included in our calculations. The collision strengths have been calculated using the B-spline Breit-Pauli R-matrix method for all fine-structure transitions among the 322 levels. The mass, Darwin, and spin-orbit relativistic effects are included in the Breit-Pauli Hamiltonian in the scattering calculation. The one-body and two-body relativistic operators are included in the multi-configuration Hartree-Fock calculations of transition probabilities. Several sets of non-orthogonal spectroscopic and correlation radial orbitals are used to obtain accurate description of Fe IX levels and to represent the scattering functions. The calculated excitation energies are in very good agreement with experiment and represents an improvement over the previous calculations. The present collision strengths show reasonable agreement with the previously available R-matrix and distorted-wave calculations. This research is supported by NASA grant from the Solar and Heliophysics Program.

Bifurcatriol, a New Antiprotozoal Acyclic Diterpene from the Brown Alga Bifurcaria bifurcata

PubMed Central

Smyrniotopoulos, Vangelis; Merten, Christian; Kaiser, Marcel; Tasdemir, Deniz

2017-01-01

Linear diterpenes that are commonly found in brown algae are of high chemotaxonomic and ecological importance. This study reports bifurcatriol (1), a new linear diterpene featuring two stereogenic centers isolated from the Irish brown alga Bifurcaria bifurcata. The gross structure of this new natural product was elucidated based on its spectroscopic data (IR, 1D and 2D-NMR, HRMS). Its absolute configuration was identified by experimental and computational vibrational circular dichroism (VCD) spectroscopy, combined with the calculation of 13C-NMR chemical shielding constants. Bifurcatriol (1) was tested for in vitro antiprotozoal activity towards a small panel of parasites (Plasmodium falciparum, Trypanosoma brucei rhodesiense, T. cruzi, and Leishmania donovani) and cytotoxicity against mammalian primary cells. The highest activity was exerted against the malaria parasite P. falciparum (IC50 value 0.65 μg/mL) with low cytotoxicity (IC50 value 56.6 μg/mL). To our knowledge, this is the first successful application of VCD and DP4 probability analysis of the calculated 13C-NMR chemical shifts for the simultaneous assignment of the absolute configuration of multiple stereogenic centers in a long-chain acyclic natural product. PMID:28767061

Synthesis, spectroscopic characterization (FT-IR, FT-Raman, and NMR), quantum chemical studies and molecular docking of 3-(1-(phenylamino)ethylidene)-chroman-2,4-dione

NASA Astrophysics Data System (ADS)

Avdović, Edina H.; Milenković, Dejan; Dimitrić Marković, Jasmina M.; Đorović, Jelena; Vuković, Nenad; Vukić, Milena D.; Jevtić, Verica V.; Trifunović, Srećko R.; Potočňák, Ivan; Marković, Zoran

2018-04-01

The experimental and theoretical investigations of structure of the 3-(1-(phenylamino)ethylidene)-chroman-2,4-dione were performed. X-ray structure analysis and spectroscopic methods (FTIR and FT-Raman, 1H and 13C NMR), along with the density functional theory calculations (B3LYP functional with empirical dispersion corrections D3BJ in combination with the 6-311 + G(d,p) basis set), were used in order to characterize the molecular structure and spectroscopic behavior of the investigated coumarin derivative. Molecular docking analysis was carried out to identify the potency of inhibition of the title molecule against human's Ubiquinol-Cytochrome C Reductase Binding Protein (UQCRB) and Methylenetetrahydrofolate reductase (MTHFR). The inhibition activity was obtained for ten conformations of ligand inside the proteins.

Molecular structure, spectroscopic (FTIR, FT-Raman, 13C and 1H NMR, UV), polarizability and first-order hyperpolarizability, HOMO-LUMO analysis of 2,4-difluoroacetophenone

NASA Astrophysics Data System (ADS)

Jeyavijayan, S.

2015-02-01

The FTIR and FT-Raman spectra of 2,4-difluoroacetophenone (DFAP) have been recorded in the regions 4000-400 cm-1 and 3500-50 cm-1, respectively. Utilizing the observed FTIR and FT-Raman data, a complete vibrational assignment and analysis of the fundamental modes of the compound were carried out. The optimum molecular geometry, harmonic vibrational frequencies, infrared intensities and Raman scattering activities, were calculated by density functional theory (DFT/B3LYP) method with 6-31+G(d,p) and 6-311++G(d,p) basis sets. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. A detailed interpretation of the infrared and Raman spectra of DFAP is also reported based on total energy distribution (TED). Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital (NBO) analysis. The MEP map shows the negative potential sites are on oxygen atom as well as the positive potential sites are around the hydrogen atoms. The UV-Vis spectral analysis of DFAP has also been done which confirms the charge transfer of DFAP. The chemical shifts of H atoms and C atoms were calculated using NMR analysis. Furthermore, the polarizability, the first hyperpolarizability and total dipole moment of the molecule have been calculated.

The champagne toast position isolates the supraspinatus better than the Jobe test: an electromyographic study of shoulder physical examination tests.

PubMed

Chalmers, Peter N; Cvetanovich, Gregory L; Kupfer, Noam; Wimmer, Markus A; Verma, Nikhil N; Cole, Brian J; Romeo, Anthony A; Nicholson, Gregory P

2016-02-01

While Jobe's test is widely used, it does not isolate supraspinatus activity. Our purpose was to examine the electromyographic (EMG) activity within the supraspinatus and deltoid with resisted abduction to determine the shoulder position that best isolates the activity of the supraspinatus. We performed EMG analysis of the supraspinatus, anterior head of the deltoid, and middle head of the deltoid in 10 normal volunteers. We measured EMG activity during resisted shoulder abduction in the scapular plane to both manual resistance and a standardized load in varying degrees of abduction and rotation. To determine which position best isolates supraspinatus activity, the ratio of supraspinatus to deltoid activity (S:D) was calculated for each position. Results were analyzed with a repeated-measures analysis of variance with Bonferroni correction. The posterior deltoid was excluded as it serves mostly to extend and externally rotate. Our study confirmed Jobe's findings of maximal supraspinatus activity at 90° of abduction. However, decreasing abduction significantly increased S:D for both resisted manual testing and testing against a standardized load (P = .002 and .001, respectively). The greatest S:D ratio (4.6 ± 3.4 for standardized load testing) was seen at the "champagne toast" position, i.e., 30° of abduction, mild external rotation, 30° of flexion, and 90° of elbow flexion. The smallest ratio (0.8 ± 0.6) was seen at Jobe's position. Testing of abduction strength in the champagne toast position, i.e., 30° of abduction, mild external rotation, and 30° of flexion, better isolates the activity of the supraspinatus from the deltoid than Jobe's "empty can" position. Copyright © 2016 Journal of Shoulder and Elbow Surgery Board of Trustees. Published by Elsevier Inc. All rights reserved.

Synthesis, DNA binding and cytotoxic activity of pyrimido[4',5':4,5]thieno(2,3-b)quinoline with 9-hydroxy-4-(3-diethylaminopropylamino) and 8-methoxy-4-(3-diethylaminopropylamino) substitutions.

PubMed

KiranKumar, Hulihalli N; RohitKumar, Heggodu G; Advirao, Gopal M

2018-01-01

Two new derivatives of pyrimido[4',5';4,5]thieno(2,3-b)quinoline (PTQ), 9-hydroxy-4-(3-diethylaminopropylamino)pyrimido[4',5';4,5]thieno(2,3-b)quinoline (Hydroxy-DPTQ) and 8-methoxy-4-(3-diethylaminopropylamino)pyrimido[4',5';4,5]thieno(2,3-b)quinoline (Methoxy-DPTQ) were synthesized and their DNA binding ability was analyzed using spectroscopy (UV-visible, fluorescence and circular dichroism), ethidium bromide dye displacement assay, melting temperature (T m ) analysis and computational docking studies. The hypochromism in UV-visible spectrum and increased fluorescence emission of Hydroxy-DPTQ and Methoxy-DPTQ in the presence of DNA suggested the molecule-DNA interaction. The association constants calculated from UV-visible and spectral titrations were of the order 10 4 to 10 6 M -1 . Circular dichroism studies corroborated the induced conformational changes in DNA upon addition of molecules. The change in the ellipticity was observed both in negative and positive peak of DNA, thus, suggesting the intercalation of molecules. The observed displacement of ethidium bromide from the DNA and increased T m , upon addition of DNA confirmed the intercalative mode of binding. This was further validated by computational docking, which showed clear intercalation of molecules into the d(GpC)-d(CpG) site of the receptor DNA. Anticancer activities of these molecules are evaluated by using MTT assay. Both molecules showed antiproliferative activity against all the three cancer cells studied, with Hydroxy-DPTQ being more potential molecule among the two. IC 50 value of Hydroxy-DPTQ and Methoxy-DPTQ were in the range of 3-5μM and 130-250μM, respectively. Copyright © 2017 Elsevier B.V. All rights reserved.

Coulomb correlations in 4d and 5d oxides from first principles—or how spin-orbit materials choose their effective orbital degeneracies

NASA Astrophysics Data System (ADS)

Martins, C.; Aichhorn, M.; Biermann, S.

2017-07-01

The interplay of spin-orbit coupling and Coulomb correlations has become a hot topic in condensed matter theory and is especially important in 4d and 5d transition metal oxides, like iridates or rhodates. Here, we review recent advances in dynamical mean-field theory (DMFT)-based electronic structure calculations for treating such compounds, introducing all necessary implementation details. We also discuss the evaluation of Hubbard interactions in spin-orbit materials. As an example, we perform DMFT calculations on insulating strontium iridate (Sr2IrO4) and its 4d metallic counterpart, strontium rhodate (Sr2RhO4). While a Mott-insulating state is obtained for Sr2IrO4 in its paramagnetic phase, the spectral properties and Fermi surfaces obtained for Sr2RhO4 show excellent agreement with available experimental data. Finally, we discuss the electronic structure of these two compounds by introducing the notion of effective spin-orbital degeneracy as the key quantity that determines the correlation strength. We stress that effective spin-orbital degeneracy introduces an additional axis into the conventional picture of a phase diagram based on filling and on the ratio of interactions to bandwidth, analogous to the degeneracy-controlled Mott transition in d1 perovskites.

Coulomb correlations in 4d and 5d oxides from first principles-or how spin-orbit materials choose their effective orbital degeneracies.

PubMed

Martins, C; Aichhorn, M; Biermann, S

2017-07-05

The interplay of spin-orbit coupling and Coulomb correlations has become a hot topic in condensed matter theory and is especially important in 4d and 5d transition metal oxides, like iridates or rhodates. Here, we review recent advances in dynamical mean-field theory (DMFT)-based electronic structure calculations for treating such compounds, introducing all necessary implementation details. We also discuss the evaluation of Hubbard interactions in spin-orbit materials. As an example, we perform DMFT calculations on insulating strontium iridate (Sr 2 IrO 4 ) and its 4d metallic counterpart, strontium rhodate (Sr 2 RhO 4 ). While a Mott-insulating state is obtained for Sr 2 IrO 4 in its paramagnetic phase, the spectral properties and Fermi surfaces obtained for Sr 2 RhO 4 show excellent agreement with available experimental data. Finally, we discuss the electronic structure of these two compounds by introducing the notion of effective spin-orbital degeneracy as the key quantity that determines the correlation strength. We stress that effective spin-orbital degeneracy introduces an additional axis into the conventional picture of a phase diagram based on filling and on the ratio of interactions to bandwidth, analogous to the degeneracy-controlled Mott transition in d 1 perovskites.

A novel withanolide with an unprecedented carbon skeleton from Physalis angulata.

PubMed

Sun, Cheng-Peng; Kutateladze, Andrei G; Zhao, Feng; Chen, Li-Xia; Qiu, Feng

2017-02-01

A novel withanolide, aromaphysalin A (1), possessing an exceptional C(11)-C(15) bond and an unprecedented 4,9-cyclized aromatic ring (ring A), is isolated from stems and leaves of Physalis angulata L. Its structure was determined by a combination of HRESIMS, 2D NMR spectra, and theoretical calculations. Compound 1 exhibited inhibitory activity on NO production with an IC 50 value of 51.64 μM. A plausible biosynthetic pathway for 1 is also discussed.

1,2,4-triazole derivative with Schiff base; thiol-thione tautomerism, DFT study and antileishmanial activity

NASA Astrophysics Data System (ADS)

Süleymanoğlu, Nevin; Ustabaş, Reşat; Direkel, Şahin; Alpaslan, Yelda Bingöl; Ünver, Yasemin

2017-12-01

Thiol-thione tautomerism of 1,2,4-triazole derivative with Schiff base was investigated by spectroscopic methods and quantum mechanical calculations. Theoretical study of thiol-thione tautomeric forms of 1,2,4-triazole derivative with Schiff base; 1,2,4-triazole-thiol form, 1-((5-mercapto-4-(thiophene-2-ylmethyleneamino)-4H-1,2,4-triazole-3-yl)methyl)-3-(thiophene-2-ylmethyl)-4-(thiophene-2-ylmethyleneamino)-1H-1,2,4-triazole-5(4H)-one (I) and 1,2,4-triazole-thione form, 3-(thiophene-2-ylmethyl)-4-(thiophene-2-ylmethyleneamino)-1-((4-(thiophene-2-ylmethyleneamino)-5-thioxo-4,5-dihydro-1H-1,2,4-triazole-3-yl)methyl)-1H-1,2,4-triazole-5(4H)-one (II) was performed by the density functional theory (DFT) method with 6-311++G(d,p) basis set. Structural parameters were obtained and spectral parameters of NMR, FTIR and UV-vis were compared with experimental ones to determine structural details. In vitro antileishmanial activity was studied against Leishmania infantum promastigots by microdilution broth assay with Alamar Blue Dye. The results indicate that 1,2,4-triazole derivative exists in both thiol and thione form and, can be evaluated as antiparasitic in term of antileishmanial activity.

Fight Bite Injuries: Aggressive Tendencies Associated with Smaller Second to Fourth Digit Ratio.

PubMed

Joyce, Cormac W; O' Regan, Andrew; Kelly, Jack L; O' Shaughnessy, Michael

2017-12-01

Fight bite injuries are typically sustained by young, combative males and are the direct consequence of an aggressive act. Second to fourth digit ratios (2D:4D) are dependent on prenatal androgen exposure and lower ratios have been shown to be linked to various psychological and physical traits, including aggression. The aim of this study was to examine the 2D:4D ratios in a cohort of patients with fight bite injuries and compare these to an age and gender-matched control group. The 2D:4D ratios were calculated using plain films of the hand from 133 patients (122 males, 11 females) with fight bite injuries. A further 133 radiographs were obtained from patients that did not have fight bite injuries and digit ratios were calculated in the same fashion. Statistical analysis was then carried out to compare the 2D:4D ratios between the different groups. The 2D:4D ratios for male fight bite patients was significantly smaller than the male control group (p < 0.05). No significant difference was observed between the female fight bite patients and the female control group (p > 0.05). Fight bite injuries are usually sustained as a result of aggression. 2D:4D ratios are reflect intrauterine androgen exposure and low ratios have been linked to aggressive tendencies. We have demonstrated that male patients who sustained fight bite injuries have a lower 2D:4D ratio then the general population, thereby suggesting that exposure to prenatal androgens can lead to aggressive tendencies in adulthood. This suggests that lower ratios may predict a predisposition to acts of aggression, and as such result in an increased likelihood of sustaining an injury such as a fight bite.

4D offline PET-based treatment verification in scanned ion beam therapy: a phantom study

NASA Astrophysics Data System (ADS)

Kurz, Christopher; Bauer, Julia; Unholtz, Daniel; Richter, Daniel; Stützer, Kristin; Bert, Christoph; Parodi, Katia

2015-08-01

At the Heidelberg Ion-Beam Therapy Center, patient irradiation with scanned proton and carbon ion beams is verified by offline positron emission tomography (PET) imaging: the {β+} -activity measured within the patient is compared to a prediction calculated on the basis of the treatment planning data in order to identify potential delivery errors. Currently, this monitoring technique is limited to the treatment of static target structures. However, intra-fractional organ motion imposes considerable additional challenges to scanned ion beam radiotherapy. In this work, the feasibility and potential of time-resolved (4D) offline PET-based treatment verification with a commercial full-ring PET/CT (x-ray computed tomography) device are investigated for the first time, based on an experimental campaign with moving phantoms. Motion was monitored during the gated beam delivery as well as the subsequent PET acquisition and was taken into account in the corresponding 4D Monte-Carlo simulations and data evaluation. Under the given experimental conditions, millimeter agreement between the prediction and measurement was found. Dosimetric consequences due to the phantom motion could be reliably identified. The agreement between PET measurement and prediction in the presence of motion was found to be similar as in static reference measurements, thus demonstrating the potential of 4D PET-based treatment verification for future clinical applications.

Model of electron lifetimes inside the plasmasphere calculated using a CRRES derived hiss wave amplitude model

NASA Astrophysics Data System (ADS)

Orlova, Ksenia; Spasojevic, Maria; Shprits, Yuri

Particle populations in the inner magnetosphere can change by orders of magnitude on very short time scales. For the last decade observations and theoretical computations showed that resonant interaction of electrons with various plasma waves plays an important role in acceleration and loss mechanisms. Using data from the CRRES plasma wave experiment, we develop quadratic fits to the mean of the wave amplitude squared for plasmaspheric hiss as a function of geomagnetic activity (Kp) and magnetic latitude (lambda) for the dayside (6

New phenylpropanoid-substituted flavan-3-ols and flavonols from the leaves of Uncaria rhynchophylla.

PubMed

Li, Ruxin; Cheng, Jintang; Jiao, Mengjiao; Li, Li; Guo, Cong; Chen, Sha; Liu, An

2017-01-01

Uncariols A (1) and B (2), two new phenylpropanoid-substituted flavan-3-ols, and (±)-uncariols C (3a/3b) and D (4a/4b), two pairs of new phenylpropanoid-substituted flavonol enantiomers, together with nine known compounds (5-13), were isolated from the leaves of Uncaria rhynchophylla. The structures of 1-4 were established primarily by NMR and HRESIMS experiments. The absolute configurations of the new ones were deduced via the circular dichroism (CD) and quantum chemical calculations of the electronic circular dichroic (ECD) spectra. In addition, all of the isolated compounds showed potent antioxidant activity in the DPPH radical scavenging test. Copyright © 2016. Published by Elsevier B.V.

SU-E-T-159: Evaluation of a Patient Specific QA Tool Based On TG119

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

Ashmeg, S; Zhang, Y; O'Daniel, J

2014-06-01

Purpose: To evaluate the accuracy of a 3D patient specific QA tool by analysis of the results produced from associated software in homogenous phantom and heterogonous patient CT. Methods: IMRT and VMAT plans of five test suites introduced by TG119 were created in ECLIPSE on a solid water phantom. The ten plans -of increasing complexity- were delivered to Delta4 to give a 3D measurement. The Delta4's “Anatomy” software uses the measured dose to back-calculate the energy fluence of the delivered beams, which is used for dose calculation in a patient CT using a pencilbeam algorithm. The effect of the modulatedmore » beams' complexity on the accuracy of the “Anatomy” calculation was evaluated. Both measured and Anatomy doses were compared to ECLIPSE calculation using 3% - 3mm gamma criteria.We also tested the effect of heterogeneity by analyzing the results of “Anatomy” calculation on a Brain VMAT and a 3D conformal lung cases. Results: In homogenous phantom, the gamma passing rates were found to be as low as 74.75% for a complex plan with high modulation. The mean passing rates were 91.47% ± 6.35% for “Anatomy” calculation and 99.46% ± 0.62% for Delta4 measurements.As for the heterogeneous cases, the rates were 96.54%±3.67% and 83.87%±9.42% for Brain VMAT and 3D lung respectively. This increased error in the lung case could be due to the use of the pencil beam algorithm as opposed to the AAA used by ECLIPSE.Also, gamma analysis showed high discrepancy along the beam edge in the “Anatomy” calculated results. This suggests a poor beam modeling in the penumbra region. Conclusion: The results show various sources of errors in “Anatomy” calculations. These include beam modeling in the penumbra region, complexity of a modulated beam (shown in homogenous phantom and brain cases) and dose calculation algorithms (3D conformal lung case)« less

Analytical torque calculation and experimental verification of synchronous permanent magnet couplings with Halbach arrays

NASA Astrophysics Data System (ADS)

Seo, Sung-Won; Kim, Young-Hyun; Lee, Jung-Ho; Choi, Jang-Young

2018-05-01

This paper presents analytical torque calculation and experimental verification of synchronous permanent magnet couplings (SPMCs) with Halbach arrays. A Halbach array is composed of various numbers of segments per pole; we calculate and compare the magnetic torques for 2, 3, and 4 segments. Firstly, based on the magnetic vector potential, and using a 2D polar coordinate system, we obtain analytical solutions for the magnetic field. Next, through a series of processes, we perform magnetic torque calculations using the derived solutions and a Maxwell stress tensor. Finally, the analytical results are verified by comparison with the results of 2D and 3D finite element analysis and the results of an experiment.

Rates of E1, E2, M1, and M2 transitions in Ni II

NASA Astrophysics Data System (ADS)

Cassidy, C. M.; Hibbert, A.; Ramsbottom, C. A.

2016-03-01

Aims: We present rates for all E1, E2, M1, and M2 transitions among the 295 fine-structure levels of the configurations 3d9, 3d84s, 3d74s2, 3d84p, and 3d74s4p, determined through an extensive configuration interaction calculation. Methods: The CIV3 code developed by Hibbert and coworkers is used to determine for these levels configuration interaction wave functions with relativistic effects introduced through the Breit-Pauli approximation. Results: Two different sets of calculations have been undertaken with different 3d and 4d functions to ascertain the effect of such variation. The main body of the text includes a representative selection of data, chosen so that key points can be discussed. Some analysis to assess the accuracy of the present data has been undertaken, including comparison with earlier calculations and the more limited range of experimental determinations. The full set of transition data is given in the supplementary material as it is very extensive. Conclusions: We believe that the present transition data are the best currently available. Full Table 4 and Tables 5-8 are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/587/A107

Structure-property relationship of 3-(4-substituted benzyl)-1,3-diazaspiro[4.4]nonane-2,4-diones as new potentional anticonvulsant agents. An experimental and theoretical study

NASA Astrophysics Data System (ADS)

Lazić, Anita M.; Božić, Bojan Đ.; Vitnik, Vesna D.; Vitnik, Željko J.; Rogan, Jelena R.; Radovanović, Lidija D.; Valentić, Nataša V.; Ušćumlić, Gordana S.

2017-01-01

The structure-property relationship of newly synthesized 3-(4-substituted benzyl)-1,3-diazaspiro [4.4]nonane-2,4-diones was studied by experimental and calculated methods. The prepared compounds were characterized by UV-Vis, FT-IR, 1H NMR and 13C NMR spectroscopy and elemental analysis. The crystal structure was elucidated by single-crystal X-ray diffraction. The 3-benzyl-1,3-diazaspiro[4.4]nonane-2,4-dione crystallizes in triclinic P-1 space group, with two crystallographically independent molecules in the asymmetric unit. Cyclopentane ring adopts an envelope conformation. A three-dimensional crystal packing is governed by hydrogen N-H⋯O bonds, numerous C-H⋯O/N and C-H … π interactions between neighboring molecules. Density functional theory (DFT) calculations with B3LYP and M06-2X methods using 6-311++G(d,p) basis set were performed to provide structural and spectroscopic information. Comparisons between experimental and calculated UV-Vis spectral properties suggest that the monomeric form of the investigated spirohydantoins is dominant in all used solvents. The effects of substituents on the absorption spectra of spirohydantoins are interpreted by correlation of absorption frequencies with Hammett equation. The lipophilicities of the investigated molecules were estimated by calculation of their log P values. Some of the spirohydantoins synthesized in this work, exhibit the lipophilicities comparable to the standard medicine anticonvulsant drug Phenytoin. The results obtained in this investigation afford guidelines for the preparation of new derivatives of spirohydantoin as potential anticonvulsant agents and for better understanding the structure-activity relationship.

Combined Diffraction and Density Functional Theory Calculations of Halogen-Bonded Cocrystal Monolayers

PubMed Central

2013-01-01

This work describes the combined use of synchrotron X-ray diffraction and density functional theory (DFT) calculations to understand the cocrystal formation or phase separation in 2D monolayers capable of halogen bonding. The solid monolayer structure of 1,4-diiodobenzene (DIB) has been determined by X-ray synchrotron diffraction. The mixing behavior of DIB with 4,4′-bipyridyl (BPY) has also been studied and interestingly is found to phase-separate rather than form a cocrystal, as observed in the bulk. DFT calculations are used to establish the underlying origin of this interesting behavior. The DFT calculations are demonstrated to agree well with the recently proposed monolayer structure for the cocrystal of BPY and 1,4-diiodotetrafluorobenzene (DITFB) (the perfluorinated analogue of DIB), where halogen bonding has also been identified by diffraction. Here we have calculated an estimate of the halogen bond strength by DFT calculations for the DITFB/BPY cocrystal monolayer, which is found to be ∼20 kJ/mol. Computationally, we find that the nonfluorinated DIB and BPY are not expected to form a halogen-bonded cocrystal in a 2D layer; for this pair of species, phase separation of the components is calculated to be lower energy, in good agreement with the diffraction results. PMID:24215390

Combined diffraction and density functional theory calculations of halogen-bonded cocrystal monolayers.

PubMed

Sacchi, Marco; Brewer, Adam Y; Jenkins, Stephen J; Parker, Julia E; Friščić, Tomislav; Clarke, Stuart M

2013-12-03

This work describes the combined use of synchrotron X-ray diffraction and density functional theory (DFT) calculations to understand the cocrystal formation or phase separation in 2D monolayers capable of halogen bonding. The solid monolayer structure of 1,4-diiodobenzene (DIB) has been determined by X-ray synchrotron diffraction. The mixing behavior of DIB with 4,4'-bipyridyl (BPY) has also been studied and interestingly is found to phase-separate rather than form a cocrystal, as observed in the bulk. DFT calculations are used to establish the underlying origin of this interesting behavior. The DFT calculations are demonstrated to agree well with the recently proposed monolayer structure for the cocrystal of BPY and 1,4-diiodotetrafluorobenzene (DITFB) (the perfluorinated analogue of DIB), where halogen bonding has also been identified by diffraction. Here we have calculated an estimate of the halogen bond strength by DFT calculations for the DITFB/BPY cocrystal monolayer, which is found to be ∼20 kJ/mol. Computationally, we find that the nonfluorinated DIB and BPY are not expected to form a halogen-bonded cocrystal in a 2D layer; for this pair of species, phase separation of the components is calculated to be lower energy, in good agreement with the diffraction results.

Chemical Research--Radiochemistry Report for Month Ending April 17, 1943

DOE R&D Accomplishments Database

Franck, J. Division Director

1952-01-01

1. A continuation of the detailed analysis of beta and soft and hard gamma activity associated with all fission product elements in a nitrate bombardment is presented. The ?cooling? time has been extended to 170 days. The data for the individual elements are presented in tables as counts/min and in figures as percentage of total beta, soft gamma, and hard gamma radiations. 2. Calculations and graphs have been made on the heat generated by the longer-lived fission products. The method of analysis is presented. 3. Two new short-lived Rh fission product activities have been found. They are probably the daughters of the two long-lived Ru activities (30d, 200d). Re-evaluation of data on 43 leads to the conclusion that the longest lived 43 activity in measureable yields is the 6.1h (formerly 6.6h). New parent-daughter relationships in the rare-earth activities are given. 4. Theoretical beta absorption curves have been made using the Fermi distribution function and linear absorption curves for small energy intervals. A Feather analysis of the absorption curve leads to the theoretical maximum energy.

Nitrogen fixation activity in biological soil crusts dominated by cyanobacteria in the Subpolar Urals (European North-East Russia).

PubMed

Patova, Elena; Sivkov, Michail; Patova, Anna

2016-09-01

The nitrogen fixation by biological soil crusts with a dominance of cyanobacteria was studied using the acetylene reduction assay in the territory of the Subpolar Urals (65°11' N, 60°18' E), Russia. The field measurements of nitrogen fixation activity were conducted in situ for two different types of soil crusts dominated by Stigonema (V1 type) and Nostoc with Scytonema (V2 type). The nitrogen fixation process had similar dynamics in both crusts but nitrogen fixation rates were different. The crusts of the V2 type showed a significantly higher acetylene reduction activity, with ethylene production rate of 1.76 ± 0.49 g C2H4 m(-2) h(-1) at 15°C, compared with V1-type soil crusts, with a rate of 0.53 ± 0.21 mg C2H4 m(-2) h(-1) at 15°C. The daily value of acetylene reduction activity in V2-type soil crusts was 32.7 ± 6.2 mg C2H4 m(-2) d(-1) and in V1-type crusts, 12.3 ± 1.8 mg C2H4 m(-2) d(-1) After recalculation for N, the daily values of nitrogen fixation were in the range 3.3-22.3 mg N m(-2) d(-1), which is a few times higher than the values of N input from the precipitation to the soil in the studied regions. The dependence of nitrogen-fixation activity on temperature and light intensity of biological soil crusts was investigated. On the basis of temperature models obtained from the dependence, the nitrogen balance was calculated for the growing season (approximately 120 days). The crusts dominated by Stigonema species were fixing 0.3 g N m(-2) (ethylene production rate, 1.10 g C2H4 m(-2)) and crusts dominated by Nostoc and Scytonema were fixing 1.3 g N m(-2) (4.10 g C2H4 m(-2)). © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Influence of radioactivity out of the field of view on 3D PET dynamic measurement with [/sup 11/C]MP4A

NASA Astrophysics Data System (ADS)

Hasegawa, T.; Suzuki, M.; Murayama, H.; Irie, T.; Fukushi, K.; Wada, Y.

1999-08-01

This study assessed the influence of radioactivity out of the field of view (out-of-FOV) on the measurement of brain acetylcholinesterase (AChE) activity with the tracer [/sup 11/C]N-methyl-4-piperidyl-acetate by positron emission tomography in three-dimensional mode. Dynamic scans on a volunteer showed that the out-of-FOV radioactivity in the chest was much higher than that of the brain immediately after tracer injection. A representative phantom measurement was performed to quantitate the systematic errors due to the out-of-FOV radioactivity. Resultant errors in the AChE activity (k3 parameter) as calculated by compartment model analysis were found to be less than one percent in all of the brain regions studied.

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

Teather, R.M.; Wood, P.J.

The interaction of the direct dye Congo red with intact beta-D-glucans provides the basis for a rapid and sensitive assay system for bacterial strains possessing beta-(1 maps onto 4), (1 maps onto 3)-D-glucanohydrolase, beta-(1 maps onto 4)-D-glucanohydrolase, and beta-(1 maps onto 3)-D-glucanohydrolase activities. A close correspondence was observed between cellulolytic activity and beta-(1 maps onto 4)-D-glucanohydrolase and beta-(1 maps onto 4), (1 maps onto 3)-D-glucanohydrolase activities in isolates from the bovine rumen. Many of these isolates also possessed beta-(1 maps onto 3)-D-glucanohydrolase activity, and this characteristic may have taxonomic significance. (Refs. 19).

Validation of the WIMSD4M cross-section generation code with benchmark results

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

Leal, L.C.; Deen, J.R.; Woodruff, W.L.

1995-02-01

The WIMSD4 code has been adopted for cross-section generation in support of the Reduced Enrichment for Research and Test (RERTR) program at Argonne National Laboratory (ANL). Subsequently, the code has undergone several updates, and significant improvements have been achieved. The capability of generating group-collapsed micro- or macroscopic cross sections from the ENDF/B-V library and the more recent evaluation, ENDF/B-VI, in the ISOTXS format makes the modified version of the WIMSD4 code, WIMSD4M, very attractive, not only for the RERTR program, but also for the reactor physics community. The intent of the present paper is to validate the procedure to generatemore » cross-section libraries for reactor analyses and calculations utilizing the WIMSD4M code. To do so, the results of calculations performed with group cross-section data generated with the WIMSD4M code will be compared against experimental results. These results correspond to calculations carried out with thermal reactor benchmarks of the Oak Ridge National Laboratory(ORNL) unreflected critical spheres, the TRX critical experiments, and calculations of a modified Los Alamos highly-enriched heavy-water moderated benchmark critical system. The benchmark calculations were performed with the discrete-ordinates transport code, TWODANT, using WIMSD4M cross-section data. Transport calculations using the XSDRNPM module of the SCALE code system are also included. In addition to transport calculations, diffusion calculations with the DIF3D code were also carried out, since the DIF3D code is used in the RERTR program for reactor analysis and design. For completeness, Monte Carlo results of calculations performed with the VIM and MCNP codes are also presented.« less

Novel pyrrole derivatives bearing sulfonamide groups: Synthesis in vitro cytotoxicity evaluation, molecular docking and DFT study

NASA Astrophysics Data System (ADS)

Bavadi, Masoumeh; Niknam, Khodabakhsh; Shahraki, Omolbanin

2017-10-01

The synthesis of new derivatives of pyrrole substituted sulfonamide groups is described. The in vitro anticancer activity of these pyrroles was evaluated against MCF7, MOLT-4 and HL-60 cells using MTT assay. The target compounds showed inhibitory activity against tested cell lines. Among the compounds, compound 1a exhibited good cytotoxic activity. The potential of this analog to induce apoptosis was confirmed in a nuclear morphological assay by Hoechst 33258 staining in the PC-12 cells. Finally, molecular docking was performed to determine the probable binding mode of the designed pyrrole derivatives into the active site of FGFR1 protein. DFT calculations were carried out at the B3LYP levels of theory with 6-31+G (d,p) basis set for compound 1a. The point group (C1) of it was obtained based on the optimized structures; the calculation of the FT-IR vibrational frequencies, 1H NMR and 13C NMR chemical shifts of the compound were carried out and compared with those obtained experimentally.

Physical activity and associated factors among young adults in Malaysia: an online exploratory survey.

PubMed

Sreeramareddy, C T; Majeed Kutty, N A; Razzaq Jabbar, M A; Boo, N Y

2012-06-01

The burden of non-communicable diseases is increasing in Malaysia. Insufficient Physical Activity, which is an important risk factor for non-communicable diseases, is less researched in Malaysia. We aimed to assess the level of physical activity and identify its correlates. An online survey was carried out during October, 2011 in the University Tunku Abdul Rahman by the opinion poll research committee. Young adults answered the Short International Physical Activity Questionnaire and a questionnaire about factors according to a socio-ecological model which was adapted from published studies. Metabolic equivalent (MET)-hours and MET-minutes were calculated. Physical activity was classified as sufficient when MET-minutes were > 840. The mean age of the 474 participants was 22.4 years (S.D. = 4.7), and 253 (53.4%) were females. Their mean and median of MET-hours of PA done during the previous seven days were 31.36 (S.D., 52.19) and 14.7 (IQR, 5.77-32.07), respectively. Physical activity done was sufficient among 242 (51.1%) participants. Using univariate analysis, being male, good self-rated health, positive intention, self-efficacy, perceived benefits, social support, and availability of facilities were associated with sufficient physical activity. Using multivariate analysis sufficient physical activity was associated with participants' intention (OR 0.75, 95% CIs 0.64, 0.88), self-efficacy (OR 0.91, 95% CIs 0.85, 0.97) and facility availability (OR 0.81, 95% CIs 0.73, 0.91). The proportion of participants with sufficient physical activity was low. Positive intention and self-efficacy associated with sufficient physical activity should be supported by availability of facilities and a safely-built environment. A nationwide survey about physical and associated socialecological factors is needed to design rational health promotion strategies.

π-Stacking, C-H/π, and halogen bonding interactions in bromobenzene and mixed bromobenzene-benzene clusters.

PubMed

Reid, Scott A; Nyambo, Silver; Muzangwa, Lloyd; Uhler, Brandon

2013-12-19

Noncovalent interactions play an important role in many chemical and biochemical processes. Building upon our recent study of the homoclusters of chlorobenzene, where π-π stacking and CH/π interactions were identified as the most important binding motifs, in this work we present a study of bromobenzene (PhBr) and mixed bromobenzene-benzene clusters. Electronic spectra in the region of the PhBr monomer S0-S1 (ππ*) transition were obtained using resonant two-photon ionization (R2PI) methods combined with time-of-flight mass analysis. As previously found for related systems, the PhBr cluster spectra show a broad feature whose center is red-shifted from the monomer absorption, and electronic structure calculations indicate the presence of multiple isomers and Franck-Condon activity in low-frequency intermolecular modes. Calculations at the M06-2X/aug-cc-pVDZ level find in total eight minimum energy structures for the PhBr dimer: four π-stacked structures differing in the relative orientation of the Br atoms (denoted D1-D4), one T-shaped structure (D5), and three halogen bonded structures (D6-D8). The calculated binding energies of these complexes, corrected for basis set superposition error (BSSE) and zero-point energy (ZPE), are in the range of -6 to -24 kJ/mol. Time-dependent density functional theory (TDDFT) calculations predict that these isomers absorb over a range that is roughly consistent with the breadth of the experimental spectrum. To examine the influence of dipole-dipole interaction, R2PI spectra were also obtained for the mixed PhBr···benzene dimer, where the spectral congestion is reduced and clear vibrational structure is observed. This structure is well-simulated by Franck-Condon calculations that incorporate the lowest frequency intermolecular modes. Calculations find four minimum energy structures for the mixed dimer and predict that the binding energy of the global minimum is reduced by ~30% relative to the global minimum PhBr dimer structure.

Atomic Data and Spectral Line Intensities for Ni XV

NASA Technical Reports Server (NTRS)

Landi, E.; Bhatia, A. K.

2011-01-01

Electron impact collision strengths, energy levels, oscillator strengths, and spontaneous radiative decay rates are calculated for Ni XV.Weinclude in the calculations the 9 lowest configurations, corresponding to 126 fine structure levels: 3s23p2, 3s3p3, 3s23p3d, 3p4, 3s3p23d, and 3s2 3p4l with l =, s, p, d, f. Collision strengths are calculated at five incident energies for all transitions: 7.8, 18.5, 33.5, 53.5, and 80.2 Ry above the threshold of each transition. An additional energy, very close to the transition threshold, has been added, whose value is between 0.004 and 0.28 Ry depending on the levels involved. Calculations have been carried out using the Flexible Atomic Code and the distorted-wave approximation. Excitation rate coefficients are calculated as a function of electron temperature by assuming a Maxwellian electron velocity distribution. Using the excitation rate coefficients and the radiative transition rates calculated in the present work, statistical equilibrium equations for level populations are solved at electron densities covering the 10(exp 8)-10(exp 14)/cu cm range and at an electron temperature of log T(sub e)(K) = 6.4, corresponding to the maximum abundance of Ni XV. Spectral line intensities are calculated, and their diagnostic relevance is discussed. This dataset will be made available in the next version of the CHIANTI database.

Vitamin D Receptor (VDR) Regulation of Voltage-Gated Chloride Channels by Ligands Preferring a VDR-Alternative Pocket (VDR-AP)

PubMed Central

Menegaz, Danusa; Mizwicki, Mathew T.; Barrientos-Duran, Antonio; Chen, Ning; Henry, Helen L.

2011-01-01

We have postulated that the vitamin D receptor (VDR) contains two overlapping ligand binding sites, a genomic pocket and an alternative pocket (AP), that mediate regulation of gene transcription and rapid responses, respectively. Flexible VDR + ligand docking calculations predict that the major blood metabolite, 25(OH)-vitamin D3 (25D3), and curcumin (CM) bind more selectively to the VDR-AP when compared with the seco-steroid hormone 1α,25(OH)2-vitamin D3 (1,25D3). In VDR wild-type-transfected COS-1 cells and TM4 Sertoli cells, 1,25D3, 25D3, and CM each trigger voltage-gated, outwardly rectifying chloride channel (ORCC) currents that can be blocked by the VDR antagonist 1β,25(OH)2-vitamin D3 and the chloride channel antagonist (4,4′-diisothiocyanatostilbene-2,2′-disulfonic acid). VDR mutational analysis in transfected COS-1 cells demonstrate the DNA-binding domain is not, but the ligand binding and hinge domains of the VDR are, required for 1,25D3 and 25D3 to activate the ORCC. Dose-response studies demonstrate that 25D3 and 1,25D3 are approximately equipotent in stimulating ORCC rapid responses, whereas 1 nm 1,25D3 was 1000-fold more potent than 25D3 and CM in stimulating gene expression. The VDR-AP agonist effects of 1,25D3, 25D3, and low-dose CM are lost after pretreatment of TM4 cells with VDR small interfering RNA. Collectively, these results are consistent with an essential role for the VDR-AP in initiating the signaling required for rapid opening of ORCC. The fact that 25D3 is equipotent to 1,25D3 in opening ORCC suggests that reconsideration of the ability of 25D3 to generate biological responses in vivo may be in order. PMID:21659475

Analytical calculation of proton linear energy transfer in voxelized geometries including secondary protons

NASA Astrophysics Data System (ADS)

Sanchez-Parcerisa, D.; Cortés-Giraldo, M. A.; Dolney, D.; Kondrla, M.; Fager, M.; Carabe, A.

2016-02-01

In order to integrate radiobiological modelling with clinical treatment planning for proton radiotherapy, we extended our in-house treatment planning system FoCa with a 3D analytical algorithm to calculate linear energy transfer (LET) in voxelized patient geometries. Both active scanning and passive scattering delivery modalities are supported. The analytical calculation is much faster than the Monte-Carlo (MC) method and it can be implemented in the inverse treatment planning optimization suite, allowing us to create LET-based objectives in inverse planning. The LET was calculated by combining a 1D analytical approach including a novel correction for secondary protons with pencil-beam type LET-kernels. Then, these LET kernels were inserted into the proton-convolution-superposition algorithm in FoCa. The analytical LET distributions were benchmarked against MC simulations carried out in Geant4. A cohort of simple phantom and patient plans representing a wide variety of sites (prostate, lung, brain, head and neck) was selected. The calculation algorithm was able to reproduce the MC LET to within 6% (1 standard deviation) for low-LET areas (under 1.7 keV μm-1) and within 22% for the high-LET areas above that threshold. The dose and LET distributions can be further extended, using radiobiological models, to include radiobiological effectiveness (RBE) calculations in the treatment planning system. This implementation also allows for radiobiological optimization of treatments by including RBE-weighted dose constraints in the inverse treatment planning process.

Analytical calculation of proton linear energy transfer in voxelized geometries including secondary protons.

PubMed

Sanchez-Parcerisa, D; Cortés-Giraldo, M A; Dolney, D; Kondrla, M; Fager, M; Carabe, A

2016-02-21

In order to integrate radiobiological modelling with clinical treatment planning for proton radiotherapy, we extended our in-house treatment planning system FoCa with a 3D analytical algorithm to calculate linear energy transfer (LET) in voxelized patient geometries. Both active scanning and passive scattering delivery modalities are supported. The analytical calculation is much faster than the Monte-Carlo (MC) method and it can be implemented in the inverse treatment planning optimization suite, allowing us to create LET-based objectives in inverse planning. The LET was calculated by combining a 1D analytical approach including a novel correction for secondary protons with pencil-beam type LET-kernels. Then, these LET kernels were inserted into the proton-convolution-superposition algorithm in FoCa. The analytical LET distributions were benchmarked against MC simulations carried out in Geant4. A cohort of simple phantom and patient plans representing a wide variety of sites (prostate, lung, brain, head and neck) was selected. The calculation algorithm was able to reproduce the MC LET to within 6% (1 standard deviation) for low-LET areas (under 1.7 keV μm(-1)) and within 22% for the high-LET areas above that threshold. The dose and LET distributions can be further extended, using radiobiological models, to include radiobiological effectiveness (RBE) calculations in the treatment planning system. This implementation also allows for radiobiological optimization of treatments by including RBE-weighted dose constraints in the inverse treatment planning process.

Paviosides A-H, eight new oleane type saponins from Aesculus pavia with cytotoxic activity.

PubMed

Lanzotti, Virginia; Termolino, Pasquale; Dolci, Marcello; Curir, Paolo

2012-05-15

A phytochemical analysis of Aesculus pavia has led to the isolation of eight novel triterpenoid saponins, based on oleane type skeleton and named paviosides A-H (1a, 1b-4a, 4b). On the basis of chemical, and 2D NMR and mass spectrometry data, the structures of the new compounds were elucidated as 3-O-[β-D-xylopyranosyl (1 → 2)] [-β-d-glucopyranosyl (1 → 4)]-β-D-glucopyranosiduronic acid 21-tigloyl-22-acetyl barringtogenol C (1a), 3-O-[β-D-xylopyranosyl (1 → 2)] [-β-D-glucopyranosyl (1 → 4)]-β-D-glucopyranosiduronic acid 21-angeloyl-22-acetyl barringtogenol C (1b), 3-O-[β-D-xylopyranosyl (1 → 2)] [-β-D-galactopyranosyl (1 → 4)]-β-D-glucopyranosiduronic acid 21-tigloyl-22-acetyl barringtogenol C (2a), 3-O-[β-D-xylopyranosyl (1 → 2)] [-β-D-galactopyranosyl (1 → 4)]-β-D-glucopyranosiduronic acid 21-angeloyl-22-acetyl barringtogenol C (2b), 3-O-[β-D-xylopyranosyl (1 → 2)] [-β-D-xylopyranosyl (1 → 4)]-β-D-glucopyranosiduronic acid 21-tigloyl-22-acetyl barringtogenol C (3a), 3-O-[β-D-xylopyranosyl (1 → 2)] [-β-D-xylopyranosyl (1 → 4)]-β-d-glucopyranosiduronic acid 21-angeloyl-22-acetyl barringtogenol C (3b), 3-O-[β-D-xylopyranosyl (1 → 2)] [-β-D-xylopyranosyl (1 → 4)]-β-D-glucopyranosiduronic acid 21-tigloyl-22-acetyl protoaescigenin (4a), and 3-O-[β-D-xylopyranosyl (1 → 2)] [-β-D-xylopyranosyl (1 → 4)]-β-D-glucopyranosiduronic acid 21-angeloyl-22-acetyl protoaescigenin (4b). The compounds showed cytotoxic activity on J-774, murine monocyte/macrophage, and WEHI-164, murine fibrosarcoma, cell lines. Among them, paviosides E-H (3a, 3b and 4a, 4b) showed higher activity with values ranging from 2.1 to 3.6 μg/mL. Structure-activity relationship studies indicated the positive effect on the activity of xylose unit in the place of glucose, while a little detrimental effect is observed when glucose is substituted by galactose. The aglycone structure and the presence of a tigloyl or an angeloyl group at C-21 do not affect significantly the inhibitory activity on both tested cell lines. Copyright © 2012 Elsevier Ltd. All rights reserved.

Electrical studies of D%AgI-(100-D)%[0.667Ag2O- 0.333{(0.4)B2O3-(0.6)TeO2}] fast ion conducting glasses

NASA Astrophysics Data System (ADS)

Kumar, E. Ramesh; Nageswar Rao, P.; Appa Rao, B.

2016-09-01

Super ion conducting glasses of composition D%AgI-(100-D)%[MAg2O-F{(F1)B2O3- (F2)TeO2}]; D=10.0 to 60.0 in steps of 10.0 for a fixed values of F1 (0.4), F2 (0.6) which are glass network formers, fixed values of modifier M(0.667), F (0.333) and D is dopant salt which was varied. These glasses were prepared by melt quenching technique. XRD spectra taken for all the samples. Electrical characterization was done in terms of AC and DC conductivities. DC and AC conductivities at room temperature increased from 10-5 to 10-1 scm-1 and DC activation energy (Edc) found to decrease from 0.36 to 0.19eV with increase in D% ratio. Measurements are performed over the frequency range 1 kHz to 3 MHz at different temperatures. From the impedance spectroscopy real and imaginary parts of impedances (Z', Z"), conductivities were calculated and plotted, and equivalent R-C circuit parameters were obtained from Cole-Cole plots. With the increase in D%, AC conductivity is observed to increase whereas the AC activation energy (Eac) is observed to decrease from 0.23 to 0.14 eV. The quantitative analysis of these results indicates that the electrical conductivity of silver borate glasses is enhanced with increase in D% ratio. Based on conductivity values these glasses are ionic conductors, in which conduction is by hopping mechanism. An attempt is made to understand the charge transportation process.

New muonic-atom test of vacuum polarization

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

Dixit, M.S.; Carter, A.L.; Hincks, E.P.

1975-12-15

In order to check the discrepancy between calculation and experiment in muonic atoms, we have remeasured the 5g-4f transitions in Pb and the 5g-4f and the 4f-3d transitions in Ba. Our new results show no discrepancy and confirm recent theoretical calculations of vacuum polarization to within 0.5%. (AIP)

FT-IR, FT-Raman spectra, density functional computations of the vibrational spectra and molecular conformational analysis of 2,5-di-tert-butyl-hydroquinone

NASA Astrophysics Data System (ADS)

Subramanian, N.; Sundaraganesan, N.; Dereli, Ö.; Türkkan, E.

2011-12-01

The purpose of finding conformer among six different possible conformers of 2,5-di-tert-butyl-hydroquinone (DTBHQ), its equilibrium geometry and harmonic wavenumbers were calculated by the B3LYP/6-31G(d,p) method. The infrared and Raman spectra of DTBHQ were recorded in the region 400-4000 cm -1 and 50-3500 cm -1, respectively. In addition, the IR spectra in CCl 4 at various concentrations of DTBHQ are also recorded. The computed vibrational wavenumbers were compared with the IR and Raman experimental data. Computational calculations at B3LYP level with two different basis sets 6-31G(d,p) and 6-311++G(d,p) are also employed in the study of the possible conformer of DTBHQ. The complete assignments were performed on the basis of the potential energy distribution (PED) of the vibrational modes, calculated using VEDA 4 program. The general agreement between the observed and calculated frequencies was established.

Improved measurement of B(D+ --> mu+nu) and the pseudoscalar decay constant fD+.

PubMed

Artuso, M; Boulahouache, C; Blusk, S; Butt, J; Dorjkhaidav, O; Li, J; Menaa, N; Mountain, R; Nandakumar, R; Randrianarivony, K; Redjimi, R; Sia, R; Skwarnicki, T; Stone, S; Wang, J C; Zhang, K; Csorna, S E; Bonvicini, G; Cinabro, D; Dubrovin, M; Lincoln, A; Briere, R A; Chen, G P; Chen, J; Ferguson, T; Tatishvili, G; Vogel, H; Watkins, M E; Rosner, J L; Adam, N E; Alexander, J P; Berkelman, K; Cassel, D G; Crede, V; Duboscq, J E; Ecklund, K M; Ehrlich, R; Fields, L; Gibbons, L; Gittelman, B; Gray, R; Gray, S W; Hartill, D L; Heltsley, B K; Hertz, D; Jones, C D; Kandaswamy, J; Kreinick, D L; Kuznetsov, V E; Mahlke-Krüger, H; Meyer, T O; Onyisi, P U E; Patterson, J R; Peterson, D; Phillips, E A; Pivarski, J; Riley, D; Ryd, A; Sadoff, A J; Schwarthoff, H; Shi, X; Shepherd, M R; Stroiney, S; Sun, W M; Urner, D; Wilksen, T; Weaver, K M; Weinberger, M; Athar, S B; Avery, P; Breva-Newell, L; Patel, R; Potlia, V; Stoeck, H; Yelton, J; Rubin, P; Cawlfield, C; Eisenstein, B I; Gollin, G D; Karliner, I; Kim, D; Lowrey, N; Naik, P; Sedlack, C; Selen, M; White, E J; Williams, J; Wiss, J; Asner, D M; Edwards, K W; Besson, D; Pedlar, T K; Cronin-Hennessy, D; Gao, K Y; Gong, D T; Hietala, J; Kubota, Y; Klein, T; Lang, B W; Li, S Z; Poling, R; Scott, A W; Smith, A; Dobbs, S; Metreveli, Z; Seth, K K; Tomaradze, A; Zweber, P; Ernst, J; Severini, H; Dytman, S A; Love, W; Mehrabyan, S; Mueller, J A; Savinov, V; Li, Z; Lopez, A; Mendez, H; Ramirez, J; Huang, G S; Miller, D H; Pavlunin, V; Sanghi, B; Shipsey, I P J; Adams, G S; Anderson, M; Cummings, J P; Danko, I; Napolitano, J; He, Q; Muramatsu, H; Park, C S; Thorndike, E H; Coan, T E; Gao, Y S; Liu, F

2005-12-16

We extract a relatively precise value for the decay constant of the meson by measuring B(D+ --> mu+nu) = (4.40 +/-0.66(+0.09)(-0.12) x 10(-4) using 281 pb(-1) of data taken on phi(3770) the resonance with the CLEO-c detector. We find fD+ = (222.6 +/- 16.7(+2.8)(-3.4)) MeV, and compare with current theoretical calculations. We also set a 90% confidence upper limit on B(D+e+nu)< 2.4 x 10(-5) which constrains new physics models.

4D-PET reconstruction using a spline-residue model with spatial and temporal roughness penalties

NASA Astrophysics Data System (ADS)

Ralli, George P.; Chappell, Michael A.; McGowan, Daniel R.; Sharma, Ricky A.; Higgins, Geoff S.; Fenwick, John D.

2018-05-01

4D reconstruction of dynamic positron emission tomography (dPET) data can improve the signal-to-noise ratio in reconstructed image sequences by fitting smooth temporal functions to the voxel time-activity-curves (TACs) during the reconstruction, though the optimal choice of function remains an open question. We propose a spline-residue model, which describes TACs as weighted sums of convolutions of the arterial input function with cubic B-spline basis functions. Convolution with the input function constrains the spline-residue model at early time-points, potentially enhancing noise suppression in early time-frames, while still allowing a wide range of TAC descriptions over the entire imaged time-course, thus limiting bias. Spline-residue based 4D-reconstruction is compared to that of a conventional (non-4D) maximum a posteriori (MAP) algorithm, and to 4D-reconstructions based on adaptive-knot cubic B-splines, the spectral model and an irreversible two-tissue compartment (‘2C3K’) model. 4D reconstructions were carried out using a nested-MAP algorithm including spatial and temporal roughness penalties. The algorithms were tested using Monte-Carlo simulated scanner data, generated for a digital thoracic phantom with uptake kinetics based on a dynamic [18F]-Fluromisonidazole scan of a non-small cell lung cancer patient. For every algorithm, parametric maps were calculated by fitting each voxel TAC within a sub-region of the reconstructed images with the 2C3K model. Compared to conventional MAP reconstruction, spline-residue-based 4D reconstruction achieved  >50% improvements for five of the eight combinations of the four kinetics parameters for which parametric maps were created with the bias and noise measures used to analyse them, and produced better results for 5/8 combinations than any of the other reconstruction algorithms studied, while spectral model-based 4D reconstruction produced the best results for 2/8. 2C3K model-based 4D reconstruction generated the most biased parametric maps. Inclusion of a temporal roughness penalty function improved the performance of 4D reconstruction based on the cubic B-spline, spectral and spline-residue models.

Spectrum and Energy Levels of Five-Times Ionized Zirconium (Zr VI).

PubMed

Reader, Joseph; Lindsay, Mark D

2016-02-01

We carried out a new analysis of the spectrum of five-times-ionized zirconium Zr VI. For this we used sliding-spark discharges together with normal- and grazing-incidence spectrographs to observe the spectrum from 160 to 2000 Å. These observations showed that the analysis of this spectrum by Khan Z. A. et al. 1985 Phys. Scr. 31 837 contained a significant number of incorrect energy levels. We have now classified ∼420 lines as transitions between 23 even-parity levels 73 odd-parity levels. The 4s 2 4p 5 , 4s4p 6 , 4s 2 4p 4 4d, 5s, 5d, 6s configurations are now complete, although a few levels of 4s 2 4p 4 5d are tentative. We determined Ritz-type wavelengths for ∼135 lines from the optimized energy levels. The uncertainties range from 0.0003 to 0.0020 Å. Hartree-Fock calculations and least-squares fits of the energy parameters to the observed levels were used to interpret the observed configurations. Oscillator strengths for all classified lines were calculated with the fitted parameters. The results are compared with values for the level energies, percentage compositions, and transition probabilities from recent ab initio theoretical calculations. The ionization energy was revised to 777380±300 cm -1 (96.38±0.04 eV).

3D Printing of Preoperative Simulation Models of a Splenic Artery Aneurysm: Precision and Accuracy.

PubMed

Takao, Hidemasa; Amemiya, Shiori; Shibata, Eisuke; Ohtomo, Kuni

2017-05-01

Three-dimensional (3D) printing is attracting increasing attention in the medical field. This study aimed to apply 3D printing to the production of hollow splenic artery aneurysm models for use in the simulation of endovascular treatment, and to evaluate the precision and accuracy of the simulation model. From 3D computed tomography (CT) angiography data of a splenic artery aneurysm, 10 hollow models reproducing the vascular lumen were created using a fused deposition modeling-type desktop 3D printer. After filling with water, each model was scanned using T2-weighted magnetic resonance imaging for the evaluation of the lumen. All images were coregistered, binarized, and then combined to create an overlap map. The cross-sectional area of the splenic artery aneurysm and its standard deviation (SD) were calculated perpendicular to the x- and y-axes. Most voxels overlapped among the models. The cross-sectional areas were similar among the models, with SDs <0.05 cm 2 . The mean cross-sectional areas of the splenic artery aneurysm were slightly smaller than those calculated from the original mask images. The maximum mean cross-sectional areas calculated perpendicular to the x- and y-axes were 3.90 cm 2 (SD, 0.02) and 4.33 cm 2 (SD, 0.02), whereas those calculated from the original mask images were 4.14 cm 2 and 4.66 cm 2 , respectively. The mean cross-sectional areas of the afferent artery were, however, almost the same as those calculated from the original mask images. The results suggest that 3D simulation modeling of a visceral artery aneurysm using a fused deposition modeling-type desktop 3D printer and computed tomography angiography data is highly precise and accurate. Copyright © 2017 The Association of University Radiologists. Published by Elsevier Inc. All rights reserved.

New Accurate Oscillator Strengths and Electron Excitation Collision Strengths for N1

NASA Technical Reports Server (NTRS)

Tayal, S. S.

2006-01-01

The nonorthogonal orbitals technique in a multiconfiguration Hartree-Fock approach is used to calculate oscillator strengths and transition probabilities of N(I) lines. The relativistic effects are allowed by means of Breit-Pauli operators. The length and velocity forms of oscillator strengths show good agreement for most transitions. The B-spline R-matrix with pseudostates approach has been used to calculate electron excitation collision strengths and rates. The nonorthogonal orbitals are used for an accurate description of both target wave functions and the R-matrix basis functions. The 24 spectroscopic bound and autoionizing states together with 15 pseudostates are included in the close-coupling expansion. The collision strengths for transitions between fine-structure levels are calculated by transforming the LS-coupled K-matrices to K-matrices in an intermediate coupling scheme. Thermally averaged collision strengths have been determined by integrating collision strength over a Maxwellian distribution of electron energies over a temperature range suitable for the modeling of astrophysical plasmas. The oscillator strengths and thermally averaged collision strengths are presented for transitions between the fine-structure levels of the 2s(sup 2)p(sup 3) (sup 4)S(sup 0), (sup 2)D(sup 0), (sup 2)P(sup 0), 2s2p(sup 4) (sup 4)P, 2s(sup 2)2p(sup 2)3s (sup 4)P, and (sup 2)P terms and from these levels to the levels of the 2s(sup 2)2p(sup 2)3p (sup 2)S(sup 0), (sup 4)D(sup 0), (sup 4)P(sup 0), (sup 4)S(sup 0), (sup 2)D(sup 0), (sup 2)P(sup 0),2s(sup 2)2p(sup 2)3s(sup 2)D, 2s(sup 2)2p(sup 2)4s(sup 4)P, (sup 2)P, 2s(sup 2)2p(sup 2)3d(sup 2)P, (sup 4)F,(sup 2)F,(sup 4)P, (sup 4)D, and (sup 2)D terms. Thermally averaged collision strengths are tabulated over a temperature range from 500 to 50,000 K.

Associations of the Levels of C4d-bearing Reticulocytes and High-avidity Anti-dsDNA Antibodies with Disease Activity in Systemic Lupus Erythematosus.

PubMed

Mora, Claudia; Medina-Rosas, Jorge; Santos, Ana Maria; Jaimes, Diego A; Arbeláez, Ana M; Romero, Consuelo; Cortes, Annie; Londono, John

2016-09-01

There are no laboratory tools that detect early flares in systemic lupus erythematosus (SLE). Our aim was to validate in our population the previous findings of the association of C4d-bearing reticulocytes (R-C4d) compared to anti-dsDNA antibodies, with disease activity assessed by the Safety of Estrogens in Lupus Erythematosus National Assessment-Systemic Lupus Erythematosus Disease Activity Index (SELENA-SLEDAI) and the British Isles Lupus Assessment Group (BILAG) 2004 scales. All patients who met the 1987 American College of Rheumatology classification criteria and were seen consecutively in 2013 at a specialized SLE care clinic were included. Disease activity was established by the SELENA-SLEDAI and BILAG 2004. Anti-dsDNA and R-C4d were quantified in peripheral blood. Comparisons were made between values of active and inactive patients, and the correlations between the SELENA-SLEDAI and serum levels of anti-dsDNA and R-C4d were measured. Sixty-two patients (83.9% women) were included. A total of 32.3% had active disease according to the SELENA-SLEDAI. There was a significant statistical difference (p = 0.0001) in the distribution of R-C4d between disease activity groups. The correlation coefficient between R-C4d and the SELENA-SLEDAI score was rs = 0.738 (p = 0.0001). R-C4d differed between patients with and without activity in the BILAG 2004 constitutional, mucocutaneous, gastrointestinal, renal, and hematological domains. R-C4d showed a higher correlation with SLE activity measured by the SELENA-SLEDAI and BILAG 2004 than anti-dsDNA did, suggesting a possible involvement in diagnosing disease activity. Prospective studies that confirm these findings and evaluate its involvement in followup are needed.

A systematic study of basis set, electron correlation, and geometry effects on the electric multipole moments, polarizability, and hyperpolarizability of HCl

NASA Astrophysics Data System (ADS)

Maroulis, George

1998-04-01

The electric multipole moments, dipole and quadrupole polarizability and hyperpolarizability of hydrogen chloride have been determined from an extensive and systematic study based on finite-field fourth-order many-body perturbation theory and coupled-cluster calculations. Our best values for the dipole, quadrupole, octopole and hexadecapole moment at the experimental internuclear separation of Re=2.408645a0 are μ=0.4238ea0, Θ=2.67ea02, Ω=3.94ea03, and Φ=13.37ea04, respectively. For the mean and the anisotropy of the dipole polarizability ααβ we recommend ᾱ=17.41±0.02 and Δα=1.60±0.03e2a02Eh-1. For the mean value of the first dipole hyperpolarizability βαβγ we advance β¯=-6.8±0.3e3a03Eh-2. Extensive calculations with a [8s6p6d3f/5s4p2d1f] basis set at the CCSD(T) level of theory yield the R-dependence of the Cartesian components and the mean of the second dipole hyperpolarizability γαβγδ(R)/e4a04Eh-3 around Re as γzzzz(R)=1907+1326(R-Re)+570(R-Re)2+10(R-Re)3-40(R-Re)4, γxxxx(R)=3900+747(R-Re)-65(R-Re)2-38(R-Re)3-7(R-Re)4, γxxzz(R)=962+222(R-Re)+88(R-Re)2+49(R-Re)3+5(R-Re)4, γ¯(R)=3230+841(R-Re)+151(R-Re)2+21(R-Re)3-9(R-Re)4, with z as the molecular axis. The present investigation suggests an estimate of (26.7±0.3)×102e4a04Eh-3 for the Hartree-Fock limit of the mean value γ¯ at Re. CCSD(T) calculations with basis sets of [8s6p6d3f/5s4p2d1f] and [9s7p5d4f/6s5p4d1f] size and MP4 calculations with the even larger [15s12p7d3f/12s7p2d1f] give (7.0±0.3)×102e4a04Eh-3 for the electron correlation effects for this property, thus leading to a recommended value of γ¯=(33.7±0.6)×102e4a04Eh-3. For the quadrupole polarizability Cαβ,γδ/e2a04Eh-1 at Re our best values are Czz,zz=41.68, Cxz,xz=26.11, and Cxx,xx=35.38, calculated with the [9s7p5d4f/6s5p4d1f] basis set at the CCSD(T) level of theory. The following CCSD(T) values were obtained with [8s6p6d3f/5s4p2d1f] at Re: dipole-quadrupole polarizability Aα,βγ/e2a03Eh-1, Az,zz=14.0, and Ax,zx=3.75, dipole-octopole polarizability Eα,βγδ/e2a04Eh-1, Ez,zzz=20.0, and Ex,xxx=3.0, and dipole-dipole-quadrupole hyperpolarizability Bαβ,γδ/e3a04Eh-2, Bzz,zz=-277, Bxz,xz=-261, Bxx,zz=246, and Bxx,xx=-416. A comparison of the mean polarizability and hyperpolarizability of some 18-electron systems shows that ᾱ(H2S)>ᾱ(HCl)>ᾱ(HOOH)>ᾱ(HOF)>ᾱ(Ar)>ᾱ(F2), and γ¯(H2S)>γ¯(HCl)>γ¯(HOOH)>γ¯(HOF)≈γ¯(Ar)>γ¯(F2).

Synthesis and characterization of oligobenzimidazoles: Electrochemical, electrical, optical, thermal and rectification properties

NASA Astrophysics Data System (ADS)

Anand, Siddeswaran; Muthusamy, Athianna

2018-03-01

A series of benzimidazole monomers, (2-(2, 4-dihydroxyphenyl)-1H-benzimidazol-5-yl)(phenyl) methanone (BIKH), 2-(3-ethoxy-2-hydroxyphenyl)-1H-benzo [d]imidazole-5-yl) (phenyl) methanone (BIKE) and 2-(5-bromo-2-hydroxyphenyl)-1H-benzo [d]imidazole-5-yl) (phenyl) methanone (BIKB) were prepared by condensing three substituted aromatic aldehydes with 3, 4-diaminobenzophenone. In aqueous alkaline medium the benzimidazoles were converted in to oligomers by oxidative polycondensation using NaOCl as oxidant. The formation of monomers and oligomers were confirmed with 1H, 13C NMR, FT-IR, and UV-visible spectroscopic techniques. The oligomers were investigated for their optical, electrical, electrochemical and thermal properties. The electrochemical and optical band gaps of monomers and oligomers were calculated using both UV-visible spectroscopy and cyclic voltametry respectively. The band gap values of monomers are compared with band gap values obtained from quantum theoretical calculations with DFT. The electrical conductivity studies of iodine doped and undoped oligomers were done using two point probe technique. It is found that these values are showing good correlation with the charge densities on imidazole nitrogen obtained from Huckel method. The conductivity of oligomers increases with increase in iodine vapour contact time. The dielectric properties of oligomers have been investigated at different temperature and frequency. The dielectric measurement data were used to calculate the AC conductivity and activation energy of oligomers. Oligomer OBIKH is having greater thermal stability due to its number of chain propagation sites than other oligomers and is shown by its high carbines residue of around 60% at 600 °C in thermogravimetric analysis. I-V characteristics of oligobenzimidazole p-n diodes have shown good rectifying nature in the range -4 to 4 V.

4SC-202 activates ASK1-dependent mitochondrial apoptosis pathway to inhibit hepatocellular carcinoma cells

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

Fu, Meili, E-mail: fumeilidrlinyi@tom.com; Wan, Fuqiang; Li, Zhengling

The aim of the present study is to investigate the potential anti-hepatocellular carcinoma (HCC) cell activity by 4SC-202, a novel class I HDAC inhibitor (HDACi). The associated signaling mechanisms were also analyzed. We showed that 4SC-202 treatment induced potent cytotoxic and proliferation–inhibitory activities against established HCC cell lines (HepG2, HepB3, SMMC-7721) and patient-derived primary HCC cells. Further, adding 4SC-202 in HCC cells activated mitochondrial apoptosis pathway, which was evidenced by mitochondrial permeability transition pore (mPTP) opening, cytochrome C cytosol release and caspase-3/-9 activation. Inhibition of this apoptosis pathway, by caspase-3/-9 inhibitors, mPTP blockers, or by shRNA-mediated knockdown of cyclophilin-D (Cyp-D,more » a key component of mPTP), significantly attenuated 4SC-202-induced HCC cell death and apoptosis. Reversely, over-expression of Cyp-D enhanced 4SC-202's sensitivity in HCC cells. Further studies showed that 4SC-202 induced apoptosis signal-regulating kinase 1 (ASK1) activation, causing it translocation to mitochondria and physical association with Cyp-D. This mitochondrial ASK1-Cyp-D complexation appeared required for mediating 4SC-202-induced apoptosis activation. ASK1 stable knockdown by targeted-shRNAs largely inhibited 4SC-202-induced mPTP opening, cytochrome C release, and following HCC cell apoptotic death. Together, we suggest that 4SC-202 activates ASK1-dependent mitochondrial apoptosis pathway to potently inhibit human HCC cells. - Highlights: • 4SC-202 exerts potent anti-proliferative and cytotoxic activity against established/primary HCC cells. • SC-202-induced anti-HCC cell activity relies on caspase-dependent apoptosis activation. • 4SC-202 activates Cyp-D-dependent mitochondrial apoptosis pathway in HCC cells. • 4SC-202 activates ASK1 in HCC cells, causing it translocation to mitochondria. • Mitochondrial ASK1-Cyp-D complexation mediates 4SC-202's activity in HCC cells.« less

Accurate 238U(n , 2 n )237U reaction cross-section measurements from 6.5 to 14.8 MeV

NASA Astrophysics Data System (ADS)

Krishichayan, Bhike, M.; Tornow, W.; Tonchev, A. P.; Kawano, T.

2017-10-01

The cross section for the 238U(n ,2 n )237U reaction has been measured in the incident neutron energy range from 6.5 to 14.8 MeV in small energy steps using an activation technique. Monoenergetic neutron beams were produced via the 2H(d ,n )3He and 3H(d ,n )4He reactions. 238U targets were activated along with Au and Al monitor foils to determine the incident neutron flux. The activity of the reaction products was measured in TUNL's low-background counting facility using high-resolution γ -ray spectroscopy. The results are compared with previous measurements and latest data evaluations. Statistical-model calculations, based on the Hauser-Feshbach formalism, have been carried out using the CoH3 code and are compared with the experimental results. The present self-consistent and high-quality data are important for stockpile stewardship and nuclear forensic purposes as well as for the design and operation of fast reactors.

Eight-dimensional quantum reaction rate calculations for the H+CH{sub 4} and H{sub 2}+CH{sub 3} reactions on recent potential energy surfaces

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

Zhou, Yong; Zhang, Dong H., E-mail: zhangdh@dicp.ac.cn

2014-11-21

Eight-dimensional (8D) transition-state wave packet simulations have been performed on two latest potential energy surfaces (PES), the Zhou-Fu-Wang-Collins-Zhang (ZFWCZ) PES [Y. Zhou, B. Fu, C. Wang, M. A. Collins, and D. H. Zhang, J. Chem. Phys. 134, 064323 (2011)] and the Xu-Chen-Zhang (XCZ)-neural networks (NN) PES [X. Xu, J. Chen, and D. H. Zhang, Chin. J. Chem. Phys. 27, 373 (2014)]. Reaction rate constants for both the H+CH{sub 4} reaction and the H{sub 2}+CH{sub 3} reaction are calculated. Simulations of the H+CH{sub 4} reaction based on the XCZ-NN PES show that the ZFWCZ PES predicts rate constants with reasonable highmore » accuracy for low temperatures while leads to slightly lower results for high temperatures, in line with the distribution of interpolation error associated with the ZFWCZ PES. The 8D H+CH{sub 4} rate constants derived on the ZFWCZ PES compare well with full-dimensional 12D results based on the equivalent m-ZFWCZ PES, with a maximum relative difference of no more than 20%. Additionally, very good agreement is shown by comparing the 8D XCZ-NN rate constants with the 12D results obtained on the ZFWCZ-WM PES, after considering the difference in static barrier height between these two PESs. The reaction rate constants calculated for the H{sub 2}+CH{sub 3} reaction are found to be in good consistency with experimental observations.« less

Evaluation and mitigation of the interplay effects for intensity modulated proton therapy for lung cancer in a clinical setting

PubMed Central

Kardar, Laleh; Li, Yupeng; Li, Xiaoqiang; Li, Heng; Cao, Wenhua; Chang, Joe Y.; Liao, Li; Zhu, Ronald X.; Sahoo, Narayan; Gillin, Michael; Liao, Zhongxing; Komaki, Ritsuko; Cox, James D.; Lim, Gino; Zhang, Xiaodong

2015-01-01

Purpose The primary aim of this study was to evaluate the impact of interplay effects for intensity-modulated proton therapy (IMPT) plans for lung cancer in the clinical setting. The secondary aim was to explore the technique of iso-layered re-scanning for mitigating these interplay effects. Methods and Materials Single-fraction 4D dynamic dose without considering re-scanning (1FX dynamic dose) was used as a metric to determine the magnitude of dosimetric degradation caused by 4D interplay effects. The 1FX dynamic dose was calculated by simulating the machine delivery processes of proton spot scanning on moving patient described by 4D computed tomography (4DCT) during the IMPT delivery. The dose contributed from an individual spot was fully calculated on the respiratory phase corresponding to the life span of that spot, and the final dose was accumulated to a reference CT phase by using deformable image registration. The 1FX dynamic dose was compared with the 4D composite dose. Seven patients with various tumor volumes and motions were selected. Results The CTV prescription coverage for the 7 patients were 95.04%, 95.38%, 95.39%, 95.24%, 95.65%, 95.90%, and 95.53%, calculated with use of the 4D composite dose, and were 89.30%, 94.70%, 85.47%, 94.09%, 79.69%, 91.20%, and 94.19% with use of the 1FX dynamic dose. For the 7 patients, the CTV coverage, calculated by using single-fraction dynamic dose, were 95.52%, 95.32%, 96.36%, 95.28%, 94.32%, 95.53%, and 95.78%, using maximum MU limit value of 0.005. In other words, by increasing the number of delivered spots in each fraction, the degradation of CTV coverage improved up to 14.6%. Conclusions Single-fraction 4D dynamic dose without re-scanning was validated as a surrogate to evaluate the interplay effects for IMPT for lung cancer in the clinical setting. The interplay effects can be potentially mitigated by increasing the number of iso-layered re-scanning in each fraction delivery. PMID:25407877

Comparison of the Pentacam equivalent keratometry reading and IOL Master keratometry measurement in intraocular lens power calculations.

PubMed

Karunaratne, Nicholas

2013-12-01

To compare the accuracy of the Pentacam Holladay equivalent keratometry readings with the IOL Master 500 keratometry in calculating intraocular lens power. Non-randomized, prospective clinical study conducted in private practice. Forty-five consecutive normal patients undergoing cataract surgery. Forty-five consecutive patients had Pentacam equivalent keratometry readings at the 2-, 3 and 4.5-mm corneal zone and IOL Master keratometry measurements prior to cataract surgery. For each Pentacam equivalent keratometry reading zone and IOL Master measurement the difference between the observed and expected refractive error was calculated using the Holladay 2 and Sanders, Retzlaff and Kraff theoretic (SRKT) formulas. Mean keratometric value and mean absolute refractive error. There was a statistically significantly difference between the mean keratometric values of the IOL Master, Pentacam equivalent keratometry reading 2-, 3- and 4.5-mm measurements (P < 0.0001, analysis of variance). There was no statistically significant difference between the mean absolute refraction error for the IOL Master and equivalent keratometry readings 2 mm, 3 mm and 4.5 mm zones for either the Holladay 2 formula (P = 0.14) or SRKT formula (P = 0.47). The lowest mean absolute refraction error for Holladay 2 equivalent keratometry reading was the 4.5 mm zone (mean 0.25 D ± 0.17 D). The lowest mean absolute refraction error for SRKT equivalent keratometry reading was the 4.5 mm zone (mean 0.25 D ± 0.19 D). Comparing the absolute refraction error of IOL Master and Pentacam equivalent keratometry reading, best agreement was with Holladay 2 and equivalent keratometry reading 4.5 mm, with mean of the difference of 0.02 D and 95% limits of agreement of -0.35 and 0.39 D. The IOL Master keratometry and Pentacam equivalent keratometry reading were not equivalent when used only for corneal power measurements. However, the keratometry measurements of the IOL Master and Pentacam equivalent keratometry reading 4.5 mm may be similarly effective when used in intraocular lens power calculation formulas, following constant optimization. © 2013 Royal Australian and New Zealand College of Ophthalmologists.

Isocoumarin derivatives from the endophytic fungus, Pestalotiopsis sp.

PubMed

Song, Ren-Yu; Wang, Xiao-Bing; Yin, Guo-Ping; Liu, Rui-Huan; Kong, Ling-Yi; Yang, Ming-Hua

2017-10-01

Five new isocoumarin derivatives, pestalactone A-C (1-3) and pestapyrone D-E (4-5), together with two known compounds (6-7) were isolated from the solid cultures of the endophytic fungus Pestalotiopsis sp. obtained from Photinia frasery. Their structures were mainly determined by extensive spectroscopic analysis, Mo 2 (OCOCH 3 ) 4 -induced electronic circular dichroism (ECD), and ECD calculation. Compounds 1 and 2 were rare isocoumarin derivatives and derived from distinctive polyketide pathways. Compound 3 exhibited potent antifungal activity against Candida glabrata (ATCC 90030) with an MIC 50 value of 3.49±0.21μg/mL. Copyright © 2017. Published by Elsevier B.V.

Effect of ammonia and methane adsorption on the electronic structure of undoped and Fe-doped 2D silica: a first-principles calculation

NASA Astrophysics Data System (ADS)

Chibisov, A. N.; Chibisova, M. A.

2018-05-01

Two-dimensional silicon oxide (2D SiO2) is a unique surface phase with interesting optical, structural and electronic properties. In this study, important novel results on the effect of Fe on the structural and electronic properties of 2D SiO2 during adsorption of CH4 and NH3 molecules are presented. Density functional theory calculations are used to investigate the interaction of CH4 and NH3 molecules with silica. The electronic structure and molecules adsorption energy are studied in detail for undoped and Fe-doped surfaces. The results show that adsorption of CH4 and NH3 molecules on the surface decreases the spin polarization of Fe/SiO2. The results are relevant to understanding the adsorption physics of 2D SiO2 for practical usage in modern nanoelectronic sensors for nanotechnology and optoelectronics.

Excited states of 4He

NASA Astrophysics Data System (ADS)

Aoyama, Shigeyoshi

2013-04-01

The study of the 4He nucleus is important because it is the most basic sub-unit (cluster) in nuclei. We have investigated the structures and the reaction mechanisms in 4He by using the correlated Gaussian basis function with the global vector representation. In order to treat the boundary condition for the ab-initio calculation of the four nucleons, we employ the Microscopic R-matrix Method (MRM) and the Complex Scaling Method (CSM) . Elastic-scattering phase shifts for four-nucleon systems are studied in an ab-initio type cluster model with MRM in order to clarify the role of the tensor force and to investigate cluster distortions in low energy d+d and t+p scattering. For 1S0, the calculated phase shifts show that the t+p and h+n channels are strongly coupled to the d+d channel for the case of the realistic interaction.

Quantum chemical and statistical study of megazol-derived compounds with trypanocidal activity

NASA Astrophysics Data System (ADS)

Rosselli, F. P.; Albuquerque, C. N.; da Silva, A. B. F.

In this work we performed a structure-activity relationship (SAR) study with the aim to correlate molecular properties of the megazol compound and 10 of its analogs with the biological activity against Trypanosoma cruzi (trypanocidal or antichagasic activity) presented by these molecules. The biological activity indication was obtained from in vitro tests and the molecular properties (variables or descriptors) were obtained from the optimized chemical structures by using the PM3 semiempirical method. It was calculated ˜80 molecular properties selected among steric, constitutional, electronic, and lipophilicity properties. In order to reduce dimensionality and investigate which subset of variables (descriptors) would be more effective in classifying the compounds studied, according to their degree of trypanocidal activity, we employed statistical methodologies (pattern recognition and classification techniques) such as principal component analysis (PCA), hierarchical cluster analysis (HCA), K-nearest neighbor (KNN), and discriminant function analysis (DFA). These methods showed that the descriptors molecular mass (MM), energy of the second lowest unoccupied molecular orbital (LUMO+1), charge on the first nitrogen at substituent 2 (qN'), dihedral angles (D1 and D2), bond length between atom C4 and its substituent (L4), Moriguchi octanol-partition coefficient (MLogP), and length-to-breadth ratio (L/Bw) were the variables responsible for the separation between active and inactive compounds against T. cruzi. Afterwards, the PCA, KNN, and DFA models built in this work were used to perform trypanocidal activity predictions for eight new megazol analog compounds.

Computational studies on non-succinimide-mediated stereoinversion mechanism of aspartic acid residues assisted by phosphate

NASA Astrophysics Data System (ADS)

Nakayoshi, Tomoki; Fukuyoshi, Shuichi; Takahashi, Ohgi; Oda, Akifumi

2018-03-01

Although nearly all of the amino acids that constitute proteins are l-amino acids, d-amino acid residues in human proteins have been recently reported. d-amino acid residues cause a change in the three-dimensional structure of proteins, and d-aspartic acid (Asp) residues are considered to be one of the causes of age-related diseases. The stereoinversion of Asp residues in peptides and proteins is thought to proceed via a succinimide intermediate; however, it has been reported that stereoinversion can occur even under conditions where a succinimide intermediate cannot be formed. In order to elucidate the non-succinimide-mediated stereoinversion pathway, we investigated the stereoinversion of l-Asp to d-Asp catalysed by phosphate and estimated the activation barrier using B3LYP/6-31+G(d,p) density functional theory (DFT) calculations. For the DFT calculations, a model compound in which the Asp residue is capped with acetyl and methyl-amino groups on the N- and C-termini, respectively, was used. The calculated activation barrier was not excessively high for the stereoinversion to occur in vivo. Therefore, this stereoinversion mechanism may compete with the succinimide-mediated mechanism.

Discovery of dihydrobenzofuran neolignans from Rubus ideaus L. with enantioselective anti-Aβ1-42 aggregation activity.

PubMed

Zhou, Le; Wang, Jie; Guo, Rui; Lin, Bin; Wang, Xiao-Bo; Huang, Xiao-Xiao; Song, Shao-Jiang

2018-05-30

Four new dihydrobenzofuran neolignans 1a/1b and 2a/2b were isolated from the fruit of Rubus ideaus. 1a/1b and 2a/2b as two pairs of enantiomers were separated on a chiral chromatographic column. Their structures were determined using a suite of techniques including 1D and 2D NMR, HRESIMS, together with theoretical electronic circular dichroism (ECD) calculation. All compounds were evaluated for their inhibition of self-induced Aβ 1-42 aggregation. Compounds 1b and 2a exhibited optimal Aβ 1-42 aggregation inhibition capability, with an inhibition potency of 81.6% and 83.4% at 20 μM, respectively. Additionally, molecular docking was performed to identify the possible factor responsible for the enantioselectivity in the anti-Aβ 1-42 aggregation activity. Copyright © 2018 Elsevier Inc. All rights reserved.

Isoindolinone-containing meroterpenoids with α-glucosidase inhibitory activity from mushroom Hericium caput-medusae.

PubMed

Chen, Lin; Li, Zheng-Hui; Yao, Jian-Neng; Peng, Yue-Ling; Huang, Rong; Feng, Tao; Liu, Ji-Kai

2017-10-01

Hericium caput-medusae is an edible and medicinal mushroom closely relative to H. erinaceus. According to our detailed chemical investigation, two novel isoindolinone-containing meroterpene dimers, caputmedusins A (1) and B (2), as well as nine analogues, caputmedusins C-K (3-11), were isolated from the fermentation broth of H. caput-medusae. Their structures were elucidated by analyses of 1D and 2D NMR spectroscopic methods. The absolute configurations of 1-4 were speculated based on the specific optical rotation and biogenetic consideration. The absolute configurations of 10 and 11 were rationalized by the calculation of 1 H NMR chemical shifts. Caputmedusins A-C (1-3) showed moderate inhibitory activity against α-glucosidase with the IC 50 values of 39.2, 36.2 and 40.8μM, respectively. Copyright © 2017 Elsevier B.V. All rights reserved.

Development of Spiro[cyclopenta[1,2-b:5,4-b']dithiophene-4,9'-fluorene]-Based A-π-D-π-A Small Molecules with Different Acceptor Units for Efficient Organic Solar Cells.

PubMed

Wang, Wengong; Shen, Ping; Dong, Xinning; Weng, Chao; Wang, Guo; Bin, Haijun; Zhang, Jing; Zhang, Zhi-Guo; Li, Yongfang

2017-02-08

Three acceptor-π-donor-π-acceptor (A-π-D-π-A) small molecules (STFYT, STFRDN, and STFRCN) with spiro[cyclopenta[1,2-b:5,4-b']dithiophene-4,9'-fluorene] (STF) as the central donor unit, terthiophene as the π-conjugated bridge, indenedione, 3-ethylrhodanine, or 2-(1,1-dicyanomethylene)rhodanine as the acceptor unit are designed, synthesized, and characterized as electron donor materials in solution-processing organic solar cells (OSCs). The effects of the spiro STF-based central core and different acceptors on the molecular configuration, absorption properties, electronic energy levels, carrier transport properties, the morphology of active layers, and photovoltaic properties are investigated in detail. The three molecules exhibit desirable physicochemical features: wide absorption bands (300-850 nm) and high molar absorption coefficients (4.82 × 10 4 to 7.56 × 10 4 M -1 cm -1 ) and relatively low HOMO levels (-5.15 to -5.38 eV). Density functional theory calculations reveal that the spiro STF central core benefits to reduce the steric hindrance effect between the central donor block and terthiophene bridge and suppress excessive intermolecular aggregations. The optimized OSCs based on these molecules deliver power conversion efficiencies (PCEs) of 6.68%, 3.30%, and 4.33% for STFYT, STFRDN, and STFRCN, respectively. The higher PCE of STFYT-based OSCs should be ascribed to its better absorption ability, higher and balanced hole and electron mobilities, and superior active layer morphology as compared to the other two compounds. So far, this is the first example of developing the A-π-D-π-A type small molecules with a spiro central donor core for high-performance OSC applications. Meanwhile, these results demonstrate that using spiro central block to construct A-π-D-π-A molecule is an alternative and effective strategy for achieving high-performance small molecule donor materials.

Associations of maternal PLA2G4C and PLA2G4D polymorphisms with the risk of spontaneous preterm birth in a Chinese population

PubMed Central

Liu, Guang-Jian; He, Jian-Rong; Kuang, Ya-Shu; Fan, Xue-Jiao; Li, Wei-Dong; Lu, Jin-Hua; Xia, Xiao-Yan; Liu, Xiao-Dan; Chen, Nian-Nian; Mai, Wei-Bi; Xia, Hui-Min; Qiu, Xiu

2017-01-01

Preterm birth is the leading cause of mortality and morbidity in infants. Its etiology is multifactorial with genes and immune homeostasis. The authors investigated whether prostaglandin (PG) synthesis related single nucleotide polymorphisms (SNPs) PLA2G4C rs1366442 and PLA2G4D rs4924618 were associated with the risk of spontaneous preterm birth (SPTB) in a Chinese population of 114 cases of SPTB and 250 controls of term delivery. The risk associations were determined by odds ratios (ORs) and their 95% confidence intervals (CIs) calculated using multivariate logistic regression. Homology modeling was performed to elucidate potential mechanism of the SNP function. The maternal AT/TT genotype of PLA2G4D rs4924618 was associated with a reduced risk of SPTB (OR, 0.61; 95% CI, 0.37–0.99), while no significant association between PLA2G4C rs1366442 and SPTB risk was identified. Structure and sequence analysis revealed that the amino acid substitution introduced by this SNP located at the conserved central core of the catalytic domain of cytosolic phospholipase A2 δ and was close to the active site. These findings suggested that the polymorphism of PLA2G4D rs4924618 may have a protective influence on the SPTB susceptibility in a Chinese population, supporting a role for genetics in the association between PG synthesis and preterm birth. PMID:28440406

Single crystal EPR, optical absorption and superposition model study of Cr3+ doped ammonium dihydrogen phosphate.

PubMed

Kripal, Ram; Pandey, Sangita

2010-06-01

The electron paramagnetic resonance (EPR) studies are carried out on Cr(3+) ion doped ammonium dihydrogen phosphate (ADP) single crystals at room temperature. Four magnetically inequivalent sites for chromium are observed. No hyperfine structure is obtained. The crystal-field and spin Hamiltonian parameters are calculated from the resonance lines obtained at different angular rotations. The zero field and spin Hamiltonian parameters of Cr(3+) ion in ADP are calculated as: |D|=(257+/-2) x 10(-4) cm(-1), |E|=(79+/-2) x 10(-4) cm(-1), g=1.9724+/-0.0002 for site I; |D|=(257+/-2) x 10(-4) cm(-1), |E|=(77+/-2) x 10(-4) cm(-1), g=1.9727+/-0.0002 for site II; |D|=(259+/-2) x 10(-4) cm(-1), |E|=(78+/-2) x 10(-4) cm(-1), g=1.9733+/-0.0002 for site III; |D|=(259+/-2) x 10(-4) cm(-1), |E|=(77+/-2) x 10(-4) cm(-1), g=1.973+/-0.0002 for site IV, respectively. The site symmetry of Cr(3+) doped single crystal is discussed on the basis of EPR data. The Cr(3+) ion enters the lattice substitutionally replacing the NH(4)(+) sites. The optical absorption spectra are recorded in 195-925 nm wavelength range at room temperature. The energy values of different orbital levels are determined. On the basis of EPR and optical data, the nature of bonding in the crystal is discussed. The calculated values of Racah interelectronic repulsion parameters (B and C), cubic crystal-field splitting parameter (D(q)) and nephelauxetic parameters (h and k) are: B=640, C=3070, D(q)=2067 cm(-1), h=1.44 and k=0.21, respectively. ZFS parameters are also determined using B(kq) parameters from superposition model. Copyright 2010 Elsevier B.V. All rights reserved.

Initial clinical evaluation of PET-based ion beam therapy monitoring under consideration of organ motion

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

Kurz, Christopher, E-mail: christopher.kurz@physik.uni-muenchen.de; Bauer, Julia; Unholtz, Daniel

2016-02-15

Purpose: Intrafractional organ motion imposes considerable challenges to scanned ion beam therapy and demands for a thorough verification of the applied treatment. At the Heidelberg Ion-Beam Therapy Center (HIT), the scanned ion beam delivery is verified by means of postirradiation positron-emission-tomography (PET) imaging. This work presents a first clinical evaluation of PET-based treatment monitoring in ion beam therapy under consideration of target motion. Methods: Three patients with mobile liver lesions underwent scanned carbon ion irradiation at HIT and postirradiation PET/CT (x-ray-computed-tomography) imaging with a commercial scanner. Respiratory motion was recorded during irradiation and subsequent image acquisition. This enabled a time-resolvedmore » (4D) calculation of the expected irradiation-induced activity pattern and, for one patient where an additional 4D CT was acquired at the PET/CT scanner after treatment, a motion-compensated PET image reconstruction. For the other patients, PET data were reconstructed statically. To verify the treatment, calculated prediction and reconstructed measurement were compared with a focus on the ion beam range. Results: Results in the current three patients suggest that for motion amplitudes in the order of 2 mm there is no benefit from incorporating respiratory motion information into PET-based treatment monitoring. For a target motion in the order of 10 mm, motion-related effects become more severe and a time-resolved modeling of the expected activity distribution can lead to an improved data interpretation if a sufficient number of true coincidences is detected. Benefits from motion-compensated PET image reconstruction could not be shown conclusively at the current stage. Conclusions: The feasibility of clinical PET-based treatment verification under consideration of organ motion has been shown for the first time. Improvements in noise-robust 4D PET image reconstruction are deemed necessary to enhance the clinical potential.« less

Study on structural and spectral properties of isobavachalcone and 4-hydroxyderricin by computational method

NASA Astrophysics Data System (ADS)

Rong, Yuzhi; Wu, Jinhong; Liu, Xing; Zhao, Bo; Wang, Zhengwu

Isobavachalcone and 4-hydroxyderricin, two major chalcone constituents isolated from the roots of Angelica keiskei KOIDZUMI, exhibit numerous biological activities. Quantum chemical methods have been employed to investigate their structural and spectral properties. The ground state structures were optimized using density functional B3LYP method with 6-311G (d, p) basis set in both gas and solvent phases. Based on the optimized geometries, the harmonic vibrational frequency, the 1H and 13C nuclear magnetic resonance (NMR) chemical shift using the GIAO method were calculated at the same level of theory, with the aim of verifying the experimental values. Results reveal that B3LYP has been a good method to study their vibrational spectroscopic and NMR spectral properties of the two chalcones. The electronic absorption spectra were calculated using the time-dependent density functional theory (TDDFT) method. The solvent polarity effects were considered and calculated using the polarizable continuum model (PCM). Results also show that substitutions of different electron donating groups can alter the absorption properties and shift the spectra to a higher wavelength region.

Synthesis and biological activities of novel 5-substituted-1,3,4-oxadiazole Mannich bases and bis-Mannich bases as ketol-acid reductoisomerase inhibitors.

PubMed

Zhang, Yan; Liu, Xing-Hai; Zhan, Yi-Zhou; Zhang, Li-Yuan; Li, Zheng-Ming; Li, Yong-Hong; Zhang, Xiao; Wang, Bao-Lei

2016-10-01

A series of novel 5-substituted-1,3,4-oxadiazole Mannich bases and bis-Mannich bases have been conveniently synthesized in good yields. Their structures were characterized by IR, (1)H NMR, (13)C NMR and elemental analysis. The preliminary bioassay results indicated that some of the compounds showed promising in vitro fungicidal activities towards several test plant fungi; some of them exhibited significant herbicidal activities against Brassica campestris and excellent in vitro inhibitory activities against rice ketol-acid reductoisomerase (KARI). Among 14 novel compounds, 8c, 8d and 8m showed potent KARI inhibitory activities with Ki value of (0.96±0.42), (3.86±0.49) and (3.10±0.71) μmol/L, respectively, and were comparable with IpOHA. These compounds could be novel KARI inhibitors for further investigation. The density functional theory (DFT) calculations and molecular docking were carried out to study the structure-activity relationship (SAR) of the active inhibitors in this Letter. Copyright © 2016 Elsevier Ltd. All rights reserved.

IR, Raman and Vibrational Optical Activity Spectra of Methyl Glycidate in Chloroform and Water: The Clusters-in-a-Liquid Solvation Model.

PubMed

Xu, Yunjie; Perera, Angelo Shehan; Cheramy, Joseph; Merten, Christian; Thomas, Javix

2018-05-16

Solvent effects, in particular those involving water as the solvent, are of significant interest to chemistry and physics communities. IR, vibrational circular dichroism (VCD), Raman, and Raman optical activity (ROA) spectra of methyl glycidate in two very different solvents, namely CCl4 and water, have been measured experimentally and simulated theoretically. While the observed spectra in CCl4 could be well modelled using the polarizable continuum model for the solvent, the situation is much different in water. The experimental VCD spectrum of methyl glycidate in water reveals strong induced VCD signatures in the water bending region, indicating the presence of the relatively long-lived methyl glycidate-watern complexes. We applied the clusters-in-a-liquid approach to identify the dominant methyl glycidate-water1,2 complexes which are the long-lived species responsible for all the spectra observed in water. We examined the influences of solvent dielectric environment and the hydrogen-bonding interactions on the conformational distribution of methyl glycidate. The geometry optimizations, frequency calculations, IR, VCD, Raman and ROA intensity calculations were performed at the B3LYP/6-311++G(2d,p) and aug-cc-pVTZ levels of theory with D3BJ dispersion correction. It is particularly satisfying to note that the clusters-in-a-liquid approach has captured all main experimental features in IR, VCD, Raman and ROA spectra of methyl glycidate in water. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Trojan Horse cross section measurements and their impact on primordial nucleosynthesis

NASA Astrophysics Data System (ADS)

Pizzone, R. G.; Spartá, R.; Bertulani, C.; Spitaleri, C.; La Cognata, M.; Lamia, L.; Mukhamedzhanov, A.; Tumino, A.

2018-01-01

Big Bang Nucleosynthesis (BBN) nucleosynthesis requires several nuclear physics inputs and, among them, an important role is played by nuclear reaction rates. They are among the most important input for a quantitative description of the early Universe. An up-to-date compilation of direct cross sections of d(d,p)t, d(d,n)3He and 3He(d,p)4He reactions is given, being these ones among the most uncertain bare-nucleus cross sections. An intense experimental effort has been carried on in the last decade to apply the Trojan Horse Method (THM) to study reactions of relevance for the BBN and measure their astrophysical S(E)-factor. The result of these recent measurements is reviewed and compared with the available direct data. The reaction rates and the relative error for the four reactions of interest are then numerically calculated in the temperature ranges of relevance for BBN (0.01

Significant linkage disequilibrium between the Huntington disease gene and the loci D4S10 and D4S95 in the Dutch population

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

Skraastad, M.I.; Van de Vosse, E.; Belfroid, R.

1992-10-01

Significant linkage disequilibrium has been found between the Huntington disease (HD) gene and DNA markers located around D4S95 and D4S98. The linkage-disequilibrium studies favor the proximal location of the HD gene, in contrast to the conflicting results of recombination analyses. The authors have analyzed 45 Dutch HD families with 19 DNA markers and have calculated the strength of linkage disequilibrium. Highly significant linkage disequilibrium has been detected with D4S95, consistent with the studies in other populations. In contrast with most other studies, however, the area of linkage disequilibrium extends from D4S10 proximally to D4S95, covering 1,100 kb. These results confirmmore » that the HD gene most likely maps near D4S95. 28 refs., 1 fig., 2 tabs.« less

Real-Time 3-Dimensional Echocardiographic Assessment of Effective Regurgitant Orifice Area in Dogs With Myxomatous Mitral Valve Disease.

PubMed

Tidholm, A; Bodegård-Westling, A; Höglund, K; Häggström, J; Ljungvall, I

2017-03-01

Effective regurgitant orifice area (EROA), calculated from the vena contracta width (VCW) as the narrowest portion of the proximal regurgitant jet, might be used to estimate severity of mitral regurgitation. However, this simplified assumption only holds when the EROA is circular, which might not be true in dogs with myxomatous mitral valve disease (MMVD). Effective regurgitant orifice area in dogs with MMVD is noncircular, and using color Doppler real-time 3-dimensional (RT3D) echocardiography, measured EROA in the en face view will be significantly different from calculated EROA. Hundred and fifty-eight privately owned dogs with naturally occurring MMVD. Prospective observational study comparing en face view of EROA with calculated EROA using VCW in 4-chamber (4Ch) and 2-chamber (2Ch) view only or combined 4Ch and 2Ch views using RT3D echocardiography. The calculated EROA using the 2Ch view showed a systematic underestimation of 17% compared with the measured en face EROA corrected for body surface area. The calculated EROA using 4Ch and 4Ch + 2Ch views showed less agreement with the en face EROA, and the difference between methods increased with increasing EROA. The difference between calculated and measured EROA showed a systematic underestimation of the calculated EROA by 36% (4Ch) and 33% (4Ch + 2Ch), respectively, compared to measured en face EROA. When replacing measured EROA with calculated EROA using VCW measurements, the 2Ch view is preferred in dogs with MMVD. Copyright © 2017 The Authors. Journal of Veterinary Internal Medicine published by Wiley Periodicals, Inc. on behalf of the American College of Veterinary Internal Medicine.

SU-E-J-192: Verification of 4D-MRI Internal Target Volume Using Cine MRI

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

Lafata, K; Czito, B; Palta, M

Purpose: To investigate the accuracy of 4D-MRI in determining the Internal Target Volume (ITV) used in radiation oncology treatment planning of liver cancers. Cine MRI is used as the standard baseline in establishing the feasibility and accuracy of 4D-MRI tumor motion within the liver. Methods: IRB approval was obtained for this retrospective study. Analysis was performed on MR images from four patients receiving external beam radiation therapy for liver cancer at our institution. Eligible patients received both Cine and 4D-MRI scans before treatment. Cine images were acquired sagittally in real time at a slice bisecting the tumor, while 4D imagesmore » were acquired volumetrically. Cine MR DICOM headers were manipulated such that each respiratory frame was assigned a unique slice location. This approach permitted the treatment planning system (Eclipse, Varian Medical Systems) to recognize a complete respiratory cycle as a “volume”, where the gross tumor was contoured temporally. Software was developed to calculate the union of all frame contours in the structure set, resulting in the corresponding plane of the ITV projecting through the middle of the tumor, defined as the Internal Target Area (ITA). This was repeated for 4D-MRI, at the corresponding slice location, allowing a direct comparison of ITAs obtained from each modality. Results: Four patients have been analyzed. ITAs contoured from 4D-MRI correlate with contours from Cine MRI. The mean error of 4D values relative to Cine values is 7.67 +/− 2.55 %. No single ITA contoured from 4D-MRI demonstrated more than 10.5 % error compared to its Cine MRI counterpart. Conclusion: Motion management is a significant aspect of treatment planning within dynamic environments such as the liver, where diaphragmatic and cardiac activity influence plan accuracy. This small pilot study suggests that 4D-MRI based ITA measurements agree with Cine MRI based measurements, an important step towards clinical implementation. NIH 1R21CA165384-01A1.« less

The ozone acetylene reaction: concerted or non-concerted reaction mechanism? A quantum chemical investigation

NASA Astrophysics Data System (ADS)

Cremer, Dieter; Kraka, Elfi; Crehuet, Ramon; Anglada, Josep; Gräfenstein, Jürgen

2001-10-01

The ozone-acetylene reaction is found to proceed via an intermediate van der Waals complex (rather than a biradical), which is the precursor for a concerted symmetry-allowed [4+2] cycloaddition reaction leading to 1,2,3-trioxolene. CCSD(T)/6-311G+(2d, 2p) and CCSD(T)/CBS (complete basis set) calculations predict the ozone-acetylene van der Waals complex to be stable by 2.2 kcal mol -1, the calculated activation enthalpy for the cycloaddition reaction is 9.6 kcal mol -1 and the reaction enthalpy -55.5 kcal mol -1. Calculated kinetic data for the overall reaction ( k=0.8 l mol -1 s-1, A=1.71×10 6 l mol -1 s-1, E a=8.6 kcal mol -1) suggest that there is a need for refined kinetic measurements.

Quantum Tunneling in Testosterone 6β-Hydroxylation by Cytochrome P450: Reaction Dynamics Calculations Employing Multiconfiguration Molecular-Mechanical Potential Energy Surfaces

NASA Astrophysics Data System (ADS)

Zhang, Yan; Lin, Hai

2009-05-01

Testosterone hydroxylation is a prototypical reaction of human cytochrome P450 3A4, which metabolizes about 50% of oral drugs on the market. Reaction dynamics calculations were carried out for the testosterone 6β-hydrogen abstraction and the 6β-d1-testosterone 6β-duterium abstraction employing a model that consists of the substrate and the active oxidant compound I. The calculations were performed at the level of canonical variational transition state theory with multidimensional tunneling and were based on a semiglobal full-dimensional potential energy surface generated by the multiconfiguration molecular mechanics technique. The tunneling coefficients were found to be around 3, indicating substantial contributions by quantum tunneling. However, the tunneling made only modest contributions to the kinetic isotope effects. The kinetic isotope effects were computed to be about 2 in the doublet spin state and about 5 in the quartet spin state.

WWER-1000 core and reflector parameters investigation in the LR-0 reactor

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

Zaritsky, S. M.; Alekseev, N. I.; Bolshagin, S. N.

2006-07-01

Measurements and calculations carried out in the core and reflector of WWER-1000 mock-up are discussed: - the determination of the pin-to-pin power distribution in the core by means of gamma-scanning of fuel pins and pin-to-pin calculations with Monte Carlo code MCU-REA and diffusion codes MOBY-DICK (with WIMS-D4 cell constants preparation) and RADAR - the fast neutron spectra measurements by proton recoil method inside the experimental channel in the core and inside the channel in the baffle, and corresponding calculations in P{sub 3}S{sub 8} approximation of discrete ordinates method with code DORT and BUGLE-96 library - the neutron spectra evaluations (adjustment)more » in the same channels in energy region 0.5 eV-18 MeV based on the activation and solid state track detectors measurements. (authors)« less

Efficacy and safety of rectal 5-aminosalicylic acid versus corticosteroids in active distal ulcerative colitis: a systematic review and network meta-analysis

PubMed Central

Zhao, Xiaojing; Zhou, Changcheng; Ma, Jingjing; Zhu, Yunjuan; Sun, Min; Wang, Peixue; Zhang, Yi; Ma, Haiqin; Zhang, Hongjie

2017-01-01

Topical 5-aminosalicylic acid (5-ASA) and corticosteroids are used frequently in the treatment of active distal ulcerative colitis (UC). Our study aimed to determine the efficacy and safety of different topical drugs used to treat active distal UC. A random-effects model within a Bayesian framework was utilized to compare treatment effects and safety as odds ratios (ORs) with corresponding 95% credible intervals (CrI). The surface under the cumulative ranking area (SUCRA) and median rank (MR) with corresponding 95% CrI were calculated to rank the treatment outcomes. In the induction of clinical and endoscopic remission, most regimens showed significant advantages over placebo except topical budesonide 0.5 mg/d and hydrocortisone 100 mg/d. According to SUCRA and MR values, rectal 5-ASA 1.5 to 2.0 g/d + Beclomethasone dipropionate (BDP) 3 mg/d rendered the highest probability of being the best regimen to achieve clinical and endoscopic remission, followed by the separate use of 5-ASA 4 g/d and BDP 3 mg/d. The occurrence of adverse events was not significantly different between each treatments and placebo. In conclusion, the combined use of topical 5-ASA and BDP proved to be the best choice for active distal UC and further well-designed researches are warranted to assess its efficacy and safety. PMID:28440311

Molecular docking and 3D-QSAR studies on triazolinone and pyridazinone, non-nucleoside inhibitor of HIV-1 reverse transcriptase.

PubMed

Sivan, Sree Kanth; Manga, Vijjulatha

2010-06-01

Nonnucleoside reverse transcriptase inhibitors (NNRTIs) are allosteric inhibitors of the HIV-1 reverse transcriptase. Recently a series of Triazolinone and Pyridazinone were reported as potent inhibitors of HIV-1 wild type reverse transcriptase. In the present study, docking and 3D quantitative structure activity relationship (3D QSAR) studies involving comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) were performed on 31 molecules. Ligands were built and minimized using Tripos force field and applying Gasteiger-Hückel charges. These ligands were docked into protein active site using GLIDE 4.0. The docked poses were analyzed; the best docked poses were selected and aligned. CoMFA and CoMSIA fields were calculated using SYBYL6.9. The molecules were divided into training set and test set, a PLS analysis was performed and QSAR models were generated. The model showed good statistical reliability which is evident from the r2 nv, q2 loo and r2 pred values. The CoMFA model provides the most significant correlation of steric and electrostatic fields with biological activities. The CoMSIA model provides a correlation of steric, electrostatic, acceptor and hydrophobic fields with biological activities. The information rendered by 3D QSAR model initiated us to optimize the lead and design new potential inhibitors.

Synthesis of new 1,2,4-triazole compounds containing Schiff and Mannich bases (morpholine) with antioxidant and antimicrobial activities.

PubMed

Ünver, Yasemin; Deniz, Sadik; Çelik, Fatih; Akar, Zeynep; Küçük, Murat; Sancak, Kemal

2016-01-01

Compound 2 was synthesized by reacting CS 2 /KOH with compound 1. The treatment of compound 2 with hydrazine hydrate produced compound 3. Then, compound 3 was converted to Schiff bases (4a-d) by the handling with several aromatic aldehydes. The treatment of triazole compounds 4a-d containing Schiff base with morpholine gave compounds 5a-d. All compounds were tested for their antioxidant and antimicrobial activities. The antioxidant test results of DPPH• radical scavenging and ferric reducing/antioxidant power methods showed good antioxidant activity. The triazole-thiol (3) was the most active, and the effect of the substituent type of the thiophene ring on the activity was same for both Schiff bases (4a-d) and Mannich bases (5a-d). Among the newly synthesized triazole derivatives, the Schiff base 4d and the Mannich base 5d carrying nitro substituent on the thiophene ring showed promising antibacterial and antifungal activity, with lower MIC values than the standard antibacterial ampicillin.

Improvement of the 2D/1D Method in MPACT Using the Sub-Plane Scheme

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

Graham, Aaron M; Collins, Benjamin S; Downar, Thomas

Oak Ridge National Laboratory and the University of Michigan are jointly developing the MPACTcode to be the primary neutron transport code for the Virtual Environment for Reactor Applications (VERA). To solve the transport equation, MPACT uses the 2D/1D method, which decomposes the problem into a stack of 2D planes that are then coupled with a 1D axial calculation. MPACT uses the Method of Characteristics for the 2D transport calculations and P3 for the 1D axial calculations, then accelerates the solution using the 3D Coarse mesh Finite Dierence (CMFD) method. Increasing the number of 2D MOC planes will increase the accuracymore » of the alculation, but will increase the computational burden of the calculations and can cause slow convergence or instability. To prevent these problems while maintaining accuracy, the sub-plane scheme has been implemented in MPACT. This method sub-divides the MOC planes into sub-planes, refining the 1D P3 and 3D CMFD calculations without increasing the number of 2D MOC planes. To test the sub-plane scheme, three of the VERA Progression Problems were selected: Problem 3, a single assembly problem; Problem 4, a 3x3 assembly problem with control rods and pyrex burnable poisons; and Problem 5, a quarter core problem. These three problems demonstrated that the sub-plane scheme can accurately produce intra-plane axial flux profiles that preserve the accuracy of the fine mesh solution. The eigenvalue dierences are negligibly small, and dierences in 3D power distributions are less than 0.1% for realistic axial meshes. Furthermore, the convergence behavior with the sub-plane scheme compares favorably with the conventional 2D/1D method, and the computational expense is decreased for all calculations due to the reduction in expensive MOC calculations.« less

Atomic Data and Spectral Line Intensities for Ni XI

NASA Technical Reports Server (NTRS)

Bhatia, A. K.; Landi, E.

2010-01-01

Electron impact collision strengths, energy levels, oscillator strengths and spontaneous radiative decay rates are calculated for Ni XI. We include in the calculations the 10 lowest configurations, corresponding to 164 fine structure levels: 3s(sup 2)3p(sup 6), 3s(sup 2)3p(sup 5)3d, 3s(sup 2)3p(sup 4)3d(sup 2), 3s3p(sup 6)3d, 3s(sup 2)3p(sup 5)4l and 3s3p6 4l with l =.s, p, d. Collision strengths are calculated at five incident energies for all transitions: 7.1, 16.8, 30.2, 48.7 and 74.1 Ry above the threshold of each transition. An additional energy, very close to the transition threshold, has been added, whose value is between 0.06 Ry and 0.25 Ry depending on the lower level. Calculations have been carried out using the Flexible Atomic Code and the distorted wave approximation. Excitation rate coefficients are calculated as a function of electron temperature by assuming a Maxwellian electron velocity distribution. Using the excitation rate coefficients and the radiative transition rates of the present work, combined with Close Coupling collision excitation rate coefficient available in the literature for the lowest 17 levels, statistical equilibrium equations for level populations are solved at electron densities covering the 10(exp 8)-10(exp 14) cu cm range and at an electron temperature of logT(sub c)(K)=6.1, corresponding to the maximum abundance of Ni XI. Spectral line intensities are calculated, and their diagnostic relevance is discussed. This dataset will be made available in the next version of the CHIANTI database.

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

Shimohigashi, Y; Araki, F; Toya, R

Purpose: The purpose of this study was to evaluate the interfractional and intrafractional motion of liver tumors in stereotactic body radiation therapy (SBRT), based on four-dimensional cone-beam computed tomography using fiducial markers. (4D-CBCT). Methods: Seven patients with liver tumors were treated by SBRT with abdominal compression (AC) in five fractions with image guidance based on 4D-CBCT. The 4D-CBCT studies were performed to determine the individualized internal margin for the planning simulation. The interfractional and intrafractional changes of liver tumor motion for all patients was measured, based on the planning simulation 4D-CBCT, pre-SBRT 4D-CBCT, and post-SBRT 4D-CBCT. The interfractional motion changemore » was calculated from the difference in liver tumor amplitude on pre-SBRT 4D-CBCT relative to that of the planning simulation 4D-CBCT for each fraction. The intrafractional motion change was calculated from the difference between the liver tumor amplitudes of the pre- and post-SBRT 4D-CBCT for each fraction. Significant interfractional and intrafractional changes in liver tumor motion were defined as a change ≥3 mm. Statistical analysis was performed using the Pearson correlation. Results: The values of the mean amplitude of liver tumor, as indicated by planning simulation 4D-CBCT, were 1.6 ± 0.8 mm, 1.6 ± 0.9 mm, and 4.9 ± 2.2 mm in the left-right (LR), anterior-posterior (AP), and superior-inferior (SI) directions, respectively. Pearson correlation coefficients between the liver tumor amplitudes, based on planning simulation 4D-CBCT, and pre-SBRT 4D-CBCT during fraction treatment in the LR, AP, and SI directions were 0.6, 0.7, and 0.8, respectively. Interfractional and intrafractional motion changes of ≥3 mm occurred in 23% and 3% of treatment fractions, respectively. Conclusion: The interfractional and intrafractional changes of liver tumor motion were small in most patients who received liver SBRT with AC. In addition, planning simulation 4D-CBCT was useful for representing liver tumor movement in patients undergoing SBRT. This work was supported by JSPS KAKENHI Grant Number 26861004.« less

Evaluation of 3D Gamma index calculation implemented in two commercial dosimetry systems

NASA Astrophysics Data System (ADS)

Xing, Aitang; Arumugam, Sankar; Deshpande, Shrikant; George, Armia; Vial, Philip; Holloway, Lois; Goozee, Gary

2015-01-01

3D Gamma index is one of the metrics which have been widely used for clinical routine patient specific quality assurance for IMRT, Tomotherapy and VMAT. The algorithms for calculating the 3D Gamma index using global and local methods implemented in two software tools: PTW- VeriSoft® as a part of OCTIVIUS 4D dosimeter systems and 3DVHTM from Sun Nuclear were assessed. The Gamma index calculated by the two systems was compared with manual calculated for one data set. The Gamma pass rate calculated by the two systems was compared using 3%/3mm, 2%/2mm, 3%/2mm and 2%/3mm for two additional data sets. The Gamma indexes calculated by the two systems were accurate, but Gamma pass rates calculated by the two software tools for same data set with the same dose threshold were different due to the different interpolation of raw dose data by the two systems and different implementation of Gamma index calculation and other modules in the two software tools. The mean difference was -1.3%±3.38 (1SD) with a maximum difference of 11.7%.

Small-bowel absorption of D-tagatose and related effects on carbohydrate digestibility: an ileostomy study.

PubMed

Normén, L; Laerke, H N; Jensen, B B; Langkilde, A M; Andersson, H

2001-01-01

The ketohexose D-tagatose is a new sweetener with a low energy content. This low energy content may be due to either low absorption of the D-tagatose or decreased absorption of other nutrients. The aims of this study were to measure the excretion of D-tagatose from the human small bowel, to calculate the apparent absorption of D-tagatose, and to study the effects of D-tagatose on the small-bowel excretion of other carbohydrates. A controlled diet was served for 2 periods of 2 d during 3 consecutive weeks to 6 ileostomy subjects. In one of the periods, 15 g D-tagatose was added to the diet daily. Duplicate portions of the diet and ileostomy effluents were freeze-dried and analyzed to calculate the apparent net absorption of D-tagatose and carbohydrates. Median D-tagatose excretion was 19% (range: 12-31%), which corresponded to a calculated apparent absorption of 81% (69-88%). Of the total amount of D-tagatose excreted [2.8 g (1.7-4.4 g)], 60% (8-88%) was excreted within 3 h. Between 3 and 5 h, 32% (11-82%) was excreted. Excretion of wet matter increased by 41% (24-52%) with D-tagatose ingestion. Sucrose and D-glucose excretion increased to a small extent, whereas no significant changes were found in the excretion of dry matter, energy, starch, or D-fructose. The apparent absorption of 15 g D-tagatose/d was 81%. D-Tagatose had only a minor influence on the apparent absorption of other nutrients.

The role of defective silica surfaces in exogenous delivery of prebiotic compounds: clues from first principles calculations.

PubMed

Rimola, Albert; Ugliengo, Piero

2009-04-14

The reaction of glycine (Gly) with a strained (SiO)(2) four-membered ring defect (D2) at the surface of an interstellar silica grain dust has been studied at ONIOM2[B3LYP/6-31+G(d,p):MNDO] level within a cluster approach in the context of hypothetical reactions occurring in the interstellar medium. The D2 opens up exothermically for reaction with Gly (Delta(r)U(0)=-26.3 kcal mol(-1)) to give a surface mixed anhydride S(surf)-O-C([double bond, length as m-dash]O)-CH(2)NH(2) as a product. The reaction barriers, DeltaU( not equal)(0), are 0.1 and 10.4 kcal mol(-1) for reactive channels involving COOH and NH(2) as attacking groups, respectively. Calculations show the surface mixed anhydride to be rather stable under the action of interstellar processes, such as reactions with isolated H(2)O and NH(3) molecules or the exposure to cosmic rays and UV radiation. The hydrolysis of the surface mixed anhydride to release again Gly was modelled by microsolvation (from 1 to 4 H(2)O molecules) mimicking what could have happened to the interstellar dust after seeding the primordial ocean in the early Earth. Results for these calculations show that the reaction is exergonic and activated, the Delta(r)G(298) becoming more negative and the DeltaG( not equal)(298) being dramatically reduced as a function of increasing number of H(2)O molecules. The present results are relevant because they show that defects present at interstellar dust surfaces could have played a significant role in capturing, protecting and delivering essential prebiotic compounds on the early Earth.

Experimental and theoretical studies of (FT-IR, FT-Raman, UV-Visible and DFT) 4-(6-methoxynaphthalen-2-yl) butan-2-one.

PubMed

Govindasamy, P; Gunasekaran, S

2015-01-01

In this work, the vibrational spectral analysis was carried out by using FT-Raman and FT-IR spectroscopy in the range 4000-50 cm(-1) and 4000-450 cm(-1) respectively for 4-(6-methoxynaphthalen-2-yl) butan-2-one (abbreviated as 4MNBO) molecule. Theoretical calculations were performed by density functional theory (DFT/B3LYP) method using 6-311G(d,p) and 6-311++G(d,p) basis sets. The difference between the observed and calculated wavenumber value of most of the fundamentals were very small. The complete vibrational assignments of wavenumbers were made on the basis of potential energy distribution (PED). The UV-Vis spectrum was recorded in the methanol solution. The energy, wavelength and oscillator's strength were calculated by Time Dependent Density Functional Theory (TD-DFT) and matched to the experimental findings. The intramolecular contacts have been interpreted using natural bond orbital (NBO) and natural localized molecular orbital (NLMO) analysis. Thermodynamic properties of 4MNBO at different temperature have been calculated. The molecular electrostatic potential surface (MESP) and Frontier molecular orbital's (FMO's) analysis were investigated using theoretical calculations. Copyright © 2015 Elsevier B.V. All rights reserved.

Comparison of newer IOL power calculation methods for post-corneal refractive surgery eyes

PubMed Central

Wang, Li; Tang, Maolong; Huang, David; Weikert, Mitchell P.; Koch, Douglas D.

2015-01-01

Objective To compare the newer formulae, the optical coherence tomography based intraocular lens (IOL) power formula (OCT formula) and the Barrett True-K formula (True-K), to the methods on the ASCRS calculator in eyes with previous myopic LASIK/PRK. Design Prospective case series. Participants One-hundred and four eyes of 80 patients who had previous myopic LASIK/PRK and subsequent cataract surgery and IOL implantation. Methods Using the actual refraction following cataract surgery as target refraction, predicted IOL power for each method was calculated. The IOL prediction error (PE) was obtained by subtracting the predicted IOL power from the power of IOL implanted. Main outcome measures Arithmetic IOL PEs, variances of mean arithmetic IOL PE, median refractive PE and percent of eyes within 0.5 D and 1.0 D of refractive PE. Results OCT produced smaller variance of IOL PE than did Wang-Koch-Maloney, and Shammas (P<0.05). With the OCT, True-K No History, Wang-Koch-Maloney, Shammas, Haigis-L, and Average of these 5 formulas, respectively, the median refractive PEs were 0.35 D, 0.42 D, 0.51 D, 0.48 D, 0.39 D, and 0.35 D, and the % of eyes within 0.5 D of refractive PE were 68.3%, 58.7%, 50.0%, 52.9%, 55.8%, and 67.3%, and within 1.0 D of RPE, 92.3%, 90.4%, 86.9%, 88.5%, 90.4%, and 94.2%, respectively. The OCT formula had smaller refractive PE compared to Wang-Koch-Maloney and Shammas, and the Average approach produced significantly smaller refractive PE than did all methods except OCT (all P<0.05). Conclusions The OCT and True-K No History are promising formulas. The ASCRS IOL calculator has been updated to include the OCT and Barrett True K formulas. Trial registration Intraocular Lens Power Calculation After Laser Refractive Surgery Based on Optical Coherence Tomography (OCT IOL); Identifier: NCT00532051; www.ClinicalTrials.gov PMID:26459996

Synthesis, spectroscopic characterization (FT-IR, FT-Raman, and NMR), quantum chemical studies and molecular docking of 3-(1-(phenylamino)ethylidene)-chroman-2,4-dione.

PubMed

Avdović, Edina H; Milenković, Dejan; Dimitrić Marković, Jasmina M; Đorović, Jelena; Vuković, Nenad; Vukić, Milena D; Jevtić, Verica V; Trifunović, Srećko R; Potočňák, Ivan; Marković, Zoran

2018-04-15

The experimental and theoretical investigations of structure of the 3-(1-(phenylamino)ethylidene)-chroman-2,4-dione were performed. X-ray structure analysis and spectroscopic methods (FTIR and FT-Raman, 1 H and 13 C NMR), along with the density functional theory calculations (B3LYP functional with empirical dispersion corrections D3BJ in combination with the 6-311 + G(d,p) basis set), were used in order to characterize the molecular structure and spectroscopic behavior of the investigated coumarin derivative. Molecular docking analysis was carried out to identify the potency of inhibition of the title molecule against human's Ubiquinol-Cytochrome C Reductase Binding Protein (UQCRB) and Methylenetetrahydrofolate reductase (MTHFR). The inhibition activity was obtained for ten conformations of ligand inside the proteins. Copyright © 2018 Elsevier B.V. All rights reserved.

Sensomics-Based Molecularization of the Taste of Pot-au-Feu, a Traditional Meat/Vegetable Broth.

PubMed

Kranz, Maximilian; Viton, Florian; Smarrito-Menozzi, Candice; Hofmann, Thomas

2018-01-10

Targeted quantification of 49 basic taste-active molecules, followed by the calculation of dose-over-threshold (DoT) factors, and taste re-engineering experiments revealed minerals, nucleotides/nucleosides, amino acids, organic acids, and carbohydrates as the key compounds of Pot-au-Feu, a traditional broth preparation from beef cuts and vegetables. Moreover, the dipeptide carnosine was identified to be the key inducer for the white-meaty and thick-sour orosensation of the broth, next to anserine and 1-deoxy-d-fructosyl-N-β-alanyl-l-histidine, the latter of which has been identified for the first time by means of a sensory-guided fractionation. Sensory studies revealed the threshold concentration of carnosine in model broth to decrease by a factor of 5 upon nonenzymatic glycosylation to reach 4.4 mmol/L for its Amadori product 1-deoxy-d-fructosyl-N-β-alanyl-l-histidine.

A New N-methoxypyridone from the Co-Cultivation of Hawaiian Endophytic Fungi Camporesia sambuci FT1061 and Epicoccum sorghinum FT1062.

PubMed

Li, Chunshun; Sarotti, Ariel M; Yang, Baojun; Turkson, James; Cao, Shugeng

2017-07-12

A new N -methoxypyridone analog ( 1 ), together with four known compounds, was isolated from the co-culture of Hawaiian endophytic fungi Camporesia sambuci FT1061 and Epicoccum sorghinum FT1062. The structure of the new compound was elucidated as 11 S -hydroxy-1-methoxyfusaricide ( 1 ) by extensive spectroscopic analysis and comparison with the literature. The absolute configuration of 1 was determined by comparison with the experimental and calculated ECD spectra. The absolute configuration of compound 3 was investigated and renamed as (+)-epipyridone by comparison of the optical rotation and CD spectrum with those of 1 . The other known compounds were identified as epicoccarine B ( 2 ), D8646-2-6 ( 4 ), and iso-D8646-2-6 ( 5 ). Compounds 4 and 5 showed modest inhibitory activity towards pathogenic fungi. Epicoccarine B ( 2 ) inhibited A2780 and TK-10 with an IC 50 value of 22 μM.

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

Spiegel, G.W.

The kinetic solvent isotope effect, KSIE, (k/sub H/sub 2/O//k/sub D/sub 2/O/), at 25.0/sup 0/C and ionic strength, I, equal to 0.20 +- 0.02 M was measured for the nucleophilic displacement of iodine ion from iodomethane, iodoacetamide, and iodoacetate ion, thiophene from S-Methylthiophenium ion, and tosylate ion from methyl tosylate by bromide ion, chloride ion, acetate ion, hydroxide ion, water, ammonia, ethylenediamine, n-butylamine, piperazine, piperidine, quinuclidine, and 1,4-Diazabicyclo(2.2.2)octane (DABCO), and the monoprotonated cations of ethylenediamine, piperazine, and DABCO. By means of solvent partition measurements at 25.0/sup 0/C and I = 0.02 M between H/sub 2/O and D/sub 2/O and a commonmore » immiscible organic solvent, the ground state activity coefficients in D/sub 2/O, the solution in H/sub 2/O being chosen as the reference state, were determined for the nitrogen-containing nucleophiles (except ammonia) and the substrates methyl tosylate, iodoacetamide, and iodoacetic acid. The solubilities at 25.0/sup 0/C of the picrate and tetraphenylborate salts of the monoprotonated cationic forms of ethylenediamine, piperazine, and DABCO were measured to determine the activity coefficients in D/sub 2/O of these ions relative to an H/sub 2/O reference state. Applying the Eyring equation, the activity coefficients of the transition states in D/sub 2/O, reference state H/sub 2/O, were calculated.« less

Reticulocytes bearing C4d as biomarkers of disease activity for systemic lupus erythematosus.

PubMed

Liu, Chau-Ching; Manzi, Susan; Kao, Amy H; Navratil, Jeannine S; Ruffing, Margie J; Ahearn, Joseph M

2005-10-01

There is an urgent need for biomarkers with which to monitor disease activity in patients with systemic lupus erythematosus (SLE). We recently showed that abnormal levels of C4d, an activation-derived fragment of complement component C4, are deposited on the surface of erythrocytes from patients with SLE. This study focused on reticulocytes, the youngest and shortest-lived erythrocytes (lifespan 24-48 hours), with the objective of testing our hypothesis that when reticulocytes emerge from the bone marrow, they are immediately exposed to and acquire C4d at levels proportionate to the extent of complement activation at that time, thereby reflecting disease activity in SLE. We conducted a cross-sectional study of 156 patients with SLE, 140 patients with other diseases, and 159 healthy controls. Levels of C4d on the surface of reticulocytes were examined using a 2-color flow cytometric assay. The results were analyzed for correlations with SLE disease activity. A wide range of increased levels of reticulocyte C4d was specifically detected in SLE patients. These levels fluctuated in SLE patients and correlated with clinical disease activity, as determined by the Safety of Estrogens in Lupus Erythematosus: National Assessment (SELENA) version of the Systemic Lupus Erythematosus Disease Activity Index (SLEDAI) and the Systemic Lupus Activity Measure (SLAM). Specifically, in cross-sectional analyses, patients with reticulocyte C4d levels in the highest quartile compared with those in the lowest quartile had significantly higher SELENA-SLEDAI (P = 0.00002) and SLAM (P = 0.02) scores. Longitudinal observation demonstrated that the reticulocyte C4d levels changed in relation to the clinical course in individual patients. These findings support our hypothesis that C4d-bearing reticulocytes may serve as biomarkers of disease activity in patients with SLE.

Retinoic acid prevents immunogenicity of milk lipocalin Bos d 5 through binding to its immunodominant T-cell epitope.

PubMed

Hufnagl, Karin; Ghosh, Debajyoti; Wagner, Stefanie; Fiocchi, Alessandro; Dahdah, Lamia; Bianchini, Rodolfo; Braun, Nina; Steinborn, Ralf; Hofer, Martin; Blaschitz, Marion; Roth, Georg A; Hofstetter, Gerlinde; Roth-Walter, Franziska; Pacios, Luis F; Jensen-Jarolim, Erika

2018-01-25

The major cow's milk allergen Bos d 5 belongs to the lipocalin protein family, with an intramolecular pocket for hydrophobic ligands. We investigated whether Bos d 5 when loaded with the active vitamin A metabolite retinoic acid (RA), would elicit differential immune responses compared to the unloaded state. By in silico docking an affinity energy of -7.8 kcal/mol was calculated for RA into Bos d 5. Loading of RA to Bos d 5 could be achieved in vitro, as demonstrated by ANS displacement assay, but had no effect on serum IgE binding in tolerant or challenge-positive milk allergic children. Bioinformatic analysis revealed that RA binds to the immunodominant T-cell epitope region of Bos d 5. In accordance, Bos d 5 significantly suppressed the CD3+ CD4+ cell numbers, proliferative response and IL-10, IL-13 and IFN-γ secretion from stimulated human PBMCs only when complexed with RA. This phenomenon was neither associated with apoptosis of T-cells nor with the activation of Foxp3+ T-cells, but correlated likely with enhanced stability to lysosomal digestion due to a predicted overlap of Cathepsin S cleavage sites with the RA binding site. Taken together, proper loading of Bos d 5 with RA may suppress its immunogenicity and prevent its allergenicity.

Validation of the Arizona Activity Frequency Questionnaire using doubly labeled water.

PubMed

Staten, L K; Taren, D L; Howell, W H; Tobar, M; Poehlman, E T; Hill, A; Reid, P M; Ritenbaugh, C

2001-11-01

Physical activity questionnaires (PAQs) are considered the most cost-efficient method to estimate total energy expenditure (TEE) in epidemiological studies. However, relatively few PAQs have been validated using doubly labeled water (DLW) in women or in samples with diverse ethnic backgrounds. This study was conducted to validate the Arizona Activity Frequency Questionnaire (AAFQ) for estimation of TEE and physical activity energy expenditure (PAEE) over 1 month using DLW as a reference method. Thirty-five relatively sedentary women completed the AAFQ before participating in an 8-d DLW protocol to measure TEE. TEE and PAEE were estimated from the AAFQ by calculating resting metabolic rate (RMR) using the equation of Mifflin et al. (AAFQmif), by measuring RMR using indirect calorimetry (AAFQic), and using MET conversion (AAFQmet). A predictive equation for TEE was generated. The mean +/- SD for TEE and PAEE from DLW were 9847 +/- 2555 kJ x d(-1) and 5578 +/- 2084 kJ x d(-1), respectively. Formulas using RMR to calculate the TEE and PAEE from the AAFQ tended to underestimate TEE and PAEE, whereas those that included only weight tended to overestimate TEE and PAEE. On the basis of the Mifflin et al. equation, the AAFQ tends to underestimate PAEE by 13%. This underestimation may be explained by the low lean body mass of the sample population and by effectiveness of the METs/RMR ratio in the obese. The following predictive equation was calculated: TEE (kJ x d(-1)) = (86.0 * average total daily METs) + (2.23 * RMRmif) - 6726. When the predictive equation is used, TEE calculated from the AAFQ is highly correlated with DLW TEE (adjusted r(2) = 0.70, P < 0.001). The AAFQ is an effective tool for the prediction of TEE and PAEE in epidemiological studies.

Study on the structure, vibrational analysis and molecular docking of fluorophenyl derivatives using FT-IR and density functional theory computations

NASA Astrophysics Data System (ADS)

Al-Tamimi, Abdul-Malek S.; Mary, Y. Sheena; Hassan, Hanan M.; Resmi, K. S.; El-Emam, Ali A.; Narayana, B.; Sarojini, B. K.

2018-07-01

The density functional calculations were performed at the B3LYP/6-311++G (5D, 7F) level to find the geometrical parameters, vibrational wavenumbers and various molecular properties of three fluorophenyl derivatives, methyl 4,4″-difluoro-5‧-methoxy-1,1':3‧,1″-terphenyl-4‧-carboxylate (MDFMTPC), 2,2'-(disulfanediyl)bis[4,6-(4-fluorophenyl)pyrimidine] (DFFPPY) and (6Z)-3,5‧-bis(4-fluorophenyl)-6-(1-hydroxyethylidene)cyclohex-2-en-1-one (FPHYCY). The phenyl ring Csbnd C, Cdbnd O and Csbnd H stretching modes produces VCD spectrum and these modes are efficient configuration markers. Using natural bond orbital analysis the stability of the molecules due to hyper-conjugative interactions were discussed. From the HOMO and LUMO energies, the chemical descriptors are compared for the title compounds. The first hyperpolarizabilities of MDFMTPC, DFFPPY and FPHYCY are respectively, 41.08, 69.27 and 38.38 times that of urea. Molar refractivity values are increasing in the order, FPHYCY > MDFMTPC > DFFPPY and this is responsible for the binding nature of the molecular assembly and can be used for the cure of different diseases. PASS analysis of the title compounds predicts chlordecone reductase inhibitor activity for MDFMTPC, thioredoxin inhibitor activity for DFFPPY and testosterone 17beta-dehydrogenase (NADP+) inhibitor activity for FPHYCY. Docking studies reveal that MDFMTPC, DFFPPY and FPHYCY can be lead compounds for developing new anti-cancerous, anti-tumor, prostate cancer drugs. Using Hirshfeld surface and 2D-finger print plots, the type and nature of intermolecular interactions were reported.

New Accurate Oscillator Strengths and Electron Excitation Collision Strengths for N I

NASA Astrophysics Data System (ADS)

Tayal, S. S.

2006-03-01

The nonorthogonal orbitals technique in a multiconfiguration Hartree-Fock approach is used to calculate oscillator strengths and transition probabilities of N I lines. The relativistic effects are allowed by means of Breit-Pauli operators. The length and velocity forms of oscillator strengths show good agreement for most transitions. The B-spline R-matrix with pseudostates approach has been used to calculate electron excitation collision strengths and rates. The nonorthogonal orbitals are used for an accurate description of both target wave functions and the R-matrix basis functions. The 24 spectroscopic bound and autoionizing states together with 15 pseudostates are included in the close-coupling expansion. The collision strengths for transitions between fine-structure levels are calculated by transforming the LS-coupled K-matrices to K-matrices in an intermediate coupling scheme. Thermally averaged collision strengths have been determined by integrating collision strengths over a Maxwellian distribution of electron energies over a temperature range suitable for the modeling of astrophysical plasmas. The oscillator strengths and thermally averaged collision strengths are presented for transitions between the fine-structure levels of the 2s22p3 4So, 2Do, 2Po, 2s2p4 4P, 2s22p23s 4P, and 2P terms and from these levels to the levels of the 2s22p23p 2So, 4Do, 4Po, 4So, 2Do, 2Po, 2s22p23s 2D, 2s22p24s 4P, 2P, 2s22p23d 2P, 4F, 2F, 4P, 4D, and 2D terms. Thermally averaged collision strengths are tabulated over a temperature range from 500 to 50,000 K.

Low second to fourth digit ratio in Dupuytren disease.

PubMed

Yokoi, Takuya; Uemura, Takuya; Kazuki, Kenichi; Onode, Ema; Shintani, Kosuke; Okada, Mitsuhiro; Nakamura, Hiroaki

2017-08-01

The ratio of the lengths of the second and fourth digits (2D:4D) has been described as reflecting endogenous prenatal androgen exposure. In general, 2D:4D is lower in men than in women and has potential as a biomarker or predictor for various diseases, athletic ability, and academic performance. Dupuytren disease has digital flexion contractures and is known to predominate in men, but the pathogenesis of the disease remains unclear. To clarify the relationships between Dupuytren disease and endogenous androgens, we performed a retrospective analysis of hand radiographs to investigate 2D:4D in Dupuytren disease. The study included male patients with Dupuytren disease (n = 22) and a control group (n = 18) of male patients with carpal tunnel syndrome. Only unaffected hands, without contractures or osteoarthritis, were evaluated for the purpose of radiographic assessment. The lengths of the phalanx and metacarpal bones in the second and fourth digits were measured by 2 independent observers who each performed 2 sets of measurements separated by a minimum 1-week interval. The 2D:4D was calculated separately for the phalanges and metacarpals, and a combined (phalanx + metacarpal) 2D:4D was also calculated. The reliability of the observer measurements was established using the intraclass correlation coefficient, and both the intra- and interobserver reliability showed excellent agreement. We found that compared with control group, the Dupuytren disease group had significantly lower phalanx and combined 2D:4D. These findings suggest that endogenous prenatal androgens could contribute to the development of Dupuytren disease, leading to its characteristic clinical presentation predominantly in men and affecting the ulnar rays.

ANITA-2000 activation code package - updating of the decay data libraries and validation on the experimental data of the 14 MeV Frascati Neutron Generator

NASA Astrophysics Data System (ADS)

Frisoni, Manuela

2016-03-01

ANITA-2000 is a code package for the activation characterization of materials exposed to neutron irradiation released by ENEA to OECD-NEADB and ORNL-RSICC. The main component of the package is the activation code ANITA-4M that computes the radioactive inventory of a material exposed to neutron irradiation. The code requires the decay data library (file fl1) containing the quantities describing the decay properties of the unstable nuclides and the library (file fl2) containing the gamma ray spectra emitted by the radioactive nuclei. The fl1 and fl2 files of the ANITA-2000 code package, originally based on the evaluated nuclear data library FENDL/D-2.0, were recently updated on the basis of the JEFF-3.1.1 Radioactive Decay Data Library. This paper presents the results of the validation of the new fl1 decay data library through the comparison of the ANITA-4M calculated values with the measured electron and photon decay heats and activities of fusion material samples irradiated at the 14 MeV Frascati Neutron Generator (FNG) of the NEA-Frascati Research Centre. Twelve material samples were considered, namely: Mo, Cu, Hf, Mg, Ni, Cd, Sn, Re, Ti, W, Ag and Al. The ratios between calculated and experimental values (C/E) are shown and discussed in this paper.

4D dose calculation and delivery with interplay effects between respiratory motion and uniform scanning proton beam

NASA Astrophysics Data System (ADS)

Zhao, Qingya

2011-12-01

Proton radiotherapy has advantages to deliver accurate high conformal radiation dose to the tumor while sparing the surrounding healthy tissue and critical structures. However, the treatment effectiveness is degraded greatly due to patient free breathing during treatment delivery. Motion compensation for proton radiotherapy is especially challenging as proton beam is more sensitive to the density change along the beam path. Tumor respiratory motion during treatment delivery will affect the proton dose distribution and the selection of optimized parameters for treatment planning, which has not been fully addressed yet in the existing approaches for proton dose calculation. The purpose of this dissertation is to develop an approach for more accurate dose delivery to a moving tumor in proton radiotherapy, i.e., 4D proton dose calculation and delivery, for the uniform scanning proton beam. A three-step approach has been carried out to achieve this goal. First, a solution for the proton output factor calculation which will convert the prescribed dose to machine deliverable monitor unit for proton dose delivery has been proposed and implemented. The novel sector integration method is accurate and time saving, which considers the various beam scanning patterns and treatment field parameters, such as aperture shape, aperture size, measuring position, beam range, and beam modulation. Second, tumor respiratory motion behavior has been statistically characterized and the results have been applied to advanced image guided radiation treatment. Different statistical analysis and correlation discovery approaches have been investigated. The internal / external motion correlation patterns have been simulated, analyzed, and applied in a new hybrid gated treatment to improve the target coverage. Third, a dose calculation method has been developed for 4D proton treatment planning which integrates the interplay effects of tumor respiratory motion patterns and proton beam delivery mechanism. These three steps provide an innovative integrated framework for accurate 4D proton dose calculation and treatment planning for a moving tumor, which extends the functionalities of existing 3D planning systems. In short, this dissertation work addresses a few important problems for effective proton radiotherapy to a moving target. The outcomes of the dissertation are very useful for motion compensation with advanced image guided proton treatment.

Actual and Idealized Crystal Field Parameterizations for the Uranium Ions in UF 4

NASA Astrophysics Data System (ADS)

Gajek, Z.; Mulak, J.; Krupa, J. C.

1993-12-01

The crystal field parameters for the actual coordination symmetries of the uranium ions in UF 4, C2 and C1, and for their idealizations to D2, C2 v , D4, D4 d , and the Archimedean antiprism point symmetries are given. They have been calculated by means of both the perturbative ab initio model and the angular overlap model and are referenced to the recent results fitted by Carnall's group. The equivalency of some different sets of parameters has been verified with the standardization procedure. The adequacy of several idealized approaches has been tested by comparison of the corresponding splitting patterns of the 3H 4 ground state. Our results support the parameterization given by Carnall. Furthermore, the parameterization of the crystal field potential and the splitting diagram for the symmetryless uranium ion U( C1) are given. Having at our disposal the crystal field splittings for the two kinds of uranium ions in UF 4, U( C2) and U( C1), we calculate the model plots of the paramagnetic susceptibility χ( T) and the magnetic entropy associated with the Schottky anomaly Δ S( T) for UF 4.

Evaluation of methods to assess physical activity in free-living conditions.

PubMed

Leenders, N Y; Sherman, W M; Nagaraja, H N; Kien, C L

2001-07-01

The purpose of this study was to compare different methods of measuring physical activity (PA) in women by the doubly labeled water method (DLW). Thirteen subjects participated in a 7-d protocol during which total daily energy expenditure (TDEE) was measured with DLW. Body composition, basal metabolic rate (BMR), and peak oxygen consumption were also measured. Physical activity-related energy expenditure (PAEE) was then calculated by subtracting measured BMR and the estimated thermic effect of food from TDEE. Simultaneously, over the 7 d, PA was assessed via a 7-d Physical Activity Recall questionnaire (PAR), and subjects wore secured at the waist, a Tritrac-R3D (Madison, WI), a Computer Science Application Inc. activity monitor (CSA; Shalimar, FL), and a Yamax Digi Walker-500 (Tokyo, Japan). Pearson-product moment correlations were calculated to determine the relationships among the different methods for estimating PAEE. Paired t-tests with appropriate adjustments were used to compare the different methods with DLW-PAEE. There was no significant difference between PAEE determined from PAR and DLW. The differences between the two methods ranged from -633 to 280 kcal.d(-1). Compared with DLW, PAEE determined from CSA, Tritrac, and Yamax was significantly underestimated by 59% (-495 kcal.d(-1)), 35% (-320 kcal.d(-1)) and 59% (-497 kcal.d(-1)), respectively. VO2peak explained 43% of the variation in DLW-PAEE. Although the group average for PAR-PAEE agreed with DLW-PAEE, there were differences in the methods among the subjects. PAEE determined by Tritrac, CSA, and Yamax significantly underestimate free-living PAEE in women.

Salivary anti-coxsackievirus-B4 neutralizing activity and pattern of immune parameters in patients with type 1 diabetes: a pilot study.

PubMed

Nekoua, Magloire Pandoua; Yessoufou, Akadiri; Alidjinou, Enagnon Kazali; Badia-Boungou, Francis; Moutairou, Kabirou; Sane, Famara; Hober, Didier

2018-05-17

Enteroviruses, especially coxsackieviruses B (CV-B), have been associated with the pathogenesis of type 1 diabetes (T1D). An anti-CV-B4 neutralizing activity in saliva of T1D patients was previously reported. Our aim was to study the association between the saliva anti-CV-B4 neutralizing activity and immune parameters in T1D patients in comparison with non-diabetic individuals. Saliva and blood samples were collected from 15 T1D patients and 8 controls. The anti-CV-B4 and anti-poliovirus type 1 (PV-1) activities of saliva and serum samples were determined by a plaque neutralization assay. Quantification of serum cytokines was performed by ELISA and the frequencies of lymphocyte subsets were evaluated using flow cytometry. The levels of salivary anti-CV-B4 neutralizing activity were higher in T1D patients than in controls (p = 0.02), whereas the serum levels of anti-CV-B4 neutralizing activity and the saliva and serum levels of anti-PV-1 neutralizing activity were not different. The proportions of effector CD4 + T cells and CD19 + B cells, but not those of CD4 + T cells, CD8 + T cells and Foxp3 + regulatory T cells, were higher in T1D patients than in controls (p = 0.02 and p = 0.01 respectively). Moreover, serum IFN-γ levels were lower in T1D patients compared to controls (p = 0.03) while IL-4 and IL-10 were not different. There was an association between saliva anti-CV-B4 activity, down-regulation of IFN-γ and B cell expansion in peripheral blood of T1D patients. The association between saliva anti-CV-B4 activity and disturbance of immune system in T1D patients deserves further investigation.

Boosting Up Performance of Inverted Photovoltaic Cells from Bis(alkylthien-2-yl)dithieno[2,3-d:2',3'-d']benzo[1,2-b:4',5'-b']di thiophene-Based Copolymers by Advantageous Vertical Phase Separation.

PubMed

Guo, Pengzhi; Luo, Guoping; Su, Qiang; Li, Jianfeng; Zhang, Peng; Tong, Junfeng; Yang, Chunyan; Xia, Yangjun; Wu, Hongbin

2017-03-29

The photovoltaic cells (PVCs) from conjugated copolymers of PDTBDT-BT and PDTBDT-FBT with 5,10-bis(4,5-didecylthien-2-yl)dithieno[2,3-d:2',3'-d']benzo[1,2-b:4,5-b']dithiophene as electron donor moieties and benzothiadiazole and/or 5,6-difluorobenzothiadiazole as electron acceptor moieties are optimized by employing alcohol-soluble PFN (poly(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)) as cathode modification interlayer. The power conversion efficiencies (PCEs) of inverted PVCs (i-PVCs) from PDTBDT-BT and PDTBDT-FBT with devices configuration as ITO/PFN/active layer/MoO 3 /Ag are increased from 4.97% to 8.54% and 5.92% to 8.74%, in contrast to those for the regular PVCs (r-PVCs) with devices configuration as ITO/PEDOT:PSS/active layer/Ca/Al under 100 mW/cm 2 AM 1.5 illumination. The optical modeling calculations and X-ray photoelectron spectroscopy (XPS) investigations reveal that the r-PVCs and i-PVCs from the copolymers exhibit similar light harvesting characteristics, and the enhancements of the PCEs of the i-PVCs from the copolymers are mainly contributed to the favorable vertical phase separation as the strongly polymer-enriched top surface layers and slightly PC 71 BM (phenyl-C 71 -butyric acid methyl ester)-enriched bottom surface layers are correspondingly connected to the anodes and cathodes of the i-PVCs, while they are opposite in the r-PVCs. As we known, it is the first time to experimentally verify that the i-PVCs with alcohol-soluble conjugated polymers cathode modification layers enjoy favorable vertical phase separation.

Development of radiopaque, biocompatible, antimicrobial, micro-particle fillers for micro-CT imaging of simulated periodontal pockets.

PubMed

Elashiry, M; Meghil, M M; Kalathingal, S; Buchanan, A; Rajendran, M; Elrefai, R; Ochieng, M; Elawady, A; Arce, R M; Sandhage, K H; Cutler, C W

2018-04-01

Approximately 10 9 bacteria can be harbored within periodontal pockets (PP) along with inflammatory byproducts implicated in the pathophysiology of systemic diseases linked to periodontitis (PD). Calculation of this inflammatory burden has involved estimation of total pocket surface area using analog data from conventional periodontal probing which is unable to determine the three-dimensional (3-D) nature of PP. The goals of this study are to determine the radiopacity, biocompatibility, and antimicrobial activity of transient micro-particle fillers in vitro and demonstrate their capability for 3-D imaging of artificial PP (U.S. Patent publication number: 9814791 B2). Relative radiopacity values of various metal oxide fillers were obtained from conventional radiography and micro-computed tomography (μCT) using in vitro models. 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assays were used to measure the biocompatibility of calcium tungstate (CaWO 4 ) particles by determination of viable keratinocytes percentage (%) after exposure. After introducing an antibacterial compound (K21) to the radiopaque agent, antimicrobial tests were conducted using Porphyromonas gingivalis (P. gingivalis) and Streptococcus gordonii (S. gordonii) strains and blood agar plates. CaWO 4 micro-particle-bearing fillers exhibited an X-ray radiopacity distinct from tooth structures that enabled 3-D visualization of an artificial periodontal pocket created around a human tooth. MTT assays indicated that CaWO 4 micro-particles are highly biocompatible (increasing the viability of exposed keratinocytes). Radiopaque micro-particle fillers combined with K21 showed significant antimicrobial activity for P. gingivalis and S. gordonii. The plausibility of visualizing PP with 3-D radiographic imaging using new radiopaque, biocompatible, transient fillers was demonstrated in vitro. Antibacterial (or other) agents added to this formula could provide beneficial therapeutic features along with the diagnostic utility. Published by Elsevier Ltd.

[Linguistic validation of the "Brief Index of Sexual Functioning for Women"].

PubMed

Baudelot-Berrogain, Nathalie; Roquejoffre, Stéphanie; Gamé, Xavier; Mallet, Richard; Mouzin, Marc; Bertrand, Nicolas; Plante, Pierre; Sarramon, Jean-Pierre; Rischmann, Pascal; Malavaud, Bernard

2006-04-01

Application to the study of sexuality in a population of 93 French women. This study was designed to linguistically validate the French version of the BISF-W (Brief Index of Sexual Functioning for Women) which provides a quantitative and qualitative assessment of female sexuality according to 7 dimensions. This version was then used to study the impact of recognized factors of sexual dysfunction on a control population. The BISF-W a self-administered quality of life questionnaire developed by Rosen, was translated and linguistically validated. This questionnaire comprises 22 questions in 7 dimensions investigating all aspects of female sexuality: D1 (desire), D2 (arousal), D3 (frequency of sexual activity), D4 (receptiveness), 05 (pleasure, orgasm), D6 (relational satisfaction), D7 (problems affecting sexuality), Composite Score (CS) D1+D2+D3+D4+D5+D6+07. The French version was administered to a study population of 93 women: 49 derived from gynaecology or urology departments and 44 derived from the general population. We calculated and compared the scores of the various dimensions of the BISF-W according to factors able to modify sexuality, such as menopause, age or parity. The results of our study show an alteration of the various dimensions of sexuality in elderly patients (D2, D5, D6, CS; p<0.05) or postmenopausal patients (D2, D5, D6, CS, p<0.05) and in multiparous women. The French version of the BISF-W gives results in line with the literature and demonstrates changes of sexuality as a function of the above mentioned variables.

Structure and dynamics of ND3BF3 in the solid and gas phases: a combined NMR, neutron diffraction, and Ab initio study.

PubMed

Penner, Glenn H; Ruscitti, Bruno; Reynolds, Julie; Swainson, Ian

2002-12-30

The decrease in D-->A bond lengths, previously reported for some Lewis acid/base complexes, in going from the gas to the solid phases is investigated by obtaining an accurate crystal structure of solid ND(3)BF(3) by powder neutron diffraction. The B-N internuclear distance is 1.554(3) A, 0.118 A shorter than the most recent gas-phase microwave value and 0.121 A shorter than the single molecule geometry optimized (1.672 A, CISD/6-311++G(d,p)) bond length. The crystal structure also shows N-D.F-B hydrogen bonds. The effects of this change in structure and of intermolecular hydrogen-bonding on nuclear magnetic shielding (i.e., chemical shifts) and the nuclear quadrupolar coupling constants (QCC) are investigated by ab initio molecular orbital and density functional theory calculations. These calculations show that the nitrogen ((15)N and (14)N) and boron ((11)B and (10)B) chemical shifts should be rather insensitive to changes in r(BN) and that the concomitant changes in molecular structure. Calculations on hydrogen-bonded clusters, based on the crystal structure, indicate that H-bonding should also have very little effect on the chemical shifts. On the other hand, the (11)B and (14)N QCCs show large changes because of both effects. An analysis of the (10)B[(19)F] line shape in solid ND(3)(10)BF(3) yields a (11)B QCC of +/-0.130 MHz. This is reasonably close an earlier value of +/-0.080 MHz and the value of +/-0.050 MHz calculated for a [NH(3)BF(3)](4) cluster. The gas-phase value is 1.20 MHz. Temperature-dependent deuterium T(1) measurements yield an activation energy for rotation of the ND(3) group in solid ND(3)BF(3) of 9.5 +/- 0.1 kJ/mol. Simulations of the temperature-dependent T(1) anisotropy gave an E(a) of 9.5 +/- 0.2 kJ/mol and a preexponential factor, A, of 3.0 +/- 0.1 x 10(12) s(-)(1). Our calculated value for a [NH(3)BF(3)](4) cluster is 16.4 kJ/mol. Both are much higher than the previous value of 3.9 kJ/mol, from solid-state proton T(1) measurements.

Potent in vivo antifungal activity against powdery mildews of pregnane glycosides from the roots of Cynanchum wilfordii.

PubMed

Yoon, Mi-Young; Choi, Nam Hee; Min, Byung Sun; Choi, Gyung Ja; Choi, Yong Ho; Jang, Kyoung Soo; Han, Seong-Sook; Cha, Byeongjin; Kim, Jin-Cheol

2011-11-23

Two new pregnane glycosides, kidjoranine 3-O-β-D-glucopyranosyl-(1 → 4)-β-D-glucopyranosyl-(1 → 4)-α-L-cymaropyranosyl-(1 → 4)-β-D-cymaropyranosyl-(1→4)-α-L-diginopyranosyl-(1 → 4)-β-D-cymaropyranoside (5) and caudatin 3-O-β-D-glucopyranosyl-(1 → 4)-β-D-glucopyranosyl-(1 → 4)-α-L-cymaropyranosyl-(1 → 4)-β-D-cymaropyranosyl-(1 → 4)-α-L-diginopyranosyl-(1 → 4)-β-D-cymaropyranoside (6), were isolated from the roots of Cynanchum wilfordii along with four known compounds (1-4). The antifungal activities of the six compounds against barley powdery mildew caused by Blumeria graminis f. sp. hordei were compared to the antifungal activity of polyoxin B. The caudatin glycosides (1, 4, and 6) showed stronger antifungal activities than polyoxin B, whereas kidjoranine glycosides (2, 3, and 5) had weaker activities than polyoxin B. A wettable powder-type formulation (C. wilfordii-WP20) of the ethyl acetate extract from C. wilfordii roots prohibited the development of barley powdery mildew much more effectively than the commercial fungicide polyoxin B-WP10. In addition, C. wilfordii-WP20 effectively controlled strawberry powdery mildew caused by Sphaerotheca humuli under greenhouse conditions. Thus, the crude extract containing the pregnane glycosides can be used as a botanical fungicide for the environmentally benign control of powdery mildews.

Influence of ionic strength and OH(-) ion concentration on the Cu(II) complex formation with EDTA in alkaline solutions.

PubMed

Norkus, E; Vaskelis, A; Zakaite, I

1996-03-01

D.c. polarographic data show that the complex formation of copper ions with EDTA depends markedly on the ionic strength of the solution at pH 8-10. This is primarily associated with the dependence of the fourth deprotonization constant of EDTA on the solution ionic strength: when it increases from 0.4 to 3.4, the pK(a4) value decreases from 9.5 to 8.2. According to polarographic and spectrophotometric data the degree of Cu(II) complexation increases at pH>10 due to transformation of the complex CuY(2-) to the more stable CuY(OH)(3-) (Y(4-), a fully deprotonized anion of EDTA), but it decreases with increase in alkalinity in a highly alkaline solution (pH>13.5). The latter result could be explained by the decrease in the EDTA anion activity. The calculated values of the activity coefficient are lower than 0.05 at pH>14.

Dinardokanshones C-E, isonardoeudesmols A-D and nardoeudesmol D from Nardostachys jatamansi DC.

PubMed

Wu, Hong-Hua; Deng, Xu; Zhang, Hu; Chen, Ying-Peng; Ying, Shu-Song; Wu, Yi-Jing; Liu, Yan-Ting; Zhu, Yan; Gao, Xiu-Mei; Xu, Yan-Tong; Li, Li

2018-06-01

Dinardokanshones C-E, three sesquiterpenoid dimers comprising an unusual nornardosinane-type sesquiterpenoid core and an aristolane-type sesquiterpenoid unit conjugated by an extra pyran or furan ring, together with monomeric sesquiterpenoids isonardoeudesmols A-D and nardoeudesmol D, were isolated from the underground parts of Nardostachys jatamansi DC. Structures of the eight compounds were elucidated by analysis of the extensive spectroscopic data, and their absolute configurations were established by analysis of NOESY and X-ray diffraction data, combined with computational electronic circular dichroism (ECD) calculations. The results of SERT activity assay revealed that isonardoeudesmol D and nardoeudesmol D significantly inhibited SERT activity, while dinardokanshones D-E and isonardoeudesmols B-C significantly enhanced SERT activity, among which dinardokanshone D exhibited the strongest effect. Copyright © 2018 Elsevier Ltd. All rights reserved.

Infrared propagators of Yang-Mills theory from perturbation theory

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

Tissier, Matthieu; Wschebor, Nicolas

2010-11-15

We show that the correlation functions of ghosts and gluons for the pure Yang-Mills theory in Landau gauge can be accurately reproduced for all momenta by a one-loop calculation. The key point is to use a massive extension of the Faddeev-Popov action. The agreement with lattice simulation is excellent in d=4. The one-loop calculation also reproduces all the characteristic features of the lattice simulations in d=3 and naturally explains the peculiarities of the propagators in d=2.

Large Charge-Transfer Energy in LiFePO4 Revealed by Full-Multiplet Calculation for the Fe L3 -edge Soft X-ray Emission Spectra.

PubMed

Asakura, Daisuke; Nanba, Yusuke; Makinose, Yuki; Matsuda, Hirofumi; Glans, Per-Anders; Guo, Jinghua; Hosono, Eiji

2018-04-17

We analyzed the Fe 3d electronic structure in LiFePO 4 /FePO 4 (LFP/FP) nanowire with a high cyclability by using soft X-ray emission spectroscopy (XES) combined with configuration-interaction full-multiplet (CIFM) calculation. The ex situ Fe L 2,3 -edge resonant XES (RXES) spectra for LFP and FP are ascribed to oxidation states of Fe 2+ and Fe 3+ , respectively. CIFM calculations for Fe 2+ and Fe 3+ states reproduced the Fe L 3 RXES spectra for LFP and FP, respectively. In the calculations for both states, the charge-transfer energy was considerably larger than those for typical iron oxides, indicating very little electron transfer from the O 2p to Fe 3d orbitals and a weak hybridization on the Fe-O bond during the charge-discharge reactions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Theoretical level energies and transition data for 4p64d4, 4p64d34f and 4p54d5 configurations of W34+ ion

NASA Astrophysics Data System (ADS)

Karpuškienė, R.; Bogdanovich, P.; Kisielius, R.

2017-05-01

The ab initio quasirelativistic approach developed specifically for the calculation of spectral parameters of highly charged ions was used to derive transition data for the tungsten ion W34+. The configuration interaction method was applied to include electron correlation effects. The relativistic effects were taken into account in the Breit-Pauli approximation. The level energies, radiative lifetimes τ, Landé g-factors are determined for the ground configuration 4p64d4 and two excited configurations 4p64d34f and 4p54d5. The radiative transition wavelengths λ and emission transition probabilities A for the electric dipole, electric quadrupole, electric octupole, magnetic dipole, and magnetic quadrupole transitions among the levels of these configurations are produced.

Anti-Phytopathogenic and Cytotoxic Activities of Crude Extracts and Secondary Metabolites of Marine-Derived Fungi

PubMed Central

Zhao, Dong-Lin; Wang, Dan; Tian, Xue-Ying; Cao, Fei; Li, Yi-Qiang; Zhang, Cheng-Sheng

2018-01-01

Thirty-one isolates belonging to eight genera in seven orders were identified from 141 strains that were isolated from several marine plants. Alternaria sp. and Fusarium sp. were found to be the predominant fungi. Evaluation of the anti-phytopathogenic bacterial and fungal activities, as well as the cytotoxicity of these 31 extracts, revealed that most of them displayed different levels of bioactivities. Due to their interesting bioactivities, two fungal strains—Fusarium equiseti (P18) and Alternaria sp. (P8)—were selected for chemical investigation and compounds 1–4 were obtained. The structure of 1 was elucidated by 1D and 2D NMR analysis, as well as high-resolution electrospray ionization mass spectroscopy (HRESIMS), and the absolute configuration of its stereogenic carbon (C-11) was established by comparison of the experimental and calculated electronic circular-dichroism (ECD) spectra. Moreover, alterperylenol (4) exhibited antibacterial activity against Clavibacter michiganensis with a minimum inhibitory concentration (MIC) of 1.95 μg/mL, which was 2-fold stronger than that of streptomycin sulfate. Additionally, an antibacterial mechanism study revealed that 4 caused membrane hyperpolarization without evidence of destruction of cell membrane integrity. Furthermore, stemphyperylenol (3) displayed potent antifungal activity against Pestallozzia theae and Alternaria brassicicola with MIC values equal to those of carbendazim. The cytotoxicity of 1 and 2 against human lung carcinoma (A-549), human cervical carcinoma (HeLa), and human hepatoma (HepG2) cell lines were also evaluated. PMID:29346329

First-principles investigations of iron-based alloys and their properties

NASA Astrophysics Data System (ADS)

Limmer, Krista Renee

Fundamental understanding of the complex interactions governing structure-property relationships in iron-based alloys is necessary to advance ferrous metallurgy. Two key components of alloy design are carbide formation and stabilization and controlling the active deformation mechanism. Following a first-principles methodology, understanding on the electronic level of these components has been gained for predictive modeling of alloys. Transition metal carbides have long played an important role in alloy design, though the complexity of their interactions with the ferrous matrix is not well understood. Bulk, surface, and interface properties of vanadium carbide, VCx, were calculated to provide insight for the carbide formation and stability. Carbon vacancy defects are shown to stabilize the bulk carbide due to increased V-V bonding in addition to localized increased V-C bond strength. The VCx (100) surface energy is minimized when carbon vacancies are at least two layers from the surface. Further, the Fe/VC interface is stabilized through maintaining stoichiometry at the Fe/VC interface. Intrinsic and unstable stacking fault energy, gammaisf and gamma usf respectively, were explicitly calculated in nonmagnetic fcc Fe-X systems for X = Al, Si, P, S, and the 3d and 4d transition elements. A parabolic relationship is observed in gamma isf across the transition metals with minimums observed for Mn and Tc in the 3d and 4d periods, respectively. Mn is the only alloying addition that was shown to decrease gamma isf in fcc Fe at the given concentration. The effect of alloying on gammausf also has a parabolic relationship, with all additions decreasing gammaisf yielding maximums for Fe and Rh.

Effect of 2,4-Dichlorophenoxyacetic Acid on Glucosylation of Scopoletin to Scopolin in Tobacco Tissue Culture

PubMed Central

Hino, Fumitsugu; Okazaki, Mitsuo; Miura, Yoshiharu

1982-01-01

2,4-Dichlorophenoxyacetic acid (2,4-D) stimulated the formation of scopoletin and scopolin in tobacco (Nicotiana tabacum L. `Bright Yellow') cell culture. It especially stimulated the uptake of scopoletin from culture medium into the cells and the glucosylation of scopoletin to its monoglucoside, scopolin. This phenomenon is peculiar to 2,4-D, in contrast to other plant hormones. 2,4-D (1 μg/ml) stimulated the glucosylation of scopoletin to scopolin by enhancing UDP-glucose:scopoletin glucosyltransferase (SGTase) activity. The enhancement of SGTase activity caused by treatment with 2,4-D was observed when the syntheses of RNA and protein were inhibited by either actinomycin-D and/or cycloheximide. However, the stimulatory effect of 2,4-D was inhibited by treatment with dinitrophenol. Furthermore, SGTase with or without treatment by 2,4-D in vivo for 24 hours, was isolated from cultured tobacco cells. The enzymes were purified about 200-fold by precipitation with (NH4)2SO4 and chromatography with Sephadex G-100, DEAE-cellulose, and hydroxyapatite. The specific activity of 2,4-D-treated SGTase was 10 times higher than that of untreated SGTase even in the purified fraction, which showed one protein band under electrophoresis. These results suggest that the enhancement of SGTase activity by 2,4-D is due to the energy-dependent activation of the enzyme already present, but not due to the de novo synthesis of the enzyme. Images PMID:16662301

Studies on the synthesis, characterization, human serum albumin binding and biological activity of single chain surfactant-cobalt(III) complexes.

PubMed

Vignesh, G; Sugumar, K; Arunachalam, S; Vignesh, S; Arthur James, R; Arun, R; Premkumar, K

2016-03-01

The interaction of surfactant-cobalt(III) complexes [Co(bpy)(dien)TA](ClO4)3 · 3H2O (1) and [Co(dien)(phen)TA](ClO4)3 · 4H2O (2), where bpy = 2,2'-bipyridine, dien = diethylenetriamine, phen = 1,10-phenanthroline and TA = tetradecylamine with human serum albumin (HSA) under physiological conditions was analyzed using steady state, synchronous, 3D fluorescence, UV/visabsorption and circular dichroism spectroscopic techniques. The results show that these complexes cause the fluorescence quenching of HSA through a static mechanism. The binding constant (Kb ) and number of binding-sites (n) were obtained at different temperatures. The corresponding thermodynamic parameters (∆G°, ∆H° and ∆S°) and Ea were also obtained. According to Förster's non-radiation energy transfer theory, the binding distance (r) between the complexes and HSA were calculated. The results of synchronous and 3D fluorescence spectroscopy indicate that the binding process has changed considerably the polarity around the fluorophores, along with changes in the conformation of the protein. The antimicrobial and anticancer activities of the complexes were tested and the results show that the complexes have good activities against pathogenic microorganisms and cancer cells. Copyright © 2015 John Wiley & Sons, Ltd.

Out-of-Band 40 DB Bandwidth of EESS (Active) Spaceborne SARS

NASA Technical Reports Server (NTRS)

Huneycutt, Bryan L.

2005-01-01

This document presents a study of out of band (OOB) 40 dB bandwidth requirements of spaceborne SARs in the Earth Exploration-Satellite Service (active) and Space Research Service (active). The purpose of the document is to study the OOB 40 dB bandwidth requirements and compare the 40 dB bandwidth B-40 as measured in simulations with that calculated using the ITU-R Rec SM.1541 equations. The spectra roll-off and resulting OOB 40 dB bandwidth of the linear FM signal is affected by the time-bandwidth product and the rise/fall times. Typical values of these waveform characteristics are given for existing EESS (active) sensors.

Auxin-activated NADH oxidase activity of soybean plasma membranes is distinct from the constitutive plasma membrane NADH oxidase and exhibits prion-like properties

NASA Technical Reports Server (NTRS)

Morre, D. James; Morre, Dorothy M.; Ternes, Philipp

2003-01-01

The hormone-stimulated and growth-related cell surface hydroquinone (NADH) oxidase activity of etiolated hypocotyls of soybeans oscillates with a period of about 24 min or 60 times per 24-h day. Plasma membranes of soybean hypocotyls contain two such NADH oxidase activities that have been resolved by purification on concanavalin A columns. One in the apparent molecular weight range of 14-17 kDa is stimulated by the auxin herbicide 2,4-dichlorophenoxyacetic acid (2,4-D). The other is larger and unaffected by 2,4-D. The 2,4-D-stimulated activity absolutely requires 2,4-D for activity and exhibits a period length of about 24 min. Also exhibiting 24-min oscillations is the rate of cell enlargement induced by the addition of 2,4-D or the natural auxin indole-3-acetic acid (IAA). Immediately following 2,4-D or IAA addition, a very complex pattern of oscillations is frequently observed. However, after several hours a dominant 24-min period emerges at the expense of the constitutive activity. A recruitment process analogous to that exhibited by prions is postulated to explain this behavior.

Magnetic Transitions in Iron Porphyrin Halides by Inelastic Neutron Scattering and Ab-initio Studies of Zero-Field Splittings

DOE PAGES

Stavretis, Shelby E.; Atanasov, Mihail; Podlesnyak, Andrey A.; ...

2015-10-02

Zero-field splitting (ZFS) parameters of nondeuterated metalloporphyrins [Fe(TPP)X] (X = F, Br, I; H 2TPP = tetraphenylporphyrin) are determined by inelastic neutron scattering (INS). The ZFS values are D = 4.49(9) cm –1 for tetragonal polycrystalline [Fe(TPP)F], and D = 8.8(2) cm –1, E = 0.1(2) cm –1 and D = 13.4(6) cm –1, E = 0.3(6) cm –1 for monoclinic polycrystalline [Fe(TPP)Br] and [Fe(TPP)I], respectively. Along with our recent report of the ZFS value of D = 6.33(8) cm –1 for tetragonal polycrystalline [Fe(TPP)Cl], these data provide a rare, complete determination of ZFS parameters in a metalloporphyrin halide series.more » The electronic structure of [Fe(TPP)X] (X = F, Cl, Br, I) has been studied by multireference ab initio methods: the complete active space self-consistent field (CASSCF) and the N-electron valence perturbation theory (NEVPT2) with the aim of exploring the origin of the large and positive zero-field splitting D of the 6A 1 ground state. D was calculated from wave functions of the electronic multiplets spanned by the d 5 configuration of Fe(III) along with spin–orbit coupling accounted for by quasi degenerate perturbation theory. Results reproduce trends of D from inelastic neutron scattering data increasing in the order from F, Cl, Br, to I. A mapping of energy eigenvalues and eigenfunctions of the S = 3/2 excited states on ligand field theory was used to characterize the σ- and π-antibonding effects decreasing from F to I. This is in agreement with similar results deduced from ab initio calculations on CrX 6 3- complexes and also with the spectrochemical series showing a decrease of the ligand field in the same directions. A correlation is found between the increase of D and decrease of the π- and σ-antibonding energies e λ X (λ = σ, π) in the series from X = F to I. Analysis of this correlation using second-order perturbation theory expressions in terms of angular overlap parameters rationalizes the experimentally deduced trend. Furthermore, D parameters from CASSCF and NEVPT2 results have been calibrated against those from the INS data, yielding a predictive power of these approaches. Methods to improve the quantitative agreement between ab initio calculated and experimental D and spectroscopic transitions for high-spin Fe(III) complexes are proposed.« less

Transition and Electron Impact Excitation Collision Rates for O III

NASA Astrophysics Data System (ADS)

Tayal, S. S.; Zatsarinny, O.

2017-12-01

Transition probabilities, electron excitation collision strengths, and rate coefficients for a large number of O III lines over a broad wavelength range, from the infrared to ultraviolet, have been reported. The collision strengths have been calculated in the close-coupling approximation using the B-spline Breit-Pauli R-matrix method. The multiconfiguration Hartree-Fock method in combination with B-spline expansions is employed for an accurate representation of the target wave functions. The close-coupling expansion contains 202 O2+ fine-structure levels of the 2{s}22{p}2,2s2{p}3, 2{p}4,2{s}22p3s,3p,3d, 4s,4p,4d,4f,5s, and 2s2{p}33s,3p,3d configurations. The effective collision strengths are obtained by averaging electron excitation collision strengths over a Maxwellian distribution of velocities at electron temperatures ranging from 100 to 100,000 K. The calculated effective collision strengths have been reported for the 20,302 transitions between all 202 fine-structure levels. There is an overall good agreement with the recent R-matrix calculations by Storey et al. for the transitions between all levels of the ground 2{s}22{p}2 configuration, but significant discrepancies have been found with Palay et al. for transitions to the 2{s}22{p}2 1 S 0 level. Line intensity ratios between the optical lines arising from the 2{s}22{p}2{}3{P}{0,1,2} - 1 D 2 transitions have been compared with other calculations and observations from the photoionized gaseous nebulae, and good agreement is found. The present calculations provide the most complete and accurate data sets, which should allow a more detailed treatment of the available measured spectra from different ground and space observatories.

FTIR, FT-RAMAN, NMR, spectra, normal co-ordinate analysis, NBO, NLO and DFT calculation of N,N-diethyl-4-methylpiperazine-1-carboxamide molecule.

PubMed

Muthu, S; Elamurugu Porchelvi, E

2013-11-01

The Fourier Transform Infrared (FT-IR) and FT-Raman of N,N-diethyl-4-methylpiperazine-1-carboxamide (NND4MC) have been recorded and analyzed. The structure of the compound was optimized and the structural characteristics were determined by density functional theory (DFT) using B3LYP method with 6-31G(d,p) and 6-311G(d,p) basis sets. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. The theoretically predicted FT-IR and FT-Raman spectra of the title molecule have been constructed. The detailed interpretation of the vibrational spectra has been carried out with aid of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology. Stability of the molecule arising from hyperconjugative interactions and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The results show that electron density (ED) in the σ(*) and π(*) antibonding orbitals and second order delocalization energies (E2) confirm the occurrence of intramolecular charge transfer (ICT) within the molecule. The electronic dipole moment (μD) and the first hyperpolarizability (βtot) values of the investigated molecule were computed using Density Functional Theory (DFT/B3LYP) with 6-31G(d,p) and 6-311G(d,p) basis sets. The calculated results also show that the NND4MC molecule may have microscopy nonlinear optical (NLO) behavior with non zero values. Mulliken atomic charges of NND4MC were calculated. The (13)C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results. The UV-Vis spectrum of the compound was recorded. The theoretical electronic absorption spectra have been calculated by using CIS, TD-DFT methods. A study on the electronic properties, such as HOMO and LUMO energies, molecular electrostatic potential (MEP) were also performed. Copyright © 2013 Elsevier B.V. All rights reserved.

Chemical constituents from Tribulus terrestris and screening of their antioxidant activity.

PubMed

Hammoda, Hala M; Ghazy, Nabila M; Harraz, Fathalla M; Radwan, Mohamed M; ElSohly, Mahmoud A; Abdallah, Ingy I

2013-08-01

Two oligosaccharides (1,2) and a stereoisomer of di-p-coumaroylquinic acid (3) were isolated from the aerial parts of Tribulus terrestris along with five known compounds (4-8). The structures of the compounds were established as O-β-D-fructofuranosyl-(2→6)-α-D-glucopyranosyl-(1→6)-β-D-fructofuranosyl-(2→6)-β-D-fructofuranosyl-(2→1)-α-D-glucopyranosyl-(6→2)-β-D-fructofuranoside (1), O-α-D-glucopyranosyl-(1→4)-α-D-glucopyranosyl-(1→4)-α-D-glucopyranosyl-(1→2)-β-D-fructofuranoside (2), 4,5-di-p-cis-coumaroylquinic acid (3) by different spectroscopic methods including 1D NMR ((1)H, (13)C and DEPT) and 2D NMR (COSY, TOCSY, HMQC and HMBC) experiments as well as ESI-MS analysis. This is the first report for the complete NMR spectral data of the known 4,5-di-p-trans-coumaroylquinic acid (4). The antioxidant activity represented as DPPH free radical scavenging activity was investigated revealing that the di-p-coumaroylquinic acid derivatives possess potent antioxidant activity so considered the major constituents contributing to the antioxidant effect of the plant. Copyright © 2013 Elsevier Ltd. All rights reserved.

Relativistic many-body calculations of excitation energies, oscillator strengths, transition rates, and lifetimes in samarium like ions

NASA Astrophysics Data System (ADS)

Safronova, Ulyana; Safronova, Alla; Beiersdorfer, Peter

2013-05-01

Excitation energies, oscillator strengths, transition probabilities, and lifetimes are calculated for (5s2 + 5p2 + 5d2 + 5 s 5 d + 5 s 5 g + 5 p 5 f) - (5 s 5 p + 5 s 5 f + 5 p 5 d + 5 p 5 g) electric dipole transitions in Sm-like ions with nuclear charge Z ranging from 74 to 100. Relativistic many-body perturbation theory (RMBPT), including the Breit interaction, is used to evaluate retarded E1 matrix elements in length and velocity forms. The calculations start from a 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 4f14 Dirac-Fock potential. First-order perturbation theory is used to obtain intermediate coupling coefficients, and the second-order RMBPT is used to determine the matrix elements. The contributions from negative-energy states are included in the second-order E1 matrix elements to achieve agreement between length-form and velocity-form amplitudes. The resulting transition energies and transition probabilities, and lifetimes for Sm-like W12+ are compared with results obtained by the relativistic Hartree-Fock approximation (COWAN code) to estimate contribution of the 4 f -core-excited states. Trends of excitation energies and oscillator strengths as function of nuclear charge Z are shown graphically for selected states and transitions. This work provides a number of yet unmeasured properti. This research was sponsored by the grant DE-FG02-08ER54951.

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

Thiyagarajan, Rajesh; Vikraman, S; Karrthick, KP

Purpose: To evaluate the impact of dose calculation algorithm on the dose distribution of biologically optimized Volumatric Modulated Arc Therapy (VMAT) plans for Esophgeal cancer. Methods: Eighteen retrospectively treated patients with carcinoma esophagus were studied. VMAT plans were optimized using biological objectives in Monaco (5.0) TPS for 6MV photon beam (Elekta Infinity). These plans were calculated for final dose using Monte Carlo (MC), Collapsed Cone Convolution (CCC) & Pencil Beam Convolution (PBC) algorithms from Monaco and Oncentra Masterplan TPS. A dose grid of 2mm was used for all algorithms and 1% per plan uncertainty maintained for MC calculation. MC basedmore » calculations were considered as the reference for CCC & PBC. Dose volume histogram (DVH) indices (D95, D98, D50 etc) of Target (PTV) and critical structures were compared to study the impact of all three algorithms. Results: Beam models were consistent with measured data. The mean difference observed in reference with MC calculation for D98, D95, D50 & D2 of PTV were 0.37%, −0.21%, 1.51% & 1.18% respectively for CCC and 3.28%, 2.75%, 3.61% & 3.08% for PBC. Heart D25 mean difference was 4.94% & 11.21% for CCC and PBC respectively. Lung Dmean mean difference was 1.5% (CCC) and 4.1% (PBC). Spinal cord D2 mean difference was 2.35% (CCC) and 3.98% (PBC). Similar differences were observed for liver and kidneys. The overall mean difference found for target and critical structures was 0.71±1.52%, 2.71±3.10% for CCC and 3.18±1.55%, 6.61±5.1% for PBC respectively. Conclusion: We observed a significant overestimate of dose distribution by CCC and PBC as compared to MC. The dose prediction of CCC is closer (<3%) to MC than that of PBC. This can be attributed to poor performance of CCC and PBC in inhomogeneous regions around esophagus. CCC can be considered as an alternate in the absence of MC algorithm.« less

Synthesis, spectroscopic analysis and theoretical study of new pyrrole-isoxazoline derivatives

NASA Astrophysics Data System (ADS)

Rawat, Poonam; Singh, R. N.; Baboo, Vikas; Niranjan, Priydarshni; Rani, Himanshu; Saxena, Rajat; Ahmad, Sartaj

2017-02-01

In the present work, we have efficiently synthesized the pyrrole-isoxazoline derivatives (4a-d) by cyclization of substituted 4-chalconylpyrrole (3a-d) with hydroxylamine hydrochloride. The reactivity of substituted 4-chalconylpyrrole (3a-d), towards nucleophiles hydroxylamine hydrochloride was evaluated on the basis of electrophilic reactivity descriptors (fk+, sk+, ωk+) and they were found to be high at unsaturated β carbon of chalconylpyrrole indicating its more proneness to nucleophilic attack and thereby favoring the formation of reported new pyrrole-isoxazoline compounds (4a-d). The structures of newly synthesized pyrrole-isoxazoline derivatives were derived from IR, 1H NMR, Mass, UV-Vis and elemental analysis. All experimental spectral data corroborate well with the calculated spectral data. The FT-IR analysis shows red shifts in vN-H and vC = O stretching due to dimer formation through intermolecular hydrogen bonding. On basis set superposition error correction, the intermolecular interaction energy for (4a-d) is found to be 10.10, 9.99, 10.18, 11.01 and 11.19 kcal/mol respectively. The calculated first hyperpolarizability (β0) values of (4a-d) molecules are in the range of 7.40-9.05 × 10-30 esu indicating their suitability for non-linear optical (NLO) applications. Experimental spectral results, theoretical data, analysis of chalcone intermediates and pyrrole-isoxazolines find usefulness in advancement of pyrrole-azole chemistry.

Infrared spectrum, structural and optical properties and molecular docking study of 3-(4-fluorophenyl)-5-phenyl-4,5-dihydro-1H-pyrazole-1-carbaldehyde.

PubMed

Mary, Y Sheena; Panicker, C Yohannan; Sapnakumari, M; Narayana, B; Sarojini, B K; Al-Saadi, Abdulaziz A; Van Alsenoy, C; War, Javeed Ahmad; Fun, H K

2015-03-05

The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments of 3-(4-fluorophenyl)-5-phenyl-4,5-dihydro-1H-pyrazole-1-carbaldehyde have been investigated experimentally and theoretically. The title compound was optimized using at HF and DFT levels of calculations. The B3LYP/6-311++G(d,p) (5D,7F) results and in agreement with experimental infrared bands. The normal modes are assigned using potential energy distribution. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using natural bonding orbital analysis. The frontier molecular orbital analysis is used to determine the charge transfer within the molecule. From molecular electrostatic potential map, it is evident that the negative electrostatic potential regions are mainly localized over the carbonyl group and mono substituted phenyl ring and are possible sites for electrophilic attack and, positive regions are localized around all para substituted phenyl and pyrazole ring, indicating possible sites for nucleophilic attack. First hyperpolarizability is calculated in order to find its role in nonlinear optics. The geometrical parameters are in agreement with experimental data. From the molecular docking studies, it is evident that the fluorine atom attached to phenyl ring and the carbonyl group attached to pyrazole ring are crucial for binding and the results draw us to the conclusion that the compound might exhibit phosphodiesterase inhibitory activity. Copyright © 2014 Elsevier B.V. All rights reserved.

Radiation experiments on Cosmos 2044: K-7-41, parts A, B, C, D, E

NASA Technical Reports Server (NTRS)

Frank, A. L.; Benton, E. V.; Benton, E. R.; Dudkin, V. E.; Marenny, A. M.

1990-01-01

The Cosmos 2044 biosatellite mission offered the opportunity for radiation measurements under conditions which are seldom available (an inclination of 82.3 deg and attitude of 294 x 216 km). Measurements were made on the outside of the spacecraft under near-zero shielding conditions. Also, this mission was the first in which active temperature recorders (the ATR-4) were flown to record the temperature profiles of detector stacks. Measurements made on this mission provide a comparison and test for modeling of depth doses and LET spectra for orbital parameters previously unavailable. Tissue absorbed doses from 3480 rad (252 rad/d) down to 0.115 rad (8.33 mrad/d) were measured at different depths (0.0146 and 3.20 g/sq cm, respectively) with averaged TLD readings. The LET spectra yielded maximum and minimum values of integral flux of 27.3 x 10(exp -4) and 3.05 x 10(exp -4)/sq cm/s/sr, of dose rate of 7.01 and 1.20 mrad/d, and of dose equivalent rate of 53.8 and 11.6 mrem/d, for LET(sub infinity)-H2O is greater than or equal to 4 keV/micron. Neutron measurements yielded 0.018 mrem/d in the thermal region, 0.25 mrem/d in the resonance region and 3.3 mrem/d in the high energy region. The TLD depth dose and LET spectra were compared with calculations from the modeling codes. The agreement is good but some further refinements are in order. In comparing measurements on Cosmos 2044 with those from previous Cosmos missions (orbital inclinations of 62.8 deg) there is a greater spread (maximum to minimum) in depth doses and an increased contribution from GCRs, and higher LET particles, in the heavy particle fluxes.

Density functional theory study of bulk and single-layer magnetic semiconductor CrPS4

NASA Astrophysics Data System (ADS)

Zhuang, Houlong L.; Zhou, Jia

2016-11-01

Searching for two-dimensional (2D) materials with multifunctionality is one of the main goals of current research in 2D materials. Magnetism and semiconducting are certainly two desirable functional properties for a single 2D material. In line with this goal, here we report a density functional theory (DFT) study of bulk and single-layer magnetic semiconductor CrPS4. We find that the ground-state magnetic structure of bulk CrPS4 exhibits the A-type antiferromagnetic ordering, which transforms to ferromagnetic (FM) ordering in single-layer CrPS4. The calculated formation energy and phonon spectrum confirm the stability of single-layer CrPS4. The band gaps of FM single-layer CrPS4 calculated with a hybrid density functional are within the visible-light range. We also study the effects of FM ordering on the optical absorption spectra and band alignments for water splitting, indicating that single-layer CrPS4 could be a potential photocatalyst. Our work opens up ample opportunities of energy-related applications of single-layer CrPS4.

An ab initio MO study of heavy atom effects on the zero-field splitting tensors of high-spin nitrenes: how the spin-orbit contributions are affected.

PubMed

Sugisaki, Kenji; Toyota, Kazuo; Sato, Kazunobu; Shiomi, Daisuke; Kitagawa, Masahiro; Takui, Takeji

2014-05-21

The CASSCF and the hybrid CASSCF-MRMP2 methods are applied to the calculations of spin-spin and spin-orbit contributions to the zero-field splitting tensors (D tensors) of the halogen-substituted spin-septet 2,4,6-trinitrenopyridines, focusing on the heavy atom effects on the spin-orbit term of the D tensors (D(SO) tensors). The calculations reproduced experimentally determined |D| values within an error of 15%. Halogen substitutions at the 3,5-positions are less influential in the spin-spin dipolar (D(SS)) term of 2,4,6-trinitrenopyridines, although the D(SO) terms are strongly affected by the introduction of heavier halogens. The absolute sign of the D(SO) value (D = D(ZZ) - (D(XX) + D(YY))/2) of 3,5-dibromo derivative 3 is predicted to be negative, which contradicts the Pederson-Khanna (PK) DFT result previously reported. The large negative contributions to the D(SO) value of 3 arise from the excited spin-septet states ascribed mainly to the excitations of in-plane lone pair of bromine atoms → SOMO of π nature. The importance of the excited states involving electron transitions from the lone pair orbital of the halogen atom is also confirmed in the D(SO) tensors of halogen-substituted para-phenylnitrenes. A new scheme based on the orbital region partitioning is proposed for the analysis of the D(SO) tensors as calculated by means of the PK-DFT approach.

FT-IR spectra of the anti-HIV nucleoside analogue d4T (Stavudine). Solid state simulation by DFT methods and scaling by different procedures

NASA Astrophysics Data System (ADS)

Alcolea Palafox, M.; Kattan, D.; Afseth, N. K.

2018-04-01

A theoretical and experimental vibrational study of the anti-HIV d4T (stavudine or Zerit) nucleoside analogue was carried out. The predicted spectra in the three most stable conformers in the biological active anti-form of the isolated state were compared. Comparison of the conformers with those of the natural nucleoside thymidine was carried out. The calculated spectra were scaled by using different scaling procedures and three DFT methods. The TLSE procedure leads to the lowest error and is thus recommended for scaling. With the population of these conformers the IR gas-phase spectra were predicted. The crystal unit cell of the different polymorphism forms of d4T were simulated through dimer forms by using DFT methods. The scaled spectra of these dimer forms were compared. The FT-IR spectrum was recorded in the solid state in the 400-4000 cm-1 range. The respective vibrational bands were analyzed and assigned to different normal modes of vibration by comparison with the scaled vibrational values of the different dimer forms. Through this comparison, the polymorphous form of the solid state sample was identified. The study indicates that d4T exist only in the ketonic form in the solid state. The results obtained were in agreement with those determined in related anti-HIV nucleoside analogues.

Defining the molecular structure of teixobactin analogues and understanding their role in antibacterial activities.

PubMed

Parmar, Anish; Prior, Stephen H; Iyer, Abhishek; Vincent, Charlotte S; Van Lysebetten, Dorien; Breukink, Eefjan; Madder, Annemieke; Taylor, Edward J; Singh, Ishwar

2017-02-07

The discovery of the highly potent antibiotic teixobactin, which kills the bacteria without any detectable resistance, has stimulated interest in its structure-activity relationship. However, a molecular structure-activity relationship has not been established so far for teixobactin. Moreover, the importance of the individual amino acids in terms of their l/d configuration and their contribution to the molecular structure and biological activity are still unknown. For the first time, we have defined the molecular structure of seven teixobactin analogues through the variation of the d/l configuration of its key residues, namely N-Me-d-Phe, d-Gln, d-allo-Ile and d-Thr. Furthermore, we have established the role of the individual d amino acids and correlated this with the molecular structure and biological activity. Through extensive NMR and structural calculations, including molecular dynamics simulations, we have revealed the residues for maintaining a reasonably unstructured teixobactin which is imperative for biological activity.

Systematic design of active spaces for multi-reference calculations of singlet-triplet gaps of organic diradicals, with benchmarks against doubly electron-attached coupled-cluster data

NASA Astrophysics Data System (ADS)

Stoneburner, Samuel J.; Shen, Jun; Ajala, Adeayo O.; Piecuch, Piotr; Truhlar, Donald G.; Gagliardi, Laura

2017-10-01

Singlet-triplet gaps in diradical organic π-systems are of interest in many applications. In this study, we calculate them in a series of molecules, including cyclobutadiene and its derivatives and cyclopentadienyl cation, by using correlated participating orbitals within the complete active space (CAS) and restricted active space (RAS) self-consistent field frameworks, followed by second-order perturbation theory (CASPT2 and RASPT2). These calculations are evaluated by comparison with the results of doubly electron-attached (DEA) equation-of-motion (EOM) coupled-cluster (CC) calculations with up to 4-particle-2-hole (4p-2h) excitations. We find active spaces that can accurately reproduce the DEA-EOMCC(4p-2h) data while being small enough to be applicable to larger organic diradicals.

Removal of 2,4-Dichlorophenolyxacetic acid (2,4-D) herbicide in the aqueous phase using modified granular activated carbon

PubMed Central

2014-01-01

Background Low cost 2,4-Dichlorophenolyxacetic acid (2,4-D) widely used in controlling broad-leafed weeds is frequently detected in water resources. The main objectives of this research were focused on evaluating the feasibility of using granular activated carbon modified with acid to remove 2,4-D from aqueous phase, determining its removal efficiency and assessing the adsorption kinetics. Results The present study was conducted at bench-scale method. The influence of different pH (3–9), the effect of contact time (3–90 min), the amount of adsorbent (0.1-0.4 g), and herbicide initial concentration (0.5-3 ppm) on 2,4-D removal efficiency by the granular activated carbon were investigated. Based on the data obtained in the present study, pH of 3 and contact time of 60 min is optimal for 2,4-D removal. 2,4-D reduction rate increased rapidly by the addition of the adsorbent and decreased by herbicide initial concentration (63%). The percent of 2,4-D reduction were significantly enhanced by decreasing pH and increasing the contact time. The adsorption of 2,4-D onto the granular activated carbon conformed to Langmuir and Freundlich models, but was best fitted to type II Langmuir model (R2 = 0.999). The second order kinetics was the best for the adsorption of 2,4-D by modified granular activated carbon with R2 > 0.99. Regression analysis showed that all of the variables in the process have been statistically significant effect (p < 0.001). Conclusions In conclusion, granular activated carbon modified with acid is an appropriate method for reducing the herbicide in the polluted water resources. PMID:24410737

Removal of 2,4-Dichlorophenolyxacetic acid (2,4-D) herbicide in the aqueous phase using modified granular activated carbon.

PubMed

Dehghani, Mansooreh; Nasseri, Simin; Karamimanesh, Mojtaba

2014-01-10

Low cost 2,4-Dichlorophenolyxacetic acid (2,4-D) widely used in controlling broad-leafed weeds is frequently detected in water resources. The main objectives of this research were focused on evaluating the feasibility of using granular activated carbon modified with acid to remove 2,4-D from aqueous phase, determining its removal efficiency and assessing the adsorption kinetics. The present study was conducted at bench-scale method. The influence of different pH (3-9), the effect of contact time (3-90 min), the amount of adsorbent (0.1-0.4 g), and herbicide initial concentration (0.5-3 ppm) on 2,4-D removal efficiency by the granular activated carbon were investigated. Based on the data obtained in the present study, pH of 3 and contact time of 60 min is optimal for 2,4-D removal. 2,4-D reduction rate increased rapidly by the addition of the adsorbent and decreased by herbicide initial concentration (63%). The percent of 2,4-D reduction were significantly enhanced by decreasing pH and increasing the contact time. The adsorption of 2,4-D onto the granular activated carbon conformed to Langmuir and Freundlich models, but was best fitted to type II Langmuir model (R2 = 0.999). The second order kinetics was the best for the adsorption of 2,4-D by modified granular activated carbon with R2 > 0.99. Regression analysis showed that all of the variables in the process have been statistically significant effect (p < 0.001). In conclusion, granular activated carbon modified with acid is an appropriate method for reducing the herbicide in the polluted water resources.

WE-G-BRD-01: A Data-Driven 4D-MRI Motion Model to Estimate Full Field-Of-View Abdominal Motion From 2D Image Navigators During MR-Linac Treatment

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

Stemkens, B; Tijssen, RHN; Denis de Senneville, B Denis

2015-06-15

Purpose: To estimate full field-of-view abdominal respiratory motion from fast 2D image navigators using a 4D-MRI based motion model. This will allow for radiation dose accumulation mapping during MR-Linac treatment. Methods: Experiments were conducted on a Philips Ingenia 1.5T MRI. First, a retrospectively ordered 4D-MRI was constructed using 3D transient-bSSFP with radial in-plane sampling. Motion fields were calculated through 3D non-rigid registration. From these motion fields a PCA-based abdominal motion model was constructed and used to warp a 3D reference volume to fast 2D cine-MR image navigators that can be used for real-time tracking. To test this procedure, a time-seriesmore » consisting of two interleaved orthogonal slices (sagittal and coronal), positioned on the pancreas or kidneys, were acquired for 1m38s (dynamic scan-time=0.196ms), during normal, shallow, or deep breathing. The coronal slices were used to update the optimal weights for the first two PCA components, in order to warp the 3D reference image and construct a dynamic 4D-MRI time-series. The interleaved sagittal slices served as an independent measure to test the model’s accuracy and fit. Spatial maps of the root-mean-squared error (RMSE) and histograms of the motion differences within the pancreas and kidneys were used to evaluate the method. Results: Cranio-caudal motion was accurately calculated within the pancreas using the model for normal and shallow breathing with an RMSE of 1.6mm and 1.5mm and a histogram median and standard deviation below 0.2 and 1.7mm, respectively. For deep-breathing an underestimation of the inhale amplitude was observed (RMSE=4.1mm). Respiratory-induced antero-posterior and lateral motion were correctly mapped (RMSE=0.6/0.5mm). Kidney motion demonstrated good motion estimation with RMSE-values of 0.95 and 2.4mm for the right and left kidney, respectively. Conclusion: We have demonstrated a method that can calculate dynamic 3D abdominal motion in a large volume, while acquiring real-time cine-MR images for MR-guided radiotherapy.« less

Spectrum and energy levels of six-times ionized yttrium (Y VII)

NASA Astrophysics Data System (ADS)

Reader, Joseph

2018-03-01

The spectrum of six-times ionized yttrium, Y VII, was photographed with a sliding-spark discharge on 10.7 m normal- and grazing-incidence spectrographs. The region of observation was 157-824 Å. The observations extend the known configurations 4s24p3, 4s4p4, 4p5, 4s24p25s, 4s24p26s to the nearly complete 4s24p24d configuration. Our results for 4s24p24d significantly revise results of Rahimullah et al (1978 Phys. Scr. 18 96); Ateqad et al (1984 J. Phys. B: At. Mol. Phys. 17 4617). A total of 168 lines and 56 energy levels are now known for this ion. The observed configurations were interpreted with Hartree-Fock calculations and least-squares fits of the energy parameters to the observed levels. Transition probabilities for all classified lines were calculated with the fitted parameters.

The DEP-6D, a new preference-based measure to assess health states of dependency.

PubMed

Rodríguez-Míguez, E; Abellán-Perpiñán, J M; Alvarez, X C; González, X M; Sampayo, A R

2016-03-01

In medical literature there are numerous multidimensional scales to measure health states for dependence in activities of daily living. However, these scales are not preference-based and are not able to yield QALYs. On the contrary, the generic preference-based measures are not sensitive enough to measure changes in dependence states. The objective of this paper is to propose a new dependency health state classification system, called DEP-6D, and to estimate its value set in such a way that it can be used in QALY calculations. DEP-6D states are described as a combination of 6 attributes (eat, incontinence, personal care, mobility, housework and cognition problems), with 3-4 levels each. A sample of 312 Spanish citizens was surveyed in 2011 to estimate the DEP-6D preference-scoring algorithm. Each respondent valued six out of the 24 states using time trade-off questions. After excluding those respondents who made two or more inconsistencies (6% out of the sample), each state was valued between 66 and 77 times. The responses present a high internal and external consistency. A random effect model accounting for main effects was the preferred model to estimate the scoring algorithm. The DEP-6D describes, in general, more severe problems than those usually described by means of generic preference-based measures. The minimum score predicted by the DEP-6D algorithm is -0.84, which is considerably lower than the minimum value predicted by the EQ-5D and SF-6D algorithms. The DEP-6D value set is based on community preferences. Therefore it is consistent with the so-called 'societal perspective'. Moreover, DEP-6D preference weights can be used in QALY calculations and cost-utility analysis. Copyright © 2016. Published by Elsevier Ltd.

Resource utilization by desert quail: time and energy, food and water

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

Goldstein, D.L.; Nagy, K.A.

1985-04-01

Time-energy budgets (TEB) of Gambel's Quail (Callipepla gambelii) were compiled during two summers in the Colorado Desert of California. Quail spent 6.77 h/d foraging, 6.2 h/d inactive during daylight hours, and 11.02 h/d inactive at night. Field metabolic rate (FMR) calculated from this activity budget was 81.8 kJ/d. Of this, 47.3 kJ/d was expended during foraging, 12.6 kJ/d in daytime inactivity, and 20.4 kJ/d in nighttime inactivity. Despite the extremely hot thermal environment (maximum ambient temperature approx. =45/sup 0/C), there was no energy cost above resting levels for thermoregulation. FMR was also measured simultaneously with doubly labeled water (DLW), andmore » averaged 90.8 kJ/d. The FMR of C. gambelii was only 40% of that predicted for a bird of its body mass. Energy assimilation efficiency, measured in laboratory feeding experiments with a mixed seed and arthropod diet, was 60.3%. An individual quail in the field thus required 150.3 kJ/d in its diet, representing a dry matter intake of 8.1 g/d. It was calculated that over the course of a year, a population of Gambel's Quail consumes seeds with a total energy content approx. =15% as great as that in seeds consumed by a population of desert rodents or harvester ants in the same area. Gambel's Quail thus may be important factors in the competition for resources among desert granivores, particularly because they can eat one of their competitors (harvester ants). 44 references, 2 figures, 7 tables.« less

The chemical chaperones tauroursodeoxycholic and 4-phenylbutyric acid accelerate thyroid hormone activation and energy expenditure

PubMed Central

da-Silva, Wagner S.; Ribich, Scott; e Drigo, Rafael Arrojo; Castillo, Melany; Patty, Mary-Elizabeth; Bianco, Antonio C.

2011-01-01

Exposure of cell lines endogenously expressing the thyroid hormone activating enzyme type 2 deiodinase (D2) to the chemical chaperones tauroursodeoxycholic acid (TUDCA) or 4-phenylbutiric acid (4-PBA) increases D2 expression, activity and T3 production. In brown adipocytes, TUDCA or 4-PBA induced T3-dependent genes and oxygen consumption (~2-fold), an effect partially lost in D2 knockout cells. In wild type, but not in D2 knockout mice, administration of TUDCA lowered the respiratory quotient, doubled brown adipose tissue D2 activity and normalized the glucose intolerance associated with high fat feeding. Thus, D2 plays a critical role in the metabolic effects of chemical chaperones. PMID:21237159

Strong decays of DJ(3000 ) and Ds J(3040 )

NASA Astrophysics Data System (ADS)

Li, Si-Chen; Wang, Tianhong; Jiang, Yue; Tan, Xiao-Ze; Li, Qiang; Wang, Guo-Li; Chang, Chao-Hsi

2018-03-01

In this paper, we systematically calculate two-body strong decays of newly observed DJ(3000 ) and Ds J(3040 ) with 2 P (1+) and 2 P (1+') assignments in an instantaneous approximation of the Bethe-Salpeter equation method. Our results show that both resonances can be explained as the 2 P (1+') with broad width via 3P1 and 1P1 mixing in D and Ds families. For DJ(3000 ), the total width is 229.6 MeV in our calculation, close to the upper limit of experimental data, and the dominant decay channels are D2*π , D*π , and D*(2600 )π . For Ds J(3040 ), the total width is 157.4 MeV in our calculation, close to the lower limit of experimental data, and the dominant channels are D*K and D*K*. These results are consistent with observed channels in experiments. Given the very little information that has been obtained from experiments and the large error bars of the total decay widths, we recommend the detection of dominant channels in our calculation.

Characterization of selected cellulolytic activities of multi-enzymatic complex system from Penicillium funiculosum.

PubMed

Karboune, Salwa; Geraert, Pierre-André; Kermasha, Selim

2008-02-13

The presence of endo-1,4-beta-D-glucanase, cellobiohydrolase, and beta-glucosidase activities in a multi-enzymatic complex system from Penicillium funiculosum was investigated. The interesting feature of these enzymes is their synergistic action for the hydrolysis of the native cellulose into glucose units. Both endo-1,4-beta-D-glucanase and cellobiohydrolase showed broader pH activity profiles, with pH optima of 4.0 and 4.0-5.0, respectively. However, beta-glucosidase activity showed a narrow pH-activity profile, with an optimum pH of 4.5. The different cellulolytic activities were stable in the acidic pH range of 2.5-6.0 and showed a similar optimal temperature of 60 degrees C. Although beta-glucosidase has shown a close catalytic efficiency as that of endo-1,4-beta-D-glucanase, its thermal stability was lower. However, the thermal stability profile of cellobiohydrolase was close to that of endo-1,4-beta-D-glucanase. The results also revealed the presence of high levels of endo-1,3-1,4-beta-D-glucanase, endo-1,3-beta- d-glucanase, and pectinase activities in the multi-enzymatic cellulolytic complex system. Moreover, the investigated multi-enzymatic complex system was effective in degrading the nonstarch polysaccharides of soybean meal.

Crystal structure, spectral property, antimicrobial activity and DFT calculation of N-(coumarin-3-yl)-N‧-(2-amino-5-phenyl-1,3,4-thiadiazol-2-yl) urea

NASA Astrophysics Data System (ADS)

Zhang, Hong-Song; Zhang, Kong-Yan; Chen, Li-Chuan; Li, Yao-Xin; Chai, Lan-Qin

2017-10-01

N-(coumarin-3-yl)-N‧-(2-amino-5-phenyl-1,3,4-thiadiazol-2-yl) urea was synthesized and characterized by elemental analysis, IR, 1H NMR, 13C NMR, UV-Vis and emission spectroscopy, as well as by single-crystal X-ray diffraction. X-ray crystallographic analyses have indicated that the crystal structure consists of two dimethyl sulfoxide (DMSO) solvent molecules and the structural geometry of DMSO is a trigonal pyramid in shape. In the crystal structure, a self-assembling two-dimensional (2-D) layer supramolecular architecture is formed through intermolecular hydrogen bonds, Cdbnd O···π (thiadiazole ring) and π···π stacking interactions. The geometry of the compound has been optimized by the DFT method and the results are compared with the X-ray diffraction data. The electronic transitions and spectral features of the compound were carried out by using DFT/B3LYP method. In addition, the antimicrobial activity was also studied, and the highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO), and HOMO-LUMO gap were also calculated.

A Comparison of the Behavior of Functional/Basis Set Combinations for Hydrogen-Bonding in the Water Dimer with Emphasis on Basis Set Superposition Error

PubMed Central

Plumley, Joshua A.; Dannenberg, J. J.

2011-01-01

We evaluate the performance of nine functionals (B3LYP, M05, M05-2X, M06, M06-2X, B2PLYP, B2PLYPD, X3LYP, B97D and MPWB1K) in combination with 16 basis sets ranging in complexity from 6-31G(d) to aug-cc-pV5Z for the calculation of the H-bonded water dimer with the goal of defining which combinations of functionals and basis sets provide a combination of economy and accuracy for H-bonded systems. We have compared the results to the best non-DFT molecular orbital calculations and to experimental results. Several of the smaller basis sets lead to qualitatively incorrect geometries when optimized on a normal potential energy surface (PES). This problem disappears when the optimization is performed on a counterpoise corrected PES. The calculated ΔE's with the largest basis sets vary from -4.42 (B97D) to -5.19 (B2PLYPD) kcal/mol for the different functionals. Small basis sets generally predict stronger interactions than the large ones. We found that, due to error compensation, the smaller basis sets gave the best results (in comparison to experimental and high level non-DFT MO calculations) when combined with a functional that predicts a weak interaction with the largest basis set. Since many applications are complex systems and require economical calculations, we suggest the following functional/basis set combinations in order of increasing complexity and cost: 1) D95(d,p) with B3LYP, B97D, M06 or MPWB1k; 2) 6-311G(d,p) with B3LYP; 3) D95++(d,p) with B3LYP, B97D or MPWB1K; 4)6-311++G(d,p) with B3LYP or B97D; and 5) aug-cc-pVDZ with M05-2X, M06-2X or X3LYP. PMID:21328398

A comparison of the behavior of functional/basis set combinations for hydrogen-bonding in the water dimer with emphasis on basis set superposition error.

PubMed

Plumley, Joshua A; Dannenberg, J J

2011-06-01

We evaluate the performance of ten functionals (B3LYP, M05, M05-2X, M06, M06-2X, B2PLYP, B2PLYPD, X3LYP, B97D, and MPWB1K) in combination with 16 basis sets ranging in complexity from 6-31G(d) to aug-cc-pV5Z for the calculation of the H-bonded water dimer with the goal of defining which combinations of functionals and basis sets provide a combination of economy and accuracy for H-bonded systems. We have compared the results to the best non-density functional theory (non-DFT) molecular orbital (MO) calculations and to experimental results. Several of the smaller basis sets lead to qualitatively incorrect geometries when optimized on a normal potential energy surface (PES). This problem disappears when the optimization is performed on a counterpoise (CP) corrected PES. The calculated interaction energies (ΔEs) with the largest basis sets vary from -4.42 (B97D) to -5.19 (B2PLYPD) kcal/mol for the different functionals. Small basis sets generally predict stronger interactions than the large ones. We found that, because of error compensation, the smaller basis sets gave the best results (in comparison to experimental and high-level non-DFT MO calculations) when combined with a functional that predicts a weak interaction with the largest basis set. As many applications are complex systems and require economical calculations, we suggest the following functional/basis set combinations in order of increasing complexity and cost: (1) D95(d,p) with B3LYP, B97D, M06, or MPWB1k; (2) 6-311G(d,p) with B3LYP; (3) D95++(d,p) with B3LYP, B97D, or MPWB1K; (4) 6-311++G(d,p) with B3LYP or B97D; and (5) aug-cc-pVDZ with M05-2X, M06-2X, or X3LYP. Copyright © 2011 Wiley Periodicals, Inc.

Crystal growth, polarized spectroscopy and Judd-Ofelt analysis of Tb:YAlO3.

PubMed

Liu, Bin; Shi, Jiaojiao; Wang, Qingguo; Tang, Huili; Liu, Junfang; Zhao, Hengyu; Li, Dongzhen; Liu, Jian; Xu, Xiaodong; Wang, Zhanshan; Xu, Jun

2018-07-05

Tb 3+ -doped YAlO 3 (YAP) single crystal was grown by Czochralski (Cz) method. Based on the polarized absorption spectra, the spectroscopic parameters were calculated to be Ω 2 =3.49×10 -20 cm 2 , Ω 4 =5.87×10 -20 cm 2 and Ω 6 =2.55×10 -20 cm 2 , and then the spontaneous transition rate, fluorescent branching ratio and radiative lifetime of 5 D 4 multiplet were obtained. The yellow emission cross sections of 5 D 4 → 7 F 4 transition were calculated to be 1.72×10 -22 cm 2 , 2.73×10 -22 cm 2 and 2.65×10 -22 cm 2 for a, b and c polarization, respectively. The fluorescence lifetime of the 5 D 4 multiplet was fitted to be 1.72ms. All the data indicate that Tb:YAP crystal is a promising candidate for yellow laser operation. Copyright © 2018. Published by Elsevier B.V.

Measurements of Deuteron-Induced Activation Cross Sections for IFMIF Accelerator Structural Materials

NASA Astrophysics Data System (ADS)

Nakao, Makoto; Hori, Jun-ichi; Ochiai, Kentaro; Sato, Satoshi; Yamauchi, Michinori; Ishioka, Noriko S.; Nishitani, Takeo

2005-05-01

Activation cross sections for deuteron-induced reactions on aluminum, copper, and tungsten were measured by using a stacked-foil method. The stacked foils were irradiated with deuteron beam at the AVF cyclotron in the TIARA facility, JAERI. We obtained the activation cross sections for 27Al(d,2p)27Mg, 27Al(d,x)24Na, natCu(d,x)62,63Zn, 61,64Cu, and natW(d,x)181-184,186Re, 187W in the 22-40 MeV region. These cross sections were compared with other experimental ones and the data in the ACSELAM library calculated by the ALICE-F code.

Role of a Water Network around the Mn4CaO5 Cluster in Photosynthetic Water Oxidation: A Fourier Transform Infrared Spectroscopy and Quantum Mechanics/Molecular Mechanics Calculation Study.

PubMed

Nakamura, Shin; Ota, Kai; Shibuya, Yuichi; Noguchi, Takumi

2016-01-26

Photosynthetic water oxidation takes place at the Mn4CaO5 cluster in photosystem II. Around the Mn4CaO5 cluster, a hydrogen bond network is formed by several water molecules, including four water ligands. To clarify the role of this water network in the mechanism of water oxidation, we investigated the effects of the removal of Ca(2+) and substitution with metal ions on the vibrations of water molecules coupled to the Mn4CaO5 cluster by means of Fourier transform infrared (FTIR) difference spectroscopy and quantum mechanics/molecular mechanics (QM/MM) calculations. The OH stretching vibrations of nine water molecules forming a network between D1-D61 and YZ were calculated using the QM/MM method. On the the calculated normal modes, a broad positive feature at 3200-2500 cm(-1) in an S2-minus-S1 FTIR spectrum was attributed to the vibrations of strongly hydrogen-bonded OH bonds of water involving the vibrations of water ligands to a Mn ion and the in-phase coupled vibration of a water network connected to YZ, while bands in the 3700-3500 cm(-1) region were assigned to the coupled vibrations of weakly hydrogen-bonded OH bonds of water. All the water bands were lost upon Ca(2+) depletion and Ba(2+) substitution, which inhibit the S2 → S3 transition, indicating that a solid water network was broken by these treatments. By contrast, Sr(2+) substitution slightly altered the water bands around 3600 cm(-1), reflecting minor modification in water interactions, consistent with the retention of water oxidation activity with a decreased efficiency. These results suggest that the water network around the Mn4CaO5 cluster plays an essential role in the water oxidation mechanism particularly in a concerted process of proton transfer and water insertion during the S2 → S3 transition.

Systematic investigation on the validity of partition model dosimetry for 90Y radioembolization using Monte Carlo simulation

NASA Astrophysics Data System (ADS)

Aziz Hashikin, Nurul Ab; Yeong, Chai-Hong; Guatelli, Susanna; Jeet Abdullah, Basri Johan; Ng, Kwan-Hoong; Malaroda, Alessandra; Rosenfeld, Anatoly; Perkins, Alan Christopher

2017-09-01

We aimed to investigate the validity of the partition model (PM) in estimating the absorbed doses to liver tumour ({{D}T} ), normal liver tissue ({{D}NL} ) and lungs ({{D}L} ), when cross-fire irradiations between these compartments are being considered. MIRD-5 phantom incorporated with various treatment parameters, i.e. tumour involvement (TI), tumour-to-normal liver uptake ratio (T/N) and lung shunting (LS), were simulated using the Geant4 Monte Carlo (MC) toolkit. 108 track histories were generated for each combination of the three parameters to obtain the absorbed dose per activity uptake in each compartment (DT{{AT}} , DNL{{ANL}} , and DL{{AL}} ). The administered activities, A were estimated using PM, so as to achieve either limiting doses to normal liver, DNLlim or lungs, ~DLlim (70 or 30 Gy, respectively). Using these administered activities, the activity uptake in each compartment ({{A}T} , {{A}NL} , and {{A}L} ) was estimated and multiplied with the absorbed dose per activity uptake attained using the MC simulations, to obtain the actual dose received by each compartment. PM overestimated {{D}L} by 11.7% in all cases, due to the escaped particles from the lungs. {{D}T} and {{D}NL} by MC were largely affected by T/N, which were not considered by PM due to cross-fire exclusion at the tumour-normal liver boundary. These have resulted in the overestimation of {{D}T} by up to 8% and underestimation of {{D}NL} by as high as  -78%, by PM. When DNLlim was estimated via PM, the MC simulations showed significantly higher {{D}NL} for cases with higher T/N, and LS  ⩽  10%. All {{D}L} and {{D}T} by MC were overestimated by PM, thus DLlim were never exceeded. PM leads to inaccurate dose estimations due to the exclusion of cross-fire irradiation, i.e. between the tumour and normal liver tissue. Caution should be taken for cases with higher TI and T/N, and lower LS, as they contribute to major underestimation of {{D}NL} . For {{D}L} , a different correction factor for dose calculation may be used for improved accuracy.

DFT Study of the Oxygen Reduction Reaction Activity on Fe−N4-Patched Carbon Nanotubes: The Influence of the Diameter and Length

PubMed Central

Chen, Xin; Hu, Rui; Bai, Fan

2017-01-01

The influences of diameter and length of the Fe−N4-patched carbon nanotubes (Fe−N4/CNTs) on oxygen reduction reaction (ORR) activity were investigated by density functional theory method using the BLYP/DZP basis set. The results indicate that the stability of the Fe−N4 catalytic site in Fe−N4/CNTs will be enhanced with a larger tube diameter, but reduced with shorter tube length. A tube with too small a diameter makes a Fe−N4 site unstable in acid medium since Fe−N and C−N bonds must be significantly bent at smaller diameters due to hoop strain. The adsorption energy of the ORR intermediates, especially of the OH group, becomes weaker with the increase of the tube diameter. The OH adsorption energy of Fe−N4/CNT with the largest tube diameter is close to that on Pt(111) surface, indicating that its catalytic property is similar to Pt. Electronic structure analysis shows that the OH adsorption energy is mainly controlled by the energy levels of Fe 3d orbital. The calculation results uncover that Fe−N4/CNTs with larger tube diameters and shorter lengths will exhibit better ORR activity and stability. PMID:28772903

GATA4-mediated cardiac hypertrophy induced by D-myo-inositol 1,4,5-tris-phosphate

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

Zhu Zhiming; Zhu Shanjun; Liu Daoyan

2005-12-16

We evaluated the effects of D-myo-inositol 1,4,5-tris-phosphate on cardiac hypertrophy. D-myo-inositol 1,4,5-tris-phosphate augmented cardiac hypertrophy as evidenced by its effects on DNA synthesis, protein synthesis, and expression of immediate-early genes c-myc and c-fos, {beta}-myosin heavy chain, and {alpha}-actin. The administration of D-myo-inositol 1,4,5-tris-phosphate increased the expression of nuclear factor of activated T-cells and cardiac-restricted zinc finger transcription factor (GATA4). Real-time quantitative RT-PCR showed that D-myo-inositol 1,4,5-tris-phosphate-induced GATA4 mRNA was significantly enhanced even in the presence of the calcineurin inhibitor, cyclosporine A. The effect of D-myo-inositol 1,4,5-tris-phosphate was blocked after inhibition of inositol-trisphosphate receptors but not after inhibition of c-Raf/mitogen-activated proteinmore » kinase kinase (MEK)/mitogen-activated protein kinase (ERK) or p38 mitogen-activated protein kinase pathways. The study shows that D-myo-inositol 1,4,5-tris-phosphate-induced cardiac hypertrophy is mediated by GATA4 but independent from the calcineurin pathway.« less

An amorphous FeMoS4 nanorod array toward efficient hydrogen evolution electrocatalysis under neutral conditions.

PubMed

Ren, Xiang; Wang, Weiyi; Ge, Ruixiang; Hao, Shuai; Qu, Fengli; Du, Gu; Asiri, Abdullah M; Wei, Qin; Chen, Liang; Sun, Xuping

2017-08-08

It is highly attractive to develop efficient hydrogen-evolving electrocatalysts under neutral conditions. In this communication, we report an amorphous FeMoS 4 nanorod array on carbon cloth (FeMoS 4 NRA/CC) prepared by hydrothermal treatment of an FeOOH nanorod array on carbon cloth (FeOOH NRA/CC) in (NH 4 ) 2 MoS 4 solution. As a 3D electrode for hydrogen evolution electrocatalysis, this FeMoS 4 NRA/CC demonstrates superior catalytic activity and strong long-term electrochemical durability in 1.0 M phosphate buffered saline (pH: 7). It needs an overpotential of 204 mV to drive a geometrical current density of 10 mA cm -2 , which is 450 mV less than that for FeOOH NRA/CC. Density functional theory calculations suggest that FeMoS 4 has a more favourable hydrogen adsorption free energy than FeOOH.

Electron impact excitation rate coefficients for P-like Ni XIV

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

Wang, K.; Shanghai EBIT Lab, Institute of Modern Physics, Department of Nuclear Science and Technology, Fudan University, Shanghai 200433; Yan, J.

2012-07-15

We have calculated the atomic data including electron impact excitations and radiative decays among the lowest 143 fine-structure levels arising from 3s{sup 2}3p{sup 3}, 3s3p{sup 4}, 3s{sup 2}3p{sup 2}3d, 3p{sup 5}, 3s3p{sup 3}3d, and 3s{sup 2}3p3d{sup 2} configurations in P-like Ni XIV. Direct excitation collision strengths are calculated employing the relativistic distorted-wave method. Resonances are included via the isolated resonance approximation using distorted-waves. Resonance contributions from S-like [3s{sup 2}3p{sup 3}, 3s3p{sup 4}, 3s{sup 2}3p{sup 2}3d,3p{sup 5}, 3s3p{sup 3}3d,3s{sup 2}3p3d{sup 2}, 3p{sup 4}3d,3s3p{sup 2}3d{sup 2},3s{sup 2}3d{sup 3}]n{sup Prime }l{sup Prime} complex series are taken into account. Effective collision strengths are reportedmore » over an electron temperature range of 1.0 Multiplication-Sign 10{sup 5}-1.0 Multiplication-Sign 10{sup 8} K. -- Highlights: Black-Right-Pointing-Pointer Radiative and collisional atomic data are presented for the lowest 143 fine-structure levels in P-like Ni XIV. Black-Right-Pointing-Pointer Calculations are performed using the FAC package. Black-Right-Pointing-Pointer Resonances enhance significantly a large amount of transitions. Black-Right-Pointing-Pointer Resonances play an important role of level population and line intensity ratios.« less

Protein requirement of young adult Nigerian females on habitual Nigerian diet at the usual level of energy intake.

PubMed

Egun, G N; Atinmo, T

1993-09-01

A short-term N balance study was conducted in twelve healthy female adults aged 21-32 years to determine their protein requirement. Four dietary protein levels (0.3, 0.4, 0.5 and 0.6 g protein/kg per d) were used. Energy intake of the subjects was kept constant at 0.18 MJ/kg per d. All subjects maintained their normal activity throughout the study period. N excretion was determined from the measurements of N in a total collection of urine, faeces, sweat and menstrual fluid for each dietary period. N balance during the four protein levels were -15.15 (SD 5.95), -5.53 (SD 6.71), +6.15 (SD 4.76) and +12.05 (SD 8.63) mg N/kg per d for 0.3, 0.4, 0.5 and 0.6 g protein/kg per d respectively. The calculated average N requirements from regression analysis was 76.0 (SD 3.37) mg N/kg per d (0.48 g protein/kg per d). The estimate of allowance for individual variation to cover the 97.5% population was 95 mg N/kg per d (0.6 g protein/kg per d). The net protein utilization (NPU) of the diet was 0.55. When compared with a similar study with men, there was a significant difference in the protein requirement between sexes. Thus, the unjustifiable sex difference in the protein allowance recommended by the Food and Agriculture Organization/World Health Organization/United Nations University (1985) Expert Consultation group must be reviewed.

Distinct Physiological Effects of Dopamine D4 Receptors on Prefrontal Cortical Pyramidal Neurons and Fast-Spiking Interneurons

PubMed Central

Zhong, Ping; Yan, Zhen

2016-01-01

Dopamine D4 receptor (D4R), which is strongly linked to neuropsychiatric disorders, such as attention-deficit hyperactivity disorder and schizophrenia, is highly expressed in pyramidal neurons and GABAergic interneurons in prefrontal cortex (PFC). In this study, we examined the impact of D4R on the excitability of these 2 neuronal populations. We found that D4R activation decreased the frequency of spontaneous action potentials (sAPs) in PFC pyramidal neurons, whereas it induced a transient increase followed by a decrease of sAP frequency in PFC parvalbumin-positive (PV+) interneurons. D4R activation also induced distinct effects in both types of PFC neurons on spontaneous excitatory and inhibitory postsynaptic currents, which drive the generation of sAP. Moreover, dopamine substantially decreased sAP frequency in PFC pyramidal neurons, but markedly increased sAP frequency in PV+ interneurons, and both effects were partially mediated by D4R activation. In the phencyclidine model of schizophrenia, the decreasing effect of D4R on sAP frequency in both types of PFC neurons was attenuated, whereas the increasing effect of D4R on sAP in PV+ interneurons was intact. These results suggest that D4R activation elicits distinct effects on synaptically driven excitability in PFC projection neurons versus fast-spiking interneurons, which are differentially altered in neuropsychiatric disorder-related conditions. PMID:25146372

Development, validation, and implementation of a patient-specific Monte Carlo 3D internal dosimetry platform

NASA Astrophysics Data System (ADS)

Besemer, Abigail E.

Targeted radionuclide therapy is emerging as an attractive treatment option for a broad spectrum of tumor types because it has the potential to simultaneously eradicate both the primary tumor site as well as the metastatic disease throughout the body. Patient-specific absorbed dose calculations for radionuclide therapies are important for reducing the risk of normal tissue complications and optimizing tumor response. However, the only FDA approved software for internal dosimetry calculates doses based on the MIRD methodology which estimates mean organ doses using activity-to-dose scaling factors tabulated from standard phantom geometries. Despite the improved dosimetric accuracy afforded by direct Monte Carlo dosimetry methods these methods are not widely used in routine clinical practice because of the complexity of implementation, lack of relevant standard protocols, and longer dose calculation times. The main goal of this work was to develop a Monte Carlo internal dosimetry platform in order to (1) calculate patient-specific voxelized dose distributions in a clinically feasible time frame, (2) examine and quantify the dosimetric impact of various parameters and methodologies used in 3D internal dosimetry methods, and (3) develop a multi-criteria treatment planning optimization framework for multi-radiopharmaceutical combination therapies. This platform utilizes serial PET/CT or SPECT/CT images to calculate voxelized 3D internal dose distributions with the Monte Carlo code Geant4. Dosimetry can be computed for any diagnostic or therapeutic radiopharmaceutical and for both pre-clinical and clinical applications. In this work, the platform's dosimetry calculations were successfully validated against previously published reference doses values calculated in standard phantoms for a variety of radionuclides, over a wide range of photon and electron energies, and for many different organs and tumor sizes. Retrospective dosimetry was also calculated for various pre-clinical and clinical patients and large dosimetric differences resulted when using conventional organ-level methods and the patient-specific voxelized methods described in this work. The dosimetric impact of various steps in the 3D voxelized dosimetry process were evaluated including quantitative imaging acquisition, image coregistration, voxel resampling, ROI contouring, CT-based material segmentation, and pharmacokinetic fitting. Finally, a multi-objective treatment planning optimization framework was developed for multi-radiopharmaceutical combination therapies.

Municipal waste stabilization in a reactor with an integrated active and passive aeration system.

PubMed

Kasinski, Slawomir; Slota, Monika; Markowski, Michal; Kaminska, Anna

2016-04-01

To test whether an integrated passive and active aeration system could be an effective solution for aerobic decomposition of municipal waste in technical conditions, a full-scale composting reactor was designed. The waste was actively aerated for 5d, passively aerated for 35 d, and then actively aerated for 5d, and the entire composting process was monitored. During the 45-day observation period, changes in the fractional, morphological and physico-chemical characteristics of the waste at the top of the reactor differed from those in the center of the reactor. The fractional and morphological analysis made during the entire process of stabilization, showed the total reduction of organic matter measured of 82 wt% and 86 wt% at the respective depths. The reduction of organic matter calculated using the results of Lost of Ignition (LOI) and Total Organic Carbon (TOC) showed, respectively, 40.51-46.62% organic matter loss at the top and 45.33-53.39% in the center of the reactor. At the end of the process, moisture content, LOI and TOC at the top were 3.29%, 6.10% and 4.13% higher, respectively, than in the center. The results showed that application of passive aeration in larger scale simultaneously allows the thermophilic levels to be maintained during municipal solid waste composting process while not inhibiting microbial activity in the reactor. Copyright © 2016 Elsevier Ltd. All rights reserved.

Magnetic Transitions in Iron Porphyrin Halides by Inelastic Neutron Scattering and Ab Initio Studies of Zero-Field Splittings.

PubMed

Stavretis, Shelby E; Atanasov, Mihail; Podlesnyak, Andrey A; Hunter, Seth C; Neese, Frank; Xue, Zi-Ling

2015-10-19

Zero-field splitting (ZFS) parameters of nondeuterated metalloporphyrins [Fe(TPP)X] (X = F, Br, I; H₂TPP = tetraphenylporphyrin) have been directly determined by inelastic neutron scattering (INS). The ZFS values are D = 4.49(9) cm⁻¹ for tetragonal polycrystalline [Fe(TPP)F], and D = 8.8(2) cm⁻¹, E = 0.1(2) cm⁻¹ and D = 13.4(6) cm⁻¹, E = 0.3(6) cm⁻¹ for monoclinic polycrystalline [Fe(TPP)Br] and [Fe(TPP)I], respectively. Along with our recent report of the ZFS value of D = 6.33(8) cm⁻¹ for tetragonal polycrystalline [Fe(TPP)Cl], these data provide a rare, complete determination of ZFS parameters in a metalloporphyrin halide series. The electronic structure of [Fe(TPP)X] (X = F, Cl, Br, I) has been studied by multireference ab initio methods: the complete active space self-consistent field (CASSCF) and the N-electron valence perturbation theory (NEVPT2) with the aim of exploring the origin of the large and positive zero-field splitting D of the ⁶A₁ ground state. D was calculated from wave functions of the electronic multiplets spanned by the d⁵ configuration of Fe(III) along with spin–orbit coupling accounted for by quasi degenerate perturbation theory. Results reproduce trends of D from inelastic neutron scattering data increasing in the order from F, Cl, Br, to I. A mapping of energy eigenvalues and eigenfunctions of the S = 3/2 excited states on ligand field theory was used to characterize the σ- and π-antibonding effects decreasing from F to I. This is in agreement with similar results deduced from ab initio calculations on CrX₆³⁻ complexes and also with the spectrochemical series showing a decrease of the ligand field in the same directions. A correlation is found between the increase of D and decrease of the π- and σ-antibonding energies e(λ)(X) (λ = σ, π) in the series from X = F to I. Analysis of this correlation using second-order perturbation theory expressions in terms of angular overlap parameters rationalizes the experimentally deduced trend. D parameters from CASSCF and NEVPT2 results have been calibrated against those from the INS data, yielding a predictive power of these approaches. Methods to improve the quantitative agreement between ab initio calculated and experimental D and spectroscopic transitions for high-spin Fe(III) complexes are proposed.

Physics of bandgap formation in Cu-Sb-Se based novel thermoelectrics: the role of Sb valency and Cu d levels.

PubMed

Do, Dat; Ozolins, Vidvuds; Mahanti, S D; Lee, Mal-Soon; Zhang, Yongsheng; Wolverton, C

2012-10-17

In this paper we discuss the results of ab initio electronic structure calculations for Cu(3)SbSe(4) (Se4) and Cu(3)SbSe(3) (Se3), two narrow bandgap semiconductors of thermoelectric interest. We find that Sb is trivalent in both the compounds, in contrast to a simple nominal valence (ionic) picture which suggests that Sb should be 5 + in Se4. The gap formation in Se4 is quite subtle, with hybridization between Sb 5s and the neighboring Se 4s, 4p orbitals, position of Cu d states, and non-local exchange interaction, each playing significant roles. Thermopower calculations show that Se4 is a better p-type system. Our theoretical results for Se4 agree very well with recent experimental results obtained by Skoug et al (2011 Sci. Adv. Mater. 3 602).

Comparison of SSS and SRS calculated from normal databases provided by QPS and 4D-MSPECT manufacturers and from identical institutional normals.

PubMed

Knollmann, Daniela; Knebel, Ingrid; Koch, Karl-Christian; Gebhard, Michael; Krohn, Thomas; Buell, Ulrich; Schaefer, Wolfgang M

2008-02-01

There is proven evidence for the importance of myocardial perfusion-single-photon emission computed tomography (SPECT) with computerised determination of summed stress and rest scores (SSS/SRS) for the diagnosis of coronary artery disease (CAD). SSS and SRS can thereby be calculated semi-quantitatively using a 20-segment model by comparing tracer-uptake with values from normal databases (NDB). Four severity-degrees for SSS and SRS are normally used: <4, 4-8, 9-13, and > or =14. Manufacturers' NDBs (M-NDBs) often do not fit the institutional (I) settings. Therefore, this study compared SSS and SRS obtained with the algorithms Quantitative Perfusion SPECT (QPS) and 4D-MSPECT using M-NDB and I-NDB. I-NDBs were obtained using QPS and 4D-MSPECT from exercise stress data (450 MBq (99m)Tc-tetrofosmin, triple-head-camera, 30 s/view, 20 views/head) from 36 men with a low post-stress test CAD probability and visually normal SPECT findings. Patient group was 60 men showing the entire CAD-spectrum referred for routine perfusion-SPECT. Stress/rest results of automatic quantification of the 60 patients were compared to M-NDB and I-NDB. After reclassifying SSS/SRS into the four severity degrees, kappa values were calculated to objectify agreement. Mean values (vs M-NDB) were 9.4 +/- 10.3 (SSS) and 5.8 +/- 9.7 (SRS) for QPS and 8.2 +/- 8.7 (SSS) and 6.2 +/- 7.8 (SRS) for 4D-MSPECT. Thirty seven of sixty SSS classifications (kappa = 0.462) and 40/60 SRS classifications (kappa = 0.457) agreed. Compared to I-NDB, mean values were 10.2 +/- 11.6 (SSS) and 6.5 +/- 10.4 (SRS) for QPS and 9.2 +/- 9.3 (SSS) and 7.2 +/- 8.6 (SRS) for 4D-MSPECT. Forty four of sixty patients agreed in SSS and SRS (kappa = 0.621 resp. 0.58). Considerable differences between SSS/SRS obtained with QPS and 4D-MSPECT were found when using M-NDB. Even using identical patients and identical I-NDB, the algorithms still gave substantial different results.

Determination of the cross section for (n,p) and (n,α) reactions on (165)Ho at 13.5 and 14.8MeV.

PubMed

Luo, Junhua; An, Li; Jiang, Li; He, Long

2015-04-01

Activation cross-sections for the (165)Ho(n,p)(165)Dy and (165)Ho(n,α)(162)Tb reactions were measured by means of the activation method at 13.5 and 14.8MeV, to resolve inconsistencies in existing data. A neutron beam produced via the (3)H(d,n)(4)He reaction was used. Statistical model calculations were performed using the nuclear-reaction codes EMPIRE-3.2 Malta and TALYS-1.6 with default parameters, at neutron energies varying from the reaction threshold to 20MeV. Results are also discussed and compared with some corresponding values found in the literature. The calculational results on the (165)Ho(n,α)(162)Tb reaction agreed fairly well with experimental data, but there were large discrepancies in the results for the (165)Ho(n,p)(165)Dy reaction. Copyright © 2015 Elsevier Ltd. All rights reserved.

Vibration-Rotation Bands of HF and DF

DTIC Science & Technology

1977-09-23

98 IZa. Comparison of Observed and Calculated Line Positions of HF, Av = I Sequence ........................... 99 f2b. Comparison of Observed and...Calculated Line Positions of HF, Av = 2 Sequence ........................... 102 12c. Comparison of Observed and Calculated Line Positions of HF, Av = 3...Sequence ........................... 107 i2d. Comparison of Observed and Calculated Line Positions ofHF, Av = 4 Sequence ........................... fi

Theoretical study of the crystal-field energy levels and two-photon absorption intensities of Tb3+ in cubic host lattices.

PubMed

Duan, Chang-Kui; Tanner, Peter A

2011-03-17

Published two photon excitation (TPE) intensities for the cubic elpasolite systems Cs(2)NaTbX(6) (X = Cl, F) have been simulated by a calculation of two photon absorption (TPA) intensities which takes into account electric dipole transitions involving the detailed crystal-field structure of 4f(7)5d intermediate states, as well as the interactions of the 4f(7) core with the d-electron. The intensity calculation employed parameters from an energy level calculation which not only presented an accurate fit, but also yielded parameters consistent with those from other lanthanide ions. The calculated intensities were used to confirm or adjust the previous assignments of energy levels, resulting in some minor revisions. Generally, the TPA intensity simulations were in better agreement with experimental data for the fluoride, rather than the chloride, system and possible reasons for this are given.

An Electrochemical Capacitor with Applicable Energy Density of 7.4 Wh/kg at Average Power Density of 3000 W/kg.

PubMed

Zhai, Teng; Lu, Xihong; Wang, Hanyu; Wang, Gongming; Mathis, Tyler; Liu, Tianyu; Li, Cheng; Tong, Yexiang; Li, Yat

2015-05-13

Electrochemical capacitors represent a new class of charge storage devices that can simultaneously achieve high energy density and high power density. Previous reports have been primarily focused on the development of high performance capacitor electrodes. Although these electrodes have achieved excellent specific capacitance based on per unit mass of active materials, the gravimetric energy densities calculated based on the weight of entire capacitor device were fairly small. This is mainly due to the large mass ratio between current collector and active material. We aimed to address this issue by a 2-fold approach of minimizing the mass of current collector and increasing the electrode performance. Here we report an electrochemical capacitor using 3D graphene hollow structure as current collector, vanadium sulfide and manganese oxide as anode and cathode materials, respectively. 3D graphene hollow structure provides a lightweight and highly conductive scaffold for deposition of pseudocapacitive materials. The device achieves an excellent active material ratio of 24%. Significantly, it delivers a remarkable energy density of 7.4 Wh/kg (based on the weight of entire device) at the average power density of 3000 W/kg. This is the highest gravimetric energy density reported for asymmetric electrochemical capacitors at such a high power density.

Structural investigation of a new antimicrobial thiazolidine compound

NASA Astrophysics Data System (ADS)

Cozar, I. B.; Pırnǎu, A.; Vedeanu, N.; Nastasǎ, C.

2013-11-01

Thiazoles and their derivatives have attracted the interest over the last decades because of their varied biological activities: antibacterial, antiviral, antifungal, inflammation or in the treatment of allergies. A new synthesized compound 3-[2-(4-Methyl-2-phenyl-thiazol-5-yl)-2-oxo-ethyl]-thazolidine-2,4-dione was investigated by FT-IR, FT-Raman, 1H, 13C NMR spectroscopies and also by DFT calculations at B3LYP/6-31G(d) level of theory. The very good correlation found between the experimental and theoretical data shows that the optimized molecular structure is very close to reality. Also the NMR spectra show a monomeric behaviour of this compound in solutions.

Structural investigation of a new antimicrobial thiazolidine compound

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

Cozar, I. B.; Pîrnău, A.; Vedeanu, N.

2013-11-13

Thiazoles and their derivatives have attracted the interest over the last decades because of their varied biological activities: antibacterial, antiviral, antifungal, inflammation or in the treatment of allergies. A new synthesized compound 3-[2-(4-Methyl-2-phenyl-thiazol-5-yl)-2-oxo-ethyl]-thazolidine-2,4-dione was investigated by FT-IR, FT-Raman, {sup 1}H, {sup 13}C NMR spectroscopies and also by DFT calculations at B3LYP/6-31G(d) level of theory. The very good correlation found between the experimental and theoretical data shows that the optimized molecular structure is very close to reality. Also the NMR spectra show a monomeric behaviour of this compound in solutions.

Lipopolysaccharide regulation of intestinal tight junction permeability is mediated by TLR-4 signal transduction pathway activation of FAK and MyD88

PubMed Central

Guo, Shuhong; Nighot, Meghali; Al-Sadi, Rana; Alhmoud, Tarik; Nighot, Prashant; Ma, Thomas Y.

2015-01-01

Gut-derived bacterial lipopolysaccharides (LPS) play an essential role in inducing intestinal and systemic inflammatory responses and have been implicated as a pathogenic factor of necrotizing enterocolitis (NEC) and inflammatory bowel disease (IBD). The defective intestinal tight junction (TJ) barrier has been shown to be an important factor contributing to the development of intestinal inflammation. LPS, at physiological concentrations, cause an increase in intestinal tight junction permeability (TJP) via a TLR-4 dependent process; however the intracellular mechanisms that mediate LPS regulation of intestinal TJP remain unclear. The aim of this study was to investigate the adaptor proteins and the signaling interactions that mediate LPS modulation of intestinal TJ barrier using an in-vitro and in-vivo model system. LPS caused a TLR-4 dependent activation of membrane-associated adaptor protein FAK in Caco-2 monolayers. LPS caused an activation of both MyD88-dependent and –independent pathways. SiRNA silencing of MyD88 prevented LPS-induced increase in TJP. LPS caused a MyD88-dependent activation of IRAK4. TLR-4, FAK and MyD88 were co-localized. SiRNA silencing of TLR-4 inhibited TLR-4 associated FAK activation; and FAK knockdown prevented MyD88 activation. In-vivo studies also confirmed that LPS-induced increase in mouse intestinal permeability was associated with FAK and MyD88 activation; knockdown of intestinal epithelial FAK prevented LPS-induced increase in intestinal permeability. Additionally, high dose LPS-induced intestinal inflammation was also dependent on TLR-4/FAK/MyD88 signal-transduction axis. Our data show for the first time that LPS-induced increase in intestinal TJP and intestinal inflammation was regulated by TLR-4 dependent activation of FAK-MyD88-IRAK4 signaling pathway. PMID:26466961

Electrical transport via variable range hopping in an individual multi-wall carbon nanotube

NASA Astrophysics Data System (ADS)

Husain Khan, Zishan; Husain, M.; Perng, T. P.; Salah, Numan; Habib, Sami

2008-11-01

E-beam lithography is used to make four leads on an individual multi-wall carbon nanotube for carrying out electrical transport measurements. Temperature dependence of conductance of an individual multi-wall carbon nanotube (MWNT) is studied over a temperature range of (297 4.8 K). The results indicate that the conduction is governed by variable range hopping (VRH) for the entire temperature range (297 4.8 K). This VRH mechanism changes from three dimensions (3D) to two dimensions (2D) as we go down to 70 K. Three-dimensional variable range hopping (3D VRH) is responsible for conduction in the temperature range (297 70 K), which changes to two-dimensional VRH for much lower temperatures (70 4.8 K). For 3D VRH, various Mott parameters such as density of states, hopping distance and hopping energy have been calculated. The 2D VRH mechanism has been applied for the temperature range (70 4.8 K) and, with the help of this model, the parameters such as localization length and hopping distance are calculated. All these parameters give interesting information about this complex structure, which may be useful for many applications.

Structural Basis for Activation of the Receptor Tyrosine Kinase KIT by Stem Cell Factor

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

Yuzawa,S.; Opatowsky, Y.; Zhang, Z.

2007-01-01

Stem Cell Factor (SCF) initiates its multiple cellular responses by binding to the ectodomain of KIT, resulting in tyrosine kinase activation. We describe the crystal structure of the entire ectodomain of KIT before and after SCF stimulation. The structures show that KIT dimerization is driven by SCF binding whose sole role is to bring two KIT molecules together. Receptor dimerization is followed by conformational changes that enable lateral interactions between membrane proximal Ig-like domains D4 and D5 of two KIT molecules. Experiments with cultured cells show that KIT activation is compromised by point mutations in amino acids critical for D4-D4more » interaction. Moreover, a variety of oncogenic mutations are mapped to the D5-D5 interface. Since key hallmarks of KIT structures, ligand-induced receptor dimerization, and the critical residues in the D4-D4 interface, are conserved in other receptors, the mechanism of KIT stimulation unveiled in this report may apply for other receptor activation.« less

Antioxidant potential of curcumin-related compounds studied by chemiluminescence kinetics, chain-breaking efficiencies, scavenging activity (ORAC) and DFT calculations

PubMed Central

Slavova-Kazakova, Adriana K; Angelova, Silvia E; Veprintsev, Timur L; Denev, Petko; Fabbri, Davide; Dettori, Maria Antonietta; Kratchanova, Maria; Naumov, Vladimir V; Trofimov, Aleksei V; Vasil’ev, Rostislav F

2015-01-01

Summary This study compares the ability to scavenge different peroxyl radicals and to act as chain-breaking antioxidants of monomers related to curcumin (1): dehydrozingerone (2), zingerone (3), (2Z,5E)-ethyl 2-hydroxy-6-(4-hydroxy-3-methoxyphenyl)-4-oxohexa-2,5-dienoate (4), ferulic acid (5) and their corresponding C 2-symmetric dimers 6–9. Four models were applied: model 1 – chemiluminescence (CL) of a hydrocarbon substrate used for determination of the rate constants (k A) of the reactions of the antioxidants with peroxyl radicals; model 2 – lipid autoxidation (lipidAO) used for assessing the chain-breaking antioxidant efficiency and reactivity; model 3 – oxygen radical absorbance capacity (ORAC), which yields the activity against peroxyl radicals generated by an azoinitiator; model 4 – density functional theory (DFT) calculations at UB3LYP/6-31+G(d,p) level, applied to explain the structure–activity relationship. Dimers showed 2–2.5-fold higher values of k A than their monomers. Model 2 gives information about the effects of the side chains and revealed much higher antioxidant activity for monomers and dimers with α,β-unsaturated side chains. Curcumin and 6 in fact are dimers of the same monomer 2. We conclude that the type of linkage between the two “halves” by which the molecule is made up does not exert influence on the antioxidant efficiency and reactivity of these two dimers. The dimers and the monomers demonstrated higher activity than Trolox (10) in aqueous medium (model 3). A comparison of the studied compounds with DL-α-tocopherol (11), Trolox and curcumin is made. All dimers are characterized through lower bond dissociation enthalpies (BDEs) than their monomers (model 4), which qualitatively supports the experimental results. PMID:26425195

Oscillator Strengths of Allowed and Intercombination Transitions in Neutral Sulfur

NASA Technical Reports Server (NTRS)

Tayal, S. S.

1998-01-01

We have calculated oscillator strengths and transition probabilities of electric-dipole allowed and intercombination transitions from fine-structure levels of the ground 3s(sup 2)3p(sup 4) configuration to the levels belonging to configurations 3s(sup 2)3p(sup 3)4s, 3s(sup 2) 3p(sup 3)5s, 3(sup 2)3p(sup 3)3d, 3s(sup 2)3p(sup 3)4d of neutral sulfur. Extensive configuration-interaction wave functions are used to represent these levels. The relativistic corrections have been included through the Breit-Pauli Hamiltonian. The results are compared with previous theoretical calculations and with measurements.

Mechanical properties of 4d transition metals in molten state

NASA Astrophysics Data System (ADS)

Singh, Deobrat; Sonvane, Yogesh; Thakor, P. B.

2016-05-01

Mechanical properties of 4d transition metals in molten state have been studied in the present study. We have calculated mechanical properties such as isothermal bulk modulus (B), modulus of rigidity (G), Young's modulus (Y) and Hardness have also been calculated from the elastic part of the Phonon dispersion curve (PDC). To describe the structural information, we have used different structure factor S(q) using Percus-Yevick hard sphere (PYHS) reference systems along with our newly constructed parameter free model potential.To see the influence of exchange and correlation effect on the above said properties of 3d liquid transition metals, we have used Sarkar et al (S)local field correction functions. Present results have been found good in agreement with available experimental data.

The effect of individual antiretroviral drugs on body composition in HIV-infected persons initiating highly active antiretroviral therapy.

PubMed

Shlay, Judith C; Sharma, Shweta; Peng, Grace; Gibert, Cynthia L; Grunfeld, Carl

2009-07-01

To examine the long-term effects of individual antiretroviral drugs on body composition among 416 persons initiating antiretroviral therapy (ART). In a substudy of a clinical trial of persons initiating ART, changes in body composition attributable to individual ART were examined. ARTs assessed were as follows: indinavir, ritonavir, nelfinavir, efavirenz, nevirapine, stavudine (d4T), zidovudine (ZDV), lamivudine (3TC), didanosine, and abacavir. Skinfolds and circumferences were measured at baseline and every 4 months. Mid arm, mid thigh, and waist subcutaneous tissue areas and nonsubcutaneous tissue areas were calculated. Rates of change per year of exposure to each individual ART drug were determined using multivariate longitudinal regression. d4T and ZDV use was associated with losses in subcutaneous tissue area and skinfold thickness. 3TC use was associated with gains in all subcutaneous tissue areas and skinfold thickness, whereas abacavir use was associated with an increase in waist subcutaneous tissue area. Indinavir was associated with gains in waist subcutaneous tissue area, whereas indinavir, efavirenz, and nevirapine were associated with increases in upper back skinfolds. d4T use was also associated with increases in all nonsubcutaneous tissue areas; 3TC use was associated with the greatest increase in waist nonsubcutaneous tissue area. In this prospective nonrandomized evaluation, the nucleoside reverse transcriptase inhibitors d4T and ZDV were associated with decreases in subcutaneous tissue areas, whereas 3TC use was associated with increased subcutaneous tissue areas and waist nonsubcutaneous tissue area.

Removal of 2,4-D from aqueous solutions by adsorption processes using two biopolymers: chitin and chitosan and their optical properties

NASA Astrophysics Data System (ADS)

El Harmoudi, H.; El Gaini, L.; Daoudi, E.; Rhazi, M.; Boughaleb, Y.; El Mhammedi, M. A.; Migalska-Zalas, A.; Bakasse, M.

2014-07-01

Chitin, extracted primarily from exoskeleton shellfish, is one of the most abundant biopolymer in the world. It is estimated to be produced annually almost as much as cellulose. The development of fishing activities in Morocco (coastline of 3500 km on both the Atlantic and the Mediterranean) induced an important fish industry waste. The aim of this work is to recover chitin, extracted from shellfish waste, and chitosan, produced by deacetylation of chitin, in the adsorption of organic pesticide 2,4-dichlorophenoxyacetate (2,4-D). The chitosan samples were prepared from chitin from crustacean shells. The chitin deacetylation was carried out in aqueous sodium hydroxide. Characterization of chitin and chitosan was performed by infrared spectroscopy, nuclear magnetic resonance and theoretical calculation of UV-Vis spectra and optical parameters. Analysis of theoretical spectra shows a substantial sensitivity to the hydroxyl and amino groups. The presented hydroxyl group in chitin determines the conformation of the molecule and also the stereochemistry of chemical reactions and kinetics. The presence of functional groups causes the substantial changes of both absorption spectra as well as permanent dipole moment. The adsorption of 2,4-D by chitin and chitosan was performed at different pH values, the pesticide-adsorbent contact time and initial pesticide concentration. The adsorption is described by Langmuir-type isotherm and Freundlich-type isotherm. Recovery tests of 2,4-D confirm the initial interest in using chitin and chitosan as a depolluting agent.

Nitroxyl Radical plus Hydroxylamine Pseudo Self-Exchange Reactions: Tunneling in Hydrogen Atom Transfer

PubMed Central

Wu, Adam; Mader, Elizabeth A.; Datta, Ayan; Hrovat, David A.; Borden, Weston Thatcher; Mayer, James M.

2009-01-01

Bimolecular rate constants have been measured for reactions that involve hydrogen atom transfer (HAT) from hydroxylamines to nitroxyl radicals, using the stable radicals TEMPO• (2,2,6,6-tetramethylpiperidine-1-oxyl radical), 4-oxo-TEMPO• (2,2,6,6-tetramethyl-4-oxo-piperidine-1-oxyl radical), di-tert-butylnitroxyl (tBu2NO•), and the hydroxylamines TEMPO-H, 4-oxo-TEMPO-H, 4-MeO-TEMPO-H (2,2,6,6-tetramethyl-N-hydroxy-4-methoxy-piperidine), and tBu2NOH. The reactions have been monitored by UV-vis stopped-flow methods, using the different optical spectra of nitroxyl radicals. The HAT reactions all have |ΔGo| ≤ 1.4 kcal mol−1 and therefore are close to self-exchange reactions. The reaction of 4-oxo-TEMPO• + TEMPO-H → 4-oxo-TEMPO-H + TEMPO• occurs with k2H,MeCN = 10 ± 1 M−1 s−1 in MeCN at 298 K (K2H,MeCN = 4.5 ± 1.8). Surprisingly, the rate constant for the analogous deuterium atom transfer reaction is much slower: k2D,MeCN = 0.44 ± 0.05 M−1 s−1 with k2H,MeCN/k2D,MeCN = 23 ± 3 at 298 K. The same large kinetic isotope effect (KIE) is found in CH2Cl2, 23 ± 4, suggesting that the large KIE is not caused by solvent dynamics or hydrogen bonding to solvent. The related reaction of 4-oxo-TEMPO• with 4-MeO-TEMPO-H(D) also has a large KIE, k3H/k3D = 21 ± 3 in MeCN. For these three reactions, the EaD – EaH values, between 0.3 ± 0.6 and 1.3 ± 0.6 kcal mol−1, and the log(AH/AD) values, between 0.5 ± 0.7 and 1.1 ± 0.6, indicate that hydrogen tunneling plays an important role. The related reaction of tBu2NO• + TEMPO-H(D) in MeCN has a large KIE, 16 ± 3 in MeCN, and very unusual isotopic activation parameters, EaD – EaH = −2.6 ± 0.4 and log(AH/AD) = 3.1 ± 0.6. Computational studies, using POLYRATE, also indicate substantial tunneling in the (CH3)2NO• + (CH3)2NOH model reaction for the experimental self-exchange processes. Additional calculations on TEMPO(•/H), tBu2NO(•/H), and Ph2NO(•/H) self-exchange reactions reveal why the phenyl groups make the last of these reactions several orders of magnitude faster than the first two. By inference, the calculations also suggest why tunneling appears to be more important in the self-exchange reactions of dialkylhydroxylamines than of arylhydroxylamines. PMID:19618933

Experiment K-7-41: Radiation Experiments on Cosmos 2044

NASA Technical Reports Server (NTRS)

Benton, E. V.; Benton, E. R.; Frank, A. L.; Dudkin, V. E.; Marenny, A. M.; Kovalev, E. E.

1994-01-01

The Cosmos 2044 biosatellite mission offered the opportunity for radiation measurements under conditions which are seldom available (an inclination of 82.3 degrees and altitude of 294 x 216 km). Measurements were made on the outside of the spacecraft under near-zero shielding conditions. Also, this mission was the first in which active temperature recorders (the ATR-4) were flown to record the temperature profiles of detector stacks. Measurements made on this mission provide a comparison and test for modeling of depth doses and LET spectra for orbital parameters previously unavailable. Tissue absorbed doses from 3480 rad (252 rad/d) down to 0.115 rad (8.33 mrad/d) were measured at different depths (0.0146 and 3.20 g/sq. cm, respectively) with averaged TLD readings. The LET spectra yielded maximum and minimum values of integral flux of 27.3 x 10-4 and 3.05 x 10(exp -4) cm(exp -2).s(exp -1).sr(exp -4) of dose rate of 7.01 and 1.20 mrad/d, and of dose equivalent rate of 53.8 and 11.6 mrem/d, for LET(infinity).H2O is greater than or equal to 4 keV/micro-m. Neutron measurements yielded 0.018 mremld in the thermal region, 0.25 mrem/d in the resonance region and 3.3 mrem/d in the high energy region. The TLD depth dose and LET spectra have been compared with calculations from the modeling codes. The agreement is good but some further refinements are in order. In comparing measurements on Cosmos 2044 with those from previous Cosmos missions (orbital inclinations of 62.8 degrees) there is a greater spread (maximum to minimum) in depth doses and an increased contribution from GCR's, and higher LET particles, in the heavy particle fluxes.

Theoretical Studies of Possible Synthetic Routes for the High Energy Density Material Td N4: Excited Electronic States

NASA Technical Reports Server (NTRS)

Lee, Timothy J.; Dateo, Christopher E.

2001-01-01

Vertical electronic excitation energies for single states have been computed for the high energy density material (HEDM) Td N4 in order to assess possible synthetic routes that originate from excited electronic states of N2 molecules. Several ab initio theoretical approaches have been used, including complete active space self-consistent field (CASSCF), state averaged CASSCF (SA-CASSCF), singles configuration interaction (CIS), CIS with second-order and third-order correlation corrections [CIS(D)) and CIS(3)], and linear response singles and doubles coupled-cluster (LRCCSD), which is the highest level of theory employed. Standard double zeta polarized (DZP) and triple zeta double polarized (TZ2P) one-particle basis sets were used. The CASSCF calculations are found to overestimate the excitation energies, while the SA-CASSCF approach rectifies this error to some extent, but not completely. The accuracy of the CIS calculations varied depending on the particular state, while the CIS(D), CIS(3), and LRCCSD results are in generally good agreement. Based on the LRCCSD calculations, the lowest six excited singlet states are 9.35(l(sup)T1), 10.01(l(sup)T2), 10.04(1(sup)A2), 10.07(1(sup)E), 10.12(2(sup)T1), and 10.42(2(sup)T2) eV above the ground state, respectively. Comparison of these excited state energies with the energies of possible excited states of N2+N2 fragments, leads us to propose that the most likely synthetic route for Td N4 involving this mechanism arises from combination of two bound quintet states of N2.

Electronic properties of two-dimensional zinc oxide in hexagonal, (4,4)-tetragonal, and (4,8)-tetragonal structures by using Hybrid Functional calculation

NASA Astrophysics Data System (ADS)

Supatutkul, C.; Pramchu, S.; Jaroenjittichai, A. P.; Laosiritaworn, Y.

2017-09-01

This work reports the structures and electronic properties of two-dimensional (2D) ZnO in hexagonal, (4,8)-tetragonal, and (4,4)-tetragonal monolayer using GGA and HSE-hybrid functional. The calculated results show that the band gaps of 2D ZnO sheets are wider than those of the bulk ZnO. The hexagonal and (4,8)-tetragonal phases yield direct band gaps, which are 4.20 eV, and 4.59 eV respectively, while the (4,4)-tetragonal structure has an indirect band gap of 3.02 eV. The shrunken Zn-O bond lengths in the hexagonal and (4,8)-tetragonal indicate that they become more ionic in comparison with the bulk ZnO. In addition, the hexagonal ZnO sheet is the most energetically favourable. The total energy differences of (4,8)-tetragonal and (4,4)-tetragonal sheets from that of hexagonal monolayer (per formula unit) are 197 meV and 318 meV respectively.

The role of the dendritic growth model dimensionality in predicting the Columnar to Equiaxed Transition (CET)

NASA Astrophysics Data System (ADS)

Seredyński, M.; Rebow, M.; Banaszek, J.

2017-06-01

The dendrite tip kinetics model accuracy relies on the reliability of the stability constant used, which is usually experimentally determined for 3D situations and applied to 2D models. The paper reports authors` attempts to cure the situation by deriving 2D dendritic tip scaling parameter for aluminium-based alloy: Al-4wt%Cu. The obtained parameter is then incorporated into the KGT dendritic growth model in order to compare it with the original 3D KGT counterpart and to derive two-dimensional and three-dimensional versions of the modified Hunt's analytical model for the columnar-to-equiaxed transition (CET). The conclusions drawn from the above analysis are further confirmed through numerical calculations of the two cases of Al-4wt%Cu metallic alloy solidification using the front tracking technique. Results, including the porous zone-under-cooled liquid front position, the calculated solutal under-cooling, the average temperature gradient at a front of the dendrite tip envelope and a new predictor of the relative tendency to form an equiaxed zone, are shown, compared and discussed for two numerical cases. The necessity to calculate sufficiently precise values of the tip scaling parameter in 2D and 3D is stressed.

Ab initio Hartree-Fock and density functional theory investigations on the conformational stability, molecular structure and vibrational spectra of 5-chloro-3-(2-(4-methylpiperazin-1-yl)-2-oxoethyl)benzo[d]thiazol-2(3H)-one drug molecule.

PubMed

Taşal, Erol; Kumalar, Mustafa

2012-09-01

In this work, the experimental and theoretical spectra of 5-chloro-3-(2-(4-methylpiperazin-1-yl)-2-oxoethyl)benzo[d]thiazol-2(3H)-one molecule (abbreviated as 5CMOT) are studied. The molecular geometry and vibrational frequencies are calculated in the ground state of molecule using ab initio Hartree-Fock (HF) and Density Function Theory (DFT) methods with 6-311++G(d,p), 6-31G++(d,p), 6-31G(d,p), 6-31G(d) and 6-31G basis sets. Three staggered stable conformers were observed on the torsional potential energy surfaces. The complete assignments were performed on the basis of the total energy distribution (TED) of the vibrational modes calculated. The comparison of the theoretical and experimental geometries of the title compound indicated that the X-ray parameters fairly well agree with the theoretically obtained values for the most stable conformer. The theoretical results showed an excellent agreement with the experimental values. The calculated HOMO and LUMO energies show that the charge transfer occurs within the molecule. Copyright © 2012 Elsevier B.V. All rights reserved.

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

Zhong, J.Y.; Zhao, G.; Zhang, J.

energy levels, spontaneous radiative decay rates, and electron impact collision strengths are calculated for La XXX. The data refer to 107 fine-structure levels belonging to the configurations (1s{sup 2}2s{sup 2}2p{sup 6})3s{sup 2}3p{sup 6}3d{sup 10}, 3s{sup 2}3p{sup 6}3d{sup 9}4l, 3s{sup 2}3p{sup 5}3d{sup 10}4l, and 3s3p{sup 6}3d{sup 10}4l (l = s, p, d, f). The collision strengths are calculated with a 20-collision-energy grid in terms of the energy of the scattered electron between 10 and 10,000 eV by using the distorted-wave approximation. Effective collision strengths are obtained at seven electron temperatures: T {sub e} (eV) = 10, 100, 300, 500, 800, 1000,more » and 1500 by integrating the collision strengths over a Maxwellian electron distribution. Coupled with these atomic data, a hydrodynamic code MED103 can be used to simulate the Ni-like La X-ray laser at 8.8 nm.« less

Effects of atorvastatin on biomarkers of immune activation, inflammation, and lipids in virologically suppressed, human immunodeficiency virus-1-infected individuals with low-density lipoprotein cholesterol <130 mg/dL (AIDS Clinical Trials Group Study A5275).

PubMed

Nixon, Daniel E; Bosch, Ronald J; Chan, Ellen S; Funderburg, Nicholas T; Hodder, Sally; Lake, Jordan E; Lederman, Michael M; Klingman, Karin L; Aberg, Judith A

Persistent immune activation and inflammation in virologically suppressed human immunodeficiency virus (HIV) infection are linked to excess cardiovascular risk. To evaluate atorvastatin as a strategy to reduce cardiovascular risk. A5275 was a multicenter, prospective, randomized, double-blind, placebo-controlled, cross-over pilot study of atorvastatin (10 mg/day for 4 weeks then 20 mg/day for 16 weeks) with a planned enrollment of 97 HIV-infected participants ≥18 years old, receiving boosted protease inhibitor-based antiretroviral therapy for ≥6 months, with plasma HIV-1 RNAs below limits of quantification ≥180 days, and fasting low-density lipoprotein (LDL) cholesterol ≥70 and <130 mg/dL. Primary endpoints were differences of changes ([week 44-week 24]-[week 20-baseline]) in CD4+ and CD8+ T-lymphocyte activation (% CD38 + /DR + ) and plasma levels of IL-6 and D-dimer. Arms were compared using the Wilcoxon rank-sum tests and also summarized changes pre-to-post atorvastatin treatment. Analyses were as-treated. Ninety-eight participants were enrolled at 31 U S sites and 73 completed study treatment. Atorvastatin treatment did not decrease T-lymphocyte or monocyte activation, circulating biomarker levels (interleukin-6, D-dimer, soluble CD14, soluble CD163, monocyte chemoattractant protein-1, interferon-gamma-induced protein-10, high-sensitivity C-reactive protein, CD40L, and P-selectin) or white blood cell Krüppel-like Factor 2/4 messenger RNA levels. Pre-to-post atorvastatin reductions in calculated LDL (-38%), oxidized-LDL (-33%), and lipoprotein-associated phospholipase A2 (-31%) were significant (P < .01). In virologically suppressed individuals with HIV infection, atorvastatin did not significantly decrease levels of soluble or cellular biomarkers of immune activation and inflammation but resulted in robust reductions in LDL cholesterol, oxLDL, and lipoprotein-associated phospholipase A 2 , biomarkers associated with cardiovascular risk. Copyright © 2016 National Lipid Association. All rights reserved.

Resonances in positron-potassium (e +-K) system with natural and unnatural parities

NASA Astrophysics Data System (ADS)

Umair, M.; Jonsell, S.

2016-01-01

We present an investigation of resonances with natural and unnatural parities in the positron-potassium system using the complex scaling method. A model potential is used to represent the interaction between the core and the valence electron. Explicitly correlated Gaussian wave functions are used to represent the correlation effects between the valence electron, the positron and the K+ core. Resonance energies and widths for two partial waves (S- and P-wave) below the {{K}}(4p,5 s,5p,4 d,4f) excitation thresholds and positronium n = 2 formation threshold are calculated for natural parity. Resonance states for P e below the {{K}}(4d) excitation threshold and positronium n = 2, 3 formation thresholds are calculated for unnatural parity which has not been previously reported. Below both positronium thresholds we have found a dipole series of resonances, with binding energies scaling in good agreement with exceptions from an analytical calculation. The present results are compared with those in the literature.

Pressure-induced structural and semiconductor-semiconductor transitions in C o0.5M g0.5C r2O4

NASA Astrophysics Data System (ADS)

Rahman, S.; Saqib, Hajra; Zhang, Jinbo; Errandonea, D.; Menéndez, C.; Cazorla, C.; Samanta, Sudeshna; Li, Xiaodong; Lu, Junling; Wang, Lin

2018-05-01

The effect of pressure on the structural, vibrational, and electronic properties of Mg-doped Cr bearing spinel C o0.5M g0.5C r2O4 was studied up to 55 GPa at room-temperature using x-ray diffraction, Raman spectroscopy, electrical transport measurements, and ab initio calculations. We found that the ambient-pressure phase is cubic (spinel-type, F d 3 ¯m ) and underwent a pressure-induced structural transition to a tetragonal phase (space group I 4 ¯m 2 ) above 28 GPa. The ab initio calculation confirmed this first-order phase transition. The resistivity of the sample decreased at low pressures with the existence of a low-pressure (LP) phase and started to increase with the emergence of a high-pressure (HP) phase. The temperature dependent resistivity experiments at different pressures illustrated the wide band gap semiconducting nature of both the LP and HP phases with different activation energies, suggesting a semiconductor-semiconductor transition at HP. No evidence of chemical decomposition or a semiconductor-metal transition was observed in our studies.

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

Mao, R; Tian, L; Ge, H

Purpose: To evaluate the dosimetry of microscopic disease (MD) region of lung cancer in stereotactic body radiation therapy (SBRT). Methods: For simplicity, we assume organ moves along one dimension. The probability distribution function of tumor position was calculated according to the breathing cycle. The dose to the MD region was obtained through accumulating the treatment planning system calculated doses at different positions in a breathing cycle. A phantom experiment was then conducted to validate the calculated results using a motion phantom (The CIRS ‘Dynamic’ Thorax Phantom). The simulated breathing pattern used a cos4(x) curve with an amplitude of 10mm. Amore » 3-D conformal 7-field plan with 6X energy was created and the dose was calculated in the average intensity projection (AIP) simulation CT images. Both films (EBT2) and optically stimulated luminescence (OSL) detectors were inserted in the target of the phantom to measure the dose during radiation delivery (Varian Truebeam) and results were compared to planning dose parameters. Results: The Gamma analysis (3%/3mm) between measured dose using EBT2 film and calculated dose using AIP was 80.5%, indicating substantial dosimetric differences. While the Gamma analysis (3%/3mm) between measured dose using EBT2 and accumulated dose using 4D-CT was 98.9%, indicating the necessity of dose accumulation using 4D-CT. The measured doses using OSL and theoretically calculated doses using probability distribution function at the corresponding position were comparable. Conclusion: Use of static dose calculation in the treatment planning system could substantially underestimate the actually delivered dose in the MD region for a moving target. Funding Supported by NSFC, No.81372436.« less

Preparation and luminescence properties of Ce3+ and Ce3+/Tb(3+)-activated Y4Si2O7N2 phosphors.

PubMed

Xia, Zhiguo; Wu, Weiwei

2013-09-28

Ce(3+) and Ce(3+)/Tb(3+)-activated Y4Si2O7N2 phosphors are synthesized by the solid-state method, which can be efficiently excited by near ultraviolet (UV) light emitting diode (LED) chips. The PL spectrum of Y4Si2O7N2:Ce(3+) shows a broad hump between 380 and 650 nm, assigned to the electron transition from the 4f energy level to different 5d sub levels of the Ce(3+) ions at different Y(3+) sites. The color of the Y4Si2O7N2:Ce(3+) phosphor can shift from blue to green by introducing Tb(3+). In addition, the energy transfer process from Ce(3+) to Tb(3+) in the Y4Si2O7N2 host was investigated and discussed in terms of both the luminescence spectra and decay curves. The energy transfer critical distance has been calculated and evaluated by the concentration quenching method. Therefore, the Ce(3+) and Ce(3+)/Tb(3+)-activated Y4Si2O7N2 phosphors can serve as key materials for phosphor-converted white-light UV-LEDs.

$B$- and $D$-meson leptonic decay constants from four-flavor lattice QCD

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

Bazavov, A.; Bernard, C.; Brown, N.

We calculate the leptonic decay constants of heavy-light pseudoscalar mesons with charm and bottom quarks in lattice quantum chromodynamics on four-flavor QCD gauge-field configurations with dynamicalmore » $u$, $d$, $s$, and $c$ quarks. We analyze over twenty isospin-symmetric ensembles with six lattice spacings down to $$a\\approx 0.03$$~fm and several values of the light-quark mass down to the physical value $$\\frac{1}{2}(m_u+m_d)$$. We employ the highly-improved staggered-quark (HISQ) action for the sea and valence quarks; on the finest lattice spacings, discretization errors are sufficiently small that we can calculate the $B$-meson decay constants with the HISQ action for the first time directly at the physical $b$-quark mass. We obtain the most precise determinations to-date of the $D$- and $B$-meson decay constants and their ratios, $$f_{D^+} = 212.6 (0.5)$$~MeV, $$f_{D_s} = 249.8(0.4)$$~MeV, $$f_{D_s}/f_{D^+} = 1.1749(11)$$, $$f_{B^+} = 189.4(1.4)$$~MeV, $$f_{B_s} = 230.7(1.2)$$~MeV, $$f_{B_s}/f_{B^+} = 1.2180(49)$$, where the errors include statistical and all systematic uncertainties. Our results for the $B$-meson decay constants are three times more precise than the previous best lattice-QCD calculations, and bring the QCD errors in the Standard-Model predictions for the rare leptonic decays $$\\overline{\\mathcal{B}}(B_s \\to \\mu^+\\mu^-) = 3.65(11) \\times 10^{-9}$$, $$\\overline{\\mathcal{B}}(B^0 \\to \\mu^+\\mu^-) = 1.00(3) \\times 10^{-11}$$, and $$\\overline{\\mathcal{B}}(B^0 \\to \\mu^+\\mu^-)/\\overline{\\mathcal{B}}(B_s \\to \\mu^+\\mu^-) = 0.00264(7)$$ to well below other sources of uncertainty. As a byproduct of our analysis, we also update our previously published results for the light-quark-mass ratios and the scale-setting quantities $$f_{p4s}$$, $$M_{p4s}$$, and $$R_{p4s}$$. We obtain the most precise lattice-QCD determination to date of the ratio $$f_{K^+}/f_{\\pi^+} = 1.1950(^{+15}_{-22})$$~MeV.« less

Polarization Dependence of Resonant Inelastic Scattering in Insulating Copper Oxides

NASA Astrophysics Data System (ADS)

Hill, John

2000-03-01

Recent work on a number of copper oxides, including Nd_2CuO_4, YBa_2Cu_3O7 and CuGeO3 is reported. In each case, an excitation of ~ 6 eV is observed when the incident energy is tuned through the Cu K-edge. Numerical calculations based on the Anderson Impurity model for Nd_2CuO4 suggest that this feature is a charge-transfer excitation to the antibonding state. Studies of the incident energy and polarization dependence of this excitation in Nd_2CuO4 reveal that the incident polarization selects the intermediate states participating in the resonance process. In particular, when the incident polarization is largely perpendicular to the copper oxide planes, a single resonance is observed at 8990 eV, corresponding to the \\underline 1s3d^94p_π intermediate state. Conversely with the incident polarization is aligned with the planes, an enhancement is observed at 8999.5 eV, associated with the \\underline 1s3d^94p_σ intermediate state. No enhancement is observed for the \\underline 1s3d^10\\underline L 4p intermediate state in either case. It is suggested that the systematic absence of this resonance is associated with non-local effects active in this intermediate state. This suggestion is supported by multi-copper-site calculations, and by our studies of CuGeO_3. In this latter compound, the CuO4 plaquettes are arranged in one dimensional edge-sharing chains, rather than the two dimensional corner sharing network of Nd_2CuO_4. Non-local effects are expected to be suppressed in such a case, and indeed two resonances are observed in CuGeO_3. This work further suggests that this technique may provide both a sensitive measure of the role of non-local effects in the excitation spectrum, and a stringent test for state-of-the-art electronic structure calculations. It is a great pleasure to acknowledge my collaborators in this work, L.E. Berman, W.A.L. Caliebe, R.L. Greene, K. Hämäläinen, K. Hirota, S. Huotari, T. Idé. C.-C. Kao, A. Kotani, T. Masuda, M. Matsubara, J.L. Peng, I. Tsukada, K. Uchinokura, and M. v. Zimmermann.

Are natural scientists more masculine than humanists? The association patterns between 2D:4D ratio and field of study.

PubMed

Kainz, Sarah; Weitzer, Jacob; Zingale, Stefania; Köllner, Johanna; Albrecht, Cornelia; Gaidora, Angelika; Rudorfer, Marie-Theres; Nürnberger, Anna; Kirchengast, Sylvia

2018-06-11

Natural sciences are still considered as typical male fields, while humanities are interpreted as typical female topics. Economic, social but also biological factors are discussed to influence the choice of study field. In the present study, the impact of prenatal sex hormone exposure - estimated by 2D:4D ratio - on the choice of study field was analyzed. Two hundred Viennese students between the ages 18 and 28 years were enrolled. Lengths of the index finger and the ring finger were measured directly from the hand of the participants. 2D:4D ratios were calculated. Male and female students differed significantly in 2D:4D ratio. As expected, female students showed significantly higher 2D:4D ratios than their male counterparts ( p < 0.001). Male scientists and male humanists differed significantly in 2D:4D ratio. The 2D:4D of male humanists was significantly higher than that of scientists ( p = 0.037). Female scientists and female humanists however, did not differ significantly in 2D:4D ratio. Both showed a typical female 2D:4D ratio. This was also true of male humanists. Consequently low prenatal androgen exposure may be associated with the choice of humanities among male students.

12 CFR 1.4 - Calculation of limits.

Code of Federal Regulations, 2010 CFR

2010-01-01

... separately to the Type III and Type V securities held by a bank. (e) Limit on investment company holdings—(1... investment limits at that interval until further notice. (d) Calculation of Type III and Type V securities holdings—(1) General. In calculating the amount of its investment in Type III or Type V securities issued...

The mechanism for water exchange in [UO(2)(H(2)O)(5)](2+) and [UO(2)(oxalate)(2)(H(2)O)](2-), as studied by quantum chemical methods.

PubMed

Vallet, V; Wahlgren, U; Schimmelpfennig, B; Szabó, Z; Grenthe, I

2001-12-05

The mechanisms for the exchange of water between [UO(2)(H(2)O)(5)](2+), [UO(2)(oxalate)(2)(H(2)O)](2)(-)(,) and water solvent along dissociative (D), associative (A) and interchange (I) pathways have been investigated with quantum chemical methods. The choice of exchange mechanism is based on the computed activation energy and the geometry of the identified transition states and intermediates. These quantities were calculated both in the gas phase and with a polarizable continuum model for the solvent. There is a significant and predictable difference between the activation energy of the gas phase and solvent models: the energy barrier for the D-mechanism increases in the solvent as compared to the gas phase, while it decreases for the A- and I-mechanisms. The calculated activation energy, Delta U(++), for the water exchange in [UO(2)(H(2)O)(5)](2+) is 74, 19, and 21 kJ/mol, respectively, for the D-, A-, and I-mechanisms in the solvent, as compared to the experimental value Delta H(++) = 26 +/- 1 kJ/mol. This indicates that the D-mechanism for this system can be ruled out. The energy barrier between the intermediates and the transition states is small, indicating a lifetime for the intermediate approximately 10(-10) s, making it very difficult to distinguish between the A- and I-mechanisms experimentally. There is no direct experimental information on the rate and mechanism of water exchange in [UO(2)(oxalate)(2)(H(2)O)](2-) containing two bidentate oxalate ions. The activation energy and the geometry of transition states and intermediates along the D-, A-, and I-pathways were calculated both in the gas phase and in a water solvent model, using a single-point MP2 calculation with the gas phase geometry. The activation energy, Delta U(++), in the solvent for the D-, A-, and I-mechanisms is 56, 12, and 53 kJ/mol, respectively. This indicates that the water exchange follows an associative reaction mechanism. The geometry of the A- and I-transition states for both [UO(2)(H(2)O)(5)](2+) and [UO(2)(oxalate)(2)(H(2)O)](2-) indicates that the entering/leaving water molecules are located outside the plane formed by the spectator ligands.

Temporal resolution required for accurate evaluation of the interplay effect in spot scanning proton therapy

NASA Astrophysics Data System (ADS)

Seo, Jeongmin; Han, Min Cheol; Yeom, Yeon Soo; Lee, Hyun Su; Kim, Chan Hyeong; Jeong, Jong Hwi; Kim, SeongHoon

2017-04-01

In proton therapy, the spot scanning method is known to suffer from the interplay effect induced from the independent movements of the proton beam and the organs in the patient during the treatment. To study the interplay effect, several investigators have performed four-dimensional (4D) dose calculations with some limited temporal resolutions (4 or 10 phases per respiratory cycle) by using the 4D computed tomography (CT) images of the patient; however, the validity of the limited temporal resolutions has not been confirmed. The aim of the present study is to determine whether the previous temporal resolutions (4 or 10 phases per respiratory cycle) are really high enough for adequate study of the interplay effect in spot scanning proton therapy. For this study, a series of 4D dose calculations were performed with a virtual water phantom moving in the vertical direction during dose delivery. The dose distributions were calculated for different temporal resolutions (4, 10, 25, 50, and 100 phases per respiratory cycle), and the calculated dose distributions were compared with the reference dose distribution, which was calculated using an almost continuously-moving water phantom ( i.e., 1000 phases per respiratory cycle). The results of the present study show that the temporal resolutions of 4 and 10 phases per respiratory cycle are not high enough for an accurate evaluation of the interplay effect for spot scanning proton therapy. The temporal resolution should be at least 14 and 17 phases per respiratory cycle for 10-mm and 20-mm movement amplitudes, respectively, even for rigid movement ( i.e., without deformation) of the homogeneous water phantom considered in the present study. We believe that even higher temporal resolutions are needed for an accurate evaluation of the interplay effect in the human body, in which the organs are inhomogeneous and deform during movement.

Evidence for Noncanonical Neurotransmitter Activation: Norepinephrine as a Dopamine D2-Like Receptor Agonist

PubMed Central

Sánchez-Soto, Marta; Bonifazi, Alessandro; Cai, Ning Sheng; Ellenberger, Michael P.; Newman, Amy Hauck

2016-01-01

The Gαi/o-coupled dopamine D2-like receptor family comprises three subtypes: the D2 receptor (D2R), with short and long isoform variants (D2SR and D2LR), D3 receptor (D3R), and D4 receptor (D4R), with several polymorphic variants. The common overlap of norepinephrine innervation and D2-like receptor expression patterns prompts the question of a possible noncanonical action by norepinephrine. In fact, previous studies have suggested that norepinephrine can functionally interact with D4R. To our knowledge, significant interactions between norepinephrine and D2R or D3R receptors have not been demonstrated. By using radioligand binding and bioluminescent resonance energy transfer (BRET) assays in transfected cells, the present study attempted a careful comparison between dopamine and norepinephrine in their possible activation of all D2-like receptors, including the two D2R isoforms and the most common D4R polymorphic variants. Functional BRET assays included activation of G proteins with all Gαi/o subunits, adenylyl cyclase inhibition, and β arrestin recruitment. Norepinephrine acted as a potent agonist for all D2-like receptor subtypes, with the general rank order of potency of D3R > D4R ≥ D2SR ≥ D2L. However, for both dopamine and norepinephrine, differences depended on the Gαi/o protein subunit involved. The most striking differences were observed with Gαi2, where the rank order of potencies for both dopamine and norepinephrine were D4R > D2SR = D2LR >> D3R. Furthermore the results do not support the existence of differences in the ability of dopamine and norepinephrine to activate different human D4R variants. The potency of norepinephrine for adrenergic α2A receptor was only about 20-fold higher compared with D3R and D4R across the three functional assays. PMID:26843180

Synthesis of a novel methyl(2E)-2-{[N-(2-formylphenyl)(4-methylbenzene) sulfonamido]methyl}-3-(2-methoxyphenyl)prop-2-enoate: Molecular structure, spectral, antimicrobial, molecular docking and DFT computational approaches

NASA Astrophysics Data System (ADS)

Murugavel, S.; Vetri velan, V.; Kannan, Damodharan; Bakthadoss, Manickam

2017-01-01

The title compound methyl(2E)-2-{[N-(2-formylphenyl)(4-methylbenzene)sulfonamido] methyl}-3-(2-methoxyphenyl)prop-2-enoate (MFMSM) has been synthesized and single crystals were grown by slow evaporation solution growth technique at room temperature. XRD, FT-IR and NMR spectra of MFMSM in the solid phase were recorded and analyzed. The optimized geometry and vibrational wave numbers were computed using DFT method. The NLO, Mulliken, MEP, HOMO-LUMO energy gap and thermodynamic properties were theoretically predicted. The NBO analysis explained the intramolecular hydrogen bonding. The global chemical reactivity descriptors are calculated for MFMSM and used to predict their relative stability and reactivity. All the calculations were carried out by B3LYP/6-311G (d,p) method. MFMSM has been screened for its antimicrobial activity and found to exhibit antifungal and antibacterial effects. Docking simulation has been performed.

Sci—Thur AM: YIS - 03: irtGPUMCD: a new GPU-calculated dosimetry code for {sup 177}Lu-octreotate radionuclide therapy of neuroendocrine tumors

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

Montégiani, Jean-François; Gaudin, Émilie; Després, Philippe

2014-08-15

In peptide receptor radionuclide therapy (PRRT), huge inter-patient variability in absorbed radiation doses per administered activity mandates the utilization of individualized dosimetry to evaluate therapeutic efficacy and toxicity. We created a reliable GPU-calculated dosimetry code (irtGPUMCD) and assessed {sup 177}Lu-octreotate renal dosimetry in eight patients (4 cycles of approximately 7.4 GBq). irtGPUMCD was derived from a brachytherapy dosimetry code (bGPUMCD), which was adapted to {sup 177}Lu PRRT dosimetry. Serial quantitative single-photon emission computed tomography (SPECT) images were obtained from three SPECT/CT acquisitions performed at 4, 24 and 72 hours after {sup 177}Lu-octreotate administration, and registered with non-rigid deformation of CTmore » volumes, to obtain {sup 177}Lu-octreotate 4D quantitative biodistribution. Local energy deposition from the β disintegrations was assumed. Using Monte Carlo gamma photon transportation, irtGPUMCD computed dose rate at each time point. Average kidney absorbed dose was obtained from 1-cm{sup 3} VOI dose rate samples on each cortex, subjected to a biexponential curve fit. Integration of the latter time-dose rate curve yielded the renal absorbed dose. The mean renal dose per administered activity was 0.48 ± 0.13 Gy/GBq (range: 0.30–0.71 Gy/GBq). Comparison to another PRRT dosimetry code (VRAK: Voxelized Registration and Kinetics) showed fair accordance with irtGPUMCD (11.4 ± 6.8 %, range: 3.3–26.2%). These results suggest the possibility to use the irtGPUMCD code in order to personalize administered activity in PRRT. This could allow improving clinical outcomes by maximizing per-cycle tumor doses, without exceeding the tolerable renal dose.« less

Time-Adjusted Internal Target Volume: A Novel Approach Focusing on Heterogeneity of Tumor Motion Based on 4-Dimensional Computed Tomography Imaging for Radiation Therapy Planning of Lung Cancer

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

Nishibuchi, Ikuno; Department of Radiation Oncology, Hiroshima Prefectural Hospital, Hiroshima; Kimura, Tomoki, E-mail: tkkimura@hiroshima-u.ac.jp

2014-08-01

Purpose: To consider nonuniform tumor motion within the internal target volume (ITV) by defining time-adjusted ITV (TTV), a volume designed to include heterogeneity of tumor existence on the basis of 4-dimensional computed tomography (4D-CT). Methods and Materials: We evaluated 30 lung cancer patients. Breath-hold CT (BH-CT) and free-breathing 4D-CT scans were acquired for each patient. The tumors were manually delineated using a lung CT window setting (window, 1600 HU; level, −300 HU). Tumor in BH-CT images was defined as gross tumor volume (GTV), and the sum of tumors in 4D-CT images was defined as ITV-4D. The TTV images were generatedmore » from the 4D-CT datasets, and the tumor existence probability within ITV-4D was calculated. We calculated the TTV{sub 80} value, which is the percentage of the volume with a tumor existence probability that exceeded 80% on ITV-4D. Several factors that affected the TTV{sub 80} value, such as the ITV-4D/GTV ratio or tumor centroid deviation, were evaluated. Results: Time-adjusted ITV images were acquired for all patients, and tumor respiratory motion heterogeneity was visualized. The median (range) ITV-4D/GTV ratio and median tumor centroid deviation were 1.6 (1.0-4.1) and 6.3 mm (0.1-30.3 mm), respectively. The median TTV{sub 80} value was 43.3% (2.9-98.7%). Strong correlations were observed between the TTV{sub 80} value and the ITV-4D/GTV ratio (R=−0.71) and tumor centroid deviation (R=−0.72). The TTV images revealed the tumor motion pattern features within ITV. Conclusions: The TTV images reflected nonuniform tumor motion, and they revealed the tumor motion pattern features, suggesting that the TTV concept may facilitate various aspects of radiation therapy planning of lung cancer while incorporating respiratory motion in the future.« less

Patient-specific dosimetry calculations using mathematic models of different anatomic sizes during therapy with 111In-DTPA-D-Phe1-octreotide infusions after catheterization of the hepatic artery.

PubMed

Kontogeorgakos, Dimitrios K; Dimitriou, Panagiotis A; Limouris, Georgios S; Vlahos, Lambros J

2006-09-01

The aim of the study was to provide dosimetric data on intrahepatic (111)In-diethylenetriaminepentaacetic acid (DTPA)-D-Phe(1)-octreotide therapy for neuroendocrine tumors with overexpression of somatostatin receptors. A dosimetric protocol was designed to estimate the absorbed dose to the tumor and healthy tissue in a course of 48 treatments for 12 patients, who received a mean activity of 5.4 +/- 1.7 GBq per session. The patient-specific dosimetry calculations, based on quantitative biplanar whole-body scintigrams, were performed using a Monte Carlo simulation program for 3 male and 3 female mathematic models of different anatomic sizes. Thirty minutes and 2, 6, 24, and 48 h after the radionuclide infusion, blood-sample data were collected for estimation of the red marrow radiation burden. The mean absorbed doses per administered activity (mGy/MBq) by the critical organs liver, spleen, kidneys, bladder wall, and bone marrow were 0.14 +/- 0.04, 1.4 +/- 0.6, 0.41 +/- 0.08, 0.094 +/- 0.013, and (3.5 +/- 0.8) x 10(-3), respectively; the tumor absorbed dose ranged from 2.2 to 19.6 mGy/MBq, strongly depending on the lesion size and tissue type. The results of the present study quantitatively confirm the therapeutic efficacy of transhepatic administration; the tumor-to-healthy-tissue uptake ratio was enhanced, compared with the results after antecubital infusions. Planning of treatment was also optimized by use of the patient-specific dosimetric protocol.

Comet 67P/Churyumov-Gerasimenko: Non-Gravitational Forces Based on its Detailed Shape

NASA Astrophysics Data System (ADS)

Keller, Horst Uwe; Mottola, Stefano; Skorov, Yuri; Davidsson, Björn; Gutiérrez, Pedro; Jorda, Laurent; Maquet, Lucie

2015-11-01

Non-gravitational forces caused by sublimation on a cometary nucleus influence its orbital parameters and its rotational properties. Based on thermal models and rough estimates of the nucleus shape properties such as its mass and density can be derived [1, 2]. The uncertainty of the nucleus shape influences the quality of the results. Changes of the angular momentum of the nucleus rotation are more strongly influenced by details of the shape and surface. The long term observations of the nucleus of comet 67P/Churyumov-Gerasimenko by OSIRIS [3] during the rendezvous with ESA’s Rosetta spacecraft result in a very detailed shape model [3]. We use a shape model with > 105 facets to simulate the distributed forces due to sublimation and to calculate their exerted torques. The determination of the overall activity and its spatial and timely distribution over the nucleus remains a major challenge. Early observations revealed that the rotation period had changed from its last perihelion passage in 2009 [4]. The detailed shape model along with thermal modeling makes it possible to calculate the diurnal activity of the facets [6, 7]. The net torque integrated over the whole surface causes a change in the angular momentum. We also calculate the forces acting on the motion of the nucleus. This can be monitored by determinations of the spacecraft positions during the Rosetta mission. We will compare our results with the traditional approach to calculate the non-gravitational forces [8].[1, 2] Davidsson, B. J. R. & Gutiérrez, P. J., Icarus, 168, 392, 2004, Icarus, 176, 453, 2005[3] H. U. Keller, C. Barbieri, P. Lamy, H. Rickman, R. Rodrigo, K.-P. Wenzel, H. Sierks, M. A’Hearn, F. Angrilli, M. Angulo, et al., SSR, 128 (1-4): 433-506, 2007.[4] Preusker, F., Scholten, F., Matz, K.-D., et al., Astronomy & Astrophysics, accepted, 2015[5] S. Mottola, S. Lowry, C. Snodgrass, P. Lamy, I. Toth, et al. A&A, 569: L2, Sept. 2014.[6] H. U. Keller, S. Mottola, B. Davidsson, S. Schröder, Y. Skorov, E. Kührt, et al.. A&A, in press[7] H. U. Keller, S. Mottola, Y. V. Skorov, and L. Jorda, Astronomy and Astrophysics Letter , 2015.[8] B. G. Marsden, Z. Sekanina, and D. K. Yeomans, Astronomical Journal, 78: 211, Mar. 1973.

Estimated use of water in the Delaware River Basin in Delaware, New Jersey, New York, and Pennsylvania, 2010

USGS Publications Warehouse

Hutson, Susan S.; Linsey, Kristin S.; Ludlow, Russell A.; Reyes, Betzaida; Shourds, Jennifer L.

2016-11-07

The Delaware River Basin (DRB) was selected as a Focus Area Study in 2011 by the U.S. Geological Survey (USGS) as part of the USGS National Water Census. The National Water Census is a USGS research program that focuses on national water availability and use and then develops new water accounting tools and assesses water availability at both the regional and national scales. One of the water management needs that the DRB study addressed, and that was identified by stakeholder groups from the DRB, was to improve the integration of state water use and water-supply data and to provide the compiled water use information to basin users. This water use information was also used in the hydrologic modeling and ecological components of the study.Instream and offstream water use was calculated for 2010 for the DRB based on information received from Delaware, New Jersey, New York, and Pennsylvania. Water withdrawal, interbasin transfers, return flow, and hydroelectric power generation release data were compiled for 11 categories by hydrologic subregion, basin, subbasin, and subwatershed. Data availability varied by state. Site-specific data were used whenever possible to calculate public supply, irrigation (golf courses, nurseries, sod farms, and crops), aquaculture, self-supplied industrial, commercial, mining, thermoelectric, and hydroelectric power withdrawals. Where site-specific data were not available, primarily for crop irrigation, livestock, and domestic use, various techniques were used to estimate water withdrawals.Total water withdrawals in the Delaware River Basin were calculated to be about 7,130 million gallons per day (Mgal/d) in 2010. Calculations of withdrawals by source indicate that freshwater withdrawals were about 4,130 Mgal/d (58 percent of the total) and the remaining 3,000 Mgal/d (42 percent) were from saline water. Total surface-water withdrawals were calculated to be 6,590 Mgal/d, or 92 percent of the total; about 54 percent (3,590 Mgal/d) of surface water withdrawn was freshwater. Total groundwater withdrawals were calculated to be 545 Mgal/d (8 percent of the total), all of which was freshwater. During 2010, calculated withdrawals by category, in decreasing order, were: thermoelectric power, 4,910 Mgal/d; public supply, 1,490 Mgal/d; self-supplied industrial, 350 Mgal/d; irrigation, 175 Mgal/d; self-supplied domestic, 117 Mgal/d; mining, 41.3 Mgal/d; aquaculture, 19.3 Mgal/d; livestock, 6.72 Mgal/d, and commercial, 5.89 Mgal/d. The amount of instream use for hydroelectric power generation purposes in 2010 was reported to be 273 Mgal/d for the Wallenpaupack Plant and 127 Mgal/d for the Mongaup River system.Total return flows in the DRB were 2,960 Mgal/d in 2010. Although municipal wastewater-treatment plants accounted for 539 (97 percent) of the return-flow sites, they accounted for about 70 percent of the total return flows in the DRB. There was limited information on return flows from thermoelectric power.

Charge dynamics of 57Fe probe atoms in La2Li0.5Cu0.5O4

NASA Astrophysics Data System (ADS)

Presniakov, I. A.; Sobolev, A. V.; Rusakov, V. S.; Moskvin, A. S.; Baranov, A. V.

2018-06-01

The objective of this study is to characterize the electronic state and local surrounding of 57Fe Mössbauer probe atoms within iron-doped layered perovskite La2Li0.5Cu0.5O4 containing transition metal in unusual formal oxidation states "+3". An approach based on the qualitative energy diagrams analysis and the calculations within the cluster configuration interaction method have been developed. It was shown that a large amount of charge is transferred via Cu-O bonds from the O: 2p bands to the Cu: 3d orbitals and the ground state is dominated by the d9L configuration ("Cu2+-O-" state). The dominant d9L ground state for the (CuO6) sublattice induces in the environment of the 57Fe probe cations a charge transfer Fe3+ + O-(L) → Fe4+ + O2-, which transforms "Fe3+" into "Fe4+" state. The experimental spectra in the entire temperature range 77-300 K were described with the use of the stochastic two-level model based on the assumption of dynamic equilibrium between two Fe3+↔Fe4+ valence states related to the iron atom in the [Fe(1)O4]4- center. The relaxation frequencies and activation energies of the corresponding charge fluctuations were estimated based on Mössbauer data. The results are discussed assuming a temperature-induced change in the electronic state of the [CuO4]5- clusters in the layered perovskite.

Resolvin D1 attenuates CCl4-induced acute liver injury involving up-regulation of HO-1 in mice.

PubMed

Chen, Xiahong; Gong, Xia; Jiang, Rong; Wang, Bin; Kuang, Ge; Li, Ke; Wan, Jingyuan

2016-01-01

Acute hepatic failure involves in excessive oxidative stress and inflammatory responses, leading to a high mortality due to lacking effective therapy. Resolvin D1 (RvD1), an endogenous lipid mediator derived from polyunsaturated fatty acids, has been shown anti-inflammatory and anti-oxidative actions, however, whether RvD1 has protective effects on hepatic failure remains elusive. In this study, the roles and molecular mechanisms of RvD1 were explored in carbon tetrachloride (CCl4)-induced acute liver injury. Our results showed that RvD1 protected mice against CCl4-induced hepatic damage, as evaluated by reduced aminotransferase activities and malondialdehyde content, elevated glutathione and superoxide dismutase activities, and alleviated hepatic pathological damage. Moreover, RvD1 significantly attenuated serum tumor necrosis factor-α and interleukin-6 levels as well as hepatic myeloperoxidase activity, whereas enhanced serum IL-10 level in CCl4-administered mice. Further, RvD1 markedly up-regulated the expression and activity of heme oxygenase-1 (HO-1). However, inhibition of HO-1 activity reversed the protective effects of RvD1 on CCl4-induced liver injury. These results suggest that RvD1 could effectively prevent CCl4-induced liver injury by inhibition of oxidative stress and inflammation, and the underlying mechanism may be related to up-regulation of HO-1.

Magnetic 4d monoatomic rows on Ag vicinal surfaces

NASA Astrophysics Data System (ADS)

Bellini, V.; Papanikolaou, N.; Zeller, R.; Dederichs, P. H.

2001-09-01

The magnetic properties of 4d monoatomic rows on Ag substrates have been studied by ab initio calculations using the screened Korringa-Kohn-Rostoker (SKKR) Green's function method within density functional theory (DFT) in its local spin density approximation (LSDA). The rows were placed at step-edge (step decoration) and on terrace positions of different vicinal Ag surfaces, i.e., fcc (711), fcc (410), and fcc (221). The results for the magnetic moments are explained in terms of the different coordination numbers of the row atoms and the different hybridization between the rather extended 4d orbitals of the row atoms and the sp-like valence electrons of the Ag substrates. For the fcc (711) vicinal surface, we explore the possibility of antiferromagnetic coupling between the atoms in each row and discuss, by means of total energy calculations, the stability of the antiferromagnetic solutions with respect to the ferromagnetic ones.

P dopants induced ferromagnetism in g-C3N4 nanosheets: Experiments and calculations

NASA Astrophysics Data System (ADS)

Liu, Yonggang; Liu, Peitao; Sun, Changqi; Wang, Tongtong; Tao, Kun; Gao, Daqiang

2017-05-01

Outstanding magnetic properties are highly desired for two-dimensional (2D) semiconductor nanosheets due to their potential applications in spintronics. Metal-free ferromagnetic 2D materials whose magnetism originated from the pure s/p electron configuration could give a long spin relaxation time, which plays the vital role in spin information transfer. Here, we synthesize 2D g-C3N4 nanosheets with room temperature ferromagnetism induced by P doping. In our case, the Curie temperature of P doped g-C3N4 nanosheets reaches as high as 911 K and the precise control of the P concentration can further adjust the saturation magnetization of the samples. First principles calculation results indicate that the magnetic moment is primarily due to strong hybridization between p bonds of P, N, and C atoms, giving the theoretical evidence of the ferromagnetism. This work opens another door to engineer a future generation of spintronic devices.

Full-dimensional quantum calculations of the vibrational states of H5(+).

PubMed

Song, Hongwei; Lee, Soo-Ying; Yang, Minghui; Lu, Yunpeng

2013-03-28

Full-dimensional quantum calculations of the vibrational states of H5(+) have been performed on the accurate potential energy surface developed by Xie et al. [J. Chem. Phys. 122, 224307 (2005)]. The zero point energies of H5(+), H4D(+), D4H(+), and D5(+) and their ground-state geometries are presented and compared with earlier theoretical results. The first 10 low-lying excited states of H5(+) are assigned to the fundamental, overtone, and combination of the H2-H3(+) stretch, the shared proton hopping and the out-of-plane torsion. The ground-state torsional tunneling splitting, the fundamental of the photon hopping mode and the first overtone of the torsion mode are 87.3 cm(-1), 354.4 cm(-1), and 444.0 cm(-1), respectively. All of these values agree well with the diffusion Monte Carlo and multi-configuration time-dependent Hartree results where available.

Big bang nucleosynthesis revisited via Trojan Horse method measurements

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

Pizzone, R. G.; Spartá, R.; Spitaleri, C.

Nuclear reaction rates are among the most important input for understanding primordial nucleosynthesis and, therefore, for a quantitative description of the early universe. An up-to-date compilation of direct cross-sections of {sup 2}H(d, p){sup 3}H, {sup 2}H(d, n){sup 3}He, {sup 7}Li(p, α){sup 4}He, and {sup 3}He(d, p){sup 4}He reactions is given. These are among the most uncertain cross-sections used and input for big bang nucleosynthesis calculations. Their measurements through the Trojan Horse method are also reviewed and compared with direct data. The reaction rates and the corresponding recommended errors in this work were used as input for primordial nucleosynthesis calculations tomore » evaluate their impact on the {sup 2}H, {sup 3,4}He, and {sup 7}Li primordial abundances, which are then compared with observations.« less

SU-D-207-03: Development of 4D-CBCT Imaging System with Dual Source KV X-Ray Tubes

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

Nakamura, M; Ishihara, Y; Matsuo, Y

Purpose: The purposes of this work are to develop 4D-CBCT imaging system with orthogonal dual source kV X-ray tubes, and to determine the imaging doses from 4D-CBCT scans. Methods: Dual source kV X-ray tubes were used for the 4D-CBCT imaging. The maximum CBCT field of view was 200 mm in diameter and 150 mm in length, and the imaging parameters were 110 kV, 160 mA and 5 ms. The rotational angle was 105°, the rotational speed of the gantry was 1.5°/s, the gantry rotation time was 70 s, and the image acquisition interval was 0.3°. The observed amplitude of infraredmore » marker motion during respiration was used to sort each image into eight respiratory phase bins. The EGSnrc/BEAMnrc and EGSnrc/DOSXYZnrc packages were used to simulate kV X-ray dose distributions of 4D-CBCT imaging. The kV X-ray dose distributions were calculated for 9 lung cancer patients based on the planning CT images with dose calculation grid size of 2.5 x 2.5 x 2.5 mm. The dose covering a 2-cc volume of skin (D2cc), defined as the inner 5 mm of the skin surface with the exception of bone structure, was assessed. Results: A moving object was well identified on 4D-CBCT images in a phantom study. Given a gantry rotational angle of 105° and the configuration of kV X-ray imaging subsystems, both kV X-ray fields overlapped at a part of skin surface. The D2cc for the 4D-CBCT scans was in the range 73.8–105.4 mGy. Linear correlation coefficient between the 1000 minus averaged SSD during CBCT scanning and D2cc was −0.65 (with a slope of −0.17) for the 4D-CBCT scans. Conclusion: We have developed 4D-CBCT imaging system with dual source kV X-ray tubes. The total imaging dose with 4D-CBCT scans was up to 105.4 mGy.« less

Biogas upgrading: optimal activated carbon properties for siloxane removal.

PubMed

Cabrera-Codony, Alba; Montes-Morán, Miguel A; Sánchez-Polo, Manuel; Martín, Maria J; Gonzalez-Olmos, Rafael

2014-06-17

A total of 12 commercial activated carbons (ACs) have been tested for the removal of octamethylcyclotetrasiloxane (D4) in dynamic adsorption experiments using different carrier gases and D4 concentrations. Characterization of the ACs included several physical and chemical techniques. The D4 adsorption capacities were strongly related with the textural development of the ACs. Results showed that the optimum adsorbent for D4 is a wood-based chemically activated carbon, which rendered an adsorption capacity of 1732 ± 93 mg g(-1) using 1000 ppm (v/v) of D4 with dry N2 as the carrier gas. When the concentration of D4 was lowered to typical values found in biogas, the adsorption capacity was halved. The presence of major biogas compounds (i.e., CH4 and CO2) and humidity further reduced the D4 adsorption capacity. The polymerization of D4 over the surface of all ACs was found to be relevant after prolonged contact times. The extent of this phenomenon, which may negatively affect the thermal regeneration of the AC, correlated reasonably well with the presence of phenolic and carboxylic groups on the carbon surfaces.

A theoretical study on 3-(4-methoxyphenyl)-1-(pyridin-2-Yl) prop-2-en-1-one

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

Öner, Nazmiye, E-mail: fizikcinaz@gmail.com; Tamer, Ömer, E-mail: omertamer@sakarya.edu.tr; Avci, Davut, E-mail: davcir@sakarya.edu.tr

This study reports the geometric parameters, vibration frequencies, {sup 13}C and {sup 1}H NMR chemical shifts of 3-(4-Methoxyphenyl)-1-(pyridin-2-yl) prop-2-en-1-one (MPP) molecule calculated by B3LYP level of density functional theory (DFT) with 6-311++G(d,p) basis set. {sup 13}C and {sup 1}H NMR chemical shifts were calculated within GIAO approach which is one of the most common approaches. Additionally, 3D molecular surfaces such as molecular electrostatic potential (MEP) and electrostatic potential (ESP), were simulated by the same level. As a result, obtained theoretical results were found to be consistent with experimental ones. All of calculations were carried out Gaussian 09 package program.

Structural and electronic properties of LaPd2As2 superconductor: First-principle calculations

NASA Astrophysics Data System (ADS)

Singh, Birender; Kumar, Pradeep

2017-05-01

In present work we have studied electronic and structural properties of superconducting LaPd2As2 compound having collapsed tetragonal structure using first-principle calculations. The band structure calculations show that the LaPd2As2 is metallic consistent with the reported experimental observation, and the density of states plots clearly shows that at the Fermi level major contribution to density of states arises from Pd 4d and As 4p states, unlike the Fe-based superconductors where major contribution at the Fermi level comes from Fe 3d states. The estimated value of electron-phonon coupling is found to be 0.37, which gives the upper bound of superconducting transition temperature of 5K, suggesting the conventional nature of this superconductor.

Electron excitation cross sections for the 2s(2)2p(3)4S(O) -- 2s(2)2p(3)2D(O) (forbidden) and 4S(O) -- 2s2p(4) 4P (resonance) transitions in O II

NASA Technical Reports Server (NTRS)

Zuo, M.; Smith, Steven J.; Chutjian, A.; Williams, I. D.; Tayal, S. S.; Mclaughlin, Brendan M.

1995-01-01

Experimental and theoretical excitation cross sections are reported for the first forbidden transition 4S(O) -- 2S(2)2p(3) 2D(O) (lambda-lambda 3726, 3729) and the first allowed (resonance) transition 4S(O) -- 2s2p(4) 4P(lambda-833) in O II. Use is made of electron energy loss and merged-beams methods. The electron energy range covered is 3.33 (threshold) to 15 eV for the S -- D transition, and 14.9 (threshold) to 40 eV for the S -- P transition. Care was taken to assess and minimize the metastable fraction of the O II beam. An electron mirror was designed and tested to reflect inelastically backscattered electrons into the forward direction to account for the full range of polar scattering angles. Comparisons are made between present experiments and 11-state R-matrix calculations. Calculations are also presented for the 4S(O) -- 2s(2)2p(3)2P(O) (lambda-2470) transition.

Diversity in sound pressure levels and estimated active space of resident killer whale vocalizations.

PubMed

Miller, Patrick J O

2006-05-01

Signal source intensity and detection range, which integrates source intensity with propagation loss, background noise and receiver hearing abilities, are important characteristics of communication signals. Apparent source levels were calculated for 819 pulsed calls and 24 whistles produced by free-ranging resident killer whales by triangulating the angles-of-arrival of sounds on two beamforming arrays towed in series. Levels in the 1-20 kHz band ranged from 131 to 168 dB re 1 microPa at 1 m, with differences in the means of different sound classes (whistles: 140.2+/-4.1 dB; variable calls: 146.6+/-6.6 dB; stereotyped calls: 152.6+/-5.9 dB), and among stereotyped call types. Repertoire diversity carried through to estimates of active space, with "long-range" stereotyped calls all containing overlapping, independently-modulated high-frequency components (mean estimated active space of 10-16 km in sea state zero) and "short-range" sounds (5-9 km) included all stereotyped calls without a high-frequency component, whistles, and variable calls. Short-range sounds are reported to be more common during social and resting behaviors, while long-range stereotyped calls predominate in dispersed travel and foraging behaviors. These results suggest that variability in sound pressure levels may reflect diverse social and ecological functions of the acoustic repertoire of killer whales.

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

Shin, D; Kang, S; Kim, D

Purpose: The dose difference between three-dimensional dose (3D dose) and 4D dose which considers motion due to respiratory can be varied according to geometrical relationship between planning target volume (PTV) and organ at risk (OAR). The purpose of the study is to investigate the dose difference between 3D and 4D dose using overlap volume histogram (OVH) which is an indicator that quantify geometrical relationship between a PTV and an OAR. Methods: Five liver cancer patients who previously treated stereotactic body radiotherapy (SBRT) were investigated. Four-dimensional computed tomography (4DCT) images were acquired for all patients. ITV-based treatment planning was performed. 3Dmore » dose was calculated on the end-exhale phase image as a reference phase image. 4D dose accumulation was implemented from all phase images using dose warping technique used deformable image registration (DIR) algorithm (Horn and Schunck optical flow) in DIRART. In this study OVH was used to quantify geometrical relationship between a PTV and an OAR. OVH between a PTV and a selected OAR was generated for each patient case and compared for all cases. The dose difference between 3D and 4D dose for normal organ was calculated and compared for all cases according to OVH. Results: The 3D and 4D dose difference for OAR was analyzed using dose-volume histogram (DVH). On the basis of a specific point which corresponds to 10% of OAR volume overlapped with expanded PTV, mean dose difference was 34.56% in minimum OVH distance case and 13.36% in maximum OVH distance case. As the OVH distance increased, mean dose difference between 4D and 3D dose was decreased. Conclusion: The tendency of dose difference variation was verified according to OVH. OVH is seems to be indicator that has a potential to predict the dose difference between 4D and 3D dose. This work was supported by the Radiation Technology R&D program (No. 2013M2A2A7043498) and the Mid-career Researcher Program (2014R1A2A1A10050270) through the National Research Foundation of Korea funded by the Ministry of Science, ICT&Future Planning.« less

SU-E-J-110: Dosimetric Analysis of Respiratory Motion Based On Four-Dimensional Dose Accumulation in Liver Stereotactic Body Radiotherapy

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

Kang, S; Kim, D; Kim, T

2015-06-15

Purpose: Respiratory motion in thoracic and abdominal region could lead to significant underdosing of target and increased dose to healthy tissues. The aim of this study is to evaluate the dosimetric effect of respiratory motion in conventional 3D dose by comparing 4D deformable dose in liver stereotactic body radiotherapy (SBRT). Methods: Five patients who had previously treated liver SBRT were included in this study. Four-dimensional computed tomography (4DCT) images with 10 phases for all patients were acquired on multi-slice CT scanner (Siemens, Somatom definition). Conventional 3D planning was performed using the average intensity projection (AIP) images. 4D dose accumulation wasmore » calculated by summation of dose distribution for all phase images of 4DCT using deformable image registration (DIR) . The target volume and normal organs dose were evaluated with the 4D dose and compared with those from 3D dose. And also, Index of achievement (IOA) which assesses the consistency between planned dose and prescription dose was used to compare target dose distribution between 3D and 4D dose. Results: Although the 3D dose calculation considered the moving target coverage, significant differences of various dosimetric parameters between 4D and 3D dose were observed in normal organs and PTV. The conventional 3D dose overestimated dose to PTV, however, there was no significant difference for GTV. The average difference of IOA which become ‘1’ in an ideal case was 3.2% in PTV. The average difference of liver and duodenum was 5% and 16% respectively. Conclusion: 4D dose accumulation which can provide dosimetric effect of respiratory motion has a possibility to predict the more accurate delivered dose to target and normal organs and improve treatment accuracy. This work was supported by the Radiation Technology R&D program (No. 2013M2A2A7043498) and the Mid-career Researcher Program (2014R1A2A1A10050270) through the National Research Foundation of Korea funded by the Ministry of Science, ICT&Future Planning (MSIP) of Korea.« less

High energy primary knock-on process in metal deuterium systems initiated by bombardment with noble gas ions

NASA Astrophysics Data System (ADS)

Gann, V. V.; Tolstolutskaya, G. D.

2008-08-01

An experimental study confirms the possibility of nuclear fusion reactions initiating in metal-deuterium targets by bombarding them with ions that are not the reagents of the fusion reaction, in particular, with noble gas ions. The yields of (d,d) and (d,t) reactions were measured as functions of energy (0.4-3.2 MeV) and mass of incident ions (He +, Ne +, Ar +, Kr + and Xe +). Irradiation by heavy ions produced a number of energetic deuterium atoms in the deuteride and deuterium + tritium metal targets. At ion energies of ˜0.1-1 MeV the d-d reaction yields are relatively high. A model of nuclear fusion reaction cross-sections in atomic collision cascades initiated by noble gas ion beam in metal-deuterium target is developed. The method for calculation tritium or deuterium recoil fluxes and the yield of d-d fusion reaction in subsequent collisions was proposed. It was shown that D(d,p)t and D(t,n) 4He reactions mainly occur in energy region of the recoiled D-atom from 10 keV to 250 keV. The calculated probabilities of d-d and d-t fusion reactions were found to be in a good agreement with the experimental data.

Involvement of Semaphorin (Sema4D) in T-Dependent Activation of B Cells.

PubMed

Kuklina, Е М; Nekrasova, I V; Valieva, Yu V

2017-08-01

The involvement of endogenous semaphorin (Sema4D) into the key stage of T-dependent differentiation of B cells, formation of plasmoblasts, was demonstrated in vitro in T/B cell co-culture under conditions of polyclonal activation of T cells. The effect of semaphorin was not associated with activation of high-affinity Sema4D receptor plexin B1, but involves lowaffinity receptor CD72. These data indicate that Sema4D-dependent signal regulates not only the initial stage of B-cell activation, proliferative response to the antigen, but also further differentiation of B cells into plasma cells.

Exploring the dynamics of reaction N((2)D)+C2H4 with crossed molecular-beam experiments and quantum-chemical calculations.

PubMed

Lee, Shih-Huang; Chin, Chih-Hao; Chen, Wei-Kan; Huang, Wen-Jian; Hsieh, Chu-Chun

2011-05-14

We conducted the title reaction using a crossed molecular-beam apparatus, quantum-chemical calculations, and RRKM calculations. Synchrotron radiation from an undulator served to ionize selectively reaction products by advantage of negligibly small dissociative ionization. We observed two products with gross formula C(2)H(3)N and C(2)H(2)N associated with loss of one and two hydrogen atoms, respectively. Measurements of kinetic-energy distributions, angular distributions, low-resolution photoionization spectra, and branching ratios of the two products were carried out. Furthermore, we evaluated total branching ratios of various exit channels using RRKM calculations based on the potential-energy surface of reaction N((2)D)+C(2)H(4) established with the method CCSD(T)/6-311+G(3df,2p)//B3LYP/6-311G(d,p)+ZPE[B3LYP/6-311G(d,p)]. The combination of experimental and computational results allows us to reveal the reaction dynamics. The N((2)D) atom adds to the C=C π-bond of ethene (C(2)H(4)) to form a cyclic complex c-CH(2)(N)CH(2) that directly ejects a hydrogen atom or rearranges to other intermediates followed by elimination of a hydrogen atom to produce C(2)H(3)N; c-CH(2)(N)CH+H is the dominant product channel. Subsequently, most C(2)H(3)N radicals, notably c-CH(2)(N)CH, further decompose to CH(2)CN+H. This work provides results and explanations different from the previous work of Balucani et al. [J. Phys. Chem. A, 2000, 104, 5655], indicating that selective photoionization with synchrotron radiation as an ionization source is a good choice in chemical dynamics research.

Dose evaluation of organs at risk (OAR) cervical cancer using dose volume histogram (DVH) on brachytherapy

NASA Astrophysics Data System (ADS)

Arif Wibowo, R.; Haris, Bambang; Inganatul Islamiyah, dan

2017-05-01

Brachytherapy is one way to cure cervical cancer. It works by placing a radioactive source near the tumor. However, there are some healthy tissues or organs at risk (OAR) such as bladder and rectum which received radiation also. This study aims to evaluate the radiation dose of the bladder and rectum. There were 12 total radiation dose data of the bladder and rectum obtained from patients’ brachytherapy. The dose of cervix for all patients was 6 Gy. Two-dimensional calculation of the radiation dose was based on the International Commission on Radiation Units and Measurements (ICRU) points or called DICRU while the 3-dimensional calculation derived from Dose Volume Histogram (DVH) on a volume of 2 cc (D2cc). The radiation dose of bladder and rectum from both methods were analysed using independent t test. The mean DICRU of bladder was 4.33730 Gy and its D2cc was4.78090 Gy. DICRU and D2cc bladder did not differ significantly (p = 0.144). The mean DICRU of rectum was 3.57980 Gy and 4.58670 Gy for D2cc. The mean DICRU of rectum differed significantly from D2cc of rectum (p = 0.000). The three-dimensional method radiation dose of the bladder and rectum was higher than the two-dimensional method with ratios 1.10227 for bladder and 1.28127 for rectum. The radiation dose of the bladder and rectum was still below the tolerance dose. Two-dimensional calculation of the bladder and rectum dose was lower than three-dimension which was more accurate due to its calculation at the whole volume of the organs.

SU-F-J-99: Dose Accumulation and Evaluation in Lung SBRT Among All Phases of Respiration

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

Azcona, JD; Barbes, B; Aristu, J

Purpose: To calculate the total planning dose on lung tumors (GTV) by accumulating the dose received in all respiration phases. Methods: A patient 4D planning CT (phase-binned, from a Siemens Somatom CT) was used to locate the GTV of a lung tumor in all respiratory phases with Pinnacle (v9.10). GTV contours defined in all phases were projected to the reference phase, where the ITV was defined. Centroids were calculated for all the GTV projections. No deformation or rotation was taken into account. The only GTV contour as defined in the reference phase was voxelized to track each voxel individually. Wemore » accumulated the absorbed dose in different phases on each voxel. A 3DCRT and a VMAT plan were designed on the reference phase fulfilling the ITV dosimetric requirements, using the 10MV FFF photon model from an Elekta Versa linac. ITV-to-PTV margins were set to 5mm. In-house developed MATLAB code was used for tumor voxeling and dose accumulation, assuming that the dose distribution planned in the reference phase behaved as a “dose-cloud” during patient breathing. Results: We tested the method on a patient 4DCT set of images exhibiting limited tumor motion (<5mm). For the 3DCRT plan, D95 was calculated for the GTV with motion and for the ITV, showing an agreement of 0.04%. For the VMAT plan, we calculated the D95 for every phase as if the GTV in that phase had received the whole treatment. Differences in D95 for all phases are within 1%, and estimate the potential interplay effect during delivery. Conclusion: A method for dose accumulation and assessment was developed that can compare GTV motion with ITV dosage, and estimate the potential interplay effect for VMAT plans. Work in progress includes the incorporation of deformable image registration and 4D CBCT dose calculation for dose reconstruction and assessment during treatment.« less

Two-photon decay in gold atoms

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

Dunford, R. W.; Kanter, E. P.; Kraessig, B.

2006-07-15

We have measured the energy differential transition probabilities for the two-photon decay of K vacancies in gold atoms (nuclear charge Z=79). This is the heaviest atom for which this information has been obtained, and so is most sensitive to relativistic effects. The experiment determined the shape of the continuum radiation for the transitions 2s{yields}1s, 3s{yields}1s, 3d{yields}1s, and (4s+4d){yields}1s at an emission pair opening angle {theta}={pi}/2. Our results for 3d{yields}1s and (4s+4d){yields}1s extend to energies above and below the region of the intermediate state resonances. No relativistic calculations exist for Au, so we compare with calculations by Mu and Crasemann andmore » Tong et al. for Ag (Z=47) and Xe (Z=54). For equal-energy, back-to-back two-photon decay, the calculations show an increase in transition probability with Z for the 2s{yields}1s and 3d{yields}1s transitions. In contrast, our data, at Z=79, corrected for the angular distribution, give a smaller transition probability than the lower-Z experimental results of Ilakovac et al. and Mokler et al. for Ag and Xe. The shapes of the two-photon continua in our data are in general agreement with theory except that we find anomalously high values for the differential two-photon transition probability for the 3s{yields}1s transition near y=0.35, where y is the fraction of the transition energy carried by the lower-energy photon.« less

New approach based on tetrahedral-mesh geometry for accurate 4D Monte Carlo patient-dose calculation

NASA Astrophysics Data System (ADS)

Han, Min Cheol; Yeom, Yeon Soo; Kim, Chan Hyeong; Kim, Seonghoon; Sohn, Jason W.

2015-02-01

In the present study, to achieve accurate 4D Monte Carlo dose calculation in radiation therapy, we devised a new approach that combines (1) modeling of the patient body using tetrahedral-mesh geometry based on the patient’s 4D CT data, (2) continuous movement/deformation of the tetrahedral patient model by interpolation of deformation vector fields acquired through deformable image registration, and (3) direct transportation of radiation particles during the movement and deformation of the tetrahedral patient model. The results of our feasibility study show that it is certainly possible to construct 4D patient models (= phantoms) with sufficient accuracy using the tetrahedral-mesh geometry and to directly transport radiation particles during continuous movement and deformation of the tetrahedral patient model. This new approach not only produces more accurate dose distribution in the patient but also replaces the current practice of using multiple 3D voxel phantoms and combining multiple dose distributions after Monte Carlo simulations. For routine clinical application of our new approach, the use of fast automatic segmentation algorithms is a must. In order to achieve, simultaneously, both dose accuracy and computation speed, the number of tetrahedrons for the lungs should be optimized. Although the current computation speed of our new 4D Monte Carlo simulation approach is slow (i.e. ~40 times slower than that of the conventional dose accumulation approach), this problem is resolvable by developing, in Geant4, a dedicated navigation class optimized for particle transportation in tetrahedral-mesh geometry.

TU-H-CAMPUS-IeP3-02: Neurovascular 4D Parametric Imaging Using Co-Registration of Biplane DSA Sequences with 3D Vascular Geometry Obtained From Cone Beam CT

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

Balasubramoniam, A; Bednarek, D; Rudin, S

Purpose: To create 4D parametric images using biplane Digital Subtraction Angiography (DSA) sequences co-registered with the 3D vascular geometry obtained from Cone Beam-CT (CBCT). Methods: We investigated a method to derive multiple 4D Parametric Imaging (PI) maps using only one CBCT acquisition. During this procedure a 3D-DSA geometry is stored and used subsequently for all 4D images. Each time a biplane DSA is acquired, we calculate 2D parametric maps of Bolus Arrival Time (BAT), Mean Transit Time (MTT) and Time to Peak (TTP). Arterial segments which are nearly parallel with one of the biplane imaging planes in the 2D parametricmore » maps are co-registered with the 3D geometry. The values in the remaining vascular network are found using spline interpolation since the points chosen for co-registration on the vasculature are discrete and remaining regions need to be interpolated. To evaluate the method we used a patient CT volume data set for 3D printing a neurovascular phantom containing a complete Circle of Willis. We connected the phantom to a flow loop with a peristaltic pump, simulating physiological flow conditions. Contrast media was injected with an automatic injector at 10 ml/sec. Images were acquired with a Toshiba Infinix C-arm and 4D parametric image maps of the vasculature were calculated. Results: 4D BAT, MTT, and TTP parametric image maps of the Circle of Willis were derived. We generated color-coded 3D geometries which avoided artifacts due to vessel overlap or foreshortening in the projection direction. Conclusion: The software was tested successfully and multiple 4D parametric images were obtained from biplane DSA sequences without the need to acquire additional 3D-DSA runs. This can benefit the patient by reducing the contrast media and the radiation dose normally associated with these procedures. Partial support from NIH Grant R01-EB002873 and Toshiba Medical Systems Corp.« less

The electric field gradient in natural iron-doped chrysoberyl Al2BeO4 and sinhalite MgAlBO4 single crystals

NASA Astrophysics Data System (ADS)

Lottermoser, Werner; Redhammer, Günther J.; Weber, Sven-Ulf; Litterst, Fred Jochen; Tippelt, Gerold; Dlugosz, Stephen; Bank, Hermann; Amthauer, Georg; Grodzicki, Michael

2011-12-01

This work reports on the evaluation of the electric field gradient (EFG) in natural chrysoberyl Al2BeO4 and sinhalite MgAlBO4 using two different procedures: (1) experimental, with single crystal Mössbauer spectroscopy (SCMBS) on the three principal sections of each sample and (2) a "fully quantitative" method with cluster molecular orbital calculations based on the density functional theory. Whereas the experimental and theoretical results for the EFG tensor are in quantitative agreement, the calculated isomer shifts and optical d-d-transitions exhibit systematic deviations from the measured values. These deviations indicate that the substitution of Al and Mg with iron should be accompanied by considerable local expansion of the coordination octahedra.

FTIR, FT-Raman spectra and ab initio, DFT vibrational analysis of 2,4-dinitrophenylhydrazine.

PubMed

Sundaraganesan, N; Ayyappan, S; Umamaheswari, H; Joshua, B Dominic

2007-01-01

The FTIR and FT-Raman spectra of 2,4-dinitrophenylhydrazine (2,4-DNPH) has been recorded in the region 4000-400 and 3500-50cm-1, respectively. The optimized geometry, frequency and intensity of the vibrational bands of 2,4-DNPH were obtained by the ab initio and density functional theory (DFT) levels of theory with complete relaxation in the potential energy surface using 6-31G(d,p) and 6-311G(d,p) basis sets. The harmonic vibrational frequencies were calculated and the scaled values have been compared with experimental FTIR and FT-Raman spectra. The observed and the calculated frequencies are found to be in good agreement. The experimental spectra also coincide satisfactorily with those of theoretically constructed bar type spectrograms.

FTIR, FT-Raman spectra and ab initio, DFT vibrational analysis of 2,4-dinitrophenylhydrazine

NASA Astrophysics Data System (ADS)

Sundaraganesan, N.; Ayyappan, S.; Umamaheswari, H.; Dominic Joshua, B.

2007-01-01

The FTIR and FT-Raman spectra of 2,4-dinitrophenylhydrazine (2,4-DNPH) has been recorded in the region 4000-400 and 3500-50 cm -1, respectively. The optimized geometry, frequency and intensity of the vibrational bands of 2,4-DNPH were obtained by the ab initio and density functional theory (DFT) levels of theory with complete relaxation in the potential energy surface using 6-31G(d,p) and 6-311G(d,p) basis sets. The harmonic vibrational frequencies were calculated and the scaled values have been compared with experimental FTIR and FT-Raman spectra. The observed and the calculated frequencies are found to be in good agreement. The experimental spectra also coincide satisfactorily with those of theoretically constructed bar type spectrograms.

In vivo diode dosimetry vs. computerized tomography and digitally reconstructed radiographs for critical organ dose calculation in high-dose-rate brachytherapy of cervical cancer.

PubMed

Hassouna, Ashraf H; Bahadur, Yasir A; Constantinescu, Camelia; El Sayed, Mohamed E; Naseem, Hussain; Naga, Adly F

2011-01-01

To investigate the correlation between the dose predicted by the treatment planning system using digitally reconstructed radiographs or three-dimensional (3D)-reconstructed CT images and the dose measured by semiconductor detectors, under clinical conditions of high-dose-rate brachytherapy of the cervix uteri. Thirty-two intracavitary brachytherapy applications were performed for 12 patients with cancer of the cervix uteri. The prescribed dose to Point A was 7 Gy. Dose was calculated for both International Commissioning on Radiation Units and Measurements (ICRU) bladder and rectal points based on digitally reconstructed radiographs and for 3D CT images-based volumetric calculation of the bladder and rectum. In vivo diode dosimetry was performed for the bladder and rectum. The ICRU reference point and the volumes of 1, 2, and 5cm(3) received 3.6±0.9, 5.6±2.0, 5.1±1.7, 4.3±1.4 and 5.0±1.2, 5.3±1.3, 4.9±1.1, and 4.2±0.9 Gy for the bladder and rectum, respectively. The ratio of the 1cm(3) and the ICRU reference point dose to the diode dose was 1.8±0.7 and 1.2±0.5 for the bladder and 1.9±0.6 and 1.7±0.5 for the rectum, respectively. 3D image-based dose calculation is the most accurate and reliable method to evaluate the dose given to critical organs. In vivo diode dosimetry is an important method of quality assurance, but clinical decisions should be made based on 3D-reconstructed CT image calculations. Copyright © 2011 American Brachytherapy Society. Published by Elsevier Inc. All rights reserved.

Bidirectional modulation of hippocampal synaptic plasticity by Dopaminergic D4-receptors in the CA1 area of hippocampus.

PubMed

Navakkode, Sheeja; Chew, Katherine C M; Tay, Sabrina Jia Ning; Lin, Qingshu; Behnisch, Thomas; Soong, Tuck Wah

2017-11-14

Long-term potentiation (LTP) is the persistent increase in the strength of the synapses. However, the neural networks would become saturated if there is only synaptic strenghthening. Synaptic weakening could be facilitated by active processes like long-term depression (LTD). Molecular mechanisms that facilitate the weakening of synapses and thereby stabilize the synapses are also important in learning and memory. Here we show that blockade of dopaminergic D4 receptors (D4R) promoted the formation of late-LTP and transformed early-LTP into late-LTP. This effect was dependent on protein synthesis, activation of NMDA-receptors and CaMKII. We also show that GABA A -receptor mediated mechanisms are involved in the enhancement of late-LTP. We could show that short-term plasticity and baseline synaptic transmission were unaffected by D4R inhibition. On the other hand, antagonizing D4R prevented both early and late forms of LTD, showing that activation of D4Rs triggered a dual function. Synaptic tagging experiments on LTD showed that D4Rs act as plasticity related proteins rather than the setting of synaptic tags. D4R activation by PD 168077 induced a slow-onset depression that was protein synthesis, NMDAR and CaMKII dependent. The D4 receptors, thus exert a bidirectional modulation of CA1 pyramidal neurons by restricting synaptic strengthening and facilitating synaptic weakening.

Improving the work position of worker based on manual material handling in rice mill industry

NASA Astrophysics Data System (ADS)

Astuti, Rahmaniyah Dwi; Susmartini, Susy; Kinanthi, Ade Putri

2017-11-01

In traditional industries still using manual material handling to weight lifting. Worker at the rice mill, especially in rice filtering activity has wrong ergonomic posture to enforce the body bends and carried loads too heavy cause of injury for lower back and waist. The work attitude is unnatural posture. This study aimed to determine the severity of the workload, the level of risk posed to the rice taking activities and suggested as an improvement to it. Identify the operator complaints used Nordic Body Map method. Rapid Entire Body Assessment (REBA) method is used to provide an assessment of the working posture of the operator. Assessment of the working posture on rice filtering process shows that REBA score is 12 with an explanation very high level of risk and action level is 4 which means the action needs to be repaired immediately. Biomechanics calculation shows result 6713.21 N, the result of the calculation of the biomechanics of worker in the rice filtering activities indicates that the activities would pose a risk or injury. Therefore, improvement in rice filtering activity by designing a tool for lowering the risk level worker. The design tools are illustrated with 2D modeling resulted in the level of risk that is working REBA score became 3 which shows a low risk level. Biomechanics calculation after designed of tools show the result is 6282.86 N. The results means the activities carried out are still in safe condition and does not pose a risk or injury.

Proton induced activity in graphite - comparison between measurement and simulation

NASA Astrophysics Data System (ADS)

Kiselev, Daniela; Bergmann, Ryan; Schumann, Dorothea; Talanov, Vadim; Wohlmuther, Michael

2018-06-01

The Paul Scherrer Institut (PSI) operates the Meson production target stations E and M with 590 MeV protons at currents of up to 2.4 mA. Both targets consist of polycrystalline graphite and rotate with 1 Hz due to the high power deposition (40 kW at 2 mA) in Target E. The graphite wheel is regularly exchanged and disposed as radioactive waste after a maximum of 3 to 4 years in operation, which corresponds to about 30 to 40 Ah of proton fluence. For disposal, the nuclide inventory of the long-lived isotopes (T1/2 > 60 d) has to be calculated and reported to the authorities. Measurements of gamma emitters, as well as 3H, 10Be and 14C, were carried out using different techniques. The measured specific activities are compared to Monte Carlo particle transport simulations performed with MCNPX2.7.0 using the BERTINI-DRESNER-RAL (default model in MCNPX2.7.0) and INCL4.6/ABLA07 as nuclear reaction models.

Pd (II) complexes of bidentate chalcone ligands: Synthesis, spectral, thermal, antitumor, antioxidant, antimicrobial, DFT and SAR studies

NASA Astrophysics Data System (ADS)

Gaber, Mohamed; Awad, Mohamed K.; Atlam, Faten M.

2018-05-01

The ligation behavior of two chalcone ligands namely, (E)-3-(4-chlorophenyl)-1-(pyridin-2-yl)prop-2-en-1-one (L1) and (E)-3-(4-methoxyphenyl)-1-(pyridin-2-yl)prop-2-en-1-one (L2), towards the Pd(II) ion is determined. The structures of the complexes are elucidated by elemental analysis, spectral methods (IR, electronic and NMR spectra) as well as the conductance measurements and thermal analysis. The metal complexes exhibit a square planar geometrical arrangement. The kinetic and thermodynamic parameters for some selected decomposition steps have been calculated. The antimicrobial, antioxidant and anticancer activities of the chalcones and their Pd(II) complexes have been evaluated. Molecular orbital computations are performed using DFT at B3LYP level with 6-31 + G(d) and LANL2DZ basis sets to access reliable results to the experimental values. The calculations are performed to obtain the optimized molecular geometry, charge density distribution, extent of distortion from regular geometry. Thermodynamic parameters for the investigated compounds are also studied. The calculations confirm that the investigated complexes have square planner geometry, which is in a good agreement with the experimental observation.

Electronic states of aryl radical functionalized graphenes: Density functional theory study

NASA Astrophysics Data System (ADS)

Tachikawa, Hiroto; Kawabata, Hiroshi

2016-06-01

Functionalized graphenes are known as a high-performance molecular device. In the present study, the structures and electronic states of the aryl radical functionalized graphene have been investigated by the density functional theory (DFT) method to elucidate the effects of functionalization on the electronic states of graphene (GR). Also, the mechanism of aryl radical reaction with GR was investigated. The benzene, biphenyl, p-terphenyl, and p-quaterphenyl radicals [denoted by (Bz) n (n = 1-4), where n means numbers of benzene rings in aryl radical] were examined as aryl radicals. The DFT calculation of GR-(Bz) n (n = 1-4) showed that the aryl radical binds to the carbon atom of GR, and a C-C single bond was formed. The binding energies of aryl radicals to GR were calculated to be ca. 6.0 kcal mol-1 at the CAM-B3LYP/6-311G(d,p) level. It was found that the activation barrier exists in the aryl radical addition: the barrier heights were calculated to be 10.0 kcal mol-1. The electronic states of GR-(Bz) n were examined on the basis of theoretical results.

Structure and binding energy of the H2S dimer at the CCSD(T) complete basis set limit.

PubMed

Lemke, Kono H

2017-06-21

This study presents results for the binding energy and geometry of the H 2 S dimer which have been computed using Møller-Plesset perturbation theory (MP2, MP4) and coupled cluster (CCSD, CCSD(T)) calculations with basis sets up to aug-cc-pV5Z. Estimates of D e , E ZPE , D o , and dimer geometry have been obtained at each level of theory by taking advantage of the systematic convergence behavior toward the complete basis set (CBS) limit. The CBS limit binding energy values of D e are 1.91 (MP2), 1.75 (MP4), 1.41 (CCSD), and 1.69 kcal/mol (CCSD[T]). The most accurate values for the equilibrium S-S distance r SS (without counterpoise correction) are 4.080 (MP2/aug-cc-pV5Z), 4.131 (MP4/aug-cc-pVQZ), 4.225 (CCSD/aug-cc-pVQZ), and 4.146 Å (CCSD(T)/aug-cc-pVQZ). This study also evaluates the effect of counterpoise correction on the H 2 S dimer geometry and binding energy. As regards the structure of (H 2 S) 2 , MPn, CCSD, and CCSD(T) level values of r SS , obtained by performing geometry optimizations on the counterpoise-corrected potential energy surface, converge systematically to CBS limit values of 4.099 (MP2), 4.146 (MP4), 4.233 (CCSD), and 4.167 Å (CCSD(T)). The corresponding CBS limit values of the equilibrium binding energy D e are 1.88 (MP2), 1.76 (MP4), 1.41 (CCSD), and 1.69 kcal/mol (CCSD(T)), the latter in excellent agreement with the measured binding energy value of 1.68 ± 0.02 kcal/mol reported by Ciaffoni et al. [Appl. Phys. B 92, 627 (2008)]. Combining CBS electronic binding energies D e with E ZPE predicted by CCSD(T) vibrational second-order perturbation theory calculations yields D o = 1.08 kcal/mol, which is around 0.6 kcal/mol smaller than the measured value of 1.7 ± 0.3 kcal/mol. Overall, the results presented here demonstrate that the application of high level calculations, in particular CCSD(T), in combination with augmented correlation consistent basis sets provides valuable insight into the structure and energetics of the hydrogen sulfide dimer.