Determination of the partition coefficients of the nonionic detergent C12E7 between lipid-detergent mixed membranes and water by means of Laurdan fluorescence spectroscopy

The membrane-water partition coefficient of the detergent C₁₂E₇ between water and C₁₂E₇/POPC mixed membranes has been determined by means of steady-state fluorescence spectroscopy. The emission spectra of the fluorescent probe Laurdan were used as an indicator of membrane composition at different membrane concentrations in the sample. The partition coefficient expressed as the ratio of the mole fractions of the detergent in the membrane and water phases is about 6^*10⁵ at low molar ratios of C₁₂E₇/POPC (R _c ) and decreases rapidly with increasingR _c . The limiting detergent content of the lamellar phase (R _c ^* >0.8) is indicated by a minimum ofP(R _c ).     

质子束治疗中非均匀组织的等效水厚度修正研究

非均匀组织等效水厚度修正是研究质子放射治疗的重要组成部分, 利用蒙特卡罗Fluka2011.2程序模拟了不同能量(50–250 MeV)的质子束入射到不同介质中的输运过程, 总结出了在不同介质中质子束初始能量与质子束Bragg峰深度关系, 并拟合出质子束在介质中的等效水厚度修正公式. 结果表明, 对不同能量的质子束入射到非均匀组织中, 通过拟合公式计算出Bragg峰深度值与Fluka模拟的质子束Bragg峰的位置相差在1 mm 之内. 如果建立起介质和水的Bragg峰比与电子密度比关系的数据库, 该公式有可能用于临床上的质子放射治疗的剂量计算中. 关键词： 蒙特卡罗 质子治疗 等效水厚度 Bragg 峰     

PdCO分子结构与势能函数

用密度泛函理论的B3LYP方法,对钯原子采用LANL2DZ收缩价基函数,碳原子和氧原子采用AUG-cc-pVTZ基组,对PdC,PdO和PdCO体系的结构进行优化,计算表明：PdC分子基态为¹Σ⁺态,键长为R_e=0.17285nm,离解能为4.919eV.PdO分子基态的平衡核间距为0.18546nm,其电子态为³Π,离解能为2.455eV,并拟合得到Murrell-Sorbie势能函数;PdCO分子有两 关键词： PdCO 分子结构 势能函数     

Breath water-based doubly labelled water method for the noninvasive determination of CO2 production and energy expenditure in mice

ABSTRACT

We explored a novel doubly labelled water (DLW) method based on breath water (BW-DLW) in mice to determine whole body CO₂ production and energy expenditure noninvasively. The BW-DLW method was compared to the DLW based on blood plasma. Mice (n?=?11, 43.5?±?4.6?g body mass (BM)) were administered orally a single bolus of doubly labelled water (1.2?g H₂¹⁸O kg BM^?1 and 0.4?g ²H₂O kg BM^?1, 99 atom% (AP) ¹⁸O or ²H). To sample breath water, the mice were placed into a respiration vessel. The exhaled water vapour was condensed in a cold-trap. The isotope enrichments of breath water were compared with plasma samples. The ²H/¹H and ¹⁸O/¹⁶O isotope ratios were measured by means of isotope ratio mass spectrometry. The CO₂ production (RCO₂) was calculated from the ²H and ¹⁸O enrichments in breath water and plasma over 5 days. The isotope enrichments of breath water vs. plasma were correlated (R²?=?0.89 for ²H and 0.95 for ¹⁸O) linearly. The RCO₂ determined based on breath water and plasma was not different (113.2?±?12.7 vs. 111.4?±?11.0?mmol?d^–1), respectively. In conclusion, the novel BW-DLW method is appropriate to obtain reliable estimates of RCO₂ avoiding blood sampling.     

Determination of nitrites and nitrates in plasma-activated deionized water by microchip capillary electrophoresis

In this work, we present the application of a fast and sensitive microanalytical method, microchip capillary electrophoresis (MCE), for the determination of NO₂⁻ and NO₃⁻ ions in deionized water treated by atmospheric pressure plasma jet (APPJ). The MCE technique consisted of an online combination of isotachophoresis with zone electrophoresis, both performed on the microchip. The argon plasma has been characterized by optical emission spectroscopy (OES) and Fourier transform infrared spectroscopy (FTIR). OES confirmed the presence of argon excited species (Ar I) emission (4p → 4s) lines, N₂ emission bands (second positive system C³Π_u → B³Π_g), and OH band (A²∑⁺ → X²Π Δv = 0), as well as the presence of NO and excited NO₂. The presence of NO₂ molecules was also confirmed by FTIR absorption spectroscopy. The performance of the developed MCE method was evaluated for linearity, limit of detection, limit of quantitation, precision, and accuracy, and the concentration of NO₂⁻ and NO₃⁻ in the water as a function of the water treatment time was monitored.     

Reproducibility of myelin water fraction analysis: a comparison of region of interest and voxel-based analysis methods

This study compared region of interest (ROI) and voxel-based analysis (VBA) methods to determine the optimal method of myelin water fraction (MWF) analysis. Twenty healthy controls were scanned twice using a multi-echo T₂ relaxation sequence and ROIs were drawn in white and grey matter. MWF was defined as the fractional signal from 15 to 40 ms in the T₂ distribution. For ROI analysis, the mean intensity of voxels within an ROI was fit using non-negative least squares. For VBA, MWF was obtained for each voxel and the mean and median values within an ROI were calculated. There was a slightly higher correlation between Scan 1 and 2 for the VBA method (R²=0.98) relative to the ROI method (R²=0.95), and the VBA mean square difference between scans was 300% lower, indicating VBA was the most consistent between scans. For the VBA method, mean MWF was found to be more reproducible than median MWF. As the VBA method is more reproducible and gives more options for visualization and analysis of MWF, it is recommended over the ROI method of MWF analysis.     

Influence of magnetic impurities on proton spin relaxation of water in clay

The¹H nuclear magnetic spin relaxation of water in slurry of kaolin clay was investigated in the presence of magnetite (black iron oxide, Fe₃O₄) at 0.2 T and room temperature. The water spectra at high magnetite contents showed two different resonances, presumably from surface-associated water and free interstitial water. The difference in observed resonance frequencies increased as much as 200 ppm with increasing magnetite content. The apparent nuclear magnetic resonance intensity decreased biexponentially as a function of magnetite added. The observedT ₂^* values at low magnetite contents were in accordance with the predicted values from the resonance intensities and the estimated magnetic susceptibilities. TheT ₁ relaxation was multiexponential in character, so a uniform penalty program was used for the analysis of distribution. At 0.2 T for¹H, kaolin slurry containing less than 5.5 ppm magnetite did not differ significantly from magnetite-free clay in the longitudinal relaxation rates of water. However, higher concentrations of magnetite produced features in theT ₁ distribution significantly different from those of magnetite-free clay. TheT ₂ could be approximated by monoexponential relaxation, probably because the fast-decaying components relaxed before they could be recorded. The apparent transverse relaxation ratesR ₂ increased linearly as a function of magnetite content. On the basis of the comparison of spin-echo and Carr-Purcell-Meiboom-Gill data, an empirical relation was derived to describe the signal loss due to diffusion. It can be expressed by a power function of magnetite amount, which is multiplied by the sum of volume-dependent and volume-independent terms.     

Dative versus electron-sharing bonding in N-imides and phosphane imides R3ENX and relative energies of the R2EN(X)R isomers (E = N,P; R = H,Cl, Me,Ph; X = H,F, Cl)*

ABSTRACT

Quantum chemical calculations using density functional theory BP86 and M06-2X functionals in conjunction with def2-TZVPP basis sets have been carried out on the title molecules. The calculation results reveal that the N-imides R₃NNX are always clearly higher in energy than the imine isomers R₂NN(X)R. In the case of phosphane imides R₃PNX and the isomers R₂PN(X)R, the substituent R plays a critical role in determining their relative stabilities. When R is hydrogen or phenyl group, R₃PNX are always higher in energy than R₂PN(X)R but the former are more stable than the latter when R = Cl. Interestingly, the Me₃PNX and Me₂PN(X)Me are quite close in energy. The energy decomposition analysis suggests that the P–N bond in the phosphane imides R₃PNX (R = H, Cl, Me, Ph; X = H, F, Cl) should be described in terms of an electron-sharing single bond between two charged fragments R₃P⁺-NX^? that is supported by (R₃P)⁺←(NX)^? π-backdonation. The π-bond contributes 14–21% of the total orbital interactions while the σ-bond provides 60–68% of ΔE_orb.     

On the Kirkwood theory of natural optical activity

Vibration-rotation intensities have been calculated for transitions between states of arbitrary vibrational symmetries, for tetrahedral molecules. For this purpose eigenfunctions of first order Coriolis interactions, which are assumed to be much smaller than anharmonic splittings, have been used. While some bands, among which fundamentals and overtones, follow the ΔR = 0 selection rule, for others the most intense vibration-rotation lines are those with ΔR maximum, in agreement with our double-resonance investigations of stretching levels of methane. One such investigation is presented here, in which the lower (3v₃, F ₂) level of CH₄ has been found at 8906·78 cm^-1, in close agreement with local-mode predictions. Several I.R. lines in this region have been assigned, the effective rotational constants being 5·214 and 5·24 cm^-1 for R = J and R ≠ J Coriolis sublevels respectively.     

Enols of 2‐nitro‐ and related 2‐substituted malonamides

The structures of 2‐substituted malonamides, YCH(CONR¹R²)CONR³R⁴ (Y = Br, SO₂Me, CONH₂, COMe, and NO₂) were investigated. When Y = Br, R¹R² = R³R⁴ = HEt; Y = SO₂Me, R¹–R⁴ = H and for Y = CONH₂ or CONHPh, R¹–R⁴ = Me, the structure in solution is that of the amide tautomer. X‐ray crystallography shows solid‐state amide structures for Y = SO₂Me or CONH₂, R¹–R⁴ = H. Nitromalonamide displays an enol structure in the solid state with a strong hydrogen bond (O^…O distance = 2.3730 Å at 100 K) and d(OH) ≠ d(O^…H). An apparently symmetric enol was observed in solution, even in appreciable percentages in highly polar solvents such as DMSO‐d₆, but K_enol values decrease on increasing the solvent polarity. The N,N′‐dimethyl derivative is less enolic. Acetylmalonamides display a mixture of enol on the acetyl group and amide in non‐polar solvents, and only the amide in DMSO‐d₆. DFT calculations gave the following order of pK_enol values for Y: H > CONH₂ > COMe ≥ COMe (on acetyl) ≥ MeSO₂ > CN > NO₂ in the gas phase, CHCl₃, and DMSO. The enol on the C?O group is preferred to the aci‐nitro compound, and the N? O? H^…O?C is less favored than the C?O? H^…O?C hydrogen bond. Copyright © 2009 John Wiley & Sons, Ltd.     

Implanted-fluorine depth profiles in molybdenum

Implanted-fluorine profiles in molybdenum have been accurately measured using¹⁹F (p,)¹⁶O resonant nuclear reaction atE _R=872.1 keV. A proper convolution-calculation method was used to extract the true distribution of fluorine from the experimental excitationyield curves. The range-distribution parameters,R _p and R _p, were thereby obtained and were compared with those obtained by Monte-Carlo simulation with a computer code developed recently in this gorup, and the TRIM'90 code. They show that the experimentalR _p values agree very well with the Monte-Carlo simulation values, while the experimental R _p values are larger than those obtained from the simulations.     

Identifying the mean residence time of soil water for different vegetation types in a water source area of the Yuanyang Terrace,southwestern China

The mean residence time of soil water (MRT_sw) for forestland and shrubland in a water source area of Yuanyang Terrace, southwestern China, was estimated using stable isotope tracer tests and the sine-wave regression model. Stable isotope analyses from precipitation and soil water were performed in 2015. The δ²H/δ¹⁸O relationship of precipitation resulted in δ²H?=?7.31δ¹⁸O?+?1.49, which is nearly identical to the local meteoric water line in Kunming, southwestern, China. The MRT_sw was simulated at five depth ranges (0–20, 20–40, 40–60, 60–80, 80–100?cm) of the two vegetation types by precipitation δ¹⁸O input data and soil water δ¹⁸O output data. The results showed that the MRT_sw values of the forestland and shrubland both increased with soil depth. However, differences in the MRT_sw of the forestland (between day 53 and 94) and of the shrubland (between day 76 and 142) were discussed. Regarding the physical properties of the soil profiles from the sample plots, non-capillary porosity decreased with soil depth in the forestland (from 48.5 to 20.5?%), and was clearly higher than that in the shrubland (from 38.8 to 18.7?%). Therefore, non-capillary porosity (macropores) could be a factor that shortens the mean residence time of soil water.     

Spatiotemporal patterns of stable isotopes and hydrochemistry in springs and river flow of the upper Karkheh River Basin,Iran

Karst springs of the Zagros Mountains contribute a significant amount to agricultural and human water demands of western and south-western Iran. For an adequate management of available water resources in semi-arid and arid regions, sufficient hydrological monitoring is needed, and hydro-chemical and isotope hydrological data provide important additional information. About 350 water samples were collected from precipitation, river water, and karst springs of the upper part of the Karkheh River Basin (20,895 km²) located between 33°35^′ and 34°55^′ North and 46°22^′ and 49°10^′ East with elevations ranging from 928 to 3563 m above sea level. Sampling was conducted in monthly time resolution from August 2011 to July 2012. All samples were analysed for hydro-chemical parameters (pH, electrical conductivity, and major ions) and stable isotopes (deuterium, oxygen-18). Isotope values of precipitation indicate a local meteoric water line (Zagros MWL δ²H=6.8 δ¹⁸O+10.1; R²=0.99) situated between the Mediterranean MWL and Global MWL. Spring and river water isotope values vary between?7.1 and?4.1 ‰, and?38 and?25 ‰ for δ¹⁸O and δ²H, respectively, responding to winter snowmelt and evaporation. This work implements stable isotopes and hydro-chemical information of springs and river water to understand hydrological and hydro-geological interrelations in karstic semi-arid areas and helps to improve the current water resources management practices of western Iran.     

Relaxometric investigations addressing the determination of intracellular water lifetime: a novel tumour biomarker of general applicability

ABSTRACT

¹H Fast-Field Cycling NMR relaxometry is proposed as a powerful method to investigate tumour cell metabolism by measuring changes in cell water content and mobility across the cellular membrane. Measurements of intracellular water residence time in cultured cells were carried out by measuring T₁ at fixed field (0.2?T) after the addition of a paramagnetic Gd complex (Prohance) at different concentrations in the external medium. Investigations on tumour cells (mammary adenocarcinoma TS/A) grown in normo- or hypoxic conditions or suspended in ‘hypo-osmotic’ solutions allowed us to demonstrate that both hypoxic and hypo-osmotic conditions cause a marked increase in water mobility as assessed by the elongation of T₁. Conversely, the metabolic change caused by glutamine (an aminoacid essential for tumour growth) deprivation caused a water mobility decrease (shorter T₁). These findings suggest that T₁ measurements at low and variable magnetic field strengths, giving access to the assessment of intracellular water lifetime, can provide important information about tumour cell metabolism in real time and non-invasively.     

Carbon-13 Kinetic Isotope Effects in the Decarbonylation Of Liquid Formic Acid in Water Solution

Abstract

Carbon-13 kinetic isotope effects (¹³C KIEs) in the decarbonylation of formic acid diluted with water 1:1 (V:V) has been studied in the 130–181°C temperature interval in sealed vacuum all glass reactions vessels. The experimental ¹³C KIEs are higher than the ¹³C KIEs values extrapolated from low 50–100°C temperature interval ¹³C KIEs observed in the decarbonylation of water free liquid formic acid but less than ¹³C KIEs expected theoretically assuming the complete carbon—oxygen (¹³C[sbnd]¹⁶O) bond rupture in the transition state. For instance the (k₁₂/k₁₃) KIE found in this study is 1.0375 at 170.2°C while the “full” ¹³C KIE is expected to be 1.0429 at this temperature. The ¹³C KIE extrapolated to 170.2°C from the low temperature data published earlier is 1.0299. - The Arrhenius activation energy for the decarbonylation of formic acid in 1:1 water solution E = 31.3 kcal/mol is by 6 kcal/mol higher than that which was obtained with 99,9% pure formic acid (E = 25,660 kcal/mol). The entropy of activation ΔS ^≠ increased from -21.4 e.u. (pure formic acid) to -15.3 e.u. in the decarbonylation of formic acid diluted with water 1:1. The increases of the enthalpy of activation, of the entropy of activation and partly of the carbon-13 kinetic isotope effect observed in the decarbonylation of formic acid in water solution have been rationalized by suggesting isotopic equilibria interfering the pure kinetic fractionation of ¹³C and intervention of the water molecules into the process of transfer of protons to the formic acid molecules lowering the absolute rate of their decomposition.     

Formation of small water cluster anions by attachment of very slow electrons at high resolution

Using a high resolution laser photoelectron attachment method, we have studied the formation of (H ₂ O) _q ^- (q = 2, 6, 7, 11, 15) cluster ions in collisions of slow free electrons (E = 1-80 meV) and Rydberg electrons (n = 12-300) with water clusters. Resonances at zero energy have been observed, the shapes of which are strongly dependent on cluster size. The results are discussed in terms of the formation of metastable negative ions. Received 8 March 1999     

Mobility of water in NaCl and brain heart infusion (BHI) solutions as studied by 17O NMR

The molecular dynamic behaviour of water molecules in aqueous solution has been determined by oxygen-17 NMR according to the anisotropic reorientation, two-correlation-time model for bound water. Solutions of brain heart infusion (BHI), NaCl and their 1:1 mixture have been analysed. The anisotropic water population was distinguished into a slow (τ^s _bw) and a fast (τ^f _bw) relaxing component. The slow relaxing component was affected by the nature of the solute, while the fast relaxing component was not. NaCl was found to bind water molecules more strongly (higher τ^s _bw) than BHI. Water was more bound in the 1:1 mixture than in the solution containing only BHI. The population of bound water (P _bw) was concentration dependent and increased with increasing solids content. BHI, at the suspension point, bound ～50% of the total water, while NaCl at saturation bound only ～10%. The 1:1 mixture bound water in a synergistic manner that resulted in a slightly higher P_bw, than in BHI at each solid concentration. The P_bw correlated well with the amount of unfreezable water (as measured by DSC) present in the BHI samples.     

Can electron paramagnetic resonance measurements predict the electrical sensitivity of SnO<Subscript>2</Subscript>-based film?

Paramagnetic singly ionized oxygen vacancies V_o and chemisorbed Sn⁴⁺-O₂⁻ species were detected by electron paramagnetic resonance measurements on SnO₂ and transition metal (Pt, Ru)-doped SnO₂ thin film that had been reduced with CO at different temperatures and then brought into contact with oxygen. The amounts of the two paramagnetic species were evaluated and are discussed as a function of the film annealing temperature in air, the reduction temperature under CO, and the type and concentration of the doping transition element. Also the structural properties of the film were identified through glancing incidence X-ray diffraction analysis. Measurements of the electrical sensitivityS(S=R _air/R _CO, whereR _air andR _CO are the resistance under air and under CO(800 ppm)/air respectively) show that the trend of the sensitivity values vs. the reduction temperature with CO could be predicted by the parallel trend of the number of Sn⁴⁺−O₂⁻ centers.     

Deep bandtail states picosecond intensity-dependent carrier dynamics of GaN epilayer under high excitation

Picosecond carrier dynamics of deep bandtail states (3.1 eV) in an unintentionally n-doped GaN epilayer at room temperature under high excitation densities (i.e., N ₀ = 1.0× 10¹⁹– 1.1× 10²⁰ cm^–3) have been investigated with nondegenerate femtosecond pump–probe (267/400 nm) reflectance ( R/R ₀). All R/R ₀ traces possess a 2 ps buildup time that represents an overall time for the initial non-thermal carrier population to relax towards the continuum extremes and then into the probed tail states. We observe a saturation of R/R ₀ initial (first 10 ps) recovery rate _i at a density of 5– 6×10¹⁹ cm^–3 close to the Mott transition threshold obtained from time-integrated PL measurements. Such a saturation phenomenon has been identified as the trap-bottleneck due to the bandtail states and deep traps. As N ₀ is further increased, _i accelerates due to the onset of Auger recombination as the trap-bottleneck becomes effective. The best fit by the Auger model for N ₀ in the range of the mid-10¹⁹–10²⁰ cm^–3 yields an Auger coefficient of C _a 5.0× 10^–30 cm⁶ s^–1.     

Infrared absorption and water structure in aerosol OT reverse micelles

Summary The structure of water in bis(2-ethylhexyl)sodium sulfosuccinate (AOT) micelles has been studied as a function of the [H₂O]/[AOT] ratio (W) by using the absorption IR due to O−H stretching modes in the 3800–3000 cm⁻¹ range. Three systems have been studied: water/AOT/carbon tetrachloride, water/AOT/n-heptane and water/AOT iso-octane. Experimental spectra are presented and discussed for the O−H stretching region both of H₂O and isotopically diluted HDO molecules in D₂O. We have restricted ourselves to the region of small amounts of water (0<W<20) where the properties of the systems change strongly with the water content. The results show that IR spectra can be expressed as sum of contributions from interfacial and bulk-like water. The fraction of water in the two “regions” within the water pool was evaluated as a function ofW. From the data a continuous variation appears in the water properties inside micellar cores rather than a two-steps hydration mechanism. The solubilization of water is described in terms of hydration of the AOT head group and Na⁺ counterions. The maximum hydration number of AOT was found to be 3.5. The same behaviour has been observed in the three solvents studied.