芥子气纯度测定不确定度分析与评定

采用酸碱滴定法测定芥子气纯度,对测量结果的不确定度进行评定。分析了测定过程中不确定度来源,包括滴定剂的标定、消耗滴定剂体积、样品称量等引入的不确定度及其计算方法,最后合成得到标准不确定度。当芥子气纯度测定结果为94.78%时,扩展不确定度为0.34%(k=2)。实验结果表明,样品称量引入的不确定度对测量结果的影响最大。     

Transportation of sulfur mustard (HD) in alkyd coating

The kinetics of absorption, desorption, and degradation of sulfur mustard (HD) in alkyd coating was experimentally studied, and a one-dimension mass transfer model for the transportation of HD molecule in alkyd coating was established on the experimental data. The obtained results indicated that the persistence of HD molecule could be greatly increased due to the absorption of HD droplets by alkyd coating, and there still occurred the desorption of HD as vapor from coating for more than 3 days even after decontamination of HD droplets onto coating. It was also experimentally shown that the majority of HD both absorbed and desorbed was accomplished at an early stage, less than 10 h, and HD molecule was able to be degraded within the alkyd coating probably through the reactions of hydrolysis and elimination. The diffusion coefficient and degradation rate constant of HD in alkyd coating were determined to be practically around 10(-9) cm2/s and 2.4 x 10(-5) min(-1), respectively.     

固相萃取-气相色谱-质谱法检测染毒尿样中芥子气-谷胱甘肽加合物的β-裂解产物

合成并纯化了芥子气-谷胱甘肽的β-裂解产物1,1′-磺酰基二(2-甲巯基)乙烷(SBMTE),纯度为98.9%.建立了固相萃取-气相色谱质谱法检测染毒尿样中SBMTE的方法,对尿样中SBMTE的提取富集、 Oasis HLB固相萃取柱净化条件等因素进行了优化.实验中采用DB-5MS毛细管柱进行分离,以化学电离源(CI)质谱选择离子模式(SIM)进行检测,并通过内标法定量.SBMTE的线性范围为1～100 ng/mL,r=0.9991,回收率为89.0%～92.6%,检出限为0.5 ng/mL.方法满足芥子气中毒人群尿中SBMTE的检测要求.     

Quantum molecular dynamics

Electron or ion dynamics are treated using spin‐dependent quantum trajectories. These trajectories are inferred from the Dirac current, which contributes Schroedinger's current and additional spin‐dependent terms, all of which are of order c⁰ in the nonrelativistic regime of particle velocity, where c is the speed of light. The many‐body problem is treated precisely as in classical dynamics. Each electron or ion has its own equation of motion, which is the time‐dependent Dirac or the time‐dependent Schroedinger equation in the relativistic or nonrelativistic regime of particle velocity, respectively. As an example the theory is applied to the electronic structure of the helium atom, in which two electrons with opposite spin states are shown to correlate such that their quantum trajectories keep them on average on opposite sides of the nucleus. As the theory is time dependent, excited states are also generated. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Quantum mechanical/molecular mechanical study of anthrax lethal factor catalysis

We report a hybrid quantum mechanical and molecular mechanical study of the catalysis of anthrax lethal factor. The calculations suggest that the zinc peptidase uses the same general base-general acid mechanism as in thermolysin and carboxypeptidase A, in which a zinc-bound water is activated by Glu687 to nucleophilically attack the scissile carbonyl carbon in the substrate. The catalysis is aided by an oxyanion hole formed by the zinc ion and the side chain of Tyr728, which provide stabilization for the fractionally charged carbonyl oxygen. The assigned role of Tyr728 differs from previous suggestions but is consistent with the established mechanism of other zinc proteases.     

A molecular orbital study of bond energies in compounds of sulfur and fluorine

CNDO/2 molecular orbital theory is employed in a study of the binding energies of the molecules SF, SF₂, SF₄, SF₆, their cations and anions, and of the molecules SSF₂, FSSF and S₂F₁₀. Computed energies, when rescaled according to energy partitioning concepts, compare favorably with available experimental data. Ionization energies and electron affinities are calculated for SF, SF₂, SF₄ and SF₆.

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Zusammenfassung Mit Hilfe der CNDO/2 Theorie werden die Bindungsenergien der SF, SF₂, SF₄ und SF₆ Moleküle, von deren positiven und negativen Ionen und von SSF₂, FSSF und S₂F₁₀ berechnet. Die berechneten Energien stimmen gut mit experimentellen Daten überein, wenn sie nach Energieaufteilungsprinzipien wiederberechnet werden. Ferner werden die Ionisierungsenergien und Elektronenaffinitäten für SF, SF₂, SF₄ und SF₆ angegeben.

     

Quantum molecular modeling of melatonin

Molecular modeling of melatonin was conducted using AM1 and ab initio quantum computations. Our study shows that four minimal energy conformations (noted I to IV) with a folded ethylamido side-chain are possible. These conformations are in correspondance (form I with form II, and form III with form IV) and are characterized by equivalent orbital frontiers and electrostatic properties. Conformations II and IV are in good agreement with pharmacophore models proposed by Jansen et al. [Bioorganic Med. Chem. 4 (1996) 1321] or by Sicsic et al. [J. Med. Chem. 40 (1997) 739].

The localization of molecular electrostatic potential and of the H and L onto the indole may explain a dominant role of this ring in the free radical scavenging mechanism.     

Nuclear magnetic resonance analysis of trace sulfur mustard chemicals in the environmental samples

Nuclear magnetic resonance （NMR） technique was used to screen and identify trace sulfur mustard chemicals in the organic and aqueous waste samples. 1H-NMR and one dimensional total correlation spectroscopy （1D TOCSY） were used for non-destructive screening analysis of the original samples. 1D TOCSY-TOCSY and 1D TOCSY incorporated with a chemical shift selective filter （1D CSSF-TOCSY） were applied in screening the contained sulfur mustard related compounds in the unknown samples. In order to meet the criteria for 1H-NMR data presentation, sample pretreatment technologies including liquid-liquid extraction, solvent exchange and solid phase extraction were used to eliminate the interference of the target resonances. Bis（2-chloroethyl） sulfide, 1, 3-Bis（vinylthio）propane and 1,3-Bis（2-hydroxyethylsulfonyl） propane were identified based on 1HNMR spectra comparison. The results were in good agreement with the list of spiking chemicals. The analytical strategies of this work can provide reference for the 1H-NMR analysis of the trace chemical warfare related compounds in official OPCW proficiency test. © 2023, Youke Publishing Co.,Ltd. All rights reserved.     

Quantum molecular dynamics study of the reaction of O2 with HOCO

The reaction of O2 with HOCO has been studied by using an ab initio direct dynamics method based on the UB3PW91 density functional theory. Results show that the reaction can occur via two mechanisms: direct hydrogen abstraction and an addition reaction through a short-lived HOC(O)O2 intermediate. The lifetime of the intermediate is predicted to be 660 +/- 30 fs. Although it is an activated reaction, the activation energy is only 0.71 kcal/mol. At room temperature, the obtained thermal rate coefficient is 2.1 x 10(-12) cm3 molecule(-1) s(-1), which is in good agreement with the experimental results.     

Quantum chemical study of the molecular patterns of MAO inhibitors and substrates

Similarities and differences between mitochondrial monoamine oxidase (MAO) substrates and inhibitors (both A and B types) are considered, studying quantitatively two molecular properties: electron density and molecular electrostatic potential (MEP ). The following molecules are considered: substrates: PHEA, BZA, tele-N-methyl-histamine, phenylethanolamine, phenylpropylamine, tryptamine, dopamine, phenoxylethylamine, noradrenaline, serotonin, and p-nitro-phenylethanolamine; inhibitors: Deprenil, Clorgyline, and Lilly 51641 (only the moiety involved in the A–B differentiation is considered). The wave functions needed to calculate the analyzed properties are of ab initio quality, and have been calculated in analogous conformations, all near the energetic minima. Electron densities distributions are qualitatively compared by means of a correlation coefficient defined over the whole space. Otherwise, patterns of the possible zones of electrostatic interactions are described by means of the distances and angles between minima, in order to differentiate MAO-A and MAO-B substrates. The results reproduce efficiently the experimental classification and enable us to predict the type of enzymatic action of molecules not yet experimentally classified.     

Simple time weighted average level air-monitoring method for sulfur mustard in work places

A simple air-monitoring method was developed and validated for vesicant sulfur mustard (HD) in the work place at time weighted average levels. XAD-2 adsorbent was used for the collection of HD vapours for 8 h followed by liquid desorption with carbon tetrachloride. The trace level analysis was carried out by gas chromatography-photoionization detection and was confirmed by gas chromatography-mass spectrometric detection in the selected ion mode.     

Quantum force molecular dynamics study of the reaction of O atoms with HOCO

The reaction of HOCO with O atoms has been studied using a direct ab initio dynamics approach based on the scaling all correlation UCCD/D95(d,p) method. Ab initio calculations point to two possible reaction mechanisms for the O+HOCO-->OH+CO2 reaction. They are a direct hydrogen abstraction and an oxygen addition reaction through a short-lived HOC(O)O intermediate. The dynamics results show that only the addition mechanism is important under the conditions considered here. The lifetime of the HOC(O)O complex is predicted to be 172+/-15 fs. This is typical of a direct and fast radical-radical reaction. At room temperature, the calculated thermal rate coefficient is 1.44 x 10(-11) cm(3) mol(-1) s(-1) and its temperature dependence is rather weak. The two kinds of reactive trajectories are illustrated in detail.     

Quantum state tomography of molecular rotation

We show how the rotational quantum state of a linear or symmetric top rotor can be reconstructed from finite time observations of the polar angular distribution under certain conditions. The presented tomographic method can reconstruct the complete rotational quantum state in many nonadiabatic alignment experiments. Our analysis applies for measurement data available in principle with existing measurement techniques. In practice, a full reconstruction requires a large amount of data and is thus experimentally challenging. Nonetheless, showing that the necessary information is present, we substantiate the use of approximate reconstruction methods with such data.     

Quantum molecular dynamics study of water on TiO2(110) surface

The adsorption of water on perfect TiO(2)(110) surface is studied by quantum molecular dynamics simulation adopting a periodic model formed by five water molecules on a (5 x 1) surface unit cell of a five layer slab of TiO(2). The total simulation time is 3.2 ps. At about 1.3 ps, one water molecule dissociates with the help of other adsorbed waters and surface bridging oxygens. During the remaining 1.9 ps, the waters and OH groups vibrate, but no more dissociation or recombination is observed. By comparing recent experimental O1s photoemission (x-ray photoelectron spectroscopy) spectra of H(2)O/TiO(2)(110) to the computed spectrum of the adsorbate in the configurations supplied by the molecular dynamics simulation, the observed peaks can be attributed to different oxygen species. The proposed assignment of the main spectral features supports the occurrence of partial water dissociation (approximately 20%) also on a perfect TiO(2) surface.     

Quantum chemical study of molecular ion complexes with hydrogen bonds (Review)

Institute of Bioorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Translated from Zhurnal Strukturnoi Khimii, Vol. 33, No. 6, pp. 157–183, November–December, 1992.     

A simple and controlled oxidative decontamination of sulfur mustard and its simulants using ozone gas

A simple and efficient oxidative decontamination method was developed for sulfur mustard (HD), a potential chemical warfare agent. The method involves treatment of chemical warfare agent HD and its simulants, i.e., dimethyl sulfide, diethyl sulfide, and 2-chloroethyl ethyl sulfide with ozone gas at ambient conditions in acetonitrile solvent. Ozone gas readily oxidizes sulfur mustard in a controlled manner to give its corresponding nontoxic sulfoxide. This transformation is selective and takes place even at subzero temperatures. The oxidation products of HD and its simulants were monitored and quantified by gas chromatography and gas chromatography–mass spectrometry.