Hydrogen in Porous Tetrahydrofuran Clathrate Hydrate

The lack of practical methods for hydrogen storage is still a major bottleneck in the realization of an energy economy based on hydrogen as energy carrier. ¹ Storage within solid‐state clathrate hydrates, ² – ⁴ and in the clathrate hydrate of tetrahydrofuran (THF), has been recently reported. ⁵ , ⁶ In the latter case, stabilization by THF is claimed to reduce the operation pressure by several orders of magnitude close to room temperature. Here, we apply in situ neutron diffraction to show that—in contrast to previous reports^{[5, 6]}—hydrogen (deuterium) occupies the small cages of the clathrate hydrate only to 30 % (at 274 K and 90.5 bar). Such a D₂ load is equivalent to 0.27 wt. % of stored H₂. In addition, we show that a surplus of D₂O results in the formation of additional D₂O ice Ih instead of in the production of sub‐stoichiometric clathrate that is stabilized by loaded hydrogen (as was reported in ref. ⁶ ). Structure‐refinement studies show that [D₈]THF is dynamically disordered, while it fills each of the large cages of [D₈]THF?17D₂O stoichiometrically. Our results show that the clathrate hydrate takes up hydrogen rapidly at pressures between 60 and 90 bar (at about 270 K). At temperatures above ≈220 K, the H‐storage characteristics of the clathrate hydrate have similarities with those of surface‐adsorption materials, such as nanoporous zeolites and metal–organic frameworks, ⁷ , ⁸ but at lower temperatures, the adsorption rates slow down because of reduced D₂ diffusion between the small cages.     

Impact of Low-Dosage Inhibitors on Clathrate Hydrate Stability

Summary: Development of more capable low-dosage hydrate inhibitors (LDHI) is of crucial importance to oil and gas industry. Those efforts have been severely hindered so far by lack of clear understanding of molecular-level mechanisms, both thermodynamic and kinetic, which make certain chemical compounds into efficient inhibitors. An accurate representation of intermolecular potentials between polymeric low dosage inhibitors and hydrate-water-gas surfaces is essential for modelling systems containing these components. A two-stage computational study was undertaken of two proven LDHIs, polyvinylpyrrolidone (PVP) and polyvinylcaprolactam (PVCap), in aqueous solutions under various conditions. We have first carried out ab initio density functional theory (DFT) calculations for PVP and PVCap polymers with molecular weight spanning from monomers to polymeric chains. Molecular dynamics were then employed to investigate thermodynamic and kinetic processes that affect hydrate nucleation and growth. Comparison with experiments has also shown that calculated potential is able to mimic the characteristic behaviour of methane hydrate and PVP complexes.     

Interaction Study of Guest with Host in Clathrate Hydrate

Lattice dynamical simulations of noble gas hydrate structuresⅠandⅡhave been performed. Potential energies were investigated to study the influence of guest species on the stability of the hydrate structure.Results show that when the diameter of inclusion molecules is between 3(?)and 4.2(?),such as Ar and Kr,the critical role of the 5~(12)cage in the stabilization of hydrates becomes effective.For Xe hydrates SⅠand SⅡ,with the help of lattice dynamical calcnlations,the modes attributions are identified directly.We proposed the resonant effect of the fingerprint frequency at about 7 meV and 10 meV which arise from the coupling of Xe molecules in the 5~(12)cage with the host lattice.     

Experimental Modeling of the Processes of Ozone Hydrate Clathrate Formation

The possible formation of ozone hydrates and their interaction with hydrogen chloride under nearstratospheric conditions were investigated. The low-temperature IR spectroscopic technique was used to demonstrate the in situ formation of ozone hydrates that were stable in the temperature range 77–220 K. It was found that HCl reacted with ozone hydrate to destruct clathrate at temperatures above 220 K. This process resulted in compositionally different chlorine oxides. Original Russian Text ? T.A. Vysokikh, T.V. Yagodovskaya, S.V. Savilov, V.V. Lunin, 2008, published in Zhurnal Fizicheskoi Khimii, 2008, Vol. 82, No. 4, pp. 792–795.     

Electric Double‐Layer Capacitor Based on an Ionic Clathrate Hydrate

Herein, we suggest a new approach to an electric double‐layer capacitor (EDLC) that is based on a proton‐conducting ionic clathrate hydrate (ICH). The ice‐like structures of clathrate hydrates, which are comprised of host water molecules and guest ions, make them suitable for applications in EDLC electrolytes, owing to their high proton conductivities and thermal stabilities. The carbon materials in the ICH Me₄NOH ? 5 H₂O show a high specific capacitance, reversible charge–discharge behavior, and a long cycle life. The ionic‐hydrate complex provides the following advantages in comparison with conventional aqueous and polymer electrolytes: 1) The ICH does not cause leakage problems under normal EDLC operating conditions. 2) The hydrate material can be utilized itself, without requiring any pre‐treatments or activation for proton conduction, thus shortening the preparation procedure of the EDLC. 3) The crystallization of the ICH makes it possible to tailor practical EDLC dimensions because of its fluidity as a liquid hydrate. 4) The hydrate solid electrolyte exhibits more‐favorable electrochemical stability than aqueous and polymer electrolytes. Therefore, ICH materials are expected to find practical applications in versatile energy devices that incorporate electrochemical systems.     

甲氨蝶呤与一氧化氮供体或一氧化氮合酶抑制剂组合物的合成

一氧化氮(nitric oxide,NO)在肿瘤病理生理过程中产生多方面的生化作用,诸如引起的某些核苷酸碱基的羟基化,参与免疫系统清除肿瘤细胞,促进肿瘤细胞凋亡和调节血管生成等．在此基础上,首次提出将NO供体(NO donor)或一氧化氮合酶(nitric oxide synthase,NOS)抑制剂分别连接到甲氨蝶呤(methotrexate,MTX,MTX本身就是NOS抑制剂)的α或γ位羧基上的设想,设计并合成出：(1)MTX-NO供体(3-羟甲基-4-苯基-1,2,5-噁二唑-2-氧化物,属于Furoxan衍生物,缩写为FU)：1a(MTX-α-FU),2a(MTX-γ-FU);(2)MTX-NOS抑制剂(L-N^ω-硝基精氨酸或L-N^ω-硝基精氨酸甲酯)：1b(MTX-α-L-N^ω-NO2-Arg),2b(MTX-γ-L-N^ω-NO2-Arg),1c(MTX-α-L-N^ω-NO2-Arg-OMe),2c(MTX-γ-L-N^ω-NO2-Arg-OMe)．在生物活性测试中,我们选择耐MTX细胞株K-562(慢性粒细胞性白血病急性病变细胞株),进行抗肿瘤活性测试,得到以下结果：(1)脂溶性差的MTX衍生物1b,2b抗肿瘤活性低于MTX,其它1a,2a;1c,2c均优于MTX;(2)连接有NO供体的MTX明显增强了MTX衍生物的抗肿瘤活性;(3)MTX中谷氨酸γ位组合物抗肿瘤活性均高于相应的α位异构体的活性．以上初步结果,将对进一步研究NO抗肿瘤作用以及新的抗肿瘤药物设计提供新的思路,对肿瘤临床化疗也有一定的参考价值．     

Standard Mixtures of Nitric Oxide

Abstract

Standard mixtures of nitric oxide may be prepared by converting NO₂ to NO in presence of a molybdenum catalyst. Quantitative conversion has been obtained in the concentration range 0–100 pnm at temperatures as low as 200°C.

It has been proved that this material is scarcely affected by poisoning when exposed to high levels of nitrogen oxides.     

Phase Transition of a Structure II Cubic Clathrate Hydrate to a Tetragonal Form

The crystal structure and phase transition of cubic structure II (sII) binary clathrate hydrates of methane (CH₄) and propanol are reported from powder X‐ray diffraction measurements. The deformation of host water cages at the cubic–tetragonal phase transition of 2‐propanol+CH₄ hydrate, but not 1‐propanol+CH₄ hydrate, was observed below about 110 K. It is shown that the deformation of the host water cages of 2‐propanol+CH₄ hydrate can be explained by the restriction of the motion of 2‐propanol within the 5¹²6⁴ host water cages. This result provides a low‐temperature structure due to a temperature‐induced symmetry‐lowering transition of clathrate hydrate. This is the first example of a cubic structure of the common clathrate hydrate families at a fixed composition.     

一氧化氮化学性质的研究进展

概括了由Louis J. Ignarro, Ferid Murad和Robert F. Furchgott三位诺贝尔奖获得者提出的一氧化氮作为血管内皮松弛因子(EDRF)的作用机制及生物学意义; 同时也总结了100多年来一氧化氮在化学本质的探讨方面做出的研究成就; 归纳了一氧化氮自由基在化学反应过程中的行为本质.     

一种新型一氧化氮电化学传感器

将一种自合成的水溶性聚对苯撑乙烯(PPV)衍生物电聚合到玻碳电极表面, 制得一种新型NO电化学传感器. 实验结果表明, 该传感器对NO具有灵敏的伏安响应, 相对裸玻碳电极两个氧化峰电位均负移达180 mV. 安培实验结果表明, NO的响应电流与其浓度在 1.8×10-7～1.0×10-4 mol/L范围内有良好的线性关系(r＝0.999 3), 检出限达到2.3×10-8 mol/L. 用旋转圆盘电极研究了NO在该传感器上的电化学行为, 并计算出NO在0.1 mol/L的磷酸盐生理缓冲溶液(PBS)中的扩散系数.     

Nitric Oxide Photoreleasers with Fluorescent Reporting

Nitric oxide (NO) plays a multifaceted role in human physiology and pathophysiology, and its controlled delivery has great prospects in therapeutic applications. The light-activated uncaging of NO from NO caging compounds allows this free radical to be released with accurate control of site and dosage, which strictly determine its biological effects. Molecular constructs able to activate fluorescence concomitantly to NO release offer the important advantage of easy and real-time tracking of the amount of NO uncaged in a non-invasive fashion even in the cell environment. This contribution provides an overview of the advances in photoactivatable NO releasers bearing fluorescent reporting functionalities achieved in our and other laboratories, highlighting the rationale design and their potential therapeutic applications.     

一氧化氮荧光分子探针

一氧化氮（NO）在生物体中扮演重要的角色,对其选择性识别引起了人们极大的兴趣。本文综述了两类NO荧光分子探针的研究进展,即含金属离子的NO荧光分子探针：如Co(Ⅱ)、Fe(Ⅱ)、 Ru(Ⅱ)、Rh(Ⅱ)和Cu(Ⅱ)配合物作为荧光打开的NO分子探针;邻苯二胺类荧光分子探针：如2,3-二氨基萘（DAN）、二氨基荧光素衍生物（DAFs）、二氨基罗丹明衍生物（DARs）、硼二吡咯甲基衍生物（BODIPY）和三碳菁衍生物（DAC）等。