诱导效应指数与脂肪族胺、醇和醚的气相碱性

用烷基诱导效应指数I和RX分子中质子亲合原子X所带电荷qx及元素电负性XN与 脂肪胺，醇、醚的气相质子亲合PA进行关联，结果表明，脂肪胺，醇、醚的气相碱 性可以用下式定量描述：PA(kJ.mol^-1)-2732.0333-2457.1510∑I-1492.2351qx- 732.6277XN利用上式对64种化合物的气相碱性进行预测，平均相对误差为0．34％ ，预测值和实验值的偏差均在实验误差范围内。     

烷氧自由基电子亲合能的估算

烷氧自由基电子亲合能的估算曹晨忠（湘谭师范学院化学系，湘潭４１１１００）分子的电子亲合能在化学上有不少应用。最近Ｄａｈｌｋｅ等［１］报道了３－取代丙烯的气相碱性与其分子的电子亲合能有关。然而，由于实验技术的限制，目前可供利用的有机化合物电子亲合能数据...     

脂肪族胺、醇、醚气相碱性的模型研究

以烷基极化效应指数(PEI)和分子中亲合原子的平衡电负性(XE)及亲合原子的Pauling电负性(X)为基本参数,研究了脂肪族胺、醇、醚的气相碱性(PA)的共同变化规律。结果表明,脂肪族胺、醇、醚的气相碱性可用下列通式来定量描述：PA(KJ/mol)=2468.6730+557.3172∑PEI-551.4261XE-1230.5770(∑PEI/XE)-111.5537X用上式预测了64种化合物的气相碱性,平均绝对相对误差仅为0.34%,预测值与文献值的偏差完全落在实验误差的范围内。     

海水中有机污染物的光度法测定

海水中有机污染物在强碱性条件下被KMnO4所氧化。通过对生成物溶液中K2MnO4浓度的光度法测量（λ=430nm）,直接测定海水中有机物含量（以COD表示）。该方法的线性范围为0．40—4．50mg／L（以邻苯二甲酸氢钾＋甲酸钠体系为标准混合物溶液）,测定海水COD的相对标准偏差RSD为8．9％,回收率为90％～114％。     

极化效应指数与脂肪族胺、醇和醚气相碱性的关系

脂肪族胺、醇和醚的气相质子亲合能(PA)与N, O原子所带电荷(qx)以及烷基的极化效应指数(PEI)的关系可表示为其中a、b、c为系数。回归分析结果表明, 上式较好地表达了脂肪族胺、醇和醚的气相碱性变化规律。     

基团极化效应与气相有机分子酸碱性

长期以来,人们测定有机物的酸碱性是在溶液中进行的,因此物质的酸碱性往往受溶剂性质的影响。自60年代高压质谱和离子回旋共振及脉冲双共振谱等高技术的发展和应用,使人们能在气相中测定有机物的酸碱性。气相中     

CH3I同步辐射光电离及生成焓、键能和质子亲合势的测定

在超声射流冷却条件下用VUV同步辐射研究了CH3I分子的光电离过程。测定了CH3I光电离及解离电离产生的CH3I^+, CH3^+和I^+的出现势, 结合已确认的热力学数据, 估算出体系中有关离子的标准生成焓、分子和分子离子的键能、自由基的质子亲合势及母体离子的解离能等数据。对CH3I分子VUV光解离电离通道进行了分析。     

偶氮染料吸附和光催化氧化动力学

以甲基橙和酸性大红两种偶氮染料为模拟污染有机物,对它们的暗吸附和光催化氧化行为进行研究.实验结果表明,两种偶氮染料的吸附受溶液酸碱度影响很大,酸性（pH=3）条件下,两种染料吸附量都很大,酸性大红吸附量更大；近中性（pH≈6）时两种染料的吸附显著减少；碱性（pH=9）条件下两种染料不发生吸附.光催化反应结果显示,碱性条件或酸性条件下两种染料降解速度都很快.说明在不同酸碱度条件下,光催化反应按不同机理进行.酸性条件下,反应在催化剂表面进行,在碱性介质中,光催化氧化在溶液中进行.提出了一个碱性条件下的动力学方程,经过进一步简化,可以得到表观一级方程,形式上和准一级L-H方程十分相似,但其含义不同.     

气提法富集气相色谱／质谱法测定水中痕量挥发有机物

作者改进了气提法富集水中痕量挥发性有机物装置。研究了实验条件对水中痕量有机物富集的影响，并确定了最佳富集条件。以气提法富集气相色谱／质谱法（ＧＣ／ＭＳ）测定了水样中痕量挥发性有机物，取得了满意的结果。     

含氟β-二酮类化合物在质子溶剂中光稳定机理的研究

本工作利用吸收光谱及核磁共振氢谱的方法对两种含-CF₃基的β-二酮类化合物在质子溶剂中引起分子内氢键的破坏,缩醛化的发生及其动力学等进行了研究。工作探讨了光照使缩醛化产物回复至原有的分子内氢键结构以及回复后体系在暗场下继续进行缩醛化的过程,虽然光照使缩醛化产物破坏的原因尚待进一步研究,但这类含有-CF₃基的β-二酮类化合物在光照条件下能回复到含有分子内氢键的体系,这一特性可使这类化合物用作一种能在质子溶剂中应用的光稳定剂。其光稳定能力在本工作中已被证实。     

Analysis and assessment of the occurrence, the fate and the behavior of nanomaterials in the environment

Nanomaterials have one dimension <100 nm and possess physico-chemical properties dictated by their unusually small size, large surface area, shape and chemical composition. New properties of nanomaterials have boosted their production and industrial applications in many fields (e.g., microelectronics, catalysis, fuel cells, materials science, textiles, biotechnology and medicine). In biomedical fields, nanomaterials are of the appropriate dimensions to interact with biological matter. However, they may also have negative effects on biological systems. Nanotechnology is a major, innovative, scientific and economic growth area, but the increasing production and use of nanomaterials have led to calls for more information regarding the potential impacts that their release may have on human health and the environment.This review addresses analytical approaches for characterization and quantification of nanomaterials in the environment and recent studies on their occurrence, fate and behavior.     

Decorating step-by-step and independently the surface and the core of dendrons

Dendrons possessing one activated vinyl group at the core and several chlorine atoms at the end of the branches are used as starting materials to study the possibility to react independently the surface functions and the core function. In particular, the most powerful sequence of reactions for decorating them by organometallic complexes as end groups and amine or alcohol at the core has been determined. In the first step, phenol phosphines are grafted as end groups of the dendrons, and they can be used for the complexation of metals. However, these phosphines must be kept free when amines are used to react with the vinyl core in the next step. Depending on the type of phosphine end groups and on the type of function of the core (amine or alcohol), the complexation of ruthenium ([RuCl₂(p-cymene)]₂) and rhodium ([RhCl(COD)]₂) derivatives by the phosphine end groups can occur without side reaction at the core.     

Isolation and identification of the anti-isohumulones and the anti-acetylhumulinic acids

The anti-isohumulones [5-(3-methylbutanoyl)-2-(3-methylbut-2-enyl)-4-hydroxy-4-(4-methylpent-3-enoyl)-cyclopentane-1,3-diones] and the anti-acetylhumulinic acids [5-(3-methylbutanoyl)-2-(3-methylbut-2-enyl)-4-ethanoyl-4-hydroxy-cyclopentane 1,3-diones] have been isolated from an isomerisation reaction mixture of humulone [2-(3-methylbutanoyl)-4,6-di(3-methylbut-2-enyl)-6-hydroxy-cyclohexane-l,3,5-trione] by counter-current distribution and identified by spectroscopic techniques. The formation mechanism is presented and the stereochemical consequences are discussed. The anti-isohumulones are the most bitter hop compounds presently known.     

"地小氢"和"月小氢"

Hydrogen is the most abundant chemical element in the Universe and is tightly related to human life. This article personifies hydrogen, bringing a close interaction between the hydrogen on the moon and the hydrogen on the Earth. Through lively and interesting dialogues, the history of hydrogen discovery and the properties are introduced, and the application of hydrogen in different aspects of the future is prospected.     

McBain and the centenary of the micelle

In 1913, J.W. McBain introduced the word “micelle” into surface and colloid chemistry in the context of the association of surfactant molecules in aqueous solution. This article gives a biographic account of McBain, and reviews the early work on micellar aggregation, leading up to the pioneering ideas of G.S. Hartley who introduced the first model of the spherical micelle that we would recognise today.     

The energy pump and the origin of the non-equilibrium flux of the dynamical systems and the networks

The global stability of dynamical systems and networks is still challenging to study. We developed a landscape and flux framework to explore the global stability. The potential landscape is directly linked to the steady state probability distribution of the non-equilibrium dynamical systems which can be used to study the global stability. The steady state probability flux together with the landscape gradient determines the dynamics of the system. The non-zero probability flux implies the breaking down of the detailed balance which is a quantitative signature of the systems being in non-equilibrium states. We investigated the dynamics of several systems from monostability to limit cycle and explored the microscopic origin of the probability flux. We discovered that the origin of the probability flux is due to the non-equilibrium conditions on the concentrations resulting energy input acting like non-equilibrium pump or battery to the system. Another interesting behavior we uncovered is that the probabilistic flux is closely related to the steady state deterministic chemical flux. For the monostable model of the kinetic cycle, the analytical expression of the probabilistic flux is directly related to the deterministic flux, and the later is directly generated by the chemical potential difference from the adenosine triphosphate (ATP) hydrolysis. For the limit cycle of the reversible Schnakenberg model, we also show that the probabilistic flux is correlated to the chemical driving force, as well as the deterministic effective flux. Furthermore, we study the phase coherence of the stochastic oscillation against the energy pump, and argue that larger non-equilibrium pump results faster flux and higher coherence. This leads to higher robustness of the biological oscillations. We also uncovered how fluctuations influence the coherence of the oscillations in two steps: (1) The mild fluctuations influence the coherence of the system mainly through the probability flux while maintaining the regular landscape topography. (2) The larger fluctuations lead to flat landscape and the complete loss of the stability of the whole system.     

On the transport and trajectories of the chernobyl debris across Canada and the arctic

A scenario is presented for the transport of the Chernobyl radioactive debris across Canada and the Arctic. It is based on the analysis of the¹⁰³Ru/¹³⁷Cs ratios in terms of the Chernobyl release pattern. The ratios which ranged from 0.2 to more than 4.0 were associated with four different phases of the Chernobyl emissions which lasted 10 days, from April 26 to May 6, 1986. Debris from the initial phase /ratios of 0.2 to 0.5/ and the last phase /ratios above 2.5/ would have entered Canada on a very broad front extending from northern Quebec to the North West Territories by way of Greenland and the Arctic; debris from the second phase /ratios of 0.5 to 2.0/ and the third phase /ratios of 2.0 to 2.5/ would have entered Canada from the west after travelling by way of northern Siberia and the Bering Sea.Paper presented at the IVth International Symposium of Radioecology of Cadarache, France, March 1988.     

麻黄-甘草药对配伍前后主要药效成分及抗炎活性的变化

利用高效液相色谱串联质谱联用法(HPLC-MS/MS)和气相色谱质谱联用法(GC-MS)分析了麻黄与甘草药对配伍前后水煎液中主要药效成分的变化,并通过小鼠的耳廓肿胀试验考察了甘草、麻黄单煎液及药对共煎液的抗炎活性变化.分别通过HPLC法和GC-MS法对甘草与麻黄中主要化学成分,甘草酸、甘草苷、麻黄碱和甲基麻黄碱进行了定量分析,通过单煎液和药对共煎液的对比,发现麻黄与甘草配伍共煎液中麻黄碱(含伪麻黄碱)的含量增加了14.52%;甲基麻黄碱(含甲基伪麻黄碱)的含量增加了64.0%;甘草酸含量增加了13.50%;而甘草苷含量降低了19.38%.药效实验证明,甘草与麻黄配伍后抗炎作用较甘草麻黄单煎液明显增强.从而在主要成分的变化程度上揭示了甘草与麻黄配伍过程中的增效机理.     

消臭抗菌纤维素纤维的制备、结构和性能

采用一种制备消臭、抗菌纤维素纤维的新方法，即先将纤维素纤维用多元羧酸进行化学修饰，然后在铜溶液中处理，生成铜螯合纤维素纤维，用红外光谱、电子自旋波谱表征了该纤维的配位结构，消臭和抗菌实验结果显示，这种功能性纤维对硫化氢，氢气、三甲胺的消臭率分别达到100％，92．1％和80．4％，对金黄色葡萄球菌，大肠杆菌和白色念珠菌的抑菌率分别为79．14％，93．59％和82．50％，用X射线衍射，电子自旋波谱分析了该纤维吸附硫化氢，氨气、三甲胺的机理。