GAS-PHASE ACETYLATION OF C-60 AND C-70 BY ION/MOLECULE REACTIONS

Gas phase reactions of C-60 and C-70 with the ion system of acetone under chemical ionization conditions have been studied. C-60 and C-70 can react with acetyl and oxonium ions, which come from self-chemical ionization of acetone, to form adduct ions. In addition, C-60 and C-70 can accept protons to produce protonated ions. C-70 is more active in the above reactions than C-60 because of its stronger gas-phase basicity. A sigma-bond between C-60 and an acyl carbon atom can be formed to produce stable acetylated C-60 ions. The above results may be relevant to the acetylation reactions of C-60 in the condensed phase.

Gas-phase Ion-molecular Reactions of C-60 and C-70 with Acetone and Quantum Chemistry Study

Gas-phase ion-molecular reactions of C-60 and C-70 with the ion system of acetone have been studied in this paper. The ions of protoned and acetylized C-60 and C-70 were formed by the reactions of C-60 and C-70 with some ions which existed in the ion system when mass spectrometer worked on chemical ionization conditions. The reactivity of C-70 is greater than that of C-60. Results of quantum chemical calculation for the adduct ions showed a sigma bond between the acyl carbon atom and C-60 may be Formed. These results will provide some valuable informations on the condense-phase acetylization of C-60.

Experimental studies of the dissociative recombination of CD3CDOD+ and CH3CH2OH2+

Aims. We determine branching fractions, cross sections and thermal rate constants for the dissociative recombination of CD3CDOD+ and CH3CH2OH2+ at the low relative kinetic energies encountered in the interstellar medium. Methods. The experiments were carried out by merging an ion and electron beam at the heavy ion storage ring CRYRING, Stockholm, Sweden. Results. Break-up of the CCO structure into three heavy fragments is not found for either of the ions. Instead the CCO structure is retained in 23 +/- 3% of the DR reactions of CD3CDOD+ and 7 +/- 3% in the DR of CH3CH2OH2+, whereas rupture into two heavy fragments occurs in 77 +/- 3% and 93 +/- 3% of the DR events of the respective ions. The measured cross sections were fitted between 1-200 meV yielding the following thermal rate constants and cross-section dependencies on the relative kinetic energy: sigma(E-cm[eV]) = 1.7 +/- 0.3 x 10(-15)(Ecm[eV])(-1.23 +/- 0.02) cm(2) and k(T) = 1.9 +/- 0.4 x 10(-6)(T/300)-0.73 +/- 0.02 cm(3) s(-1) for CH3CH2OH2+ as well as k(T) = 1.1 +/- 0.4 x 10(-6)(T/300)(-0.74 +/- 0.05) cm(3) s(-1) and s(Ecm[eV]) = 9.2 +/- 4 x 10(-16)(Ecm[eV])-1.24 +/- 0.05 cm(2) for CD3CDOD+

Fragmentation reactions of adduct ions [M+CH3CO](+) of isomeric phenylenediamines

The dissociation routes of the adduct ions [M+CH3CO](+) formed by ion-molecule reaction of isomeric phenylenediamines with acetyl ion from acetone under chemical ionization condition were investigated by using collision-induced dissociation (CID) technique performed at ion kinetic energies of 40eV. The adduct ions are intermediate ion-neutral complexes.

Two-component model for the interstellar scattering in direction to the Vela pulsar

This paper discusses a rigorous treatment of the refractive scintillation of pulsar PSR B0833-45 caused by a two-component interstellar scattering medium. It is assumed that the interstellar scattering medium is composed of a thin screen ISM and an extended interstellar medium. We consider that the scattering of the thin screen concentrates in a thin layer presented by a delta function distribution and that the scattering density of the extended irregular medium satisfies the Gaussian distribution. We investigate and develop equations for the flux density structure function corresponding to this two-component ISM geometry in the scattering density distribution and compare our result with that of the Vela pulsar observations. We conclude that the refractive scintillation caused by this two-component ISM scattering gives a more satisfactory explanation for the observed flux density variation of the Vela pulsar than does the single extended medium model. The level of refractive scintillation is strongly sensitive to the distribution of scattering material along the line of sight. The logarithmic slope of the structure function is sensitive to thin screen location and is relatively insensitive to the scattering strength of the thin screen medium. Therefore, the proposed model can be applied to interpret the structure function of flux density observed in pulsar PSR B0833-45. The result suggests that the medium consists of a discontinuous distribution of plasma turbulence embedded in the Vela supernova remnant. Thus our work provides some insight into the distribution of the scattering along the line of sight to the Vela pulsar.

Production of Superheavy Nuclei in Massive fusion reactions

A master equation is constructed to treat the nucleon transfer process in heavy ion fusion reactions to form superheavy nucleus. The relative motion concerning the energy, the angular momentum and the fragment deformation relaxations is explicitly treated to couple with the diffusion process. The nucleon transition probabilities, which are derived microscopically, are thus time dependent. The calculated evaporation residue cross-sections for both cold and hot fusion are in good agreement with the known experimental data.

Study of electron-transfer reactions across an externally polarized water/1,2-dichloroethane interface by scanning electrochemical microscopy

A novel method to study electron-transfer (ET) reactions between ferrocene in 1,2-dichloroethane (DCE) and a redox couple of K3Fe(CN)(6) and K4Fe(CN)(6) in water using scanning electrochemical microscopy (SECM) with a three-electrode setup is reported. In this work, a water droplet that adheres to the Surface of a platinum disk electrode is immersed in a DCE solution. The aqueous redox couple serves both as a reference electrode on the platinum disk and as an electron donor/acceptor at the polarized liquid/liquid inter-face. With the present experimental approach, the liquid/liquid interface can be polarized externally, while the electron-transfer reactions between the two phases can be monitored independently by SECM. The apparent heterogeneous rate constants for the ET reactions were obtained by fitting the experimental approach curves to the theoretical values. These rate constants obey the Butler-Volmer theory i.e., them, are found to be potential dependent.

Studies on the adduct reaction of disubstituted benzenes with ion system of acetone in gas phase

Ion - molecule reactions of disubstituted benzene with ion system of acetone and deuterium - labelled acetone under chemical ionization conditions were examined and the fragmentation reactions of the adduct ions formed by the ion - molecule reactions were studied using collision - induced dissociation (CID) technique. It was found that the electron - releasing groups favored the adduct reactions, whereas the electron - withdrawing groups did not. The position and properties of substituted groups affected the relative abundance of the adduct ions. The fragmentation reaction of the adduct ion formed by ortho - phenylenediamine with acetyl ion was similar to the reductive alkylation reaction of amine in condensed phase.

Advances in gas-phase electrophilic aromatic substitution reaction

Recent advances in the gas - phase reaction of aromatics with cationic electrophiles are reviewed. The overall substitution reaction is analyzed in terms of its elementary steps. Mechanistic studies have been focused on the structure and reactivity of covalent and non - covalent ionic intermediates, which display a rich chemistry and provide benchmark reactivity models. Particular attention has been devoted to proton transfer reactions, which may occur intra or intermolecularly in arenium intermediates.

Studies of the ortho effect in fragmentations of acetyl ion adducts of disubstituted benzenes

The ion-molecule reactions of disubstituted benzenes under chemical ionization conditions with acetyl chloride as reagent gas were examined, and the fragmentation reactions of the adduct ions (mostly proton and acetyl ion adducts) were studied by collision-induced dissociation. Electron-releasing substituents favored the adduct reactions, and electron-withdrawing groups did not. The position and properties of substituting groups had an effect on the relative abundances of the adduct ions. Several examples of the ortho effect were observed. The fragmentation reaction of the adduct ions formed by ortho-benzenediamine with the acetyl ion was similar to the reductive alkylation reaction of amines in the condensed phase. Copyright (C) 2001 John Wiley & Sons, Ltd.

Mass spectrometry study combined with theoretical calculation on the unimolecular fragmentation of tetrahydroimidazole-substituted methylene beta-diketones

Studies of low-energy collision-induced dissociation and isotopic labeling on ionized tetrahydroimidazole-substituted methylene P-diketones by tandem mass spectrometry showed that their unimolecular fragmentations may involve the reactions of intermediate ion/neutral complexes and multistep rearrangements. The corresponding mechanisms were proved by semiemipirical calculations of PM3 and AM1 methods.

Formation of heterocyclic C-60 derivative by gas-phase ion/molecule reaction

Ion/molecule reactions of C-60 with vinyl acetate under chemical ionization conditions have been studied here. Compared with C2H3O+ from acetone, C2H3O+ from vinyl acetate undergoes the reactions more easily, a new heterocycle between C-60 and the studied ion is formed The generation of two sigma-bonds and little angle tensile force of pentatomic ring make it more stable.

The radio counter-jet of the QSO 3C 48

We present multi- frequency radio observational results of the quasar 3C 48. The observations were carried out with the Very Large Array ( VLA) at five frequencies, 0.33, 1.5, 4.8, 8.4, and 22.5 GHz, and with the Multi- Element Radio Linked Interferometer Network ( MERLIN) at the two frequencies of 1.6 and 5 GHz. The source shows a one- sided jet to the north within 1", which then extends to the northeast and becomes diffuse. Two bright components ( N2 and N3), containing most of the flux density, are present in the northern jet. The spectral index of the two components is alpha(N2) similar to -0.99 +/- 0.12 and alpha(N3) similar to - 0.84 +/- 0.23 ( S proportional to nu(alpha)). Our images show the presence of an extended structure surrounding component N2, suggestive of strong interaction between the jet and the interstellar medium ( ISM) of the host galaxy. A steep- spectrum component, labelled S, located 0.25 " southwest to the flat- spectrum component which could be the core of 3C 48, is detected at a significance of > 15 sigma. Both the location and the steepness of the spectrum of component S suggest the presence of a counter- jet in 3C 48.

微纳米级液/液界面间离子转移反应的研究

液／液界面通常被看作是人工膜和生物膜的简单模型，液界面电分析化学的主要研究对象是界面上的电荷（电子和离子）转移反应以及伴随发生的相关化学反应。本论文简要回顾了液/液界面电分析化学的发展历程，介绍了液/液界面上电分析化学的基本理论。目前，应用扫描电化学显微镜结合微、纳米电极技术研究液/液界面上的电荷转移反应是电分析化学领域的研究热点之一。本文在本实验室以往研究工作的基础上，将扫描电化学显微镜、微、纳米管技术和各种电化学方法相结合，一方面进一步深入研究了在可极化液/液界面上、高驱动力作用下的加速离子转移反应的动力学，另一方面探讨了支持电解质浓度对简单及加速离子在低离子强度溶液相间的转移反应的影响。主要结果如下：1．通过选择适当的研究模型（二苯基18冠6加速Na+、Li+在水1/2-二氯乙烷界面上的转移反应）、实验条件及将三电极系统、纳米管与扫描电化学显微镜相结合，进一步研究了加速离子转移反应的驱动力与异相反应速率常数之间的关系。由实验得到，加速离子转移反应的速率常数匆与反应驱动力直接相关。在低驱动力区，Inkf与驱动力的关系遵循经典的Butier～Voh“方程；高马时力区，反应的动力学逐渐进入Marcus翻转区，即反应的速率常数随驱动力的增加而减小，此与Marcus 理论相一致。本实验是第一次在加速离子转移反应中观察到Marcus翻转现象。2．应用循环伏安法、方波法、计时安培法和微/纳米管技术研究了加速钾离子从水相向高阻抗有泪毛相转移的反应。同时系统讨论了低浓度电解质对水相及有机相TMA~+简单离子转移反应的影响。实验中绷门发现纳米管可被用子有机相无外加支持电解质的加速离子转移反应的研究。而在含少量或不含电解质的两相间的TMA+离子转移反应中，可以清楚的观察到迁移在TMA+转移过程中所起的作用。另外也较详细讨论了简单离子在界面转移的机理。

绞股蓝离体培养中影响皂甙产量的几个因素研究

绞股蓝(Gynostemma pentaphyllum)系葫芦科绞股蓝属植物，药用价值广泛，但其野生资源日趋减少，绞股蓝主要药效成分为绞股 蓝皂甙。利用组织和细胞培养生产绞股蓝皂甙是合理开发利用和保护绞股蓝资源的可能途径之一。本文对绞股蓝组织培养中培养基 的蔗糖和激素的组成以及各种胁迫条件：渗透压、重金属离子、真菌诱导物等对皂苷产量的影响进行了初步研究。其中，渗透压、 重金属离子、真菌诱导物对绞股蓝愈伤组织皂甙产量的影响尚未见报道。1. 蔗糖对绞股蓝愈伤组织之生长影响显著，2,4-D对绞股 蓝愈伤组织皂甙含量、产量影响显著。增加蔗糖用量，减少2，4-D的用量可提高皂甙产量。2. Mn++ 用量的提高抑制绞股蓝愈伤组 织的生长，但可促进皂甙含量、产量的提高。Mn++用量提高至MS培养基的20-30倍时可使皂甙产量增加近一倍，而提高Cu++浓度的 作用不明显。3. 甘露醇用量增加抑制绞股蓝愈伤组织的生长，但可使皂甙含量、产量提高。0.680mol·l-1甘露醇可使皂甙产量提 高83%，而Nacl较大抑制愈伤组织的生长并使皂甙产量降低。4. 米曲霉粗提物对绞股蓝愈伤组织生长先略微促进，然后抑制，而根 霉粗提物则使愈伤组织生长受抑制；两者对皂甙含量、产量的作用相似：在较低浓度范围内升高，然后下降。米曲霉粗提物可提高 产量一倍，根霉粗提物可提高42%。这些结果为高产细胞系的筛选和生长、生产培养条件的优化积累了资料。在综述部分，对植物 细胞培养中组织和器官分化、细胞结构变化、生化水平的变化与次生物合成和积累的关系作了讨论。Gynostemma pentaphyllum blongs to Gynostemma, Cucurbitaccae. It has a wide medical use, but its wild resource is threatened by people's excessive use. Its effective medical components are gypenosides. For reasonable use and protect its resource, it is a possible way to product gypenosides by plant tissue and cell culture. This paper has a primary study on the components of sucrose and hormones and a variety of stress conditions: osmostic pressure, heavy metal ion, fungal elicitors in the medium for the calli culture. The effects of osmostic pressure, heavy metal ion and fungal elicitors on the calli of Gynostemma pentaphyllum have not been reported. 1. Sucrose had a significant effect on the growth of the calli, 2,4 D had notable effects on the gypenosides content and production of the calli. Increased the concentration of sucrose and decreased the concentration of 2,4 D improved the production of gypenosides. 2. Increased the concentration of Mn++ inhibited the growth of the calli, but improved the content and production of gypenosides. The optimum concentration was 20-30 times as MS medium which improved the production 100%. Increased the concentration of Cu++ had not a notable effect. 3. Increased the concentration of mannitol inhibited the growth of the calli, but improved the content and production of gypenosides. The optimum concentration was 0.680mol·l-1 which improved the production 83%. Nacl apparently inhibited the growth of the calli and decreased the production of gypenosides. 4. The crude preparation of Aspergillus oryzae inhibited the growth of the calli that in low concentration. The crude praparation of Rhizopus formosensis inhibited the growth of the calli throughout. Their effects on the content and production of gypenosides are alike, but the former is higher than the latter. On the optimum concentration, each crude preparation improved the production 100% (Aspergillus oryzae), 42%(Rhizopus formosensis). These results has accumulated some informantion on the select of high yield cell strains and choose the best culture conditons for the growth and gypenosides product of the calli. In the review, it is discussed that the differentiation on tissue-organal, cellular and biochemical levels related to the synthesis and accumulation of secondary metabolites in plant culuture.