NiY分子筛表面酸性影响其选择性吸附脱硫性能的机理研究

采用原位红外光谱技术,以噻吩、环己烯和苯为模型探针分子,分别考察单一烃分子在NiY分子筛上的吸附与反应行为以及噻吩与烯烃、芳烃间的竞争吸附和催化反应行为。单一探针分子吸附研究发现,NiY分子筛中与Ni物种相关的Lewis(L)酸位是噻吩的选择性吸附活性位;噻吩和环己烯在NiY分子筛中Brnsted(B)酸位上发生的质子化和低聚反应明显弱于HY分子筛。双探针分子竞争吸附研究发现,环己烯二聚体在NiY中强B酸位上的强化学吸附与噻吩存在显著的竞争吸附行为。另外,苯和噻吩在NiY上的竞争吸附现象在373K时明显减弱。由此,在选择性吸附脱硫过程中,减少吸附剂表面B酸中心可降低烯烃对噻吩的竞争吸附,另外适当提高吸附体系的温度可以有效避免芳烃对噻吩的竞争吸附。     

Study of the solid-state hydrolysis of chitosan in presence of HCl

Chemical depolymerization of chitosan was obtained in the solid state by means of gaseous HCl. This new method allowed us to simultaneously form the hydrochloric salt and saturate the hydration water with acid. The depolymerization was carried out by keeping the product at a given temperature for the desired time. The measurements of the molecular weight distributions demonstrated the ability to control the reaction and produce oligomers with chosen dimensions. This solid-state hydrolysis favors the presence of a four-fold distribution that can be related to the original morphology and crystallinity of the initial material. The effects of the hydrolysis on the crystallinity, the crystalline structure, and the supramolecular order of the obtained chitosans were also studied. Finally, the washing of the hydrolyzed products in concentrated alkaline or acidic media allowed us to eliminate the lowest DPs and thus to narrow the molecular weight distribution. In this case, the crystallinity was also increased up to values beyond 70%. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3181–3191, 1997     

两种含杂环的氨基萘醌化合物的合成

以2,3-二氯-1,4-萘醌为主要原料,分别与吗啡啉和糠胺在一定条件下反应生成2种含杂环的氨基萘醌类化合物。2,3-二氯-1,4-萘醌与吗啡啉及2,3-二氯-1,4-萘醌与糠胺物质的量比均为1∶2,反应温度为60℃,溶剂为乙醇。2,3-二氯-1,4-萘醌与吗啡啉反应时间为1 h,产物2-氯-3-吗啡啉基萘-1,4-二酮(a)收率为93.5%;2,3-二氯-1,4-萘醌与糠胺反应时间为4 h,产物N~2,N~3-二(2-呋喃甲基)-1,4-二((2-呋喃甲基)亚胺)-1,4-二氢化萘-2,3-二氯化铵(d)收率为46.7%。对产物进行IR、Uv、MS和H-NMR等分析表征。     

Mechanism of TBD-catalyzed hydrolysis of acetonitrile

1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD) has recently been shown to be an effective organocatalyst for the hydrolysis reaction of acetonitrile. This reaction involves the acetamide-forming reaction of acetonitrile hydrolysis and the further hydrolysis of acetamide to form acetic acid and NH₃. Density functional theory (DFT) and Hartree–Fock (HF) methods were employed to comprehensively investigate these two hydrolysis steps to elucidate the TBD-catalyzation mechanism. Structures and energies of the reactants, intermediates, transition states and products along the reaction path were presented. Charge population and bond orders were given by natural bond orbital (NBO) analysis to clarify the computed atomic and molecular behaviors. The results showed that compared with the noncatalyzed reaction, the TBD-catalyzed process had significantly lower energy barriers in both the hydration steps and the isomerization steps. As a result, the whole reaction process could be accelerated and the TBD-catalyzation mechanism was clarified.     

钛表面固定特异性识别内皮祖细胞的多肽适配子

在钛表面固定可与循环血液中的内皮祖细胞(EPC)特异性结合的多肽适配子,构建内皮祖细胞的特异性识别表面,用于心血管材料的表面改性.首先,采用固相合成法合成可与EPC特异性结合的多肽适配子,其序列为TPSLEQRTVYAK,并在羧基端进行生物素修饰;然后,采用磷酸处理钛表面,在钛表面获得化学键合的羟基,该羟基化表面与3-...     

Assignment of the absolute configuration of blasticidin A and revision of that of aflastatin A

The absolute configuration of blasticidin A, a strong inhibitor of aflatoxin production by Aspergillus parasiticus, was assigned by adding the data of relative configurations at its diol and pentaol moieties to previously known stereochemistry. Similarity of the NMR data of blasticidin A to those of aflastatin A allowed us to revise the stereochemistry of the diol and pentaol moieties of aflastatin A.     

Influence of Apoptin on Up-regulation of the Expression of Bad and Bax

The chicken anemia virus protein, apoptin, which manifests selectivity and specificity to tumor cells, induces a p53-independent and Bcl-2-insensitive type of apoptosis in various human tumor cells. In this study, the apoptin gene was cloned from the total DNA of chicken anemia virus, and the recombinant vector was constructed. We used oligonucleotide microarray to study the changes of four genes, including Bcl-2, Bcl-xL, Bad and Bax. The post-transfection with the recombinant was also studied. The pro-apoptotic genes(Bad and Bax) and anti-apoptosis genes(Bcl-2 and Bcl-xL) were up-regulated in contrast to the controls. According to the published data, either Bcl-2 or Bcl-xL can form non-functional heterodimers by Bad and Bax binding together, resulting in blocking partly the release of cytochrome c from mitochondria. However, apoptosis could be inhibited by neither the endogenous Bcl-xL nor Bcl-2 over-expression. The experiments show that the apoptin-induced apoptotic pathway is related to the up-regulation of Bad and Bax. Bad was up-regulated by apoptin; then this up-regulated product of Bad was in favor of displacing Bax from binding to Bcl-xL or Bcl-2. Consequently. Bax exerted a pro-apoptotic dysfunction to mitochondria, thereby inducing the release of cytochrome c. Finally, apoptin induced the apoptosis of HHCC cells. These results indicate that the oligonucleotide microarray can reveal the genes related to the apoptosis induced by apoptin in HHCC cells.     

Multi-instrumental analysis of asphalts of archaeological interest

Use was made of thermal and other techniques to characterise three native asphalt samples. The purpose was to support archaeological investigations reconstructing their thermal history and composition. The first sample (from a Roman quarry in central Italy) proved to have 37% impurities, no sign of oxidation or degradation and to have never been heated to above 100°C. The second sample (from a Roman ship sunk south of France) was pure, but partially oxidised, with a saturated fraction in its structure. Analyses of the latter sample, obtained from the eye of a Thracian bronze head, revealed that the asphalt had been heated to over 100°C and then mixed with natural wax.     

Introduction to measurement of color of fluorescent materials

Fluorescent pigments and dyes add brightness and color to our lives, but brightness and light to the consumer can spell difficulties in color matching and formulation for a manufacturer. While fluorescent pigments have been used for many years, the proper formulation and quality control of colored materials containing them has been a challenge, primarily due to lack of proper instrumentation to make the necessary measurements. Another difficulty has been a general lack of understanding of how such materials achieve fluorescence. This paper, and those also published in this section, are intended to present an overview of the general principles associated with measuring fluorescent color. It addresses the chemistry and physics of what causes fluorescent pigments to work and gives some examples of applications for the pigments. Considerations as to why standard spectrophotometers and colorimeters fail to give completely accurate results in measuring such materials are discussed. After an overview of the effects of different illuminants on fluorescent pigments, I will discuss how geometry of measurement can affect results, and how several national laboratories are making such measurements.     

鲎试剂检测乌司他丁中细菌内毒素探讨

根据中国药典2000版二部内毒素检查法,对不同批号的乌司他丁进行了细菌内毒素检测,并与家兔法进行了比较。     

Kinetics of Thermal Decomposition of Plumbo-jarosite

An investigation was carried out on the kinetics of thermal decomposition of plumbo-jarosite. The kinetic models of dissociation of the compounds in the ore were identified. The results of the kinetic studies and the mechanism of the process are discussed. The thermal decomposition of plumbo-jarosite occurs in three stages: the first up to 763, the second up to 1023 and the third up to 1223 K, the corresponding activation energy values being 62.2, 60.3 and 98.0 kJ mol^–1 , respectively. This revised version was published online in July 2006 with corrections to the Cover Date.     

Viscosity of aqueous solutions of some diamines

Viscosities of the systems, ethylenediamine (ED) + water (W), 1,2-diaminopropane (DAP) + W, trimethylenediamine (TMD) + W and N,N-dimethyltrimethylenediamine (DMTMD) + W, have been measured for the whole range of composition at temperatures ranging from 303.15 to 323.15?K. The viscosities have been plotted against the mole fraction of diamines, showing some common characteristics for all the systems. On addition of diamines to water viscosities rise up very rapidly and pass through maxima. Following the maxima viscosities decline quite rapidly and monotonously up to about 0.6 mole fraction of diamines, which then fall down rather slowly. The hydrophobic and hydrophilic effects are considered responsible for the ascending part of viscosities in water-rich region, although the former is thought to be much more predominant than the latter. The height of viscosity maxima and their shifting to more water-rich region have been explained preferentially in terms of the hydrophobic effect. The declining part of viscosities is thought to be due to continuous destruction of cage structures formed by hydrophobic interaction. The excess viscosities have been calculated and plotted against mole fractions of diamines. The characteristics of excess viscosities have been explained by the same reasonings as used to explain viscosities.     

Acid hydrolysis of carboxymethylcellulose of low degree of substitution

Cotton cellulose was swollen in a sodium hydroxide solution and carboxymethylated by a two-bath method for different periods of time for each process. The kinetics of acid hydrolysis and the crystallinity of the swollen and carboxymethylated samples were measured. The proportion of broken bonds, rate constants for hydrolysis, and permeability of cellulose to hydrolyzing agents were calculated. The susceptibility of glycosidic linkages to acid hydrolysis was improved by carboxymethylation more than by swelling in alkali. The increased accessibility of carboxymethylcellulose to acid was regarded as a consequence of increased intra-and intercrystalline swelling and of the glycosidic bonds' weakness caused by the electron-attracting carboxymethyl group on the C-6 position.     

透射电子显微镜在聚合物不同层次结构研究中的应用

聚合物材料的性能与功能取决于各级结构,其中化学结构决定材料的基本功能与性能,而不同层次聚集态结构能够改变材料的性能和赋予材料特殊功能,如高取向超高分子量聚乙烯的模量比相应非取向样品提高3个数量级,聚偏氟乙烯的β和γ结晶结构则能赋予其压电、铁电等特殊功能.因此,明确聚合物不同层次聚集态结构的形成机制、实现各层次结构的精准...     

Nanocomposites of aliphatic polyesters: An overview of the effect of different nanofillers on enzymatic hydrolysis and biodegradation of polyesters

In the present review the findings concerning the effect of nanofillers to biodegradation and enzymatic hydrolysis of aliphatic polyesters were summarized and discussed. Most of the published works are dealing with the effect of layered silicates such as montmorillonite (unmodified and modified with organic compounds), carbon nanotubes and spherical shape additives like SiO₂ and TiO₂. The degradation of polyester due to the enzymatic hydrolysis is a complex process involving different phenomena, namely, water absorption from the polyesters, enzymatic attack to the polyester surface, ester cleavage, formation of oligomer fragments due to endo- or exo-type hydrolysis, solubilization of oligomer fragments in the surrounding environment, diffusion of soluble oligomers by bacteria and finally consumption of the oligomers and formation of CO₂ and H₂O. By studying the published works in nanocomposites, different and sometimes contradictory results have been reported concerning the effect of the nanofillers on aliphatic polyesters biodegradation. Most of the papers suggested that the addition of nanofillers provokes a substantial enhancement of polyester hydrolysis due to the catalyzing effect of the existed reactive groups (–OH and –COOH), to the crystallinity decrease, to the higher hydrophilicity of nanofillers and thus higher water uptake, to the higher interactions, etc. However, there are also some papers that suggested a delay effect of nanofillers to the polyesters degradation mainly due to the barrier effect of nanofillers and the lower available surface for enzymatic hydrolysis.     

Dependence of the Rate of Electrodeposition of Metals at Mono- and Multielectrodes on Voltage in the Case of an Exaltation Mechanism of Mass Transport

Dependences of the rate of copper deposition on mono- and multielectrodes out of dilute solutions of acetic acid at voltages of 20–250 V are compared. It is established that the same rate of deposition in the case of a multielectrode (25 electrodes with a diameter of 0.1 mm) takes place at a voltage that is lower by 2.7 times than that in the case of a monoelectrode with a diameter of 0.5 mm and the same area. The same results are obtained during electrodeposition of cadmium and thallium. In order to explain this effect, a two-layered model of potential distribution is suggested. In accordance with this model, the resistance of electrolyte in the vicinity of a multielectrode is equal to the sum of the resistance of the layer nearest to the electrode (where it is determined by the sum of conductances to each microelectrode) and the external layer, where the potential distribution is close to hemispherical. It is shown that calculations in accordance with this model allow one to give an estimate of the effect's scale that agrees with experiment and to predict its possible limits following an increase in the number of electrodes that make up a multielectrode.     

Bioinformatic analysis of molecular network of glucosinolate biosynthesis

Glucosinolates constitute a major group of secondary metabolites in Arabidopsis, which play an important role in plant interaction with pathogens and insects. Advances in glucosinolate research have defined the biosynthetic pathways. However, cross-talk and interaction between glucosinolate pathway and other molecular pathways are largely unknown. Here three bioinformatics tools were used to explore novel components and pathway connections in glucosinolate network. Although none of the software tools were prefect to predict glucosinolate genes, combination of results generated by all the tools led to successful prediction of all known glucosinolate genes. This approach was used to predict new genes in glucosinolate network. A total of 330 genes were found with high potential to relate to glucosinolate biosynthesis. Among them 64 genes were selected to construct glucosinolate network because their individual connection to at least one known glucosinolate gene was predicted by all the software tools. Microarray data of candidate gene mutants were used for validation of the results. The mutants of nine genes predicted by glucosinolate seed genes all exhibited changes in the expression of glucosinolate genes. Four of the genes have been well-known to functionally interact with glucosinolate biosynthesis. These results indicate that the approach we took provides a powerful way to reveal new players in glucosinolate networks. Creation of an in silico network of glucosinolate biosynthesis will allow the generation of many testable hypotheses and ultimately enable predictive biology.     

基底电位对硫醇自组装膜形成的影响

应用电位阶跃法,在不同组装电位下制备金/正十二硫醇自组装单分子膜.交流阻抗谱表征该硫醇膜的电化学性质,发现金基底的电位对硫醇自组装膜的形成有重要影响.在-0.8~-0.4 V的电位区间内,随着组装电位的增加,该自组装膜的致密性、有序性增加,缺陷减少,并于0.4 V时达到最佳.组装电位高于0.4 V,膜的致密性、有序性降低,缺陷增多.本文为硫醇及其衍生物的电位调控组装提供了重要依据.