沉淀法高效制备聚多巴胺纳米粒子

为得到分散性和稳定性较好的聚多巴胺纳米粒子,利用“沉淀-再分散法”高效制备了聚多巴胺纳米粒子水分散液。 首先利用溶液氧化法制备了分散在水/乙醇中的聚多巴胺纳米粒子,然后向分散液中加入丙酮使聚多巴胺纳米粒子絮凝。 收集沉降物,用丙酮冲洗并干燥后,加水重新分散得到纯化的聚多巴胺纳米粒子水分散液。 丙酮沉淀法得到的聚多巴胺纳米粒子形貌规整,分散性好,粒径分布在250 nm左右,在水中具有良好的储存稳定性和光热性能,与传统的超速离心提纯法相比,产率可提高57.4%。 此方法为其之后在药物载体及光热治疗等方面的应用研究提供了便利。     

First-second shell interactions in metal binding sites in proteins: a PDB survey and DFT/CDM calculations

The role of the second shell in the process of metal binding and selectivity in metalloproteins has been elucidated by combining Protein Data Bank (PDB) surveys of Mg, Mn, Ca, and Zn binding sites with density functional theory/continuum dielectric methods (DFT/CDM). Peptide backbone groups were found to be the most common second-shell ligand in Mg, Mn, Ca, and Zn binding sites, followed (in decreasing order) by Asp/Glu, Lys/Arg, Asn/Gln, and Ser/Thr side chains. Aromatic oxygen- or nitrogen-containing side chains (Tyr, His, and Trp) and sulfur-containing side chains (Cys and Met) are seldom found in the second coordination layer. The backbone and Asn/Gln side chain are ubiquitous in the metal second coordination layer as their carbonyl oxygen and amide hydrogen can act as a hydrogen-bond acceptor and donor, respectively, and can therefore partner practically every first-shell ligand. The second most common outer-shell ligand, Asp/Glu, predominantly hydrogen bonds to a metal-bound water or Zn-bound histidine and polarizes the H-O or H-N bond. In certain cases, a second-shell Asp/Glu could affect the protonation state of the metal ligand. It could also energetically stabilize a positively charged metal complex more than a neutral ligand such as the backbone and Asn/Gln side chain. As for the first shell, the second shell is predicted to contribute to the metal selectivity of the binding site by discriminating between metal cations of different ionic radii and coordination geometries. The first-shell-second-shell interaction energies decay rapidly with increasing solvent exposure of the metal binding site. They are less favorable but are of the same order of magnitude as compared to the respective metal-first-shell interaction energies. Altogether, the results indicate that the structure and properties of the second shell are dictated by those of the first layer. The outer shell is apparently designed to stabilize/protect the inner-shell and complement/enhance its properties.     

Recent Progress in Direct Partial Oxidation of Methane to Methanol

The direct conversion of methane to methanol has attracted a great deal of attention for nearly a century since it was first found possible in 1902, and it is still a challenging task. This review article describes recent advancements in the direct partial oxidation of methane to methanol. The history of direct oxidation of methane and the difficulties encountered in the partial oxidation of methane to methanol are briefly summarized. Recently reported developments in gas-phase homogeneous oxidation, heterogeneous catalytic oxidation and liquid phase homogeneous catalytic oxidation of methane axe reviewed.     

Development of high-temperature pulsed slit nozzle and its application to supersonic jet absorption spectrometry

A high-temperature pulsed slit nozzle, consisting of a circular pulsed nozzle and an interface to convert a circular flow into a slit flow has been constructed. The absorption spectrum is measured by scanning the wavelength of the monochromator equipped with a xenon arc lamp and by detecting the transmitted light through a jet with a photomultiplier. A rotationally cooled spectrum is clearly observed for aniline only when a long slit nozzle is employed. The absorptivity increases proportionally to the slit length at least up to 6 cm. The time for recording a spectrum is 3.5 min, which is reduced to several seconds by transmitting a white light through a jet and by measuring the spectrum with an optical multichannel analyzer. The detection limit is estimated to a partial vapor pressure of 0.4 torr for aniline. The present system can be conveniently used in routine analysis, because of a wide spectral coverage of the lamp source.     

CuCl2/NaY体系表面分散态研究

铜负载分子筛作为催化剂或吸附剂，在石油化工、环境保护等方面有许多用途[1，2]．已有研究发现，铜交换的Y型分子筛对NO分解等反应具有较高活性及稳定性［3-5］．因此研究铜负载Y型分子筛对有关吸附剂和催化剂的制备有重要意义．我们实验室在研究活性组分在载体表面分散现象时     

On the Criteria of Instability for Electrochemical Systems

Both cyclic-voltammetry-based and impedance-based experimental criteria that have been developed recently for the oscillatory electrochemical systems are critically appraised with two typical categories of oscillators.Consistent conclusions can be drawn by the two criteria for the category of oscillators that involve the coupling of charge transfer mainly with surface steps(e.g.ad-and desorption)such as in the electrooxidation of C1 organic molecules.Whereas,impedance-based criterion is not applicable to the category of oscillators that involve the coupling of charge transfer mainly with mass transfer(e.g.diffusion and convection) such as in the Fe(CN)6^3- reduction accompanying periodic hydrogen evolution.The reason is that the negative impedance cannot include the feedback information of convection mass transfer induced by the hydrogen evolution.However,both positive and negative nonlinear feedbacks,i.e., the diffusion-limited depletion and convection-enhanced replenishment of the Fe(CN)6^3- surface concentration,that coexist between the bistability,i.e.,Fe(CN)6^3- reduction with and without hydrogen evolution at lower and higher potential sides respectively,are all reflected in the crossed cyclic voltammogram(CCV).It can be concluded that the voltammetry-based criterion(in time domain)is more intuitive,less time-consuming and has a wider range of applications than the impedancebased one (in frequency domain).     

Tasumatrols P – T,Five New Taxoids from Taxus sumatrana

The phytochemical investigation of the more polar fractions from the leaves and twigs of Taxus sumatrana (Taxaceae) afforded five new taxane diterpene esters, tasumatrols P–T ( 1 – 5 ) possessing an 11(15→1),11(10→9)‐diabeotaxane skeleton. Compounds 1, 4 , and 5 contain an α‐hydroxy group at C(14), while 3 has no OH group at either C(13) or C(14). Compound 2 is a natural 4,5‐acetonide derivative, while 4 has an unusual spiro‐connected 2‐hydroxy‐2‐phenyl‐1,3‐dioxolane ring. Ten known taxoids, were also isolated in the course of the chromatographic fractionation. Five additional new O‐acetyl derivatives 3a, 4a, 4b, 5a , and 5b were prepared from the taxanes 3 – 5 . The structures of all new compounds were established on the basis of their spectroscopic analyses. Compound 1 showed mild cytotoxic activity against human Hela and Daoy tumor cells.     

A new study of the enzymatic hydrolysis of carboxymethyl cellulose with a bulk acoustic wave sensor

A new bulk acoustic wave (BAW) cellulase sensing technique, which is based on the enzymatic hydrolysis process of sodium carboxymethylcellulose (CMC) by cellulase, was established. The frequency shift curves of BAW sensor indicated that the viscosity of the tested solutions decreased during the hydrolysis process. The hydrolysis rate of CMC by cellulase was calculated from the frequency shift curves. The hydrolysis rate of CMC under different pH conditions at 30°C showed that cellulase had high hydrolysis ability approximately at pH 5.0. Kinetic parameters (the Michaelis constant K_m and the maximum rate V_max) of the process were estimated by using a linear method of Lineweaver–Burk plot. K_m is 1.95±0.25 mg ml⁻¹ and V_max is −(4.25±0.58)×10⁻³ g^1/2 cm^−3/2 cP^1/2 min⁻¹. Also the activation energy (E_a) of the enzymatic hydrolysis, with a value of 51.99±1.26 kJ mol⁻¹, was estimated in this work.     

Precise and accurate determination of the stoichiometry of CuInS2 semiconductor material by electrochemical methods

Summary CuInS₂ is one of the important I–III–VI₂ ternary compounds which has in recent years received increasing interest in semiconductor science. In this study an electrochemical method has been developed based on a limited amount of available sample (0.5–10mg) for the precise and accurate determination of CuInS₂ composition. After decomposition of the sample in concentrated HNO₃ under pressure, copper and indium were sequentially determined by constant potential coulometry, and sulfur (as sulfate) by amperometric titration. Various experimental parameters which ensure high precision and accuracy of the results were carefully evaluated and calibrated. The overall errors for the determination of copper, indium and sulfur in a 10 mg sample were found to be +0.10%, –0.12% and +0.16%, respectively, which fullfills the requirement for accurate stoichiometric assessment.

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Reproduzierbare und genaue Bestimmung der Stöchiometrie von CuInS₂-Halbleitermaterial mit Hilfe elektrochemischer Verfahren

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Presented at the 10th International Symposium on Microchemical Techniques, August 25–29, 1986, Antwerp, Belgium     

Study of quasi-monodisperse In2O3 nanocrystals: synthesis and optical determination

In this communication, we report a successful synthesis of quasi-monodisperse In2O3 nanocrystals with high crystallinity in a high-temperature organic solution. The average size of nanocrystals can be tuned using a dynamic injection technique. TEM and XRD investigations indicate that each nanocrystal is a single crystal. The optical determination implies that the photoluminescence behavior of these In2O3 nanocrystals is different from that of the bulk, probably due to the combination of weak quantum-confinement-effects and the nature of high crystallinity in nanocrystals.