组氨酸、组胺醇和组胺钴(Ⅱ)配合物氧合性能的比较研究

本文用UV-Vis光谱和氧电极法对结构相似的His-Co、Hio-Co、Hit-Co 3组配合物氧合性能进行了对比研究。由配合物光谱随pH变化的A-pH曲线,可知3组配合物均在pH 6.0以后开始发生氧合反应,在pH 6.0～10.0的范围内His-Co有2种氧合物种生成,其他2组配合物均只有1种氧合配合物生成。用等摩尔比法对氧合配合物的组成比进行了测定,得知Co∶His与Co∶Hio的配位比为1∶2,而Co∶Hit为1∶3;在室温水溶液中和pH 7的条件下,用UV-Vis在波长384 nm下分别考察了3组配合物的氧合性能和它们的抗老化能力,结果表明3组配合物在室温水溶液中均可发生氧合反应,但氧合性能有很大差异,His-Co经过110 h累计560次可逆循环,仍然具有5%氧合性能,而Hio、Hit分别经过59次/54 h、5次/10.2 h循环后氧合性能衰减至5%。3组配合物的抗老化能力的大小顺序为:His-Co>>Hio-Co>Hit-Co。研究结果初步说明:三配位原子配体配合物的可逆吸氧性能好于二配位原子配体的配合物,氨基酸配合物优于氨基醇配合物。     

一类非牛顿流弱解的扰动

主要研究一类可压缩粘性非牛顿流方程弱解的扰动性质.在已知弱解存在的基础上,证明了选取适当范数时,沿着给定的时间序列,密度和速率的扰动趋于零.     

具有奇性与真空粘性依赖于密度的非牛顿流局部强解的存在唯一性

研究一维有界区间上粘性依赖于密度且具有奇性、初始允许真空的可压缩非牛顿流.通过正则化奇性项以及逐步迭代构造初边值问题的逼近解,对逼近解取极限得到其局部强解的存在唯一性,进一步推广了相关文献中关于非牛顿流解的存在性结果.     

Zethrene and Dibenzozethrene: Masked Biradical Molecules?

The syntheses, structures, and physical properties of dibenzozethrenes were explored. The results thus obtained were compared with those for zethrenes. Dibenzozethrenes were synthesized by the nickel‐catalyzed cyclodimerization of 9‐ethynyl‐1‐iodoanthracenes. The substituents in zethrene and dibenzozethrene twisted their backbones, and remarkably influenced their properties. Unlike closed‐shell disubstituted derivatives, the parent zethrene and dibenzozethrene are singlet open‐shell biradicals, which were studied by variable‐temperature ¹H NMR, ESR, SQUID and computational methods. Since substituents were observed to affect significantly the biradical properties, the relevant mechanisms were analyzed. The nonlinear optical performance of each of these compounds depends on its π‐conjugation and biradical properties. Dibenzozethrenes have larger two‐photon absorption cross‐sections than zethrenes, as most strongly evidenced by the parent dibenzothrene [σ_max=4323 GM at 530 nm].     

Enantioselective sulfenylation of α-nitroesters catalyzed by diarylprolinols

The organocatalytic sulfenylation of α-nitroesters mediated by diaryl-l-prolinols was developed. A range of α-sulfenylated α-nitroesters were obtained in good yields with moderate to good enantioselectivities.     

The effect of tourmaline on cell membrane of nitrosomonas europaea and biodegradation of micropollutant

As a kind of ammonia‐oxidizing bacteria, Nitrosomonas europaea (N. europaea) was chosen as a research model to study the alteration of cell membrane in the presence of tourmaline and biodegradation of acetochlor. atomic force microscopy images reveal that the presence of tourmaline substantially changes the structure of the outer membrane of the cell responsible for the cell permeability. SEM images show that the introduction of tourmaline makes the cell lose its ability to resist lysozyme owing to the damages. The fluorescence polarization has shown a significant decrease in membrane fluidity and the increase of permeability of cell membrane. Ca²⁺ and Mg²⁺ was measured using inductively coupled plasma mass spectrometry and was found in the supernatant from the cells treated by tourmaline. Tourmaline can improve the efficiency of biodegradation of acetochlor for N. europaea. It is proposed that the cell permeability is slightly increased, and the absorbability of nutrition from the medium becomes easier. As a result, N. europaea grows faster in the presence of tourmaline than the native cells. Copyright © 2014 John Wiley & Sons, Ltd.     

A simple fabrication method for tapered capillary tip and its applications in high‐speed CE and ESI‐MS

Fabrication of capillaries with tapered tips is an important technique that is required in many analytical chemistry areas, such as ESI‐MS, CE, electrochemical analysis, and microinjection. This paper describes a simple and effective grinding‐based fabrication method for capillaries with tapered tips. A novel grinding mode utilizing the combination of rotation and precession of an elastic capillary was developed, which significantly improved the controllability to the grinding process as well as the capillary tip shape. The capillary was fabricated by fixing it in an electric drill installed perpendicularly, and grind the capillary tip rotated around its own axis as well as the drill axis on sandpapers. Compared with conventional fabrication techniques for capillary tips, the present method is easy to control the capillary tip shape in routine laboratories without the requirement of expensive equipments or poisonous reagent (e.g. hydrofluoric acid (HF) solution). Various capillaries with different tip diameters and tip taper angles could be fabricated using the present method with good controllability and reproducibility. These capillaries were applied in high‐speed CE and ESI‐MS analysis to demonstrate the feasibility and potential of this fabrication method.     

An expeditious approach to access 2-arylimidazo[1,2-a]pyridin-3-ol from 2-amino pyridine through a novel Petasis based cascade reaction

An expeditious cascade protocol for the synthesis of functionalized imidazo[1,2-a]pyridin-3-ols was developed based on the Petasis reaction. With the availability of commercial reagents and high efficiency in expanding molecule diversity, this methodology is superior to the existing procedures for the synthesis of imidazo-pyridin-3-ol analogues.     

Two novel polycyclic spiro lignans from Gymnotheca involucrata

Two novel lignans, gymnothespirolignans A (1) and B (2), possessing a rare polycyclic spiro skeleton, were isolated from the endemic plant of Gymnotheca involucrata Pei. Their structures were determined by spectroscopic evidences and the absolute configurations were confirmed by single crystal X-ray diffraction analysis. Compounds 1 and 2 showed promising antiviral activities against RSV with an IC₅₀ value of 31.87 and 17.51 μM, respectively.     

The synthesis of a new cardiac sympathetic nerve imaging agent N-[11C]CH3-dopamine and biodistribution study

In this study, we synthesized and characterized N-[¹¹C]methyl-dopamine ([¹¹C]MDA) for cardiac sympathetic nerve imaging. [¹¹C]MDA was synthesized by direct N-methylation of dopamine with [¹¹C]methyl iodide and purified by semi-preparation reverse high pressure liquid chromatography (HPLC). The total synthesis time was 45 min including HPLC purification. The radiochemical yields of [¹¹C]MDA was 20 ± 3 %, without decay correction. The radiochemical purity was >98 % and the specific activity was about 50 GBq/mmol. The biological properties of [¹¹C]MDA were evaluated by biodistribution study in normal mice. PET imaging was performed in healthy Chinese mini-swines. Biodistribution study showed that [¹¹C]MDA had high myocardium uptake. PET/CT imaging showed [¹¹C]MDA had clear and symmetrical myocardium uptake, which was blocked obviously by injecting imipramine hydrochloride. [¹¹C]MDA would be a promising candidate of radiotracer for cardiac sympathetic nervous system imaging.