An evaluation of exogenous application of protoporphyrin IX and its dimethyl ester as a photodynamic diagnostic agent in poorly differentiated human nasopharyngeal carcinoma

5-Aminolevulinic acid and its esterified analogues have been under much investigation to enhance the endogenous production of protoporphyrin IX (PpIX) in tumor cells. However, in this work, we studied the in vitro and in vivo efficacy of exogenously administered PpIX and its esterified analogue, PpIX dimethyl ester (PME), in poorly differentiated human nasopharyngeal carcinoma (NPC/CNE-2) as a photodynamic diagnostic (PDD) agent. NPC/CNE-2 at its earliest time, 1 h after incubation with PME in in vitro studies, has exhibited 64% (P <0.01) higher tumor to normal cell (T/N) fluorescence ratio than with PpIX. In an in vivo mouse xenograft model, comparable photosensitizer concentration in tumor after intravenous administration was observed at 1-3 h time points, but at 9 h, PME had 31% (P=0.05) greater concentration in tumor compared with PpIX. In addition, by constituting PME and PpIX in different topical gel composites, of which, PME gel composition of 8:2 Plasdone and Gantrez resulted in the highest T/N ratio at 6 h after application (34%; P <0.05) in comparison with other gel composites. Evaluation of PME and PpIX constituted in the delivery vehicles investigated showed comparable selectivity for tumor at 1-3 h, thus neither photosensitizer is more efficient than the other for PDD at the early time points; however, beyond 6 h, PME had higher selectivity for tumor compared with PpIX. Thus, further investigation is warranted to improve the drug delivery vehicle for greater tumor selectivity at a shorter incubation time.     

Simultaneous quantification of differently glycosylated, acetylated, and 2,3-dihydro-2,5-dihydroxy-6-methyl-4H-pyran-4-one-conjugated soyasaponins using reversed-phase high-performance liquid chromatography with evaporative light scattering detection

A novel method utilizing high-performance liquid chromatography (HPLC) with evaporative light scattering detection (ELSD) and electrospray ionisation mass spectrometry (ESI-MS) was developed for the analysis of soyasaponins, a divers group of triterpenic compounds with one or two sugar side chains, occurring in soy. Group A soyasaponins in different degrees of acetylation, as well as group B soyasaponins in both their 2,3-dihydro-2,5-dihydroxy-6-methyl-4H-pyran-4-one (DDMP)-conjugated and non-conjugated forms could be separated and quantified using authentic soyasaponin standards, in one single run. The method was tested by the determination of the soyasaponin content and composition of eight soygerm samples of different origin. Differences in the composition and the degree of acetylation of the group A soyasaponins were observed among these samples. The group B soyasaponins showed much less variability and they were mainly present in their DDMP-conjugated form.     

含双二苯基膦甲烷铜(Ⅰ)配合物的研究进展

本文概述了含双二苯基膦甲烷铜(Ⅰ)配合物的化学进展,总结了配合物的合成方法:置换法、还原法、电化学方法和直接加成法,全面论述了双核、三核、多核和异核配合物的结构特征,探讨了该类配合物的重要荧光性质。     

Catalytic Adsorptive Stripping Voltammetry of Germanium(IV) in the Presence of Gallic Acid and Vanadium(IV)‐EDTA

A highly sensitive and selective catalytic adsorptive cathodic striping procedure for the determination of trace germanium is presented. The method is based on adsorptive accumulation of the Ge(IV)‐gallic acid (GA) complex onto a hanging mercury drop electrode, followed by reduction of the adsorbed species. The reduction current is enhanced catalytically by addition of vanadium(IV)‐EDTA. The optimal experimental conditions include the use of 0.03 mol/L HClO₄ (pH1.6), 6.0×10^?3 mol/L GA, 3.0×10^?3 mol/L V(IV), 4.0×10^?3 mol/L EDTA, an accumulation potential of ?0.10 V(vs. Ag/AgCl), an accumulation time of 120 s and a differential pulse potential scan mode. The peak current is proportional to the concentration of Ge(IV) over the range of 3.0×10^?11 to 1.0×10^?8 mol/L and the detection limit is 2×10^?11 mol/L for a 120 s adsorption time. The relative standard deviation at 5.0×10^?10 mol/L level is 3.1%. No serious interferences were found. The method was applied to the determination of germanium in ore, mineral water and vegetable samples with satisfactory results.     

Ab initio potential energy surface and excited vibrational states for the electronic ground state of Li_2H

A 285-pomt multi-reference configuration-interaction involving single and double excitations ( MRS DCI) potential energy surface for the electronic ground state of L12H is determined by using 6-311G (2df,2pd)basis set.A Simons-Parr-Finlan polynomial expansion is used to fit the discrete surface with a x2 of 4.64×106 The equn librium geometry occurs at Rc=0.172 nm and,LiHL1=94.10°.The dissociation energy for reaction I2H(2A)→L12(1∑g)+H(2S) is 243.910 kJ/mol,and that for reaction L12H(2A')→HL1(1∑) + L1(2S) is 106.445 kl/mol The inversion barrier height is 50.388 kj/mol.The vibrational energy levels are calculated using the discrete variable representation (DVR) method.     

Two Novel Alkaloids from Zanthoxylum nitidum

Two novel alkaloids, 4,5‐dihydroxy‐1‐methyl‐3‐oxo‐2‐(trichloromethyl)‐3H‐indolium chloride ( 1 ) and 4‐(2‐methoxyethyl)‐N,N‐dimethylbenzenamine ( 2 ), were isolated from the EtOH extract of the roots of Zanthoxylum nitidum. Their structures were identified on the basis of spectroscopic and mass‐spectrometric analyses.     

仪器分析测试技术信息化教学探索与实践

针对高职学生的特点，以仪器分析测试技术课程实训教学为例，按照课前布置学习任务，学生翻转课堂学习，"教、学、做"一体化课堂教学，课后复习巩固的形式，开展信息化教学的探索与实践，并对信息化教学的效果和存在的问题进行了分析。通过信息化教学改革，仪器分析测试技术课程突破了传统教学时空的限制，激发了学生学习的兴趣，构建了"学生主体、教师主导"的教学新模式，提高了课堂教学效果，对推动高职课堂信息化教学的改革具有一定的借鉴意义。     

聚氯乙烯复合热稳定剂中铅镉钡的同时测定

聚氯乙烯（PVC）材料广泛应用于建筑、电讯、交通、电子、化工、包装等行业。然而，PVC加工时存在着一个致命的弱点，就是其流动温度为136℃，分解温度为140℃，两者相差仅4℃，给加工带来很大难度，为了能顺利加工就必须加入热稳定剂，热稳定剂是PVC加工不可缺少的主要助剂之一。热稳定剂种类繁多，我国目前大量使用的稳定剂为铅盐及金属皂等稳定剂，产量高达4．5万吨。由于铅、镉、钡等金属元素具有一定的毒性，使用中易造成环境污染，有害于人体健康，因此必须严格加以控制。     

Order from Chaos: Self‐Assembly of Nanoprism from a Mixture of Tetratopic Terpyridine‐Porphyrin Conformers

Porphyrins have been widely used in the self‐assembly of metallo‐supramolecules. In this study, we introduced 2,2':6,2"‐terpyridine (tpy) into a porphyrin core to synthesize a tetratopic building block with multiple conformers. During the self‐assembly with Zn(II), such a mixture of conformers was able to form a discrete nanoprism with all building blocks in one conformation. Detailed characterizations, including NMR, ESI‐MS and traveling‐wave ion mobility‐mass spectrometry (TWIM‐MS), all supported the formation of the desired assemblies. AFM and TEM further confirmed the dimensions of assembled nanoprisms. Moreover, the photophysical properties of the ligands and complexes were noticeably different depending upon size and metal ion center.     

SYNTHESIS AND MESOMORPHIC PROPERTIES OF FISHBONE-LIKE LIQUID CRYSTALLINE POLYSILSESQUIOXANES——Ⅰ. FISHBONE-LIKE, β-DIKETONE-BASED LIQUID CRYSTALLINE POLYSILSESQUIOXANES AND THEIR COPPER COMPLEXES*

Two kinds of fishbone-like, β-diketone-based liquid crystalline polysilsesquioxanes(FBDKLCP'S), homopolymeric (H-FBDKLCP) and copolymeric (C-FBDKaLCP) have been first synthesized via the hydrosilylation reaction of a vinyl-terminated β-diketone with the homopolymeric ladderlike polyhydrosilsesquioxane (LPHSQ) and random copolymethylhydrosilsesquioxane (LRPMHSQ) respectively. These new kinds of FBDKLCP with M of 10~4 is thermotroic liquid crystalline polymer and its clearing temperatures T_i's and mesophase range △T's are much higher than those of the corresponding comb-like β-diketone liquid crystalline polysiloxane (DKLCP) by about 200℃. Similar results have been observed with the comparison of the two different structure Cu-coordinating compounds The significant increases in T_((?))'s and △T's of the FBDKLCP and Cu-FBDKLCP are mainly attributed to the great rigidity of the ladderlike polysilsesquioxane backbone.