Direct optical detection of singlet oxygen from a single cell

Singlet oxygen has been detected in single nerve cells by its weak 1270 nm phosphorescence (a1deltag --> X3sigmag-) upon irradiation of a photosensitizer incorporated in the cell. Thus, one can now consider the application of direct optical imaging techniques to mechanistic studies of singlet oxygen at the single-cell level.     

Thermal degradation of wood treated with guanidine compounds in air: Flammability study

Wood has been treated with guanidine phosphate, guanidine nitrate, guanidine carbonate and guanidine chloride to impart flame retardancy. The samples were subjected to differential thermal analysis (DTA) and thermogravimetry (TG) from ambient temperature to 800°C in air to study their thermal behaviors. From the resulting data, kinetic parameters for different stages of thermal degradation were obtained following the method of Broido. For the decomposition of wood and flame retardant wood, the activation energy was found to decrease from 116 to 54 kJ mol^–1; the char yield was found to increase from 5.6 to 34.9%, LOI from 18 to 41.5, which indicated that the flame retardancy of treated wood was improved. Effects of the different compounds on the degradation and flammability of wood have also been proposed.This revised version was published online in November 2005 with corrections to the Cover Date.     

Fluorescence ratiometric pH sensor prepared from covalently immobilized porphyrin and benzothioxanthene

A fluorescence ratiometric sensor for pH determination is described in this paper. The sensor incorporated the pH-sensitive dye meso-5,10,15,20-tetra-(4-allyloxyphenyl)porphyrin (TAPP) as an indicator and a pH-insensitive dye N-(2-methacryloxyethyl)benzo[k,l]thioxanthene-3,4-dicarboximide (MBTD), a benzothioxanthene derivative, as a reference for fluorescence ratiometric measurement. To prevent leakage of the dyes, both were photocopolymerized with acrylamide, hydroxyethyl methacrylate, and triethylene glycol dimethacrylate on the silanized glass surface. The reproducibility and response time of the prepared sensor were sufficient. Most common coexisting inorganic ions and organic compounds did not interfere with pH sensing. In the acidic pH range from 1.5 to 5.0 the fluorescence intensity ratio of the two dyes varied linearly as a function of pH. The sensing membrane was found to have a lifetime of at least one month. The sensor was applied to the analysis of waste water and artificial samples.     

三元无规芳—脂族聚酯酰胺的热致液晶行为

采用低湿溶液缩聚的方法合成了对苯二甲酰氯，二甲基联苯胺和己二醇为单体的芳酯族液晶聚酯酰胺。用ＤＳＣ，Ｘ光衍射分析和偏光显微镜等手段研究了该系列聚酯酰胺的热致液晶行为，确认了二甲基联苯胺单体用量在２０％（ｍｏｌ）的情况下，所得聚酯酰胺仍为向列型液晶聚合物。由于聚酯酰胺分子间聚酰胺链段之间的氢键作用，随着二甲基联苯胺用量增加至６０ｍｏｌ％时，所得的聚酯酰胺己无液晶转变温度，其液晶区间即从熔融温度直至分     

钴膦簇合物的催化环丙烷化反应

本文首次利用碳基钴簇合物ＰｈＰＣｏ_３（ＣＯ）_９催化剂，在常压和－２０℃－０℃，用苯乙烯和重氮乙酸乙酯进行环丙烷化反应，合成了菊酸酯，重氮乙酸乙酯可全部转化，酯的选择性可达８５％。产物经减压分馏后，由ＩＲ和￣１ＨＮＭＲ分析，确证了产物为菊酸酯，表明了羰基钴簇合物对苯乙烯的环丙烷化反应有良好的催化性能，为四面体异核簇合物用于不对称催化反应打下了基础。     

Supramolecular assemblies of a naturally derived sophorolipid

Acidic sophorolipid (SL) molecules derived from yeasts represent a novel type of asymmetrical bolaamphiphiles due to their unique structural features that include an asymmetrical polar head size (disaccharide vs COOH), a kinked hydrophobic core (cis-9-octadecenoic chain), and a non-amide polar-nonpolar linkage. Light microscopy, small- and wide-angle X-ray scattering, FT-IR spectroscopy, and dynamic laser light scattering were used to investigate the supramolecular structures of the self-assembled aggregates of SL molecules at different pH values. In acidic conditions (pH < 5.5), giant twisted and helical ribbons of 5-11 microm width and several hundreds of micrometers length were observed for the first time. Increase in solution pH values slowed ribbon formation, decreased ribbon yield, and increased the helicity and entanglements of the giant ribbons. An interdigitated lamellar packing model of acidic SL-COOH molecules with a long period of 2.78 nm, stabilized by both the strong hydrophobic association between the cis-9-octadecenoic chains and strong disaccharide-disaccharide hydrogen bonding, is proposed. The neutralization of SL-COOH in water to SL-COONa produced clear solutions with the formation of short-range ordered aggregates. At concentrations below 1.0 mg/mL, the size of self-assembled aggregates increased as the concentration increased. At concentrations above 1.0 mg/mL, narrowly distributed micellar aggregates with a constant hydrodynamic radius (R(h)) of about 100 nm are formed. The large micelles show strong angular dependence with the fast mode appearing at scattering angle theta >/= 60 degrees.     

膦化聚2,6—二甲基1,4—苯醚负载钯催化剂的表征及其催化性能

报道了四种不同P/Pd摩尔比的膦化聚2,6-二甲基1,4-苯醚负载把催化剂的加氢和异构化性能;通过XPS、电镜和远红外对催化剂进行了表征;并考察了溶剂和温度对催化剂活性的影响.     

Synthesis and Photophysical and Electrochemical Study of Tyrosine Covalently Linked to High‐Valent Copper(III) and Manganese(IV) Complexes

As bio‐inspired chemical model of the oxygen‐evolving complex (OEC) in photosystem II, a new tyrosine‐modified corrole ligand 3 and its high‐valent copper and manganese complexes 3a and 3b were synthesized and characterized. The copper complexes 1a and 2a of corrole 1 and 2 were also prepared for comparison. The emission property indicates that the emission of ligands 2 and 3 is located at 670 nm, but no emission is observed for their metal complexes due to its suppression by the metal center. The electrochemical study shows that 3a might dimerize at the first two reversible oxidations, a behavior which was not observed in the case of 1a and 2a . The corrolato manganese(IV) complex 3b shows one reversible reduction and one quasireversible oxidation at ?0.17 and 0.77 V vs. Ag/Ag⁺, respectively.     

高效液相色谱检测Zn（Ⅱ）、Cd（Ⅱ）、Co（Ⅱ）、Pb（Ⅱ）、Ni（Ⅱ）、Cu（Ⅱ）、Hg（Ⅱ）

用双-(2-羟乙基)二硫代甲酸铵(HEDC)在反相液相色谱中作检测某些金属离子的衍生化试剂，HEDC的金属螯合物微溶于水，可直接水样注射于C18柱中进行检测，范围为0．006～10mg／L相对偏差1％～2％，检测波长254nm，金属汞的整合物在HPLC分析前进行浓缩富集检测限可低至0．06～25μg／L，相对偏差小于2％。     

New efficient organocatalytic oxidation of benzylic compounds by molecular oxygen under mild conditions

Efficient aerobic oxidation of benzylic compounds has been achieved under no irradiation using a new organocatalytic system in the presence of acridine yellow and N-hydroxyphthalimide with assistance of a catalytic amount of molecular bromine. Various substrates, especially alkylaromatics, were effectively oxygenated to the corresponding carbonyl compounds with molecular oxygen as oxidant under mild conditions. For instance, indan was oxidized with 92% conversion and 79% selectivity for 1-indanone under 0.3 MPa of O₂ at 75 °C.