Influence of the molecular structure and the nature of the solvent on the absorption and fluorescence characteristics of rhodamines

A study of the equilibrium of the molecular forms of rhodamine 19 in aqueous and ethanolic solution is carried out by determining the absorption and fluorescence characteristics of the zwitterionic and the cationic forms of the dye. The optical properties of rhodamine 19 are compared with those obtained for rhodamine 6G and also with those previously reported for rhodamine 3B and for the molecular forms of rhodamine B in water and ethanol. Different aspects of the molecular structure of the rhodamines and solvent effects are discussed, as well as their influence on the photophysical properties of the rhodamines. The aggregation of the molecular forms of rhodamine 19 is also studied in water and ethanol.     

New study of the stability and of the spectroscopy of the molecular anions NCO- and CNO-

Using highly correlated wave functions, the ground and the low lying excited states of the molecular NCO(-) and CNO(-) anions have been reinvestigated. The stability of the electronic ground state of the two isomers with respect to dissociation and to electron detachment has been checked along the isomerization pathway. The regions of stability of the excited electronic states have been analyzed and identified and it is shown that only the ground state is stable and the corresponding potential energy surface presents three equilibrium positions. The rovibronic spectroscopy of the X (1)Σ(+) state of both NCO(-) and CNO(-) isomers has been determined by a variational approach leading to remarkable agreement with experimental data.     

高耐压HDPE自增强管挤出系统及试样的结构与性能

本文针对管件在输送压力流体时的特殊应力状态,提出了管材周向自增强的构想,据此设计出了自增强挤出系统.该系统利用芯棒旋转,使大分子链沿管周向取向并在适当的压力、温度条件下生成串晶结构,从而大大提高了管材的周向强度及模量.利用DSC、WAXD和SEM等检测手段对试件的凝聚态结构进行分析,找到了周向强度提高的理论依据.     

On the synthesis and polymerization of t-butyl-p-vinylperbenzoate and the grafting of its homo- and copolymers

The monomer initiator t-butyl-p-vinylperbenzoate (TBVP) was synthesized and its homo- and copolymerization with styrene, methacrylonitrile, isoprene and phenylmethacrylate was investigated. TBVP is preponderantly incorporated in all four systems; values of Q = 2.27 and e = ?0.13 characterize TBVP as a weak donor with a high monomer reactivity. Kinetic considerations show that all propagation steps in which TBVP takes part are faster or at least as fast as the self-propagation steps of the comonomers used. Rate constants and activation energies of the thermal decomposition of poly(t-butyl-p-vinylperbenzoate) and poly(t-butyl-p-vinylperbenzoate-co-styrene) were determined. The polymer initiators were used for grafting experiments with styrene, acrylonitrile, and methyl methacrylate. The data evaluated for the grafting efficiency, the success of grafting, and the degree of grafting show that these polymers of p-vinylperbenzoate are efficient initiators.     

Synthesis and pharmacological effects of the enantiomers of the N-phenethyl analogues of the ortho and para e- and f-oxide-bridged phenylmorphans

The N-phenethyl analogues of (1R*,4aR*,9aS*)-2-phenethyl-1,3,4,9a-tetrahydro-2H-1,4a-propanobenzofuro[2,3-c]pyridin-6-ol and 8-ol and (1R*,4aR*,9aR*)-2-phenethyl-1,3,4,9a-tetrahydro-2H-1,4a-propanobenzofuro[2.3-c]pyridin-6-ol and 8-ol, the ortho- (43) and para-hydroxy e- (20), and f-oxide-bridged 5-phenylmorphans (53 and 26) were prepared in racemic and enantiomerically pure forms from a common precursor, the quaternary salt 12. Optical resolutions were accomplished by salt formation with suitable enantiomerically pure chiral acids or by preparative HPLC on a chiral support. The N-phenethyl (-)- para-e enantiomer (1S,4aS,9aR-(-)-20) was found to be a mu-opioid agonist with morphine-like antinociceptive activity in a mouse assay. In contrast, the N-phenethyl (-)-ortho-f enantiomer (1R,4aR,9aR-(-)-53) had good affinity for the mu-opioid receptor (K(i) = 7 nM) and was found to be a mu-antagonist both in the [(35)S]GTP-gamma-S assay and in vivo. The molecular structures of these rigid enantiomers were energy minimized with density functional theory at the level B3LYP/6-31G* level, and then overlaid on a known potent mu-agonist. This superposition study suggests that the agonist activity of the oxide-bridged 5-phenylmorphans can be attributed to formation of a seven membered ring that is hypothesized to facilitate a proton transfer from the protonated nitrogen to a proton acceptor in the mu-opioid receptor.     

Simulation of the cyclopropanecarbaldehyde and cyclopropylethanone photoisomerization processes and calculation of the quantum yields of the reactions

The cyclopropanecarbaldehyde → 2-butenal and cyclopropylethanone → 3-pentenone-2 photoisomerization processes were simulated. The calculated quantum yields of the products are in quantitative agreement with experimental data. The validity of the method proposed for the calculation of quantum yields of photochemical reactions was confirmed. It was found that if the condition of relative smallness of the optical transition probabilities as compared to the quantum beat frequency is met, the quantum yields can be quantitatively estimated with satisfactory accuracy directly from the transition probabilities without running the full calculation of the phototransformation kinetics. It was shown that the integral characteristics of photochemical reactions (quantum yields) are highly responsive to the conformational state of the molecules involved in the process.     

Cleavage of silicon- and germanium-transition metal bonds. Dependences of the stereochemistry on the nature of the ligands and the geometry of complexes

The cleavages of some new optically active complexes containing CoSi (orGe), MnSi (orGe), ReGe and WGe bonds are described. Electrophiles cleave the CoSi bond with good retention of configuration at silicon, while the MnSi bond is not cleaved under the same conditions. The M′Si and M′Ge bonds (where M'  transition metal) are cleaved by nucleophiles with retention or inversion of configuration. In the case of triginal bipyramidal geometry (cobalt complexes) the stereochemical outcome of the reaction is strongly dependent upon electronic effects, the size of the ligand trans to the CoSi (orGe) bond, and the nature of the nucleophilic reagant, in accord with the general rules for nucleophilic substitution at silicon. In contrast the transition metalsilicon orgermanium bonds in the octahedral complexes of manganese, rhenium and tungsten are always cleaved with poor retention of configuration regardless of the nature of the ligands or the nucleophilic reagent. The results provide the first cases in which the stereochemistry of nucleophilic displacement at silicon is independent of the electronic features of both the leaving group and the nucleophile.     

Analysis and assessment of the occurrence, the fate and the behavior of nanomaterials in the environment

Nanomaterials have one dimension <100 nm and possess physico-chemical properties dictated by their unusually small size, large surface area, shape and chemical composition. New properties of nanomaterials have boosted their production and industrial applications in many fields (e.g., microelectronics, catalysis, fuel cells, materials science, textiles, biotechnology and medicine). In biomedical fields, nanomaterials are of the appropriate dimensions to interact with biological matter. However, they may also have negative effects on biological systems. Nanotechnology is a major, innovative, scientific and economic growth area, but the increasing production and use of nanomaterials have led to calls for more information regarding the potential impacts that their release may have on human health and the environment.This review addresses analytical approaches for characterization and quantification of nanomaterials in the environment and recent studies on their occurrence, fate and behavior.     

Study of the preparation of sustained-release microspheres containing zedoary turmeric oil by the emulsion-solvent-diffusion method and evaluation of the self-emulsification and bioavailability of the oil

The purpose of this study was to design a sustained-release formulation of an oily drug. The sustained-release microspheres with self-emulsifying capability containing zedoary turmeric oil (ZTO) were prepared by the quasi-emulsion-solvent-diffusion method. The micromeritic properties, the efficiency of emulsification and the drug-release behavior of the resultant microspheres were investigated. The bioavailability of the microspheres was compared with conventional ZTO self-emulsifying formulations for oral administration using 12 healthy rabbits. An HPLC method was employed to determine the concentration of germacrone in plasma, which was used as an index of ZTO. Spherical and compacted microspheres with average diameters of 100-600 microm have been prepared, and their release behavior in distilled water containing 1.2% (w/v) of polysorbate-80 can be controlled by the ratio of polymer/Areosil200 in the microspheres. The resultant emulsions with mean droplet sizes of 200-500 nm are produced when the microspheres are immersed in phosphate buffer (pH 6.8) under gentle agitation. The stability and the droplet size of the resultant emulsions are also affected by the polymer/Areosil200 ratio in the formulation, while the amount of talc has a marked effect on the self-emulsifying rate. The plasma concentration-time profiles with improved sustained-release characteristics were achieved after oral administration of the microspheres with a bioavailability of 135.6% with respect to the conventional self-emulsifying formulation (a good strategy for improving the bioavailability of an oily drug). In conclusion, the sustained-release microspheres with self-emulsifying capability containing ZTO have an improved oral bioavailability. Our study offers an alternative method for designing sustained-release preparations of oily drugs.     

肾上腺素氧化反应的研究——氧化反应动力学和机理以及自由及中间体

用紫外吸收光谱法结合计算机模拟研究了肾上腺素(Adjn)在Cu(Ⅱ)离子催化下, 用H_2O_2氧化产生肾上腺素红(Adom)的反应动力学, 考查了反应的速率随体系中肾上腺素的初始浓度, Cu(Ⅱ)离子浓度和H_2O_2浓度的变化情况。在流动法或添加自由基稳定剂的条件下, 利用顺磁共振法检测丁肾上腺素自氧化, 光氧化和Cu(Ⅱ)离子催化H_2O_2氧化产生的半醌自由基。考查了Cu(Ⅱ)离子催化下自由基的相对浓度随反应条件的变化情况。在反应动力学和顺磁共振实验的基础上所提出的可能的反应机理, 半定量地解释此反应动力学实验结果和顺磁共振实验中的自由基行为。     

萘并呋喃类化合物的染料化光氧化及其杂环衍生物的合成与表征

萘并呋喃类化合物1、7在四苯基卟啉存在与氧低温反应给出相应的二氧杂环丁烷类产物2、8，室温下分别全部分解成乙酰基乙酰氧基化合物4、9。2和盐酸作用可给出呋喃3-位甲基及所在萘半环β位的二氯代产物6。4与盐酸反应通过失去萘α位的酰基，形成羟基呋喃化合物3，1在三溴化硼酸解下亦可得同一产物。4在醋酸钠/酸酐中环构生成3-乙酰基吡喃酮(5)。     

笼型倍半硅氧烷形态分析及对杂化材料相容性和机械性能的影响

采用水解缩合方法制备了八乙烯基笼型倍半硅氧烷(OVPOSS), 并将其引入到聚甲基丙烯酸甲酯(PMMA)自凝树脂中, 得到有机-无机杂化材料. 通过傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、差示扫描量热仪(DSC)、塑料球压痕硬度计、高温高速摩擦磨损测试仪和悬臂梁冲击实验等对其形貌和性能进行了研究. 结果表明, OVPOSS以晶体状态存在于PMMA树脂中. 通过DSC热性能曲线、FOX方程和Gordon-Talyor方程曲线发现, 当POSS含量较高时, PMMA-POSS杂化体系能够发生相分离, 对杂化材料的机械性能有一定的影响.     

Chemiluminescence of CaH and AIH in the reaction of the metal atoms and formaldehyde

Chemiluminescence from the reaction of calcium and aluminum with various hydrogen containing compounds in a flowing gas system and in a heat pipe oven are described. Red chemiluminescence of CaH was observed in the reaction of calcium, and weak chemiluminescence of AlH was seen in the reaction of aluminum with formaldehyde (H₂CO). It is proposed that a reaction between metal atoms and formaldehyde may be used as a source of diatomic metallic hydrides.     

Kinetics and mechanism of the condensation of pyridoxal hydrochloride with L-tryptophan and D-tryptophan,and the chemical transformation of their products

The kinetics and mechanism of interaction between pyridoxal and L-tryptophan, D-tryptophan, and their derivatives are studied. It is found that condensation reactions proceed via three kinetically distinguishable stages: (1) the rapid intraplanar addition of the NH₂ groups of the amino acids to pyridoxal with the formation of amino alcohols; (2) the rotational isomerism of amino alcohol fragments with their subsequent dehydration and the formation of a Schiff base with a specific configuration; (3) the abstraction of α-hydrogen in the product of condensation of pyridoxal with L-tryptophan, or the abstraction of СО₂ in the product of condensation of pyridoxal with D-tryptophan with the formation of quinoid structures, hydrolysis of which results in the preparation of pyridoxamine and keto acid or pyridoxal and tryptamine, respectively. Schiff bases resistant to further chemical transformations are formed in the reaction with tryptophan methyl ester.     

Prediction of the surface tension of mixed electrolyte solutions based on the equation of Patwardhan and Kumar and the fundamental Butler equations

The predictive equation of Patwardhan and Kumar for the water activity of mixed electrolyte solutions has been used together with the fundamental Butler equations to establish a new simple predictive equation for the surface tension of mixed electrolyte solutions. This newly proposed equation can provide the surface tensions of multicomponent solutions using only the data of the corresponding binary subsystems of equal ionic strength. No binary interaction parameters are required. The predictive capability of the equation has been tested with the experimental data for 26 concentrated multicomponent electrolyte solutions at different temperatures and compared with the model of Li et al. Both equations agree well with the experimental results of systems examined over entire experimental composition ranges, but the new equation generally gives better predictions for most 1:1 electrolyte systems examined, and considerable improvement in predictions has been achieved for all the mixtures containing 1:2 and 2:2 electrolytes and for 1:1 electrolyte systems at higher temperatures.     

4-(1,2-亚乙二氧基)环己酮及其2-甲醛和2-羧酸酯的烯胺和烯醇反应的研究

4-(1,2-亚乙二氧基)环己酮及其2-甲醛和2-羧酸酯的烯胺和烯醇与丙烯酸型的和丙二酸型的试剂反应,获得了与6-(1,2-亚乙二氧基)-5,6,7,8-四氢-2(1H)- 喹啉酮很相近的四个化合物(5,11,18,19)和六个其它化合物(4,7,8,9,16,17).探讨了这十个均未见于文献的新化合物的生成机理,并得到一个制备5- 四氢萘胺衍生物的新方法     

Investigation of the Chemo- and Stereoselectivity of the Ketene-Claisen Rearrangement

A novel type of ketene-Claisen rearrangement in which the precursor of the rearrangement is generated in situ by reaction of optically active allyl thioethers with dichloroketene is described. A characteristic feature of this rearrangement is the excellent chemoselectivity in favor of allyl thioethers vs. allyl ethers, i.e., exclusive chirality transfer of the allylic sulfur moiety is observed with 12, 13 , and 25--27 . The cyclic, optically active allyl thioethers (+)-(R)- 4 and (?)-(S)- 4 and the open-chain allyl thioethers 11--13 rearrange with in situ generated dichloroketene to the optically active thioesters (?)-(S)- 28 , (+)-(R)- 28 , and 31-33 , respectively. A chirality-transfer of > 99% in the cyclic cases (+)-(R)- 4 and (?)-(S)- 4 , and 96--98 % in the open-chain cases 11--13 is observed. Furthermore, the dichloroketene-Claisen rearrangement is characterized by a high asymmetric 1,2-induction. The chiral allylic sulfides 25--27 give the optically active thioesters 36--38 with a 1,2-induction > 99% as determined by NMR-shift experiments.     

Specific features of the copolymerization of acrylonitrile and acrylamide in the presence of low-molecular-mass and polymeric trithiocarbonates and properties of the obtained copolymers

Regularities of the formation of acrylonitrile-acrylamide copolymers obtained from initial monomer feeds containing 1–50 wt % acrylamide in DMSO solutions with the participation of low-molecular-mass and polymeric trithiocarbonates as reversible addition-fragmentation chain transfer agents are studied for the first time. It is shown that the copolymerization in the presence of low-molecular-mass trithiocarbonates proceeds via a pseudo-living mechanism. The synthesized copolymers prove to be inefficient as reversible addition-fragmentation chain transfer agents, a result that leads to products with bimodal molecular-mass distributions. The rheological characteristics of solutions, as well as the thermal behavior of the copolymers obtained in the absence and in the presence of reversible addition-fragmentation chain transfer agents, are studied. The effect of the synthesis conditions on the properties of the synthesized copolymers is discussed.