In vitro PHOTODEGRADATION OF CHLORPROMAZINE

The in vitro photodecomposition of chlorpromazine (CPZ) was investigated with the aim to evaluate possible reactive determinants that could play a role in the occurrence of the in vivo -observed photosensitivity. In view of the in vivo situation, CPZ was dissolved in low concentration in buffered aqueous solution (pH 7.4) or in dilute human serum and irradiated with low intensity (5–7 W m^-2) UV-A and UV-B. No distinct difference was found between UV-A or UV-B irradiation as far as photoproduct formation is concerned. This suggests the same degradation mechanism at both wavelength ranges. In buffered aqueous solution, irradiation of CPZ resulted in 65 and 90% 2-hydroxypromazine (PZOH), 5 and 7% promazine (PZH) and 2 and 0% chlorpromazinesulfoxide (CPZSO) under aerobic and anaerobic conditions, respectively. In dilute human serum, there was only a shift in the PZH/PZOH ratio, probably as a result of H-atom or electron donation by sulfur containing groups present in proteins. The results demonstrate that photodegradation of CPZ in vitro , under conditions relevant to the in vivo situation, proceeds almost entirely by dechlorination rather than by radical cation formation (the essential pathway of CPZSO production). Thus we conclude that the thiyl radical cation probably does not play a major role in the in vivo -observed phototoxic reactions.     

INTRAUTERINE 5-AMINOLEVULINIC ACID INDUCES SELECTIVE FLUORESCENCE AND PHOTODYNAMIC ABLATION OF THE RAT ENDOMETRIUM*

Abstract— 5-Aminolevulinic acid (ALA), a precursor of protoporphyrin IX (Pp IX), was administered into the rat uterine cavity in an attempt to selectively ablate the endometrium. Doses of ALA ranging from 4 to 50 mg were injected into one uterine horn of rats while the vehicle (saline) was injected into the contralateral horn. Animals were divided into three groups. In group one, the uterine horns were removed and processed for either fluorescent mi- croscopy or spectrophotofluorometry 3 h later. In group two, rats were allowed to survive for either 2 or 10 days, and then the uterine horns were harvested and processed histologically. In group three, both uterine horns were exposed to transmural light (approximately 150 J/cm*) 3 h after administration of ALA or saline and processed histologically either 2 or 10 days later. Fluorescent microscopy showed fluorescence in the endometrium and not in the myometrium. The maximum emission spectra of endometrial fluorescence occurred at 630 and 690 nm, characteristic of Pp IX. In contrast, no fluorescence was detected in saline-treated uterine horns. Light exposure resulted in extensive damage only to the ALA-treated endometrium. There was no indication of regeneration 10 days after treatment. We conclude from these studies that ALA administered into the lumen of the rat uterus is selectively converted into Pp IX within the endometrium. Furthermore, photoactivation of the Pp IX results in selective ablation of the endometrium.     

Cis-UROCANIC ACID DOWN-REGULATES THE INDUCTION OF ADENOSINE 3'', 5''-CYCLIC MONOPHOSPHATE BY EITHER trans-UROCANIC ACID OR HISTAMINE IN HUMAN DERMAL FIBROBLASTS in vitro

It has been demonstrated that UVB radiation (290-320 nm) suppresses mammalian cell-mediated immunity by effecting the trans to cis isomerization of urocanic acid (UCA) in the stratum corneum, the uppermost layer of the skin. Trans-urocanic acid has been shown to be the photoreceptor for UVB-induced immune suppression and the cis-isomer has been demonstrated to be immunosuppressive. Little is known, however, about how the isomerization of UCA may affect the proximal or distal cells of the skin or the immune system. We report here that trans-UCA is biologically active in vitro in human dermal fibroblasts, inducing adenyl cyclase as measured by cAMP (adenosine 3',5'-cyclic monophosphate) formation in a dose-dependent manner similar to the action of histamine. Trans-UCA and histamine stimulate 50% of maximum activity at concentrations of 3.3 microM and 13.8 microM respectively. Cis-UCA does not increase cAMP in these human fibroblasts but actively down regulates the increase of cAMP induced by either histamine or trans-UCA. Cis-UCA down regulated the histamine response by 75% and the trans-UCA response by 60% at a concentration range of 1 mM to 1 nM. The trans-UCA induction of cAMP can also be downregulated with an H2 histamine receptor antagonist cimetidine. These results support the hypothesis that a cellular target for cis-UCA is the dermal fibroblast and the effects reported here may represent the initial biochemical and cellular event for UVB-induced immune suppression i.e. the immediate step following the isomerization of trans to cis-UCA is the down regulation of cAMP by cis-UCA. Regulation of such an important second messenger such as cAMP could then allow cascading signals to occur, leading to immune suppression.     

Ab initio study of possible intermediates in the no(4Π) catalyzed geometric isomerizations of olefins

The geometries of acyclic and three-membered ring (nitroxide) H₄C₂NO radicals in their ground ²Π electronic states have been optimized completely at ab initio UHF and ROHF theoretical levels with the STO-3G and the 6-31G** basis sets. The optimizations favour the cyclic nitroxide structure energetically. However ΔE(acyclic - cyclic) at the UHF and ROHF/6-31G** levels are only 3.2 and 1.9 kcal mol^-1, respectively. Incomplete MP2/6-311G** optimizations support these results. The zero-point energy computed at the ROHF/6-31G** level for the nitroxide radical is 2.5 kcal mol^-1 higher than that for the acyclic structure, thus reversing the relative energies by 0.6 kcal mol^-1. The energies of the two radical structures, relative to the sum of those for ethylene and NO, are very close to literature values of the activation energies for the thermal, NO catalyzed geometrical isomerizations of olefins. Thus cyclic nitroxide intermediates may play a role not only in the Hg 6(³P₁) photosensitized, but also in the thermal, NO-catalyzed geometric isomerizations of olefins. Paper dedicated to Professor Otto P. Strausz; presented in part at the 75th Canadian Chemical Congress and Exhibition, Edmonton, May 31 – June 4, 1992.     

Contour Dynamics with Non-uniform Background Vorticity

In this paper it is demonstrated how a contour dynamics method can be used to simulate the behaviour of vortices in the presence of non-uniform background vorticity in general, and on the γ-plane in particular. For standard contour dynamics in case of zero, or uniform background vorticity, the initial continuous vorticity distributions of the vortices are replaced by appropriate piecewise-uniform distributions. Then, the evolution of the contours separating the several regions of uniform vorticity, are followed in time. In the case of non-uniform background vorticity, it is necessary to replace the sum of the (relative) vorticity of the vortices and the background vorticity by a piecewise-uniform distribution. This has several consequences for applying the method of contour dynamics, which are discussed in this paper. The resulting method is tested on some numerical examples. One of them is (qualitatively) compared with laboratory experiments carried out in a rotating tank.     

西藏拉萨市周边温棚蔬菜样品中农药残留量的研究

用农药残毒速测仪和气相色谱 火焰光度检测器（GC FPD）2种方法对拉萨市周边4个温室蔬菜基地抽样采集的26个蔬菜样品测定其农药残留量.结果,用速测仪检测出7个蔬菜样品中有农药残留存在.为进一步验证其结果,参考国家农业标准NY/T 761-2008,建立了气相色谱火焰光度(GC-FPD)检测蔬菜样品中敌敌畏、氧化乐果、二嗪农、乐果、甲基对硫磷、马拉硫磷、对硫磷、水胺硫磷、喹硫磷9种有机磷农药残留的分析方法,建立的气相色谱分析方法：检出限为0.039 7～0.182 0 μg·mL^-1、回收率为51.64%～91.04%、方法的精密度为1.61%～10.80%.用该方法对农药残留超标的蔬菜样品进行分析,结果未检测到上述9种有机磷农药的残留.实验结果为从事农药残留检测工作者在分析方法的选择和评价拉萨市蔬菜农药残留状况提供参考.     

DELPHI有机共轭体系MM力场的优化和应用

运用我们建议的SC-HMO方法优化了有机共轭烯烃的DELPHIMM力场。将优化所得力场和参数用于计算各类型101个共轭化合物的分子几何构型、生成热、偶极矩和IR频率等, 结果可与MM3法相比。     

Evidence for a Second Transport Porosity for the Diffusion of Tritiated Water (HTO) in a Sedimentary Rock (Opalinus Clay - OPA): Application of Through- and Out-Diffusion Techniques

The diffusion of tritiated water (HTO) in Opalinus clay (OPA) samples from bore cores from the Benken area (Northern Switzerland) was studied using the radial through- and out-diffusion technique. Results from inverse modelling of out-diffusion data for HTO indicated the presence of two preferential diffusion pathways: a fast and a slow one. Analysing through-diffusion data, however, provides hardly any information concerning a second transport-relevant porosity. Only by also analysing the out-diffusion phase can finer details of the diffusion process and information on sample heterogeneity be recognised. The extracted values for the effective diffusion coefficient are in the order of 3 × 10^–11 m² s^–1 for the faster transport porosity and roughly an order of magnitude smaller for the slower type of porosity. We had to account for tritium sorption on the clay minerals by a small but non-zero K_d-value in the order of 10^–5 m³ kg^–1 in order to reproduce the data with acceptable precision. In the model applied both porosities are considered as being independent from each other. Roughly 30% of the tracer diffused through the second, slower porosity; such a fact might be interesting for future performance assessments for radioactive waste repositories hosted by clay formations. Based on our present picture from water-saturated OPA, on a microscopic scale three different kind of waters can be discriminated: free water, double layer water and interlayer water. However, using HTO as tracer only, it could not be deduced which type of water-filled pores finally account for the transport-relevant porosity.Author for correspondence: Tel.: +41-56-3102257; Fax: +41-56-3104438; E-mail: luc.vanloon@psi.ch     

钒氧酞菁薄膜瞬态光电压性能的研究

本文分别用1064nm, 532nm和 355nm激发波长的YAG脉冲激光对所制备的phase Ⅱ结构钒氧酞菁膜Al\phase ⅡVOPc\ITO夹心电池进行瞬态光电压响应研究.随着3种波长激发光脉冲强度的增加, 瞬态光电压信号均增强. 激发光波长1064nm、532nm处于酞菁膜Q-带吸收区肩部, 光电压的极性与激发光入射方向无关, 均为负信号; 而激发光波长 355nm处于酞菁膜B-带, 光电压的极性与激发光入射方向有关, 从ITO极方向激发产生正电压信号, 从A1极激发产生负电压信号. 激发光波长对夹心电池的光电压产生有明显的作用, 光电压产生过程中应存在不同的机理. 这与前文^[1]对同一夹心电池稳态光电压响应研究所推断的结论一致.     

ChemInform Abstract: XeNO3+: A Gaseous Cation Characterized by a Remarkably Strong Xe—O Bond.

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