Loss of stability by migration and chemical reaction of Santonox R in branched polyethylene under anaerobic and aerobic conditions

Plaques of branched polyethylene stabilized with 0.1 wt.% 4,4′-thiobis(6-tert-butyl-3-methylphenol) [Santonox^® R] were aged at different temperatures between 75 and 95 °C in anaerobic (nitrogen or water) and aerobic (air or water saturated with air) media. Antioxidant concentration profiles were obtained by oxidation induction time (OIT) measurements using differential scanning calorimetry. Results obtained by high performance liquid chromatography of extracts confirmed that the gradual decrease in OIT with increasing ageing time was due to migration of antioxidant to the surrounding medium. The antioxidant concentration profiles along the plaque thickness direction were flat in the plaques aged in the non-aqueous media indicating that the migration of antioxidant to the surrounding medium was controlled by the low evaporation rate at the material boundary. Crystals of antioxidant were detected by optical microscopy on the samples exposed to nitrogen. The similarity of the antioxidant concentration profiles obtained after ageing in nitrogen and in air suggested that the fraction of the antioxidant oxidized is negligible in comparison with the loss of antioxidant by migration to the surrounding media. The antioxidant concentration profiles along the plaque thickness direction obtained after ageing in water were less flat, suggesting faster dissolution in the water phase than evaporation in the case of non-aqueous ageing. The antioxidant diffusivity could be determined from the aqueous experiments and was in reasonable agreement with data reported by Moisan. For the samples exposed to water, the loss of antioxidant was faster from the samples exposed to water saturated with air. This difference is attributed to a faster degradation of the antioxidant in the oxygen-containing water phase increasing the mass transport from the polymer phase boundary to the water phase.     

Reaction of N-acylthioureas with electrophilic reagents : Synthesis of 1,3,5-oxadiazinium salts, 1,3,5-thiadiazinium salts, 1,2,4-dithiazolium salts and benzothiazoles

N-Acylthioureas 1 can be easily transformed into 2,4-diamino-6-aryl-1,3,5-oxadiazinium salts 12, 2,4-diamino-6-aryl-1,3,5-thiadiazinium salts 13,3-amino-5-aryl-1,2,4-dithiazolium salts 19 and 2-acylimino-benzothiazolines 22, respectively by reaction with different electrophiles. The structure of the compounds prepared is confirmed by analytical data as well as by chemical transformations.     

High Performance Liquid Chromatography‐Electrochemistry‐Electrospray Ionization Mass Spectrometry (HPLC/EC/ESI‐MS) for Detection and Characterization of Roscovitine Oxidation Products

On‐line LC‐EC/ESI‐MS has been established as a fast and simple method to mimic some types of oxidation reaction of various drugs and to study the formation and structure of the resulting products. This technique has been applied to a 2,6,9‐trisubstituted purine, R‐roscovitine, which is known to be an inhibitor of some cyclin‐dependent kinases (CDKs) and a potential anticancer drug. Oxidation of R‐roscovitine in an electrochemical cell (EC), operated under various conditions, resulted in appearance of 6 major products. These were further analyzed by high‐resolution mass spectrometry, their structures were elucidated by accurate mass measurement and compared to previously identified R‐roscovitine in vitro/in vivo metabolites. Although none of the observed products was structurally identical to those identified previously in vitro/in vivo, all of them, except for the methoxylated products, resembled similarity due to appearing through the same reaction type. R‐roscovitine in the EC cell underwent N‐dealkylation of the isopropyl moiety, hydroxylation of the aromatic side‐chain, dihydroxylation, methoxylation and dimer formation. The hydroxylation product was identified as Olomoucine II, a R‐roscovitine derivative, which displays 10‐times higher CDK‐inhibiting activity than R‐roscovitine and the occurrence of which, as R‐roscovitine product, has not yet been observed in vitro/in vivo.     

Microbial carbonylation and hydroxylation of 20(R)-panaxadiol by Aspergillus niger

20(R)-panaxadiol (PD) was metabolised by the fungus Aspergillus niger AS 3.3926 to its C-3 carbonylated metabolite and five other hydroxylated metabolites (1–6). Their structures were elucidated as 3-oxo-20(R)-panaxadiol (1), 3-oxo-7β-hydroxyl- 20(R)-panaxadiol (2), 3-oxo-7β,23α-dihydroxyl-20(R)-panaxadiol (3), 3,12-dioxo- 7β,23β-dihydroxyl-20(R)-panaxadiol (4), 3-oxo-1α,7β-dihydroxyl-20(R)-panaxadiol (5) and 3-oxo-7β,15β-dihydroxyl-20(R)-panaxadiol (6) by spectroscopic analysis. Among them, compounds 2–6 were new compounds. Pharmacological studies revealed that compound 6 exhibited significant anti-hepatic fibrosis activity.     

以结晶紫与亚硝基R盐吸光光度法测定镍

在氨性（ＰＨ９－９．５）条件下，镍（Ⅱ）与结晶紫及亚硝基Ｒ盐反应形成紫色络合物，表观摩尔吸光系数ε５３６＝２．２９×１０＾５Ｌ，ｍｏｌ＾－１，镍浓度在０．０１２０ｍｇ／Ｌ范围内遵守比耳定律，组成摩尔比为Ｎｉ：ＣＶ：Ｒ＝１：２：１，本法快速，为光度测定微量镍的高灵敏方法之一，用于土壤、人发等试样中镍的测定、结果满意。     

手性3,7-二甲基-5,6-二羟基-辛-7-烯醛中间体的合成

以天然长叶薄荷酮[R-(+)-Pulegone]为起始原料,经过一系列立体选择性化学反应步骤,成功地建立了3个手性中心,从而完成了具有抗艾滋病活性Didemnaketals类似物的关键中间体3,7-二甲基-5,6-二羟基-辛-7-烯醛中间体的合成.发现PCC与三级环氧醇8和9的非对映选择性反应,使得9被完全氧化,而8以93%的产率回收,其de值高达98%.     

满山香中的联苯环辛二烯木脂素

满山香[Schisandra propinqua(Wall.)Hook.f.et Thoms]为五味子科植物,云南民间代五味子药用^[1],由于从五味子科植物中已分离到不少保肝降酶,抗艾滋病毒,抗癌和PAF拮抗等活性成分,其研究受到重视^[2-4],主含满山香根和提取物的复方注射液曾在云南省几所医院临床用于治疗肺癌,但其研究仅分离鉴定了两个三萜 酸([2],为进一步寻找有效成分,我们对满山香茎藤进行了研究,从中分得8种联苯环辛二烯木脂素,经波谱和分析鉴定它们的结构为：acetylgomisin R(1) angeloylgomisin R(2),gomisinA(3),gomisin B(4),gomisinN(5),gomisinO(6),6-O-benzoylgomosin O(7)和Schisantherin A(8),1为新化合物,2系首次从五味子属植物中分得,其它均为首次从满山香中分得。     

反相液相色谱中溶质保留参数间的定量关系研究

 比较了Snyder经验公式中的K0w 与S和溶质计量置换保留模型 (SDM R)中溶质保留参数Z(1mol溶剂化溶质被溶剂化固定相吸附时 ,在其接触表面处释放出溶剂或置换剂的总摩尔数 )与lgI(与 1mol溶质对固定相的亲和势有关的常数 )之间的定量关系。SDM R中的两个参数间不仅对同系物溶质可以有很好的线性关系 ,而且对非同系物溶质也有很好的线性关系。其线性关系的好坏主要取决于这两个参数数值范围的大小 ,与文献中报告的线性关系取决于是否单因素影响溶质的保留和完全由统计学规律决定的结论不同。     

Synthesis of a New β-Mercaptoalcohol

Mercaptoalcohols are a rare class of natural products. Some optically active mercaptoalcohols have been used as catalysts in asymmetric reduction of prochiral Ketone1,2. In this letter, we report the synthesis of a new optically active (-mercaptoalcohols, (R)-1,1-diphenyl-2-mercapto-3-methyl-1-butanol 7, from L- valine.Our first attempt is showed in Scheme 1. According to literature's method L-valine was converted to (S)-2-Hydroxy-3-methylbutanoic acid 21,2. 2 was treated with MeOH/SOCl2…     

Laser-enhanced ionization and laser-induced atomic fluorescence as element-specific detection methods for gas chromatography. Application to organotin analysis

The applicability of (1R,2R)-1,3-diacetoxy-1-(4-nitrophenyl)-2-propyl isothiocyanate [(R,R)-DANI] as a recently developed chiral derivatizing agent for the enantioseparation of a series of β-blockers is described. The thiourea diastereomers formed were analyzed by reversed-phase high-performance liquid chromatography, mixtures of water and methanol or acetonitrile being used for elution. Conditions of derivatizations (temperature, reagent excess and reaction time) were optimized, and the effects of organic modifiers on the retention and separation were investigated; the diastereomers could readily be baseline separated with methanol-containing mobile phases with resolutions between 1.58 and 2.72.