L-半胱氨酸盐酸盐合成工艺的优化

建立了邻二氮菲-Fe3+法测定L-半胱氨酸盐酸盐含量的计算模型,吸光度与含量间的关系为y10 842.1x,方差R0.999 0;通过正交试验优化了L-半胱氨酸盐酸盐的合成工艺条件,经SPSS软件统计分析结果表明,L-半胱氨酸盐酸盐合成的优化条件为:反应时间4 h、HCl浓度4 mol/L、反应温度80℃,产品收率高达99.51%,比文献收率提高了9.5%。     

金属锌-盐酸还原法制备L-半胱氨酸的工艺研究

本文研究了用金属锌-盐酸还原L-胱氨酸制备L-半胱氨酸的工艺。通过单因素、正交实验设计考察了酸浓度、原料与还原剂用量、反应温度和时间对产率的影响，结果表明最适宜的工艺条件是L-胱氨酸与锌粉用量比（质量比）是2：1，盐酸浓度为2mol／L，在70℃下反应2h，产品收率达90％。用红外光谱、熔点和比旋光度对产品进行表征，结果证实为目标产物。     

S-甲基-L-半胱氨酸的合成

以 L-半胱氨酸为原料 ,磷酸三甲酯为甲基化试剂合成了 S-甲基 - L-半胱氨酸。研究了 p H值、温度等反应条件对产品品质和收率的影响。发现在严格控制 p H为 7.0 ,反应温度不高于 37°C的条件下 ,并不出现消旋作用。这一合成路线可用于工业上大规模生产     

微生物转化法合成L-半胱氨酸的研究

以DL-2-氨基-△2-噻唑啉-4-羧酸(DL-ATC)为转化底物,采用来自假单胞菌(Pseudomonas sp.)TS1138的L-半胱氨酸合成酶系对DL-ATC进行生物转化合成L-半胱氨酸.对转化条件进行了研究,得出TS1138菌株合成L-半胱氨酸的最适转化条件;反应温度为42～44℃,转化时间为2.5 h,底物质量浓度为6g/L,酶源细胞浓缩倍数为5倍.动力学研究表明,TS1138菌株L-半胱氨酸合成酶系的米氏常数(Km)为7.1 997 mmol/L,最大初反应速度Vmax=41.6629 mmol/(L·min).     

酶法拆分氮-15标记S-苄基-半胱氨酸的研究

S-苄基-半胱氨酸是化学法制备氮-15（^15N）标记胱氨酸及其衍生物的重要前体,以S-苄基-D,L-半胱氨酸为拆分底物,对氨基酰化酶酶促拆分工艺如反应温度、初始pH值、酶和底物的用量、反应时间等工艺参数进行了考察。在较佳的工艺条件下,苄基-L-半胱氨酸拆分的单程收率达到45%,未出现同位素丰S-度稀释现象。     

化学酶法合成γ-L-谷氨酰-L-半胱氨酸

以Bacillus subtilis NX-2产γ-谷氨酰转肽酶为催化剂,以L-谷氨酰胺和S-苄基-L-半胱氨酸为底物,利用转肽反应合成了S-苄基-γ-L-谷氨酰-L-半胱氨酸,考察了反应时间、初始酶浓度、供体/受体比以及投料方式等条件对反应过程的影响.结果表明,在L-谷氨酰胺浓度为20 mmol/L,S-苄基-L-半胱氨酸浓度为20 mmol/L,酶浓度为0.0208 U/mL以及pH9条件下,于40℃水浴中反应3 h,S-苄基-γ-L-谷氨酰-L-半胱氦酸得率为5.14 mmol/L,对谷胺酰胺的转化率为25.7%.采用分批投料方式可有效提高谷氨酰供体转化率.S-苄基-γ-L-谷氨酰-L-半胱氨酸以三氟甲磺酸脱除苄基保护基,经RPC纯化后可得产物GGC,产物纯度为91.2%,收率为75.7%.     

壳聚糖/聚乙烯醇/半胱氨酸复合水凝胶的制备及其性能研究

以壳聚糖(CS)、聚乙烯醇(PVA)和L-半胱氨酸(L-cysteine)为原料,以甲基丙烯酸缩水甘油酯(GMA)为交联剂,通过化学交联和光固化反应合成了壳聚糖/聚乙烯醇/半胱氨酸复合水凝胶。考察了半胱氨酸用量、光引发剂用量等对复合水凝胶性能的影响。试验表明,制备出的水凝胶薄膜溶胀能力和耐溶剂性能均随L-半胱氨酸的增加先增大后减小,加入少量L-半胱氨酸后断裂伸长率由13%增长到200%以上,加入过量的L-半胱氨酸使得断裂伸长率和强度下降。引发剂的加入对材料形貌有一定的影响。在L-半胱氨酸加入量为与GMA摩尔质量比1∶1时性能最优。     

以L-半胱氨酸盐酸盐为原料制备D-半胱氨酸工艺研究

由L-半胱氨酸盐酸盐制得L-半胱氨酸,在水杨醛存在条件下,L-半胱氨酸,L-酒石酸及丙酮在溶剂冰乙酸中加热回流,制得D-2,2-二甲基四氢噻唑-4-羧酸-L-酒石酸盐,收率45％以上,再将其溶解浓缩得D-半胱氨酸,收率85．9％。     

对溴溴苄的合成工艺研究

以对溴甲苯为原料,采用溶剂光溴化法合成对溴溴苄,考察了配比、反应时间对反应的影响,得出了最适宜工业化的工艺条件：四氯化碳为溶剂,150 W钨灯为光源,n（对溴甲苯）∶n（溴）1∶0.98,反应时间5.5 h,采用乙醇重结晶的后处理方法提纯减压蒸馏后的粗品,得到的产品纯度达98.5%,收率51%左右。     

L-半胱氨酸对酪氨酸酶的抑制动力学研究

用酶动力学方法考察了L-半胱氨酸对酪氨酸酶单酚酶和二酚酶活性的抑制效应。结果表明,L-半胱氨酸对酪氨酸酶单酚酶和二酚酶活性均有抑制作用,导致单酚酶活力和二酚酶活力下降50%的L-半胱氨酸浓度(IC50)分别为20.3μmol/L和52.0μmol/L。在降低蘑菇酪氨酸酶酶活的同时,L-半胱氨酸能明显延长单酚酶和二酚酶的延滞时间。探讨了二酚酶延滞时间产生的原因:L-半胱氨酸与酪氨酸酶催化氧化产物多巴醌反应,形成了无色的L-DOPA的L-半胱氨酸衍生物,从而阻断了多巴色素的形成,直至体系中的L-半胱氨酸反应完全后,多巴醌才开始转化为多巴色素。L-半胱氨酸对二酚酶的抑制作用表现为不可逆的竞争性抑制。     

Many Drugs of Abuse May Be Acutely Transformed to Dopamine,Norepinephrine and Epinephrine In Vivo

It is well established that a wide range of drugs of abuse acutely boost the signaling of the sympathetic nervous system and the hypothalamic–pituitary–adrenal (HPA) axis, where norepinephrine and epinephrine are major output molecules. This stimulatory effect is accompanied by such symptoms as elevated heart rate and blood pressure, more rapid breathing, increased body temperature and sweating, and pupillary dilation, as well as the intoxicating or euphoric subjective properties of the drug. While many drugs of abuse are thought to achieve their intoxicating effects by modulating the monoaminergic neurotransmitter systems (i.e., serotonin, norepinephrine, dopamine) by binding to these receptors or otherwise affecting their synaptic signaling, this paper puts forth the hypothesis that many of these drugs are actually acutely converted to catecholamines (dopamine, norepinephrine, epinephrine) in vivo, in addition to transformation to their known metabolites. In this manner, a range of stimulants, opioids, and psychedelics (as well as alcohol) may partially achieve their intoxicating properties, as well as side effects, due to this putative transformation to catecholamines. If this hypothesis is correct, it would alter our understanding of the basic biosynthetic pathways for generating these important signaling molecules, while also modifying our view of the neural substrates underlying substance abuse and dependence, including psychological stress-induced relapse. Importantly, there is a direct way to test the overarching hypothesis: administer (either centrally or peripherally) stable isotope versions of these drugs to model organisms such as rodents (or even to humans) and then use liquid chromatography-mass spectrometry to determine if the labeled drug is converted to labeled catecholamines in brain, blood plasma, or urine samples.     

Insect antifeedant properties of anthranoids from the genusVismia

Vismiones and ferruginins, representatives of a new class of lypophilic anthranoids from the genusVismia were found to inhibit feeding in larvae of species ofSpodoptera, Heliothis, and inLocusta migratoria.     

Direct observation of freeze-thaw instability of latex coatings via high pressure freezing and cryogenic SEM

Despite its industrial importance, the subject of freeze-thaw (F/T) stability of latex coatings has not been studied extensively. There is also a lack of fundamental understanding about the process and the mechanisms through which a coating becomes destabilized. High pressure (2100 bar) freezing fixes the state of water-suspended particles of polymer binder and inorganic pigments without the growth of ice crystals during freezing that produce artifacts in direct imaging scanning electron microscopy (SEM) of fracture surfaces of frozen coatings. We show that by incorporating copolymerizable functional monomers, it is possible to achieve F/T stability in polymer latexes and in low-VOC paints, as judged by the microstructures revealed by the cryogenic SEM technique. Particle coalescence as well as pigment segregation in F/T unstable systems are visualized. In order to achieve F/T stability in paints, latex particles must not flocculate and should provide protection to inorganic pigment and extender particles. Because of the unique capabilities of the cryogenic SEM, we are able to separate the effects of freezing and thawing, and study the influence of the rate of freezing and thawing on F/T stability. Destabilization can be caused by either freezing or thawing. A slow freezing process is more detrimental to F/T stability than a fast freezing process; the latter actually preserves suspension stability during freezing. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004 in Chicago, IL. Tied for first place in The John A. Gordon Best Paper Competition.     

Ethanol and (−)-α-Pinene: Attractant Kairomones for Bark and Ambrosia Beetles in the Southeastern US

In 2002–2004, we examined the flight responses of 49 species of native and exotic bark and ambrosia beetles (Coleoptera: Scolytidae and Platypodidae) to traps baited with ethanol and/or (−)-α-pinene in the southeastern US. Eight field trials were conducted in mature pine stands in Alabama, Florida, Georgia, North Carolina, and South Carolina. Funnel traps baited with ethanol lures (release rate, about 0.6 g/day at 25–28°C) were attractive to ten species of ambrosia beetles (Ambrosiodmus tachygraphus, Anisandrus sayi, Dryoxylon onoharaensum, Monarthrum mali, Xyleborinus saxesenii, Xyleborus affinis, Xyleborus ferrugineus, Xylosandrus compactus, Xylosandrus crassiusculus, and Xylosandrus germanus) and two species of bark beetles (Cryptocarenus heveae and Hypothenemus sp.). Traps baited with (−)-α-pinene lures (release rate, 2–6 g/day at 25–28°C) were attractive to five bark beetle species (Dendroctonus terebrans, Hylastes porculus, Hylastes salebrosus, Hylastes tenuis, and Ips grandicollis) and one platypodid ambrosia beetle species (Myoplatypus flavicornis). Ethanol enhanced responses of some species (Xyleborus pubescens, H. porculus, H. salebrosus, H. tenuis, and Pityophthorus cariniceps) to traps baited with (−)-α-pinene in some locations. (−)-α-Pinene interrupted the response of some ambrosia beetle species to traps baited with ethanol, but only the response of D. onoharaensum was interrupted consistently at most locations. Of 23 species of ambrosia beetles captured in our field trials, nine were exotic and accounted for 70–97% of total catches of ambrosia beetles. Our results provide support for the continued use of separate traps baited with ethanol alone and ethanol with (−)-α-pinene to detect and monitor common bark and ambrosia beetles from the southeastern region of the US.     

ICP-MS法测定地球化学样品中As、Cr、Ge、V等18种微量痕量元素的研究

建立了测定地球化学样品中包括As、Cr、Ge、V等18种微量、痕量元素的ICP-MS方法。地化试样用HF-HNO3混酸分解后,以1 1 HNO3溶解干渣。由于制样不使用盐酸,避免了Cl对As、Cr、Ge、V的质谱干扰。用国家一级地球化学标准物质GBW 07309制备溶液优化仪器工作参数,并用于校准。方法测定限(6s)为:0.007~6.4μg/g,精密度(RSD%,n=12)为:29%~9.4%,经过国家一级地球化学标准物质的分析验证,结果与标准值吻合。方法已应用于国土资源调查的试样分析。