由山苍子油合成假性紫罗兰酮的相转移催化研究

本文以季铵盐、季鏻盐、PEG为相转移催化亮剂,对山苍子油和丙酮在氢氧化钠存在下合成假性紫罗兰酮的反应进行了研究,反应收率可提高6—14％,四乙基碘化铵与三苯基苄基氯化磷具有显著的催化效果。对不同相转移催化剂的可能作用机理进行了探讨。     

局部麻醉药盐酸达克罗宁高效合成工艺

以对羟基苯乙酮和溴丁烷为起始原料,利用相转移催化剂通过两步反应合成药用级的盐酸达克罗宁。首先利用相转移催化剂催化生成中间体对丁氧基苯乙酮,再与哌啶盐酸盐、多聚甲醛反应生成产物。合成产物经1H-NMR和MS结构确证。结果表明,该反应总产率超过90%,简单易操作,适合工业生产。     

超声波和超临界流体对酶活性的影响

酶是生物催化剂,具有一般催化剂所没有的独特优点,但由于容易失活而限制了其在工业上的应用。超声波是一种物理能量形式,在一定的条件下可与酶协同作用促进反应。超临界流体作为良好的非水反应溶剂,在生物工程中有着广泛的应用前景。简要介绍了超声波、超临界流体对酶活性的各种影响因素、作用机理及研究进展。     

微波辐射相转移催化合成二烯丙基二硫化物的研究

本文用微波辐射相转移催化法合成了二烯丙基二硫化物,研究了微波辐射功率、微波辐射时间、相转移催化剂的量以及反应物的摩尔比等因素对产品产率的影响。最佳反应条件为:以蒸馏水为溶剂,四丁基溴化铵作相转移催化剂,n(二硫化钠)∶n(烯丙基氯)=0.65∶1,ω(二硫化钠)∶ω(四丁基溴化铵)=47.67∶1,微波功率195W,微波辐射时间12 min,收率82.2%。证明合成的二烯丙基二硫化物对HepG2细胞具有细胞毒性。     

超声波辅助下脂肪酶催化高酸值废油脂制备生物柴油

探讨了超声波辅助条件下脂肪酶催化高酸值废油脂转化为生物柴油的反应。来源于Aspergillus oryzae和Candida antarctica的固定化脂肪酶,在超声波辅助下,对高酸值废油脂转化为生物柴油具有高的催化活性。以来自于C.antarctica的固定化脂肪酶Novozym435为催化剂,以酸价为157mg KOH/g的高酸值废油脂为原料在超声波辅助下与丙醇反应,在脂肪酶用量为油质量的8%、初始醇油摩尔比为3∶1、反应温度控制在40~45℃、超声波频率和功率分别采用28kHz和100W的条件下,反应50min转化率达到94.86%。在此条件下,不同碳原子数(C1~C5)的直链和支链醇均有较高的转化率,在短链醇的选择上具有宽广的适应性。超声波还减少了反应产物和反应体系中其他黏性杂质在固定化脂肪酶表面的吸附,回收的Novozym435相较单纯机械搅拌条件下回收的外观干净、分散良好无结块现象、易于洗涤和再次利用,具有良好的操作稳定性。     

手性Schiff－Base在手性PTC条件下的双不对称诱导烷基化

本文报道了以苯甲醛甘氨酸酯〔乙酯,（—）—簿荷醇酯〕西佛碱作为反应底物,烯丙基溴,溴苄,对硝基溴作为烷基化试剂,在以（—）—Ｎ—基氯化辛可宁丁,（＋）－Ｎ基氯化辛可宁作为催化剂的固液相转移条件下的双不对称诱导烷基化反应,进而水解得到α—光学活性氨基酸。光学产率为２．５７—２２．４％,实验中观察到了双不对称诱导效应。     

超声波的生物学效用及其在转基因中的应用

超声波主耍引起空化现象。超声波的生物学效用是多方面的,既可引起生物大分子以至于细胞的损伤;又可促进生物大分子的合成,加速生化反应。超声波诱导基因转移是目前发展起来的一种比较理想的转基因技术。     

NKC-9干氢型树脂催化合成油酸甲酯

采用强酸性阳离子交换树脂作催化剂,对油酸和甲醇反应合成油酸甲酯的工艺进行研究。分别筛选了4种型号的树脂,其中以NKC-9干氢型树脂催化效果最好。考察了酸醇摩尔比、反应温度、催化剂用量、脱水剂用量、反应时间和催化剂重复使用性等因素对转化率的影响。结果表明:反应的适宜条件为酸醇摩尔比1∶2,反应温度70℃,催化剂用量为油酸质量的50%,脱水剂无水CaCl2用量为催化剂用量的10%,反应时间2 h。在此条件下,转化率可达93.85%。催化剂重复使用6次后转换率仍保持在90%以上。研究显示,采用NKC-9干氢型树脂催化合成油酸甲酯具有良好的工业应用潜力。     

氮杂环卡宾二氧化碳加合物催化转酯反应制备生物柴油

为了开发一种无金属有机催化剂用于生物柴油的制备,合成了一系列咪唑(啉)类氮杂环卡宾的二氧化碳加合物(N-heterocyclic carbenes CO2adducts,NHC-CO2),通过加热使其释放游离卡宾,并催化转酯反应制备生物柴油。为了比较催化活性,不同结构的NHC—CO2被用于大豆油的转酯反应中。结果发现:当使用咪唑类催化剂时,产物中甲酯含量大于90%,而当使用咪唑啉型催化剂,甲酯含量不足20%,这说明咪唑类催化剂更适合本研究中的转酯反应。催化剂最佳用量为大豆油的2%(摩尔百分比),最佳醇油比为12∶1。本研究中催化剂前体释放游离卡宾进入反应介质,反应迅速,产品分离简单,是制备生物柴油的有效绿色方法。     

两相体系中低聚半乳糖的合成

利用乳糖酶转移半乳糖苷活力,以环己烷和乙酸乙酯为有机相主体总蛋白在１５％水分手条件下,得到占总产物３５％以上的低聚半乳糖。在这两相体系中,研究了温度、缓冲液ＰＨ、乳糖浓度、半乳糖和葡萄糖,以及酶的固定化等因素对低地乳糖合成的影响：温度及起始乳糖浓度对低聚糖的影响不明显;加入半乳糖和葡萄糖对低聚糖的合成有一定的影响;以树脂Ｄ３４５固定化乳糖酶作生物催化剂,低聚糖的得率可达６４．７８％。     

Synthesis of l‐threitol‐based crown ethers and their application as enantioselective phase transfer catalyst in Michael additions

A few new l ‐threitol‐based lariat ethers incorporating a monoaza‐15‐crown‐5 unit were synthesized starting from diethyl l ‐tartrate. These macrocycles were used as phase transfer catalysts in asymmetric Michael addition reactions under mild conditions to afford the adducts in a few cases in good to excellent enantioselectivities. The addition of 2‐nitropropane to trans ‐chalcone, and the reaction of diethyl acetamidomalonate with β‐nitrostyrene resulted in the chiral Michael adducts in good enantioselectivities (90% and 95%, respectively). The substituents of chalcone had a significant impact on the yield and enantioselectivity in the reaction of diethyl acetoxymalonate. The highest enantiomeric excess (ee ) values (99% ee ) were measured in the case of 4‐chloro‐ and 4‐methoxychalcone. The phase transfer catalyzed cyclopropanation reaction of chalcone and benzylidene‐malononitriles using diethyl bromomalonate as the nucleophile (MIRC reaction) was also developed. The corresponding chiral cyclopropane diesters were obtained in moderate to good (up to 99%) enantioselectivities in the presence of the threitol‐based crown ethers.     

双戊烯合成萜马加成物反应的研究

本文以稀土金属氧化物(盐)为催化剂,催化工业双戊烯与顺丁烯二酸酐连续进行异构/Diels-Alder反应,合成出萜烯/马来酸酐加成物;用气相色谱法跟踪研究了反应的进程,并模拟了反应的动力学方程,初步鉴定了主产物的结构。结果表明本合成反应条件温和,反应易于控制,催化剂易于回收,产物得率比文献值高近20个百分点,产物纯度大于90％,且产物性能能满足进一步合成的要求。     

EFFECTS OF POTASSIUM ON THE PHOTOSYNTHETIC RECOVERY OF THE TERRESTRIAL CYANOBACTERIUM,NOSTOC FLAGELLIFORME (CYANOPHYCEAE) DURING REHYDRATION1

Effects of potassium on the photosynthetic recovery of Nostoc flagelliforme (Berk. & Curtis) Bornet & Flahault were investigated to determine its exact role during rehydration. Potassium enhanced recovery of the ability to reduce the primary quinone‐type acceptor (Q_A) and plastoquinone (PQ) pool and the area over the fluorescence rise curve was increased by 127%. The proportions of closed PSII reaction centers at phases J and I and the net rate of closure of PSII reaction centers were decreased by, respectively, 19%, 8%, and 23% with the addition of potassium, due to changes in the ability of PSII for multiple turnovers needed to reduce the PQ pool. Potassium significantly enhanced the probability of electron transfer beyond Q_A and the recovery of electron transport flux per PSII reaction center. Electron transport from water to methyl viologen for samples rehydrated in K⁺‐free BG₁₁ medium was 54% of those with the addition of potassium. However, electron flow from water to p‐benzoquinone and from reduced 2,6‐dichlorophenol‐indophenol to methyl viologen showed little change with the addition of potassium. The fast phase and slow phase of millisecond delayed light emission and the ATP content for samples rehydrated in K⁺‐free BG₁₁ medium were, respectively, 71.6%, 50.7%, and 77.1% of those with the addition of potassium. These suggested that potassium affected electron transfer from PQ to plastocyanin through the cytochrome b₆f complex and the proton motive force across the thylakoid membranes, probably reflecting its role in charge balance during H⁺ transport by the cytochrome b₆f complex.     

A review on lipase-catalyzed reactions in ultrasound-assisted systems

The named “green chemistry” has been receiving increasing prominence due to its environmentally friendly characteristics. The use of enzymes as catalysts in processes of synthesis to replace the traditional use of chemical catalysts present as main advantage the fact of following the principles of the green chemistry. However, processes of enzymatic nature generally provide lower yields when compared to the conventional chemical processes. Therefore, in the last years, the ultrasound has been extensively used in enzymatic processes, such as the production of esters with desirable characteristics for the pharmaceutical, cosmetics, and food industry, for the hydrolysis and glycerolysis of vegetable oils, production of biodiesel, etc. Several works found in the open literature suggest that the energy released by the ultrasound during the cavitation phenomena can be used to enhance mass transfer (substrate/enzyme), hence increasing the rate of products formation, and also contributing to enhance the enzyme catalytic activity. Furthermore, the ultrasound is considered a “green” technology due to its high efficiency, low instrumental requirement and significant reduction of the processing time in comparison to other techniques. The main goal of this review was to summarize studies available to date regarding the application of ultrasound in enzyme-catalyzed esterification, hydrolysis, glycerolysis and transesterification reactions.     

The involvement of biological quinones in the formation of hydroxyl radicals via the Haber-Weiss reaction

The present investigation was made to evaluate biologically relevant quinones as possible catalysts in the generation of hydroxyl radicals from hydrogen peroxide and superoxide radicals. ESR spectra demonstrated that menadione, plastoquinone, and ubiquinone derivatives could all be reduced to their semiquinone forms by electron transfer from superoxide radicals. Reductive homolytic cleavage of H₂O₂ was observed to be dependent upon the presence of semiquinones in the reaction medium. Our data strongly support the concept that quinones normally involved in physiological processes may also play a role as catalysts of the Haber-Weiss reaction in the biological generation of hydroxyl radicals.     

Synthesis of xylal- and arabinal-based crown ethers and their application as asymmetric phase transfer catalysts

New xylal- and arabinal-based monoaza-15-crown-5 ethers were synthesized starting from l - and d -xylose, and l - and d -arabinose, respectively. These monosaccharide-based chiral macrocycles were tested as phase transfer catalysts in a few asymmetric reactions. The xylal-based crown compounds proved to be efficient catalysts in a few liquid-liquid phase reactions. The epoxidation of trans-chalcone and the Darzens condensation of α-chloroacetophenone with benzaldehyde took place with complete diastereoselectivity and up to 77% ee and 58% ee, respectively. It was found that the substituents in the aromatic ring of the chalcone and the α-chloroacetophenone had an influence on the enantioselectivity. The highest ee values were obtained in the epoxidation of 4-chlorochalcone (81% ee) and in the reaction of a 2-naphthyl analogue (96% ee), while in the Darzens condensation of 4-phenyl-α-chloroacetophenone with benzaldehyde, a maximum ee of 91% was detected. The configuration of the monosaccharide unit in the crown ring influenced the absolute configuration of the epoxyketones synthesized.     

PHOTOSYNTHETIC NITRITE REDUCTASE II. FURTHER PURIFICATION AND BIOCHEMICAL PROPERTIES OF THE ENZYME

1. Further purification of photosynthetic nitrite reductase (PNiR),which catalyzes the transfer of hydrogen (or electron) fromthe photolytic system to nitrite, is reported in this paper.Chromatography on DEAE- cellulose and Sephadex gel-filtrationwere effective for the purification of PNiR.
2. PNiR could befractionated into two components. It was inferredfrom the dataobtained that one of these components is identicalwith PPNR,and the other one may probably be a hitherto unreportedflavinenzyme containing FMN as prosthetic group.
3. The propertiesof these two components of PNiR were described,and the interrelationshipbetween these catalysts and possibleintermediary carriers ofthis electron transfer system was discussed.

¹Dedicated to Prof. H. TAMIYA on the occasion of his 60th birthday.This investigation was supported by a Grant in Aid for FundamentalScientific Research from the Ministry of Education (No. 407130-1961)and a Grant in Aid for Organized Scientific Research from theMinistry of Education (No. 95037-1960), which are gratefullyacknowledged here. The authors also wish to acknowledge thatthe progress of this study was facilitated by a Grant from theKAISEI-KAI. A preliminary report on this work was read beforethe 25th Annual Meeting of the Botanical Society of Japan (1960,Osaka).     

The use of power ultrasound coupled with magnetic separation for the solid phase synthesis of compound libraries

Enhanced reaction rates are observed when power ultrasound is utilized as a substitute for mixing during solid phase organic chemical reactions on a paramagnetic support. Power ultrasound is also used to facilitate the washing of the paramagnetic support as it is magnetically separated from the reaction mixture. Selective examples from a library targeting the kappa-opioid receptor are presented.     

Enhanced dibenzothiophene biodesulfurization in a microchannel reactor

A microchannel reactor system was used in a biodesulfurization process in which the rate of biodesulfurization in the oil/water phase of the microchannel reaction was more than nine-fold that in a batch (control) reaction. In addition, the microchannel reaction system using a bacterial cell suspension degraded alkylated dibenzothiophene that was not degraded by the batch reaction system. This work provides a foundation for the application of a microchannel reactor system consisting of biological catalysts using an oil/water phase reaction.     

长毛对虾卵子皮层反应的研究

Morphology of the cortical reaction in the eggs of Penaeus penicillatus was studied with the light microscopy,scanning electron microscopy　and transmission electron microscopy. The cortical reaction is divided into four stages. These stages are unreacted stages, early stages, corona stages and dissipation stage. The cortical rods were released and formed a jelly coating around the surface of the egg. The jelly coating remained until the first cleavage had finished. In the end, the hatching membrane appeared around the egg. It is believed that these cortical reaction are responsible for the prevention of polyspermy by both a chemical and physical block and that also may establish a microenvironment inside a touch chorionic membrane for the developing embryo.