Synthesis of Wax Esters by Lipase-catalyzed Esterification with Immobilized Lipase from Candida sp. 99-125

Wax esters were synthesized in a solvent free system catalyzed by immobilized lipase from Candida sp. 99-125, with oleic acid and cetyl alcohol. The effects of substrate molar ratio, lipase dosage and water removal were investigated in a 50 ml flask incubated in a thermostatic cultivation cabinet. The optimized conditions were: temperature 40 ℃, shaking at 170 r·min-1, acid/alcohol molar ratio 1:0.9, lipase dosage in 10% (by mass) of oleic acid, and open reaction for water removal. As a result, the conversion rate reached 98% for reaction of 8 h. The volume of reactor was scaled up to 1 L three-neck flask. The optimized parameters were: 200 r·min-1 agitation speed, 2.5% (by mass) lipase dosage, others were the same as the parameters described above. The conversion rate reached 95% for reaction of 24 h. The lipase retained 46% conversion rate after reuse for 6, 7 batches. The products were purified by removing remained cetyl alcohol and fatty acids with ethanol and saturated sodium carbonate so-lution, respectively. The purity of the wax ester, cetyl oleate, was 96%. The physical and chemical properties of cetyl oleate were tested and compared with those of jojoba oil. The results show that the product cetyl oleate has great potential to use as the substitute of natural jojoba oil.

Synthesis and Crystal Structure of 4-(4,6-dimethoxyl -pyrimidin-2-yl)-3-thiourea Carboxylic Acid Methyl Ester

The title compound 4-（4,6-dimethoxylpyrimidin-2-yl）-3-thiourea carboxylic acid methyl ester was synthesized by the reaction of 2-amino-4,6-dimethoxyl pyrimidine, potassium thiocyanate and methyl chloroformate in ethyl acetate. Single crystals suitable for X-ray measurement were obtained by recrystallization with the solvent of dimethyl formamide at the room temperature. The structure was characterized by elemental analysis and IR and determined by X-ray diffraction analysis＇ Crystallographic data： C9H12N4O4S, Mr = 272.29, monoclinic, space group C2/m with a = 1.6672（3）, b = 0.66383（12）, c = 1.1617（2） nm, β = 109.275（2）°, V = 1.2136（4） nm^3, Dc = 1.490 g/cm^3,μ = 0.281 mm^-1, F（000） = 568, Z = 4, R1 = 0.0341and wR2 = 0.1042.

An Alternative Synthesis and Crystal Structure Characterization of Nutrient Fortifier N-(1-(Phenylacetyl)-L-prolyl) Glycine Ethyl Ester

A nutritional fortifier N-(1-(phenylacetyl)-L-prolyl)glycine ethyl ester(4)was successfully synthesized through two synthetic schemes and characterized by IR,^1H-NMR,^13C-NMR,elemental analysis and X-ray single-crystal diffraction.The intermediate N-phenylacetyl-L-proline(2)was synthesized by the solid-liquid reaction of L-proline and phenylacetyl chloride directly.Compound 2(C13 H15 NO3,Mr=233.26)belongs to the orthorhombic system,space group P212121 with a=8.9468(3),b=9.3190(3),c=14.0453(4)A,V=1171.03(6)A^3,Z=4,Dc=1.323 g/cm^3,μ=0.773 mm^-1,F(000)=496.0,the final R=0.0313 and wR=0.0797 for all data.Compound 4(C17 H22 N2 O4,Mr=318.36)is of orthorhombic system,space group P212121 with a=6.5831(2),b=8.5536(2),c=28.9138(9)A,V=1628.11(8)A^3,Z=4,Dc=1.299 g/cm3,μ=0.763 mm-1,F(000)=680.0,the final R=0.0353 and wR=0.0816 for all data.

Synthesis and Crystal Structure of 2-[(4-Methoxy- 6-methylthio-2-pyrimidinyl)aminocarbonyl- aminosulfonyl] Benzoic Acid Methyl Ester

The title compound 2-[(4-methoxy-6-methylthio-2-pyrimidinyl)aminocarbonyl- aminosulfonyl]benzoic acid methyl ester (C15H16N4O6S2, Mr = 412.44) was obtained by the reaction of (4-methoxy-6-methylthio-2-pyrimidinyl)amine with 2-methoxylcarbonylbenzene-sulfonylisocya- nate. The crystal is of monoclinic, space group P21/c with a =11.169(3), b = 9.508(3), c = 17.690(5) ? b = 91.593(5), Z = 4, V = 1877.9(10) 3, Dc = 1.459 g/cm3, F(000) = 856, m(MoKa) = 0.324 mm-1, R = 0.0690 and wR = 0.1368 for 3301 observed reflections (I > 2s(I)). The N(1)H…N(3) and N(2)H…O(4) hydrogen bonds can be observed. In the molecule the phenyl plane(I), pyrimi- din-2-yl-urea bridge plane(Ⅱ) and ester plane(Ⅲ) form three conjugated systems.

Synthesis and Crystal Structure of 4-(4,6-Dimethoxylpyrimidin-2-yl)-3-thiourea Carboxylic Acid Ethyl Ester

4-（4,6-Dimethoxyl-pyrimidin-2-yl）-3-thiourea carboxylic acid ethyl ester was synthesized by the reaction of 2-amino-4,6-dimethoxyl pyrimidine, potassium thiocyanate and methyl chloroformate in ethyl acetate. Single crystals suitable for X-ray measurement were obtained by recrystallization with the solvent of dimethyl formamide at room temperature. The crystal structure was determined by X-ray diffraction analysis. Crystallographic data： C10H14N4O4S, M, = 286.31, monoclinic, space group C2/c with a = 2.5309（3）, b = 0.67682（6）, c = 1.74237（19） nm, β = 114.744（3）°, V= 2.7106（5） nm3, Dc = 1.403 g/cm3, p = 0.225 mm-1, F（000） = 1200, Z= 8, R= 0.0514 and wR= 0.1529.

LC-APCI-MS/MS法测定大鼠血浆中维胺酯浓度及其药代动力学研究

本文建立一种高灵敏度的液质联用方法用于快速测定大鼠血浆中维胺酯的浓度。采用蛋白沉淀法制备样品；色谱柱为Agilent TC C18柱（150mm×4．6mm ID，5um），流动相为甲醇-水-甲酸（93：7：0．1），辛伐他汀作为内标；在三重四极杆串联质谱仪上，采用大气压化学离子化（APCI），正离子方式选择性离子模式进行监测；血浆浓度在0．05～50ng·mL^-1线性关系良好，定量限为10Pg·mL^-1，日内、日间精密度分别在95．97％～104．43％，RSD在4．63％～10．69％。本文利用该方法对大鼠进行药代动力学研究，3个剂量（2．5、5和10mg·kg^-1）大鼠灌胃给药后的药代动力学参数分别为T1/2（11．28±7．23）、（8．90±3．82）、（8．01±5．65）h；AUC0-∞：（103．41±61．46）、（190．23±74．99）、（421．66±229．20）ng·h·mL^-1；MRT：（6．31±0．75）、（5．98±0．71）、（6．18±0．97）h；CL／F：（30．10±13．67）、（29．58±10．59）、（31．18±17．51）L·h^-1·kg^-1；F1／F：（414．94±159．82）、（356．16±139．85）、（369．28±322．72）L·kg^-1.

维胺酯-β-环糊精包合物的研究

应用３因素８水平的均匀设计方法，优化出维胺酯－β－环糊精包合物最佳制备条件，所得包合物的包合率为９９．３％，其表观稳定常数为１３９４Ｍ－１．

α-羟基-β-对甲苯磺酰氨基羧酸甲酯的质谱研究

氨基酸是蛋白质的基本组成单元,在有机合成及生物代谢中都是十分重要的物质.特别是α-羟基-β-氨基酸是一些重要生物活性物质的结构单元,例如著名的抗癌药紫杉醇的侧链.本文讨论5个α-羟基-β-氨基酸衍生物在EI和MALDI-TOF条件下的质谱性质.……

Adsorption and flotation mechanism of a ketoxime-dithiocarbonate surfactant to chalcopyrite

The adsorption mechanism of O-isopropyl-S-[2-(hydroxyimino) propyl] dithiocarbonate ester(IPXPO) to chalcopyrite was investigated by using contact angle, in-situ atomic force microscopy(in-situ AFM), cyclic voltammetry(CV) and X-ray photoelectron spectroscopy(XPS). The results of contact angle and in-situ AFM demonstrated that IPXPO adsorbed on chalcopyrite increases surface hydrophobicity and roughness. It was found by CV experiments that a layer passive film was formed. The results of XPS spectra further revealed that the thiol S atom, oxime N atom, and O atom in the IPXPO molecule might react with copper atoms to form Cu-S, Cu-N, and Cu-O bonds, respectively. An artificial mixed minerals flotation test indicated that under the condition of pH=6.79 and IPXPO initial concentration 5×10^(-5)mol/L, the flotation recovery of chalcopyrite reached about 90%, while for pyrite only 25%, suggesting that IPXPO is an excellent collector for flotation separation and enrichment of chalcopyrite.

Asymmetric bioreduction of γ- and δ-keto acids by native carbonyl reductases from Saccharomyces cerevisiae

Optically pure(R)-γ-and(R)-δ-lactones can be prepared by intramolecular cyclization of chiral hydroxy acids/esters reduced asymmetrically from γ-and δ-keto acids/esters using Saccharomyces cerevisiae(S.cerevisiae) as a whole-cell biocatalyst.However,some of the enzymes catalyzing these reactions in S.cerevisiae are still unknown up to date.In this report,two carbonyl reductases,OdCRl and OdCR2,were successfully discovered,and cloned from S.cerevisiae using a genome-mining approach,and overexpressed in Escherichia coli(E.coli).Compared with OdCR1,OdCR2 can reduce 4-oxodecanoic acid and 5-oxodecanoic acid asymmetrically with higher stereoselectivity,generating(R)-γ-decalactone(99% ee) and(R)-δ-decalactone(98% ee) in 85% and 92%yields,respectively.This is the first report of native enzymes from S.cerevisiae for the enzymatic synthesis of chiral γ-and δ-lactones which is of wide uses in food and cosmetic industries.

The Synthesis of Some Novel N-[α-(Isoflavone-7-O-) Acetyl]Amino Acid Derivatives

A series of novel N-[α-(isoflavone-7-O-)acetyl] amino acid methyl esters were prepared from the efficient and regioselective alkylation of isoflavones with chloroacetyl amino acid derivatives under mild condition.

A New Jatrophane Diterpenoid Ester from Euphorbia turczaninowii

A new jatrophane diterpenoid ester （2S, 3S, 4R, 5R, 7S, 8R, 13R, 15R） - 3, 5, 7, 8, 15- pentaacetoxy-9, 14-dioxojatropha-6（17）, 11E-diene was isolated from the whole plant of Euphorbia turczaninowii Kar. ＆ Kit.. Its structure was characterized by spectral analysis and confurmed by X-ray crystallographic analysis.

((3-(3-硅胶丙基)硫基)丙基)硫酸酯作为可回收催化剂用于合成4,4'-芳亚甲基-双(1H-吡唑-5-醇)(英文)

Sulfuric acid ([3-(3-silicapropyl)sulfanyl]propyl)ester is employed as a recyclable catalyst for the condensation reaction between aromatic aldehydes and 3-methyl-l-phenyl-5-pyrazolone. This condensation reaction was performed in ethanol under refluxing conditions giving 4,4'-alkylmethylene-bis(3-methyl-5-pyrazolones) in 74-90% yields. The heterogeneous catalyst was recycled and used in eleven runs for the reaction between benzaldehyde and 3-methyl-l-phenyl-5-pyrazolone without losing catalytic activity.

Comparison of three fluorescence labeling and tracking methods of endothelial progenitor cells in laser-injured retina

AIM： To compare three kinds of fluorescent probes for in vitro labeling and in vivo tracking of endothelial progenitor cells（EPCs） in a mouse model of laser-induced retinal injury.METHODS： EPCs were isolated from human umbilical cord blood mononuclear cells and labeled with three different fluorescent probes： 5-（and-6）-carboxyfluorescein diacetate succinimidyl ester（CFSE）, 1,1′-dilinoleyl-3,3,3′,3′-tetramethylindo-carbocyanine perchlorate linked acetylated low-density lipoprotein（Di I-Ac LDL）, and green fluorescent protein（GFP）. The fluorescent intensity of EPCs was examined by confocal microscopy. Survival rate of labeled EPCs was calculated with trypan blue staining, and their adhesive capability was assessed. A mouse model of retinal injury was induced by laser, and EPCs were injected into the vitreous cavity. Frozen section and fluorescein angiography on flat-mounted retinal samples was employed to track the labeled EPCs in vivo.RESULTS： EPCs labeled with CFSE and Di I-Ac LDL exhibited an intense green and red fluorescence at the beginning; the fluorescence intensity decreased gradually to 20.23% and 49.99% respectively, after 28 d. On the contrary, the florescent intensity of GFP-labeled EPCs increased in a time-dependent manner. All labeled EPCs showed normal morphology and no significant change in survival and adhesive capability. In the mouse model, transplantation of EPCs showed a protective effect against retinal injury. EPCs labeled with CFSE and Di I-Ac LDL were successfully tracked in mice during the development of retinal injury and repair; however, GFP-labeled EPCs were not detected in the laser-injured mouse retina.CONCLUSION： The three fluorescent markers used in this study have their own set of advantages and disadvantages. CFSE and Di I-Ac LDL are suitable for short-term EPClabeling, while GFP should be used for long-term labeling. The choice of fluorescent markers should be guided by the purpose of the study.

Formation of Hybrid Ring Structure of Cyanurate/Isocyanurate in the Reaction be-tween 2,4,6-Tris(4-Phenyl-Phenoxy)-1, 3,5-Triazine and Phenyl Glycidyl Ether

Reaction products of 2,4,6-tris(4-phenyl-phenoxy)-1,3,5-triazine derived from 4-phenylphenol cyanate ester and phenyl glycidyl ether were analyzed. In addition to an isocyanurate compound and an oxazolidone compound which were well known as reaction products of cyanate esters and epoxy resins, compounds with hybrid ring structure of cyanurate/isocyanurate were determined. Gibbs free energies of the compound having hybrid ring structure of cyanurate/isocyanurate with two isocyanurate moiety were found to be lower than that of the compound with cyanurate ring structure through calculations. Calculation data supported the existence of hybrid ring structure of cy-anurate/isocyanurate. It was revealed that isomerization from cyanurate to isocyanurate occurs via hybrid ring structure of cyanurate/isocyanurate in the reaction of aryl cyanurate and epoxy.

Asymmetric synthesis of syn-aryl-(2S,3R)-2-chloro-3-hydroxy esters via an engineered ketoreductase-catalyzed dynamic reductive kinetic resolution

We report here a generic,green synthesis of 17 valuable syn-aryl-(2S,3R)-2–chloro-3–hydroxy esters(syn-(2S,3R)-1)in 73%-99%isolated yields along with 6.1:1–83:1 dr and 31%~>99%ee,through dynamic reductive kinetic resolution of racemic arylα–chloroβ-keto esters(2)catalyzed by an engineered ketoreductase which was obtained via ep PCR-based directed evolution.The hectogram scale synthesis of syn-(2S,3R)-1b at a substrate concentration of 120 g/L showcased the application potential of the biocatalytic method developed presently.

Synthesis and anti-HIV activities of phorbol derivatives

In this study,37 derivatives of phorbol esters were synthesized and their anti-HIV-1 activities evaluated,building upon our previous synthesis of 51 phorbol derivatives.12-Para-electron-acceptor-trans-cinnamoyl-13-decanoyl phorbol derivatives stood out,demonstrating remarkable anti-HIV-1 activities and inhibitory effects on syncytia formation.These derivatives exhibited a higher safety index compared with the positive control drug.Among them,12-(trans-4-fluorocinnamoyl)-13-decanoyl phorbol,designated as compound 3c,exhibited the most potent anti-HIV-1 activity(EC_(50)2.9 nmol·L^(−1),CC50/EC_(50)11117.24)and significantly inhibited the formation of syncytium(EC_(50)7.0 nmol·L^(−1),CC50/EC_(50)4891.43).Moreover,compound 3c is hypothesized to act both as an HIV-1 entry inhibitor and as an HIV-1 reverse transcriptase inhibitor.Isothermal titration calorimetry and molecular docking studies indicated that compound 3c may also function as a natural activator of protein kinase C(PKC).Therefore,compound 3c emerges as a potential candidate for developing new anti-HIV drugs.

迟发性痤疮的治疗以及护理观察

目的:探讨药物并面部护理治疗女性迟发性痤疮的临床疗效。方法:将60例患者口服丹参酮胶囊,每次1g,Tid;维胺脂胶囊,每次50mg,Tid,外搽迪维霜,Bid,同时进行面部护理,每周1次。结果:痊愈25例(41.67%),显效27例(45.00%),好转6例(10.00%),无效2例(3.33%),总有效率达到86.67%。结论:药物并面部护理是目前治疗女性迟发性座疮的一种疗效显著的方法。

维胺酯胶囊中维胺酯的含量及有关物质的HPLC法研究

目的测定维胺酯胶囊中维胺酯的含量及有关物质。方法采用日本分光JASCO-1500系列高效液相色谱仪,KromasilC18柱(250 mm×4.6 mm,5μm),以甲醇-醋酸(100∶0.2)为流动相,流速为0.75 ml.min-1,紫外检测波长370 nm,灵敏度AuFs=0.02,柱温为25℃。结果维胺酯在2.0～12.0 mg.L-1范围内线性关系良好(r=0.999 9),平均回收率99.9%(n=3),方法精密度RSD=0.64%;有关物质各杂质峰与主峰之间的分离良好。结论该法操作简便,专属性强,结果准确可靠,可有效控制药品质量。

清热解毒软胶囊、维胺酯、安体舒通联用治疗面部寻常痤疮的临床疗效观察

目的观察清热解毒软胶囊、维胺酯、安体舒通胶囊联用治疗面部寻常痤疮的临床疗效。方法随机将300例寻常痤疮患者分为2组,治疗组250例,口服清热解毒软胶囊、维胺酯和安体舒通。对照组50例,口服阿奇霉素、维胺酯。2组均以10d为1个疗程,4个疗程后观察疗效。结果治疗组总有效率96.0%,对照组总有效率74.0%,2组差异有统计学意义(P<0.05)。结论清热解毒软胶囊,维胺脂,安体舒通联用治疗面部寻常座疮疗效显著,临床症状改善快。