芴基、酰亚胺基和萘基聚合物气体分离膜的研究进展

聚合物链间距和链刚度是影响聚合物膜对气体渗透性能的决定因素,刚性基团(如芴基、酰亚胺基及萘基)引入聚合物链中,基于其大体积和扭曲结构能够有效阻碍分子链堆积,从而降低分子链堆积密度,使聚合物具有较高的自由体积,能有效改善膜对气体的渗透选择性。本文综述了近5年含芴基、酰亚胺基和萘基聚合物在气体分离中的研究,按结构分类,详细介绍了三类聚合物的合成以及膜对气体的选择性,分析了影响气体选择性的主要因素。最后,综合现有刚性聚合物的特点,从改性高气体渗透性低选择性材料、改性生物基材料及制备复合混合基质膜等角度出发,展望了此类材料的未来发展趋势,为制备高性能气体分离膜提供参考。

基于法尼醇X受体通路探讨壮药依山红对胆汁淤积大鼠的影响

目的探讨壮药依山红对α-萘异硫氰酸酯(alpha-naphtyl isothiocyanate,ANIT)诱导胆汁淤积大鼠的影响及其作用机制。方法采用120只SD大鼠,随机分成6组,分别为正常组、模型组、熊去氧胆酸组及壮药依山红高、中、低剂量组,每组20只。除正常组外,余用ANIT灌胃建立胆汁淤积大鼠模型。连续给药15天后,称量计算大鼠肝脾指数;血清生化法检测血清丙氨酸氨基转移酶(alanine aminotransferase,ALT)、门冬氨酸氨基转移酶(aspartate aminotransferase,AST)、碱性磷酸酶(alkaline phosphatase,AKP)等转氨酶指标,测定总胆红素(total bilirubin,TBIL)、直接胆红素(direct bilirubin,DBIL)、总胆汁酸(total bile acids,TBA)等胆红素指标;苏木素—伊红(hematoxylin-Eosin,HE)染色法评估肝组织病理学变化,油红O染色评估肝脏脂滴代谢情况;蛋白免疫印迹法及实时荧光定量聚合酶链式反应检测法尼醇X受体(farnesoid X receptor,FXR)、钠牛磺胆酸共转运肽(Na+-taurocholate co-transporting polypeptide,NTCP)、多药耐药相关蛋白2(multidrug resistance-associated protein 2,MRP2)、胆汁盐转运蛋白(bile salt export pump,BSEP)蛋白和mRNA表达水平。结果与正常组比,模型组大鼠肝脾指数、血清转氨酶(ALT、AST、AKP)及胆红素(TBIL、DBIL、TBA)显著升高(P<0.05),肝组织受损。壮药依山红各剂量及熊去氧胆酸显著降低这些指标(P<0.05),改善肝组织学病变,减少脂滴沉积,效果呈剂量依赖性。同时,依山红各剂量组大鼠肝组织中NTCP、MRP2蛋白的表达量均明显升高(P<0.05);高剂量组大鼠肝组织中BSEP蛋白相对表达量显著下降(P<0.05)。与模型组相比,依山红高、中剂量组大鼠肝组织中Fxr、Ntcp、Mrp2 mRNA的相对表达量显著升高(P<0.05);依山红低剂量组大鼠仅Mrp2 mRNA表达量显著升高(P<0.05);依山红各剂量大鼠肝组织中Bsep mRNA表达水平显著下降(P<0.05)。结论壮药依山红可通过调节FXR及其调控的胆汁转运相关蛋白的表达,对ANIT诱导胆汁淤积模型大鼠起到保肝利胆的作用。

Preparation of a new solid acid and its catalytic performance in di(1-naphthyl)methane hydrocracking

A new solid acid was prepared by trifluoromethanesulfonic acid （TFMSA） impregnation into an acid‐treated attapulgite （ATA）. Di（1‐naphthyl）methane （DNM） hydrocracking was used as the probe reaction to evaluate the catalytic performance of TFMSA/ATA for cleaving Car–Calk bridged bonds in coals. The results show that DNM was specifically hydrocracked to naphthalene and 1‐methylnaphthalene over TFMSA/ATA in methanol in the absence of gaseous hydrogen. In partic‐ular, TFMSA/ATA was demonstrated to be stable after four cycles with slight loss in catalytic activi‐ty. Furthermore, a proposed H＋transfer mechanism successfully interprets the TFMSA/ATA‐cata‐lyzed hydrocracking reaction of DNM.

Preparation and spectroscopic, and thermal decomposition kinetic studies of europium(Ⅲ) complex [Eu(HNBD)_3] (HNBD: 1-(6-hydroxy-1-naphthyl)-1,3-butanedione)

The complex of Eu（IH） with 1-（6-hydroxy- 1-naphthyl）- 1,3-butanedione （HNBD） was prepared for the first time and characterized by elemental analysis, IR, UV, fluorescence spectrum, and DTA-TG-DTG techniques. The IR and UV-visible spectra showed that Eu（Ⅲ） ion was coordinated to the HNBD ligand. The fluorescence spectrum showed the presence of Eu^3＋ characteristic emission. The TG-DTA-DTG curves showed that the thermal decomposition of the anhydrous complex was a two-stage process and the final residue was Eu2O3. The thermal decomposition kinetic parameters of the complex were evaluated from TG-DTG data by using three kinds of integral methods （Coat-Redfem equation, Horowitz and Metzger equation, Madhusudanan-Krishnan-Ninan equation）. The kinetic parameters of the first stage are E^＊ = 164.02 kJ.moll, A = 1.31 × 10^15 s^-l, AS^＊= 42.27 J·K^-l·mol^-l, △H^＊ = 159.51 kJ·mol^-l, △G^＊= 136.54 kJ·mol^-l, and n = 3.1, those of the second stage are E^＊= 128.52 kJ·mol^-l, A = 1.44× 106 s^-1, △S^＊= - 136.89 J·K^-l·mol^-l, △H^＊ = 120.41 kJ·mol^-l, △G^＊= 283.85 kJ·mol^-l, and n = 1.1.

Synthesis and Crystal Structure of 4,4'-(4-(1-Naphthyl)-4-phenyl-1,3-butadienylidene)-bis[N,N-diethylbenzenamine]

The title compound （C40H42N2） has been synthesized by the reaction of l-（l- naphthyl）-l-phenyl-3-chloropropylene and bis（4-（diethylamino） phenyl）methanone, and characterized by IR, ^1H NMR, MS and X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/c with a = 17.047（3）, b = 10.807（2）, c = 18.494（4） A, β = 105.727（4）°, V= 3279.4（11） A^3, Mr = 550.76, Z = 4, Dc = 1.115 g/cm^3,μ（MoKa） = 0.085 mm^-1, F（000） = 1184, the final R = 0.0625 and wR = 0.1384 for 2276 observed reflections （1 〉 2σ（I））. X-ray analysis reveals that the butadiene fragment adopts a planar cisiod conformation and makes a dihedral angel of 69.4（2）° with the naphthalene ring.

Synthesis, Crystal Structure and Herbicide Activity of Three Phenyl-naphthyl Methanone Derivatives

Three phenyl-naphthyl methanone derivatives have been designed and synthesized through alkylation and Friedel-Crafts acylation reactions.All the compounds were characterized by IR,1H NMR,13C NMR and H RMS.The single crystal structure of the compounds has been further determined by X-ray diffraction.(4-Ethoxynaphthalen-1-yl)(2-methylphenyl)methanone(3a)crystallizes in monoclinic system,P21/c space group with a=13.144(3),b=11.041(2),c=11.320(2)?,β=106.65(3)°,V=1573.7(5)?3,Dc=1.225 Mg/m3,Z=4,F(000)=616,μ(MoKα)=0.078 mm-1,R=0.0928 and wR=0.1556.(4-Ethoxynaphthalen-1-yl)(2-hydroxyphenyl)methanone(3b)belongs to the monoclinic system,P21/c space group with a=9.985(2),b=10.814(2),c=14.353(3)?,β=105.49(3)°,V=1493.6(5)?3,Dc=1.300 Mg/m3,Z=4,F(000)=616,μ(MoKα)=0.087 mm-1,R=0.0568 and wR=0.1262.(4-Methoxynaphthalen-1-yl)(4-methylphenyl)methanone(3c)crystallizes in monoclinic system,P21/c space group with a=7.6130(15),b=15.068(3),c=12.880(3)?,β=100.63(3)°,V=1452.1(5)?3,Dc=1.264 Mg/m3,Z=4,F(000)=584,μ(MoKα)=0.081 mm-1,R=0.0804 and wR=0.1349.The presence of van der Waals forces leads to the stability of the compounds.Especially,compounds 3a^c showed herbicidal activity against the monocotyledon plant barnyard grass(Echinochloa crus-galli).At the concentration of 0.75 mmol/m^2,compound 3b(Ct=0.436±0.116 mg/g)exhibited better activity than pyrazoxyfen(Ct=0.537±0.073 mg/g).

Stereoselective Synthesis and Crystal Structure Analysis of N-Naphthyl-2-deoxy-α-D-ribopyranosylamine

A new compound N-naphthyl-2-deoxy-α-D-ribopyranosylamine was synthesized and structurally determined. It crystallizes in the orthorhombic system, space group P212121 with a = 8.361（2）, b = 12.432（3）, c = 12.791（4） A^°, Z= 4, V= 1329.6（6） A^°^3, Dc= 1.295 g/cm^3, F（000） = 552, Cl5H17NO3 and Mr= 259.30. All the active hydrogen atoms are involved in the formation of hydrogen bonds in the molecule.

Synthesis and Structure-Antitumor Activity of 4,6-Diamino-1,2-Dihydro-2 ,2-Dimethyl-1-(Substituted-Naphthyl- 2)-1,3,5-Triazines

Introduction 4,6-Diamino-1,2-dihydro-2,2-dimethyl-1-substituted-1,3,5-triazines (Ⅰ) are dihydrofolate reductase(DHFR) inhibitors, hence they possess the inhibition to the growth of bacteria and cancer cells. Baker’s antifolate (Ⅱ) has shown promise as an antitumor agertt in clinical trials. The study of the structure-activity relationships of I shows that the inhibition to vertebrate DHFR is significantly influenced by the hydrophobicity of 1-substituent, i.e., the stronger the hydrophobicity of the 1-substituent, the more potent the inhibition of the compound to vertebrate DHFR.

SYNTHESIS AND CHARACTERIZATION OF N-(1-NAPHTHYL) SUCCINIMIDE

In this paper a modified two-step procedure for synthesis of N-（1-naphthyl） suecinimide （NaS） was developed, and the molecular structure of NaS was properly characterized by XRD, FT-IR, 1H NMR, DSC, etc. The results show that the melting point of our product is 159 ℃-160.5 ℃, and the characteristic infrared absorption band of carbonyl group splits into two peaks （1705cm^-3/1779cm^-3）, which are found to be quite different from the documented data （rap 147℃ -149℃; IR C=0-1700cm^-3）. Besides, photophysical spectroscopy was found to be powerful to study the molecular structure and crystal morphology of NaS compound.

黄芪多糖对急性肝内胆汁淤积性肝损伤大鼠模型的影响

探究黄芪多糖对急性肝内胆汁淤积性肝损伤大鼠血清丙氨酸氨基转移酶(alanine transaminase,ALT)、天冬氨酸氨基转移酶(Aspartate transaminase,AST)、肿瘤坏死因子a(tumornecrosisfactor-a,TNF-a)、白细胞介素6(interleukin6,IL-6)水平的影响。将雄性健康SD大鼠54只随机分为空白组、实验组(模型组、熊去氧胆酸组及黄芪多糖低、中、高剂量组),每组9只。除空白组、模型组外,其余四组大鼠均给予熊去氧胆酸溶液及黄芪多糖低、中、高(0.2、0.4、0.8 g/kg)溶液,1次/d,共7 d。于第5 d,实验组给予1%α-萘异硫氰酸酯(ANIT)油溶液灌胃建立模型,空白组给予等容积橄榄油。观察大鼠一般情况,采用全自动生化分析仪检测血清ALT、AST含量,采用ELISA法检测血清中炎性因子TNF-α、IL-6表达水平。与空白组相比,模型组ALT、AST、TNF-α、IL-6均升高,具有显著性差异(P<0.01)。与模型组相比,熊去氧胆酸组及黄芪多糖低剂量组、中剂量组、高剂量组均降低,具有显著性差异(P<0.01)。与熊去氧胆酸组相比,黄芪高剂量组效果最为显著,ALT、AST、TNF-α、IL-6均降低,具有显著性差异(P<0.01)。黄芪多糖可以缓解ANIT诱导的急性肝内胆汁淤积性肝损伤并降低ALT、AST、TNF-α、IL-6水平。

SYNTHESIS OF POLYSTYRENE-BLOCK-POLYCAPROLACTAM WITH 1,1-BIS-(1′-NAPHTHYL) ETHYLENE AS A DEACTIVATING AGENT

The insertion of 1,1-bis (1′-naphthyl) ethylene monomer unit into the active polystyrene chain end greatly decreased the reactivity of the active chain end to the carbonyl group, and allowed the polymeric chain end to react only with the double bond in N-methacryloyl caprolactam, resulting in N-acylcaprolactam functionalized polystyrene in 100% conversion. New diblock copolymer of polystyrene with polycaprolactam was synthesized by direct reaction of the functionalized polymer with caprolactam without adding additional alkali metal or their caprolactam salts.

电子级萘基环氧树脂的制备及其构效关系研究

通过一步法合成、降氯和分子蒸馏等工艺,制备了三种不同位点的高纯电子级萘基环氧树脂,分别为1,5-二羟基萘缩水甘油醚(1,5-DNGE)、1,6-二羟基萘缩水甘油醚(1,6-DNGE)和2,7-二羟基萘缩水甘油醚(2,7-DNGE)。通过控制环氧值、固化剂和固化程序一致性,分析了萘环上不同位点结构与性能的关系。选择聚醚胺(D230)和4-甲基六氢苯酐(MEHHPA)两种固化剂,研究了三种萘基环氧树脂的固化动力学,探究了萘环上不同位点的反应活性。研究结果表明:制备的三种不同位点的双官能度高纯萘基环氧树脂,三者纯度接近100%,总氯、水解氯和无机氯含量分别低于1000、200和1 ppm,适用于电子级环氧树脂的要求;在D230体系中,1,6-DNGE活化能最低,而在MEHHPA体系中,2,7-DNGE活化能最低。由于1,5-DNGE和2,7-DNGE的分子结构更对称,交联度高,所以玻璃化转变温度、橡胶弹性模量、交联密度、线膨胀系数、介电和热失重数据都较1,6-DNGE更优异;1,6-DNGE却具有最高的储能模量[E’(50℃)>2600 MPa]、损耗模量(tanδ>1.1)和韧性,加工性能更好,非常适合制备综合性能优异的复合材料,为电子封装行业提供了综合性能优异的高纯电子级萘基环氧树脂和应用价值。

萘环非共价改性石墨烯环氧纳米复合材料的制备及性能研究

探究了不同结构的分散液对石墨烯作用力的大小,并通过显微镜和拉曼光谱对石墨烯分散液进行了相关表征,发现2-羟基萘缩水甘油醚(2-NGE)与石墨烯之间具有最强的萘环π-π相互作用。然后在1,6-二羟基萘缩水甘油醚(1,6-DNGE)中引入2-NGE悬挂链,以4,4’-二氨基二苯甲烷(DDM)为固化剂,探究“内部抗塑化”作用和不同浓度的2-NGE石墨烯分散液对体系的影响。研究结果表明:1,6-DNGE/2-NGE-10%-G5体系展现出了最优异的综合性能,与1,6-DNGE相比,拉伸强度、模量和冲击强度分别提高了12.74%、21.67%和55.74%。这些优异的性能是基于“内部抗塑化”体系的构建和石墨烯的良好分散性而共同实现的,证明了在极低石墨烯负载条件下(0.0269%)实现了对高性能材料的高效利用。通过这种简便、实用的方法,实现了快速大规模制备高性能石墨烯环氧纳米复合材料。

Pocket Modification of x-Amine Transaminase AtATA for Overcoming the Trade-Off Between Activity and Stability Toward 1-Acetonaphthone

Amine transaminases(ATAs)catalyze the asymmetric amination of prochiral ketones or aldehydes to their corresponding chiral amines.However,the trade-off between activity and stability in enzyme engineering represents a major obstacle to the practical application of ATAs.Overcoming this trade-off is important for developing robustly engineered enzymes and a universal approach for ATAs.Herein,we modified the binding pocket of co-ATA from Aspergillus terreus(AtATA)to identify the key amino acid residues controlling the activity and stability of AtATA toward 1-acetonaphthone.We discovered a structural switch comprising four key amino acid sites(R128,V149,L182,and L187),as well as the"best"mutant(AtATAD224K/V149A/L182 F/L187F;termed M4).Compared to the parent enzyme AtATAD224K(AtATAPa),M4 increased the catalytic efficiency(k_(cat)/K_(m)^(1-acetonaphthone),where kcatis the constant of catalytic activities and is 10.1 min^(-1),K_(m)^(1-acetonaphthoneis) Michaelis-Menten constant and is 1.7 mmol·L^(-1))and half-life(t1/2)by 59-fold to 5.9 L·min^(-1)·mmol-1and by 1.6-fold to 46.9 min,respectively.Moreover,using M4 as the biocatalyst,we converted a 20 mmol·L^(-1)aliquot of 1-acetonaphthone in a 50 mL scaled-up system to the desired product,(R)-(+)-1(1-naphthyl)ethylamine((R)-NEA),with 78%yield and high enantiomeric purity(R>99.5%)within 10 h.M4 also displayed significantly enhanced activity toward various 1-acetonaphthone analogs.The related structural properties derived by analyzing structure and sequence information of robust ATAs illustrated their enhanced activity and thermostability.Strengthening of intramolecular interactions and expansion of the angle between the substratebinding pocket and the pyridoxal 5’-phosphate(PLP)-binding pocket contributed to synchronous enhancement of ATA thermostability and activity.Moreover,this pocket engineering strategy successfully transferred enhanced activity and thermostability to three other ATAs,which exhibited 8%-22%sequence similarity with AtATA.This research has important implications for overcoming the trade-off between ATA activity and thermostability.

柱前荧光衍生化RP-HPLC测定环维黄杨星D含量

目的 建立环维黄杨星D含量测定方法。方法 环维黄杨星D同异氰酸萘酯反应后 ,RP HPLC荧光法测定。色谱柱为C1 8柱 ;流动相为甲醇 水 (85∶15 ) ;流速 :1mL·min- 1 ;荧光检测激发波长 30 5nm ,发射波长 385nm ;柱温35℃。结果 衍生化反应重复性好 ,RSD为 1 2 1% ,主峰与相关物质分离良好。结论 本法简单、准确 ,可用于环维黄杨星D及其相关物质含量测定。

N-(1-萘基)-乙二胺荧光光度法测定痕量亚硝酸根

研究了盐酸介质中N-(1-萘基)-乙二胺(NED)与亚硝酸根的反应. 基于NED的荧光强度被亚硝酸根猝灭的现象, 建立了一种荧光测定NO-2的新方法, 并对反应机理进行了讨论. 在优化实验条件下, NO-2在1.07～214.0 μg·L-1范围内与NED的荧光猝灭强度呈线性关系, 方法的检出限为0.069 μg·L-1. 该法用于测定水样中痕量亚硝酸根的含量, 结果令人满意.

产酯酶海洋微生物的筛选、鉴定及系统发育分析

通过以三丁酸甘油酯和α-乙酸萘酯为底物,建立了一种快速、准确的酯酶产生菌的筛选方法,并从样品中分离到1株产酯酶活力和稳定性较高的菌株EB-1,对其进行了形态学、生理生化特征鉴定和16S rDNA序列分析。结果表明,该菌株与Bacillus subtilis subsp.subtilis模式菌株的同源性高达99.79%;又根据其产黑色素这一特性,最终将其确定为Bacillus subtilis var.niger,其16S rDNA序列在GenBank的注册号为EU016526。

盐酸萘乙二胺分光光度法测定肉制品中的亚硝酸盐

用盐酸萘乙二胺分光光度法对市售的9种肉制品中的亚硝酸盐含量进行了测定,并选取其中的3种进行了精密度试验和回收率试验,RSD在1.3～1.6之间,回收率在95%～103%之间。所测9种肉制品样品中亚硝酸盐含量在0.64mg/kg～12.31mg/kg之间,均符合我国食品添加剂使用卫生标准。散装腊肉腊肠的亚硝酸盐含量高于真空包装的腊肉腊肠中亚硝酸盐含量;在同一种包装制品中,腊肉的肥肉部分亚硝酸盐含量高于瘦肉部分的亚硝酸盐含量。

基于纳米金固定半抗原的电化学免疫传感器灵敏检测克伦特罗

研制了一种基于纳米金固定半抗原的间接竞争电化学免疫传感器,可灵敏检测克伦特罗。在金电极表面组装1,6-己二硫醇单分子膜,通过AuS共价作用连接纳米金颗粒,通过吸附作用固定克伦特罗-牛血清白蛋白偶联物。样品中的待测组分与固定化的克伦特罗偶联物竞争结合单克隆抗体,碱性磷酸酯酶标记的二抗选择性地与电极表面捕获的一抗反应,进而催化底物1-萘酚磷酸酯水解生成1-萘酚,在电极表面氧化产生电信号。在优化的实验条件下,克伦特罗浓度在0.1～1000μg/L范围内与电流强度线性相关,线性方程为I(A)=8.79×10-7-2.66×10-7logC(μg/L),相关系数0.9960,检出限达20 ng/L。同时测定了猪肉及猪肝样品中克伦特罗含量,相对标准偏差平均值为7.0%,加标回收率在89.1%～105.6%之间,与传统的间接竞争酶联免疫吸附法对照,结果无显著性差异。

茵栀黄颗粒的保肝作用研究

目的:研究茵栀黄颗粒的保肝作用。方法:采用D-氨基半乳糖(D-GalN)、四氯化碳(CCl_4)造成急性肝损伤,以血清ALT与AST、肝组织病变程序为指标,并以茵栀黄颗粒口服液为阳性对照,观察茵栀黄颗粒的药效。另外,给小鼠ig异硫氰酸-1-奈脂,以血清胆红素为指标,观察茵栀黄颗粒的作用。结果:1.8g/kg、3.6g/kg茵栀黄颗粒组均能降低D-GalN所致的小鼠血清ALT、AST升高,3.6g/kg茵栀黄颗粒组还能减轻肝组织病变程度。1.0g/kg、2.0g/kg茵栀黄颗粒组均能降低CCl_4所致的大鼠血清ALT、AST升高,2.0g/kg茵栀黄颗粒组还能减轻肝组织病变程度。1.8g/kg、3.6g/kg茵栀黄颗粒组均能降低异硫氰酸-1-奈脂所致总胆红素和结合胆红素升高。结论:茵栀黄颗粒对D-GalN、CCl_4所致的急性肝损伤均有明显的保护作用,对异硫氰酸-1-奈脂所致小鼠血清高胆红素有明显的降低作用。