气相色谱/质谱联用测定大鼠脑部的神经甾体

应用气相色谱 质谱联用技术建立了大鼠脑部神经甾体的测定方法。游离型甾体和甾体硫酸酯分两步萃取。第一步用乙酸乙酯提取游离型甾体,第二步用氯仿/2 丁醇提取甾体硫酸酯,然后经固相萃取纯化。甾体硫酸酯进行溶剂解形成游离型甾体。游离型甾体和甾体硫酸酯分别经七氟丁酸酐衍生化后进行气相色谱 质谱分析。经初步研究雄性大鼠脑部游离型神经甾体孕烯醇酮(PREG)、黄体酮(PROG)、别孕烯醇酮(AP)和脱氢表雄酮(DHEA)的含量分别为（8.53±1.11） ng/g ,（ 7.01±2.60） ng/g ,（ 1.     

新型NO供体的合成及其体外释放NO性能

新型NO供体的合成及其体外释放NO性能;金属卟啉;NO载体;合成;体外释NO作用     

Effects of Y (Ⅲ) Ions on the Fluorescence Properties of Ce(Ⅲ) Ion and the Organic Ligands in the Complex

The enhancement effects of Y ( Ⅲ) ions on the fluorescence of Ce ( Ⅲ) in Ce ( Ⅲ)-Y ( Ⅲ)-PMMA (polymethylmethacrylate ) or Ce ( Ⅲ)-Y ( Ⅲ)-PVC (polyvinyl chloride ) complex systems were observed. The influence of Y ( Ⅲ) ions on the emission spectra of PMMA ligands in PMMA-Y ( Ⅲ) and the fluorescent enhance- ment of Y( Ⅲ) on Ce( Ⅲ) emission in PMMA-Ce-Y by Y( Ⅲ) ion were studied. It was also of interest to note that when Y ( Ⅲ) ions were added into PMMA and into bpy(bipyridine ), respectively, the emission spectrum of PMMA ligands was split into fine structure bands by Y ( Ⅲ), and the fluorescence intensities of bpy ligands in bpy-Y ( Ⅲ) complexes were considerably increased.     

基于2,6-二甲基萘的杂环聚芳醚酮的合成

由1,5-二(4'-氟苯甲酰基)-2,6-二甲基萘(1)和类双酚单体(2a～2d)通过N—C偶联聚合反应合成了一系列基于2,6-二甲基萘的新型杂环聚芳醚酮(3a～3d).采用FTIR、1H-NMR、DSC、TGA、GPC等手段对聚合物进行结构表征和性能测试,并研究了其溶解性及特性黏数.结果表明,聚合物在室温下易溶于氯仿、DMAc、NMP、吡啶和间甲酚等非质子极性有机溶剂,其氯仿溶液能形成无色透明、韧性较好的膜,特性黏数(ηinh)在0.76～1.40 dL/g范围内.聚合物3b～3d的数均分子量(Mn)和分散指数(PDI)分别在78000～104000和1.66～2.21范围内.该类聚合物的玻璃化转变温度(Tg)均大于280℃,在氮气氛围和800℃时的残余量在53%～69%范围内.该类聚合物在氮气中5%和10%的热失重温度分别在423～440℃和434～467℃范围内.     

Cross-linking of polyolefins: a study by thermoporosimetry with benzene derivatives as swelling solvents.

The solvents o-, m-, p-xylene, p-dichlorobenzene, 1,2,4-trichlorobenzene, and naphthalene were calibrated as condensates used in the thermoporosimetry technique. Exponential relationships were found connecting the pore radii R(p) (in nm) and the freezing-point depression of the swelling solvent deltaT (in degrees C) on the one hand and the apparent energy of crystallization W(a) (in J cm(-3)) and deltaT on the other hand: R(p) = t exp[-1/(c deltaT)]; W(a) = W0 exp(deltaT/f). Pore- or mesh-size distributions can be derived from differential scanning calorimetry results by using the following equation: dV(p)/dR(p) = k{[cY(T)deltaT2]/[W(a)R(p)]}. All the numerical parameters were determined. Polyethylene and polypropylene samples, cross-linked with high-energy electrons or gamma-rays, were submitted to thermoporosimetry study. Relative mesh-size distributions, which depend on the polymer/solvent pair, were calculated for these polyolefins with o-, m-, and p-xylene as solvent and were found to be in the same sequence as those of their degrees of swelling and the irradiation doses received.     

α-氨基酸乙酯卤根合铂(II)的合成和构型研究

Sixteen new halogenoethylaminoacidato Pt(II) complexes were synthesized and characterized, of which eightiodo complexes (PtA2I2) (A = DL-a-AlaOEt, L-a-alaOEt, DL-a-PheOEt, L-a-PheOEt, DI-A-AspOEt, L-a-AspOEt, DL-a-SerOEt and L-a-Lys OEt), four chloro compounds (PtA2Cl2)(A = DL-a-PheOEt, DL-a-AspOEt, L-a-Asp OEt) and (DL-a-PheHOEt)2(PtCl4) were obtained by reaction of K2 (PtX4)(X = I^-, Cl^-) with the corresponding ethylaminoacidates in water. The other chlorethylaminoacidato Pt(II) complexes (PtA2Cl2) (A = DL-a-AlaOEt, L-a-AlaOEt, L-a-PheOEt, DL-a-Ser OEt) were synthesized in acetone by exchange reaction of the corresponding iodo complexes with AgCl in order to avoid hydrolysis of the ethyl aminoacidates. Molar conductivity determination showed that all the Pt(II) complexes obtained were neutral molecules with the exception of (DL-a-PheHOEt)2(PtCl4) which existed as an anion. As shown by diole moment determination and modified thiourea reaction, iodo complexes 1-7 and some of the chloro complexes (PtA2Cl2) (A = DL-a-alaOEt, D-a-AlaOEt, DL-a-SerOEt) were of cis-configuration and the other chloro complexes were of trans-configuration.     

Production yields of H(D) atoms in the reactions of N(2)(A (3)Sigma(u) (+)) with C(2)H(2), C(2)H(4), and their deuterated variants

The production yields of H(D) atoms in the reactions of N(2)(A (3)Sigma(u) (+)) with C(2)H(2), C(2)H(4), and their deuterated variants were determined. N(2)(A (3)Sigma(u) (+)) was produced by excitation transfer between Xe(6s[32](1)) and ground-state N(2) followed by collisional relaxation. Xe(6s[32](1)) was produced by two-photon laser excitation of Xe(6p[12](0)) followed by concomitant amplified spontaneous emission. H(D) atoms were detected by using vacuum-ultraviolet laser-induced fluorescence (LIF). The H(D)-atom yields were evaluated from the LIF intensities and the overall rate constants for the quenching, which were determined from the temporal profiles of the NO tracer emission. The absolute yields were evaluated by assuming that the yield for NH(3)(ND(3)) is 0.9. Although no HD isotope effects were observed in the overall rate constants, there were isotope effects in the H(D)-atom yields. The H-atom yields for C(2)H(2) and C(2)H(4) were 0.52 and 0.30, respectively, while the D-atom yields for C(2)D(2) and C(2)D(4) were 0.33 and 0.13, respectively. The presence of isotope effects in yields suggests that H(2)(D(2)) molecular elimination processes are competing and that molecular elimination is more dominant in deuterated species than in hydrides.     

An improved method for the analysis of major antioxidants of Hibiscus esculentus Linn

Major antioxidants of aqueous ethanol extract from Lady's Finger (Hibiscus esculentus Linn) were systematically investigated in this study. Firstly, high-performance liquid chromatography (HPLC) was applied to identify antioxidant peaks in a sample by spiking the sample extract with 2,2'-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) free radical, which was prepared from manganese dioxide and ABTS. Secondly, in order to identify the elution period of major antioxidant peaks, the antioxidant capacities of different fractions from solid-phase extraction (SPE) were measured, and the chromatograms of fractions were also recorded. Lastly, multiple mass spectrometry (MS(n)) was used to elucidate the possible chemical structures of antioxidants, and nuclear magnetic resonance (NMR) was further applied for structure confirmation. The major antioxidant compounds in lady's finger were identified to be quercetin derivatives and (-)-epigallocatechin using HPLC-MS and HPLC-MS(n) (n = 2-4) techniques. It was found that about 70% of total antioxidant activity was contributed by four quercetin derivatives. The structures of major antioxidants, which were isolated by semi-preparative RP-HPLC with two tandem C18 columns, were further confirmed using UV-vis absorption spectroscopy and 13C NMR spectra. Quercetin 3-O-xylosyl (1' --> 2') glucoside, quercetin 3-O-glucosyl (1' --> 6') glucoside, quercetin 3-O-glucoside and quercetin 3-O-(6'-O-malonyl)-glucoside were first identified and characterized as major antioxidants in lady's finger.     

Gel-based proteomics reveals potential novel protein markers of ozone stress in leaves of cultivated bean and maize species of Panama

We examined responses of cultivated bean (Phaseolus vulgaris L. cv. IDIAP R-3) and maize (Zea mays L. cv. Guarare 8128) plants exposed to ozone (O(3)) using a leaf injury assessment and proteomics approach. Plants grown for 16 days in greenhouse were transferred to an O(3) chamber and exposed continuously to 0.2 ppm O(3) or filtered pollutant-free air for up to 72 h. CBB-stained gels revealed changes in ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisCO) protein. By Western analysis changes in marker proteins for O(3) damage in leaves by 1-DE were checked. In bean leaves, two superoxide dismutase (SOD) protein (19 and 20 kDa) were dramatically decreased, while ascorbate peroxidase (APX, 25 kDa), small heat shock protein (HSP, 33 kDa), and a naringenin-7-O-methyltransferase (NOMT, 42 kDa) were increased by O(3). In maize leaves, expression levels of catalase (increased), SOD (decreased), and APX (increased) were drastically changed by O(3) depending on the leaf stage, whereas crossreacting HSPs (24 and 30 kDa) and NOMT (41 kDa) proteins were strongly increased in O(3)-stressed younger leaves. These results indicated a clear modulation of oxidative stress-, heat shock-, and secondary metabolism-related proteins by O(3). Finally, 2-DE at 72 h after O(3) exposure revealed changes (induction/suppression) in expression levels of 25 and 12 protein spots in bean and maize leaves, respectively. Out of these, ten and nine nonredundant proteins in bean and maize, respectively, were identified by MS. A novel pathogenesis-related protein 2 may serve as a potential marker for O(3) stress in bean.     

自组装制备聚(丙烯酸叔丁酯-b-甲基丙烯酸二甲胺基乙酯)壳交联胶束

以1-氯代乙苯为引发剂、氯化亚铜/N,N,N′,N″,N″-五甲基二乙撑三胺(PMDETA)为催化体系、丁酮-异丙醇为混合溶剂,通过原子转移自由基聚合法制备不同分子量的大分子引发剂聚丙烯酸叔丁酯(1-PECl)及不同嵌段比的两亲性嵌段共聚物聚(丙烯酸叔丁酯-b-甲基丙烯酸二甲胺基乙酯)(P(tBA-b-DMAEMA))。通过1H-NMR表征了P(tBA-b-DMAEMA)的结构,GPC测试了其分子量及分子量分布。P(tBA-b-DMAEMA)在选择性溶剂中自组装形成核-壳结构的胶束,引用了乙烯基乙二醇二碘醚(BIEE)为交联剂与链段PDMAEMA发生化学交联反应从而得到稳定的壳交联胶束结构,并通过马尔文粒径仪研究了自组装所得胶束的温度及pH敏感性。     

由Diels-Alder反应合成新型热稳定性含硅双马来酰亚胺──合成及表征

由Ｄｉｅｌｓ－Ａｌｄｅｒ反应合成新型热稳定性含硅双马来酰亚胺──合成及表征郝建军,江璐霞,蔡兴贤（四川联合大学材料科学与工程学院高分子材料系,成都,６１００６５）关键词双马来酰亚胺,有机硅,Ｄｉｅｌｓ－Ａｌｄｅｒ反应,合成,表征采用单体扩链增韧［１］...     

Synthesis and spectral studies of macrocyclic Pb(Ⅱ), Zn(Ⅱ), Cd(II)and La(Ⅲ) complexes derived from 1,4-bis(3-aminopropoxy)butane with metal nitrate and salicylaldehyde derivatives

Eight new macrocyclic complexes were synthesized by template reaction of 1,4-bis(3-aminopropoxy)butane with metal nitrate and 1,3-bis(2-forrnylphenyl)propane or 1,4-bis(2-formylphenyl)butane and their structures were proposed on the basis of elemental analysis, FTIR, UV-vis, molar conductivity measurements, 1H NMR and mass spectra. The metals to ligand molar ratios of the complexes were found to be 1:1. The complexes are 1:2 electrolytes for Pb(II), Zn(II) and Cd(II) complexes and 1:3 electrolytes for La(lIl) as shown by their molar conductivities (Am) in DMSO at 10-3 tool L-l. Due to the existence of free ions in these complexes,such complexes are electrically conductive. The configurations of La(Ⅲ) and Pb(U) were proposed to probably octahedral and Zn(II) and Cd(II) complexes were proposed to probably tetrahedral.     

Triton X-100微乳液体系中铁的萃取与分离

近年来 ,在以表面活性剂分子有序组合油包水 (W/O)微乳液体系中进行萃取分离已引起人们的重视 [1～ 3] .本文根据微乳液体系较相应胶束有更低的表面张力和更高增溶量的特性 ,首次利用非离子型水包油 (O/W)壬基酚聚氧乙烯醚(Triton X- 1 0 0 )微乳液在无机盐硫酸铵的存在下萃取分离铁 ,与传统的有机溶剂萃取分离方法比较 ,此法具有不挥发、无毒、快速和操作简单等特点 ;与高聚物水溶液体系萃取 ,有相同的萃取效果 ,但药品用量相对减少 .GBC932 AA原子吸收分光光度计 (澳大利亚 ) ;p Hs- 2 5酸度计 (上海雷磁仪器厂 ) .铝试剂为质量分数 …     

NMR, UV, FT-IR, FT-Raman spectra and molecular structure (monomeric and dimeric structures) investigation of nicotinic acid N-oxide: A combined experimental and theoretical study

In this work, the experimental and theoretical UV, NMR, and vibrational features of nicotinic acid N-oxide (abbreviated as NANO, C(6)H(5)NO(3)) were studied. The ultraviolet (UV) absorption spectrum of studied compound that dissolved in water was examined in the range of 200-800nm. FT-IR and FT-Raman spectra in solid state were observed in the region 4000-400cm(-1) and 3500-50cm(-1), respectively. The (1)H and (13)C NMR spectra in DMSO were recorded. The geometrical parameters, energies and the spectroscopic properties of NANO were obtained for all four conformers from density functional theory (DFT) B3LYP/6-311++G(d,p) basis set calculations. There are four conformers, C(n), n=1-4 for this molecule. The computational results identified the most stable conformer of title molecule as the C1 form. The complete assignments were performed on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. (13)C and (1)H nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by using the gauge-invariant atomic orbital (GIAO) method. The electronic properties, such as excitation energies, absorption wavelengths, HOMO and LUMO energies, were performed by CIS approach. Finally the calculation results were applied to simulate infrared, Raman, and UV spectra of the title compound which show good agreement with observed spectra.     

N,N'-ethylenebis(pyridoxylideneiminato) and N,N'-ethylenebis(pyridoxylaminato): synthesis, characterization, potentiometric, spectroscopic, and DFT studies of their vanadium(IV) and vanadium(V) complexes

The Schiff base N,N'-ethylenebis(pyridoxylideneiminato) (H(2)pyr(2)en, 1) was synthesized by reaction of pyridoxal with ethylenediamine; reduction of H(2)pyr(2)en with NaBH(4) yielded the reduced Schiff base N,N'-ethylenebis(pyridoxylaminato) (H(2)Rpyr(2)en, 2); their crystal structures were determined by X-ray diffraction. The totally protonated forms of 1 and 2 correspond to H(6)L(4+), and all protonation constants were determined by pH-potentiometric and (1)H NMR titrations. Several vanadium(IV) and vanadium(V) complexes of these and other related ligands were prepared and characterized in solution and in the solid state. The X-ray crystal structure of [V(V)O(2)(HRpyr(2)en)] shows the metal in a distorted octahedral geometry, with the ligand coordinated through the N-amine and O-phenolato moieties, with one of the pyridine-N atoms protonated. Crystals of [(V(V)O(2))(2)(pyren)(2)].2 H(2)O were obtained from solutions containing H(2)pyr(2)en and oxovanadium(IV), where Hpyren is the "half" Schiff base of pyridoxal and ethylenediamine. The complexation of V(IV)O(2+) and V(V)O(2) (+) with H(2)pyr(2)en, H(2)Rpyr(2)en and pyridoxamine in aqueous solution were studied by pH-potentiometry, UV/Vis absorption spectrophotometry, as well as by EPR spectroscopy for the V(IV)O systems and (1)H and (51)V NMR spectroscopy for the V(V)O(2) systems. Very significant differences in the metal-binding abilities of the ligands were found. Both 1 and 2 act as tetradentate ligands. H(2)Rpyr(2)en is stable to hydrolysis and several isomers form in solution, namely cis-trans type complexes with V(IV)O, and alpha-cis- and beta-cis-type complexes with V(V)O(2). The pyridinium-N atoms of the pyridoxal rings do not take part in the coordination but are involved in acid-base reactions that affect the number, type, and relative amount of the isomers of the V(IV)O-H(2)Rpyr(2)en and V(V)O(2)-H(2)Rpyr(2)en complexes present in solution. DFT calculations were carried out and support the formation and identification of the isomers detected by EPR or NMR spectroscopy, and the strong equatorial and axial binding of the O-phenolato in V(IV)O and V(V)O(2) complexes. Moreover, the DFT calculations done for the [V(IV)O(H(2)Rpyr(2)en)] system indicate that for almost all complexes the presence of a sixth equatorial or axial H(2)O ligand leads to much more stable compounds.     

聚芳醚腈共聚物的合成与性能

以二卤代苯甲腈，对苯二酚，间苯二酚为原料，制备了几种不同间苯二酚／对苯二酚比的聚芳醚腈树脂。采用流涎成膜法制备了它们的薄膜。对薄膜样品进行了红外光谱分析和热分析，测定了力学性能，在扫描电子显微镜上观察了薄膜拉伸断面。     

Pervaporation separation and mass transport of ethylbutanoate solution by polyether block amide (PEBA) membranes

Dense and composite membranes were developed from polyether block amide (PEBA). Polyacrylonitrile (PAN) and polysulfone (PSf) were used as the porous supports for the composite membranes. The membranes were tested for pervaporation separation of ethylbutanoate (ETB) solutions. Sorption and desorption experiments were also performed to provide data for analysis of mass transport based on resistance-in-series model.

The composite membranes with polyether block amide (PEBA) casted on PSf (PEBA/PSf) showed superior pervaporation performance than that casted on PAN (PEBA/PAN). The analysis of transport resistances revealed that: (1) the resistances in liquid boundary of ETB were highest and, therefore, were the controlling resistances; and (2) the transport resistances in the porous supports were much lower than those in the membrane top layers.

The results on plasticizing coefficients showed that ETB plasticized the membranes (positive, k_ii) but water did not (negative, k_jj). Negative coupling coefficients (k_ij) indicated that water reduced diffusivity of ETB in the membranes and the presence of ETB enhanced water diffusion in the membranes due to positive k_ji.     

Mono and binuclear Ag(I), Cu(II), Zn(II) and Hg(II) complexes of a new azo-azomethine as ligand: synthesis, potentiometric, spectral and thermal studies

New azo-azomethine dyes were prepared by reaction of p-aminobenzoic acid, o-anisidine, o-nitroaniline, and p-bromoaniline with salicylaldehyde respectively to form azo compounds and then condensation by urea to form 4-(R-arylazo 2-salicylaldene)-urea azo-azomethine derivatives (I(a-d)). The complexes of these ligands with Ag(I), Cu(II), Zn(II) and Hg(II) metal ions were prepared. The structure of the free ligands and their complexes were characterized by using elemental analysis (C, H, N), (1)H NMR, IR and UV-Vis-spectra. The proton dissociation constants of the ligands and the stability constant of their complexes have been determined potentiometrically in 40% (v/v) alcohol-water medium as well as the stoichiometry of complexes were determined conductometrically. The data reveal that the stoichiometries for all complexes were prepared in molar ratios (1:1) and (1:2) (M:L). The electrolytic and nonelectrolytic natures of the complexes were assigned based on molar conductance measurements. The thermogravimetric (TG), and differential thermal analyses (DTA) were studied in nitrogen atmosphere with heating rate 10°C/min. The kinetic and thermodynamic parameters for thermal decomposition of complexes have been calculated by graphical method using Coats-Redfern (CR) method.     

Synthesis and Characterization of New Functional Poly(ester-anhydride)s Based on Succinic and Sebacic Acids

Summary: New functional poly(ester-anhydride)s with allyl pendant groups in the side chains were obtained by polycondensation of sebacic acid (SBA) and poly(3-allyloxy-1,2-propylene succinate) (OSAGE) terminated with carboxyl groups. The carboxyl groups in OSAGE and in SBA were converted to mixed anhydride groups by acetylation with acetic anhydride. After that, prepolymers obtained were condensed in vacuum to yield higher molecular weight poly(ester-anhydride)s. The influence of SBA and OSAGE content in poly(ester-anhydride)s on their selected properties e.g. molecular weight, thermal and solubility characteristics as well as degradation rate and mode, were examined. Poly(ester-anhydride)s were degraded in aqueous buffer of pH 7.4 at 37 °C. The hydrolytic degradation was monitored by determination of weight loss of samples and by determination of ester to anhydride groups ratio.     

Quantitative determination of alpha(s2)- and alpha(s1)-casein in goat's milk with different genotypes by capillary electrophoresis

A capillary electrophoresis (CE) method has been applied for the quantitative determination of alpha(s1)- and alpha(s2)-CN in goat's milk. Several analytical parameters were evaluated showing the reliability of this CE method. Coefficients of determination (R2) greater than 99% were obtained and determination limits of 1.23 and 0.98 mg/ml were achieved for alpha(s1)- and alpha(s2)-CN, respectively. The analytical parameters studied in terms of accuracy, precision and recovery were within acceptable limits. Among 18 samples of 4 different genotypes (BB, EE, BF and FF) for alpha(s1)-CN were analysed, different amounts were obtained from the genotypes.