Fe3O4/TiO2 纳米材料靶上脱盐的基质辅助激光解析/电离质谱新方法研究

建立了一种简便、高效的靶上脱盐新方法。利用Fe3O4/TiO2磁性纳米材料对肽段的吸附作用,将其作为载体用于靶上肽段富集和脱盐。在对纳米材料使用量、浸洗条件进行优化的基础上,成功地鉴定了溶于10mol/L尿素溶液的100fmol的肌红蛋白样品,也对溶于3mol/L尿素溶液中的10fmol的肌红蛋白样品进行了成功地分析鉴定。通过对肌红蛋白样品进行预处理和质谱分析重复实验,表明该方法重现性好,且简便、高效,所需时间短,一次可同时处理多个样品,易于实现通量化,为有效地解决目前蛋白质组分析中所面临的基质辅助激光解析/离子化飞行时间质谱耐盐性差的问题提供了一种新的手段。     

3-氨基-二氢噻吩-2-酮类Schiff碱的合成和生物活性研究

通过3-氨基-二氢噻吩-2-酮(DL-高半胱氨酸硫内酯)盐酸盐与取代苯甲醛反应, 得到3-氨基-二氢噻吩-2-酮类Schiff碱. 合成了9个化合物, 其中7个为首次报道的新Schiff碱类化合物. 化合物结构经IR, ¹H NMR和元素分析证实, 并对这些化合物进行了室内毒力测试, 结果表明此类化合物具有很好的杀菌、抑菌活性.     

纯水中金属钕诱发芳香醛烯丙基化反应的研究

在Nd-SnCl₂-H₂O体系中, 用烯丙基溴超声诱发下进行了一系列芳香醛的烯丙基反应, 室温反应50～60 min得76%～93%烯丙基化产物; 而不用超声波时同样体系中搅拌3～4 h高烯丙基醇产率为30%～86%. 该方法时间短、产率高、环境友好.     

Synthesis, Crystal Structure and Bioactivities of 1-（4-Chlorophenyl）-3- [ 5-（pyrid-4-yl）- 1,3,4-thiadiazol-2-yl] urea

The title compound 1-(4-chlorophenyl)-3-[5-(pyrid-4-yl)-1,3,4-thiadiazol-2-yl]urea (C14H10ClN5OS, Mr = 331.79) has been synthesized by the reaction of 2-amino-5-(pyrid-4-yl)- 1,3,4-thiadiazole with 4-chlorobenzoyl azide, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to triclinic system, space group P with a = 5.8550(8), b = 7.5668(10), c = 16.416(2) , α = 78.364(2), β = 81.204(2), γ = 84.749(2)°, V = 702.58(16) 3, Z = 2, Dc = 1.568 g/cm3, μ = 0.429 mm-1, F(000) = 340, the final R = 0.0442 and wR = 0.1092 for 2001 observed reflections (I > 2σ(I)). X-ray diffraction analysis reveals that the title molecule is nearly planar. In the crystal structure, the molecules are linked by strong intermolecular N-H…N hydrogen bonds together with weak nonclassical intermolecular (C-H…Y, Y = N, O and Cl) hydrogen bonds and stacked through π-π interactions. The preliminary bioassay shows that the title compound exhibits good fungicidal activities against Rhizoctonia solani, Botrytis cinerea and Dothiorella gregaria.     

Synthesis, Crystal Structure and Electrochemistry Properties of a (N,N'-Ethylene-bis(salicylaldiminato)) Nickel(Ⅱ) Complex, [Ni2(salen)2]·NCS-NH4

A new Ni(Ⅱ) complex [Ni2(salen)2]·(NCS)·NH4 (salen = N,N'-bis(salicylidenea-mino)ethanato) has been prepared and structurally characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. It crystallizes in the orthorhombic system, space group Pbca with a = 16.8725(13), b = 19.0046(15), c = 20.0583(16) (A), Z = 8, V = 6431.8(9) (A)3, C33H32N6Ni2O4S1, Mr= 726.13, Dc = 1.500 g/cm3, F(000) = 3008, μ = 1.284 mm-1, the final R = 0.0394 and wR = 0.0767 for 4449 observed reflections with Ⅰ＞2σ(Ⅰ). The complex involves a N,N'-ethylene-bis(salicylaldiminato) Schiff base, an isothiocyanato anion and an ammonium cation. The nickle(Ⅱ) ion adopts a distorted square coordination geometry with N2O2 set of Schiff base ligand. The complexes are linked into a dimmer via intermolecular hydrogen bonds and the [Ni(salen)] moieties are connected together to form a 2-D layer structure by intermolecular N-H…O hydrogen bonds and π-π stacking. Cyclic-voltammetry method was used to characterize electrochemically the complex.     

电化学氢化物发生-原子吸收光谱法测定不同价态的无机砷

不同价态的无机砷在玻碳电极上具有较高的电化学氢化物发生效率,同时又存在较为明显的差异。通过选择不同的电流条件,采用电化学氢化物发生与原子吸收光谱联用技术有效地实现了无机砷的形态分析。对试验参数和干扰情况进行了研究。As(Ⅲ)和As(Ⅴ)检出限分别为0.2μg.L-1和0.4μg.L-1;对砷量为20μg.L-1的条件下作了方法的精密度试验,测定结果的相对标准偏差(n=6)对As(Ⅲ)为1.9%和对As(Ⅴ)为3.1%。应用此方法分析了人发标准物质(GBW 09101),测得总砷量与证书值相符。     

表面活性离子液体溴化N-十二烷基异喹啉与非离子表面活性剂Triton X-100在水溶液中的混合胶束

用等温滴定微量热法测定表面活性离子液体溴化N-十二烷基异喹啉([C₁₂iQuin]Br)与非离子表面活性剂Triton X-100混合物在水溶液中的临界胶束浓度。并以¹H核磁共振(NMR)和二维核Overhauser效应增强谱(2D NOESY)研究[C₁₂iQuin]Br与Triton X-100在混合胶束中的作用机理。研究结果显示：混合胶束中,Triton X-100分子的苯环定位于混合胶束的内核,聚氧乙烯链卷曲在异喹啉环周围。本文还应用规则溶液理论和浊点法对比研究了十二烷基三甲基溴化铵(DTAB)-Triton X-100混合胶束体系的相关性质。     

包覆重钙粉为填充剂的橡胶加工及性能

重钙粉作为填充剂被广泛应用于橡胶加工过程,但由于其表面具有极性,分散性较差,导致与橡胶材料界面结合较差,影响了橡胶产品的抗拉强度、断裂伸长率等力学性能。 本文采用沉淀法,在CaCl₂-H₂O-NH₃-CO₂体系中生成碳酸钙直接结晶于重钙粉颗粒表面,实现对重钙粉的表面包覆,将n(CaCl₂)：n(重钙粉)=1：100、5：100、10：100的包覆重钙粉填充到天然橡胶和再生胶中,橡胶的力学性能与填充未包覆重钙粉的橡胶相比有了一定的提升。 通过比较,在填充量较大(8.5%、15%)时,包覆重钙粉橡胶产品在硬度、定伸应力等力学性能上要好于轻钙粉橡胶产品;在填充量(5%、8.5%)时,包覆重钙粉橡胶产品的抗拉强度、断裂伸长率接近于白炭黑,硬度高于白炭黑橡胶产品。     

Pentamethylcyclopentadienylrhodium(III) and -iridium(III) Complexes Showing P,O Coordination: Unprecedented Insertion of tcne and tcnq into a C−H Bond

Strongly electron withdrawing cyanoolefins tetracyanoethylene (tcne) and 7,7,8,8-tetracyano-p-quinodimethane (tcnq) react with [(η⁵-C₅Me₅)MCl(MDMPP-P,O)] (M=Rh, Ir; MDMPP-P,O=PPh₂(2-O-6-MeO-C₆H₃), a P,O chelating phosphane) by insertion into the C−H bond adjacent to the M−O σ bond. The crystal structure of the iridium complex formed upon insertion of tcne is shown.