木材溶液中羟基与异氰酸酯反应的研究

以涂料工业广泛应用的新型助剂二元酸酯 (DBE)为液化试剂 ,盐酸为催化剂 ,将苯甲基化木材溶液化后 ,与不同结构的异氰酸酯反应 .利用FT IR及1 3C NMR分析液化苯甲基木质纤维素与不同结构异氰酸酯得到了聚氨酯树脂 ,证明了木材中羟基可以用来作为聚醚多元醇与异氰酸酯制备聚氨酯材料 .通过准确测量体系中游离的NCO含量 ,从而得出不同结构异氰酸酯与木材溶液中羟基的反应规律 .实验结果表明 ,异氰酸酯的存在大大促进了木材结构中羟基的释放 ,由于不同异氰酸酯的活性不同 ,使得羟基值变化亦不相同 ,其顺序为IPDI>HDI>TDI .为了保证最终的材料性能 ,选择TDI和IPDI作为木材溶液制备聚氨酯树脂的异氰酸酯组份较好     

三苯基锡(Ⅳ)荒酸盐Ph3SnS2CN(C2H5)2的波谱及结构研究

合成了三苯基锡(Ⅳ)Ⅳ，Ⅳ-二乙基荒酸盐。通过元素分析、红外光谱和核磁共振氢谱对其结构进行了表征。用X-射线单晶衍射测定了该化合物的晶体结构；结果表明，化合物中锡原子呈五配位畸变三角双锥构型。     

Synthesis and Crystal Structure of (CH2)3(3, 5-Me2Pz)2·[PhBr2Sn(CH2)SnBr2Ph]·2HBr·2H2O (Pz = pyrazole)

The reaction of bis(dibromophenylstannyl)methane with 1, 3-bis(3, 5-dimethyl- pyrazol-1-yl)propane in a 1:1 or 1:2 ratio yields only 1:1 adduct which partly hydrolyzes to the title complex (C26H38Br6N4O2Sn2, Mr = 1155.42) during crystal growing. The title complex is of triclinic, space group P ī with a = 10.886(1), b = 12.508(1), c = 13.879(1) ?, α = 85.762(2), β = 85.159(2), γ = 84.020(2)°, V = 1868.8(4) ?3, Z = 2, Dc = 2.046 g/cm3, λ(MoKα) = 0.71073 ?, μ = 7.778 mm-1, F(000) = 1088, R = 0.0488 and wR = 0.1157 for 7560 observed reflections with I ≥ 2σ(I). The crystal structure analysis indicates that there is no direct interaction between the ligand and bis(dibromophenylstannyl)methane, and two tin atoms are bridged by two bromide atoms from the partial hydrolysis of this adduct.     

功能化离子液体液化木粉及其酚醛复合材料

合成了氯代1-(2-羟乙基)-3-甲基咪唑离子液体[He MIM]Cl、溴代1-乙胺基-3-甲基咪唑离子液体[Ae MIM]Br和氯代1-羧乙基-3-甲基咪唑离子液体[Ce MIM]Cl 3种功能化咪唑离子液体,并分别进行了红外与氢核磁结构表征.然后用3种离子液体液化木粉,液化3 h后向体系直接加入苯酚、甲醛和氢氧化钠,制备酚醛复合材料,并采用FTIR、XRD、DSC和SEM对酚醛复合材料进行结构、性能与形貌测试,研究离子液体种类对木粉液化率及酚醛树脂性能的影响.结果表明,离子液体及其液化木粉产物制备的酚醛复合材料性能得到明显改善.[Ce MIM]Cl液化效果最好,90℃液化率高达24.6%,当[Ce MIM]Cl与木粉质量比为10∶1时,制备的酚醛复合材料的游离醛释放量由原来的3.64%降低到0.92%.离子液体[Ae MIM]Br能将酚醛复合材料的冲击强度由原来的0.93 k J/m2提高到6.96 k J/m2,而[Ae MIM]Br及其液化的木粉产物制备的酚醛复合材料拉伸强度从原来的3.28 MPa提高到9.70 MPa.     

中药柴胡总皂苷急性肝毒性的代谢组学研究

运用UPLC-MS联用技术对空白对照组、柴胡总皂苷(SS)组大鼠在给药后第3天和第5天的尿液样本进行分析检测,获得了以质荷比和保留时间为变量的矩阵数据。据此建立各组大鼠的尿液代谢轮廓图,并利用主成分分析(PCA)建立了SS的代谢组学毒性模型。结合肝组织病理,探讨了柴胡总皂苷的急性肝毒性。对于SS组与正常组,大鼠尿液代谢轮廓图表现出了一定的差异。在代谢组学毒性模型中,给药第3天和第5天的PCA分类均偏离正常组,而第5天的偏离程度强于第3天。同时,在第5天的肝组织病理切片中发现了组织病变。由此表明,给药组大鼠的代谢组偏离了正常组,这种偏离正是肝急性毒性的表现,且给药到第5天的肝毒性强于第3天,表明肝毒性与给药累积剂量呈正相关,表现出了明显的急性和累积肝毒性。     

Syntheses and Crystal Structures of Two Tin(Ⅳ) Complexes with Aminosilane Bearing Ligand

Aminosilane bearing bulky substituents on nitrogen: LH2(L=Me2Si(NDipp-)2 , Dipp=2,6-diisopropylphenyl) was reacted with BuLi in toluene. The resulting bulky chelating dianion Me2Si(NDipp-)2 was used to synthesize the unusual spirocyclic heterotriatomic complex [Me2Si(NDipp)2]2Sn (1) by its reaction with SnCl4 and the bulky heterotriatomic complex Me2Si(NDipp)2SnPh2 (2) with Ph2SnCl2.1 belongs to the monoclinic system, space group P21/n with a=13.193(2), b=20.663(3), c=20.403(3), β=99.954(2)o, V=5478.3(15)3 , C55H85.5N4Si2Sn, Mr=977.64, Z=4, Dc=1.185Mg/m3 , μ(MoKα)=0.547mm-1 , F(000)=2086, S=1.000, the final R=0.0614 and wR=0.1322 for 14446 observed reflections (I2σ(I)) and R=0.0797 and wR=0.1456 for all data. 2 belongs to the triclinic system, space group Pī with a=10.36(15), b=13.204(7), c=14.363(7), α=90.214(10), β=106.182(7), γ=109.854(8)o, V=1764.4(15)3 , C38H50N2SiSn, Mr=681.58, Z=2, Dc=1.283 Mg/m3 , μ(MoKα)=0.785 mm-1 , F(000)=712, S=1.002, the final R=0.0498 and wR=0.0955 for 7533 observed reflections (I2σ(I)) and R=0.0676 and wR=0.1018 for all data. In the structure of 1, the tin atom is located in the spirocyclic center of the two fused four-membered SnN 2 Si rings. The two complexes were characterized by 1H NMR, elemental analysis, and single-crystal X-ray structural analysis.     

柱切换液相色谱法快速定量检测参附注射液中乌头碱类生物碱和人参皂苷

利用柱切换液相色谱,建立了参附注射液中苯甲酰新乌头原碱、苯甲酰乌头原碱、苯甲酰次乌头原碱、新乌头碱、次乌头碱和乌头碱6种乌头碱类生物碱,以及Rg1、Re、Rf、Rb1、Rc、Ro、Rb2、Rb3、Rd 9种人参皂苷的分析方法。首先利用强阳离子交换的在线固相小柱选择性富集和净化样品中生物碱类成分,优化了色谱条件;并采用EC－C18柱作为人参皂苷的分析柱,通过优化实验条件,结合柱切换方式,去除了样品中辅料等大极性基质成分对色谱柱的污染,实现了生物碱分析和人参皂苷分析的自动切换。结果显示,样品中的生物碱和人参皂苷分离良好,线性相关系数（r2）均大于0.999,连续进样精密度的相对标准偏差（RSD） < 2.0%,重复性的RSD < 2.0%;其中6种生物碱的平均回收率为95.1%～98.6%,检出限为4.0～8.2 ng/mL;9种人参皂苷的平均回收率为91.7%～104%。所构建的基于柱切换液相色谱技术的在线固相萃取方法能够有效去除样品中的基质干扰,快速完成参附注射液中3种单酯型生物碱和9种人参皂苷的快速定量,同时也可对3种双酯型生物碱进行限量检测,可应用于药物的质量评价。     

应用2D NMR技术研究罗汉果醇及其苷的结构

从传统中药罗汉果中分离得到一系列三萜皂苷类化合物,其苷元为罗汉果醇,应用1D和2D NMR脉冲梯度场反相技术(gCOSY,gNOESY,gHMQC,gHMBC) 研究了罗汉果醇及其苷的结构,对其碳氢NMR信号进行了全归属,应用gNOESY技术研究了罗汉果醇的立体构型,并探讨了取代基对苷元质子和碳化学位移的影响.     

加速溶剂萃取法提取中药材中黄芪甲苷

采用加速溶剂萃取仪(ASE)以甲醇为溶剂提取黄芪药材中的黄芪甲苷,利用高效液相色谱-蒸发光散射检测器(HPLC-ELSD)进行含量测定.考察了不同的提取温度、提取时间、循环次数等条件下的提取效果,确定了最佳的ASE提取条件.同传统的提取方法相比,ASE法溶剂用量少,耗时短,提取效率高.并通过回收率和精密度的测定,证明加速溶剂萃取技术完全可以用于中药材中的黄芪甲苷的提取.     

Ethylene polymerization with novel phenoxy-imine catalysts bearing 4-vinylphenyl group

This contribution reports ethylene polymerization behavior of titanium complexes incorporating bis(phenoxyimine) ligands. Six phenoxy-imine Ti(IV) complexes {6-R1-2-[CH=N(2,6-difluoro-3,5-diR2-4-R3Ph)]C6H3O}2TiCl2(1: R1 = H, R2 = H, R3 = H; 2: R1 = H, R2 = H, R3 = 4-vinylphenyl; 3: R1 = CH3, R2 = H, R3 = H; 4: R1 = CH3, R2 = H, R3 = 4-vinylphenyl; 5: R1 = CH3, R2 = F, R3 = H; 6: R1 = CH3, R2 = F, R3 = 4-vinylphenyl) have been synthesized and evaluated for ethylene polymerization using dried MAO(simplified as DMAO) as cocatalyst. An obvious catalytic heterogeneity of Cat 2(Complex 2/DMAO) towards ethylene polymerization was observed, which was illustrated by decreased activity, multimodal molecular weight distribution and partially improved particle morphology comparing with Cat 1. Moreover, Cat 3 exhibits "living" characteristics in the process under certain conditions(25 °C, less than 20 min). Otherwise, the moderate to high ethylene polymerization activity of ca. 105-106 g PE/(mol Ti·h) and high molecular weight(Mw = 105-106) of polyethylene can be obtained by changing the skeleton structure of these complexes.