一种席夫碱凝胶因子的制备及凝胶化研究

合成并表征了一种可自组装的Schiff碱凝胶因子(gelator)N,N-′(1,4-苯基二亚甲基叶立德)-二[3,4,5-三(十二烷氧基)苯胺](简称PBBA);研究了该凝胶因子在一些有机溶剂中凝胶化性能;用傅里叶变换红外光谱(FT-IR)、X射线衍射(XRD)、扫描电镜(SEM)等分析方法对凝胶进行了表征;研究了不同浓度的凝胶因子对溶胶-凝胶以及凝胶-溶胶转变温度的影响.研究表明该凝胶因子是通过范德华力,π-π堆积等次价键的作用而聚集自组装成三维网状结构,再与溶剂相互作用形成凝胶的.     

氨基葡萄糖Schiff碱及其锌金属配合物的合成

以氨基葡萄糖硫酸盐为原料,分别与苯甲醛、水杨醛反应合成Schiff碱,设定不同的温度、反应时间、投料比,采用正交实验找到较优化的反应条件.再分别用2种Schiff碱和七水硫酸锌反应,考虑物料比这个单因素,合成Schiff碱锌配合物.结果表明,在反应温度45℃,反应时间5 h,反应物投料比1:2时,苯甲醛和氨基葡萄糖形成的Schiff碱收率为42.81%,水杨醛和氨基葡萄糖形成的Schiff碱收率为74.01%.在物料比为1:2时,苯甲醛Schiff碱合成的锌配合物收率较高,达到53.49%,水杨醛Schiff碱合成的锌配合物收率达到80.00%.     

基于单吡咯并四硫富瓦烯的稳定电荷转移盐凝胶的构筑

设计合成了一种含有冠醚和L-谷氨酰胺基团的单吡咯并四硫富瓦烯三元低分子量凝胶因子.实验表明,本体凝胶在引入无机氧化剂的情况下可以转变为稳定的电荷转移盐凝胶.进一步研究表明,分子间氢键、π-π堆积、S…S相互作用和电荷转移相互作用是形成有机凝胶的主要驱动力.凝胶在外界刺激作用下呈现可逆的宏观相态变化,电荷转移盐凝胶可以可逆转化为原始的凝胶体系;在四氢呋喃中形成的本体凝胶对水非常敏感,少量水的加入即可导致凝胶迅速坍塌.该研究为构筑功能性软材料提供了新的研究思路.     

噻吩-2-甲醛缩苯肼Schiff碱及金属配合物的合成与性质

以噻吩-2-甲醛与苯肼为原料,通过回流缩合形成Schiff碱,并进一步与锌(Ⅱ)和镍(Ⅱ)金属离子配位得到2种金属配合物.结果表明,合成的噻吩-2-甲醛缩苯肼Schiff碱的结构与理论结构相符,且分别与锌(Ⅱ)和镍(Ⅱ)离子配位形成了稳定的金属配合物.抗菌实验结果显示Schiff碱及其金属配合物均有一定的抗菌活性,且Schiff碱金属配合物的抗菌活性更好.     

基于赖氨酸环二肽水凝胶因子的合成与凝胶化研究

在严格控制投料比的条件下,赖氨酸环二肽与Fmoc-OSu反应首先得到Fmoc单取代赖氨酸环二肽,进而再与环酸酐发生酰胺化反应得到一类具有热可逆性的小分子水凝胶因子.SEM和TEM显示凝胶因子在水中自组装成直径纤细的微纳米纤维结构,相互紧密缠绕形成三维网络结构;红外和荧光光谱分析表明在水凝胶形成的过程中π-π堆积和氢键共同发挥驱动力的作用.根据XRD测试结果,采用Rietveld法全谱图拟合精修得到了FL-Ga水凝胶干胶的晶体结构模型,表明凝胶因子以单分子层方式进行聚集.      

水溶型CdSe量子点的制备及与Schiff碱的相互作用拆分头孢氨苄对映体

以绿色无毒、生物相容性好的羧甲基纤维素钠为稳定剂,通过简单的过程成功地在水相中制备了CdSe量子点(QDs).用TEM、XRD、XPS表征的结果表明：所制备的CdSe量子点近似于单分散,平均粒径为2.1 nm. UV-Vis和荧光 (PL) 光谱表明：控制反应物Se前躯体的量可有效调控量子点粒径,实现量子点在480～560 nm荧光可调,且量子点具有窄且对称的荧光光谱.量子点与Schiff碱相互作用表明：Schiff碱在一定范围内能有效增强量子点荧光,过量的Schiff碱却能淬灭量子点的荧光.     

Schiff碱N-氧化吡啶-2-甲醛缩α-氨基苯乙酮的合成及其晶体结构

合成Schiff碱N-氧化吡啶-2-甲醛缩α-氨基苯乙酮并获得其单晶结构.用UV-Vis和IR谱进行表征.其分子式为:C14H12N2O2,Mr=241.26,晶体属于单斜晶系,空间群P21/n,晶胞参数:a=0.81496(11)nm,b=1.556 20(2)nm,c=0.954 60(14)nm,β=105.607(3)°,V=1.16600(3)nm3,Z=4,Dc=1.374 g/cm3,μ=0.094mm-1,F(000)=508,结构偏离因子R1=0.0734,wR2=0.2256.X-射线分析显示Schiff碱的晶体结构是由d…π和π…π相互作用堆积而成的三维结构.     

偶氮苯水杨醛Schiff碱及金属配合物的合成与抗菌活性

以水杨醛与苯胺为原料合成偶氮苯水杨醛,并进一步与邻氨基苯酚反应生成了相应的Schiff碱,Schiff碱再与锌(Ⅱ)、锰(Ⅱ)、铁(Ⅱ)三种金属离子络合得到三种金属配合物;采用元素分析、电导率测定、紫外光谱和红外拉曼光谱对Schiff碱及其金属配合物的结构进行表征.结果表明:合成的偶氮苯水杨醛缩邻氨基苯酚配体的结构与理论结构相符,且分别与锌(Ⅱ)、锰(Ⅱ)、铁(Ⅱ)离子配位形成了稳定的金属配合物.对配体及其配合物进行了抗菌活性测试,结果表明配合物的抗菌活性强于Schiff碱配体.     

Cu(Ⅱ)-邻-N-水杨醛烯基苯酚配合物的结构和荧光性质

以合成的邻-N-水杨醛烯基苯酚和咪唑为配体,与Cu( )离子自组装形成配合物Cu(C13H9NO2)(C3H4N2).X-射线单晶衍射表明,配合物晶体属正交晶系,空间群为Pca21,晶胞参数:a=0.93944(1.4)nm,b=1.7579(0.3)nm,c=1.8261(0.3)nm,V=3.0158(8)nm3,Mr=342.84,Z=4,ρcalc=1.510mg/m3,R1=0.0641,wR2=0.1357.在配合物结构中,三齿Schiff碱配体中的两个氧原子、一个氮原子和咪唑的一个氮原子分别与铜( )离子配位,形成扭曲的平面正方形结构.配合物分子通过π-π堆积作用形成三维堆积超分子结构.晶体的荧光光谱表明,配体共轭体系在配位后扩大了共轭面,从而使波长红移,刚性面的增加使荧光强度增强.     

金刚烷胺缩3,5-二溴水杨醛Schiff碱的合成、表征及抗菌活性研究

首先用NaOH的乙醇溶液处理金刚烷胺盐酸盐,得到金刚烷胺.金刚烷胺再与3,5-二溴水杨醛脱水生成金刚烷胺缩3,5-二溴水杨醛Schiff碱(IUPAC命名:N-3,5-二溴亚水杨醛基金刚烷胺,以下简称Schiff碱).Schiff碱用元素分析、红外光谱、核磁共振氢谱等手段进行了表征.测试了四个不同浓度的Schiff碱对金黄色葡萄球菌及大肠杆菌抗菌作用.试验结果表明,当Schiff碱溶液浓度为1.0×10-1mo1.L-1时对金黄色葡萄球菌表现出较强的抑菌作用,当浓度为1.0×10-4mo1.L-1时,表现出较弱的抑菌作用;四个不同浓度Schiff碱对大肠杆菌没有抑菌作用.     

脱氢枞胺-取代水杨醛Schiff碱的电喷雾串联质谱研究

 采用电喷雾电离串联质谱技术对7种最新合成的脱氢枞胺-取代水杨醛Schiff碱(DASSSB)样品进行了研究。结果显示,这些化合物的ESI-MS/MS裂解方式与它们分子中水杨醛苯环上取代基的性质和位置有关：当水杨醛苯环上4位连接供电子取代基时,分子以C=N双键断裂为主,生成 ［M+H-283］⁺ 碎片离子;当水杨醛苯环上5位连接吸电子取代基时,分子以C=N双键β位的C-C键发生断裂为主,生成 ［M+H-254］⁺ 碎片离子。DASSSB二级质谱产生的特征子离子可作为对此类化合物进行定性定量分析的依据。     

MCM-41固载席夫碱钴配合物在环己烷氧化反应中的应用

制备γ-氨丙基三乙氧基硅烷修饰的MCM-41分子筛固载型双水杨醛缩乙二胺合钴(Cosalen)配合物,采用傅里叶变换红外光谱、X线衍射、比表面积测定、热重-差热(TG-DSC)、紫外-可见光光谱(UV-Vis)、透射电镜等方法对分子筛固载型配合物Cosalen/MCM-41的结构进行表征,并对比Cosalen/MCM-41与Cosalen/NaY的催化性能。研究结果表明:Cosalen已进入分子筛孔道内;在以氧气为氧源的环己烷氧化反应中,Cosalen/MCM-41催化剂具有较好的活性和对环己醇、环已酮的选择性。该催化反应产物中环已基过氧化氢(CHHP)的量很少,表明Cosalen/MCM-41催化剂能加速环已基过氧化氢的分解;以Cosalen/MCM-41为催化剂,在初始氧气压力为0.80 MPa,温度为130℃,环己烷与催化剂的质量比为100,叔丁基过氧化氢0.06 g的相对温和条件下反应2 h,环己烷的转化率达到5.96%,醇酮选择性87.03%。     

水杨醛邻氨基苯酚Schiff碱及其配合物的合成与表征

合成了水杨醛邻氨基苯酚希夫碱配体及其与 Cd( SCN) 2 ,Zn( SCN) 2 ,Mn( SCN) 2 形成的配合物 ,用红外光谱、紫外光谱对配体及配合物的结构进行了表征     

Micro-arc oxidization fabrication and ethanol sensing performance of Fe-doped TiO<Subscript>2</Subscript> thin films

In-situ pure TiO₂ and Fe-doped TiO₂ thin films were synthesized on Ti plates via the micro-arc oxidation (MAO) technique. The as-fabricated anatase TiO₂ thin film-based conductometric sensors were employed to measure the gas sensitivity to ethanol. The results showed that Fe ions could be easily introduced into the MAO-TiO₂ thin films by adding precursor K₄(FeCN)₆·3H₂O into the Na₃PO₄ electrolyte. The amount of doped Fe ions increased almost linearly with the concentration of K₄(FeCN)₆·3H₂O increasing, eventually affecting the ethanol sensing performances of TiO₂ thin films. It was found that the enhanced sensor signals obtained had an optimal concentration of Fe dopant (1.28at%), by which the maximal gas sensor signal to 1000 ppm ethanol was estimated to be 7.91 at 275°C. The response time was generally reduced by doped Fe ions, which could be ascribed to the increase of oxygen vacancies caused by Fe³⁺ substituting for Ti⁴⁺.     

席夫碱自组装膜对铜缓蚀性能的研究

合成了双水杨醛缩邻苯二胺席夫碱,在铜片表面制备了席夫碱的自组装分子膜.利用电化学工作站分析了席夫碱自组装膜对铜片的缓蚀效果,利用金相显微镜观察1 mol/L HCl腐蚀后铜片表面形貌.结果表明:双水杨醛缩邻苯二胺席夫碱对铜有一定的缓蚀效果,自组装膜在1 mol/L的盐酸溶液中缓蚀效率达到85.3％.自组装膜的缓蚀效率与浓度有关,浓度高的自组装膜对铜片的缓蚀作用明显高于低浓度的自组装膜.     

超临界CO2/水交替微观驱油特征研究

针对水气交替驱过程中CO_2与水能否接触、对剩余油动用能力等热点问题,利用高温高压微观可视模型,研究了不同密度CO_2驱后剩余油分布类型及挖潜对策,描述了水气交替微观封堵特征及对剩余油动用能力。实验结果表明,超临界CO_2的高密度特性,可扩大CO_2向油藏中下部的扩散运移;CO_2驱后剩余油以油膜类、盲端类、等势点类、未波及区域为主,其中等势点及未波及区域是下步挖潜主要对象;水气交替的注水阶段与注气阶段呈现出不同的贾敏效应,其中注气阶段贾敏效应明显;水气交替可显著改善等势点类剩余油,但未波及区域动用程度不高。     

The interaction of GSSG modified magnetic nanoparticles with SPC-A1 cells in vitro

Magnetic nanoparticles(MNPs) are promising materials for various biomedical applications,including magnetic resonance imaging,stem cell tracking,gene/drug delivery,and cancer treatment.To increase the effectiveness of MNPs,high capture efficiency and controlled uptake of the particles by cells is required.In this paper we report the cytotoxicity and cellular uptake into SPC-A1 cells of oxidized glutathione(GSSG)-modified MNPs(GSSG@Fe3O4).Experimental findings indicated that GSSG@Fe3O4 were biocompatible,and could be efficiently taken up by SPC-A1 cells(up to 160 pg iron per cell).The internalized GSSG@Fe3O4 was retained in the cell cytoplasm for 6 generations.The uptake of GSSG@Fe3O4 into SPC-A1 cells was energy-,concentration-and time-dependent.Pinocytosis may be involved in the internalization process of GSSG@Fe3O4 into SPC-A1 cells,but this mechanism remains to be elucidated.The controlled and efficient localization of GSSG@Fe3O4 into the cytosol and long intracellular retention provides theoretical and experimental insight into the biomedical applications for these molecules.     

土壤农杆菌C58遗传转化东北红豆杉的初步研究

This paper demonstrates that callus of Taxus cuspidata could be transformed genetically by Agrobacterium tumefaciens C₅₈ and the bacterial genes transformed into the plant genome could express. Explants and calli of T.cuspidata were inoculated with C₅₈ for different time and the highest crown gall formation frequency (15.0%) was achieved with 20-day-old callus inoculated for 5 minutes. Explants were less susceptibility than calli. In contrast to untransformed callus tissue, the crown gall could proliferate on hormone-free medium and produced nopaline. By HPLC analysis, gall cells were able to synthesize taxol (0.0013% dry weight.)     

波流环境下双孔浮射流运动特性

利用粒子图像测速技术(PIV)对波流环境下双孔浮射流的速度场进行测量,对不同组次的相位平均速度场、时均速度场进行定性描述;通过引入考虑横流、波浪、浮力影响的综合特征长度l_(mb),给出了轴线垂向速度衰减过程分区的定量结果。研究表明,波流作用下会产生污染物云团现象,加快双孔射流速度衰减;波浪的作用能够减弱孔间相互影响;浮力的作用能够减小射流体偏转角度和侧向展宽;无量纲的轴线垂向速度变化可以分为近区(z/l_(mb)3)、过渡区(3z/l_(mb)6)、远区(z/l_(mb)6)3个区段。     

Optimization of mechanical properties of Sn-3.8Ag-0.7Cu alloys by the additions of Bi,In and Ti

Bi, In and Ti were added to Sn-3.8Ag-0.7Cu (SAC387) solder alloy to optimize the mechanical performance. The alloying effects of Bi, In and Ti on the microstructure, thermal and mechanical properties of SAC387 based solder alloys were investigated. The results demonstrate that adding 3.5 ?wt % of Bi could refine the microstructure, optimize the thermal properties, and improve the tensile strength. Meanwhile, the ductility of the solder alloys reduced evidently. Adding 2.8 ?wt % of In into SAC387–3.5 ?wt %Bi alloy could increase both the strength and ductility, which is attributed to the beneficial effect of In addition, as adding In could improve the solubility of Bi in the β-Sn matrix. Meanwhile, the melting point was reduced, and the wettability improved with the addition of In. Introducing amounts of Ti into SAC387–3.5 ?wt % Bi-2.8 ?wt % In alloy could further increase the strength. However, the ductility was significantly reduced when 0.8 ?wt % of Ti was added due to the formation of the coarse Ti₂Sn₃ phase. The undercooling was remarkably reduced with the addition of Ti. The nanoindentation tests demonstrate that the hardness increased mainly due to the hardening effect of the Bi addition. Among all the samples prepared, alloy SAC387–3.5 ?wt % Bi exhibited the highest creep resistance at the ambient temperature. Further adding In and Ti into SAC387–3.5 ?wt % Bi alloys reduced the creep resistance of the solder alloys. The mechanism associated with the different mechanical responses is also discussed in this study.