联接基长度对Gemini表面活性剂流变性质的影响

用毛细管振荡剪切流动法研究了联接基团为聚亚甲基链的阳离子Gemini表面活性剂的流变性质。实验结果表明,无论是普通单链单头基或Gemini表面活性剂,其流变性质主要由胶团的大小和形状所决定;随着联接基团长度的增加,胶团的轴比率变小,导致流动阻力减小,粘度降低。此外对于球形和棒状胶团溶液,其流变性质主要以粘性为主．弹性可忽略不计。在低剪切速率下,溶液属于牛顿型流体;而在高剪切速率下,则表现出准塑性流体性质。     

交联聚丙烯酰胺微球的形状与大小及封堵特性研究

采用流变、扫描电镜(SEM)、动态光散射(DLS)、核孔膜过滤和填充砂管驱替实验,研究了纳米级水溶胀交联聚丙烯酰胺微球的性能.结果表明,在一定的剪切速率范围内,微球浓度为100～900 mg/L的分散体系的黏度随剪切速率增加而增大,表现出较明显的剪切增稠的胀流体特性,微球浓度为50 mg/L的分散体系的黏度随着剪切速率...     

两种联接链的季铵盐Gemini表面活性剂水溶液流变行为

季铵盐Gemini表面活性剂C12-s-C12•2Br(s=2)水溶液在25 ℃,3～9 mmol•kg－1和10～40 mmol•kg－1两个浓度范围区受剪切速率γ影响不同,前者在γ=0～1875 s－1内均为牛顿型,后者在各自临界剪切速率γ*之后由牛顿型转变为膨胀型,且零剪切粘度η0随浓度c急剧增大,这是由于溶液中的线状胶团相互缠绕所致.当在联接链中增加乙氧基（C12-s-En-C12•2Br, s=2, n=1、2、3）,由于单元分子几何形状发生明显变化,只生成球状胶团,使其在c=3～120 mmol•kg－1和γ=0～1 875 s－1范围内始终表现为牛顿型,η0仅随c和γ略为增大.降低温度有利于剪切力诱导流型转变,但若在一段温度范围内溶液始终保持牛顿型,温度对η0影响很小.     

漆酚基乳化剂对水包油型生漆乳液流变行为的影响

以漆酚基乳化剂(UE)和聚乙烯醇(PVA)为混合乳化剂制备了水包油(O/W)型生漆乳液(RLE),用RHEOMETER(R/S)对RLE的流变性进行了研究.讨论了UE10浓度(cUE10)、混合乳化剂浓度(cME)、UE的结构对RLE流变性的影响.结果表明,RLE的黏度随着cUE10的增加而增大,用不同cUE10制备的RLE都有剪切变稀的特性,表现出假塑性流体的行为;当cME≤6.7%,RLE表现出假塑性流体的行为,而当cME≥10.0%,RLE则表现出膨胀型流体的特征;用不同UE制备的RLE均表现出假塑性流体的特征,其流变行为符合Herschel-Bulkley模型,随着UE分子中聚氧乙烯链的增长,RLE的黏度增大,RLE粒子间所形成的某种静态空间网状结构强度增强.     

纳米埃洛石管对HPAM性能的影响

采用油酸改性纳米埃洛石管(HNTs)将部分水解聚丙烯酰胺(HPAM)与改性HNTs(O-HNTs)共混制备一种稳定的分散体系HPAM/O-HNTs。采用红外和接触角对O-HNTs的化学结构进行表征,并系统考察HPAM/O-HNTs的增黏性、耐温耐盐性、抗剪切性和驱油效果。结果表明：O-HNTs分子链中含有长烷基链、双键等疏水基团,具有疏水作用。加入O-HNTs后,HPAM/O-HNTs黏度明显提高,表现为优异的增黏性。HPAM/O-HNTs在30～90℃的NaCl(0～12000 mg·L^-1)和CaCl₂(0～12000 mg·L^-1)溶液中的黏度均比HPAM高,表现出优异的耐温抗盐性能。90℃条件下,随着剪切速率增大,HPAM/O-HNTs黏度逐渐减小。500 r·s^-1条件下溶液黏度大于17.2 mPa䦆Wingdings 2VB@s,表现出优异的抗剪切性能。在相同条件下,HPAM/O-HNTs的驱油采收率比HPAM高12.3%,驱油效果显著。     

不同构型聚α-烯烃分子润滑性的分子动力学模拟

采用分子动力学方法研究不同构型的直链和支链化润滑油聚α-烯烃(PAO)在剪切铁板间的黏度、 摩擦性以及油膜内PAO分子的聚集行为, 从微观角度解释了PAO分子结构与润滑油膜稳定性的关系. 模拟结果表明, 相比于直链PAO, 支链化PAO润滑油剪切黏度受剪切速率影响较小; 支链化PAO剪切摩擦系数小于直链PAO润滑油; 对比直链PAO分子, 支链化PAO分子由于侧链的存在, 可在润滑体系内多层吸附层间形成复杂的网状结构, 降低PAO分子在剪切力作用下的移动. 这种网状结构有利于润滑油膜的稳定, 延长了润滑油的使用寿命.     

高剪切速率对PCL/RGO附生结晶行为影响的原位研究

以聚己内酯(PCL)/还原氧化石墨烯(RGO)复合材料为研究对象, 利用同步辐射小角X射线散射(SAXS)和广角X射线衍射(WAXD)原位分析了75 s^?1的高速率剪切作用前后的附生晶体结构演变及其对本体晶体形成的影响. 研究结果表明, 在剪切后降温160 s后, PCL分子链开始在RGO表面附生, 形成表面结晶层, 同时形成部分PCL本体晶体; 在200~480 s的等温结晶阶段, 大量PCL本体片晶生成并形成规整的周期结构. 较高的剪切速率使体系的黏度降低, 因此在较高的剪切温度下PCL分子链更容易由伸直链转变为无规线团, 不利于PCL分子链在RGO表面形成表面结晶层. 在剪切速率为75 s^?1时, 70 ℃的剪切温度更有利于PCL分子链在RGO表面附生形成表面结晶层.     

D-半胱氨酸自组装膜对D-或L-天冬氨酸结晶行为的影响

在相同的实验条件下,研究了D-半胱氨酸自组装膜对D-或L-天冬氨酸结晶行为的影响.实验结果表明,不同手性的天冬氨酸在D-半胱氨酸自组装膜提供的手性模板环境下表现出某些令人感兴趣的结晶特点.在自组装膜的诱导作用下,D-或L-天冬氨酸都沿着[100]方向择优生长.然而,显微镜图象和高效液相色谱（HPLC）结果都表明,D-或L-天冬氨酸在D-半胱氨酸自组装膜上的结晶数量却有明显不同,L-天冬氨酸的结晶数量远远大于D-天冬氨酸的结晶数量.D-和L-天冬氨酸分子存在镜面对称关系,与D-半胱酸自组装膜接近过程中,空间位阻的差别造成了L-或D-天冬氨酸结晶数量的显著差异.     

聚2-丙烯酰胺-2-甲基丙磺酸水凝胶-玻璃体系中水凝胶压缩模量对摩擦行为的影响

研究了在玻璃基板表面,滑动速率(v)为10-6～100m/s的具有不同压缩模量(E)的聚2-丙烯酰胺-2-甲基丙磺酸(PAMPS)水凝胶的摩擦行为.结果表明,在高摩擦速率(v10-3m/s)下,摩擦力f∝v,呈流体动压润滑特征;而在低摩擦速率(v10-4m/s)区域,f随v增加略有下降,不符合流体动压润滑机制.低速区随v增加f的下降不是缘于测试过程中正压力的松弛,而是由水凝胶表面缠结网络剪切变稀及混合润滑共同导致的.低速区f对v的敏感性受E的影响不大.与模型预测不同,E低的PAMPS水凝胶表现出较低的f及临界流体动压润滑速率(vc),这与低E的PAMPS水凝胶表面较低的电荷密度及较易形变有关.     

人肝癌细胞HepG2与正常肝细胞L02的O-糖链的比较分析

以培养的原发性肝细胞癌HepG2细胞和正常肝细胞L02为研究对象, 用细胞裂解液提取总蛋白, 然后采用Carlson还原性β-消除法释放O-糖链, 以阳离子交换柱结合C₁₈柱纯化分离O-糖链, 用电喷雾电离质谱(ESI-MS)和串联质谱(MS/MS)对O-糖链进行序列鉴定, 以β-环糊精为内标对2种细胞系的O-糖链进行定量比较分析. 结果表明, 在肝癌细胞系HepG2中检测到10种O-糖链, 正常细胞系L02中检测到9种O-糖链, 其中9种O-糖链是2种细胞系中共有的, 但HepG2中存在癌细胞中特有的缩短的O-糖链N1A1(NeuAc-GalNAc, sialyl Tn 抗原). t检验结果表明, HepG2与L02相比, 在检测到的10种O-糖链中有5种的含量具有极显著性差异(P<0.01), 2种的含量具有显著性差异(P<0.05).     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.