部分水解的预交联凝胶型聚丙烯酰胺的水化层结构

部分水解的预交联凝胶型聚丙烯酰胺在水溶液中的吸水溶胀能对油藏高渗透区域产生有效封堵,有利于提高驱油效率.分子模拟结果表明,凝胶颗粒的溶胀主要归因于侧链亲水基团在水溶液中的水化作用,这些带负电的亲水基团中心原子通过氢键和静电作用在其周围极化出一层排列规整、有序而紧密的水化层,并将水分子束缚其中;同时水化层内的水分子之间依赖氢键网络促进水化层的稳定.本文从微观结构、动力学和氢键等方面比较了各亲水基团中心原子的水化能力,发现—COO-官能团具有较强的束缚水分子的能力,对水化层的稳定有重要影响.     

预交联凝胶调驱剂的研究现状与应用进展

综述了预交联凝胶调驱剂的实验室合成研究和矿场应用进展,重点介绍了PPG性能改良（包括耐温耐盐性能、柔性弹性及小尺度智能材料及缓膨性能改良）及预交联凝胶调驱剂在高盐高温油藏、低温低盐砂岩厚油层、聚驱应用及复合使用弱凝胶封堵高渗区域和大裂缝中的应用。并对预交联凝胶调驱剂的发展方向进行了展望。参考文献48篇。     

光敏感双亲性梳状SMA聚合物的合成及其胶束化

以含香豆素型苯乙烯类光敏单体(coumarin-containing styrene monomer, CS)与苯乙烯(St)、马来酸酐(MA)为反应单体, 以偶氮二异丁腈(AIBN)为引发剂制备了光敏感三元苯乙烯-马来酸酐共聚物(SMA)双亲交替聚合物P(St/CS-alt-MA), 再利用羧酸酐基元与正辛胺的室温胺解反应获得光敏感双亲性梳状聚合物P(St/CS-alt-MAA8). 用傅立叶变换红外光谱(FTIR)、凝胶渗透色谱(GPC)、1H核磁共振(1H-NMR)等对该双亲梳状聚合物进行结构表征. 通过香豆素基元的光二聚作用, 使梳状聚合物溶解在DMSO中进行光照预交联; 非交联与预交联聚合物分别在选择性溶剂中自组装形成胶束; 利用羧酸基元与NaOH的离子化作用改变聚合物胶束的亲疏水性质. 动态激光光散射(DLS)与芘荧光探针实验表明预交联聚合物胶束较非交联胶束粒径大, 负载芘的能力强; 离子化作用使聚合物胶束解离重组成粒径更小的胶束, 但预交联胶束较非交联胶束小, 离子化后胶束疏水微区更加紧密, 负载芘的能力也增大.     

快速响应的温敏性聚(N-异丙基丙烯酰胺)水凝胶 Ⅰ.以CaCO_3为成孔剂制备方法、表征及动力学研究

以不同粒径的CaCO3粒子为成孔剂 ,合成了快速响应的温敏性聚 (N 异丙基丙烯酰胺 ) (PNIPA)水凝胶 .利用扫描电镜观察到水凝胶具有特殊的孔状结构 ,得到水凝胶的孔径大小为几十微米左右 .动力学研究表明 ,该水凝胶在温敏膨胀或收缩时 ,具有快速的响应速率 ,在 10min内的失水率可达 90 % .比较了干凝胶和4 0℃下失水后的凝胶两种不同状态下水凝胶的膨胀曲线 ,发现两者的溶胀动力学曲线明显不同 ,前者的曲线有拐点 .同时发现与失水收缩速率相比 ,水凝胶具有较慢的吸水膨胀速率 .     

速响应的温敏性聚(N-异丙基丙烯酰胺)水凝胶Ⅰ.以CaCO3为成孔剂制备方法、表征及动力学研究

以不同粒径的CaCO3粒子为成孔剂,合成了快速响应的温敏性聚(N-异丙基丙烯酰胺)(PNIPA)水凝胶.利用扫描电镜观察到水凝胶具有特殊的孔状结构,得到水凝胶的孔径大小为几十微米左右.动力学研究表明,该水凝胶在温敏膨胀或收缩时,具有快速的响应速率,在10 min内的失水率可达90%.比较了干凝胶和40℃下失水后的凝胶两种不同状态下水凝胶的膨胀曲线,发现两者的溶胀动力学曲线明显不同,前者的曲线有拐点.同时发现与失水收缩速率相比,水凝胶具有较慢的吸水膨胀速率.     

弛豫法研究预交联颗粒凝胶的界面扩张流变性质

采用界面张力弛豫方法研究了一种新型聚合物--预交联颗粒凝胶(PPG)的界面流变性质, 考察了电解质及传统直链聚丙烯酰胺与PPG的相互作用对体系界面性质的影响, 计算得到了各体系界面扩张弹性和黏性的全频谱, 并通过归一法计算得到了相应的Cole-Cole图. 结果表明, 随着体相浓度的增加, PPG在界面层中形成网络结构, 界面扩张弹性和黏性大幅增强. 电解质能够中和PPG结构中的电荷, 明显降低扩张弹性和黏性. 直链聚丙烯酰胺与PPG在界面上可能形成更为复杂的结构, 膜的黏弹性由PPG决定.     

钯催化胺化反应合成高性能材料——聚亚胺砜

利用三(二亚苄基丙酮)二钯(Pd2(dba)3)与1.1′-联萘-2.2′-二苯膦(BINAP)组成的催化体系,高效地催化4,4′-二氯二苯砜和芳香二胺的Buchwald-Hartwig交叉偶联反应,制备出新型聚亚胺砜.聚合物结构通过核磁氢谱、红外谱图、凝胶渗透色谱和元素分析等方法进行表征,表征结果与目标产物相吻合,并具有较高的分子量(Mw>2.5×104).利用DSC、TG和XRD等对其性能进行测试,结果表明,该类聚合物为无定形态,具有较高的玻璃化转变温度(Tg>200℃)、良好的热稳定性(Td>400℃)和溶解性能.其中含异丙基的PIS-3不仅可溶解在强极性溶剂中,并且在室温条件下(25℃)可溶于四氢呋喃中.     

新型含硼聚芳醚酮的制备、性能及在偶氮聚芳醚酮合成中的应用

利用双酚A型聚芳醚酮与联硼酸频哪醇酯在[Ir(COD)Cl]2和4,4'-二叔丁基-2,2'-联吡啶催化下反应,制备了新型含硼酸酯双酚A型聚芳醚酮,通过控制联硼酸频哪醇酯的投入量来实现硼酸酯的定量引入.再经过高碘酸钠作用得到含硼酸双酚A型聚芳醚酮,最后,通过高效Suzuki-Miyaura反应将偶氮定量引入到聚芳醚酮主链.利用核磁共振(1H NMR)确定了聚合物的结构,利用凝胶渗透色谱(GPC)确定了聚合物的分子量,利用差示扫描量热分析(DSC)和热失重分析(TGA)研究了聚合物的热性能,利用紫外-可见光谱(UVVis)研究了偶氮聚芳醚酮的光谱学性能.     

聚丙烯酸钠和丝素蛋白自膨胀水凝胶的制备及其释药性能

通过自由基聚合的方法合成制备了自膨胀PAAS-SF semi-IPN水凝胶(聚丙烯酸钠-丝素半互穿网络水凝胶),并进一步探讨其作为微创治疗中组织植入物的潜能.主要研究了SF(丝素蛋白)和AA(丙烯酸)的重量比对PAAS-SFsemi-IPN水凝胶的结构、膨胀性以及力学性能的影响.此外,我们还研究了抗生素药物阿莫西林(AMO)在PAAS-SFsemi-IPN水凝胶中的包载与释放性能.结果表明,随着水凝胶中SF含量的增加,膨胀率增大,压缩强度减小,药物释放速率加快,且PAAS-SF20 semi-IPN水凝胶在120 h内能释放(83.4±0.9)%的药物.所开发的自膨胀PAAS-SFsemi-IPN水凝胶具有高膨胀率和良好的药物释放能力,将在药物输送或其它植入材料领域有良好的应用前景.     

交联聚丙烯酰胺溶液染色研究

采用显微镜研究了预交联聚合物凝胶溶液的染色过程,结果表明由于静电作用,亚甲基蓝溶液中阳离子基团与凝胶颗粒中的阴离子基团相互作用形成一种深蓝色的缔合物;交联聚物线团也可以与亚甲基蓝分子形成深蓝色的缔合物,使交联聚合物线团显色,能够直接观测到交联聚合物线团在溶液中的形态。采用扫描电镜、动态光散射、流变仪和岩心封堵实验研究了染色后交联聚合物的线团形态尺寸和溶液的流变性、封堵特性。结果表明,染色后的交联聚合物线团仍是几百纳米左右的在水中分散的球形体,在形态和尺寸上与未染色的交联聚合物溶液没有发生较大的变化;染色后交联聚合物溶液在一定剪切速率范围内表现为胀流性和负触变性。     

Effect of Direct yellow 50 removal from an aqueous solution using nano bentonite; adsorption isotherm,kinetic analysis and also thermodynamic behavior

The developing countries are suffering from the toxicity of different industrial effluents, especially dyes that contaminate water systems. This study successfully explained the preparation and characterization of nano bentonite to extract Direct Yellow Fifty (DY50). Direct Yellow 50 is an organic contaminant that may affect the quality of water. The characterization of prepared nanoparticles was done using Scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier-transform infrared (FTIR). The impact of different operating conditions was studied using different pH, dose, temperature, contact time, and initial DY50 concentrations. The obtained results indicated that nano bentonite could adsorb about 94 % at initial concentrations of 40 mg/L, respectively. The optimum removal conditions were observed at an acidic pH (pH 3) using a sorbent material dosage of 0.05 g for 4 h at 30 °C. The adsorption isotherm, kinetic analysis, and thermodynamic behavior were studied using linear equation form, and the adjusted R² was compared to detect the preferred models. The adsorption behavior pseudo-second order kinetics, and fitted Langmuir isotherm model, respectively, showed the chemisorption interactions between adsorbed and sorbed molecules. Thermodynamic behavior indicated that the reaction was exothermic. Finally, this study strongly recommended using nano bentonite for DY50 removal from an aqueous solution.     

光化学荧光分析法研究(Ⅵ)——混合色素的光化学速差动力学荧光分析法测定

以光化学荧光衍生化法测定苋菜红(AM)和直接耐晒嫩黄5GL(DY)2种偶氮色素,研究了同时测定这2种色素混合物的光化学速差动力学荧光分析的原理和方法。AM和DY的浓度分别在0～220ng/mL和0～120ng/mL范围内呈良好的线性关系,相关系数皆为0.999,检出限为0.64ng/mLAM和0.045ng/mLDY。相对标准偏差分别为1.6%(n=8)和1.8%(n=7)。该法用于人工合成混合样品的测定效果良好。     

分子筛对葡萄糖淀粉酶的吸附性能研究

测定了黑曲霉葡萄糖淀粉酶(E.C.3.2.1.3)在三种改性的、具有中孔和大孔的分子筛上的吸附等温线并将吸附量和吸附等温线的形状与分子筛的等电点、孔容、孔径及酸性相关联。讨论了孔结构和不同酶吸附量对分子筛固定化葡萄糖淀粉酶活力的影响。发现葡萄糖淀粉酶在再造孔分子筛上的单层饱和吸附量与再造孔的方法密切有关,三种不同再造孔方法制得的分子筛具有不同的骨架Si/Al比、不同的孔分布和比表面积。不同的Si/Al比导致不同的酸性质和等电点。酶吸附量与载体的表面酸性、等电点以及吸附时溶液的pH有关。分子筛对酶的吸附以静电作用为主。其次,当中孔孔径和孔容越大时,单层饱和吸附量亦越大。随着分子筛对葡萄糖淀粉酶的吸附量增加,固定化酶的活力增大,但固定化酶的比活力随吸附量的增加、中孔孔容和孔径的减小而下降。     

原料对自由落下床中生物质与煤共热解行为的影响

在500～700℃和生物质混合比0～100％(质量分数)条件下,利用自由落下床反应器考察原料对生物质与煤共热解行为的影响.所用煤原料为大雁褐煤(DY)和铁法烟煤(TF),而生物质原料为农业废弃物秸秆(LS)和木材加工余料白松木屑(SD).结果表明,即使在自由落下床中停留时间短的条件下,生物质与煤共热解的协同效应仍然发生...     

Formation of stable alkenyl carbenium ions in high yield by adsorption of 1-methylcyclopentene on zeolite Y at low temperature

The formation of dimerized alkenyl carbenium ions, characterized by an IR band at 1513 cm-1 and a UV band at 323 nm, was observed by adsorption of 1-methylcyclopentene on HY and DY zeolites at temperatures as low as 150 K.     

Probing the electronic structure and conformational flexibility of individual light-harvesting 3 complexes by optical single-molecule spectroscopy

We present fluorescence-excitation spectra of individual light-harvesting 3 (LH3 or B800-820) complexes of Rhodopseudomonas acidophila at 1.2 K. The optical single-molecule studies were employed to investigate the electronic structure as well as the conformational flexibility of the individual pigment-protein complexes. The optical spectra resemble those of individual light-harvesting 2 (LH2) complexes, in agreement with the structural similarity of both types of complexes. Although variations among the LH3 spectra are large, there is a distinct difference in the spectral features of the 800 and 820 nm region that appears in all the complexes studied. In the B800 region 4-6 narrow bands are present whereas in the B820 region a limited number of relatively broad bands are observed. These observations can generally be interpreted in terms of localized excitations in the 800 nm region and delocalized excitations in the 820 nm region. The observed heterogeneous spectral behavior, especially in the B820 band, indicates that the B820 pigments of LH3 are sensitive to light-induced local conformational changes. It is suggested that a rotation of the C(3)-acetyl chain of a BChl a pigment bound to the beta-subunit of the light-harvesting complex is the origin of the conformational flexibility and affects the optical properties of the whole pigment-protein complex.     

Efficient light-harvesting,energy migration,and charge transfer by nanographene-based nonfullerene small-molecule acceptors exhibiting unusually long excited-state lifetime in the film state

Electron-acceptor small-molecules possessing a long exciton lifetime and a narrow energy band gap, opposing the energy gap law, are highly desirable for high-performance organic photovoltaics (OPVs) by realizing their efficient light-harvesting ability (LH), exciton diffusion (ED), and charge transfer (CT). Toward this goal, we designed an acceptor–donor–acceptor (A–D–A) type nonfullerene acceptor (NFA), TACIC, having an electron-donating, self-assembling two-dimensional (2D) nanographene unit, thienoazacoronene, at the center with electron-withdrawing groups at both ends. The TACIC film exhibited a narrow band gap (1.59 eV) with excellent LH. Surprisingly, the TACIC film showed an extremely long exciton lifetime (1.59 ns), suppressing undesirable nonradiative decay by its unique self-assembling behavior. When combined with a conjugated polymer donor, PBDB-T, slow ED and CT were observed (60 ps) with the excitation of TACIC owing to the large TACIC domain sizes. Nevertheless, the unusually high efficiencies of ED and CT (96% in total) were achieved by the long TACIC exciton lifetime. Additionally, unusual energy transfer (EnT) from the excited PBDB-T to TACIC was seen, demonstrating its dual LH role. The OPV device with PBDB-T and TACIC showed a high incident photon-to-current efficiency (IPCE) exceeding 70% at up to 710 nm and a power conversion efficiency of ∼10%. This result will open up avenues for a rational strategy of OPVs where LH, ED, and CT from the acceptor side as well as LH, EnT, ED, and CT from the donor side can be better designed by using 2D nanographene as a promising building block for high-performance A–D–A type NFAs.

A nonfullerene acceptor, TACIC, showed efficient light-harvesting, exciton diffusion, and charge transfer.     

Versatile ligational behavior of azopyrazolone derived from hydralazine

Five complexes of 3-methyl-4?-(phenylhydrazono)-1-phthalazinyl-2-pyrazolin-5-one (LH) were synthesized. The ligand and complexes were characterized using elemental analyses and various analytical techniques such as IR, UV, NMR, mass spectra, magnetic susceptibility measurements, and thermal decomposition studies such as TG/DTG. The geometries of the complexes with special emphasis on the versatile ligational behavior of LH are discussed. All five complexes have octahedral geometry. In four of the complexes [M(LH)Cl₃] where M?=?Fe(III)/Cr(III) and [M(LH)(OAc)₂H₂O] and M?=?Cu(II)/Ni(II), the ligand was neutral and tridentate. Another copper complex [CuL(OAc)(H₂O)₂] in which the ligand is tridentate, mono-anionic one was also obtained in an excess of aqueous solution. Antifungal studies of the compounds are also carried out.     

Mixture diffusion of sulfonated dyes into cellulose membrane. III. Application of parallel diffusion model to binary system of direct dyes with different affinity

Mixture diffusion of two dyes (C.I. Direct Blue 15 (DB15) and C.I. Direct Yellow 12 (DY12)) with different affinity onto the substrate into cellulose membrane from the binary solution was studied at 55°C. Uptake curves and concentration–distance profiles were measured experimentally in the ratios (DB15:DY12) 1:0.5, 1:1 and 1:2. It was examined whether the diffusion of the dyes could be analyzed based on the parallel diffusion theory of surface and pore diffusion. It was revealed that the diffusion of DB15 with higher affinity could be analyzed based on the model in the ratios 1:0.5 and 1:1, although the theoretical value deviated slightly from the data in the concentration–distance profile in the ratio 1:1. On the other hand, the diffusion of DY12 with smaller affinity could not be described by the model, because the diffusivity of the dye changed during the adsorption process against the assumption of the model.