羧甲基羟丙基纤维素溶液流变性质的研究

用旋转粘度计研究了羧甲基羟丙基纤维素(CMHPC)复合醚水溶液在25～80℃温度范围内的热稳定性,以及水溶液和盐溶液的流变性质。借助阿氏(Arrheaius)方程得到的CMHPC粘流活化能介于离子型羧甲基纤维素醚(PAC)和非离子型纤维素醚(HEC)之间。研究发现,CMHPC体系中羧甲基含量较高时流动曲线类似PAC,符合Ostwad-Der Waele幂律模型,而羟丙基含量较高时,流动曲线类似HEC,偏离幂律模型。在CMHPC水溶液中加入小分子电解质时,羧甲基受屏蔽,流变行为主要受羟丙基的影响,曲线将发生偏离。本文还考察了CMHPC溶液的抗盐能力。     

水溶性羧甲基羟丙基纤维素的某些性质

研究了不同羧甲基取代度和不同羟丙基取代度的羧甲基羟丙基纤维素(CMHPC)的某些性质。与某些离子型及非离子型纤维素醚比较表明,CMHPC兼备有离子型和非离子型纤维素醚的性。在稀的无机酸或有机酸中,CMHPC较离子型羧甲基纤维素有较好的溶解性和更高的溶液粘度,更缓慢的降解速度。CMHPC的水汽吸值以及溶液的表面张力值介于离子型与非离子型纤维素醚之间。它具有能溶于一价和二价盐的良好综合耐盐性,离子型纤维素醚能耐一价盐但不能耐二价盐;某些非离子型纤维素醚能耐二价盐但不能耐一阶盐。CMHPC红外吸收光谱图表明具有羧甲基特征峰1610cm~(-1)以及羟丙基(上的甲基)的特征峰1380cm~(-1)。高烃丙基取代度的CMHPC具有非离子型羟丙基纤维素醚溶于某些极性有机溶剂的性质。CMHPC在聚醋酸乙烯乳液中表现出良好的增稠性,配伍性和稳定性。添加有CMHPC增稠剂的乳液粘度长期保持稳定。CMHPC的差热曲线,热重曲线,微商热重曲线表明,它具有较高的热分解温度和较缓慢的热分解速度。是一种用于增稠领域和钻井泥浆处理剂的良好热稳定性材料。     

金属交联羧甲基羟丙基纤维素反应的研究

 使用新型有机钛络合物交联羧甲基羟丙基纤维素(CMHPC),仍得凝胶具备较高的耐温性,热分析结果亦表明交联产物有良好的热稳定性。对有机钛及其它一些金属离子交联CMHPC反应的行为和红外谱图分析显示,CMHPC与金属离子作用时,不仅由羧甲基提供活性络合部位,而且羟丙基也参予反应,交联机制受取代度和反应条件的影响。     

金属交联羧甲基羟丙基纤维素反应的研究

使用新型有机钛络合物交联羧甲基羟丙基纤维素(CMHPC),仍得凝胶具备较高的耐温性,热分析结果亦表明交联产物有良好的热稳定性。对有机钛及其它一些金属离子交联CMHPC反应的行为和红外谱图分析显示,CMHPC与金属离子作用时,不仅由羧甲基提供活性络合部位,而且羟丙基也参予反应,交联机制受取代度和反应条件的影响。     

羧甲基羟丙基纤维素混合醚耐盐性研究

通过X-射线衍射、红外吸收光谱和浊度测定,研究了羧甲基羟丙基纤维素(CMHPC)结构和溶解性能的关系。结果表明,CMHPC的溶解性能归因于纤维素中导入了羧甲基和羟丙基两种亲水基团,以及因导入这两种基团所引起的纤维素消晶作用。CMHPC不仅能溶于浓的NaCl溶液,而且能溶于二价碱土金属盐溶液。通过溶液折射率和盐粘比值的测定,研究了金属盐对CMHPC水化的影响。结果表明,金属离子的去水化能力顺序是:Na~+相似文献   

羧甲基纤维素锂(CMC-Li)的合成流变和静电纺丝功能化材料研究

对离子型纤维素醚静电纺丝研究依旧是当前研究的难点. 研究表明, 成功合成新的离子型纤维素醚CMC-Li, 并对比羧甲基纤维钠(CMC-Na)进行流变测试, 两者都表现出非牛顿流体的特性, 且取代度和黏度相近的CMC-Li比CMC-Na具有更低的非牛顿指数, 对于同类物质低取代度、高浓度的溶液表现出更低的非牛顿指数. 并针对聚合物的结构特点, 易与水溶性端羟基高分子量的聚环氧乙烷(PEO)配成静电纺丝优良共纺溶液, 当速率为4 mL/h, 电压为25 kV, 纺丝距离为12 cm时能得到外观形貌较好的平均直径为70 nm左右的纳米纤维. CMC-Li具有更好的纺丝性能, 对CMC-Li包覆碳化功能化复合材料研究进行初步的探讨. 通过使用红外(IR)、流变仪、扫描电镜(SEM)分析取得较好的效果.     

氢键给体和受体对纤维素醚复合薄膜后处理的影响研究

纤维素醚是一类水溶性大分子,它可以作为氢键受体和聚丙烯酸(PAA)形成氢键复合物。利用层层组装的方法制备出羟乙基纤维素(HEC)与PAA的界面复合薄膜,选取氢键给体单宁酸(TA)和氢键受体甲基纤维素(MC)、羟丙基纤维素(HPC)、聚乙烯吡咯烷酮(PVPON)溶液分别对薄膜进行浸泡后处理。研究表明浸泡后处理是一个动态的过程,会改变薄膜的厚度和组成,对于薄膜的实际应用具有指导意义,为多组分复合薄膜的制备提供了新思路。     

N,O-羧甲基化羟丙基壳聚糖的制备及结构表征

用NaOH作为催化剂, 在异丙醇悬浮体系中环氧丙烷(PO)与壳聚糖(CS)在60 ℃下反应8 h, 制备取代度超过0.8的羟丙基壳聚糖(HPCS). HPCS在水溶液中与氯乙酸反应, 制备了一种结构新颖的两性聚合物N,O-羧甲基化羟丙基壳聚糖(HPCMS), 羧甲基取代度可控制在0.42～1.38之间. 采用NMR和FTIR对产物结构进行表征. 结果表明, 在壳聚糖的羟丙基化改性过程中, C6位羟基首先与环氧丙烷反应, 生成HPCS; 在与氯乙酸反应过程中, HPCS上的羟基和氨基同时与氯乙酸发生取代反应.     

羧甲基羟丙基瓜尔胶的流变特性

考查了羧甲基羟丙基瓜尔胶溶液的流变特性,发现其水溶液呈典型的假塑性,不同浓度下溶液表观粘度随剪切速率的变化可以用Ostwald-Dewaele方程描述;零切粘度与温度的关系符合Andrade方程;溶液的粘度在酸性条件下随溶液pH的减小迅速降低,在碱性条件下则变化不大;溶液对NaCl很敏感,表现出典型的聚电解质的特征。     

羟丙基甲基纤维素丁二酸酯(HPMCS)的制备与性能

以羟丙基甲基纤维素(HPMC)为原料、丁二酸酐为酯化剂、无水醋酸钠为催化剂,在醋酸中通过酯化反应制备了羟丙基甲基纤维素丁二酸酯(HPMCS).通过改变反应温度、酯化剂和催化剂的用量,得到了5种具有不同丁二酰基含量的羟丙基甲基纤维素丁二酸酯.采用电导率滴定法测定了丁二酰基的含量.采用红外光谱(FT-IR)、粘度分析和流变分析对其进行了结构表征和性能测试.结果表明:平均每个大分子链上丁二酰基的含量(摩尔比)为6.57～12.42;质量分数为1%HPMCS溶液的凝胶温度从48.7℃降至41.95℃,而相同浓度的HPMC的凝胶温度为59.85℃;丁二酰基含量越多和分布越均匀,凝胶温度越低,但凝胶强度则越大.     

Sorption of radioactive cobalt in natural Mexican clinoptilolite

The ability of a natural Mexican clinoptilolite to sorb radioactive cobalt from aqueous solution was studied. The zeolite was stabilized partially with sodium and the content of Na⁺ in the samples was determined by neutron activation analysis. Ion exchange experiments were performed with solution labeled with radioactive⁶⁰Co at pH 6.5. XRD patterns were used to verify if the crystallinity of the aluminosilicate was affected by ionic exchange. A fast sorption uptake was observed and it was found that 0.408 meq/g of zeolite of Na⁺ ions were replaced by cobalt ions, followed by a desorption process where the uptake decrease to 0.314 meq/g of zeolite. This behavior is a consequence of the partial dehydration of the zeolite.     

Interaction of three pradimicin derivatives with divalent cations in aqueous solution

This study focused on further analysis of the aggregation behavior of pradimicin derivatives and their interaction with cations in aqueous solution. BMY was compared with two other pradimicin antibiotics (T2 and FB) with the same aglycone moiety but consisting of different substitute groups. The surface tension measurement showed a clear critical micelle concentration at 1-2 mM of the BMY aqueous solution. The role of Zn2+ in replacing the Ca2+ was examined using 1H nuclear magnetic resonance (NMR) method. From changes in the NMR spectrum and precipitability, it was concluded that zinc ion has lower affinity and higher precipitating ability to BMY than the divalent cations of alkaline earth metal. The aggregation behavior of T2 and FB in aqueous solution was also studied using NMR method. The results suggest that the supramolecular behavior of T2 is similar to BMY whether or not Ca2+ ions are present in solution and that there are two binding sites for calcium ions in a T2 molecule. Unlike BMY and T2, the NMR spectrum of FB does not show distinct change upon Ca2+ addition. The interaction of pradimicin antibiotics with divalent metal ions was thought to be related to ionic electronegativity and to the amphoteric property of the antibiotics.     

Coordination geometry of cadmium at the zinc and copper sites of superoxide dismutases: a study using perturbed angular correlation of gamma-rays from excited 111Cd.

111Cd time-differential perturbed gamma-gamma angular correlation (PAC) has been used to investigate the Zn site in yeast and bovine copper and zinc-containing superoxide dismutases by substitution of the zinc ions with excited 111Cd(2+) ions. The PAC spectra obtained from the enzymes in aqueous solution reveal a single coordination geometry of 111Cd(2+) showing that the coordination of 111Cd(2+) to the Zn site in the two subunits is identical. Furthermore, the PAC spectra of the yeast and bovine enzymes show that the Zn sites are very similar in the two enzymes. The PAC experiments show a clear difference depending on whether the copper ion is in the oxidized or the reduced state. In the latter case the results resemble those obtained for derivatives with no metal ion at the Cu site. Hence the coordination geometry of the Zn site in these two situations must be similar, and it is very unlikely that the imidazole ring of His61 bridges the two metal ions in the reduced enzyme. The PAC spectrum of 111Cd(2+) ions at the Zn site with copper(II) ions at the Cu site is in agreement with that predicted by applying the angular overlap model (AOM) to the known crystal structure of the bovine enzyme, with known nuclear quadrupole interactions for the ligands involved. Furthermore results from experiments with copper in the reduced state show that reduction of the copper ion causes a significant change at the Zn site. An explanation for this conformational change has been proposed by computer modelling. The PAC experiments also show that it is possible to incorporate cadmium ions into the Cu site in the absence of copper ions, and the result has also been interpreted in terms of the AOM.     

Novel three-stage kinetic model for aqueous benzene adsorption on activated carbon

We propose a novel kinetic model for adsorption of aqueous benzene onto both granular activated carbon (GAC) and powdered activated carbon (PAC). The model is based on mass conservation of benzene coupled with three-stage adsorption: (1) the first portion for an instantaneous stage or external surface adsorption, (2) the second portion for a gradual stage with rate-limiting intraparticle diffusion, and (3) the third portion for a constant stage in which the aqueous phase no longer interacts with activated carbon. An analytical solution of the kinetic model was validated with the kinetic data obtained from aqueous benzene adsorption onto GAC and PAC in batch experiments with two different solution concentrations (C(0)=300 mg L(-1), 600 mg L(-1)). Experimental results revealed that benzene adsorption for the two concentrations followed three distinct stages for PAC but two stages for GAC. The analytical solution could successfully describe the kinetic adsorption of aqueous benzene in the batch reaction system, showing a fast instantaneous adsorption followed by a slow rate-limiting adsorption and a final long constant adsorption. Use of the two-stage model gave incorrect values of adsorption coefficients in the analytical solution due to inability to describe the third stage.     

Adsorption equilibrium and kinetics of copper ions and phenol onto modified adsorbents

The adsorption equilibrium and kinetics of single and binary component copper ions and phenol onto powdered activated carbon (PAC), alginate beads and alginate-activated carbon beads (AAC) were studied. Adsorption equilibrium data for single component copper ions and phenol onto the adsorbents could be represented by the Langmuir equation. Multicomponent equilibrium data were correlated by the extended Langmuir and ideal adsorbed solution theory (IAST). The IAST gave the best fit to our data. The amount of copper ions adsorbed onto the AAC beads in the binary component was greater than that of phenol. The internal diffusion coefficients were determined by comparing the experimental concentration curves with those predicted from surface diffusion and pore diffusion model.     

NaCl溶液中纤连蛋白在TiO_2表面吸附的动力学模拟

对NaCl水溶液环境中,纤连蛋白(FNIII_(10))分子在金红石型TiO_2 (110)表面的吸附行为进行了分子动力学模拟.根据模拟溶液各成分与TiO_2表面原子之间的径向分布函数、离子在水溶液中的扩散系数及FNIII10和离子的吸附构象等相关参数发现,分布于TiO_2表面的稳定双层水分子是固液界面的主要特征,FNIII10分子通过天冬氨酸残基侧链末端的羧基基团(COO~-)同表面Ti原子之间的强相互作用,结合赖氨酸残基侧链及位于FNIII_(10)始端的精氨酸残基N端的氨基基团(NH_3~+)与表面桥氧原子之间的氢键作用,牢固地吸附在TiO_2表面.溶液中吸附在TiO_2表面的Na~+可与羧基氧原子配合形成稳定的吸附构型,而分布在第二水层外侧的Cl-对纤连蛋白分子在TiO_2(110)表面的吸附点位基本无影响.     

Swelling behavior of amphiphilic hydrogels of copolymers of the vinyl ether of ethylene glycol and vinyl isobutyl ether,and their interaction with cationic surfactant

Amphiphilic hydrogels of copolymers of the vinyl ether of ethylene glycol and vinyl isobutyl ether were synthesized by -radiation-induced free radical polymerization. Hydrogels with certain copolymer compositions showed thermo-sensitive behavior in aqueous solutions. The swelling behavior of the hydrogels in cetylpyridinium bromide aqueous solution was studied. Increased swelling of the hydrogels was observed in the surfactant solutions. The increased swelling was more prominent for the hydrogels with a higher content of hydrophobic moiety in the copolymer composition, and with higher surfactant concentration. The reason for this phenomenon is discussed. Treatment of some hydrogels in the surfactant solutions resulted in higher swelling ability in distilled water with distinct thermo-induced contraction over a narrow temperature interval.     

Nanoparticles of octakis[3-(3-amino-1,2,4-triazole)propyl]octasilsesquioxane as ligands for Cu(II), Ni(II), Cd(II), Zn(II), and Fe(III) in aqueous solution

Nanoparticles of octakis[3-(3-amino-1,2,4-triazole)propyl]octasilsesquioxane (ATZ-SSQ) were tested as ligands for transition-metal ions in aqueous solution with a special attention to sorption isotherms, ligand-metal interaction, and determination of metal ions in natural waters. The adsorption potential of the material ATZ-SSQ was compared with related [3(3-amino-1,2,4-triazole)propyl]silica gel (ATZ-SG). The adsorption was performed using a batchwise process and both organofunctionalized surfaces showed the ability to adsorb the metal ions from aqueous solution. The Langmuir model was used to simulate the sorption isotherms. The results suggest that the sorption of these metals on ATZ-SSQ and ATZ-SG occurs mainly by surface complexation. The equilibrium condition is reached at time lower than 3 min for ATZ-SSQ, while for ATZ-SG is only reached at time of 25 min. The maximum metal ion uptake values for ATZ-SSQ were higher than the corresponding values achieved with the ATZ-SG. In order to obtain more information on the ligand-metal interaction of the complexes on the surface of the ATZ-SSQ nanomaterial, ESR study with various degrees of copper loadings was carried out. The ATZ-SSQ was tested for the determination (in flow using a column technique) of the metal ions present in natural waters.