微囊化海藻酸离子移变凝胶的制备、结构与性能

通过静电脉冲技术制备了海藻酸-壳聚糖-海藻酸(Alginate-Chitosan-Alginate,ACA)微胶囊,红外光谱分析表明,ACA是一种以聚电解质配合物为囊膜,以海藻酸钠离子吸附剂为囊心物的微胶囊型离子吸附体系.扫描电镜测试表明,ACA吸附重金属离子的过程是微胶囊囊内海藻酸凝胶化的过程,其解吸附过程是海藻酸凝胶转变成海藻酸溶液的过程.与传统离子交换树脂相比,ACA对Pb²⁺的吸附具有较高的去除率、很强的富集能力和较低的极限吸附浓度,并且能够被多次重复使用.ACA的离子交换速率比传统离子交换树脂快得多,离子交换过程中,交换离子和吸附剂海藻酸分子的相互扩散大大提高了离子交换速率.     

海藻酸盐水凝胶作为递送载体在组织再生中的应用

海藻酸盐是一类存在于褐藻中的线性亲水多糖,由D-甘露糖醛酸(M)和L-古洛糖醛酸(G)以不同比例的重复单元组成.它是用于水凝胶合成的天然生物材料之一,通过简单的离子交联,即可与Ca2+等多价无机阳离子发生"蛋盒反应",形成水凝胶.海藻酸盐骨架上存在大量–OH和–COOH极性基团,通过化学或物理方法对其进行修饰,使其可以在温度、pH、光等刺激的响应下实现细胞或生物活性分子的可控释放.目前组织再生领域的主要应用策略之一是利用生物相容性材料,结合生物活性分子和细胞,以促进受损组织的再生.水凝胶材料在保护嵌入的细胞并模仿天然细胞外基质方面具有潜力.海藻酸盐也因为其易于凝胶化和良好的生物相容性,被广泛用于组织再生领域.本综述中,我们总结了用于组织再生,特别在伤口愈合、骨和心脏修复领域的海藻酸盐水凝胶的不同交联方法,重点分析了对刺激具有响应性的海藻酸盐水凝胶的特征以及其作为递送载体在组织再生中的应用.     

用荧光光谱跟踪钙-海藻酸水溶液的Sol-gel转变

为了克服传统方法在测定凝胶化点的同时, 作用力对物理交联点的破坏和对大分子链运动的干扰, 探索和建立不施加应力的凝胶化点测定方法, 采用荧光光谱跟踪了异硫氰酸荧光黄(FITC)标记海藻酸与钙离子在水溶液中螯合的物理凝胶化. 随着凝胶化的进行, 荧光相对强度和各向异性比在凝胶化时间曲线的80 min时出现了明显的转折点, 与Winter方法得到的凝胶化点(80 min)完全一致. 因此可以利用FITC标记的荧光发射相对强度及各向异性比来决定钙-海藻酸体系凝胶化点.     

海藻酸作为新型药物转运载体的开发

海藻酸（Alginate或ALG）的药理学基础和在药物上的实际应用证明，海藻酸具有良好的生物相容性，由于在温和条件下与二价阳离子形成凝胶等独特的物理化学性能，用它作为缓释包衣、结肠给药、微球栓塞、纳米给药、基因治疗、眼部给药、外科修复材料和透皮给药等新剂型药物转运载体，可使药物疗效提高，毒副作用减小，用药更方便。本文综述了国内海藻酸产品的现状，阐述了海藻酸的开发前景。     

海藻酸钠水溶液的Sol-Gel转变与凝胶化点的决定

测定了 4个分子量和分子量分布不同、M G不同的海藻酸钠试样在不同浓度下的恒温 (2 5℃ )动态粘弹谱 ,发现 4个试样随溶液浓度升高都会发生溶胶 凝胶 (Sol gel)转变 .实验结果表明 ,该转变符合Winter和Chambon的凝胶化点临界状态的松弛模量G(t)方程 ,由tanδ不依赖于ω的判据求出了海藻酸钠水溶液随浓度变化发生Sol gel转变、出现物理凝胶化的凝胶化点溶液浓度cgel和临界指数n .cgel=7 6wt%～ 8 0wt% ,基本与分子量无关 ;分子量较高的 3个试样的n =0 32～ 0 38,而分子量低的试样的n =0 6 1.该结果表明 ,物理凝胶化主要是由大分子重复单元间的相互作用决定 ,分子链越长则凝胶化点的交联结构越完善     

阳离子诱导海藻酸水溶液凝胶化的临界行为与自相似性

以作者对阳离子诱导海藻酸水溶液凝胶化的研究结果为中心,介绍了海藻酸钠水溶液随浓度增大和二价金属阳离子(Ca2 、Cu2 )的加入而发生的溶液-凝胶转变的临界点和相关临界指数,探讨了临界凝胶的自相似性和分形结构,以及动态标度理论对物理交联体系的适用性.基于对阳离子诱导海藻酸水溶液凝胶化及其临界行为的研究结果,提出了从凝胶化的出发点--溶液来对凝胶化进行分类的设想,根据起始组分分子链的长短将凝胶化过程分为生长型和交联型两类.     

微波法制备氮掺杂碳点/海藻酸纳米复合物及其电沉积技术研究

以海藻酸为碳源,乙二胺为氮掺杂剂,采用简单方便的微波法制备得到氮掺杂碳点(N-CDs)/海藻酸纳米复合物.通过透射电镜观察到所制得的N-CDs/海藻酸纳米复合物有纳米粒子存在,它们的平均粒径为4.6 nm.荧光性能分析表明N-CDs/海藻酸纳米复合物在365 nm紫外光下呈现明显的蓝色荧光,并且其荧光发射性能具有激发光波长依赖性. N-CDs/海藻酸纳米复合物还保留了海藻酸与Ca~(2+)作用形成凝胶的性能以及与一些二价金属离子的配位能力,可以直接应用于阳极电沉积和配位电沉积.利用电沉积技术具有空间选择性和时间可控性的特点,可以在电极上构建不同形状和荧光图案的N-CDs/海藻酸电沉积膜,还可以对电沉积膜的厚度进行调控.此外,利用电沉积技术制备的N-CDs/海藻酸电沉积膜电极可用于进行电化学检测.     

苯乙烯-双烯A交联共聚凝胶、溶胶的生成与转化

本文结合提取、凝胶色谱等方法测定了苯乙烯-双烯A交联共聚过程的转化率曲线。通过研究发现,凝胶在交联共聚一开始就产生,且整个反应过程都在不断地生成;转化率40％以前几乎无溶胶生成,此后生成的溶胶仍不断地向凝胶转化;刚生成溶胶时其分子量高、分布窄,其后分子量变低、分布变宽;T_g以上温度的热处理发生进一步聚合反应,当双烯A摩尔浓度<3.3×10~(-4)时,溶胶分数增加,A-MA摩尔浓度>5.0×10~(-4)时,凝胶分数增加,这是双烯A悬吊双键及单体苯乙烯进一步反应的结果。     

海藻酸-壳聚糖-海藻酸凝胶离子取代机理

研究了海藻酸-壳聚糖-海藻酸(ACA)凝胶的离子取代机理.光学显微镜照相法证实ACA离子取代过程中溶胶-凝胶相界面的存在.动边界模型描述ACA离子取代凝胶对二价离子的取代动力学过程,结果表明,模型可靠.离子取代凝胶对二价离子的取代属于颗粒扩散控制机理.与离子交换树脂比较,ACA离子取代速率要快得多,ACA离子取代过程不同于传统离子交换树脂离子交换过程,它是金属离子在溶胶凝胶相转移过程中的取代过程;ACA是一种崭新的离子移变凝胶型离子吸附剂.     

用凝胶色谱法在室温下测定聚对苯二甲酸丁二醇酯(PBT)分子量和分子量分布的研究

 通过溶度参数等有关理论进行计算、分析及实验验证,找到了邻氯苯酚/氯仿(1/3,ml/ml)可作为聚对苯二甲酸丁二醇酯(PBT)的溶剂和室温淋洗剂。用自行制备的一系列分子量不同的PBT样品标定柱,建立了用凝胶色谱在室温下测定PBT分子量和分子量分布的方法,并得到了PBT和PS在邻氯苯酚/氯仿(1/3,ml/ml)体系中,25.0℃的[η]-M方程。发现在此GPC体系中普适标定法可以适用。     

Critical exponents and self-similarity for sol-gel transition in aqueous alginate systems induced by in situ release of calcium cations

The sol-gel transition in aqueous alginate systems induced by in situ released calcium cations was monitored with rheology methods. Four alginate samples with different molecular weights and M/G ratios were used over the concentration C(Alg) of 2 approximately 6 wt % with different mole ratios f of Ca2+ to the alginate repeat unit. The scaling for the zero shear viscosity eta(0) before the gel point and the equilibrium modulus Ge after the gel point was described as eta(0) approximately epsilon(-k) and Ge approximately epsilon(z), respectively, where the relative distance to the gel point f(gel) was epsilon = (/f-f(gel)/)/f(gel). The relaxation critical exponent n was determined with Winter's criterion, and the critical exponents k and z estimated respectively from independent measurements of eta(0) and Ge gave n from z/(k + z). Before the gel point, the storage and loss moduli G' and G' obtained at various epsilon can be superposed fairly well to form the master curve. The critical exponents n, k, and z were also evaluated from the shift factors and the structure self-similarity was found in the critical gel. The critical exponents evaluated with different methods agreed well with each other, suggesting two categories of the gelation as growth and cross-link. For the alginate with lower molecular weight, the critical exponents were almost independent of alginate concentration and close to the percolation prediction. For the alginate with higher molecular weight, the critical exponents, however, changed with alginate sample and concentration. The relative alginate concentration C(Alg)/C(Alg)* was found to serve as a criterion to divide these two transitions.     

Influences of nonsolvent and temperature on critical viscoelastic behaviors of ternary polyacrylonitrile solutions around the sol-gel threshold

Viscoelastic experiments were performed to study the influence of nonsolvent and temperature on critical viscoelastic behaviors of ternary polyacrylonitrile (PAN) solutions around the sol-gel threshold. The dynamic critical parameters around the sol-gel threshold were determined using dynamic rheometer. The sol-gel transition takes place at a critical gel temperature at which the scaling law of G′(ω) ∼ G″(ω) ∝ ωⁿ holds, allowing an accurate determination of the critical gel temperature by means of the frequency independence of the loss tangent. Although the gel points of PAN solutions increase with increasing H₂O content, the results show that the scaling exponent n at the gel point is found to be universal for all ternary PAN solutions, which is independent of temperature and H₂O content, indicating the similarity of the fractal structure in the critical PAN gels. The gelation of ternary PAN solutions induced by adding a nonsolvent and by decreasing the temperature is demonstrated to be a thermoreversible process, which implies that the PAN gels are physical gels. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2637–2643, 2008     

Dynamic scaling of polymer gels comprising nanoparticles

We present dynamic light scattering (DLS) measurements of soft poly(methyl-methacrylate) (PMMA) and polyacrylamide (PA) polymer gels prepared with trapped bodies (latex spheres or magnetic nanoparticles). We show that the anomalous diffusivity of the trapped particles can be analyzed in terms of a fractal Gaussian network gel model for the entire time range probed by DLS technique. This model is a generalization of the Rouse model for linear chains extended for structures with power law network connectivity scaling, which includes both percolating and uniform bulk gel limits. For a dilute dispersion of strongly scattering particles trapped in a gel, the scattered electric field correlation function at small wavevector ideally probes self-diffusion of gel portions imprisoning the particles. Our results show that the time-dependent diffusion coefficients calculated from the correlation functions change from a free diffusion regime at short times to an anomalous subdiffusive regime at long times (increasingly arrested displacement). The characteristic time of transition between these regimes depends on scattering vector as approximately q(-2), while the time decay power exponent tends to the value expected for a bulk network at small q. The diffusion curves for all scattering vectors and all samples were scaled to a single master curve.     

Dynamic light scattering in semi-interpenetrating polymer networks based on polyacrylamide and poly(N-vinylcaprolactam)

Semi-interpenetrating networks based on polyacrylamide gel and linear thermosensitive poly(N-vinylcaprolactam) are obtained for the first time and studied via the method of dynamic light scattering. Contributions associated with dynamic fluctuations and frozen inhomogeneities to scattering are determined. It is shown that the ensemble-average scattering intensity strongly depends on the quantity and dimensions of frozen inhomogeneities. As temperature increases, scattering due to both dynamic fluctuations and spatial inhomogeneities tends to increase. At the temperature of the conformational transition of poly(N-vinylcaprolactam), the intensity of scattering increases abruptly, whereas the correlation function assumes the shape of a strongly stretched exponent that corresponds to high relaxation times (??1 s). It is found that the relaxation-time distribution restored with the use of the inverse Laplace transform contains several modes. For all the studied networks, the correlation length of the mode of cooperative motion (the fast mode) is independent of the concentration of poly(N-vinylcaprolactam) and coincides with the correlation length of the mode of collective motion for the polyacrylamide gel.     

Gelation of aqueous pectin solutions: a dynamic light scattering study

We report the dynamic light scattering study of the gelation of aqueous solutions of the biopolymer, pectin, induced by the addition of calcium chloride. The time correlation function data are analyzed under the framework of the coupling model. As the solution enters the semidilute regime where gelation sets in, the relaxation process shows a stretched exponential behavior. The stretching exponent decreases and the characteristic time of the stretched exponential diverges as the system evolves to a gel. Aqueous pectin solutions in the presence of 0.1 M NaCl show similar behavior. Thus, the molecular relaxation modes of pectin solutions can be well described by the coupling model.     

Critical dynamics of the binary system nitroethane/3-methylpentane: relaxation rate and scaling function

Shear viscosity and dynamic light scattering measurements as well as ultrasonic spectrometry studies of the nitroethane/3-methylpentane mixture of critical composition have been performed at various temperatures near the critical temperature, T(c). A combined evaluation of the shear viscosity and mutual diffusion coefficient data yielded the amplitude, xi(0), of the fluctuation correlation length, xi, assumed to follow power law, and the relaxation rate, Gamma, or order parameter fluctuations. The latter was found to follow power law with the theoretical universal exponent. The amplitudes xi(0) = 0.23 +/- 0.02 nm and Gamma(0) = (125 +/- 5) x 10(9) s(-1) nicely agree with literature values. Using the relaxation rates resulting from the viscosity and diffusion coefficient data, the scaling function has been calculated assuming the ultrasonic spectra to be composed of a critical part and a noncritical background contribution. The experimental scaling function fits well to the predictions of the Bhattacharjee-Ferrell dynamic scaling model with scaled half-attenuation frequency, Omega(BF)1/2= 2.1. The amplitude of the sonic spectra yields the amount |g| = 0.26 of the adiabatic coupling constant, g, in fair agreement with -0.29 from another thermodynamic relation.     

Thermoreversible gels of polymers in recycled motor oil

A study of the dynamic viscoelastic properties of gels of Ethylene Vinyl Acetate (EVA) and Styrene‐Butadiene‐Styrene (SBS) copolymers in recycled motor oil is presented. Both systems form gels with enhanced elastic moduli, with respect to SBS/aromatic oil gels which have been used to develop synthetic binders. Although the procedure described by Winter is conveniently applied to obtain gel‐sol transition of EVA/oil gels, it is not suitable for SBS/oil gels which do not give rise to a homogeneous liquid when they melt. For EVA/oil gels the relaxation exponent at the gel point is Δ=0.5, which according to Muthukumar's model corresponds to a fractal dimension d_f=2. The variation of the elastic modulus with polymer concentration follows the scaling law G_e‐cⁿ, with n=2.8 for EVA/oil and n=1.3 for SBS/oil. In the case of EVA/oil gels the validity of theoretical models relating fractal dimension to n exponent is discussed.     

Dynamic light scattering by optically anisotropic colloidal particles in polyacrylamide gels

The translational and rotational motions of optically anisotropic spherical particles embedded in cross-linked polyacrylamide gels is studied by dynamic light scattering. The particles are liquid crystal droplets solidified in the nematic phase. The amount of cross linkers is varied to cross the sol-gel transition where the system becomes nonergodic for both translational and rotational diffusion modes of the probes. The translational and rotational dynamic correlation functions are obtained by measuring the intensity correlation function between crossed polarizers in the parallel and perpendicular geometries. Data from nonergodic systems is analyzed using an extension, to include rotations, of the method of Pusey and van Megen [Physica A 157, 705 (1989)]. Both diffusion modes are observed to be arrested as the rigidity of the gel increases.