基于温敏水凝胶的可调胶体晶体制备

基于单分散胶体粒子悬浊液在温敏水凝胶表面可以形成湿润型胶体晶体的现象, 利用温敏水凝胶对水的控释作用制备了温度敏感的可调制胶体晶体. 在室温下利用提拉法在温敏水凝胶聚N-异丙基丙烯酰胺(PNIPAAm)表面制备湿润型胶体晶体膜. 由于胶体粒子的有序排列, 胶体晶体显示出一个尖锐的反射峰. 当温度上升到34 ℃以上时, 由于PNIPAAm水凝胶中的水被释放, 导致胶体晶体中粒子浓度降低, 粒子间距增加; 反射峰发生红移. 这些特性可以通过温度变化进行调制.     

重金属离子敏感型聚合物胶体晶体的研究

以含有双硫键的二丙烯酰胱胺与双丙烯酰胺作为交联剂, 与单体丙烯酰胺紫外光引发聚合, 嵌入聚苯乙烯胶体晶体, 制备了聚丙烯酰胺胶体晶体水凝胶. 将水凝胶中双硫键打断形成巯基, 利用巯基可与重金属离子偶合的作用, 水凝胶体积收缩而改变胶体晶体中胶粒之间的距离, 根据胶体晶体带隙位移, 可分析水中重金属离子的浓度. 紫外可见光反射图谱表明, 胶体晶体带隙最大可蓝移约80 nm. 带隙移动与时间的关系曲线表明, 胶体晶体水凝胶对重金属离子有较好的灵敏度. 该体系可用于分析铅、锌等重金属离子.     

多孔聚N-异丙基丙烯酰胺水凝胶的制备与缓释性能

以N-异丙基丙烯酰胺(NIPA)、N,N-亚甲基双丙烯酰胺(MBA)和聚乙二醇(PEG)为原料,以60Co-γ射线为放射源制备了快速响应聚N-异丙基丙烯酰胺(PNIPA)多孔水凝胶。用红外光谱分析了水凝胶的结构,并测定了水凝胶的溶胀动力学、退溶胀动力学和平衡溶胀率。结果表明,PEG分子仅在聚合交联过程中充当成孔剂,不参与反应,反应后可被除去;水凝胶具有明显的温度敏感性,成孔剂的添加提高了水凝胶的溶胀性能和LCST。选用阿司匹林为模型药物,对水凝胶的药物缓释性能进行了初步研究。     

温度与pH快速响应性P(NIPAM-co-AAc)水凝胶的制备及其性能

以氯化钠水溶液作为反应介质,成功制备了温度与pH快速响应性聚(N-异丙基丙烯酰胺-co-丙烯酸)[P(NIPAM-co-AAc)]水凝胶,研究了氯化钠水溶液的浓度对凝胶性能的影响.通过红外光谱(FT-IR)、扫描电镜(SEM)、测溶胀比对凝胶性能进行了表征.结果表明:凝胶具有相同的化学组成与结构,但具有不同的微观形态;随着反应介质中氯化钠浓度的增加,凝胶在20℃蒸馏水中的平衡溶胀比增大,并表现出较强的温度与pH敏感性以及较快的去溶胀速率.     

快速温度敏感聚(N-异丙基丙烯酰胺-co-丙烯酰胺)水凝胶的制备及性能研究

于 4 8℃下制备快速温度敏感聚 ( N -异丙基丙烯酰胺 -co-丙烯酰胺 )水凝胶 ,其在室温具有较大的平衡溶胀率 .通过改变丙烯酰胺的含量可以调节水凝胶的较低临界溶解温度     

聚丙烯酰胺-g-聚苯胺的导电水凝胶的制备及性能研究

通过两步聚合得到既具有良好力学强度又具有优良导电性能的聚丙烯酰胺-g-聚苯胺复合水凝胶.首先,丙烯酰胺和N-(4-氨苯基)丙烯酰胺在钴源γ-射线辐照下共聚形成聚丙烯酰胺水凝胶;然后,苯胺在具有微观多孔结构的聚丙烯酰胺凝胶中吸附,在过硫酸铵的作用下与凝胶的苯胺侧基发生接枝聚合,得到聚丙烯酰胺-g-聚苯胺水凝胶,并形成聚苯胺连续导电通道.改变辐照时间和辐照剂量率,所获得的聚丙烯酰胺水凝胶的凝胶分数随着辐照剂量的增加逐渐增大,而溶胀率随着辐照剂量的增加呈先增后减的趋势,表明凝胶的交联程度随辐照剂量呈规律性变化;辐照交联聚合的单体浓度对凝胶的性能,如溶胀率、微观结构和机械性能等也有影响.酸掺杂后,聚丙烯酰胺-g-聚苯胺复合凝胶的电导率达到9 S/m.     

聚(2-丙烯酰胺基-2-甲基丙磺酸/丙烯酰胺)水凝胶合成与性能研究

以2-丙烯酰胺基-2-甲基丙磺酸和丙烯酰胺为原料,以PEG6000为成孔剂,采用水溶液法合成多孔性聚(2-丙烯酰胺基-2-甲基丙磺酸/丙烯酰胺)水凝胶,研究了凝胶的溶胀性和电场作用下的退溶胀性能.在凝胶制备过程中,PEG6000分子充当成孔剂,通过综合性能比较和红外光谱测试可知,所得凝胶具有多孔结构,这种孔洞结构有利于水分子的进出.结果显示,当引发剂为0.005 mol/L,交联剂为0.008 mol/L,摩尔比AMPS:PEG6000=100∶1,AMPS:AAm=2∶1时,可得综合性能较好的PAMA凝胶.     

P(NIPA-co-NVP)温敏性凝胶微粒的药物释放与降解

本文采用N-异丙基丙烯酰胺(NIPA)与N-乙烯基吡咯烷酮(NVP),以N,N-亚甲基双丙烯酰胺(MBA)为交联剂,氧化-还原试剂引发,通过反相悬浮共聚制备了微粒状热缩温敏水凝胶;研究了共聚单体配比及交联剂用量对凝胶温敏性能和溶胀性能的影响,并利用其温敏性以水杨酸为模型药物进行了药物吸附-释放实验;利用红外光谱和显微技术对微凝胶的结构和形态进行了表征,并初步探讨了该凝胶降解的可能性。实验发现:NVP单体的加入使共聚凝胶的体积相变温度和平衡溶胀率都明显升高,药物吸附率增加,而溶胀-退溶胀的响应速度及水保留率降低,释药率降低;该凝胶在pH1,37℃条件下能够降解,降解率随单体中NVP含量的增加而增加,随交联剂用量的增加而降低。     

PAMPS/SiO_2杂化水凝胶的合成及电场敏感性研究

以2-丙烯酰胺-2-甲基丙磺酸(AMPS)为有机原料,正硅酸乙酯(TEOS)为无机原料,过硫酸钾为引发剂,N,N'-亚甲基双丙烯酰胺为交联剂,通过原位-凝胶水溶液聚合法合成了一系列不同二氧化硅含量和不同聚离子浓度的聚(2-丙烯酰胺-2-甲基丙磺酸)/二氧化硅杂化电场敏感性水凝胶.通过扫描电子显微镜(SEM)表征凝胶的结构,研究水凝胶在去离子水以及氯化钠溶液中的溶胀和消溶胀行为.结果表明,系列凝胶的平衡溶胀度介于224.9至325.6之间,复合凝胶的溶胀速率随TEOS用量的增加而降低;除理想杂化凝胶外,随着聚离子浓度的升高,凝胶在氯化钠溶液中的消溶胀速率逐渐减小.对凝胶的电场敏感性研究表明,当聚离子浓度大于氯化钠溶液浓度时,凝胶进一步溶胀,反之则消溶胀,其中杂化凝胶的再溶胀性能减弱,而消溶胀行为变得更为明显.同时制得的理想杂化凝胶,较纯有机凝胶具有更为理想的力学性能,最大抗压缩强度可达23.4 MPa.     

聚合结晶化胶体阵列结构的压敏光响应性质

制备了由单分散聚苯乙烯微球构成的结晶化胶体阵列结构, 并制备了结晶化胶体阵列聚丙烯酰胺水凝胶薄膜. 通过微区反射光谱研究了其光子带隙位置随外加压力的变化规律. 实验结果表明, 该薄膜在垂直表面方向存在光子带隙, 并在一定载荷范围内带隙波长随外加压力呈可逆线性变化.     

Effects of particle volume fraction on distortion of particle-arrayed structure during immobilization of colloidal crystals formed by poly(methyl methacrylate)-grafted silica in acetonitrile

Changes of particle array structure with particle volume fraction during immobilization of colloidal crystals, formed by poly(methyl methacrylate)-grafted silica in acetonitrile, were investigated. Immobilization of colloidal crystals formed in acetonitrile was carried out by two-step photo-radical copolymerization of methyl methacrylate and ethylene dimethacrylate to make organogel, followed by solidification after exchanging the solvent with methyl methacrylate. Crystallite size in colloidal crystals formed in acetonitrile was mostly unchanged with particle volume fraction in the range of 0.11–0.18, while the size and number of single crystals decreased during gelation. Disordering in particle array in immobilized colloidal crystals in gel and poly(methyl methacrylate) matrix was observed to decrease with increasing particle volume fraction less than 0.18 due to strong electrostatic repulsion between particles.     

Effects of stretching on microstructures of polymer-immobilized non-close-packed colloidal crystalline array

Non-close-packed silica colloidal crystalline array was immobilized by polymer, and effects of stretching on the change of the optical properties and microstructure of the colloidal crystalline arrays have been demonstrated. The immobilization was a two-step polymerization process: the first step was with hydrophilic polyethylene glycol acrylate (PEGA) polymer gel, and the second step was with 2-hydroxyethyl acrylate polymer matrix. The structure of the three-dimensional array was maintained during the immobilizing process with lock in periodic order. The peak wavelength of Bragg diffraction of the polymer-immobilized colloidal crystalline array shifted to shorter wavelength with stretching. The peak shift was caused by the compression of the polymer proportional to the stretching ratio, and the compression was homogeneous throughout the polymer-immobilized colloidal crystalline arrays. These results show that by using polymer-immobilized non-close-packed colloidal crystalline array, mechanically tunable photonic crystals can be realized, and they open the possibility of tuning the microstructure of colloidal crystalline array for photonic crystal.     

In situ monitoring of structural changes during colloidal self-assembly

Reflectance spectroscopy is utilized to monitor structural changes during the self-assembly of a monodisperse colloidal system at the meniscus of a sessile drop on an inert substrate. Treating the ordered colloidal structure as a photonic crystal is equivalent to monitoring the changes in the photonic band gap (PBG) as the colloidal system self-assembles heterogeneously into a crystal through solvent evaporation in ambient conditions. Using a modified Bragg's law model of the photonic crystal, we can trace the structural evolution of the self-assembling colloidal system. After a certain induction period, a face-centered cubic (FCC) structure emerges, albeit with a lattice parameter larger than that of a true close-packed structure. This FCC structure is maintained while the lattice parameter shrinks continuously with further increase in the colloidal concentration due to drying. When the structure reaches a lattice parameter 1.09 times the size of that of a true close-packed structure, it undergoes an abrupt decrease in lattice spacing, apparently similar to those reported for lattice-distortive martensitic transformations. This abrupt final lattice shrinkage agrees well with the estimated Debye screening length of the electric double layer of charged colloids and could be the fundamental reason behind the cracking commonly seen in colloidal crystals.     

The Critical Effect of Niobium Doping on the Formation of Mesostructured TiO2: Single‐Crystalline Ordered Mesoporous Nb‐TiO2 and Plate‐like Nb‐TiO2 with Ordered Mesoscale Dimples

Highly ordered mesoporous niobium‐doped TiO₂ with a single‐crystalline framework was prepared by using silica colloidal crystals with ca. 30 nm in diameter as templates. The preparation of colloidal crystals composed of uniform silica nanoparticles is a key to obtain highly ordered mesoporous Nb‐doped TiO₂. The XPS measurements of Nb‐doped TiO₂ showed the presence of Nb⁵⁺ and correspondingly Ti³⁺. With the increase in the amount of doped Nb, the crystalline phase of the product was converted from rutile into anatase, and the lattice spacings of both rutile and anatase phases increased. Surprisingly, the increase in the amount of Nb led to the formation of plate‐like TiO₂ with dimpled surfaces on one side, which was directly replicated from the surfaces of the colloidal silica crystals.     

X-Ray scattering study of ionic colloidal crystals

The scattering study of ionic colloidal crystals by using one- and two-dimensional ultra-small-angle scattering techniques is reviewed with a special reference to dilute dispersions. Because of large lattice constants of colloidal crystals, ultra-small angle regions need to be covered either by long distance optical systems combined with a synchrotron X-ray source or by adopting the Bonse–Hart optics. The crystal structure, lattice constant, and crystal orientation can be precisely determined.     

Stepwise controlled immobilization of colloidal crystals formed by polymer-grafted silica particles

Colloidal crystals formed by polymer-grafted silica particles were immobilized by a stepwise procedure consisting of gelation by radical copolymerization followed by solidification by ring-opening radical polymerization. In the first step, the poly(methyl methacrylate) (PMMA)-grafted silica colloidal crystal suspension was incorporated into the gel without altering the crystal structure by copolymerization of cross-linker, 1,2-dimethylacryloyloxyethane (DME) and methyl methacrylate (MMA). In the second step, ring-opening radical polymerization was performed after substituting the solvent with vinylidene-1,3-dioxolane. By this two-step procedure, the silica particle array of colloidal crystals was immobilized and made into durable material.     

Effect of crystallization rate and colloidal stability on structural rearrangements during growth of colloidal monolayers

The structural rearrangements during growth of colloidal crystals were investigated using a combination of light microscopy and image analysis based on a Delaunay triangulation procedure. We followed the creation and disappearance of square lattice domains during the convection-promoted formation of colloidal monolayers by drying. We found that the concentration of square lattice domains increased with the crystal growth rate and that there is a direct relation between the concentration of square lattice domains formed at the crystal-suspension interface and the lower concentration of these domains in the colloidal monolayer; hence, the degree of rearrangement from square lattice domains to a close-packed triangular structure is not significantly affected by the crystal growth rate for colloidally stable suspensions. The colloidal stability, manipulated by the addition of salt, has a profound influence on the structural features of the growing monolayers. Particles that adhere strongly to each other, and to the substrate, tend to resist rearrangement; hence, the defect density is high in the colloidal monolayers and the structural reorganization of the square lattice domains to the more stable close-packed triangular structure occurred gradually over large distances from the crystal-suspension interface.     

Rupture and regeneration of colloidal crystals as studied by two-dimensional ultra-small-angle X-ray scattering

The structure of colloidal crystals of silica particles in water was studied by using the two-dimensional (2D) ultra-small-angle X-ray scattering (USAXS) technique. By violent shaking of the dispersion, large (body-centered cubic, bcc) crystals were broken into microcrystals while the lattice structure and lattice constant were preserved. The 2D-USAXS profiles revealed that the [111] direction of bcc microcrystals was parallel to the capillary axis and their orientational distribution with respect to the capillary axis was random. While a prepeak was observed in the one-dimensional USAXS measurements, no such peak was detected by the 2D-USAXS technique. The prepeak was concluded to be due to {110} being rotated by 54.7 degrees (the angle between [001] and [111]) from the capillary axis. The diffraction from the plane was out of the horizontal plane and was observed at a lower angle as a prepeak by detector scanning in the horizontal direction.     

Structural evolution of colloidal crystals with increasing ionic strength

We have directly observed the structural evolution of colloidal crystals as a function of increasing ionic strength using confocal scanning laser microscopy. Silica colloids were sedimented onto a glass substrate in deionized water to create large, single domain crystals. The solution ionic strength was then increased by one of three methods of controlled electrolyte addition: (1) direct injection of electrolyte solutions, (2) single step diffusion of electrolyte solutions through a dialysis membrane, and (3) multiple step diffusion of electrolyte solutions of increasing ionic strength through a dialysis membrane. During direct injection of electrolyte solutions, initially large, single domain colloidal crystals were shear melted and then evolved into polycrystalline structures at low ionic strengths and gels at higher ionic strengths. Diffusion of electrolyte solutions though dialysis membranes in a single step produced gradient-driven transport that also melted initial single domain crystals to yield polycrystalline and gel structures similar to the injection approach. Interestingly, the multistep diffusion of several electrolyte solutions through dialysis membranes facilitated retention of large, single domain crystals even as particles came into adhesive contact. This was achieved by reducing the contraction rate of the crystalline lattice to allow sufficient time for diffusion-limited configurational rearrangements to occur within the evolving structure. These mechanically robust, single domain colloidal crystals may find important applications as templates for photonic materials and sensors.     

A universal approach to fabricate ordered colloidal crystals arrays based on electrostatic self-assembly

We present a novel and simple method to fabricate two-dimensional (2D) poly(styrene sulfate) (PSS, negatively charged) colloidal crystals on a positively charged substrate. Our strategy contains two separate steps: one is the three-dimensional (3D) assembly of PSS particles in ethanol, and the other is electrostatic adsorption in water. First, 3D assembly in ethanol phase eliminates electrostatic attractions between colloids and the substrate. As a result, high-quality colloidal crystals are easily generated, for electrostatic attractions are unfavorable for the movement of colloidal particles during convective self-assembly. Subsequently, top layers of colloidal spheres are washed away in the water phase, whereas well-packed PSS colloids that are in contact with the substrate are tightly linked due to electrostatic interactions, resulting in the formation of ordered arrays of 2D colloidal spheres. Cycling these processes leads to the layer-by-layer assembly of 3D colloidal crystals with controllable layers. In addition, this strategy can be extended to the fabrication of patterned 2D colloidal crystals on patterned polyelectrolyte surfaces, not only on planar substrates but also on nonplanar substrates. This straightforward method may open up new possibilities for practical use of colloidal crystals of excellent quality, various patterns, and controllable fashions.