凝胶光子晶体

光子晶体是一种介电常数（或折射率）可以周期性调制的结构,其自激辐射抑制和光子局域化性质使其可以简便而有力的限制、控制和调控光子。近年来,利用胶体晶体自组装性质与水凝胶的传统应用相结合制成的凝胶光子晶体在药物释放、光学开关、金属探针、生物传感器等的新应用方面的研究蓬勃发展,在新材料开发及临床应用等方面取得巨大进展。本文概述了胶体晶体自组装并对该类凝胶光子晶体进行了分类介绍并对其发展趋势进行了评述和展望。     

反蛋白石光子晶体凝胶的pH响应

首先采用Stber方法制备了一系列亚微米级单分散二氧化硅小球,而后通过垂直沉降自组装方法制备了颜色鲜艳的二氧化硅三维有序结构胶体晶体模板,最后再采用模板聚合法在220 nm二氧化硅小球自组装的阵列间隙中共聚甲基丙烯酸和乙二醇二甲基丙烯酸酯,经氢氟酸刻蚀二氧化硅模板后得到多孔有序的反蛋白石光子晶体.当pH值从5升至8时,反蛋白石凝胶光子晶体的反射峰波长从514 nm移动至590 nm,颜色变化显著,从蓝绿色变成红色,突变点为pH=6.5,而且pH响应在100 s左右即可达到平衡.对交联剂用量的研究结果表明,随着交联剂乙二醇二甲基丙烯酸酯用量从4%增加到16%,光子晶体响应pH时的红移量减小.     

聚乙烯醇二维光子晶体水凝胶的制备及乙醇响应行为

以单分散的聚苯乙烯微球乳液为原料, 采用针尖注射法制备了聚苯乙烯二维光子晶体阵列, 采用聚乙烯醇填充二维光子晶体阵列, 以戊二醛为交联剂, 得到聚乙烯醇二维光子晶体水凝胶(PVA·2DPCH). 通过测定PVA·2DPCH在不同浓度的乙醇/水溶液中的德拜环直径(D)变化, 研究了PVA·2DPCH对乙醇的响应行为. 结果表明, 在乙醇体积分数为0~60%范围内, PVA·2DPCH对乙醇没有明显响应, 德拜环直径基本保持不变; 当乙醇体积分数超过60%时, PVA·2DPCH对乙醇表现出敏感响应, 其德拜环直径随乙醇体积分数的增大而增大, 响应时间仅需30 s; 在乙醇体积分数为60%~100%范围内, PVA·2DPCH的德拜环直径变化(ΔD)与乙醇体积分数(V_e)呈线性相关: 当60%≤V_e≤75%时, 其线性回归方程为ΔD=50.30V_e-31.74, r²=0.9734; 当75%<V_e≤100%时, 其线性回归方程为ΔD=111.14 V_e-74.03, r²=0.9902. 以制备的PVA·2DPCH为乙醇传感器, 利用德拜环法测定市售酒精消毒液中乙醇含量, 方法简单快速, 兼具无标记、 可视化检测的特点.     

镉离子响应性凝胶光子晶体传感膜的构建

将光子晶体与响应性水凝胶结合,采用“三明治”填充方法,以聚苯乙烯（PS）胶体晶体为模板,丙烯酰胺和烯丙基硫脲为单体制备得到一种对镉离子具有特异响应性的凝胶光子晶体传感膜,并对其进行了形貌表征和响应性研究。结果表明,该传感膜具有排列整齐的反蛋白石结构,可对不同浓度的Cd²⁺输出不同的光学信号。随着Cd²⁺浓度的增大,传感膜的Bragg衍射峰发生蓝移,并伴随有显著的颜色变化。在最优配比,适宜pH和离子强度条件下,衍射峰的最大位移值可达51.1 nm。在研究过程中发现其他干扰金属离子的存在不会影响传感膜对Cd²⁺的特异性响应,并且表现出了较快的响应速度。在多次循环实验中传感膜由于具备高度交联结构而表现出了良好的机械性和化学稳定性。该传感膜的构建为Cd²⁺的快速高效及裸眼可视检测提供了可能性。     

壬基酚分子印迹二维光子晶体水凝胶传感器

以聚苯乙烯二维光子晶体为模板,壬基酚(NP)为印迹分子,甲醇为溶剂,甲基丙烯酸为功能单体,二甲基丙烯酸乙二醇酯为交联剂(EGDMA),2,2-二乙氧基苯乙酮(DEAP)为引发剂,经紫外光引发聚合,得到了可特异性识别壬基酚的分子印迹二维光子水凝胶传感器.通过测量德拜衍射环直径(D)的变化(ΔD)来判断传感器的响应性能.实验结果表明,在壬基酚溶液中,水凝胶的体积膨胀导致凝胶中光子晶体的粒子间距增大,德拜衍射环直径减小.随着溶液中NP的浓度从0增加到1×10^?5 mol/L,德拜衍射环的直径减小了8.0 mm,相应的光子晶体的颗粒间距增加了25.1 nm.在1×10^-13～1×10^-8 mol/L范围内,德拜衍射环直径的变化与壬基酚浓度的对数值(lgc)呈线性关系,制备的传感器检出限低至1×10^?13 mol/L,具有较高的灵敏度、良好的特异性识别能力和稳定的可重复利用性,并且可以实现对壬基酚的可视化检测.     

红霉素分子印迹二维光子晶体水凝胶传感器的研究

以红霉素为印迹分子,聚苯乙烯二维光子晶体为模板,甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸甲酯为交联剂,2,2-二乙氧基苯乙酮为引发剂,紫外光引发聚合,在甲醇-乙酸(9∶1, V/V)中洗脱印迹分子,得到能够特异性识别红霉素的分子印迹二维光子晶体水凝胶.通过测试德拜环直径变化,研究了此水凝胶在红霉素溶液中的响应性能.实验结果表明,当红霉素的浓度从0增加到1×10-6 mol/L时,德拜环直径增加6 mm, 相应的晶格间距减小30 nm.此外,水凝胶在1×10-6 mol/L红霉素的类似物罗红霉素、琥乙红霉素溶液中,德拜环直径仅分别增加1.5和2.0 mm,表明此光子晶体水凝胶具有良好的选择性,有望用于红霉素低成本的简易检测.     

糖蛋白印迹二维光子晶体水凝胶传感器的构建

制备了一种特异性识别糖蛋白的二维光子晶体分子印迹水凝胶。以刀豆蛋白A(Con A)为模板分子,甲叉双丙烯酰胺(MBA)为交联剂,丙烯酰胺(AAm)与4-乙烯基苯硼酸为功能单体,N,N,N′,N′-四甲基乙二胺(TEMED)为引发剂,过硫酸铵(APS)为催化剂,在聚苯乙烯二维光子晶体(PC)表面产生聚合反应形成水凝胶,接着用10%的乙酸溶液洗脱模板分子,制备了可对Con A特异性识别的二维光子晶体分子印迹水凝胶(MIPs)传感器。结果表明,当MIPs的交联度为10%时,德拜环的直径变化最显著,对目标物的识别最灵敏。该传感器对Con A在0～0.5 mg/mL范围内具有良好的响应与识别能力,可用于目标物的富集和即时检测。同时,苯硼酸的引入,增加了印迹空穴的识别位点,进一步改善了印迹材料对糖类分子的特异识别性。该水凝胶传感器在卵清白蛋白(OVA)、牛血红蛋白(BHb)、溶菌酶(Lyz)、胰蛋白酶(Try)溶液中德拜环的直径变化远小于识别相同浓度的Con A引起的德拜环直径的变化,表现出良好的选择性。该方法操作简单,成本低廉,可重复使用,不需特殊仪器设备,可拓展到其它糖蛋白,实现糖类目标蛋白的...     

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.     

二维光子晶体水凝胶传感器检测邻苯二甲醛

邻苯二甲醛（OPA）是一种新型化学消毒剂,在医疗机构中广泛使用,为保证使用效果和安全性,在临床使用中必须对其浓度进行检测和验证。本研究在二维光子晶体（2DPC）水凝胶中修饰乙二胺（EDA）并嵌入氨基,使水凝胶氨基功能化,制备了一种响应性2DPC水凝胶。2DPC水凝胶聚合物链上嵌入的氨基可与OPA反应,随着OPA浓度增加,水凝胶的交联密度增大,从而导致水凝胶体积发生相变,即发生收缩现象,2DPC的微球间距逐渐减小,而德拜衍射环直径逐渐增大。通过测量德拜衍射环直径的变化,并根据公式计算得到2DPC的微球间距的变化。结果表明,在101～106nmol/L范围内,OPA浓度的对数值与微球间距呈良好的线性关系。因此,基于氨基功能化的2DPC水凝胶传感器可实现对OPA的定量检测。本方法检测线性范围宽,检出限为0.21 nmol/L(3σ/k)。采用此水凝胶传感器检测了稀释的临床消毒剂中的OPA,回收率为100%～103%,相对标准偏差为1.8%～5.5%。本研究构建的2DPC水凝胶传感器可用于临床内窥镜等器械消毒剂中OPA的检测。     

Rhodamine Mechanophore Functionalized Mechanochromic Double Network Hydrogels with High Sensitivity to Stress

Mechanochromic hydrogels, a new class of stimuli-responsive soft materials, have potential applications in a number of fields such as damage reporting and stress/strain sensing. We prepared a novel mechanochromic hydrogel using a strategy that has been developed to prepare dual-network(DN) hydrogels. A hydrophobic rhodamine derivative(Rh mechanophore) was covalently incorporated into a first network as a cross-linker. This first network embedded with Rh mechanophore within the DN hydrogel was pre-stretched. This guaranteed that the stress could be transferred extensively to the Rh-crosslinked first network once the hydrogel was under an applied force. Interestingly, we found that the threshold stress required to activate the mechanochromism of the hydrogel was less than 200 kPa, and much less than those in previous reports. Moreover, because of the excellent sensitivity of the hydrogel to stress, the DN hydrogel exhibited reversible freezing-induced mechanochromism. Benefiting from the sensitivity of Rh mechanophore to both p H and force, the DN hydrogel showed p H-regulated mechanochromic behavior. Our experimental results indicate that the preparation strategy we used introduces sensitive mechanochromism into the hydrogel and preserves the advantageous mechanical properties of the DN hydrogel. These results will be beneficial to the design and preparation of mechanochromic hydrogels with high stress sensitivity, and foster their practical applications in a number of fields such as damage reporting and stress/strain sensing.     

A Double Network Hydrogel with High Mechanical Strength and Shape Memory Properties

Double network (DN) hydrogels as one kind of tough gels have attracted extensive attention for their potential applications in biomedical and load-bearing fields. Herein, we import more functions like shape memory into the conventional tough DN hydrogel system. We synthesize the PEG-PDAC/P(AAm-co-AAc) DN hydrogels, of which the first network is a well-defined PEG (polyethylene glycol) network loaded with PDAC (poly(acryloyloxyethyltrimethyl ammonium chloride)) strands, while the second network is formed by copolymerizing AAm (acrylamide) with AAc (acrylic acid) and cross-linker MBAA (N, N'-methylenebisacrylamide). The PEG-PDAC/P(AAm-co-AAc) DN gels exhibits high mechanical strength. The fracture stress and toughness of the DN gels reach up to 0.9 MPa and 3.8 MJ/m³, respectively. Compared with the conventional double network hydrogels with neutral polymers as the soft and ductile second network, the PEG-PDAC/P(AAm-coAAc) DN hydrogels use P(AAm-co-AAc), a weak polyelectrolyte, as the second network. The AAc units serve as the coordination points with Fe³⁺ ions and physically crosslink the second network, which realizes the shape memory property activated by the reducing ability of ascorbic acid. Our results indicate that the high mechanical strength and shape memory properties, probably the two most important characters related to the potential application of the hydrogels, can be introduced simultaneously into the DN hydrogels if the functional monomer has been integrated into the network of DN hydrogels smartly.     

雌二醇的水凝胶毛细管电泳免疫分析

雌二醇是雌性激素中最重要和作用最强的一种激素 .临床上 ,雌二醇的长期监测可用于研究与激素相关的致癌物作用机理、绝经期妇女的雌激素补充及不孕病人的跟踪治疗等方面 .研究发现 ,人体中雌二醇含量与某些肿瘤如乳腺癌、子宫癌和肝癌等密切相关 [1] .由于雌二醇在体液中含量很低 ,难于测定 .免疫分析法的出现给雌二醇的测定带来了变革 ,提高了测定的灵敏度和特异性 .目前测定雌二醇的免疫分析方法有放射免疫分析法 ( RIA) [2 ]、酶免疫分析法 ( EIA) [3～ 7]、荧光免疫分析法 ( FIA) [8]和化学发光与生物发光免疫分析法 [9,10 ] .但 R…     

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     

Water-Resistant and Stretchable Conductive Ionic Hydrogel Fibers Reinforced by Carboxymethyl Cellulose

Conductive ionic hydrogels (CIH) have been widely studied for the development of stretchable electronic devices, such as sensors, electrodes, and actuators. Most of these CIH are made into 3D or 2D shape, while 1D CIH (hydrogel fibers) is often difficult to make because of the low mechanical robustness of common CIH. Herein, we use gel spinning method to prepare a robust CIH fiber with high strength, large stretchability, and good conductivity. The robust CIH fiber is drawn from the composite gel of sodium polyacrylate (PAAS) and sodium carboxymethyl cellulose (CMC). In the composite CIH fiber, the soft PAAS presents good conductivity and stretchability, while the rigid CMC significantly enhances the strength and toughness of the PAAS/CMC fiber. To protect the conductive PAAS/CMC fiber from damage by water, a thin layer of hydrophobic polymethyl acrylate (PMA) or polybutyl acrylate (PBA) is coated on the PAAS/CMC fiber as a water-resistant and insulating cover. The obtained PAAS/CMC-PMA and PAAS/CMC-PBA CIH fibers present high tensile strength (up to 28 MPa), high tensile toughness (up to 43 MJ/m³), and good electrical conductivity (up to 0.35 S/m), which are useful for textile-based stretchable electronic devices.     

Structurally Enhanced Hydrogel Nanocomposites with Improved Swelling and Mechanical Properties

In this work, structurally enhanced hydrogel nanocomposites based on 2-acrylamido-2 methyl propane sulfonic acid (AMPS)-acrylamide (AAM) copolymer with high hydrophilic group content were prepared by in-situ copolymerization by using different types of clay (montmorillonite, mica and halloysite). Nanocomposite hydrogels were characterized by Fourier-Transform Infrared Spectroscopy (FTIR) and X-ray diffraction (XRD) analyses and determination of swelling degrees of the samples. Mechanical properties of the samples were also investigated by determination of the compressive elastic modulus. It was also found that exfoliated or highly expanded intercalated nanocomposite structure was obtained and clay incorporation into the AMPS-AAM hydrogel structure improved its swelling capacity. The highest swelling capacity (1030 g H₂O/g) was observed for the nanocomposite sample prepared with the montmorillonite amount of 5% (w). Furthermore, mechanical strength of the hydrogels against compression forces was significantly improved by the clay addition. It was found that the type of clay, in other word filler geometry, affected the compressive elastic modulus (E) of the samples. It was concluded that halloysite, which is considered to be a one dimensional (1D) nanotubular filler was less effective to enhance the compressive elastic modulus (E) of such materials compared with the montmorillonite and mica having two dimensional (2D) platelet or disk-like shapes at a particular amount of clay.     

快速响应的温敏性聚(N-异丙基丙烯酰胺)水凝胶的合成及表征

快速响应的温敏性聚(N-异丙基丙烯酰胺)水凝胶的合成及表征;N-异丙基丙烯酰胺;水凝胶;温敏性;快速响应     

Multicomponent Alginate-Derived Hydrogel Microspheres Presenting Hybrid Ionic-Covalent Network and Drug Eluting Properties

The development of multifunctional encapsulation biomaterials could help the translation of cell-based therapies into standard medical care. One of the major hurdles in the field of encapsulated cell transplantation is the current lack of materials presenting optimal properties, including long term stability, mechanical durability and non-immunogenic character. Modification of sodium alginate (Na-alg) with polyethylene glycol (PEG) derivatives, without restricting its gelling abilities, appeared as an efficient strategy to produce dual ionic-covalent spherical hydrogels with enhanced mechanical performance as well as drug-eluting microspheres (MS) for the mitigation of inflammatory response after transplantation. In this study, the combination of PEGylated alginates equipped with cross-reactive functionalities and the anti-inflammatory drug ketoprofen (KET) resulted in the assembly of multifunctional (MF) hybrid MS, merging the advantages of ionic-covalent hydrogels with the ability for controlled drug delivery. Physical characterization confirmed their improved mechanical resistance, their higher shape recovery performance and increased stability toward non-gelling ions, as compared to pure Ca-alg hydrogels. In vitro release kinetics revealed the controlled and sustained delivery of KET for over two weeks.     

一种高强度准聚轮烷水凝胶的制备及性能研究

通过点击化学在聚乙二醇单甲醚(MPEG)端基分别修饰了葡萄糖(Glc)、甘露糖(Man)和半乳糖(Gal),制备了一系列端基为糖的聚乙二醇单甲醚(MPEG-Glc、MPEG-Man和MPEG-Gal),此类端基为糖的MPEG和α-环糊精(α-CD)混合后能够形成稳定的准聚轮烷(PPR)水凝胶,而端基没有修饰糖的MPEG和α-CD只能形成黏度较大的溶液而无法形成稳定存在的凝胶.通过流变仪测试可知水凝胶的弹性模量高达1.0×105 Pa,远大于文献中通过黏土等增强的PPR水凝胶的强度,我们认为该MPEG端基的糖之间能够形成新的"糖交联"点从而有效提高了凝胶的强度.通过向水凝胶中加入和MPEG端基的糖具有相互作用的苯硼酸半酯聚合物(PNIPAM-co-PBOB)或刀豆蛋白(Con A),发现在凝胶中加入PNIPAM-co-PBOB或Con A后可明显降低PPR水凝胶的强度.通过扫描电镜(SEM)和X射线衍射(XRD)对水凝胶的形貌以及微观结构进行表征分析,发现此凝胶的微观结构和文献中报道的PPR水凝胶基本一致,进一步证明了上述结论.     

交联聚(N-异丙基丙烯酰胺)/(海藻酸钠/聚(N-异丙基丙烯酰胺))半互穿网络水凝胶的制备及其溶胀性能

将线性聚(N-异丙基丙烯酰胺)(PNIPAAm)和海藻酸钠(SA)分子同时引入到PNIPAAm凝胶中,制备了交联聚(N-异丙基丙烯酰胺)/(海藻酸钠/聚(N-异丙基丙烯酰胺))半互穿网络(Cr-PNIPAAm/(SA/PNIPAAm)semi-IPN)水凝胶。在弱碱性条件下(pH=7.4),改变SA与线性PNIPAAm的质量比对Cr-PNIPAAm/(SA/PNIPAAm)semi-IPN水凝胶的溶胀度没有太大的影响。在酸性条件下(pH=1.0),其溶胀度随着SA与线性PNIPAAm质量比的减小而增大。由于亲水性SA与线性PNIPAAm的协同作用,Cr-PNIPAAm/(SA/PNIPAAm)semi-IPN水凝胶的消溶胀速率得到很大提高。