内嵌纳凝胶阴离子交换聚甲基丙烯酸羟乙酯复合晶胶分离苯乳酸研究

采用超声乳化聚合法制备了聚甲基丙烯酸丁酯纳凝胶,然后经结晶致孔法制备了内嵌纳凝胶的甲基丙烯酸羟乙酯纳晶胶,对其接枝功能单体N,N,N-三甲基乙烯基苯甲氯化铵,得到内嵌纳凝胶阴离子交换纳晶胶,用于从发酵液中分离苯乳酸。结果表明:所得纳晶胶具有良好的渗透性能和轴向分散性能,在流速为1 cm·min^-1时,不同配比纳晶胶对牛血清白蛋白的吸附容量为3.9～5.4 mg·ml^-1;将质量比为8∶2(HEMA∶pBMA)的纳晶胶用于从转化液中分离苯乳酸,所得苯乳酸的纯度达89.24%,回收率93.74%,分离效果好,表明其在生物分离方面有良好的应用前景。     

Ethanol‐responsive characteristics of polyethersulfone composite membranes blended with poly(N‐isopropylacrylamide) nanogels

Ethanol‐responsive smart membranes with different microstructures are prepared from blends of polyethersulfone (PES) and poly(N‐isopropylacrylamide) (PNIPAM) nanogels by immersion precipitation phase inversion method in a convenient and controllable manner. The introduction of PNIPAM nanogels forms the microporous structures on the surface of the top skin layer and on the pore walls of the finger‐like porous sublayer of membranes. The ethanol‐responsive characteristics of the proposed PES composite membranes are systematically investigated. With increasing ethanol concentration in the range from 0 to 15 wt %, the trans‐membrane flux of ethanol solution increases. The microstructures and the resultant ethanol‐responsive characteristics of the composite membranes can be regulated by the content of PNIPAM nanogels blended in the membranes. The more the content of PNIPAM nanogels blended in the membranes, the more the number of the submicron pores is, and thus the better the ethanol‐responsive characteristics of the composite membranes. The proposed ethanol‐responsive smart membranes are expected to be combined with the traditional pervaporation membranes as a smart vavle to achieve continuous and highly efficient ethanol production during the biological fermentation. The preparation technique and results in this study provide valuable guidance for further design and the industrial‐scale fabrication of novel composite membranes for application in ethanol separation systems. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41032.     

Preparation of thermoresponsive poly(N-vinylcaprolactam-co-2-methoxyethyl acrylate) nanogels via inverse miniemulsion polymerization

Stimuli-responsive polymeric nanogels hold great potential in biological applications. In this work, thermoresponsive polymeric nanogels were conveniently prepared through inverse miniemulsion polymerization of two monomers with a good biocompatibility, N-vinylcaprolactam and 2-methoxyethyl acrylate. A macromolecular crosslinker, poly(ethylene glycol) dimethacrylate (PEGDMA), was used to achieve a better thermoresponsiveness, compared with low-molecular-weight crosslinkers. The prepared poly(N-vinylcaprolactam-co-2-methoxyethyl acrylate) (poly(NVCL-co-MEA)) nanogels could be well redispersed in aqueous systems, displaying a reversible thermoresponsive transition behavior. The influences of the synthesis parameters including the emulsifier content, PEGDMA content, and monomer composition on the particle properties of poly(NVCL-co-MEA) nanogels both in inverse emulsions and in aqueous dispersions were systematically investigated. Furthermore, the impacts of the monomer composition and PEGDMA content on the thermoresponsiveness of poly(NVCL-co-MEA) nanogels were also studied. Promisingly, the introduction of MEA monomeric units to the copolymer chains only slightly reduced the thermoresponsiveness of poly(NVCL-co-MEA) nanogels. This feature allows to improve the biocompatibility of polymeric nanogels by using MEA as the comonomer without need to compromise the thermoresponsiveness of nanogels. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48237.     

Prerequisite Characteristics of Nanocarriers Favoring Oral Insulin Delivery: Nanogels as an Opportunity

Extensive research has been carried out for developing nanocarriers to overcome the major barriers preventing success in oral insulin therapy, which includes (a) identification of in vivo barriers, (b) incorporation of prerequisite characteristics into single nanocarrier, and (c) exclusion of the use of additional potentially toxic chemicals as enzyme inhibitors or permeation enhancers. The present review identifies the prerequisite characteristics of single nanocarrier that could avoid major hindrance being faced in oral insulin delivery. An effort is made to discuss the involvement of prerequisite characters to overcome the major hurdles, which prevent the success in oral insulin delivery.     

基于pH敏感型葡聚糖水凝胶微球的药物载体

以葡聚糖为原料,采用反相微乳液技术制备了一种含有席夫碱结构的葡聚糖基水凝胶纳米微球作为载体,通过交联剂聚乙烯亚胺(PEI)的静电吸附作用对药物模型8-羟基芘-1,3,6-三磺酸三钠盐(HPTS)进行了包埋,利用FTIR、SEM和DLS等对微球的结构和形貌进行了表征。结果表明,这种葡聚糖纳米水凝胶载药前后均具有良好的球形结构,平均粒径分别在459和648 nm左右。载药效果及药物释放行为研究发现,该葡聚糖纳米水凝胶可对HPTS进行有效负载,且其释放行为具有明显的酸性环境敏感性,酸性越强,释放越快。含有席夫碱结构的葡聚糖纳米凝胶微球可作为pH敏感型载体应用于药物递送领域。     

Reduction‐Sensitive Dextran Nanogels Aimed for Intracellular Delivery of Antigens

Targeting of antigens to dendritic cells (DCs) to induce strong cellular immune response can be established by loading in a nano‐sized carrier and keeping the antigen associated with the particles until they are internalized by DCs. In the present study, a model antigen (ovalbumin, OVA) is immobilized in cationic dextran nanogels via disulfide bonds. These bonds are stable in the extracellular environment but are reduced in the cytosol of DCs due to the presence of glutathione. Reversible immobilization of OVA in the nanogels is demonstrated by the fact that hardly any release of the protein occurred at pH 7 in the absence of glutathione, whereas rapid release of OVA occurs once the nanogels are incubated in buffer with glutathione. Furthermore, these OVA conjugated nanogels show intracellular release of the antigen in DCs and boost the MHC class I antigen presentation, demonstrating the feasibility of this concept for the aimed intracellular antigen delivery.     

P(HEMA-co-MAA)纳米凝胶的制备与pH响应性

以甲基丙烯酸羟乙酯(HEMA)和甲基丙烯酸(MAA)为聚合单体,异辛烷为分散介质,Span80和Tween80为复配乳化剂,采用反相微乳液聚合法制得不同单体配比的聚(甲基丙烯酸羟乙酯-co-甲基丙烯酸)(P(HEMA-co-MAA))纳米凝胶。确定了产物的pKa值及实际单体物质的量比,对产物的形貌进行了表征并研究了产物的pH响应性.结果显示,MAA物质的量分数为20%的纳米凝胶的pKa值为5.83,在pH=3和pH=7时其数均粒径分别为48 nm和90 nm;当环境pH接近pKa值时,纳米凝胶分散液的浊度明显降低,溶胀率明显上升,表观黏度急剧增加,说明纳米凝胶具有良好的pH响应性。     

Nanogel Encapsulated Hydrogels As Advanced Wound Dressings for the Controlled Delivery of Antibiotics

Biocompatible and degradable dual-delivery gel systems based on hyperbranched dendritic−linear−dendritic copolymers (HBDLDs) is herein conceptualized and accomplished via thiol-ene click chemistry. The elasticity of the hydrogels is tunable by varying the lengths of PEG (2, 6, 10 kDa) or the dry weight percentages (20, 30, 40 wt%), and are found to range from 2–14.7 kPa, comparable to human skin. The co-delivery of antibiotics is achieved, where the hydrophilic drug novobiocin sodium salt (NB) is entrapped within the hydrophilic hydrogel, while the hydrophobic antibiotic ciprofloxacin (CIP) is encapsulated within the dendritic nanogels (DNGs) with hydrophobic cores (DNGs-CIP). The DNGs-CIP with drug loading capacity of 2.83 wt% are then physically entrapped within the hybrid hydrogels through UV curing. The hybrid hydrogels enable the quick release of NB and prolonged released of CIP. In vitro cell infection assays showed that the antibiotic-loaded hybrid hydrogels are able to treat bacterial infections with significant bacterial reduction. Hybrid hydrogel band aids are fabricated and exhibited better antibacterial activity compared with commercial antimicrobial band aids. Remarkably, most hydrogels and hybrid hydrogels show enhanced human dermal cell proliferation and could be degraded into non-toxic constituents, showing great promise as wound dressing materials.