Synthesis of fast-swelling superabsorbent hydrogels: effect of crosslinker type and concentration on porosity and absorption rate

Fast-swelling highly porous superabsorbent hydrogels were synthesized through a rapid solution polymerization of concentrated partially neutralized acrylic acid under normal atmospheric conditions. Acetone and sodium bicarbonate were used as porosity generators (porogens) during polymerization process for porosity generation. N,N^′-methylenebisacrylamide (MBA) and 1,4-butanedioldiacrylate were used as the water- and the oil-soluble crosslinkers, respectively. The temperature changing of the reaction mixture during polymerization and foam formation process was monitored and investigated in details. Time and sequence of addition of the porogens and gelation time were recognized to be important to increase efficiency of the porogens. The concentration of the crosslinkers on gelation time was optimized to achieve highly porous products. It was found that higher crosslinker concentration, especially in the case of MBA, causes decreased gelation times. Shorter gelation time resulted in more porogen bubbles trapped in the viscose reaction mixture led to products with higher porosity. The effect of type and concentration of the crosslinking agents on the process and swelling behavior of the hydrogels (in water and saline solutions) were investigated. Power law relationships were found for the variation of swelling in terms of either crosslinker or saline concentration. Less sensitivity to the change of salinity was achieved by employing higher amount of crosslinker.     

Cross‐linking induced thermoresponsive hydrogel with light emitting and self‐healing property

Development of self‐healing hydrogels with thermoresponse is very important for artificial smart materials. In this article, the self‐healing hydrogels with reversible thermoresponses were designed through across‐linking‐induced thermoresponse (CIT) mechanism. The hydrogels were prepared from ketone group containing copolymer bearing tetraphenyl ethylene (TPE) and cross‐linked by naphthalene containing acylhydrazide cross‐linker. The mechanical property, light emission, self‐healing, and thermo‐response of the hydrogels were investigated intensively. With regulation of the copolymer composition, the hydrogels showed thermoresponse with the LCST varied from above to below body temperature. At the same time, the hydrogels showed self‐healing property based on the reversible characteristic of the acylhydrazone bond. The hydrogel also showed temperature‐regulated light emission behavior based on AIE property of the TPE unit. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 869–877     

Stimulus‐Responsive Hydrogel for Ophthalmic Drug Delivery

Blindness and vision impairment are major global health problems. Effective ophthalmic drug delivery poses a significant challenge because of protective physiological barriers and various biological clearance mechanisms that result in extremely low ocular bioavailability. Over the past several decades, several safe and effective ophthalmic drug delivery approaches have been promoted to combat these problems and to improve ocular bioavailability. Among these approaches, the stimulus‐responsive hydrogel for topical drug delivery has gained increasing attention because of its prolonged drug retention at the local site and enhanced ocular bioavailability. This review summarizes and presents recent advances and perspectives of a stimulus‐responsive hydrogel for ophthalmic drug delivery.     

Investigation of Sustained BMP Delivery in the Prevention of Medication‐Related Osteonecrosis of the Jaw (MRONJ) in a Rat Model

Medication‐related osteonecrosis of the jaw (MRONJ) poses an ongoing challenge for clinicians and researchers. Currently, there is a lack of preventative measures available for at‐risk patients undergoing tooth extractions, especially those with prior bisphosphonate treatment due to osteoporosis or bone metastasis diagnoses. Here, these issues are addressed using a preventative tissue engineering strategy against MRONJ development. This study evaluates the efficacy of a poly(ethylene glycol)‐heparin hydrogel as a tool for the delivery of arginylglycylaspartic acid (RGD) and recombinant human bone morphogenic protein‐2 (rhBMP‐2). Three groups of skeletally mature rats each receive two doses of intravenous zoledronic acid prior to surgery and undergo extraction of the right first mandibular molar with gingival closure. Experimental groups either have the sockets left empty, filled with hydrogel minus rhBMP‐2, or filled with hydrogel plus rhBMP‐2. Eight weeks postoperatively specimens are analyzed using radiological, histological, and scanning electron microscopy (SEM) techniques. µCT analysis shows increased bone formation with hydrogel/rhBMP‐2 delivery compared to the empty socket. Hydrogel‐treated groups display increased presence of osteocytes and increased osteoclastic action compared to the empty sockets. These results represent the first step toward improved delivery of rhBMP‐2 and a potential MRONJ preventative for patients undergoing bisphosphonate treatment.     

载银离子PLGA-PEG-PLGA温度敏感水凝胶的制备及体外抗菌性能

利用聚乙二醇(PEG 1000)引发乙交酯和 D,L-丙交酯开环共聚合, 制备了聚丙交酯乙交酯(PLGA)三嵌段共聚物(PLGA-PEG-PLGA)温敏水凝胶材料; 利用核磁共振氢谱( ¹H NMR)确定了产物的结构及组成. 通过还原硝酸银的方法制备银纳米粒子(AgNPs), 并将其与PLGA-PEG-PLGA三嵌段共聚物水凝胶混合, 制得新型AgNPs/PLGA-PEG-PLGA复合水凝胶; 对该复合水凝胶的相关性能进行了表征. AgNPs/PLGA-PEG-PLGA复合水凝胶仍然具有温敏性能, 随着温度升高可发生溶胶-凝胶的相转变; 还可以持续释放银纳米粒子, 从而发挥抗菌性能. 体外细胞实验结果表明, AgNPs/PLGA-PEG-PLGA复合水凝胶具有良好的生物相容性, 未见明显细胞毒性, 是具有应用前景的新型复合水凝胶.     

Conformational change of proline residues observed in swollen and shrunken phases: γ‐Ray synthesis and variable temperature circular dichroism spectra of a thermo‐responding polymer,poly(acryloyl‐Pro‐OMe)

Poly(acryloyl‐L ‐proline‐methyl ester) ( 1 ) has optically active side chain, and constitutes thermoresponsive hydrogels upon crosslinking. In this study, we have prepared uncrosslinked polymer of 1 with a 10‐kGy irradiation dose of γ‐ray. For this polymer, 1 , variable temperature circular dichroism (CD) and ¹H NMR spectra have been studied in the range of 0–30 °C. The intense CD spectrum at 0 °C suggests that the side chains in 1 have an ordered orientation. The CD intensity decreases gradually with increasing temperature. The decreased intensity of CD spectra indicates that the disordering occurs for the side‐chain orientation. The CD band shape changes discontinuously at 20 °C. In the ¹H NMR spectra, signals disappear above 20 °C. These spectral change at 20 °C indicate that the phase transition occurs at around 20 °C from swollen to shrunken phase. Even after the phase transition, the CD spectra are still changing with isochromic point at 212 nm. It appears that the side‐chain conformation is still changing from one state to the other state in the shrunken phase polymers. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4524–4530, 2000     

荧光探针法研究壳聚糖水凝胶形成过程及其性能

基于芘(Py)单体荧光光谱结构对微观环境变化的敏感性,以及介质粘度及Py分子间距对Py激基络缔合物形成的影响,以戊二醛交联壳聚糖(CS)水凝胶体系为例研究了Py荧光探针法监测水凝胶形成过程及其溶胀性能的可行性。结果表明,Py荧光光谱精细结构的变化(以I~3/I~1为参量)或Py激基缔合物荧光强度与单体荧光强度之比(I~E/I~M)的变化与CS水凝胶的形成及溶胀程度有很好的对应关系。此外,CS凝胶网状结构中包埋的聚N-异丙基丙烯酰胺(PNIPAM)的构象变化也可由探针光谱变化反映出来。利用这种荧光探针方法有助于从分子水平上探知凝胶形成过程的微观本质。此外,这种方法也可作为光纤传导监测凝胶形成过程和溶胀的基础。     

Structure and properties of cellulose/poly(N‐isopropylacrylamide) hydrogels prepared by IPN strategy

Interpenetrating polymer network (IPN) strategy was developed to fabricate novel hydrogels composed of cellulose and poly(N‐isopropylacrylamide) (PNIPAAm) with high mechanical strength and adjustable thermosensitivity. Cellulose hydrogels were prepared by chemically cross‐linking cellulose in NaOH/urea aqueous solution, which were employed as the first network. The second network was subsequently obtained by in situ polymerization/cross‐linking of N‐isopropylacrylamide in the cellulose hydrogels. The results from FTIR and solid ¹³C NMR indicated that the two networks co‐existed in the IPN hydrogels, which exhibited uniform porous structure, as a result of good compatibility. The mechanical and swelling properties of IPN hydrogels were strongly dependent on the weight ratio of two networks. Their temperature‐sensitive behaviors and deswelling kinetics were also discussed. This work created double network hydrogels, which combined the advantages of natural polymer and synthesized PNIPAAm collectively in one system, leading to the controllable temperature response and improvement in the physical properties. Copyright © 2009 John Wiley & Sons, Ltd.     

温敏性半乳糖基化壳聚糖水凝胶的制备及其对HL-7702细胞增殖行为影响的研究

以壳聚糖(CS)为原料,在1-乙基-3-(3-二甲胺丙基)碳-二亚胺盐酸盐(EDC.HCL)和N-羟基琥珀酰亚胺(NHS)的活化作用下,合成了半乳糖基化壳聚糖(GC)单体,并与N-异丙基丙烯酰胺(NIPAAm)反应,制备了温敏性半乳糖基化壳聚糖N-异丙基丙烯酰胺共聚水凝胶(Gal-CS-g-PNIPAAm).通过红外光谱(FTIR)、光电子能谱(XPS)和扫描电子显微镜(SEM)等测试方法对其成分和结构进行了表征,并对其溶胀率和表面亲疏水性进行了研究.在Gal-CS-g-PNIPAAm凝胶表面培养人正常肝细胞系(HL-7702),研究其生长、脱附及转载(再增殖)行为.结果表明Gal-CS-g-PNIPAAm水凝胶具有良好的温度响应性和生物相容性,与PNIPAAm水凝胶相比,Gal-CS-g-PNIPAAm凝胶表面更有利于HL-7702细胞增殖.将温度降低至临界温度(LCST,32.5℃)以下,细胞可以从凝胶表面自发脱附,与酶消化脱附相比,细胞损伤更少.Gal-CS-g-PNIPAAm凝胶表面脱附的细胞比PNIPAAm凝胶表面脱附的细胞活性更高,表明PNIPAAm水凝胶引入GC单体后,凝胶的生物相容性得到改善,且脱附后细胞的增殖活力明显增加.     

壳聚糖基智能水凝胶的研究进展

壳聚糖是一种天然高分子,含有氨基和羟基等特征基团;水凝胶是一种高分子交联网络体系,具有亲水性,在水中能够溶胀并保持大量水分而不溶解;“智能化”是自发地对外界环境刺激产生响应的一种特性.壳聚糖基智能水凝胶具有良好的生物相容性和可降解性,正倍受广大研究学者的关注.文章综述了近年来关于pH敏感型、温度敏感型以及pH/温度双重敏感型壳聚糖基智能水凝胶的研究概况,介绍了壳聚糖基水凝胶在医学领域如组织工程、药物释放方面的应用并对其未来的发展方向进行了探讨.