Formation Mechanism and Tensile Mechanical Properties of Poly(acrylamide-co-octylphenol polyoxyethylene (10) acrylate) Hydrophobic Association Hydrogels With High Toughness

Poly(acrylamide-co-octylphenol polyoxyethylene (10) acrylate) hydrophobic association hydrogels, which is abbreviated to poly(AM-co-OP10/AC) HA-gels, were prepared through micellar copolymerization of acrylamide (AM) and a small amount of octylphenol polyoxyethylene (10) acrylate (OP10/AC) in the presence or absence of sodium dodecyl sulfate (SDS). For poly(AM-co-OP10/AC) HA-gels, formation mechanism was discussed in detail, which can reasonably explain the reason that tensile mechanical properties of the hydrogels (containing SDS) are much higher than those of the hydrogels (not containing SDS). In addition, according to the tensile experimental results of poly(AM-co-OP10/AC) HA-gels, the effect of composition content in the initial solutions on tensile mechanical properties was investigated in detail. The results clearly indicate tensile strength, elastic modulus and elongations for poly(AM-co-OP10/AC) HA-gels strongly depended on composition content in the initial solutions.     

Photocrosslinked hydrogels based on copolymers of poly(ethylene glycol) and lysine

A group of new, water-soluble poly(ether-urethane)s, derived from poly(ethylene glycol) and the amino acid L -lysine, provide pendent carboxylic acid groups along the polymer backbone at regular intervals. The carboxylic acid groups were utilized for the attachment of acrylate and methacrylate pendent chains (hydroxyethyl acrylate, hydroxyethyl methacrylate, aminoethyl methacrylate, and aminoethyl methacrylamide), leading to functionalized polymers. The pendent chains were attached via ester and/or amide bonds having different degrees of hydrolytic stability. The attachment reactions proceeded with high yields (up to 95%). The functionalized polymers were subsequently photopolymerized (UV irradiation) to obtain crosslinked hydrogels. Crosslinked membranes with the highest degree of mechanical strength were obtained when the crosslinking reaction was performed in dioxane with benzoin methyl ether (0.1 wt %) as the initiator. the crystallinity, thermomechanical properties, and hydrolytic stability of the crosslinked membranes were studied. All membranes were transparent and highly swellable (equilibrium water content: 64–88%). The tensile strength in the swollen state ranged from 0.15 to 1.09 MPa. Under physiological conditions (phosphate buffered water, 0.1M, pH 7.4, 37°C) the hydrolytic stability of the hydrogels varied depending on the bonds used in the attachment of the acrylate pendent chains: Hydrogels with hydroxyethyl acrylate pendent chains dissolved within 30 days, while hydrogels containing aminoethyl methacrylamide pendent chains remained unchanged throughout a 30 day period. Using high molecular weight FITC-dextrans as model compounds, complete release from the swollen hydrogels required between 60 and 150 h. Overall, the evaluation of poly(ethylene glycol)-lysine derived, photocrosslinked hydrogels indicated that these materials provide a range of potentially useful properties. © 1994 John Wiley & Sons, Inc.     

Interpolymer complexes of poly(acrylic acid) with poly(2-hydroxyethyl acrylate) in aqueous solutions

Complexes formed from poly(acrylic acid) and poly(2-hydroxyethyl acrylate) were studied in aqueous solutions by viscometric, turbidimetric, FTIR spectroscopic, and thermogravimetric analysis methods. The formation of interpolymer complexes stabilized by hydrogen bonds was observed. It was found that the compositions of these interpolymer complexes are strongly dependent on the concentration of polymers, the order of mixing the solutions, and the pH. It was demonstrated that the complexation ability of poly(2-hydroxyethyl acrylate) is relatively low compared to other known nonionic water-soluble polymers. However, it can be significantly increased via hydrophobic modification of the poly(acrylic acid) using cetyl pyridinium bromide.     

Influence of crosslinker and ionic comonomer concentration on glass transition and demixing/mixing transition of copolymers poly(N-isopropylacrylamide) and poly(sodium acrylate) hydrogels

Hydrogels based on N-isopropylacrylamide and sodium acrylate as ionic comonomer were synthesized by free radical polymerization in water using N,N′-methylenebisacrylamide as crosslinker and ammonium persulfate as initiator. The glass transition of dried copolymers poly(N-isopropylacrylamide) (PNIPA) and poly(sodium acrylate) (SA) gels and demixing/mixing transition of PNIPA-SA hydrogels swollen with increasing amounts of water were studied using conventional differential scanning calorimetry. In the crosslinked polymers, the glass transition linearly increases, and the transition range becomes broader, with increasing crosslinker content. Increasing content of ionic comonomer also produces an increase of glass transition temperature, which moves to higher temperatures with higher sodium acrylate fraction. The influence of chemical structure of PNIPA-SA hydrogels on the lower critical solution temperature (LCST) of PNIPA-SA/water mixtures during heating and cooling was quantified as function of the content of the crosslinker and the ionic comonomer, as well as water content of the hydrogel in the range from 95 to 70 wt%. At parity of water content, the LCST occurs at higher temperatures for gels containing higher amounts of sodium acrylate. Similarly, the introduction of N,N′-methylenebisacrylamide causes an increase of the LCST, which grows with increasing of crosslinking degree of the hydrogel.     

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。     

Swelling and drug release behavior of poly(2-hydroxyethyl methacrylate/itaconic acid) copolymeric hydrogels obtained by gamma irradiation

The new copolymeric hydrogels based on 2-hydroxyethyl methacrylate (HEMA) and itaconic acid (IA) were prepared by gamma irradiation, in order to examine the potential use of these hydrogels in controlled drug release systems. The influence of IA content in the gel on the swelling characteristics and the releasing behavior of hydrogels, and the effect of different drugs, theophylline (TPH) and fenethylline hydrochloride (FE), on the releasing behavior of P(HEMA/IA) matrix were investigated in vitro. The diffusion exponents for swelling and drug release indicate that the mechanisms of buffer uptake and drug release are governed by Fickian diffusion. The swelling kinetics and, therefore, the release rate depends on the matrix swelling degree. The drug release was faster for copolymeric hydrogels with a higher content of itaconic acid. Furthermore, the drug release for TPH as model drug was faster due to a smaller molecular size and a weaker interaction of the TPH molecules with(in) the P(HEMA/IA) copolymeric networks.     

海藻酸钠和聚N-异丙基丙烯酰胺半互穿网络水凝胶的溶胀动力学研究

以海藻酸钠 (SA)和N 异丙基丙烯酰胺 (NIPAM)为原料 ,制备出具有温度敏感性的半互穿网络水凝胶 (SA PNIPAMsemi IPN) .主要研究了海藻酸钠用量、水介质温度及pH值对该凝胶溶胀速率的影响 .结果表明 ,在PNIPAM最低临界溶解温度 (LCST)以下 ,该凝胶的溶胀速率随着凝胶网络中SA组分的增加而增大 ,且溶胀速率取决于高分子链的松弛速率 ;pH对凝胶溶胀速率的影响与温度有关 ,温度对溶胀速率的影响与pH有关 .     

Radiolytic synthesis of Ag-poly(BIS-co-HEMA-co-IA) nanocomposites

Ag-poy(BIS-co-HEMA-co-IA) nanocomposites are prepared via in situ reduction of silver salt embedded in swollen polymer gels by employing gamma irradiation. Hydrogels based on 2-hydroxyethyl methacrylate, itaconic acid and four types of poly(alkylene glycol) acrylate or methacrylate (Bisomers) were previously prepared using gamma irradiation. The nanocomposites are characterized by using UV–vis, swelling measurements and thermal analysis. Evolution of plasmon absorption detected by UV–vis spectrophotometry indicated generation of Ag nanoparticles in polymer hydrogels. Altering the structure of the hydrogels did not lead to alternation of the position of the absorption maximum. The bulk property of equilibrium swelling is dependent on the presence of the Ag nanostructures. The initial thermal stability of the polymer is slightly increased due to presence of silver as nanofiller.     

Cellulose Nano Whiskers (CNWs) Loaded-Poly(sodium acrylate) Hydrogels. Part-I. Effect of Low Concentration of CNWs on Water Uptake

In this work, de-watered cellulose pulp(DCP), obtained from a paper mill, have been acid-hydrolyzed to yield cellulose nano-whiskers (CNWs). As revealed from FESEM measurements, these CNW were found to possess a median length of 258.5 nm, diameter of 35.2 nm, and an aspect ratio of 7.3. The CNWs were also characterized by TGA, XRD and FTIR analysis. The CNWs were found to possess a fairly high Crystallinity Index (CI) of 0.925. The addition of cellulose at low concentration range, i.e., from 25 to 125 mg (nearly 1.25 to 6.25 weight percent of polymer sodium acrylate) caused an enhancement in water uptake of resulting hydrogels .The CNWs-loaded poly(SA) hydrogels showed chain relaxation controlled swelling in the medium of pH 7.4 as was confirmed from the swelling exponent ‘n’ values obtained using power function law‥ The second order kinetic model was found to fit well to the kinetic water uptake data. However, all the samples, when prepared in the form of films, did not show any remarkable increase in their mechanical strength.     

Preparation of poly(N-isopropylacrylamide) emulsion gels and their drug release behaviors

Stimuli-sensitive drug delivery systems (DDSs) have attracted considerable attention in medical and pharmaceutical fields; thermosensitive DDS dealing with poly(N-isopropylacrylamide) (poly(NIPA)) have been widely studied. Novel NIPA emulsion gels, i.e., NIPA hydrogels containing distributed oil (oleyl alcohol) microdroplets, were synthesized by means of an emulsion-gelation method in which the polymerization of hydrogels in an aqueous phase in an oil-in-water (O/W) emulsion and the loading of a lipophilic drug (indomethacin) dissolved in an oil phase were accomplished simultaneously. The pulsatile (on-off) drug release from the NIPA emulsion gel loading indomethacin to a phosphate buffered saline (PBS) solution was successfully controlled by a temperature swing between 25 degrees C (release off) and 40 degrees C (release on). The mechanism of the pulsatile drug release was discussed in relation to the diffusion rate, distribution ratio, solvent exchange of NIPA hydrogels, and drug release from an NIPA organogel. The mechanism was as follows: the solvent exchange occurred within the NIPA emulsion gel (the NIPA gel-network absorbed oleyl alcohol with indomethacin) at temperatures above the LCST, and the diffusion rate of indomethacin through the solvent-exchanged gel was higher at 40 degrees C than at 25 degrees C.     

Characterisation of macroporous poly(methyl methacrylate) coated with plasma-polymerised poly(2-hydroxyethyl acrylate)

Macroporous poly(methyl methacrylate) networks with varying cross-linking density and porosity were coated with plasma-polymerised poly(2-hydroxyethyl acrylate) grafted on the pores surface. The result is a mechanically reinforced hydrogel (PMMA-gr-plPHEA) whose properties are characterised in this work using several experimental techniques. Bulk PMMA and bulk PHEA were also characterised as reference materials. The diffusion and water sorption properties of these hydrogels were studied through equilibrium water sorption isotherms and desorption starting with the sample equilibrated in immersion in liquid water or in a vapour atmosphere. Glass transition, dynamic-mechanical relaxation and thermal degradation were characterised in order to study the interphase interaction in these biphasic systems. All these experimental techniques suggested that plasma-polymerised PHEA is more homogeneously interpenetrated with highly cross-linked macroporous PMMA than if the porous substrate is a loosely cross-linked polymer network.     

Effect of Sodium Alginate on the Properties of Thermosensitive Hydrogels

Sodium alginate (SA ) was combined with poly(N ‐isopropylacrylamide) (PNIPAAm ) to prepare thermosensitive hydrogels through semi‐interpenetrating polymer network (semi‐IPN ) and fully interpenetrating polymer network (full‐IPN ). The thermosensitive, swelling, mechanical, and thermal properties of pure PNIPAAm , SA /PNIPAAm semi‐IPN , and Ca‐alginate/PNIPAAm full‐IPN hydrogels were investigated. The formation of semi‐IPN and full‐IPN significantly improved the hydrogels’ swelling capability and mechanical properties without altering their thermosensitivity. 5‐Fluorouracil (5‐Fu) was selected as a model drug to study the release behaviors of the hydrogels. It was found that in vitro controlled drug release from semi‐IPN hydrogels showed an initial release burst, followed by a slower and sustained release, before reaching equilibrium. Full‐IPN hydrogels showed slow and sustained release during the whole process. Temperature and pH were found to affect the rate of drug release. Ca‐alginate/PNIPAAm full‐IPN hydrogels have potential application as drug delivery matrices in controlled drug release.     

Amphiphilic block copolymers based on poly(2-acryloyloxyethyl phosphorylcholine) prepared via RAFT polymerisation as biocompatible nanocontainers

Amphiphilic block copolymers composed of poly(butyl acrylate) and poly(2-acryloyloxyethyl phosphorylcholine) have been prepared using reversible addition fragmentation transfer (RAFT) polymerisation. The conversion of the polymerisation was determined using online FT NIR spectroscopy. NMR spectroscopy was used not only to support the results obtained from FT NIR spectroscopy but also prove the formation of micelles. Due to the strong aggregation tendency of these block copolymers and the resulting difficulties concerning the molecular weight analysis test experiments were carried out replacing poly(2-acryloyloxyethyl phosphorylcholine) with poly(2-hydroxyethyl acrylate). Micelle size and the aggregation behaviour were investigated using dynamic light scattering. The sizes of the nanocontainers obtained were found to be influenced by the block length as well as the solvent leading to micelles in the range between 40 and 160 nm. The toxicity of the RAFT agent used was then analysed by cell growth inhibition tests.     

Rheology and Drug Release Properties of Bioresorbable Hydrogels Prepared from Polylactide/Poly(ethylene glycol) Block Copolymers

Ring-opening polymerization of L(D)-lactide was realized in the presence of poly(ethylene glycol) (PEG), yielding PLLA/PEG and PDLA/PEG block copolymers. Bioresorbable hydrogels were prepared from aqueous solutions containing both copolymers due to interactions and stereocomplexation between PLLA and PDLA blocks. The rheological properties of the hydrogels were investigated under various conditions by changing copolymer concentration, temperature, time and frequency. The hydrogels constitute a dynamic and evolutive system because of continuous formation/destruction of crosslinks and degradation. Drug release studies were performed on hydrogel systems containing bovine serum albumin (BSA). The release profiles appear almost constant with little burst effect. The release rate depends not only on gelation conditions such as time and temperature, but also on factors such as drug load, as well as molar mass and concentration of the copolymers.     

Poly(l‐glutamic acid)‐based micellar hydrogel with improved mechanical performance and proteins loading

Soft tissues, such as fat and skin, present high flexibility and are capable of withstanding large deformation in various functions. Hydrogels that can resemble the mechanical performance of soft tissue are unique and widely demanded. In this study, micellar hydrogels based on biocompatible poly(l ‐glutamic acid) (PLGA) were designed with the enhanced capacity to bear large deformation. Amphipathic triblock copolymer poly(ethylene glycol) acrylate‐co‐poly(ε‐caprolactone)‐co‐poly (ethylene glycol) acrylate (APEG‐PCL‐APEG) with two terminal double bonds was synthesized and self‐assembled into micelles. At the same time, graft copolymers, poly(l ‐glutamic acid)‐g‐hydroxyethyl methacrylate (PLGA‐g‐HEMA) with double bonds were synthesized. APEG‐PCL‐APEG micelles and PLGA‐g‐HEMA were mixed to construct micellar hydrogel via radical polymerization. The crystalline structure and hydrophobic aggregation of copolymers (APEG‐PCL‐APEG) were found to associate with PCL molecular weight. Due to the hydrophobic stress dissipation and crystalline structure of the micelles, the softness and toughness of hydrogels were promoted, exhibiting a 25% increase in ultimate strain. Moreover, the micellar hydrogels were able to load proteins with long‐term retention. In addition, under dynamic mechanical stimulation, the release of proteins could be accelerated. Besides, the micellar hydrogels also supported rabbit adipose‐derived stem cells (rASCs) growth, thus exhibiting the potential toward soft tissue engineering. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1115–1125     

Effects of thermosensitivity of poly (N-isopropylacrylamide) hydrogel upon the duration of a lag phase at the beginning of drug release from the hydrogel

The release rates of three kinds of drugs, with different charges, from poly (N-isopropylacrylamide) hydrogels were studied. The release rate was observed to be temperature dependent for the types of drug. When the temperature was lower than the phase transition temperature, the release rate was higher at lower temperatures and increased as the temperature rose. The amount of drugs released from a poly (N-isopropylacrylamide) hydrogel disk was plotted against the square root of time. It was found that the amount of drugs released was proportional to the square root of time over a certain time interval. A lag phase was observed before the amount of drug released became proportional to the square root of time. The longest time lag was observed at the phase transition temperature of poly (N-isopropylacrylamide); LCST (33°C). This suggests that the penetration rate of water into the hydrogels is lowest at the phase transition temperature and drastically changes around it. The release rates of drugs was also affected by the charges of the drug molecules. This may be caused by the interaction of drug molecules with polymer chains. When anionic drugs are released, the electrostatic repulsion seems to act between polymer chains and drug molecules. Therefore, the lag phase observed at the beginning of the release of anionic drugs was shorter, as compared with other kinds of drugs at any temperatures between 25 and 40°C. On the other hand, when cationic drugs are released, the time lag was longer at temperatures higher than 33°C as compared with the time lag at lower temperatures. At temperatures higher than 33°C, drugs are released from the surface skin layer of the hydrogel where water molecules are less mobile than those in bulk distilled water. The drug release thus shows a long lag phase.     

快速响应大孔聚(N-异丙基丙烯酰胺-co-丙烯酸)水凝胶的合成及表征

以聚乙二醇6000为成孔剂,由自由基引发N-异丙基丙烯酰胺(NIPA)和丙烯酸(AAc)共聚交联得到大孔凝胶,研究了凝胶对环境温度的响应性能.在凝胶制备过程中,PEG6000分子充当成孔剂,得到的凝胶具有大孔结构.这种大孔结构有利于水分子的进出,大孔凝胶对温度变化有较快的响应速率.增加亲水单体AAc的含量,凝胶的LCST有所升高,凝胶的亲水性增强,在较低温度下凝胶的溶胀率也随之升高.振荡实验表明,所得的大孔凝胶具有反复使用的能力.     

A Mathematical Study on Effect of 2-Hydroxyl Ethyl Acrylate on Controlled Drug Diffusion from Smart Hydrogels Based on Poly(acrylamide-co-hydroxy ethyl acrylate-co-acrylic acid)

A series of poly (AM-co-HEA-co-AA) hydrogels have been synthesized and characterized by varying 2-hydroxy ethyl acrylate (HEA) content in the range of 0–16.22% in feed. The swelling ratio of resulting hydrogels was drastically decreased 10 times, i.e., from 101.12 to 9.23 in an almost linear fashion; but the dimensional stability of these hydrogels was increased significantly from 5 to 46 days with increasing HEA content. The hydrogels exhibited Smart nature in varying pH (2–10), temperature (15–65°C), ionic strength of NaCl solution (0.1M-1.5M), and different cation chloride salt solution having same ionic strength (0.1M). The swelling mechanism was shifted from non-Fickian to Fickian (at pH 2–7), super case to non-Fickian (at pH 10) with increasing HEA content. The controlled release of model drug (salicylic acid) from these hydrogels was investigated using early-time, late-time and Etters diffusion models and compared with the experimental data. It was observed that early model doesn't fit, but Etter and late-time model fitted excluding the initial phase. However, it was also observed that with increasing HEA content, the applicability of Etter's model improved, and for 16.22% HEA containing hydrogel Etters model was fitted in the full range, indicating that by varying hydrogel composition, the diffusion characteristics can be altered.     

Preparation and characterization of poly(N-isopropylacrylamide)-modified poly(2-hydroxyethyl acrylate) hydrogels by interpenetrating polymer networks for sustained drug release

In order to investigate the influence of hydrophobic moieties formed by poly(N-isopropylacrylamide) (PNIPAm) in a hydrogel matrix on the release behavior of the hydrogel, a series of poly(N-isopropylacrylamide) (PNIPAm)-modified poly(2-hydroxyethyl acrylate-co-2-hydroxyethyl 2-hydroxyethyl methacrylate) (P(HEA-co-HEMA)) via interpenetrating polymer networks (IPNs) were prepared by a sequential UV solution polymerization. Interestingly, it was found that P(HEA-co-HEMA)/PNIPAm IPN indicated a single glass transition temperature (T(g)) and the T(g)s of the IPNs increased with an increase in the PNIPAm component. This phenomenon may be attributed to hydrogen bonding between the two polymer networks, but the hydrogen bonding exerts less influence on the swelling behavior of the IPNs, due to the fact that IPNs can respond to changes in temperature like PNIPAm. Using 2-[(diphenylmethyl)sulphiny]acetamide (modafinil, MOD) and p-hydroxybenzoic acid (HBA) as model drug compounds, the release behavior of the IPNs was studied at body temperature, and it was found that the presence of PNIPAm could retard drug release regardless of the solubility of the drugs. Release profiles of HBA from the IPNs and their component samples as a function of time at 37 degrees C.     

Impact of the Type of Crosslinking Agents on the Properties of Modified Sodium Alginate/Poly(vinyl Alcohol) Hydrogels

Here, we report on studies on the influence of different crosslinking methods (ionic and chemical) on the physicochemical (swelling ability and degradation in simulated body fluids), structural (FT-IR spectra analysis) and morphological (SEM analysis) properties of SA/PVA hydrogels containing active substances of natural origin. First, an aqueous extract of Echinacea purpurea was prepared using a Soxhlet apparatus. Next, a series of modified SA/PVA-based hydrogels were obtained through the chemical crosslinking method using poly(ethylene glycol) diacrylate (PEGDA, M_n = 700 g/mol) as a crosslinking agent and, additionally, the ionic reaction in the presence of a 5% w/v calcium chloride solution. The compositions of SA/PVA/E. purpurea-based hydrogels contained a polymer of natural origin—sodium alginate (SA, 1.5% solution)—and a synthetic polymer—poly(vinyl alcohol) (PVA, M_n = 72,000 g/mol, 10% solution)—in the ratio 2:1, and different amounts of the aqueous extract of E. purpurea—5, 10, 15 or 20% (v/v). Additionally, the release behavior of echinacoside from the polymeric matrix was evaluated in phosphate-buffered saline (PBS) at 37 °C. The results indicate that the type of the crosslinking method has a direct impact on the release profile. Consequently, it is possible to design a system that delivers an active substance in a way that depends on the application.