Aqueous Free-radical Polymerization Research Articles

A new inhibitor of quaternary copolymer against calcium carbonate scaling in high-temperature geothermal fluids

An effective quaternary copolymer inhibitor against calcium carbonate scaling in 120 °C geothermal fluids, with an inhibition ratio of over 95 %, was synthesized through aqueous free radical polymerization of itaconic acid (IA), acrylic acid (AA), hydroxy ethyl methacrylate (HEMA), and sodium allylsulfonate (SAS). The synthesis process involved using ammonium persulfate as an initiator and tert-butanol as the molecular weight regulator. A four-factor, three-level orthogonal experiment was conducted to optimize the synthesis process, resulting in a monomer ratio of m(IA):m(AA) = 1:7, 15 % initiator concentration, a reaction temperature of 90 °C, and a reaction time of 2.5 h. Fourier transform infrared spectroscopy (FT-IR) analysis revealed the presence of carboxyl, sulfonic acid, hydroxyl, and ester groups in the copolymer, while thermogravimetric analysis (TGA) confirmed its thermal stability. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) examinations of calcium carbonate crystals indicated that the copolymer scale inhibitor caused significant damage to the surface morphology and crystal structure. This scaling inhibitor is useful for efficient geothermal energy utilization.

Phase diagram for the gelation of temperature-responsive and biocompatible poly(oligo ethylene glycol methyl ether methacrylate) polymers in aqueous free-radical polymerization reactions

Phase diagram for the gelation of temperature-responsive and biocompatible poly(oligo ethylene glycol methyl ether methacrylate) polymers in aqueous free-radical polymerization reactions

Synthesis of multi-responsive poly(NIPA-co-DMAEMA)-PBA hydrogel nanoparticles in aqueous solution for application as glucose-sensitive insulin-releasing nanoparticles.

This study aimed to present an innovative method for synthesizing pH-thermo-glucose responsive poly(NIPA-co-DMAEMA)-PBA hydrogel nanoparticles via single-step aqueous free radical polymerization. The synthesis process involved free radical polymerization in an aqueous solution, and the resulting nanoparticles were characterized for their physical and chemical properties by 1H NMR, Dynamic Light Scattering (DLS) and Scanning Electron Microscopy (SEM). Insulin-loaded poly(NIPA-co-DMAEMA)-PBA hydrogel nanoparticles were prepared and evaluated for their insulin capture and release properties at different pH and temperature, in addition to different glucose concentrations, with the release profile of insulin quantitatively evaluated using the Bradford method. 1H NMR results confirmed successful PBA incorporation, and DLS outcomes consistently indicated a transition to a more hydrophobic state above the Lower Critical Solution Temperature (LCST) of NIPA and DMAEMA. While pH responsiveness exhibited variation, insulin release generally increased with rising pH from acidic to neutral conditions, aligning with the anticipated augmentation of anionic PBA moieties and increased hydrogel hydrophilicity. Increased insulin release in the presence of glucose, particularly for formulations with the lowest mol % PBA, along with a slight increase for the highest mol % PBA formulation when increasing glucose from 1 to 4mg/mL, supported the potential of this approach for nanoparticle synthesis tailored for glucose-responsive insulin release. This work successfully demonstrates a novel method for synthesizing responsive hydrogel nanoparticles and underscores their potential for controlled insulin release in response to glucose concentrations. The observed pH-dependent insulin release patterns and the influence of PBA content on responsiveness highlight the versatility and promise of this nanoparticle synthesis approach for applications in glucose-responsive drug delivery systems. Poly(NIPA) nanoparticles containing PBA moieties are normally synthesized in two or more steps in the presence of organic solvents. Here we propose a new method for the synthesis of multiresponsive hydrogel poly(NIPA-co-DMAEMA)-PBA nanoparticles in aqueous medium in a single reaction to provide a fast and effective strategy for the production of glucose-responsive multi-systems in aqueous media from free radical polymerization.

Gelation of acrylic acid with Ag+ and conversion to Ag nanoparticle as potential system for biomedical applications

Silver (Ag) has been used to cross-link poly (acrylic acid) (PAAc) to obtain antibacterial nanocomposite hydrogel for controlled drug delivery systems. Ag+/PAAc composite hydrogel was prepared by free radical aqueous polymerization of acrylic acid (AAc) using potassium persulfate (KPS) as the initiator in the presence of silver nitrate (AgNO3). Sodium borohydride (NaBH4) was used to reduce the Ag ions present within the hydrogel matrix to generate Ag nanoparticles (Ag NPs). Transmission electron microscopy (TEM) characterization of the sample indicated the formation of Ag nanoparticles that distributed uniformly in the PAAc networks. UV–visible spectrophotometry showed an absorption peak at 425 nm that attribute to the well-known surface Plasmon resonance of the Ag bound in NPs. X-ray diffraction (XRD) pattern showed the appearance of some peaks corresponding to the face-centered cubic (f.c.c.) Ag phase. Energy dispersive spectroscopy (EDS) studies revealed that Ag NPs are successfully formed inside the Ag+/PAAc composite hydrogel. The gelation and crosslinking of PAAc chains with Ag+ by strong interactions between Ag cations and polyanions, deprotonated carboxylic groups of PAAc were identified from the Fourier transform infrared (FTIR) spectrogram. Field emission scanning electron microscopy (FESEM) exhibited an interconnected porous structure with an average pore size of about 10 μ for composite hydrogel that can absorb 440 g water/g dried sample. Dried samples were also loaded with amoxicillin and antibiotic release was studied. The antimicrobial activity of the Ag+ and Ag-NPs hydrogels was tested against Staphylococcus aureus, Bacillus cereus, Pseudomonas aeruginosa and Escherichia coli.

Anionic starch-based hybrid cryogel-embedded ZnO nanoparticles: tuning the elasticity and pH-functionality of biocomposites with dicarboxylic acid units.

Weakly anionic semi-interpenetrating polymer network (semi-IPN) biocomposites based on starch (ST)-incorporated poly(acrylamide-co-itaconic acid)/ZnO (ST-PAI/ZnO) were synthesized by a simple one-pot method via free radical aqueous polymerization. Hybrid biocomposites exhibited lower equilibrium swelling compared with neat copolymer gel. For both hydrogels and cryogels, swelling followed a decreasing order as copolymer PAI > starch-free PAI/ZnO > ST-PAI/ZnO gels. With the addition of 9% ST and ZnO, the swelling ratio of gels decreased from 898 to 68.3, resulting in a significant increase in elastic modulus. Compared with a fixed amount of ST, biocomposite cryogels exhibited significantly higher modulus than hydrogels. With the addition of 9% ST, the elastic modulus of cryogels reached 22.2 kPa while it was 2.7 kPa for the hydrogels. An equation expressing the effective cross-linking density of semi-IPNs presented by a cubic polynomial as a function of starch was obtained. As pH increased with the presence of dicarboxylic acid units, a gradual increase in swelling occurred at two different pH values. A gradually reproducible swelling change of semi-IPNs was depicted with pH ranging from 2.1 to 11.2. Biocomposite cryogels showed rapid swelling in a buffer solution of pH 11.2 and rapid shrinking in pH 2.1. Salt-induced swelling testing showed that the ability to reduce the degree of swelling and solubility of starch was Br- > Cl- > NO3- > SO42- for anions consistent with the Hofmeister series. Adsorption efficiency for the removal of methyl violet (MV) dye was analyzed using Langmuir, Freundlich, Dubinin-Radushkevich and Temkin isotherm models. The results confirmed that the Langmuir isotherm and pseudo-second-order model are suitable for describing MV adsorption on semi-IPN biocomposites. The synthesized biocomposites with good swelling/deswelling kinetics in different pH-buffer solutions, high saline absorbency, desirable adsorption efficiency, and acceptable pH-dependent swelling reversibility can be considered as smart hybrid materials for the adsorption of the dye in water purification tasks.

Polymerization Behavior and Rheological Properties of a Surfactant-Modified Reactive Hydrophobic Monomer

The structures and properties of hydrophobic association polymers can be controlled using micelles. In this work, we synthesize a reactive hydrophobic surfactant monomer, KS-3, from oleic acid, N,N-dimethylpropylenediamine, and allyl chloride. A strong synergistic effect between KS-3 and cocamidopropyl betaine in aqueous solution enhances the hydrophilic dispersibility of KS-3, thereby transforming spherical micelles into cylindrical micelles. KS-3 was grafted onto a polyacrylamide chain via aqueous free-radical polymerization to obtain RES, a hydrophobic association polymer. Structural analysis revealed that the RES polymers assembled in wormlike micelles were more tightly arranged than those assembled in spherical micelles, resulting in a compact network structure in water, smooth surface, and high thermal stability. Rheological tests revealed that the synthesized polymers with wormlike and spherical micelles exhibited shear-thinning properties along with different structural strengths and viscoelasticities. Therefore, controlling the micellar state can effectively regulate the polymer properties. The polymers obtained through wormlike micelle polymerization have potential applications in fields with high demands, such as drug release, water purification, and oilfield development.

Quince seed mucilage/β-cyclodextrin/Mmt-Na+-co-poly (methacrylate) based pH-sensitive polymeric carriers for controlled delivery of Capecitabine

In current work, quince seed mucilage and β-Cyclodextrin based pH regulated hydrogels were developed using aqueous free radical polymerization to sustain Capecitabine release patterns and to overcome its drawbacks, such as high dose frequency, short half-life, and low bioavailability. Developed networks were subjected to thermal analysis, Fourier transforms infrared spectroscopy, powder x-ray diffraction, elemental analysis, scanning electron microscopy, equilibrium swelling, and in-vitro release investigations to assess the network system's stability, complexation, morphology, and pH responsiveness. Thermally stable pH-responsive cross-linked networks were formed. Nanocomposite hydrogels were prepared by incorporating Capecitabine-containing clay into the swollen hydrogels. All the formulations exhibited equilibrium swelling ranging from 67.98 % to 92.98 % at pH 7.4. Optimum Capecitabine loading (88.17 %) was noted in the case of hydrogels, while it was 74.27 % in nanocomposite hydrogels. Excellent gel content (65.88 %–93.56 %) was noticed among developed formulations. Elemental analysis ensured the successful incorporation of Capecitabine.Nanocomposite hydrogels released 80.02 % longer than hydrogels after 30 h. NC hydrogels had higher t1/2 (10.57 h), AUC (121.52 μg.h/ml), and MRT (18.95 h) than hydrogels in oral pharmacokinetics. These findings imply that the pH-responsive carrier system may improve Capecitabine efficacy and reduce dosing frequency in cancer therapy. Toxicity profiling proved the system's safety, non-toxicity, and biocompatibility.

Research and performance evaluation of modified nano‐silica gel plugging agent

AbstractDue to the difficulties in plugging high‐pressure injection wells, the short period of plugging, and the use of modified nano‐silica, a novel chemical gel plugging agent has been created. Modification of silica using silane coupling agents, and using the aqueous free radical polymerization method synthesized chemical plugging agent with AM, AA, and DMDAAC. The optimum synthesis conditions were screened by single‐factor analysis: mass ratio m(AM):m(AA):m(DMDAAC) = 8:1.5:1, modified nano‐silica concentration of 1.0%, total monomer mass concentration of 8.0%, initiator concentration of 0.3%, the cross‐linker concentration of 0.4%, and coagulant concentration of 0.6%. The performance of the chemical plugging agent was evaluated under the target oil formation conditions. The experimental results showed that the chemical plugging agent exhibited good temperature resistance at 40–100°C, good salt resistance at mineralization (0.5–2.5) × 104 mg/L, and the chemical plugging agent breaks through pressure gradients of 1.12, 15.42 and 90.15 MPa/m in the wellbore, fracture and core, respectively, compared with most gel plugging agents, this plugging agent is more suitable for sealing with pressure work. After adding the breakout agent, the fluid after breakout is fluid‐like with low viscosity, which is convenient for reverse discharge and will not cause harm to the reservoir and ensure the subsequent normal construction operation.

Preparation and performance of bacterial cellulose-based enzyme-carrying composite hydrogels as wound healing material

As a biosynthetic polymer, Bacterial cellulose (BC) has been largely used in biomedical and technological fields for the excellent biocompatibility and water holding capability. In this study, BC hydrogel were mass-produced from G. xylinus. A novel gel, BC nanocomposite (BC/NC) hydrogel, was prepared via in situ free radical aqueous polymerization from NIPAM in the presence of Clay was added as physical crosslinker. The physical and chemical properties were evaluated, and the results showed that the properties of the composite hydrogel were improved, for example, the Young’s modulus rose by nearly 30%, from 4.7 to 6.0 Mpa with the increasing of NIPAM. BC/NC-lys hydrogel were prepared by treating BC/NC hydrogel with Lysostaphin solution, and the cytocompatibility and antibacterial activities were assessed in vitro. The effects of composite hydrogel on wound healing were examined in rat skin models, the cure rate was up to 92.35% in the test group and only 78.83% in the control group after 14 days. The composite BC/NC3-lys hydrogel were developed in the hope of accelerating the wound healing process as well as decreasing the infection rate.

Development and Evaluation of Cellulose Derivative and Pectin Based Swellable pH Responsive Hydrogel Network for Controlled Delivery of Cytarabine.

In the present study, pH-sensitive, biodegradable, and biocompatible Na-CMC/pectin poly(methacrylic acid) hydrogels were synthesized using an aqueous free radical polymerization technique and encapsulated by cytarabine (anti-cancer drug). The aim of the project was to sustain the plasma profile of cytarabine through oral administration. Sodium carboxymethyl cellulose (Na-CMC) and pectin were cross-linked chemically with methacrylic acid (MAA) as a monomer, using methylene bisacrylamide (MBA) as cross-linker and ammonium per sulfate (APS) as an initiator. Prepared hydrogel formulations were characterized for their texture, morphology, cytarabine loading efficiency, compositional and structural properties, thermal nature, stability, swelling response, drug release profile (pH 1.2 and pH 7.4), and in-vivo pharmacokinetic evaluation. Cytarabine-loaded hydrogels were also evaluated for their safety profile by carrying out toxicity studies in rabbits. Results demonstrated efficient encapsulation of cytarabine into the prepared network with loading ranging from 48.5-82.3%. The highest swelling ratio of 39.38 and maximum drug release of 83.29-85.27% were observed at pH 7.4, highlighting the pH responsiveness of the grafted system. Furthermore, cytarabine maximum release was noticed over 24 h, ensuring a sustained release response for all formulations. Histopathological studies and hemolytic profiles confirmed that the prepared hydrogel system was safe, biocompatible, and non-irritant, showing no symptoms of any toxicities and degeneration in organs. Moreover, pharmacokinetic estimation of the cytarabine-loaded hydrogel showed a remarkable increase in the plasma half-life from 4.44 h to 9.24 h and AUC from 22.06 μg/mL.h to 56.94 μg/mL.h. This study revealed that the prepared hydrogel carrier system has excellent abilities in delivering the therapeutic moieties in a controlled manner.

Development and Evaluation of Sodium Alginate/Carbopol 934P-Co-Poly (Methacrylate) Hydrogels for Localized Drug Delivery.

This research was carried out to create a pH-responsive polymeric system for the targeted drug delivery of Diloxanide furoate. It relied on sodium alginate (Na-Alg) and Carbopol 934P as building blocks. Using an aqueous free radical polymerization method, SCH1-SCH12 was created with varying polymer, MAA, and MBA input ratios. Positive outcomes were seen in the swelling and release profiles at higher pH levels. Hydrogel formation, as well as component compatibility, thermal stability, and Diloxanide furoate loading, were all validated by instrumental characterization. A drug loading percentage of 83.56% was determined, with the swelling reaching 743.19%. For the formulation with MBA, the gel fraction was 94.58%. The release of diloxanide furoate increased to 91.77% at neutral pH. The formulation containing Carbopol 934P provided the highest mucoadhesion force (3993.42 dynes/cm2). The created hydrogel has been shown to be biocompatible by toxicological testing of the network. Based on the findings, the created polymeric nexus proved promising for pH-dependent localized and regulated delivery of Diloxanide furoate.

Observation and Modeling of a Sharp Oxygen Threshold in Aqueous Free Radical and RAFT Polymerization.

It is known that oxygen (O2) stops radical polymerization (RP). Here, it was found that the reaction turn-off occurs abruptly at a threshold concentration of O2, [O2]t, for both free RP and reversible addition-fragmentation chain-transfer polymerization (RAFT). In some reactions, there was a spontaneous re-start of conversion. Three cases were investigated: RP of (i) acrylamide (Am) and (ii) sodium styrene sulfonate (SS) and (iii) Am RAFT polymerization. A controlled flow of O2 into the reactor was employed. An abrupt turn-off was observed in all cases, where polymerization stops sharply at [O2]t and remains stopped when [O2] > [O2]t. In (i), Am acts as a catalytic radical-transfer agent during conversion plateau, eliminating excess [O2], and polymerization spontaneously resumes at [O2]t. In no reaction, the initiator alone was capable of eliminating O2. N2 purge was needed to re-start reactions (ii) and (iii). For (i) and (ii), while [O2] < [O2]t, O2 acts a chain termination agent, reducing the molecular weight (Mw) and reduced viscosity (RV). O2 acts as an inhibitor for [O2] > [O2]t in all cases. The radical-transfer rates from Am* and SS* to O2 are >10,000× higher than the initial chain propagation step rates for Am and SS, which causes [O2]t at very low [O2].

PH Responsive Hydrogels for the Delivery of Capecitabine: Development, Optimization and Pharmacokinetic Studies.

The objective of the current study was to achieve a sustained release profile of capecitabine (CAP), an anticancer agent frequently administered in conventional dosage form due to its short plasma half-life. A drug-loaded smart pH responsive chitosan/fenugreek-g-poly (MAA) hydrogel was synthesized by an aqueous free radical polymerization technique. The developed network was evaluated for capecitabine loading %, swelling response, morphology, structural and compositional characteristics, and drug release behavior. Significantly higher swelling and in vitro drug release rate were exhibited by formulations at pH 7.4 than at pH 1.2, demonstrating the pH responsive character of hydrogels. Swelling percentage and CAP loading ranged within 74.45-83.54% and 50.13-72.43%, respectively. Maximum release, up to 93%, was demonstrated over 30 h, evidencing the controlled release pattern of CAP from hydrogels. The optimized formulation was further screened for acute oral toxicity studies. No signs of oral, dermal, or ocular toxicities were noticed, confirming safety evidence of the network. Furthermore, pharmacokinetic analysis demonstrated the sustained release response of CAP from hydrogels as confirmed by a significant increase in plasma half-life (t1/2) (13 h) and AUC (42.88 µg h/mL) of CAP. Based on these findings, fabricated hydrogels are strongly recommended as a biocompatible carrier for colorectal delivery of active agents.

Synthesis and performance evaluation of carboxyl‐rich low phosphorus copolymer scale inhibitor

AbstractA novel low phosphorus terpolymer scale inhibitor P(IA‐MA‐SHP) was prepared by aqueous free radical polymerization using itaconic acid (IA), maleic acid (MA), and sodium hypophosphite (SHP) as raw materials. It was mainly used as an efficient scale inhibitor to inhibit CaCO3. The structures of the copolymers were characterized by Fourier transform infrared,1H‐NMR, and13C‐NMR, and the thermal properties, and scale sample crystal structure morphology of the copolymers were analyzed by thermogravimetric analysis, x‐ray diffraction (XRD), and scanning electron microscope (SEM). The effects of dosage, monomer ratio, temperature, and reaction time on the scale inhibition effect were investigated, and the optimal synthesis conditions were determined. The results show that: when the monomer ratio isn(IA):n(MA) = 1.0:1.0, the mass fraction of SHP is 10%, the amount of ammonium persulfate initiator is 12%, the reaction temperature is 90°C, and the reaction time is 4 h, when the dosage of the agent is 20 mg L−1, the scale inhibition rate of CaCO3is 94.30%, while it also has a favorable inhibitory effect on CaSO4. The results of SEM and XRD show that the copolymer scale inhibitor can distort the lattice and has a favorable adsorption and dispersion effect. In addition, it has a positive effect on controlling the scale.

In-vitro and in-vivo evaluation of biocompatible polymeric microgels for pH- driven delivery of Ketorolac tromethamine

The aim of the current study was to prepare glutamic acid crosslinked poly(itaconic acid/methacrylic acid) microgels for pH-responsive delivery of ketorolac tromethamine, using aqueous free radical polymerization technique. The polymerization of polymer with monomers was carried out by a crosslinking agent N′, N′-methylene bisacrylamide in the presence of initiator ammonium persulfate. The prepared microgels were characterized for structure, surface morphology, thermal stability, and crystallinity. Similarly, studies such as sol-gel analysis, drug loading, and polymer volume fraction were performed for the fabricated microgels. The pH-sensitivity of the developed microgels was investigated at three different pH values i.e., pH 1.2, 4.6, and 7.4 by swelling and in-vitro drug release studies. Maximum swelling and drug release were found at pH 7.4 as compared to pH 1.2 and 4.6, which indicated the pH-sensitive nature of the prepared microgels. The toxicity of the prepared microgels was evaluated by cell line and HET-CAM test, which demonstrated no toxic effect of the prepared microgels. In-vivo study was carried out on rabbits and high plasma concentration was reported for the drug loaded microgels as compared to drug solution and commercial product Keten. Hence, the prepared microgel system could be employed as an excellent carrier for the controlled drug delivery system.

Biocompatible polymeric blend for pH driven delivery of cytarabine: Effect of feed contents on swelling and release kinetics.

Purpose of this study was to prepare chitosan/tamarind crosslinked poly (methacrylic acid) hydrogels for pH responsive delivery of cytarabine by using aqueous free radical polymerization technique. Polymers were chemically cross-linked with monomer (methacrylic acid) using methylene bisacrylamide as cross-linking agent and ammonium per sulphate as a reaction initiator in aqueous medium. Developed hydrogels were characterized for morphology, physical existence, drug loading (%), compositional and structural analysis, thermal behavior and stability, drug release analysis (pH 1.2 and pH7.4), and in vivo release kinetics. pH sensitive behavior was established by observing swelling and release behavior at different pH values (1.2 and 7.4). Biocompatibility of network was evaluated through acute oral toxicity studies in rabbits. Results revealed that cytarabine was efficiently loaded in prepared hydrogels with an entrapment efficiency of 54.67%-108.59%. Highest swelling ratio of 38.67 was noticed at pH7.4. Maximum pH sensitive behavior was seen at pH7.4 showing maximum drug release up to 94.51%. All developed formulations followed zero order release as confirmed from regression coefficient (R2 =0.9912-0.9991). In-vivo studies confirmed enhanced bioavailability of cytarabine. Histopathological examination and hemocompatibility studies proved that developed hydrogel system was safe, biocompatible, nonhemolytic in nature exhibiting no symptoms of dermal, ocular toxicities, and no changes in biochemical parameters of blood and histology of key organs. So, developed hydrogel system can be employed as an excellent drug delivery device where controlled drug delivery is desired.

Experimental Study on the Polymer/Graphene Oxide Composite as a Fluid Loss Agent for Water-Based Drilling Fluids.

The wellbore instability caused by the penetration of drilling fluids into the formation is a vital problem in the drilling process. In this study, we synthesized a polymer/graphene oxide composite (PAAN-G) as a fluid loss additive in water-based drilling fluids. The three monomers (acrylamide (AM), 2-acrylamide-2-methyl-1-propane sulfonic acid (AMPS), N-vinylpyrrolidone (NVP)) and graphene oxide (GO) were copolymerized using aqueous free radical polymerization. The composition, micromorphology, and thermal stability properties of PAAN-G were characterized by Fourier transform infrared (FT-IR) spectroscopy and thermogravimetric analysis (TGA). According to the American Petroleum Institute (API) standards, the influence of PAAN-G on the rheological and filtration properties of bentonite-based mud was evaluated. Compared with PAAN, PAAN-0.2G has more stable rheological properties at high temperatures. The experimental results showed that even at a high temperature of 240 °C, PAAN-G can still maintain a stable fluid loss reduction ability. In addition, PAAN-G is also suitable for high-salt formations; it can still obtain satisfactory filtration volume when the concentration of sodium chloride (NaCl) and calcium chloride (CaCl2) reached 25 wt %. Besides, we discussed the fluid loss control mechanism of PAAN-G through particle size distribution and scanning electron microscopy (SEM).

Free- and reversible deactivation radical (co)polymerization of isobutylene in water under environmentally benign conditions

The synthesis of a linear polyisobutylene is achieved for the first time by free radical polymerization. The reaction was performed in environmentally friendly conditions, i.e., in an aqueous medium using cyclodextrin solubilizer, around room temperature. This mild and straightforward radical polymerization resulted in a predominantly linear polymer with low dispersity. Isobutylene was also copolymerized with acrylamide via this cyclodextrin assisted aqueous free-radical polymerization, leading to new poly(isobutylene-co-acrylamide) amphiphilic copolymers. The feed composition of copolymerization had a huge effect on the composition and, therefore, the resulting copolymer's solubility. Reversible addition-fragmentation chain transfer radical polymerization (RAFT) of isobutylene was also carried out using a PEG-based symmetrical macro chain transfer agent. Poly(PEG-b-isobutylene-b-PEG) block-copolymer was formed in this one-pot reaction. This novel polymerization method for isobutylene opens new, environmentally benign routes to produce novel copolymers for various applications.

Smart pH-responsive Co-polymeric Hydrogels for Controlled Delivery of Capecitabine: Fabrication, Optimization and In Vivo Toxicology Screening.

Despite exhibiting promising anticancer potential, the clinical significance of capecitabine (a potent prodrug of 5-fluorouracil used for the treatment of colorectal cancer) is limited owing to its acidic and enzymatic hydrolysis, lower absorption following the oral administration, poor bioavailability, short plasma half-life, and poor patient compliance. The present study was aimed to fabricate the capecitabine as a smart pH-responsive hydrogel network to efficiently facilitate its oral delivery while shielding its stability in the gastric media. The smart pH-sensitive HP-β-CD/agarose-g-poly(MAA) hydrogel network was developed using an aqueous free radical polymerization technique. The developed hydrogels were characterized for drug-loading efficiency, structural and compositional features, thermal stability, swelling behaviour, morphology, physical form, and release kinetics. The pH-responsive behaviour of developed hydrogels was established by conducting the swelling and release behaviour at different pH values (1.2 and 7.4), demonstrating significantly higher swelling and release at pH 7.4 as compared with pH 1.2. The capecitabine-loaded hydrogels were also screened for acute oral toxicity in animals by analysing the body weight, water and food intake, dermal toxicity, ocular toxicity, biochemical analysis, and histological examination. The characteristic evaluations revealed that capecitabine (anticancer agent) was successfully loaded into the hydrogel network. The range of capecitabine loading was from 71.22% to 90.12%. An interesting feature of hydrogel was its pH-responsive behaviour which triggers release at basic pH (94.25%). Optimum swelling (95%)was seen at pH 7.4. Based upon regression coefficient R2(0.96 - 0.99) the best-fit model was zero-order. The extensive toxicity evaluations evidenced a good safety profile with no signs of oral, dermal, or ocular toxicities, as well as no variations in blood parameters and histology of vital organs. Our findings conclusively evinced that the developed hydrogel exhibited excellent pharmaceutical and therapeutic potential and thus can be employed as a pH-responsive system for the controlled delivery of anticancer agents.

Nanostructures, Thermoresponsiveness, and Assembly Mechanism of Hydrogel Microspheres during Aqueous Free-Radical Precipitation Polymerization.

Although techniques to produce uniformly sized hydrogel microspheres (microgels) by aqueous free-radical precipitation polymerization are well established, the details of the polymerization process remain mysterious. In the present study, the structural evolution and thermoresponsiveness of the developing microgels during the polymerization were evaluated by temperature-controlled high-speed atomic force microscopy. This analysis clarified that the swelling properties of the precursor microgels formed in the early stages of the polymerization are quite low due to the high incorporation of cross-linkers and that non-thermoresponsive deca-nanosized spherical domains are already present in the precursor microgels. Furthermore, we succeeded in tracking the formation of nuclei and their growth process, which has never been fully understood, in aqueous solution by real-time observations. These findings will help us to design functional microgels with the desired nanostructures via precipitation polymerization.