Double‐crosslinked reversible redox‐responsive hydrogels based on disulfide–thiol interchange

We present novel redox‐responsive hydrogels based on poly(N‐isopropylacrylamide) or poly(acrylamide), consisting of a reversible disulfide crosslinking agent N,N′‐bis(acryloyl)cystamine and a permanent crosslinking agent N,N′‐methylenebisacrylamide for microfluidic applications. The mechanism of swelling/deswelling behavior starts with the cleavage and reformation of disulfide bonds, leading to a change of crosslinking density and crosslinking points. Raman and ultraviolet‐visible spectroscopy confirm that conversion efficiency of thiol–disulfide interchange up to 99%. Rheological analysis reveals that the E modulus of hydrogel is dependent on the crosslinking density and can be repeatedly manipulated between high‐ and low‐stiffness states over at least 5 cycles without significant decrease. Kinetic studies showed that the mechanical strength of the gels changes as the redox reaction proceeds. This process is much faster than the autonomous diffusion in the hydrogel. Moreover, cooperative diffusion coefficient (D_coop) indicates that the swelling process of the hydrogel is affected by the reduction reaction. Finally, this reversibly switchable redox behavior of bulky hydrogel could be proven in microstructured hydrogel dots through short‐term photopatterning process. These hydrogel dots on glass substrates also showed the desired short response time on cyclic swelling and shrinking processes known from downsized hydrogel shapes. Such stimuli‐responsive hydrogels with redox‐sensitive crosslinkers open a new pathway in exchanging analytes for sensing and separating in microfluidics applications. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2590–2601     

Effect of polymer and ion concentration on mechanical and drug release behavior of gellan hydrogels using factorial design

Developing optimized hydrogel products requires an in-depth understanding of the mechanisms that drive hydrogel tunability. Here, we performed a full 4 × 4 factorial design study investigating the impact of gellan, a naturally derived polysaccharide (1%, 2%, 3%, or 4% w/v) and CaCl₂ concentration (1, 3, 7, or 10 mM) on the viscoelastic, swelling, and drug release behavior of gellan hydrogels containing a model drug, vancomycin. These concentrations were chosen to specifically provide insight into gellan hydrogel behavior for formulations utilizing polymer and salt concentrations expanding beyond those commonly reported by previous studies exploring gellan. With increasing gellan and CaCl₂ concentration, the hydrogel storage moduli (0.1–100 kPa) followed a power-law relationship and on average these hydrogels had higher liquid absorption capability and greater total drug release over 6 days. We suggest that the effects of gellan and CaCl₂ concentration and their interactions on hydrogel properties can be explained by various phenomena that lead to increased swelling and increased resistance to network expansion.     

Hydrogel Microchambers Integrated with Organic Electrodes for Efficient Electrical Stimulation of Human iPSC‐Derived Cardiomyocytes

A hydrogel‐based microchamber with organic electrodes for efficient electrical stimulations of human induced pluripotent stem cell‐derived cardiomyocytes (hiPSC‐CMs) is described. The microchamber is made from molecularly permeable, optically transparent, and electrically conductive polyvinyl alcohol (PVA) hydrogel and highly capacitive carbon electrode modified with poly(3,4‐ethylenedioxythiophene) (PEDOT). Spheroids of hiPSC‐CMs are cultured in microchambers, and electrically stimulated by the electrode for maturation. The large interfacial capacitance of the electrodes enables several days of electrical stimulation without generation of cytotoxic bubbles even when the electrodes are placed near the spheroids. The spheroids can be cultivated in the closed microchambers because of the permeated nutrients through the hydrogel, thus the spheroids are stably addressable and the culture medium around the sealed microchambers can be simply exchanged. Synchronized beating of the spheroids can be optically analyzed in situ, which makes it possible to selectively collect electrically responsive cells for further use. As the hydrogel is electrically conductive, the amount of electrical charge needed for maturing the spheroids can be reduced by configuring electrodes on the top and the bottom of the microchamber. The bioreactor will be useful for efficient production of matured hiPSC‐CMs for regenerative medicine and drug screening.     

Precipitated droplets in-situ cross-linking polymerization and its applications

A novel, green and effective approach to fabricate uniform functional spherical polymer particles remains a huge challenge. Herein, we present a novel one-pot approach superior to traditional precipitation polymerization, called precipitated droplets in-situ cross-linking (PDIC) polymerization, by which uniform particles are fabricated on large scale without any toxic organic solvents or stabilizers. With this approach, functional spherical polymer particles can be fabricated continuously only relying on gravity, and the preparation process is thus super-fast. For example, polyacrylic acid (PAA) hydrogel particles with ultra-high adsorption capacity are fabricated within only 60 s. Moreover, we have successfully fabricated different functional hydrogel particles, including anticoagulant, reinforced and bactericidal particles, based on the monomers of 2-acrylamide-2-methylpropanesulfonic acid (AMPS), acrylamide (AM) and [2-(methacryloyloxy)ethyl]trimethylammonium chloride (DMC), respectively. This approach has several advantages: (i) the technology is green; (ii) the size and porosity of the particles can be well-controlled; (iii) various functional spherical hydrogel particles can be fabricated by using corresponding monomers. More importantly, this approach fits the commercialization of functional hydrogel particles on demand.     

Effect of tensile load on the actuation performance of pH‐sensitive hydrogels

pH‐responsive hydrogels are capable of converting chemical energy to mechanical work. To optimize their use as actuators, their response when operating against an external load must be fully characterized. Here, the actuation strain of a model pH‐sensitive hydrogel as a function of different constant loads is studied. The experimental actuation strain, produced by switching the pH from 2 to 12, decreases significantly and monotonically with increasing initial tensile load. Two models are developed to predict the actuation strain as a function of applied stress. Simple mechanical models based on the change in hydrogel modulus and cross sectional area due to the change in pH are unsatisfactory as they predict only a small change in actuation strain with increasing external stress. However, the model based on the elastic and mixing free energy functions derived from the Flory–Huggins theory is found to accurately account for the actuation strain as a function of stress. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 218–225     

Bioprinting of Collagen: Considerations,Potentials, and Applications

Collagen is the most abundant extracellular matrix protein that is widely used in tissue engineering (TE). There is little research done on printing pure collagen. To understand the bottlenecks in printing pure collagen, it is imperative to understand collagen from a bottom‐up approach. Here it is aimed to provide a comprehensive overview of collagen printing, where collagen assembly in vivo and the various sources of collagen available for TE application are first understood. Next, the current printing technologies and strategy for printing collagen‐based materials are highlighted. Considerations and key challenges faced in collagen printing are identified. Finally, the key research areas that would enhance the functionality of printed collagen are presented.     

Facile synthesis of temperature-sensitive ABA triblock copolymers by dispersion RAFT polymerization

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Synthesis of guar gum-based hydrogel for sugarcane field solid conditioning

The water crisis is increased everywhere in recent years, which has affected the water demand in different sectors like industries, agriculture, residential, etc. The present research aims to the development of superabsorbent polymer (SAP) using bio-material. The hydrogel is synthesized by grafting Guar gum (GG) with methyl methacrylate (MMA) and crosslinking with polyethylene glycol (PEG). The developed GG-based hydrogelwas characterized by various analytical instruments. The Scanning Electron Microscopy (SEM) demonstrated hydrogels havepores of size 50 ​μm–10 ​μm. The Transmission Electron Microscopy (TEM) analysis has shownthat thematerial consists of spherical shapesand particles of size 141.11nm–182.19 ​nm.The Fourier-Transform Infrared Spectroscopy (FTIR) and Thermogravimetric analysis (TGA) study have confirmedthepresence of functional groups of material, and thermal resistivity. The absorption capacity of developed hydrogelwas found to be 110 ​ml per gram (110% of its dry weight). The hydrogelwasapplied in the field of sugarcane crop and measured soil moisture content after 20 days of application. A better resultwas found of moisture content in the area of hydrogel application (28%) compared to the area without hydrogel application (10%). Moreover, the comparison of different hydrogels is also shown in a study, and the developed hydrogel proves good moisture retention capacity. This technology could be promising in terms of improving perennial crop productivity and combating moisture stress in agriculture. As a soil conditioning material for agricultural applications, the synthesized hydrogel showed tremendous potential.     

Modulation of Self-healing of Polyion Complex Hydrogel by Ion-specific Effects

We have prepared polyion complex (PIC) hydrogel consisting of poly(3-(methacryloylami no) propyl-trimethylamonium chloride) and poly(sodium p-styrenesulfonate) polyelectrolytes via a two-step polymerization procedure and have investigated specific ion effects on the selfhealing of the PIC hydrogel. Our study demonstrates that the mechanical properties of the PIC hydrogel are strongly dependent on the type of the ions doped in the hydrogel. The ion-specific effects can be used to modulate the self-healing efficiency of the PIC hydrogel. As the doped anions change from kosmotrops to chaotropes, the self-healing efficiency of the PIC hydrogel increases. A more chaotropic anion has a stronger ability to break the ionic bonds formed within the hydrogel, leading to a higher efficiency during the healing.