High water‐content thermoresponsive hydrogels via electrostatic macrocrosslinking of cellulose nanofibrils

Atom transfer radical polymerization (ATRP) has been utilized to synthesize tri‐ and star‐block copolymers of poly(di(ethylene glycol)methyl ether methacrylate) (PDEGMA) and quaternized poly(2‐(dimethylamino)ethyl methacrylate) (qPDMAEMA). The block copolymers, all with a minimum of two cationically charged blocks, were sequentially used for electrostatic macrocrosslinking of a dilute dispersion of anionic TEMPO‐oxidized cellulose nanofibrils (CNF, 0.3 wt%), forming free‐standing hydrogels. The cationic block copolymers adsorbed irreversibly to the CNF, enabling the formation of ionically crosslinked hydrogels, with a storage modulus of up to 2.9 kPa. The ability of the block copolymers to adsorb to CNF was confirmed by quartz crystal microbalance with dissipation monitoring (QCM‐D) and infrared spectroscopy (FT‐IR), and the thermoresponsive properties of the hydrogels were investigated by rheological stress and frequency sweep, and gravimetric measurements. This method was shown to be promising for the facile production of thermoresponsive hydrogels based on CNF. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3415–3424     

Enzyme‐Induced Matrix Softening Regulates Hepatocarcinoma Cancer Cell Phenotypes

The progression of cancer is often accompanied by changes in the mechanical properties of an extracellular matrix. However, limited efforts have been made to reproduce these biological events in vitro. To this end, this study demonstrates that matrix remodeling caused by matrix metalloproteinase (MMP)‐1 regulates phenotypic activities and modulates radiosensitivity of cancer cells exclusively in a 3D matrix. In this study, hepatocarcinoma cells are cultured in a collagen‐based gel tailored to present an elastic modulus of ≈4.0 kPa. The subsequent exposure of the gel to MMP‐1 decreases the elastic modulus from 4.0 to 0.5 kPa. In response to MMP‐1, liver cancer cells undergo active proliferation, downregulation of E‐cadherin, and the loss of detoxification capacity. The resulting spheroids are more sensitive to radiation than the spheroids cultured in the stiffer gel not exposed to MMP‐1. Overall, this study serves to better understand and control the effects of MMP‐induced matrix remodeling.     

Bioadhesive properties of a polyaminoacidic hydrogel: evaluation by ATR FT-IR spectroscopy

The bioadhesive properties of a novel chemical hydrogel based on a polymer of protein-like structure, have been investigated by using ATR FT-IR spectroscopy. In particular, the copolymer PHG obtained by partial derivatization of PHEA with GMA was chemically crosslinked by UV irradiation at 313 nm. Crosslinked PHG was treated with water to obtain a swelled sample, named PHG-UV gel, that was brought into contact with a phosphate buffer/citric acid solution at pH 7.0 in the absence or in the presence of mucin at various concentrations (0.01, 0.1 and 1 wt.-%). Preliminary dynamic swelling studies have evidenced the occurrence of an interaction between the PHG-UV gel and the glycoprotein. This result was confirmed by ATR FT-IR measurements. A diffusion model using a solution of Ficks' second law was employed to determine the diffusion coefficient of water into PHG-UV gel as a consequence of adsorption and/or interdiffusion which occur at the PHG-UV gel/mucin solution interface. Experimental results suggest a potential use of PHG-UV gel to prepare bioadhesive devices.     

A Novel Gelatin–Carbon Nanotubes Hybrid Hydrogel

This letter focuses on the first result of the preparation and the swelling behavior of a novel hybrid gelatin hydrogel with carbon nanotubes. A novel hybrid gelatin hydrogel with carbon nanotubes was synthesized by a physical mixing method. The structure of the novel hydrogel obtained was characterized by SEM. Besides, the swelling behavior of the synthesized hydrogel was measured at two different temperatures. The results indicate that carbon nanotubes added could maintain the stability of the hybrid hydrogel without cross‐linking at 37 °C. This suggests that the hybrid gelatin hydrogel with carbon nanotubes could be used in biomedical field. Besides, its application in protein separation is discussed.

SEM image of the gelatin‐MWNTs hybrid gel at 10 000 × magnification.     

Thermomechanical Analysis of Polysaccharide Hydrogels in Water

Application of thermomechanometry to the measurement of hydrogels containing a large amount of water was carried out by static and dynamic methods. A thermomechanical analyzer (TMA) equipped with a quartz compression probe immersed in water was used. Polysaccharide hydrogels containing ca 98% water were measured. Creep of hydrogels in water was analyzed in a stress range from 1.04⋅10³ to 5.2⋅10³ Pa and loading rate from 0.3⋅10³ to 3.0⋅10³ Pa min⁻¹.Stress relaxation was measured in compressed ratio range from 0.02 to 0.45 m m⁻¹ and in compressing rate was 0.09 to 0.15 m m⁻¹ min⁻¹. Dynamic viscoelasticity was measured by TMA when dynamic Young’s modulus which was larger than 1⋅10⁴ Pa in frequencies ranging from 0.02~0.2 Hz. This revised version was published online in July 2006 with corrections to the Cover Date.     

Biodegradable thermo‐ and pH‐responsive hydrogels for oral drug delivery

In this article, novel smart hydrogels based on biodegradable pH sensitive poly(L ‐glutamic acid‐g‐2‐hydroxylethyl methacrylate) (PGH) chains and temperature‐sensitive hydroxypropylcellulose‐g‐acrylic acid (HPC‐g‐AA) segments were designed and synthesized. The influence of pH and temperature on the equilibrium swelling ratios of the hydrogels was discussed. The optical transmittance of the hydrogels was also changed as a function of temperature, which reflecting that the HPC‐g‐AA part of the hydrogels became hydrophobic at the temperature above the lower critical solution temperature (LCST). At the same time, the LCST of the hydrogels had a visible pH‐dependent behavior. Scanning electron microscopic analysis revealed the morphology of the hydrogels before and after enzymatic degradation. The biodegradation rate of the hydrogels was directly related to the PGH content and the pH value. The in vitro release of bovine serum albumin from the hydrogels were investigated. The release profiles indicated that both the HPC‐g‐AA and PGH contents played important roles in the drug release behaviors. These results show that the smart hydrogels seem to be of great promise in pH–temperature oral drug delivery systems. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

A facile pathway for the fast synthesis of colloidal crystal‐loaded hydrogels via frontal polymerization

In this work, a dually sensitive colloidal crystal (CC)‐loaded hydrogel has been synthesized via frontal polymerization (FP) in a facile and rapid way. First, a polystyrene CC film was fabricated by vertical deposition on the inner wall of a test tube. Then, a mixture of acrylic acid (AAc), 2‐hydroxyethyl methacrylate (HEMA), and glycerol along with the initiator and crosslinker was added to this test tube to carry out FP, resulting in the formation of CC‐loaded hydrogel. The influence of the mass ratios of HEMA/AAc on front velocity and temperatures were studied. The swelling behavior, the morphology, and the stimuli‐responsive behavior of the CC‐loaded hydrogels prepared via FP were thoroughly investigated on the basis of swelling measurement, scanning electron microscopy, and reflection spectra. Results show that the as‐prepared CC‐loaded hydrogels exhibit excellent dual sensitivity to both methanol concentrations and pH values with very short response time, which can be observed visually without the aid of instruments. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Dual thermo‐ and pH‐sensitive network‐grafted hydrogels formed by macrocrosslinker as drug delivery system

Dual thermo‐ and pH‐sensitive network‐grafted hydrogels made of poly(N,N‐dimethylaminoethyl methacrylate) (PDMAEMA) network and poly(N‐isopropylacrylamide) (PNIPAM) grafting chains were successfully synthesized by the combination of atom transfer radical polymerization (ATRP), reversible addition‐fragmentation chain transfer (RAFT) polymerization, and click chemistry. PNIPAM having two azide groups at one chain end [PNIPAM‐(N₃)₂] was prepared with an azide‐capped ATRP initiator of N,N‐di(β‐azidoethyl) 2‐chloropropionylamide. Alkyne‐pending poly(N,N‐dimethylaminoethyl methacrylate‐co‐propargyl acrylate) [P(DMAEMA‐co‐ProA)] was obtained through RAFT copolymerization using dibenzyltrithiocarbonate as chain transfer agent. The subsequent click reaction led to the formation of the network‐grafted hydrogels. The influences of the chemical composition of P(DMAEMA‐co‐ProA) on the properties of the hydrogels were investigated in terms of morphology and swelling/deswelling kinetics. The dual stimulus‐sensitive hydrogels exhibited fast response, high swelling ratio, and reproducible swelling/deswelling cycles under different temperatures and pH values. The uptake and release of ceftriaxone sodium by these hydrogels showed both thermal and pH dependence, suggesting the feasibility of these hydrogels as thermo‐ and pH‐dependent drug release devices. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011