Chandra Sekhar Biswas

Random copolymer gels of N-isopropylacrylamide and N-ethylacrylamide: effect of synthesis solvent compositions on their properties

Random copolymer gels of N-isopropylacrylamide (NIPAM) and N-ethylacrylamide (NEAM) were synthesized using a 1:1 monomer molar ratio in different methanol–water (xm = 0, 0.06, 0.13, 0.21, 0.31 0.43, 0.57, 0.76, where xm = mole fraction of methanol) mixtures. The samples were characterized using different techniques like Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), swelling ratio measurements, deswelling kinetics study, atomic force microscopy (AFM), and rheology. We found that, with the variation of the solvent composition (methanol–water mixtures) the properties of the gels varied significantly. These results can be explained on the basis of the interactions of the two different kinds of monomers with different methanol–water mixtures, their different kinds of thermoresponsiveness and hydrophilicity, and their different cononsolvent properties toward methanol–water mixtures.

Reduced graphene oxide composites with water soluble copolymers having tailored lower critical solution temperatures and unique tube-like structure

Nanohybrids of graphene with water soluble polymer were synthesized using ‘grafting from’ method. GO, prepared by modified Hummers’ method, was first reacted with sodium azide. Alkyne-terminated RAFT-CTA was synthesized by reaction of propargyl alcohol and S-1-dodecyl-S’-(α,α‘-dimethyl-α”-acetic acid) trithiocarbonate. RAFT-CTA was grafted onto the GO sheets by facile click-reaction and subsequently, N-isopropylacrylamide (NIPAM) and N-ethyleacrylamide (NEAM) were polymerized on graphene sheets via RAFT polymerization method. The respective copolymers with different ratios were also prepared. The nanohybrids were characterized by FTIR, XRD, TGA, Raman, SEM, and AFM. Both SEM and AFM clearly showed rod-like structures for rGO-PNEAM. XRD showed a small peak at 2θ = 19.21°, corresponding to d-spacing ≈ 4.6 Å. In addition, the nanohybrids showed a very broad temperature range for the LCST in water between ca. 30 and 70 °C.

Synthesis, characterization, and drug release properties of macroporous dual stimuli responsive stereo regular nanocomposites gels of poly(N-isopropylacrylamide) and graphene oxide

Nanocomposite stereoregular hybrid gels of poly(N-isopropylacrylamide) were prepared in 1:1 methanol–water mixture in the presence rare earth yttrium trifluoromethanesulfonate Lewis acid and graphene oxide (GO). The nanocomposite gels were characterized by swelling ratio measurements at different temperatures and different pH, deswelling kinetics, scanning electrone microscopy, FTIR, thermogravimetric analysis, powder XRD, Raman spectroscopy, LCST measurement by DSC etc. Drug release experiments also done by using tramadol hydrochloride as a model drug to check their suitability in application. All results were explained on the basis of porosity, cononsolvency of the synthesis solvents, hydrophilicity, isotacticity, pH effect, interactions between solvents and polymer molecules, interactions between polymer and GO or interactions between GO and solvents etc.

Investigation of micromechanical properties of hard sphere filled composite hydrogels by atomic force microscopy and finite element simulations

Atomic force microscopy (AFM) indentation is the most suitable way to characterize micromechanical properties of soft materials such as bio tissues. However, the mechanical data obtained from force-indentation measurement are still not well understood due to complex geometry of the bio tissue, nonlinearity of indentation contact, and constitutive relation of hyperelastic soft material. Poly-N-isopropyl acrylamide (PNIPAM) filled with 5wt% polystyrene (PS) sphere particles material system can be utilized as a simplified model for mimicking a whole host of soft materials. Finite element model has been constructed to simulate indentation as in AFM experiments using colloidal probes for a parametric study, with the main purpose of understanding the effect of particles on overall behavior of mechanical data and local deformation field under indentation contact. Direct comparison between finite element simulation and indentation data from AFM experiments provides a powerful method to characterize soft materials properties quantitatively, addressing the lack of analytical solutions for hard-soft composites, both biological and synthetic ones. In this framework, quantitative relations are found between the depth, at which the particle was embedded, the particle size and the elastic modulus of the overall composite. Comprehensive characterizations were established to distinguish indentation on a particle residing on top of the hydrogel from a particle embedded inside the hydrogel matrix. Finally, different assumptions of interface friction at the boundary between the particle and the hydrogel have been tested and directly compared with experimental measurements.

Atomic force microscopy methodology and AFMech Suite software for nanomechanics on heterogeneous soft materials

Atomic force microscopy has proven to be a valuable technique to characterize the mechanical and morphological properties of heterogeneous soft materials such as biological specimens in liquid environment. Here we propose a 3-step method in order to investigate biological specimens where heterogeneity hinder a quantitative characterization: (1) precise AFM calibration, (2) nano-indentation in force volume mode, (3) array of finite element simulations built from AFM indentation events. We combine simulations to determine internal geometries, multi-layer material properties, and interfacial friction. In order to easily perform this analysis from raw AFM data to simulation comparison, we propose a standalone software, AFMech Suite comprising five interacting interfaces for simultaneous calibration, morphology, adhesion, mechanical, and simulation analysis. We test the methodology on soft hydrogels with hard spherical inclusions, as a soft-matter model system. Finally, we apply the method on E. coli bacteria supported on soft/hard hydrogels to prove usefulness in biological field.Atomic force microscopy is an indispensable method in characterizing soft materials but the complexity of biological samples makes reproducible measurements difficult. Here the authors use a 3-step method to investigate biological specimens in which vertical and lateral heterogeneity hinders a precise quantitative characterization.

Effect of a functional polymer on the rheology and microstructure of sodium alginate

Here, we report on the effect of functional copolymer poly(N-isopropylacrylamide-co-4-vinyl-phenylboronic acid) (NIBA) on the rheology and network structure formed by sodium alginate (SA) through linear and nonlinear viscoelasticity measurements. The hydrogel moduli at pH 3 increased with increasing NIBA addition, while the yield point decreased. Furthermore, these hydrogels showed strain-softening behavior, weak G″-overshoot marking the onset of nonlinearity, and good self-healing properties after large deformation. The zero-strain nonlinearity parameter (Q0) was found to be more sensitive to NIBA-addition than the linear viscoelastic properties. The blends showed a clear peak in the startup test except for SA alone and the peak intensity increased with increasing NIBA-concentration. Finally, based on all data, gelation mechanism and interaction of SA and NIBA will be clarified.

Crosslinking hydroxylated reduced graphene oxide with RAFT-CTA: A nano-initiator for preparation of well-defined amino acid-based polymer nanohybrids

Here, we demonstrate a novel reversible addition-fragmentation chain transfer agent (RAFT-CTA)-modified reduced graphene oxide nanosheets (CTA-rGONSs) by crosslinking rGONSs with a RAFT-CTA via esterification reaction. These nano CTA-rGONSs were used to polymerize a hydrophobic amino acid-based methacrylamide (N-acryloyl-l-phenylalanine methyl ester) monomer with different monomer/initiator ratios. Thermogravimetric analysis showed that the polymer-graphene composites were thermally more stable than GO itself. Mn of the polymers increased with increasing monomer/initiator ratio, while the polydispersity index decreased, indicating controlled polymerization. The composites were stable in DMF even after two months.