In Situ Swelling Behavior of Chitosan-Polygalacturonic Acid/Hydroxyapatite Nanocomposites in Cell Culture Media

The molecular and mechanical characteristics of in situ degradation behavior of chitosan-polygalacturonic acid/hydroxyapatite (Chi-PgA-HAP) nanocomposite films is investigated using Fourier Transform Infrared spectroscopy (FTIR), Atomic Force Microscopy (AFM), and modulus mapping techniques for up to 48 days of soaking in cell culture media. The surface molecular structure of media-soaked samples changes over the course of 48 days of soaking, as indicated by significant changes in phosphate vibrations (1200–900 cm−1) indicating apatite formation. Chitosan-Polygalacturonic acid polyelectrolyte complexes (PECs) govern structural integrity of Chi-PgA-HAP nanocomposites and FTIR spectra indicate that PECs remain intact until 48 days of soaking. In situ AFM experiments on media-soaked samples indicate that soaking results in a change in topography and swelling proceeds differently at the initial soaking periods of about 8 days than for longer soaking. In situ modulus mapping experiments are done on soaked samples by probing ∼1–3 nm of surface indicating elastic moduli of ∼4 GPa resulting from proteins adsorbed on Chi-PgA-HAP nanocomposites. The elastic modulus decreases by ∼2 GPa over a long exposure to cell culture media (48 days). Thus, as water enters the Chi-PgA-HAP sample, surface molecular interactions in Chi-PgA-HAP structure occur that result in swelling, causing small changes in nanoscale mechanical properties

Mineral and Protein-Bound Water and Latching Action Control Mechanical Behavior at Protein-Mineral Interfaces in Biological Nanocomposites

The nacre structure consists of laminated interlocked mineral platelets separated by nanoscale organic layers. Here, the role of close proximity of mineral to the proteins on mechanical behavior of the protein is investigated through steered molecular dynamics simulations. Our simulations indicate that energy required for unfolding protein in the proximity of mineral aragonite is several times higher than that for isolated protein in the absence of the mineral. Here, we present details of specific mechanisms which result in higher energy for protein unfolding in the proximity of mineral. At the early stage of pulling, peaks in the load-displacement (LD) plot at mineral proximity are quantitatively correlated to the interaction energy between atoms involved in the latching phenomenon of amino acid side chain to aragonite surface. Water plays an important role during mineral and protein interaction and water molecules closer to the mineral surface are highly oriented and remain rigidly attached as the protein strand is pulled. Also, the high magnitude of load for a given displacement originates from attractive interactions between the protein, protein-bound water, and mineral. This study provides an insight into mineral-protein interactions that are predominant in biological nanocomposites and also provides guidelines towards design of biomimetic nanocomposites

The role of fluid polarity in the swelling of sodium-montmorillonite clay: A molecular dynamics and Fourier transform infrared spectroscopy study

Swelling clays are found extensively in various parts of the world, and sodium-montmorillonite (Na-MMT) is the main constituent of an expansive clay mineral. In this work, the swelling behavior of Na-MMT clay with a wide range of organic fluids, high polar through low polar fluids, is studied using a combination of Fourier transform infrared (FTIR) technique and molecular dynamics (MD) simulations. The construction of the representative clay–fluid models is carried out, and the nature of nonbonded interactions between clay and fluids is studied using MD. Our FTIR and MD simulations results suggest the significant nonbonded interactions between Na-MMT clay and polar fluids, such as formamide and water. The nonbonded interactions of Na-MMT with methanol and acetone are significantly less than those in Na-MMT with polar fluids. The interactions of the fluids with various entities of the clay such as SiO, FeOH, MgOH, and AlOH captured via the spectroscopy experiments and modeling provide a finer understanding of the interactions and their contributions to swelling. The MD simulations are able to capture the band shifts observed in the spectra obtained in the spectroscopy experiments. This work also captures the conformations of interlayer sodium ions with formamide, water, methanol, and acetone during swelling. These nonbonded interactions provide insight into the molecular mechanism that the polarity of fluids plays an important role in the initiation of interlayer swelling, alteration in the orientations, and evolution of microstructure of swelling clays at the molecular scale. Keywords: Swelling clays, Montmorillonite, Fourier transform infrared (FTIR) technique, Molecular dynamics (MD), Organic fluids, Polarit

Conductivity Model and Photoacoustic FT-IR Surface Depth Profiling of Heterogeneous Polymers

A novel thermal model is developed for surface depth profiling of heterogeneous polymeric surfaces using step-scan photoacoustic Fourier transform (SS PA FT-IR) spectroscopy. This approach is based on the propagation of thermal waves generated during the photoacoustic effect which travel to the film-air (F-A) interface, thus generating acoustic signals above the surface, which upon Fourier transform, result in infrared spectra. The developed model volumetrically slices the surface into finite homogeneous layers parallel to the film-air (F-A) interface and a composition of each ith layer is assumed to be the same, but the layers among themselves (ith + I and ith - 1) may or may not exhibit compositional changes. Overall thermal properties of the multi-layered surface consist of the sum of in-series connected thermal conductor layers. The proposed model can be utilized to polymeric films containing the following parametrically analyzed inclusions: (1) inclusions with no interphase between the matrix polymeric and (2) inclusions with a finite interphase. This model is flexible, allowing variations of the particle size, shape, and surface/interfacial microstructural changes. It was tested for depths of penetrations in the range of 5-50 mum for carbon black inclusions imbedded into a two-component (2K) polyurethane (PUR) film deposited on acrylonitrile-butadiene-styrene (ABS) substrate. These studies show that the experimental results are consistent with the proposed model, allowing predictions of interphase layers on particles; for example, a 10 nm water layer adsorbed on carbon black particle surfaces can be detected. (C) 2003 Elsevier Science Ltd. All rights reserved

Role of Polymer Interactions with Clays and Modifiers on Nanomechanical Properties and Crystallinity in Polymer Clay Nanocomposites

We present the effect of organic modifier on crystallinity and nanomechanical properties of polymer clay nanocomposites (PCNs) using two different polymers while maintaining the same nanoclay and organic modifier. Experimental results and interaction energy maps of Polybutylene-Terephthalate- (PBT-) PCN system indicate that the underlying mechanisms of change in crystallinity and improvement in mechanical properties as proposed in altered phase theory are valid. Experimental and molecular simulation studies of PBT-PCN and Nylon6-PCN reveal that a higher crystallinity polymer could require significantly higher attractive and repulsive interaction energies between polymer and organic modifiers to change the crystallinity of the polymer in the PCN significantly and thus improve mechanical properties of the PCN

Effect of Carbon Black on Adhesion to Plastics in Solventborne 2K Polyurethanes

These studies show that when the pigment volume content (PVC) of carbon black particles increases in polyurethanes (PUR), NCO consumption increases, and the extent of H-bonded C=O species near the film-substrate (F-S) interface is enhanced. During crosslinking, polyurea (PUA) is produced, and its concentration levels near the F-S interface are diminished for unpigmented coatings, whereas for the same system containing carbon black, the PUA formation is enhanced. Although the presence of carbon black particles at the F-S interface results in diminished adhesion of 2K PUR to acrylonitrile-butadiene-styrene (ABS), adhesion is also affected by the presence of OH and C=O functionalities on ABS, which are potential sites for H-bonding to PUR. Stronger hydrogen donor affinity of N-H functionalities in PUA as compared to the N-H groups on PUR leads to increased H-bonding in the presence of carbon black. Enhanced intermolecular H-bonding in PUR due to the presence of carbon black particles competes wit the F-S interfacial H-bonding that promotes adhesion