Synthesis of Polystyrene Grafting Filler Nanoparticles: Effect of Grafting on Mechanical Reinforcement

A series of polystyrene (PS) nanoparticles were prepared by grafting polystyrene from both aggregated silica and colloidally dispersed silica nanoparticles using atom-transfer radical polymerisation (ATRP). Cross-linking and macroscopic gelation were minimised by using a miniemulsion system. The thermal and mechanical behaviour of the nanocomposites have been examined by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA).

Graft Copolymerization of Methyl Methacrylate onto Cellulose in Homogeneous Medium – Effect of Solvent and Initiator

Homogeneous graft copolymerization of methyl methacrylate (MMA) onto cellulose was carried out in N, N – dimethyl acetamide/LiCl (DMAc/LiCl) and dimethyl sulfoxide/ paraformaldehyde (DMSO/PF) solvent system taking ceric ammonium nitrate (CAN), benzoyl peroxide (BPO) and tin (II)-2-ethyl hexanoate [Sn(Oct)2] as initiators. Different grafting parameters like graft yield (GY), grafting efficiency (GE) and total conversion of monomer to polymer (TC) were evaluated at different reaction conditions of temperature, time, and variation of the amount of monomer and initiator. The viscosity average molecular weight of grafted PMMA and number of grafts per cellulose chain were also calculated. The products were characterized by FT-IR and 1H-NMR analyses and possible reaction mechanisms were deduced. Thermal degradation of the grafted products was also studied by thermo-gravimetric analysis (TG) and differential thermo-gravimetry (DTG).

QCM-D Study on Relationship of PEG Coated Stainless Steel Surfaces to Protein Resistance

Nonspecific protein adsorption generally occurs on any solid surfaces and usually has adverse consequences. Adsorption of proteins onto a solid surface is believed to be the initial and controlling step in biofouling. Surfaces modified with end-tethered poly(ethylene glycol) (PEG) have been shown to be protein-resistant to some degree. In this study, the adsorption of β-casein and lysozyme was performed on 6 different types of surfaces where PEG was tethered onto stainless steel by polyethylene imine (PEI) through either OH or NHS end groups. Protein adsorption was also performed on the bare stainless steel surface as a control. The adsorption was conducted at 23 °C and pH 7.2. In situ QCM-D was used to determine PEG adsorption kinetics, plateau PEG chain densities, protein adsorption kinetics and plateau protein adsorbed quantities. PEG grafting density was the highest for a NHS coupled chain, around 0.5 chains / nm2. Interestingly, lysozyme which has smaller size than β-casein, appeared to adsorb much less mass than that of β- casein. Overall, the surface with high PEG grafting density exhibited a good protein rejection.

Swelling Behavior and Cytotoxicity of Maleic Acid Grafted Chitosan

Chitosan is an attractive polysaccharide obtained by deacetylation of an abundant natural biopolymer called chitin. Chitin and chitosan are excellent materials. To improve the potential of chitin and chitosan modification is needed. In the present study, grafting of maleic acid on to chitosan by cerium ammonium nitrate in acetic acid solution was investigated with use of a microwave and reflux system. The grafted chitosan was characterized by using a Fourier-transform infrared spectrometry. The solubility and swelling behavior of grafted chitosans were determined in acetate buffer (pH 3.6), citrophosphate buffer (pH 5.6 and pH 7.0), and boric buffer (pH 9.2) solutions. The sample obtained by microwave system with use of a chitosan/maleic anhydride/ceric ammonium nitrate 0.2/3.922/0.99 gram of raw material within 30 minute showed the maximum swelling ratio (13.6) in boric buffer solution.

Are PEG Molecules a Universal Protein Repellent?

Poly (ethylene glycol) (PEG) molecules attached to surfaces have shown high potential as a protein repellent due to their flexibility and highly water solubility. A quartz crystal microbalance recording frequency and dissipation changes (QCM-D) has been used to study the adsorption from aqueous solutions, of lysozyme and α-lactalbumin proteins (the last with and without calcium) onto modified stainless steel surfaces. Surfaces were coated with poly(ethylene imine) (PEI) and silicate before grafting on PEG molecules. Protein adsorption was also performed on the bare stainless steel surface as a control. All adsorptions were conducted at 23°C and pH 7.2. The results showed that the presence of PEG molecules significantly reduced the adsorption of lysozyme and α- lactalbumin (with calcium) onto the stainless steel surface. By contrast, and unexpected, PEG molecules enhanced the adsorption of α-lactalbumin (without calcium). It is suggested that the PEG -α- lactalbumin hydrophobic interaction plays a dominant role which leads to protein aggregation at the surface for this latter observation. The findings also lead to the general conclusion that PEG molecules are not a universal protein repellent. PEG-on-PEI surfaces were better at inhibiting the adsorption of lysozyme and α-lactalbumin (with calcium) than with PEG-on-silicate surfaces.

pH-Responsiveness Properties of a Biodigradable Hydrogels Based on Carrageenan-g-poly(NaAA-co-NIPAM)

A novel thermo-sensitive superabsorbent hydrogel with salt- and pH-responsiveness properties was obtained by grafting of mixtures of acrylic acid (AA) and N-isopropylacrylamide (NIPAM) monomers onto kappa-carrageenan, kC, using ammonium persulfate (APS) as a free radical initiator in the presence of methylene bisacrylamide (MBA) as a crosslinker. Infrared spectroscopy was carried out to confirm the chemical structure of the hydrogel. Moreover, morphology of the samples was examined by scanning electron microscopy (SEM). The effect of MBA concentration and AA/NIPAM weight ratio on the water absorbency capacity has been investigated. The swelling variations of hydrogels were explained according to swelling theory based on the hydrogel chemical structure. The hydrogels exhibited salt-sensitivity and cation exchange properties. The temperature- and pH-reversibility properties of the hydrogels make the intelligent polymers as good candidates for considering as potential carriers for bioactive agents, e.g. drugs.

Modification and Characterization of Bacterial Cellulose Biopolymer as Proton Conducting Membrane

This study describes the preparation of a novel proton conducting membranes based on bacterial cellulose (BC) modified by grafting of 2-acrylamido-2-methyl-1 -propanesulfonic acid (AMPS) through UV-induced graft polymerization. These AMPS-g-BC membranes have been characterized by various techniques including FTIR, SEM and TGA, to find their successful grafting of AMPS on BC, surface morphology and thermal stability, respectively. Physical properties of AMPS-g-BC membranes have been assessed in terms of Lamda value( λ ), ion exchange capacity(IEC) and proton conductivity. The relationship between degree of grafting and AMPS concentration used for grafting has been determined by weight gain method. An optimum proton conductivity equal to 2.89x10-2 S cm-1 and IEC value equal to 1.79 mmol g-1 have been obtained when 20 wt% AMPS concentration is used for grafting (i.e. the corresponding membrane is notated as AMPS20-g-BC).

Dextran Modified Silicon Photonic Microring Resonator Sensors

We present a dextran modified silicon microring resonator sensor for high density antibody immobilization. An array of sensors consisting of three sensor rings and a reference ring was fabricated and its surface sensitivity and the limit of detection were obtained using polyelectrolyte multilayers. The mass sensitivity and the limit of detection of the fabricated sensor ring are 0.35 nm/ng mm-2 and 42.8 pg/mm2 in air, respectively. Dextran modified sensor surface was successfully prepared by covalent grafting of oxidized dextran on 3-aminopropyltriethoxysilane (APTES) modified silicon sensor surface. The antibody immobilization on hydrogel dextran matrix improves 40% compared to traditional antibody immobilization method via APTES and glutaraldehyde linkage.

Preparation of Polylactic Acid Graft Polyvinyl Acetate Compatibilizers for 50/50 Starch/PLLA Blending

Polylactic acid-g-polyvinyl acetate (PLLA-g-PVAc) was used as a compatibilizer for 50/50 starch/PLLA blend. PLLA-g- PVAc with different mol% of PVAc contents were prepared by grafting PVAc onto PLLA backbone via free radical polymerization in solution process. Various conditions such as type and the amount of initiator, monomer concentration, polymerization time and temperature were studied. Results showed that the highest mol% of PVAc grafting (16 mol%) was achieved by conducting graft copolymerization in toluene at 110°C for 10 h using DCP as an initiator. Chemical structure of the PVAc grafted PLLA was confirmed by 1H NMR. Blending of modified starch and PLLA in the presence compatibilizer with different amounts and mol% PVAc was acquired using internal mixer at 160°C for 15 min. Effects of PVAc content and the amount of compatibilizer on mechanical properties of polymer blend were studied. Results revealed that tensile strength and tensile modulus of polymer blend with higher PVAc grafting content compatibilizer showed better properties than that of lower PVAc grafting content compatibilizer. The amount of compatibilizer was found optimized in the range of 0.5-1.0 Wt% depending on the mol% PVAc.

Combining Gene and Chemo Therapy using Multifunctional Polymeric Micelles

Non-viral gene carriers composed of biodegradable polymers or lipids have been considered as a safer alternative for gene carriers over viral vectors. We have developed multi-functional nano-micelles for both drug and gene delivery application. Polyethyleneimine (PEI) was modified by grafting stearic acid (SA) and formulated to polymeric micelles (PEI-SA) with positive surface charge for gene and drug delivery. Our results showed that PEI-SA micelles provided high siRNA binding efficiency. In addition, siRNA delivered by PEI-SA carriers also demonstrated significantly high cellular uptake even in the presence of serum proteins. The post-transcriptional gene silencing efficiency was greatly improved by the polyplex formulated by 10k PEI-SA/siRNA. The amphiphilic structure of PEI-SA micelles provided advantages for multifunctional tasks; where the hydrophilic shell modified with cationic charges can electrostatically interact with DNA or siRNA, and the hydrophobic core can serve as payloads for hydrophobic drugs, making it a promising multifunctional vehicle for both genetic and chemotherapy application.

Computational Design of Inhibitory Agents of BMP-Noggin Interaction to Promote Osteogenesis

Bone growth factors, such as Bone Morphogenic Protein-2 (BMP-2) have been approved by the FDA to replace grafting for some surgical interventions, but the high dose requirement limits its use in patients. Noggin, an extracellular protein, blocks the effect of BMP-2 by binding to BMP. Preventing the BMP-2/noggin interaction will help increase the free concentration of BMP-2 and therefore should enhance its efficacy to induce bone formation. The work presented here involves computational design of novel small molecule inhibitory agents of BMP-2/noggin interaction, based on our current understanding of BMP-2, and its known putative ligands (receptors and antagonists). A successful acquisition of such an inhibitory agent of BMP-2/noggin interaction would allow clinicians to reduce the dose required of BMP-2 protein in clinical applications to promote osteogenesis. The available crystal structures of the BMPs, its receptors, and the binding partner noggin were analyzed to identify the critical residues involved in their interaction. In presenting this study, LUDI de novo design method was utilized to perform virtual screening of a large number of compounds from a commercially available library against the binding sites of noggin to identify the lead chemical compounds that could potentially block BMP-noggin interaction with a high specificity.