Shiping Zhu

Protein resistant surfaces: Comparison of acrylate graft polymers bearing oligo-ethylene oxide and phosphorylcholine side chains

The objective of this work was to compare poly(ethylene glycol) (PEG) and phosphorylcholine (PC) moieties as surface modifiers with respect to their ability to inhibit protein adsorption. Surfaces were prepared by graft polymerization of the methacrylate monomers oligo(ethylene glycol) methyl ether methacrylate (OEGMA, MW 300, PEG side chains of length n=4.5) and 2-methacryloyloxyethyl phosphorylcholine (MPC, MW295). The grafted polymers thus contained short PEG chains and PC, respectively, as side groups. Grafting on silicon was carried out using surface-initiated atom transfer radical polymerization (ATRP). Graft density was controlled via the surface density of the ATRP initiator, and chain length of the grafts was controlled via the ratio of monomer to sacrificial initiator. The grafted surfaces were characterized by water contact angle, x-ray photoelectron spectroscopy, and atomic force microscopy. The effect of graft density and chain length on fibrinogen adsorption from buffer was investigated using radio labeling methods. Adsorption to both MPC- and OEGMA-grafted surfaces was found to decrease with increasing graft density and chain length. Adsorption on the MPC and OEGMA surfaces for a given chain length and density was essentially the same. Very low adsorption levels of the order of 7 ng/cm2 were seen on the most resistant surfaces. The effect of protein size on resistance to adsorption was studied using binary solutions of lysozyme (MW 14 600) and fibrinogen (MW 340 000). Adsorption levels in these experiments were also greatly reduced on the grafted surfaces compared to the control surfaces. It was concluded that at the lowest graft density, both proteins had unrestricted access to the substrate, and the relative affinities of the proteins for the substrate (higher affinity of fibrinogen) determined the composition of the layer. At the highest graft density also, where the adsorption of both proteins was very low, no preference for one or the other protein was evident, suggesting that adsorption did not involve penetration of the grafts and was occurring at the outer surface of the graft layer. It thus seems likely that preference among different proteins based on ability to penetrate the graft layer would occur, if at all, at a grafting density intermediate between 0.1 and 0.39 /cm2. Again the MPC and OEGMA surfaces behaved similarly. It is suggested that the main determinant of the protein resistance of these surfaces is the “water barrier layer” resulting from their hydrophilic character. In turn the efficacy of the water barrier depends on the monomer density in the graft layer.

Controlled orientation of liquid-crystalline polythiophene semiconductors for high-performance organic thin-film transistors

The silane self-assembled monolayer (SAM) modification of a SiO2 gate dielectric surface improved the molecular ordering of organic channel semiconductor in organic thin-film transistors (OTFTs), leading to a significant improvement in transistor performance. Mobility of up to 0.18cm2∕Vs (current on∕off ratio of 107) was obtained for OTFTs with a liquid-crystalline polythiophene semiconductor built on an octyltrichlorosilane-modified SiO2 gate dielectric layer, a 450 times improvement over those built on a nonmodified dielectric layer. The mobility enhancement was attributed to the edge-on orientation of the polythiophene molecules induced by the silane SAM layer as deduced from the crystal domain structures in the atomic force microscopic images.

Modeling of molecular weight development in atom transfer radical polymerization

A kinetic model has been developed for atom transfer radical polymerization processes using the method of moments. This model predicts monomer conversion, number-average molecular weight and polydispersity of molecular weight distribution. It takes into account the effects of side reactions including bimolecular radical termination and chain transfers. The determining parameters include the ratios of the initiator, catalyst and monomer concentrations, as well as the ratios of the rate constants of propagation, termination, transfer and the equilibrium constant between radicals and their dormant species. The effects of these parameters on polymer chain properties are systematically simulated. The results show that an ideal living radical polymerization exhibiting a linear relationship between number-average molecular weight versus conversion and polydispersity approaching unity is only achievable under the limiting condition of slow monomer propagation and free of radical termination and transfers. Improving polymerization rate usually accompanies a loss of this linearity and small polydispersity. For polymerization systems having a slow initiation, the dormant species exercise a retention effect on chain growing and tend to narrow the molecular weight distribution. Increasing catalyst concentration accelerates the initiation rate and thus decreases the polydispersities. It is also shown that for a slow initiation system, delaying monomer addition helps to reduce the polydispersities. Radical termination and transfers not only slow down the monomer conversion rates but also broaden polymer molecular weight distributions. Under the limiting conditions of fast propagation and termination and slow initiation, the model predicts the conventional free radical polymerization behaviors.

Preparation of CO2/N2‐Triggered Reversibly Coagulatable and Redispersible Polyacrylate Latexes by Emulsion Polymerization Using a Polymeric Surfactant

We report here a novel approach for making reversibly coagulatable and redispersible polyacrylate latexes by emulsion (co)polymerization of methyl methacrylate (MMA) using a polymeric surfactant, poly(2-(dimethylamino)ethyl methacrylate)(10) -block-poly(methyl methacrylate)(14) . The surfactant was protonated with HCl prior to use. The resulted PMMA latexes were readily coagulated with trace amount of caustic soda. The coagulated latex particles, after washing with deionized water, could be redispersed into fresh water to form stable latexes again by CO(2) bubbling with ultrasonication. The recovered latexes could then be coagulated by N(2) bubbling with gentle heating. These coagulation and redispersion processes were repeatable by the CO(2) /N(2) bubbling.

Preparation of N2/CO2 triggered reversibly coagulatable and redispersible latexes by emulsion polymerization of styrene with a reactive switchable surfactant.

This work reports the development of a reversibly coagulatable and redispersible polystyrene latex system that can be triggered by N(2)/CO(2). The coagulatability and redispersibility of the latexes were achieved by employing 0.9-5.6 wt % (N-amidino)dodecyl acrylamide (DAm), a reactive switchable surfactant, in an emulsion polymerization of styrene under CO(2) atmosphere. The resulted latex particles were readily coagulated by N(2) bubbling at 60 °C and redispersed by CO(2) bubbling and ultrasonication, which switched amidine moieties between neutral and ionic states. The coagulation/redispersion processes were repeatable. The prepared latexes showed good stabilities against electrolytes, especially with higher charges.

Packed column reactor for continuous atom transfer radical polymerization : Methyl methacrylate polymerization using silica gel supported catalyst

A continuous column reactor packed with silica gel supported CuBr-HMTETA catalyst has been successfully developed for ATRP of MMA. The reactor had a good catalytic stability up to 100 h. The MMA conversion decreased with an increasing feeding flow rate. The polymerization kinetics was first order with respect to the monomer. The molecular weight increased linearly with conversion, demonstrating the living character. Possible flow back-mixing and polymer trapping in the pores of silica gel caused some broadening in the molecular weight distribution. This type of packed column reactor is believed to be a significant development for possible commercial exploitation of the ATRP process.

Chain Conformation of a New Class of PEG-Based Thermoresponsive Polymer Brushes Grafted on Silicon as Determined by Neutron Reflectometry

The thermoresponsive PEG-based copolymer poly[2-(2-methoxyethoxy)ethyl methacrylate-co-oligo(ethylene glycol) methacrylate) (P(MEO(2)MA-co-OEGMA)] was grafted onto a silicon wafer, and its chain conformation in aqueous solution was studied by neutron reflectometry. The effects of temperature and salt concentration on the polymers conformation were evaluated. With increasing temperature, it was found that the polymer brushes underwent a transition from an extended state to a compressed state, and eventually a collapsed state above the lower critical solution temperature. The presence of salt significantly affected the well-extended brushes but had little effect on compressed and collapsed brushes. This PEG-based thermoresponsive surface exhibited good protein adsorption resistance. Interestingly, extended and collapsed brushes showed the same level of protein repulsion, something that was not expected.

Lignin: a nature-inspired sun blocker for broad-spectrum sunscreens

We report the evaluation of lignin for the development of high-performance broad-spectrum sunscreens. Lignin is added into several commercial sunscreen products. Significant enhancements in ultraviolet (UV) absorbance are observed. The results show that the sunscreen effect of sun protection factor (SPF) 15 could reach that of SPF 30 with the addition of 2 wt% lignin. Adding 10 wt% lignin makes SPF 15 outperform SPF 50. It is also interesting to find that the sunscreen performance improves with UV-radiation time. After 2 h of UV radiation, the UV absorbance of the 10 wt% lignin SPF 15 lotion increases dramatically. This has been attributed to certain synergistic effects between lignin and other sunscreen actives in the lotions, as well as the antioxidant property of lignin. This nature-inspired lignin system may provide a green alternative to replace some synthetic sunscreen actives.

Catalyst impregnation and ethylene polymerization with mesoporous particle supported nickel-diimine catalyst

A nickel-diimine catalyst (1,4-bis(2,6-diisopropylphenyl) acenaphthene diimine nickel(II) dibromide, DMN) was supported on mesoporous particles having parallel hexagonal nanotube pore structure (MCM-41 and MSF) for ethylene polymerization. The effects of supporting methods and particle morphological parameters, such as pore size and length, on the catalyst impregnation were systematically investigated. Pretreating the supports with methylaluminoxane (MAO) followed by DMN impregnation gave much higher catalyst loading and higher catalytic activity than the direct impregnation of DMN. The particle structure significantly affected the catalyst impregnation and this effect was explained with a semi-quantitative molecular diffusion model. Compared to homogeneous catalysts, significant reduction in activity was observed with the supported systems in ethylene polymerization. Extraction of active sites from the supports during polymerization was observed. The mesoporous supports exerted steric effects on unleached active sites, lowering chain walking ability, and producing polymers having lower short chain branch density. Replication of the particle morphology was observed in some polymer samples.

Flexible and Porous Nanocellulose Aerogels with High Loadings of Metal-Organic Framework Particles for Separations Applications

Flexible and porous aerogels are obtained by combining functional metal-organic frameworks (MOFs) and structural cellulose nanocrystals via a straightforward water-based sol-gel process, followed by freeze-drying. The aerogels have a hierarchical porous structure with controllable MOF loading up to 50 wt%. These hybrid materials can be used as absorbents for water purification.