Abstract: Protein adhesion plays a major role in determining the biocompatibility of materials. The first stage of implant integration is the adhesion of protein followed by cell attachment. Surface modification of implants (surface chemistry and topography) to induce and control protein and cell adhesion is currently of great interest. This communication presents data on protein adsorption (bovine serum albumin and fibrinogen) onto model hydrophobic (CH3) and hydrophilic (OH) surfaces, investigated using a quartz crystal microbalance (QCM) and grazing angle infrared spectroscopy. Our data suggest that albumin undergoes adsorption via a single step whereas fibrinogen adsorption is a more complex, multistage process. Albumin has a stronger affinity toward the CH3 compared to OH terminated surface. In contrast, fibrinogen adheres more rapidly to both surfaces, having a slightly higher affinity toward the hydrophobic surface. Conformational assessment of the adsorbed proteins by grazing angle infrared spectroscopy (GA...

Abstract: Single-walled carbon nanotubes (SWCNT) functionalized with amino groups were prepared via chemical modification of carboxyl groups introduced on the carbon nanotube surface. Two different approaches (amide and amine-moieties) were used to produce the amino-functionalized nanotubes. The amino-termination allows further chemistry of the functionalized SWCNTs and makes possible covalent bonding to polymers and biological systems such as DNA and carbohydrates. The functionalization of the SWCNTs was characterized in detail using FTIR and XPS.

Abstract: Summary: Electro-active shape-memory composites were synthesized using conducting polyurethane (PU) composites and multi-walled carbon nanotubes (MWNTs) Surface modification of the MWNTs (by acid treatment) improved the mechanical properties of the composites The modulus and stress at 100% elongation increased with increasing surface-modified MWNT content, while elongation at break decreased MWNT surface modification also resulted in a decrease in the electrical conductivity of the composites, however, as the surface modified MWNT content increased the conductivity increased (an order of 10−3 S · cm−1 was obtained in samples with 5 wt-% modified-MWNT content) Electro-active shape recovery was observed for the surface-modified MWNT composites with an energy conversion efficiency of 104% Hence, PU-MWNT composites may prove promising candidates for use as smart actuators The electro-active shape-recovery behavior of PU-MWNT composites The pictured transition occurs within 10 s when a constant voltage of 40 V is applied

Abstract: In this paper, we demonstrate the first use of a catecholic initiator for surface-initiated polymerization (SIP) from metal surfaces to create antifouling polymer coatings. A new bifunctional initiator inspired by mussel adhesive proteins was synthesized, which strongly adsorbs to Ti and 316L stainless steel (SS) substrates, providing an anchor for surface immobilization of grafted polymers. Surface-initiated atom transfer radical polymerization (SI-ATRP) was performed through the adsorbed biomimetic initiator to polymerize methyl methacrylate macromonomers with oligo(ethylene glycol) (OEG) side chains. X-ray photoelectron spectroscopy, surface FT-IR, and contact angle analysis confirmed the sequential grafting of initiator and polymer, and ellipsometry indicated the formation of polymer coatings of up to 100 nm thickness. Cell adhesion experiments performed with 3T3-Swiss albino fibroblasts showed substantially reduced cell adhesion onto polymer grafted Ti and 316L SS substrates as compared to the unmodified metals. Moreover, micropatterning of grafted polymer coatings on Ti surfaces was demonstrated by combining SI-ATRP and molecular assembly patterning by lift-off (MAPL), creating cell-adhesive and cell-resistant regions for potential use as cell arrays. Due to the ability of catechols to bind to a large variety of inorganic surfaces, this biomimetic anchoring strategy is expected to be a highly versatile tool for polymer thin film surface modification for biomedical and other applications.

Abstract: We present a study on the electronic behavior of films of as-prepared and purified single-walled carbon nanotubes (SWNTs) and demonstrate the important role that chemical functionalization plays in modifying their electronic properties, which in turn throws further light on the mechanism of action of SWNT-based sensors. Films of electric arc SWNTs were prepared by spraying, and optical spectroscopy was used to measure the effective film thickness. The room-temperature conductivities (σRT) of thin films deposited from as-prepared and purified SWNTs are in the range σRT = 250−400 S/cm, and the nonmetallic temperature dependence of the conductivity indicates the presence of tunneling barriers, which dominate the film conductivity. Chemical functionalization of SWNTs with octadecylamine (ODA) and poly(m-aminobenzenesulfonic acid) (PABS) significantly decreases the conductivity; σRT = 3 and 0.3 S/cm for SWNT-ODA and SWNT-PABS, respectively.

Abstract: Several TiO2-based photocatalytic systems that have considerable visible light response have been developed, such as the photodegradation of organic pollutants on sensitized TiO2 by visible light, construction of visible-light-active novel TiO2 photocatalysts by matrix or surface modification. In this paper, we review briefly our recent progress in the TiO2 photocatalytic degradation of organic pollutants by visible light, some related work by other groups is also involved.

Abstract: Often hard implants undergo detachment from the host tissue due to inadequate biocompatibility and poor osteointegration. Changing surface chemistry and physical topography of the surface influences biocompatibility. At present, the understanding of biocompatibility of both virgin and modified surfaces of bioimplant materials is limited and a great deal of research is being dedicated to this aspect. In view of this, the current review casts new light on research related to the surface modification of biomaterials, especially materials for prosthetic applications. A brief overview of the major surface modification techniques has been presented, followed by an in-depth discussion on laser surface modifications that have been explored so far along with those that hold tremendous potential for bioimplant applications.

Abstract: Inductive coupled rf-plasma at 13.56 MHz was used to modify multiwalled carbon nanotubes (MWCNTs). This technique can be easily used to tailor the chemical composition of carbon nanotubes by attaching a wide variety of functional groups at their surface: oxygen-, nitrogen-, and fluorine-containing groups have been grafted. The influence of various plasma conditions (power, type of gas, treatment time, pressure, position of the CNT sample inside the chamber) on the functionalization of the MWCNT surface was analyzed by x-ray photoelectron spectroscopy. The results show that for too high oxygen plasma power, chemical etching occurs at the surface of the CNT, thus destroying its structure. On the other hand, for optimal values of the plasma parameters, functional groups (hydroxide, carbonyl, carboxyl, amine, fluorine, etc.) were found to bond to the CNT surface, suggesting that both the concentration and type of the functional groups are in close connection with the plasma conditions. These results were compared to interaction energies predicted by ab initio calculations for different functional groups under consideration, showing that functionalization by oxygen plasma produces mainly functional groups with lower interaction energy.

Abstract: The interest in using cellulose fibres as reinforcing elements in composite materials based on polymeric matrices is constantly growing, mainly because of the many advantages associated with this renewable material. However, the preparation of cellulose-based composites is perturbed by the highly hydrophilic character of the fibres, which is associated with a low interfacial compatibility with hydrophobic polymeric matrices, as well as with a loss of mechanical properties after moisture uptake. In order to reduce the hydrophilic character of cellulose fibres and to improve the strength of their adhesion to the matrix, it is necessary to undertake a structural modification of their surface. Several approaches have been studied, namely (i) physical treatments such as corona, plasma, laser, vacuum ultraviolet and γ-radiation treatments; (ii) chemical grafting by direct condensation, including surface compatibilisation with hydrophobic moieties and co-polymerisation with the matrix. The copolymerisation appro...

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Abstract: Functionalization of carbon nanotubes (CNTs) is important for enhancing deposition of metal nanoparticles in the fabrication of supported catalysts. A facile approach for oxidizing CNTs is presented using a sonochemical method to promote the density of surface functional groups. This was successfully employed in a previous study [J. Phys. Chem. B 2004, 108, 19255] to prepare highly dispersed, high-loading Pt nanoparticles on CNTs as fuel cell catalysts. X-ray photoelectron spectroscopy (XPS), transmission electron microscopy, cyclic voltammetry, and settling speeds were used to characterize the degree of surface functionalization and coverage. The sonochemical method effectively functionalized the CNTs. A mixture of CO/CO and COO was observed along with evidence for weakly bound CO at longer treatment times. The integrated XPS C 1s core level peak area ratios of the oxidized-to-graphitic C oxidation states, as well as the atom % oxygen from the O 1s level, showed an increase in peak intensity (attributed ...

Abstract: The effect of fibre treatments and matrix modification on mechanical properties of flax fibre bundle/polypropylene composites was investigated. Treatments using chemicals such as maleic anhydride, vinyltrimethoxy silane, maleic anhydride-polypropylene copolymer and also fibre alkalization were carried out in order to modify the interfacial bonding between fibre bundles and polymeric matrix. Composites were produced by employing two compounding ways: internal mixing and extrusion. Mechanical behaviour of both flax fibre bundle and hybrid glass/flax fibre bundle composites was studied. Fracture surfaces were investigated by scanning electron microscopy. Results suggest that matrix modification led to better mechanical performance than fibre surface modification. A relevant fact is that silanes or MA grafted onto PP matrix lead to mechanical properties of composites even better than those for MAPP modification, and close to those for glass fibre/PP.

Abstract: Ionic flux through a composite membrane structure, containing vertically aligned carbon nanotubes crossing a polystyrene matrix film, was studied as a function of chemical end groups at the entrance to carbon nanotubes' (CNTs) cores. Plasma oxidation during the membrane fabrication process introduced carboxylic acid groups on the CNTs' tips that were modified using carbodiimide mediated coupling between the carboxylic acid and an accessible amine groups of the functional molecule. Functionalization molecules included straight chain alkanes, anionically charged dye molecules, and an aliphatic amine elongated by polypeptide spacers. Functionalization was confirmed by FTIR spectroscopy, and areal functional density was estimated by transmission electron microscopy studies of thiol terminated sites decorated by nanocrystalline gold. The transport through the membrane of two different sized but equally charged molecules (ruthenium bipyridine [Ru-(bipy)32+] and methyl viologen [MV2+]) was quantified in a U-tube...

Abstract: Although multicomponent core-shell type nanomaterials are one of the highly desired structural motifs due to their simultaneous multifunctionalities, the fabrication strategy for such nanostructures is still in a primitive stage. Here, we present a redox-transmetalation process that is effective as a general protocol for the fabrication of high quality and well-defined core-shell type bimetallic nanoparticles on the sub-10 nm scale. Various core-shell type nanomaterials including Co@Au, Co@Pd, Co@Pt, and Co@Cu nanoparticles are fabricated via transmetalation reactions. Compared to conventional sequential reduction strategies, this transmetalation process has several advantages for the fabrication of core-shell type nanoparticles: (i) no additional reducing agent is needed and (ii) spontaneous shell layer deposition occurs on top of the core nanoparticle surface and thus prevents self-nucleation of secondarily added metals. We also demonstrate the versatility of these core-shell structures by transferring Co@Au nanoparticles from an organic phase to an aqueous phase via a surface modification process. The nanostructures, magnetic properties, and reaction byproducts of these core-shell nanoparticles are spectroscopically characterized and identified, in part, to confirm the chemical process that promotes the core-shell structure formation.

Abstract: Side-chain functionalized polymers have a profound impact on complex materials synthesis with a variety of applications ranging from liquid crystalline and electro-optical materials to drug delivery systems. In the last decade, the use of self-assembly towards the synthesis of side-chain functionalized polymers has been investigated extensively as a result of its modular character and ease of synthesis. This tutorial review describes recent advances in the literature and establishes basic design principles and synthetic approaches towards the fabrication of supramolecular materials that are based on side-chain functionalized polymers.

Abstract: The development of heterogeneous catalytic systems for carrying out liquid phase chemical and biochemical transformations is a major area of research, which has great significance for the development of cleaner and more efficient processes. This review reflects the growing significance of renewable polymeric supports for such catalysts. The focus of this review is chitosan, a material produced in enormous quantities each year and derived predominantly from the shells of crustaceans. This material has many benefits, some of which have hardly been exploited in catalysis. A survey of methodology for the functionalization of chitosan, and how the functional chitosans are used in catalysis, is given.

Abstract: Nanocrystals of Gd2O3 have been prepared by various methods, using, e.g., trioctylphosphine oxide (TOPO), diethylene glycol (DEG) or glycine. The crystalline particles were of sizes 5 to 15 nm. Different carboxylic acids, e.g., oleic acid or citric acid, were adsorbed onto the surface of the particles made with DEG. IR measurements show that the molecules coordinate to the Gd2O3 surface via the carboxylate group in a bidentate or bridging manner. The organic-acid/particle complexes were characterised by XRPD, TEM, FTIR, Raman, and XPS.

Abstract: A strategy to covalently attach biological molecules to the electrochemically active surface of indium oxide nanowire (In2O3 NW) mat devices is presented. A self-assembled monolayer (SAM) of 4-(1,4-dihydroxybenzene)butyl phosphonic acid (HQ-PA) was generated on an indium tin oxide (ITO)-coated glass and In2O3 NWs surface. The chemical steps required for surface derivatization were optimized on an ITO surface prior to modifying the In2O3 NWs. The hydroquinone group contained in the HQ-PA SAM was electrochemically oxidized to quinone (Q-PA) at +330 mV. The monolayer of Q-PA was allowed to react with a thiol-terminated DNA. The DNA was paired to its complementary strand tagged with a fluorescence dye. Attachment of DNA was verified using fluorescence microscopy. A device was subsequently prepared on a SiO2-supported mat of In2O3 NWs by depositing gold electrodes on the mat surface. The reaction strategy optimized on ITO was applied to this In2O3 NW-based device. Arrays of In2O3 NWs on a single substrate were...

Abstract: The utilization of nanoporous substrates in applications such as selective ion transport, biomolecule separation, seeded templating, and catalysis necessitates the ability to efficiently control pore surface properties. We approached this task by preparing nanoporous polymer monoliths from ABC triblock copolymer precursors that assemble into a cylindrical morphology, where the A block constitutes matrix, C is the removable minor component, and B provides the functionality on the surface of the pores. Polystyrene−polydimethylacrylamide−polylactide (PS−PDMA−PLA) triblock copolymers were prepared by a combination of controlled ring-opening and free-radical polymerization techniques. After selective etching of the PLA cylinders from shear-aligned monoliths, a nanoporous polystyrene matrix containing a hexagonally packed array of hydrophilic, PDMA-coated channels was obtained. Extremely high degrees of alignment and order could be attained, and nanoporous substrates with second-order orientation factors of as ...

Abstract: Membrane-based biomedical processes have increased considerably in recent years. However, the natural disadvantages of common membrane materials, such as hydrophobic surface and poor biocompatibility, cause many side effects in use and cumber further applications. In this work, to meet the requirements of biomedical applications, a novel sugar-containing monomer (d-gluconamidoethyl methacrylate (GAMA)) was grafted on polypropylene microporous membrane (PPMM) with an UV-induced polymerization to improve both the surface hydrophilicity and hemocompatibility. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy were employed to confirm the surface modification on the membranes. Water contact angle, protein adsorption, and platelet adhesion measurements were used to evaluate the anti-fouling property and the hemocompatibility of the membranes. It was found that the GAMA grafting degree increases reasonably with the increase of GAMA monomer concentration, ...