Showing papers on "Surface modification published in 2007"

Supramolecular chemistry on water-soluble carbon nanotubes for drug loading and delivery.

Abstract: We show that large surface areas exist for supramolecular chemistry on single-walled carbon nanotubes (SWNTs) prefunctionalized noncovalently or covalently by common surfactant or acid-oxidation routes. Water-soluble SWNTs with poly(ethylene glycol) (PEG) functionalization via these routes allow for surprisingly high degrees of π-stacking of aromatic molecules, including a cancer drug (doxorubicin) with ultrahigh loading capacity, a widely used fluorescence molecule (fluorescein), and combinations of molecules. Binding of molecules to nanotubes and their release can be controlled by varying the pH. The strength of π-stacking of aromatic molecules is dependent on nanotube diameter, leading to a method for controlling the release rate of molecules from SWNTs by using nanotube materials with suitable diameter. This work introduces the concept of “functionalization partitioning” of SWNTs, i.e., imparting multiple chemical species, such as PEG, drugs, and fluorescent tags, with different functionalities onto t...

Removal of Heavy Metals from Aqueous Systems with Thiol Functionalized Superparamagnetic Nanoparticles

Abstract: We have shown that superparamagnetic iron oxide (Fe3O4) nanoparticles with a surface functionalization of dimercaptosuccinic acid (DMSA) are an effective sorbent material for toxic soft metals such as Hg, Ag, Pb, Cd, and Tl, which effectively bind to the DMSA ligands and for As, which binds to the iron oxide lattices. The nanoparticles are highly dispersible and stable in solutions, have a large surface area (114 m2/g), and have a high functional group content (1.8 mmol thiols/g). They are attracted to a magnetic field and can be separated from solution within a minute with a 1.2 T magnet. The chemical affinity, capacity, kinetics, and stability of the magnetic nanoparticles were compared to those of conventional resin based sorbents (GT-73), activated carbon, and nanoporous silica (SAMMS) of similar surface chemistries in river water, groundwater, seawater, and human blood and plasma. DMSA-Fe3O4 had a capacity of 227 mg of Hg/g, a 30-fold larger value than GT-73. The nanoparticles removed 99 wt % of 1 mg...

Phosphonic Acid-Modified Barium Titanate Polymer Nanocomposites with High Permittivity and Dielectric Strength

Abstract: Materials with high dielectric permittivity are important in electronic components such as capacitors, gate dielectrics, memories, and power-storage devices. Conventional highpermittivity materials such as barium titanate (BT) can be processed into thin films by using chemical solution deposition yielding a relative permittivity (er) of about 2500 and relatively low dielectric loss but require high-temperature sintering, which is not compatible with many substrate materials. Polymer-based dielectrics, such as biaxially oriented polypropylene (BOPP), have good processability with high dielectric strengths (∼ 640 V lm) suitable for high-energy-density capacitors, but the storage capacity (ca. 1–1.2 J cm) is limited by the low er (ca. 2.2) of these materials. [6] Various approaches to high-er materials based on nanocomposites containing metal particles or other conductive materials have been pursued. Such nanocomposites have afforded huge er values but the resulting materials are limited by the high-temperature processing required, high dielectric loss, or low dielectric strength. Polymer/ceramic nanocomposites in which high-er metal oxide nanoparticles such as BT and lead magnesium niobate–lead titanate (PMN–PT) are incorporated into a polymer host are of significant current interest. The combination of high-er nanoparticles with high-dielectric-strength polymer hosts offers the potential to obtain processable highperformance dielectric materials. Simple solution processing of BT particles in a polymer host generally results in poor film quality and inhomogeneities, which are mainly caused by agglomeration of the nanoparticles. Addition of surfactants, such as phosphate esters and oligomers thereof, can improve the dispersion of BT nanoparticles in host polymers and consequently the overall nanocomposite film quality. However, in such systems, residual free surfactant can lead to high leakage current and dielectric loss. Thus, approaches to bind surface modifiers to BT nanoparticles via robust chemical bonds are highly desirable. Ramesh et al. have reported on the use of trialkoxysilane surface modifiers for the dispersion of BT nanoparticles in epoxy polymer hosts resulting in nanocomposites with reasonably high er, up to 45. [12] With the objective of identifying ligands that can form stable bonds to a BT surface through coordination or condensation, we have investigated a series of different ligand functionalities. In this Communication, we report that phosphonic acid ligands effect robust surface modification of BT and related nanoparticles and that the use of particles modified with suitable phosphonic acid ligands leads to well-dispersed BT nanocomposite films with high er and high dielectric strength. We have investigated the binding of a variety of ligands to the surface of BT nanoparticles, as the stability of the binding on the surface is vital to effective surface modification. We examined the following set of ligands, each bearing an aliphatic octyl chain with a different terminal binding group: C8H17-X, where X = PO(OH)2 (OPA), SO2ONa (OSA), Si(OCH3)3 (OTMOS), and CO2H (OCA). Trialkoxysilanes are widely used surface modifiers for silicate, indium tin oxide, and other metal oxide surfaces. Phosphonic acids have been reported to modify TiO2, ZrO2, and indium tin oxide surfaces and are thought to couple to the surface of metal oxides either by heterocondensation with surface hydroxyl groups or coordination to metal ions on the surface. Carboxylic acid and sulfonic acid groups may also bind to the surface in a similar manner. A sample of each ligand was mixed with BT nanoparticles (30–50 nm, 0.5 mmol ligand/ g BT) in an ethanol/water solution and stirred at 80 °C, followed by extensive washing with ethanol or water and centrifugation to remove excess and/or physisorbed ligand. The treated BT nanoparticles were dried and characterized by using Fourier transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA). Figure 1a shows a comparison of FTIR spectra in the C–H stretching region for the BT nanoparticles treated with the ligands described above, followed by washing. These results C O M M U N IC A IO N

Functional inorganic nanofillers for transparent polymers

Abstract: The integration of inorganic nanoparticles into polymers has been used for the functionalization of polymer materials with great success. Whereas in traditional polymer composites, micron sized particles or agglomerates typically cause significant light scattering hampering optical applications, in nanocomposites the particle dimensions are small enough for the production of highly transparent composites. A challenge for the generation of such materials is to develop an integrated synthesis strategy adapting particle generation, surface modification and integration inside the polymer. Surface grafting using polymerizable surfactants or capping agents allows for linking the particles to the polymer. Novel techniques such as in situ polymerization and in situ particle processing are beneficial to avoid aggregation of inorganic particles inside the polymer matrix. The functions associated with inorganic fillers are widespread. Layered silicates and related materials are nowadays commercially available for improving mechanical and barrier properties in packaging. With the availability of highly transparent materials, the focus has shifted towards optical functions such as luminescence and UV-protection in transparent polymers. IR-active fillers are used in laser-holography for transparent poly(methyl methacrylate) (PMMA) nanocomposites. Refractive index modulation and ultrahigh refractive index films were developed based on inorganic materials such as PbS. The integration of magnetic nanoparticles has a great potential for applications such as electromagnetic interference shielding and magneto-optical storage.This tutorial review will summarize functions associated with the integration of inorganic nanofillers in polymers with a focus on optical properties.

Surface transfer p-type doping of epitaxial graphene.

Abstract: Epitaxial graphene thermally grown on 6H-SiC(0001) can be p-type doped via a novel surface transfer doping scheme by modifying the surface with the electron acceptor, tetrafluoro-tetracyanoquinodimethane (F4-TCNQ). Synchrotron-based high-resolution photoemission spectroscopy reveals that electron transfer from graphene to adsorbed F4-TCNQ is responsible for the p-type doping of graphene. This novel surface transfer doping scheme by surface modification with appropriate molecular acceptors represents a simple and effective method to nondestructively dope epitaxial graphene for future nanoelectronics applications.

Hydrophilization and hydrophobic recovery of PDMS by oxygen plasma and chemical treatment—An SEM investigation

Abstract: Rapid prototyping of polydimethylsiloxane (PDMS) is frequently used to build microfluidic devices. PDMS is inherently hydrophobic; however, the surface can be temporarily rendered hydrophilic by exposing the surface to oxygen plasma. Hydrophilic microchannels are sometimes advantageous over hydrophobic microchannels due to increased cell adhesion or increase in electro osmotic flow (EOF) leading to ease of liquid filling in microchannels. However, the hydrophilic surface is unstable and that low molecular weight (LMW) chains diffuse from the bulk of the PDMS and cover up the thermodynamically unstable surface. This is one reason for the hydrophilic unstability of PDMS. Present study shows that not only chemistry of the creation of silanol groups on the surface, but also morphology of the film surface nanostructuring of PDMS plays an important role in hydrophilization of PDMS. Present paper tries to understand the mechanism of hydrophobic recovery taking into consideration physical and chemical parameters using SEM characterization.

The Rise of Azide–Alkyne 1,3-Dipolar ‘Click’ Cycloaddition and its Application to Polymer Science and Surface Modification

Abstract: New methods to synthesize and functionalize polymers are of constant interest to the polymer scientist. The 1,3-dipolar cycloaddition between an azide and terminal alkyne has received much attention since the reports that copper(i) provides high yields and regioselective synthesis of 1,4-substituted 1,2,3-triazoles. This coupling chemistry has been rapidly adopted by polymer scientists in the synthesis and post-polymerization modification of polymers. This Review will provide the historical context of the recent development of the copper-mediated azide–alkyne cycloaddition and its use in polymer science, particularly in dendrimer synthesis/functionalization, surface immobilization/modification, orthogonally functionalizing polymers, and its integration with ATRP (atom transfer radical polymerization).

Hierarchical silicon etched structures for controlled hydrophobicity/superhydrophobicity.

Abstract: Silicon surface hydrophobicity has been varied by using silane treatments on silicon pyramid surfaces generated by KOH anisotropic etching. Results demonstrated that by altering the surface hydrophobicity, the apparent contact angle changed in accord with the Wenzel equation for surface structures with inclined side walls. Hierarchical structures were also constructed from Si pyramids where nanostructures were added by Au-assisted electroless HF/H2O2 etching. Surface hydrophobicity and superhydrophobicity were achieved by surface modification with a variety of silanes. Stability of the Cassie state of superhydrophobicity is described with respect to the Laplace pressure as indicated by the water droplet meniscus in contact with the hierarchical structures. The contact angle hysteresis observed is also discussed with respect to water/substrate adhesion.

Nanocrystalline Zeolites and Zeolite Structures: Synthesis, Characterization, and Applications

Abstract: Nanocrystalline zeolites are porous nanomaterials with crystal sizes of less than 100 nm that possess unique external and internal surface reactivity. Nanocrystalline zeolites, such as silicalite, ZSM-5 and Y, were synthesized and extensively characterized by powder X-ray diffraction, nitrogen adsorption isotherms, dynamic light scattering, and electron microscopy. Spectroscopic characterization of the nanocrystalline zeolites by FTIR and solid-state NMR provided detailed structural information about internal and external surface sites. The nanocrystalline zeolites were also used as building blocks to form larger, hollow zeolite structures with encapsulated metal or organic species. The surface properties of nanocrystalline zeolites and hollow zeolite structures were tailored through functionalization of surface silanol groups. Applications of nanocrystalline zeolites and zeolite structures in the selective catalytic reduction of NOx and the photoreduction of Cr(VI) to Cr(III) in aqueous solution were inv...

Functionalizing Carbon Nanotubes by Plasma Modification for the Preparation of Covalent-Integrated Epoxy Composites

Abstract: A novel method for preparing a fully integrated nanotube composite material through the use of functionalized multi-walled carbon nanotubes (MWNTs) is presented in this study. The functionalization of MWNTs was performed via plasma treatment; subsequently, maleic anhydride (MA) was grafted onto the MWNTs (CNTs-MA). Nanotube-reinforced epoxy polymer composites were prepared by first mixing the CNTs-MA and a diamine curing agent, followed by a further reaction with the epoxy matrix. In this hybrid nanocomposite system, the CNTs-MA were covalently integrated into the epoxy matrix and became part of the cross-linked structure rather than just a separate component. Fourier transform infrared (FT-IR) and high resolution X-ray photoelectron (XPS) spectroscopes were used to characterize the functional groups on the surface of the MWNTs after the plasma modification. In addition, observations of scanning electronic microscopy (SEM) and transmission electron microscopy (TEM) images showed that the functionalized na...

Combination of Living Radical Polymerization and Click Chemistry for Surface Modification

Abstract: A novel reversible addition fragmentation technique chain transfer agent (RAFT CTA) was synthesized which permits the possibility of using RAFT polymerization and click chemistry together for surface modification Using this RAFT CTA, the surface of silica nanoparticles was modified with polystyrene and polyacrylamide brushes via the “grafting to” approach A click reaction was used to attach polymers onto the surface which produced relatively high grafting density Both tethered polystyrene and polyacrylamide chains were found in the brush regime The combination of ATRP and click chemistry was also explored for surface modification To our knowledge, this is first report of RAFT polymerization and click chemistry together for surface modification

Corrosion degradation and prevention by surface modification of biometallic materials

Abstract: Metals, in addition to ceramics and polymers, are important class of materials considered for replacement of non-functional parts in the body. Stainless steel 316, titanium and titanium alloys, Co-Cr, and nitinol shape memory alloys are the most frequently used metallic materials. These alloys are prone to corrosion in various extents. This review briefly discusses the important biomaterials, their properties, and the physiological environment to which these materials are exposed. Corrosion performance of currently used metallic materials has been assessed and threat to the biocompatibility from corrosion products/metal ions is discussed. The possible preventive measures to improve corrosion resistance by surface modification and to increase the bioactivity of the metallic surfaces have also been discussed. Importance of the formation of oxide layers on the metal surface, another aspect of corrosion process, has been correlated with the host response. The gap areas and future direction of research are also outlined in the paper.

Surface modification of polyester biomaterials for tissue engineering

Abstract: Surfaces play an important role in a biological system for most biological reactions occurring at surfaces and interfaces. The development of biomaterials for tissue engineering is to create perfect surfaces which can provoke specific cellular responses and direct new tissue regeneration. The improvement in biocompatibility of biomaterials for tissue engineering by directed surface modification is an important contribution to biomaterials development. Among many biomaterials used for tissue engineering, polyesters have been well documented for their excellent biodegradability, biocompatibility and nontoxicity. However, poor hydrophilicity and the lack of natural recognition sites on the surface of polyesters have greatly limited their further application in the tissue engineering field. Therefore, how to introduce functional groups or molecules to polyester surfaces, which ideally adjust cell/tissue biological functions, becomes more and more important. In this review, recent advances in polyester surface modification and their applications are reviewed. The development of new technologies or methods used to modify polyester surfaces for developing their biocompatibility is introduced. The results of polyester surface modifications by surface morphological modification, surface chemical group/charge modification, surface biomacromolecule modification and so on are reported in detail. Modified surface properties of polyesters directly related to in vitro/vivo biological performances are presented as well, such as protein adsorption, cell attachment and growth and tissue response. Lastly, the prospect of polyester surface modification is discussed, especially the current conception of biomimetic and molecular recognition.

Control of the electrode work function and active layer morphology via surface modification of indium tin oxide for high efficiency organic photovoltaics

Abstract: Indium tin oxide (ITO) substrates modified with self-assembled monolayers (SAMs) were used to control the anode work function and active layer morphology of organic solar cells based on poly(3-hexylthiophene)/[6:6]-phenyl-C61 butyric acid methyl ester heterojunctions. By using SAMs with the terminal groups –NH2, –CH3, and –CF3, the authors were able to control the hole injection barrier of the ITO closer to the highest occupied molecular orbital level of active layer and surface energy of the ITO substrate. A solar cell device with CF3 SAM treated ITO was found to exhibit high efficiency performance, about 3.15%.

Grafting Polymers on Surfaces: A New Powerful and Versatile Diazonium Salt-Based One-Step Process in Aqueous Media

Abstract: Covalent surface modification of conductive, semiconductive, and insulating substrates with thin organic polymers films induced by redox activation of aryl diazonium salts in the presence of vinyl monomers has been investigated in acidic aqueous media. This new process, called diazonium-induced anchoring process (DIAP), is an efficient technique to impart covalent adhesion of polyvinyl coatings onto raw inorganic or organic surfaces without any conductivity requirement. Typically, aryl diazonium salts are reduced with iron powder to give surface-active aryl radicals leading (i) to the formation of a grafted polyphenylene-like film on the substrate surface and (ii) to the initiation of the radical polymerization of the vinylic monomer in solution. The resulting radical-terminated macromolecular chains formed in solution are then able to react with the polyphenylene primer layer to form a very homogeneous thin organic film on the surface. The final organic thin coating is strongly grafted on materials surfa...

Reactive Nature of Dopamine as a Surface Functionalization Agent in Iron Oxide Nanoparticles

Abstract: Dopamine forms an initial structure coordinated to the surface of the iron oxide nanoparticle as a result of improved orbital overlap of the five-membered ring and a reduced steric environment of the iron complex. However, through transfer of electrons to the iron cations on the surface and rearrangement of the oxidized dopamine, a semiquinone is formed. Because of free protons in the system, oxygens on the surface are protonated, which allows for the Fe2+ to be released into the solution as a hydroxide. This released fragment of the nanoparticle will then eventually oxidize in air to a form of an iron(III) oxyhydroxide. All of the reported results demonstrate that the reactivity between Fe3+ and dopamine quickly facilitates the degradation of the nanoparticles. The energetic modeling studies substantiate our proposed decomposition mechanism and thus conclude that the use of dopamine as a robust anchor for iron oxide or iron oxide shell particles will not fulfill the need for stable ferrofluids in most bi...

One‐Step Synthesis of Highly Water‐Soluble Magnetite Colloidal Nanocrystals

Abstract: A high-temperature solution-phase hydrolysis approach has been developed for the synthesis of colloidal magnetite nanocrystals with well-controlled size and size distribution, high crystallinity, and high water solubility. The synthesis was accomplished by the hydrolysis and reduction of iron(III) cations in diethylene glycol with a rapidly injected solution of sodium hydroxide at an elevated temperature. The high reaction temperature allows for control over size and size distribution and yields highly crystalline products. The superior water solubility is achieved by using a polyelectrolyte, that is, poly(acrylic acid) as the capping agent, the carboxylate groups of which partially bind to the nanocrystal surface and partially extend into the surrounding water. The direct synthesis of water-soluble nanocrystals eliminates the need for additional surface modification steps which are usually required for treating hydrophobic nanocrystals produced in nonpolar solvents through the widely recognized pyrolysis route. The abundant carboxylate groups on the nanocrystal surface allow further modifications, such as bioconjugation, as demonstrated by linking cysteamine to the particle surface. The monodisperse, highly water-soluble, superparamagnetic, and biocompatible magnetite nanocrystals should find immediate important biomedical applications.

Design of a superhydrophobic surface using woven structures.

Abstract: The relationship between surface tension and roughness is reviewed. The Cassie-Baxter model is restated in its original form, which better describes the most general cases of surface roughness. Using mechanical and chemical surface modification of nylon 6,6 woven fabric, an artificial superhydrophobic surface was prepared. A plain woven fabric mimicking the Lotus leaf was created by further grafting 1H,1H-perfluorooctylamine or octadecylamine to poly(acrylic acid) chains which had previously been grafted onto a nylon 6,6 woven fabric surface. Water contact angles as high as 168 degrees were achieved. Good agreement between the predictions based on the original Cassie-Baxter model and experiments was obtained. The version of the Cassie-Baxter model in current use could not be applied to this problem since the surface area fractions in this form is valid only when the liquid is in contact with a flat, porous surface. The angle at which a water droplet rolls off the surface has also been used to define a superhydrophobic surface. It is shown that the roll-off angle is highly dependent on droplet size. The roll-off angles of these superhydrophobic surfaces were less than 5 degrees when a 0.5 mL water droplet was applied.