Specific and non-specific interactions of procaine with activated carbon surfaces

The adsorption of procaine on eight activated carbon surfaces from simulated intestinal fluid (SIF) was evaluated using a rotating bottle method and isoperibol calorimetry. The adsorption data were fit using the modified Langmuir-like equation to calculate the non-specific and specific adsorption capacities. The surface atomic compositions were determined by X-ray photoelectron spectroscopy (XPS). A linear relationship was found between the relative non-specific adsorption capacity and the unoxidized hydrocarbon content of the activated carbon surfaces, which indicated that the non-specific adsorption site for procaine is the bare carbon surface. The apparent area occupied per procaine molecule, calculated from the specific capacity, was linearly correlated to the sum of the relative percentages of the C-O and O-C=O functional states on the surfaces. This suggested that the primary adsorption sites for procaine on the activated carbon surfaces were the oxygen-containing functional states of C-O and O-C=O, where procaine was adsorbed via hydrogen bonding. The differential heats of displacement for procaine on the four activated carbon surfaces are approximately equal to each other, which indicated that the interactions between procaine and the functional states on all surfaces are energetically equivalent.     

Superhydrophobicity on two-tier rough surfaces fabricated by controlled growth of aligned carbon nanotube arrays coated with fluorocarbon

Considerable effort has been expended on theoretical studies of superhydrophobic surfaces with two-tier (micro and nano) roughness, but experimental studies are few due to the difficulties in fabricating such surfaces in a controllable way. The objective of this work is to experimentally study the wetting and hydrophobicity of water droplets on two-tier rough surfaces for comparison with theoretical analyses. To compare wetting on micropatterned silicon surfaces with wetting on nanoscale roughness surfaces, two model systems are fabricated: carbon nanotube arrays on silicon wafers and carbon nanotube arrays on carbon nanotube films. All surfaces are coated with 20 nm thick fluorocarbon films to obtain low surface energies. The results show that the microstructural characteristics must be optimized to achieve stable superhydrophobicity on microscale rough surfaces. However, the presence of nanoscale roughness allows a much broader range of surface design criteria, decreases the contact angle hysteresis to less than 1 degrees , and establishes stable and robust superhydrophobicity, although nanoscale roughness could not increase the apparent contact angle significantly if the microscale roughness dominates.     

Phenobarbital interactions with derivatized activated carbon surfaces

The interactions between phenobarbital and activated carbon surfaces were studied in detail in this work. This was accomplished by utilizing different reagents to manipulate the surface polar functional group compositions of different activated carbons, and determining how those modifications changed phenobarbital adsorption. Oxidation of an activated carbon surface caused a systematic decrease in the basal carbon surface, resulting in a concurrent systematic decrease in the non-specific adsorption of phenobarbital. Even more interesting, it was shown for the first time that chemical reduction of some of the carbonyl-containing functional groups on the activated carbon surface caused a significant increase in the specific adsorption of phenobarbital without any significant effect on the non-specific adsorption. These results support the notion that the OH groups on activated carbon surfaces are the specific adsorption sites for phenobarbital from aqueous solutions, and that the basal carbon surface is the region where non-specific adsorption takes place.     

Preparation and characterization of helical carbon/silica nanofibers with lamellar mesopores on the surfaces

Helical 1,2-ethylene-silica nanofibers with lamellar mesopores on the surfaces and twisted rod-like mesopores inside were prepared according to literature procedures. After carbonization, helical carbon/ silica nanofibers with lamellar mesopores on the surfaces and twisted rod-like micropores inside were obtained. The morphologies and pore architectures of the carbon]silica nanofibers were characterized using transmission electron microscopy, field-emission scanning electron microscopy, powder X-ray diffraction and N2 sorptions. Although the mesopores inside shrank into micropores, the helical nanostructure remained. Moreover, several carbon/silica nanofibers with lamellar mesopores on the surfaces and concentric circular micropores inside were also obtained. After being calcined in air, helical silica nanofibers with lamellar mesopores on the surfaces and twisted rod-like micropores inside were produced as well.     

Interaction of alcohols and ethers with a-CF(x) films

The surfaces of the magnetic data storage hard disks used in computers are coated with a thin film of amorphous carbon and a layer of perfluoropolyalkyl ether (PFPE) lubricant. Both protect the surface of the magnetic layer from contact with the read-write head flying over the disk surface. Although the most commonly used carbon films are amorphous hydrogenated carbon, a-CH(x), it has been suggested that the thermal properties of amorphous fluorinated carbon films, a-CF(x), might be superior. This work has probed the interaction of small fluorinated ethers and alcohols with the surfaces of a-CF(x) films to understand the effects of carbon film fluorination on the interaction of the lubricant with its surface. Temperature-programmed desorption was used to measure the desorption energies of small fluorocarbons from the a-CF(x) surface and to compare their desorption energies with those from the surfaces of a-CH(x) films. These measurements reveal that, similarly to a-CH(x) films, a-CF(x) films expose a heterogeneous surface on which fluorocarbons adsorb at sites with a range of binding energies. The fluorocarbon ethers all have lower heats of adsorption than their hydrocarbon counterparts, suggesting that the ethers adsorb by donation of electron density from the oxygen lone-pair electrons to sites on the surface. Fluorinated alcohols have roughly the same heats of adsorption as their hydrocarbon counterparts. There is little significant difference between the interactions of fluorinated ethers (or alcohols) with the surfaces of either a-CF(x) or a-CH(x) films.     

Stable dispersions of silver nanoparticles in carbon dioxide with fluorine-free ligands

Iso-stearic acid, a short, stubby compound with branched, methylated tails has been shown to have high solubility in carbon dioxide. Tail solvation by carbon dioxide makes iso-stearic acid a good choice for use as a ligand to sterically stabilize metallic nanoparticles. Iso-stearic acid coated silver nanoparticles have been stably dispersed in carbon dioxide with hexane cosolvent. Neat carbon dioxide has successfully dispersed iso-stearic acid coated silver nanoparticles that had been deposited on either quartz or polystyrene surfaces. These results are the first reports of sterically stabilized nanoparticles in carbon dioxide without the use of any fluorinated compounds.     

Superhydrophobic bionic surfaces with hierarchical microsphere/SWCNT composite arrays

Superhydrophobic bionic surfaces with hierarchical micro/nano structures were synthesized by decorating single-walled or multiwalled carbon nanotubes (CNTs) on monolayer polystyrene colloidal crystals using a wet chemical self-assembly technique and subsequent surface treatment with a low surface-energy material of fluoroalkylsilane. The bionic surfaces are based on the regularly ordered colloidal crystals, and thus the surfaces have a uniform superhydrophobic property on the whole surface. Moreover, the wettability of the bionic surface can be well controlled by changing the distribution density of CNTs or the size of polystyrene microspheres. The morphologies of the synthesized bionic surfaces bear much resemblance to natural lotus leaves, and the wettability exhibited remarkable superhydrophobicity with a water contact angle of about 165 degrees and a sliding angle of 5 degrees.     

Reactivity and Coaggregation of p-Nitrophenyl Esters with Polymer Micelles at Solid Surfaces

The polymer micelle, poly[(N-(n-dodecyl)-4-vinylpyridiniumco-N-ethyl-4-vinylpyridinium) bromide], PDE, containing 30% dodecyl groups has been found to promote the adhesion of lipophiles to various surfaces including quartz, polystyrene, and poly(methyl methacrylate) cuvette surfaces from aqueous solutions. The adsorption of PDE/ester coaggregates to the surfaces was studied by hydrolysis of p-nitrophenyl esters in aqueous PDE(30) solutions. The extent of reaction of p-nitrophenyl myristate, an ester with a linear acyl carbon chain length of 14, can be viewed as a probe to study the adhesion of the PDE/ester coaggregates to the cuvette surfaces. The difference between initial concentration of ester and concentration of hydrolysis product, p-nitrophenoxide ion, gives the concentration of unreacted ester in the aggregates or film adhering to the solid surface. Up to 40% of p-nitrophenyl myristate was found unreacted on the surface of quartz cuvettes after apparent completion of the reaction. No adhesion of the related caproate ester with a linear acyl carbon chain length of 6 was detected. Copyright 2000 Academic Press.     

Carbon microspheres with supported silver nanoparticles prepared from pollen grains

In this paper, we present a new method to fabricate carbon microspheres with supported silver nanoparticles on the surfaces. In this method, pollen grains were first treated with AgNO(3) aqueous solution, then preoxidized in air at 300 degrees C and carbonized in nitrogen at 600 degrees C, resulting in the silver/carbon nanocomposites. The silver/carbon nanocomposites were characterized by means of SEM, TEM, TG, and XRD. The size and distribution of the silver nanoparticles on the carbon microsphere surface could be controlled by tuning the AgNO(3) treatment conditions.     

Carbon nanofibers decorated with poly(furfuryl alcohol)-derived carbon nanoparticles and tetraethylorthosilicate-derived silica nanoparticles

The present paper introduces a novel method to functionalize nanofiber surfaces with carbon or silica nanoparticles by dip coating. This novel approach holds promise of significant benefits because dip coating of electrospun and carbonized nanofiber mats in poly(furfuryl alcohol) (abbreviated as PFA) is used to increase surface roughness by means of PFA-derived carbon nanoparticles produced at the fiber surface. Also, dip coating in tetraethylorthosilicate (abbreviated as TEOS) is shown to be an effective method for decorating carbon nanofibers with TEOS-derived silica nanoparticles at their surface. Furthermore, dip coating is an inexpensive technique which is easier to implement than the existing methods of nanofiber decoration with silica nanoparticles and results in a higher loading capacity. Carbon nanofiber mats with PFA- or TEOS-decorated surfaces hold promise of becoming the effective electrodes in fuel cells, Li-ion batteries and storage devices.     

Laser desorption/ablation combined with nuclear analytical methods for materials characterization

Ubiquitous elements like carbon and oxygen always contaminate surfaces and, therefore, are the soucre of important analytical errors at trace level. Even in the case of radioactivation (with charged particles), where the sample can be etched after irradiation, analytical problems exist. In this work, we show that laser desorption/ablation can efficiently clean surfacaes, in the case of GaAs samples, resulting in better analytical conditions. Under ultra high vacuum, these surfaces remain clean long enough, so that the analysis of carbon and oxygen can be carried out using various nuclear methods, according to the needs of the analyst.     

Preparation,Characterization and Application of Modified Surfaces with 3,5-Bis(3,5-dinitrobenzoyl-amino) benzoic acid

Summary: The spontaneous adsorption of the dendron 3,5-Bis (3,5-dinitrobenzoylamino) benzoic acid (D-NO₂) onto gold and carbon electrodes produced conductive surfaces with electroactive chemical functions. A comparative electrochemical behavior of both electrodes after dendron immobilization led us to conclude that the self-assembly of D-NO₂ on carbon is faster and stronger. Considering this advantage, the surface of magnetic maghemite nanoparticles (MNPs) was modified using D-NO₂. Firstly, MNPs were modified with APS as silane coupling agent and afterwards, D-NO₂ was covalently attached to the surface, achieving nitro-functionalized MNPs. Subsequently, the immobilization of these modified MNPs onto glassy carbon surfaces was explored to generate a novel platform promising for biosensors development.     

Effects of surface heterogeneity of carbon nanotubes in adsorption of colloid nanoparticles studied by means of computer simulations

This work deals with a construction of an implicit solvent model which can be used in molecular dynamics simulations of systems comprising colloid nanoparticles and carbon nanotubes. Such systems, due to finite sizes of both components, cannot be accurately approximated by a smaller slab geometry and thus represent a particularly difficult case in terms of computer simulations. Adsorption of large colloid nanoparticles on the surfaces of carbon nanotubes were studied and we determined the adsorption energy profiles of the nanoparticles on the carbon nanotubes surfaces. We also determined the adsorption isotherms which help to understand a preferred location of the nanoparticles on the nanotubes surfaces.     

Noncovalent engineering of carbon nanotube surfaces by rigid,functional conjugated polymers

We report a new nonwrapping approach to noncovalent engineering of carbon nanotube surfaces by short, rigid functional conjugated polymers, poly(aryleneethynylene)s. Our technique not only enables the dissolution of various types of carbon nanotubes in organic solvents, which represents the first example of solubilization of carbon nanotubes via pi-stacking without polymer wrapping, but could also introduce numerous neutral and ionic functional groups onto the carbon nanotube surfaces.     

Functionalization of glassy carbon with diazonium salts in ionic liquids

The paper reports on the chemical functionalization of glassy carbon electrodes with 4-bromobenzene (4-BBDT) and 4-(4'-nitrophenylazo)benzene diazonium tetrafluoroborate (4-NAB) salts in ionic liquids. The reaction was carried out at room temperature in air without any external electrical bias in either hydrophobic (1-butyl-3-methylimidazolium hexafluorophosphate) or hydrophilic (1-butyl-3-methylimidazolium methyl sulfate) ionic liquids. The resulting surfaces were characterized using X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and electrochemical measurements. Electrochemical reduction of the terminal nitro groups allowed the determination of surface coverage and formation of an amine-terminated carbon surfaces. The results were compared to glassy carbon chemically modified in an aqueous solution in the presence of 1% sodium dodecyl sulfate (SDS) with the same diazonium salt. Furthermore, Raman spectroscopy coupled with electrochemical measurements allowed to distinguish between the reduction of -NO2 to -NH2 group and the -N=N- to -NH-NH- bond.     

Interfacing carbon nanotubes with living cells

We developed a polymer coating for carbon nanotubes (CNTs) that mimics the mucin glycoprotein coating of mammalian cells. CNTs coated with these mucin mimic polymers have two novel properties: they can bind to carbohydrate receptors, providing a means for biomimetic interactions with cell surfaces, and, importantly, they are rendered nontoxic to cells.     

Interaction Forces Between Graphitic Carbon Black Surfaces Coated with Polymers Using Atomic Force Microscopy

Carbon black dispersions are stabilized using polymeric dispersants. The stabilization is provided by adsorbed polymer layers around surfaces through interaction forces. Therefore, it is valuable to measure the interaction forces between bare and polymer-coated surfaces using atomic force microscopy to predict the behavior of dispersions. Three polymeric dispersants (Hypermer LP1, Hypermer B246, and OLOA 11000) are used in the present work to disperse the graphitic carbon black particles in an organic solvent, decaline. Hypermer B246 and OLOA 11000 produced repulsive interactions and, hence, are effective stabilizers for carbon black surfaces. Hypermer LP1 produced attractive interactions, making it an ineffective stabilizer for carbon black. Attractive interactions were also observed in blank dispersions. The experimentally determined interaction curves are compared with theoretical curves, the Derjaguin approximation. The repulsive steric interactions are also analyzed quantitatively based on the Alexander and de Gennes scaling law.     

Preparation and Characterization of Carbon Fibers from Lyocell Precursors Grafted with Polyacrylamide via Electron-Beam Irradiation

Carbon fibers, which act as reinforcements in many applications, are often obtained from polyacrylonitrile (PAN). However, their production is expensive and results in waste problems. Therefore, we focused on producing carbon fibers from lyocell, a cellulose-based material, and analyzed the effects of the process parameters on their mechanical properties and carbon yields. Lyocell was initially grafted with polyacrylamide (PAM) via electron-beam irradiation (EBI) and was subsequently stabilized and carbonized. Thermal analysis showed that PAM grafting increased the carbon yields to 20% at 1000 °C when compared to that of raw lyocell, which degraded completely at about 600 °C. Stabilization further increased this yield to 55%. The morphology of the produced carbon fibers was highly dependent on PAM concentration, with fibers obtained at concentrations ≤0.5 wt.% exhibiting clear, rigid, and round cross-sections with smooth surfaces, whereas fibers obtained from 2 and 4 wt.% showed peeling surfaces and attachment between individual fibers due to high viscosity of PAM. These features affected the mechanical properties of the fibers. In this study, carbon fibers of the highest tensile strength (1.39 GPa) were produced with 0.5 wt.% PAM, thereby establishing the feasibility of using EBI-induced PAM grafting on lyocell fabrics to produce high-performance carbon fibers with good yields.     

Carbon papers with conductive polymer coatings for use in solid-state supercapacitors

Conductive polymer-coated carbon papers have been fabricated through polymerisation of pyrrole-based monomers oxidised with various heteropolyacids. Smooth surfaces are obtained when multiple coatings are applied to the carbon surface and give good contact with the Nafion^® electrolyte. Cyclic voltammetry was used to study the electrodes and a.c. impedance and charge / discharge cycling was used to study membrane electrode assemblies (MEA). MEAs were fabricated using a hot-press technique.     

The crosslinking of epoxy resins at interfaces. V. Amine-cured resins at carbon and graphite surfaces

The effects of carbon blacks, chopped carbon fibers, and crushed carbon fibers on the crosslinking chemistry of a diglycidyl epoxy resin/m-phenylenediamine system were examined by infrared (IR) spectroscopy and differential scanning calorimetry (DSC). The carbon and graphite surfaces were given oxidizing and reducing treatment to simulate the surface treatment of carbon fibers used in the manufacture of composites. The oxidized carbon surfaces initially accelerated epoxy–amine reactions but inhibited the later stages of the reaction such that the final extent of cure was reduced. The oxidized carbons also preferentially adsorbed the amine curing agent, resulting in a stoichiometric imbalance at the interface.