Intense Raman D Band without Disorder in Flattened Carbon Nanotubes.

Above a critical diameter, single- or few-walled carbon nanotubes spontaneously collapse as flattened carbon nanotubes. Raman spectra of isolated flattened and cylindrical carbon nanotubes have been recorded. The collapse provokes an intense and narrow D band, despite the absence of any lattice disorder. The curvature change near the edge cavities activates a D band, despite framework continuity. Theoretical calculations based on Placzek approximation fully corroborate this experimental finding. Usually used as a tool to quantify defect density in graphenic structures, the D band cannot be used as such in the presence of a graphene fold. This conclusion should serve as a basis to revisit materials comprising structural distortion where poor carbon organization was concluded on a Raman basis. Our finding also emphasizes the different visions of a defect between chemists and physicists, a possible source of confusion for researchers working in nanotechnologies.

Weak polyelectrolyte brushes: re-entrant swelling and self-organization.

We have studied the combined influence of pH and ionic strength on the properties of brushes of a weak polyion, poly(acrylic acid), in conditions of grafting density close to the mushroom-brush crossover. By combining atomic force microscopy AFM and quartz crystal microbalance, we show that at low ionic strengths the conformational change of grafted polyions is non-monotonic with increasing pH due to the counterintuitive variation of the ionization degree. Thus, reentrant swelling of the polymer chains is observed with increasing pH. This effect is more important at low polymer grafting densities, when it is accompanied by in-plane heterogeneous distribution at intermediate pH values. In addition, we observed self-assembly on the polymer brush (formation of holes and islands) at pH values below pKa, due to the short-range attractive interaction between uncharged grafted chains. The sensitivity of the ionization of grafted chains to the physicochemical environment was also studied by measuring the interaction force between a silica tip and polymer brushes by atomic force microscopy. The dependence of the ionization of polyions on the presence of the tip points toward important charge regulation effects, in particular at pH values corresponding to partial ionization of the polyion.

Variability of slot size in orthodontic brackets.

Objective: The accuracy of the information incorporated into brackets is a determining factor for the efficacy of torque applied to teeth. The aim of this study was to compare the dimensions of a bracket's slots with the nominal values announced by the manufacturer. Materials and methods: A total of 730 maxillary right central brackets manufactured by seven companies (Dentsply Gac, American Orthodontics, Rocky Mountain Orthodontics, GC Orthodontics, 3M Unitek, and Dentaurum) were studied. The sample included 0.018 × 0.025 and 0.022 × 0.028 in., metal and ceramic, conventional and self-ligating brackets. Images were obtained with an Olympus BX51 optical microscope. Slot dimensions were measured at the base and at the face on both mesial and distal sides using ImageJ software. Data were analyzed using Wilcoxon, sign tests, two- and three-way ANOVA, and Tukey's tests. Intraclass correlation coefficient was employed to assess the intraobserver and interobserver variability. The threshold for statistical significance was p ≤ .05. Results: Statistical analysis showed that the slot dimensions of 90% to 97% of studied brackets were significantly different from nominal values. In general, slot size was oversized, with a face size larger than the base size. Comparison between mesial and distal sides showed that up to 45% of the brackets were significantly asymmetrical. The manufacturer had a significant effect for base and face widths (p = .0001) and for length (p = .003). Conclusion: This study shows that a large proportion of measured brackets displays dimensional inaccuracies when compared with stated values. Clinically, the slot oversize and the divergence of slot walls cause an increase of wire-slot play, inducing a loss of torque control. Practitioners cannot fully trust the precision of used appliances and should be aware that adjustments could be needed in the finishing stages of the treatment.

Electrowetting of Weak Polyelectrolyte-Coated Surfaces.

Polymer coatings are commonly used to modify interfacial properties like wettability, lubrication, or biocompatibility. These properties are determined by the conformation of polymer molecules at the interface. Polyelectrolytes are convenient elementary bricks to build smart materials, given that polyion chain conformation is very sensitive to different environmental variables. Here we discuss the effect of an applied electric field on the properties of surfaces coated with poly(acrylic acid) brushes. By combining atomic force microscopy, quartz crystal microbalance, and contact angle experiments, we show that it is possible to precisely tune polyion chain conformation, surface adhesion, and surface wettability using very low applied voltages if the polymer grafting density and environmental conditions (pH and ionic strength) are properly formulated. Our results indicate that the effective ionization degree of the grafted weak polyacid can be finely controlled with the externally applied field, with important consequences for the macroscopic surface properties.

Electrodeposition of polymer nanodots with controlled density and their reversible functionalization by polyhistidine-tag proteins.

We present a simple and rapid procedure for producing polymer-coated substrates that can be easily functionalized by ion-chelating proteins. The procedure consists of depositing 18 nm metal-chelating cyclam-modified polymer nanoparticles (cyclam-nps) onto a conductive substrate (an Indium Tin Oxide (ITO) electrode) from an aqueous dispersion of Cu(2+)-loaded cyclam-nps while being subjected to a direct current (DC) field. The density of deposited nps as measured by AFM is shown to be in direct correlation to the concentration of nps in the dispersion with deposition of the particles taking less than 5 s. Because of the functionalization of the nps with cyclam groups, they can be used as anchoring sites for 6-Histidine (6-His) tagged proteins through complexation with divalent metal ions. In this work 6-His Green Fluorescent Protein (6-His GFP) is used as a model protein. The characterization by fluorescence microscopy clearly shows that the protein affinity was ion dependent and that the 6-His GFP density can be controlled by np density, which is itself easily tunable. AFM observations confirmed the immobilization of 6-His GFP onto cyclam-nps and its subsequent removal by treatment with ethylenediaminetetraacetic acid (EDTA).

Nanoscaled tin dioxide films processed from organotin-based hybrid materials: an organometallic route toward metal oxide gas sensors.

Nanocrystalline tin dioxide (SnO(2)) ultra-thin films were obtained employing a straightforward solution-based route that involves the calcination of bridged polystannoxane films processed by the sol-gel process from bis(triprop-1-ynylstannyl)alkylene and -arylene precursors. These films have been thoroughly characterized by FTIR, contact angle measurements, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), atomic force (AFM) and scanning electron (SEM) microscopies. Annealing at a high temperature gave 30-35 nm thick cassiterite SnO(2) films with a mean crystallite size ranging from 4 to 7 nm depending on the nature of the organic linker in the distannylated compound used as a precursor. In the presence of H(2) and CO gases, these layers led to highly sensitive, reversible and reproducible responses. The sensing properties were discussed in regard to the crystallinity and porosity of the sensing body that can be tuned by the nature of the precursor employed. Organometallic chemistry combined with the sol-gel process therefore offers new possibilities toward metal oxide nanostructures for the reproducible and sensitive detection of combustible and toxic gases.

Low-temperature H2 sensing in self-assembled organotin thin films.

Self-assembled nanoporous tin-based hybrid thin films prepared by the sol-gel method from organically-bridged ditin hexaalkynides detect hydrogen gas from 50 to 200 °C at the 200-10,000 ppm level. This finding opens a fully new class of gas-sensing materials as well as a new opportunity to integrate organic functionality in gas sensing metal oxides.

Multifunctional gels from polymeric spin-crossover metallo-gelators.

The gelation abilities toward organic solvents of a series of triazole-based coordination polymers of formula [M(C(n)trz)(3)]A(2) (M = Fe(II) or Zn(II); C(n)trz = 4-n-alkyl-1,2,4-triazole with n = 13, 16, 18; A = monovalent anions, abbreviated as MC(n)A) have been studied to form thermally responsive multifunctional metallogels, in particular for the iron polymers that present the spin-crossover phenomenon. Indeed thermo-reversible physical gels exhibiting thermally reversible magnetic and optical crossovers are formed in decane and toluene. The FeC(18)ptol/decane and FeC(18)ptol/toluene phase diagrams are described (ptol = p-toluene sulfonate anion), together with the rheological properties of the gels determined as a function of the solvent, the gelator concentration as well as temperature. Microscopic observations of the gel structure are correlated to the composition and rheological properties of the gels. Magnetic and thermal studies show that both the gel-liquid and spin-crossover phenomena can be adjusted through the composition of the gel mixture.

Dispersion and film-forming properties of poly(acrylic acid)-stabilized carbon nanotubes.

We present a detailed study of the influence of pH on the dispersion and film-forming properties of poly(acrylic acid)-stabilized carbon nanotubes. Poly(acrylic acid) (PAA) is a weak polyelectrolyte, with a pH-responsive behavior in aqueous solution. We obtain quantitative UV-visible measurements to show that the amount of polyelectrolyte in optimal pH conditions is weak, showing a good efficiency of the polymer as a carbon nanotube dispersing agent. The best dispersion conditions are achieved at pH 5, a value close to the pK(a) of PAA. Apart from this tenuous pH value, the PAA is not efficient at stabilizing nanotubes and atomic force microscopy allows us to explain the delicate balance between the PAA adsorption and the suspension stability. This study finally permits optimal conditions for making homogeneous and conductive composite films to be determined.

Multiresponsive hybrid microgels and hollow capsules with a layered structure.

Various stimuli-responsive composite particles with a high control of their internal structure and their corresponding hollow capsules are synthesized and characterized by photon correlation spectroscopy, TEM, and AFM. Core-shell particles with a silica core and a thermoresponsive shell are obtained by polymerization of N-isopropylacrylamide (NIPAM) in the presence of silica seeds grafted with a high density of gamma-methacryloxypropyltrimethoxysilane (MPS). The influence of the synthesis conditions is studied. The shell thickness increases when the monomer concentration increases in a limited range where uniform composite particles with a single core are obtained. At constant monomer concentration, the shell thickness does not depend on the size of the silica seeds, but the presence of free unbound microgels is observed when the silica surface area decreases. A range of particle diameters and shell thicknesses is thus obtained, which can lead to the corresponding hollow capsules by exposure to hydrofluoric acid solution. The volume phase transition temperature of these materials can be easily tuned by replacing the NIPAM monomer by another N-alkylacrylamide derivative. However, the incorporation of comonomers such as acrylic acid (AA) and a phenylboronic acid (PBA) derivative inhibits the formation of core-shell structures. In order to get pH or glucose responsiveness, these functional groups can be incorporated in the outer shell of a core-double shell structure, with pNIPAM as intermediate shell. pH-responsive and glucose-responsive composite particles are obtained by this method with a high control of their internal structure.

Solutions of negatively charged graphene sheets and ribbons.

Negatively charged graphene layers from a graphite intercalation compound spontaneously dissolve in N-methylpyrrolidone, without the need for any sonication, yielding stable, air-sensitive, solutions of laterally extended atom-thick graphene sheets and ribbons with dimensions over tens of micrometers. These can be deposited on a variety of substrates. Height measurements showing single-atom thickness were performed by STM, AFM, multiple beam interferometry, and optical imaging on Sarfus wafers, demonstrating deposits of graphene flakes and ribbons. AFM height measurements on mica give the actual height of graphene (ca. 0.4 nm).

Thermally induced gelling of oil-in-water emulsions comprising partially crystallized droplets: the impact of interfacial crystals.

We produced triglyceride-in-water emulsions comprising partially crystallized droplets, stabilized by a mixture of protein and low molecular weight surfactant. The emulsions were emulsified in the melted state of the oil phase and stored at low temperature (4 degrees C) right after fabrication to induce oil crystallization. The systems were then warmed to room temperature for a short period of time and cooled again to 4 degrees C. Owing to this treatment referred to as temperature cycling or "tempering", the initially fluid emulsions turned into hard gels. We followed the bulk rheological properties of the materials during and after tempering. The storage modulus, G', exhibited a dramatic increase when tempering was applied. We showed that the systems evolved following two distinct regimes that depend on the average droplet size and on the surfactant-to-protein molar ratio. Gelling may involve partial coalescence of the droplets, i.e., film rupturing with no further shape relaxation because of the solid nature of the droplets. Alternatively, gelling may occur without film rupturing, and is reminiscent of a jamming transition induced by surface roughness. We discussed the origin of these two mechanisms in terms of the properties (size and protuberance) of the interfacial oil crystals.

Three-dimensional opal-like silica foams.

The synthesis of novel meso-/macroporous SiO2 monoliths by combining a nano-building-blocks-based approach with the confined geometry of a tailored air-liquid foam structure is described. The resulting macrostructure in which ordered close-packed colloidal silica nanoparticles constitute the monolith's scaffolds very closely resembles the tailored periodic air-liquid foam template. The void spaces between adjacent particles create textural mesoporosity; therefore, the as-prepared silica networks are characterized by hierarchical porosity at the macroscopic and mesoscopic length scales. The fine-tuning of both the liquid foam's fraction and the bubble size allows a rational design over the macroscopic cell morphologies (shape, Plateau border's length, and width). Striking results of this approach are the weak shrinkage of the as-synthesized opal-like scaffolds during the thermally induced sintering process and, in contrast with previous studies, the formation of closed-cell structures. Particle organization and the foam film surface roughness are investigated by atomic force microscopy (AFM), showing the influence of the liquid flow, within the foams' Plateau borders and films, on the final assemblies.