Synthesis and characterization of oxidized cellulose

Samples of oxidized cellulose (OC) with various carboxyl contents and degrees of crystallinity were obtained by the oxidation of native and mercerized cellulose with a solution of nitrogen(IV) oxide in CCl₄. A detailed characterization of these OC samples was performed. The effect of oxidation conditions (concentration of N₂O₄ in the solution and oxidation time) and starting cellulose material on OC characteristics (carboxyl, carbonyl and nitrogen content, degree of crystallinity and polymerization, surface area and swelling, and acidic properties) was investigated. Reactivity in the oxidation process was higher in mercerized cellulose than in native cellulose. The action of dilute solutions (10–15%) of N₂O₄ did not affect the degree of crystallinity of cellulose samples. Under these conditions, the oxidation took place mainly in amorphous regions and on the surface of crystallites. Oxidation in a concentrated (40%) N₂O₄ solution led to the destruction of crystallites, which increased the surface area and swelling of cellulose in water. The surface area and the swelling of OC samples increased with a decrease in the index of crystallinity. The acidic properties of OC were shown to increase with an increase of swelling in water. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4785–4791, 2004     

Hollow latex particles as submicrometer reactors for polymerization in confined geometries

A method was developed for free‐radical polymerization in the confines of a hollow latex particle. Hollow particles were prepared via the dynamic swelling method from polystyrene seed and divinylbenzene and had hollows of 500–1000 nm. So that these hollow poly(divinylbenzene) particles could function as submicrometer reactors, the particles were filled with a monomer (N‐isopropylacrylamide) via the dispersion of the dried particles in the molten monomer. The monomer that was not contained in the hollows was removed by washing and gentle abrasion. Free‐radical polymerization was then initiated by γ radiolysis in the solid state. Transmission electron microscopy showed that poly(N‐isopropylacrylamide) formed in the hollow interior of the particles, which functioned as submicrometer reactors. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5706–5713, 2004     

Polyelectrolyte complexes. VI. Polycation structure,polyanion molar mass,and polyion concentration effects on complex nanoparticles based on poly(sodium 2‐acrylamido‐2‐methylpropanesulfonate)

The formation and characterization of some interpolyelectrolyte complex (IPEC) nanoparticles based on poly(sodium 2‐acrylamido‐2‐methylpropanesulfonate) (NaPAMPS), as a function of the polycation structure, polyanion molar mass, and polyion concentration, were followed in this work. Poly(diallyldimethylammonium chloride) and two polycations (PCs) containing (N,N‐dimethyl‐2‐hydroxypropyleneammonium chloride) units in the backbone (PCA₅ and PCA₅D₁) were used as starting polyions. The complex stoichiometry, (n^?/n⁺)_iso, was pointed out by optical density at 500 nm (OD₅₀₀), polyelectrolyte titration, and dynamic light scattering. IPEC nanoparticle sizes were influenced by the polycation structure and polyanion molar mass only before the complex stoichiometry, which was higher for the more hydrophilic polycations (PCA₅ and PCA₅D₁) and for a higher NaPAMPS molar mass, and were almost independent of these factors after that, at a flow rate of the added polyion of about 0.28 mL × (mL PC)^?1 × h^?1. The IPEC nanoparticle sizes remained almost constant for more than 2 weeks, both before and after the complex stoichiometry, at low concentrations of polyions. NIPECs as stable colloidal dispersions with positive charges in excess were prepared at a ratio between charges (n^?/n⁺) of 0.7, and their storage colloidal stability, as a function of the polycation structure and polyion concentration (from 0.8 to ca. 7.8 mmol/L), was demonstrated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2495–2505, 2004     

Block copolymer nanoparticles of controlled sizes via ring‐opening metathesis polymerization

This article describes the formation and characterization of self‐assembled nanoparticles of controlled sizes based on amphiphilic block copolymers synthesized by ring‐opening metathesis polymerization. We synthesized a novel hydrophobic derivative of norbornene; this monomer could be polymerized using Grubbs' catalyst [Cl₂Ru(CHPh)(PCy₃)₂] forming polymers of controlled molecular weight. We synthesized amphiphilic block copolymers of controlled composition and showed that they assemble into nanoparticles of controlled size. The nanoparticles were characterized using dynamic light scattering and transmission electron microscopy. Tuning the composition of the block copolymer enables the tuning of the diameters of the nanoparticles in the 30‐ to 80‐nm range. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3352–3359, 2004     

Nano-electrochemical detection of hydrogen or protons using palladium nanoparticles: distinguishing surface and bulk hydrogen.

The benefits of using nanoparticle-modified electrodes are exemplified through the electrochemical detection of protons and/or hydrogen. It is shown that a palladium-nanoparticle-modified boron-doped diamond allows voltammetric information relating to the relative roles played by the surface and the bulk metal to be obtained for the proton-hydrogen system at palladium surfaces which is not accessible using palladium macroelectrodes or microelectrodes.     

Microwave synthesis of magnetic Fe3O4 nanoparticles used as a precursor of nanocomposites and ferrofluids

Methods to synthesize magnetic Fe₃O₄ nanoparticles and to modify the surface of particles are presented in the present investigation. Fe₃O₄ magnetic nanoparticles were prepared by the co-precipitation of Fe³⁺ and Fe²⁺, NH₃·H₂O was used as the precipitating agent to adjust the pH value, and the aging of Fe₃O₄ magnetic nanoparticles was accelerated by microwave (MW) irradiation. The obtained Fe₃O₄ magnetic nanoparticles were characterized by Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), X-ray powder diffraction (XRD) and vibrating sample magnetometer (VSM). The average size of Fe₃O₄ crystallites was found to be around 8–9 nm. Thereafter, the surface of Fe₃O₄ magnetic nanoparticles was modified by stearic acid. The resultant sample was characterized by FT-IR, scanning electron microscopy (SEM), XRD, lipophilic degree (LD) and sedimentation test. The FT-IR results indicated that a covalent bond was formed by chemical reaction between the hydroxyl groups on the surface of Fe₃O₄ nanoparticles and carboxyl groups of stearic acid, which changed the polarity of Fe₃O₄ nanoparticles. The dispersion of Fe₃O₄ in organic solvent was greatly improved. Effects of reaction time, reaction temperature and concentration of stearic acid on particle surface modification were investigated. In addition, Fe₃O₄/polystyrene (PS) nanocomposite was synthesized by adding surface modified Fe₃O₄ magnetic nanoparticles into styrene monomer, followed by the radical polymerization. The obtained nanocomposite was tested by thermogravimetry (TG), differential scanning calorimetry (DSC) and XRD. Results revealed that the thermal stability of PS was not significantly changed after adding Fe₃O₄ nanoparticles. The Fe₃O₄ magnetic fluid was characterized using UV–vis spectrophotometer, Gouy magnetic balance and laser particle-size analyzer. The testing results showed that the magnetic fluid had excellent stability, and had susceptibility of 4.46×10⁻⁸ and saturated magnetization of 6.56 emu/g. In addition, the mean size d (0.99) of magnetic Fe₃O₄ nanoparticles in the fluid was 36.19 nm.     

Thermal decomposition of a generation 4.5 PAMAM dendrimer platinum drug conjugate

A nanoscale multivalent platinum drug based on a poly(amidoamine) [PAMAM] dendrimer (generation 4.5, carboxylate surface) has been synthesized and fully characterized using a variety of spectroscopic, chromatographic and thermal methods. Treatment of the dendrimer with an aqueous solution containing an excess diaquo(cis-1,2-diaminocyclohexane)platinum(II) produces a conjugate containing approximately forty (diaminocyclohexane)platinum(II) moieties at the surface of the dendrimer. This material undergoes smooth two-stage thermal decomposition to provide residual platinum oxide reflecting the platinum loading in the drug.     

Ag纳米颗粒的光吸收和透射电镜研究

用硼氢化钠作还原剂,制备出两种相对稳定的含银纳米颗粒的水溶胶,用透射电镜（TEM）和光学吸收谱对这些颗粒进行了表征.当被还原的银离子较少时,所形成的银纳米颗粒较小,吸收峰呈现二极等离子体共振吸收峰.当被还原的银离子较多时,银纳米颗粒尺寸变大,并出现二极和四极共振吸收峰.在Ag纳米颗粒形成后,对其溶液稀释,发现其峰形保持不变,而峰位会出现红移,最大红移量可达到10 nm.透射电镜研究表明,低浓度溶胶中的Ag纳米颗粒尺寸较为均匀,平均直径12 nm.高浓度溶胶中的纳米颗粒尺寸呈双尺寸分布特点,少量颗粒直径小于14 nm,大部分颗粒直径大于20 nm.     

Thermal conductance for single wall carbon nanotubes

We report a theoretical analysis of the phonon thermal conductance, κ(T), for single wall carbon nanotubes (SWCN). In a range of low temperatues up to 100 K, κ(T) of perfect SWCN is found to increase with temperature, approximately, in a parabolic fashion. This is qualitatively consistent with recent experimental measurements where the tube-tube interactions are negligibly weak. When the carbon-carbon bond length is slightly varied, κ(T) is found to be qualitatively unaltered which implies that the anharmonic effect does not change the qualitative behavior of κ(T). Received 12 June 2001