Decomposition of dinuclear manganese complexes for the preparation of nanostructured oxide materials

The crystal structures of several dinuclear complexes of manganese are reported, and the decomposition and analysis of the nanostructured products derived from them are presented. 1,4,7,10-Tetraazacyclododecane (cyclen) forms dinuclear complexes 1-4 containing doubly oxo-bridged or oxo-acetato bridging ligands depending on the manganese salt used for the reaction. Doubly oxo-bridged 1 crystallizes in the orthorhombic space group Pnma, a = 22.3850(14) A, b = 9.1934(5) A, c = 13.2424(10) A, V = 2725.2(3) A(3). 2, containing [Mn(SCN)5](3-) conteranions, crystallizes in monoclinic space group I2/a with a = 18.2699(10) A, b = 11.2384(6) A, c = 18.6432(9) A, alpha = 90.00 degrees, beta = 114.510(6) degrees, gamma = 90.00 degrees, V = 3483.0(3) A(3). Oxo-acetato-bridged 3 crystallizes in orthorhombic space group Pca21, a = 13.9322(11) A, b = 16.2332(13) A, c = 14.6794(8) A, V = 3320.0(4) A(3). Compound 4 consists of a templated quasi-one-dimensional manganese oxalate crystallized in the triclinic space group P1, a = 9.5442(11) A, b = 10.3758(10) A, c = 21.851(2) A, alpha = 83.720(12) degrees, beta = 80.106(13) degrees, gamma = 85.457(13) degrees, V = 2114.9(4) A(3). Compounds 1, 3, and 4 decompose to nanostructured oxide materials, which may be isolated in bulk as lamellar-structured particles or microspheres or deposited on substrates.     

Stress induced half-metallicity in surface defected germanium nanowires

Germanium nanowires (GeNWs) with single, double, quadruple and octuple surface dangling bonds (SDBs) are investigated using density-functional-theory calculations. We show that single SDB defected GeNWs remain semiconducting as their non-defected form while double or multiple SDB defects result in either semiconducting or metallic GeNWs, depending on the defect's locations on the surface. More importantly, we show that the electronic properties of surface defected GeNWs can also be fine-tuned by applying tensile and compressive strains. Upon the right loading, the surface defected GeNWs become half-metallic. In addition, we determine that the surface defected GeNWs can be classified into three classes: (1) GeNWs with zero magnetic moment, which are either metallic or semiconducting; (2) GeNWs with net magnetic moments equal to the number of SDBs, which are semiconducting with distinct spin-up and spin-down configurations; and (3) GeNWs with net magnetic moments significantly lower than the number of SDBs. We also find that only the defected GeNWs that fall under (3) are potentially half-metallic. Our results predict that half-metallic GeNWs can be obtained via engineering of the surface defects and the structures without the presence of impurity dopants.     

Computation of triple differential cross-sections with the inclusion of exchange effects in atomic K-shell ionization by relativistic electrons for symmetric geometry

The triple differential cross-section for K-shell ionization of silver and copper atoms by relativistic electrons have been computed in the coplanar symmetric geometry with the inclusion of exchange effects following the multiple scattering theory of Das and Seal [1] multiplied by suitable spinors. Present computed results are marginally improved in some cases from the previous computed results [2]. Present results are compared with measured values [3] and with previous computation results [2]. Some other theoretical computational results are also presented here for comparison.      

A pulse radiolysis study of the reactions of the hydrated electron and hydroxyl radical with the oxalate ion in neutral aqueous solution

The rate constants of the reactions of e _aq ^? and the OH^· radical with the oxalate ion in a neutral aqueous solution were measured by means of the pulse radiolysis technique. They were found to be (3.5 ± 0.5) × 10⁷ and (1.5 ± 0.2) × 10⁷ l mol^?1 s^?1, respectively. The radical anion ^?OOC-C^·OO^2? is characterized by an optical absorption band that has a maximum at 270 nm and a molar absorption coefficient of (2400 ± 200) l mol^?1 cm^?1. The radical anion ^·OOC-COO^?, the product of the reaction with the OH^· radical, exhibits absorption that has no maximum and increases in intensity with a decrease in the wavelength extending to the UV region (?₂₂₀ = 1800 l mol^?1 cm^?1). The mechanism of radiation-chemical transformations in aqueous oxalate solutions is discussed.     

Glycerol effects on the formation and rheology of cubic phase and related gel emulsion

We have investigated the effects of glycerol on the formation and rheological behavior of cubic phase (I(1)) and related O/I(1) gel emulsion in a water/C(12)EO(8)/dodecane system at 25 degrees C. The phase behavior of the water/C(12)EO(8)/dodecane system was studied by optical observation and structures of different liquid crystalline phases were identified by small-angle X-ray scattering (SAXS) techniques. Addition of dodecane (2 wt%) to aqueous solutions of C(12)EO(8) in a concentrated region (40 wt%) leads to the formation of the I(1) phase (which was absent without the addition of oil). The I(1) phase solubilized some amount of oil and at higher oil concentrations the I(1)+O phase was formed, allowing the preparation of O/I(1) gel emulsion. Rheological measurements have shown that the complex viscosity, |eta( *)|, of the I(1) phase is tremendously high ( approximately 10(7) Pas) and it increases with increasing oil concentration, attains a maximum value near the phase boundary, and then decreases drastically in the I(1)+O region. The increasing |eta( *)| or decreasing tandelta(G(')/G(')) can be ascribed with the interactions among the neighboring micelles. The decreasing trend of the |eta( *)| in the I(1)+O region is simply due to the low volume fraction of the I(1) phase. It has been shown that glycerol decreases the viscosity of the I(1) phase and related gel emulsion, which is due to the I(1)-hexagonal phase (H(1)) microstructural transition. Digital images show the physical appearance of the emulsion, which depends on the glycerol concentration changes from translucent to transparent.     

Micellization and Clouding Phenomenon of Phenothiazine Drug Promethazine Hydrochloride: Effect of NaCl and Urea Addition

Herein we report the micellization and clouding behavior of promethazine hydrochloride (PMT) in absence and presence of NaCl/ureas. The critical micelle concentration (CMC) of PMT is measured by conductivity method and the values decrease with increasing the NaCl concentration. With increasing the temperature, the CMC first increases then decreases. At 25°C, the maximum CMC values were obtained (with or without NaCl). The thermodynamic parameters are evaluated which indicate more stability of the PMT solution in presence of NaCl. PMT shows phase separation also. The cloud point (CP) of PMT decreases with increase in pH due to deprotonation of the drug molecules. Ureas decreased the CP and the behavior is explained on the basis of removal of water from the head group region.     

Synthesis and Characterization of Organosilicon Substituted Fluorenyl Derivatives

Friedel‐Crafts cycloalkylation of biphenyl with 2,3‐dichlorobutyltrichlorosilane(Cl₃Si‐CH₂CHClCHClCH₃) at a temperature of 100°C in the presence of anhydrous aluminum chloride catalyst gave cyclized product, 9‐methyl‐9‐(2‐trichlorosilylethyl)fluorene 1a , in 33% yield. Methylation of 1a with nucleophilic reagent such as methyl magnesium chloride, gave 9‐methyl‐9‐(2‐trimethylsilylethyl)fluorene 2 while bromination of 2 with excess amount of bromine in DMF resulted in 2,7‐dibromo‐9‐methyl‐9‐(2‐trichlorosilyl)fluorene 3 in good yield. All the compounds were structurally identified by GC/MS, ¹H and ¹³C‐NMR spectroscopy.     

Effect of ferrofluid concentration on electrical and magnetic properties of the Fe3O4/PANI nanocomposites

Magnetic nanocomposites can be controlled and tailored to provide the desired mechanical, physical, chemical, and biomedical properties depending on the final applications. The coating of ferrite nanoparticles with polymers affords the possibility of minimizing agglomeration in large-scale commercial synthesis of nanocomposite materials. The process of coating not only provides effective encapsulation of individual nanoparticles, but also controls the growth in size, thus, yielding a better overall size distribution. In this paper, in-situ polymerization of aniline was carried out in different concentration of the ferrofluid with the aim to obtain agglomerate free nanocomposites. The role of the ferrite concentration was investigated by the spectral, morphological, conductivity, and magnetic properties of Fe₃O₄/polyaniline (PANI) nanocomposites. XRD revealed the presence of spinel phase of Fe₃O₄ and the particle size was calculated to be 14.3 nm. Spectral analysis confirmed the formation of PANI encapsulated Fe₃O₄ nanocomposite. Conductivity of the nanocomposites was found to be in the range of 0.001–0.003 S/cm. Higher saturation magnetization of 3.2 emu/g was observed at 300 K, revealing a super paramagnetic behavior of this nanocomposite.     

Preparation of chitosan–polyethylene glycol coated cotton membranes for wound dressings: preparation and characterization

Cotton fabric was coated with chitosan (CS) and polyethylene glycol (PEG) followed by freeze‐drying. The influence of PEG on the physical characteristics and the surface morphology was investigated. The scanning electron microscopy of the coated fabric revealed a porous structure. The porosity of the material was 54–70% and the pore size was in the range of 75–120µm. The increase in the PEG content in the blend composition led to an enhanced destabilization of pores, leading to an increase in the pore size with elongated morphology. There seems to be phase separation between the two components which is an important factor for the observed behavior of the porous structure. The Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) showed that the CS and PEG have limited interaction. DSC suggested that addition of PEG to CS does not interfere with the crystallization behavior due to limited interaction with CS. The thermogravimetric analysis (TGA) showed that the membranes are thermally stable and PEG enhances the thermal stability of the CS coated membranes. The air and water permeability of the membranes tended to decrease with the increase in the PEG content. Copyright © 2008 John Wiley & Sons, Ltd.