Electrochemical and chemical polymerization of acrylamide

The electrochemical and chemical polymerization of acrylamide (AA) has been studied. The electrolysis of the monomer in N,N-dimethylformamide (DMF) containing (C₄H₉)₄NClO₄ as the supporting electrolyte leads to polymer formation in both anode and cathode compartments. The cathodic polymer dissolves in the reaction mixture and the anodic polymer precipitates during the course of polymerization. A plausible mechanism for the anodic and cathodic initiation reaction has been given. The chemical polymerization of acrylamide that has been initiated by HClO₄ is analogous to its anodic polymerization. The polymer yield increases with an increase in concentration of the monomer and HClO₄. Raising the reaction temperature also enhances the polymerization rate. The overall apparent activation energy of the polymerization was determined to be ca. 19 kcal/mole. The copolymerization of acrylamide was carried out with methyl methacrylate (MMA) in a solution of HClO₄ in DMF. The reactivity ratios are r₁ (AA) = 0.25 and r₂ = 2.50. The polymerization with HClO₄ appears to be by a free radical mechanism. When the polymerization of acrylamide is carried out with HClO₄ in H₂O, a crosslinked water-insoluble gel formation takes place.     

2,5-Dihydroxyacetophenone oxime as an analytical reagent for the amperometric determination of copper,palladium, and nickel

Summary Copper, palladium and nickel can be titrated amperometrically with 2,5-dihydroxyacetophenone oxime at –0.15, –0.4 and, –1.2 V vs. S. C. E. respectively, the optimum p_H values being 4.6, 4.0, and 9.0. Alkali and alkaline earth metals, Al, Bi, Cd, Co, Cr. Fe(II), Hg, Mn, Ni, Pb, Th, Zn, UO, W, and Zr do not interfere with the estimation of copper and palladium. The interferences due to the presence of silver and iron(III) can be eliminated by adding excess of KCl and KF respectively. Most heavy metals interfere with the estimation of nickel and should be eliminated before titration.

---

Zusammenfassung Kupfer, Palladium und Nickel können mit 2,5-Dihydroxyaeetophenonoxim bei –0,15, –0,4 bzw. –1,2 V gegen eine gesättigte Kalomelelektrode amperometrisch titriert werden, wobei man das p_H am besten auf 4,6, 4,0 bzw. 9,0 hält. Alkalimetalle, Erdalkalien, Al, Bi, Cd, Co, Cr, Fe(II), Hg, Mn, Ni, Pb, Th, Zn, UO₂, W und Zr stören die Bestimmung des Kupfers und des Palladiums. Silber und Eisen können mit Kaliumchlorid gefällt bzw. mit Kaliumfluorid maskiert werden. Die meisten Schwermetalle stören die Nickelbestimmung und müssen daher vor der Titration entfernt werden.

     

A molecular mechanics approach for analyzing tensile nonlinear deformation behavior of single-walled carbon nanotubes

In this paper, by capturing the atomic information and reflecting the behaviour governed by the nonlinear potential function, an analytical molecular mechanics approach is proposed. A constitutive relation for single-walled carbon nanotubes (SWCNT’s) is established to describe the nonlinear stress-strain curve of SWCNT’s and to predict both the elastic properties and breaking strain of SWCNT’s during tensile deformation. An analysis based on the virtual internal bond (VIB) model proposed by P. Zhang et al. is also presented for comparison. The results indicate that the proposed molecular mechanics approach is indeed an acceptable analytical method for analyzing the mechanical behavior of SWCNT’s. The project supported by the National Natural Science Foundation of China (10121202, 90305015 and 10328203), the Key Grant Project of Chinese Ministry of Education (0306) and the Research Grants Council of the Hong Kong Special Administrative Region, China (HKU 7195/04E).     

The order parameter model for structural relaxation in glass

The order parameter model assumes that the state of a glass or liquid depends on T, P and a number of order parameters Z_i. Structural relaxation is due to the kinetically impeded evolution of the order parameters following a rapid change in T or P. The linear relaxation function for the evolution of property Q (V or H) in response to a change in X (T or P) is of the form φ_QX = Σ_igⁱ_QX exp(?tτ_i). Expressions are derived for the qeighting coefficients gⁱ_QX in terms of the dependences of V and H on the various order parameters. It is shown that gⁱ_VT = gⁱ_HP and that gⁱ_VTgⁱ_HP/gⁱ_VPgⁱ_HT = II, where II is the Prigogine-Defay ratio. The corresponding relations among the relaxation functions are φ_VT = φ_HP and φ_VTφ_HP/φ_VPφ_HT ? II. The predictions of the order parameter model for structural relaxation are compared with and found generally to agree with existing literature data. A number of suggestions for future investigations to test this model are made.     

A variational principle for fully developed laminar heat transfer in uniform channels I

Summary A variational principle for forced convection in laminar flow in uniform channels is formulated. The concepts of thermal potential, dissipation function and thermal force have been introduced and a Lagrangian formulation of the thermal flow field using generalized coordinates is given. Special consideration is given to heat transfer in plug flow when the thermal field is a linear function of the generalized coordinates. The concept of normal and ignorable coordinates is introduced. An example showing the use of Lagrangian equations is worked out.     

Development,In-Vitro Characterization and Preclinical Evaluation of Esomeprazole-Encapsulated Proniosomal Formulation for the Enhancement of Anti-Ulcer Activity

Objective: The present study aimed to develop and optimize esomeprazole loaded proniosomes (EZL-PNs) to improve bioavailability and therapeutic efficacy. Method: EZL-PNs formulation was developed by slurry method and optimized by 33 box-Bhekhen statistical design software. Span 60 (surfactant), cholesterol, EZL concentration were taken as independent variables and their effects were evaluated on vesicle size (nm), entrapment efficiency (%, EE) and drug release (%, DR). Furthermore, optimized EZL-PNs (EZL-PNs-opt) formulation was evaluated for ex vivo permeation, pharmacokinetic and ulcer protection activity. Result: The EZL-PNs-opt formulation showed 616 ± 13.21 nm of vesicle size, and 81.21 ± 2.35% of EE. EZL-PNs-opt exhibited negative zeta potential and spherical confirmed scanning electron microscopy. EZL-PNs-opt showed sustained release of EZL (95.07 ± 2.10% in 12 h) than pure EZL dispersion. The ex-vivo gut permeation result exhibited a significantly (p < 0.05) enhanced flux than pure EZL. The in vivo results revealed 4.02-fold enhancement in bioavailability and 61.65% protection in ulcer than pure EZL dispersion (43.82%). Conclusion: Our findings revealed that EZL-PNs formulation could be an alternative delivery system of EZL to enhance oral bioavailability and antiulcer activity.     

Preparation of nano-hydroxyapatite/poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactide) biocomposite microspheres

Nano-hydroxyapatite (HA)/poly(l-lactide) (PLLA) composite microspheres with relatively uniform size distribution were prepared by a solid-in-oil-in-water (s/o/w) emusion solvent evaporation method. The encapsulation of the HA nanopaticles in microshperes was significantly improved by grafting PLLA on the surface of the HA nanoparticles (p-HA) during emulsion process. This procedure gave a possibility to obtain p-HA/PLLA composite microspheres with uniform morphology and the encapsulated p-HA nanoparticle loading reached up to 40 wt% (33 wt% of pure HA) in the p-HA/PLLA composite microspheres. The microstructure of composite microspheres from core-shell to single phase changed with the variation of p-HA to PLLA ratios. p-HA/PLLA composite microspheres with the diameter range of 2–3 μm were obtained. The entrapment efficiency of p-HA in microspheres could high up to 90 wt% and that of HA was only 13 wt%. Surface and bulk characterizations of the composite microspheres were performed by measurements such as wide angle X-ray diffraction (WAXD), thermal gravimetric analysis (TGA), environmental scanning electron microscope (ESEM) and transmission electron microscopy (TEM).     

Synthesis and characterization of supramolecular optically active bisamides derived from amino acids

The synthesis and phase transitional behaviour of three pairs of enantiomeric supramolecular hexacatenar liquid crystals (LCs) derived from natural α-amino acids such as l/d-alanine, l/d-leucine and l/d-valine are described. Their preparation with high enantiomeric purity was accomplished by condensing optically active (amino acid residue containing) trialkoxy amines with a 3,4,5-trialkoxy cinnamic acid core using a peptide coupling reagent namely, 2-(1H-benzotriazol-1-yl)-1,1,3,3-tetramethyl-uronium hexafluorophosphate (HBTU). The mesomorphic behaviour of these self-complementing mesogens was ascertained by polarising optical microscopy, differential scanning calorimetry and X-ray diffraction. The compounds exhibit columnar (Col) phase over a wide thermal range. Particularly, a pair of enantiomers derived from l/d-leucine residues notably stabilize hexagonal Col (Col_h) phase over a wide temperature range of ?5 °C to 180 °C. Circular dichroism (CD) and FTIR studies suggest the chiral (helical) organization of mesogens within the columns through intermolecular hydrogen bonding; thus, these enantiomers represent one of the rarely reported examples of LCs exhibiting supramolecular Col_h phase at room temperature. The gelation studies reveal the ability of these bisamides to form stable supramolecular gels in ethanol caused through H-bonding interactions.     

The effect of drying method on the properties and nanoscale structure of cellulose whiskers

Cellulose whiskers were prepared from wood- and cotton-based microcrystalline cellulose and dried by two methods: freeze-drying or air-drying. The effect of drying method on the properties and structure of the whiskers were studied. Furthermore, the influence of the source of cellulose on the nanoscale structure was investigated. Drying method was observed to slightly influence the thermal stability of cellulose whiskers, whereas the char residue varied significantly depending on the drying process performed. Small- and wide-angle X-ray scattering and solid state nuclear magnetic resonance spectroscopy were used to examine the crystallinity and nanoscale structure of the dried whiskers. It was observed that the crystal structure and crystallinity of cellulose whiskers remained during all treatments, whereas their nanoscale structure was significantly influenced by drying method, neutralization, and source of cellulose. Relationships between thermal behavior and nanoscale structure were reported and discussed.