Synthesis and comparative solution properties of single‐, twin‐, and triple‐tailed associating ionic polymers based on diallylammonium salts

The cycloterpolymerizations of single‐, twin‐, and triple‐tailed hydrophobes with hydrophilic monomer N,N‐diallyl‐N‐carboethoxymethylammonium chloride and sulfur dioxide afforded a series of cationic polyelectrolytes (CPEs) in excellent yields. These CPEs, upon the acidic hydrolysis of the pendent ester groups, gave the corresponding pH‐responsive cationic acid salts, which, upon a treatment with sodium hydroxide, were converted to polybetaines (PBs), anionic polyelectrolytes (APEs), and PB/APE polymers containing various proportions of zwitterionic (PB) and anionic fractions (APE) in the polymer chain. At a shear rate of 0.36 s⁻¹ at 30 °C, salt‐free water solutions of the CPEs (2 g/dL) containing 8, 4, and 2.67 mol % of the single‐, twin‐, and triple‐tailed hydrophobes (all having 8 mol % octyloxy tails) had apparent viscosity values of 70, 2800, and 396,000 cps, respectively. The PB/APE polymer with a ratio of 33:67 for the zwitterionic and anionic fractions in the polymer chain gave the highest viscosity value. The superior viscosity behavior of the polymers containing the triple‐tailed hydrophobe was attributed to the blocky nature of the comonomer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5480–5494, 2006     

Oxygen inhibition in thiol–acrylate photopolymerizations

The overall effects of oxygen on thiol–acrylate photopolymerizations were characterized. Specially, the choice of thiol monomer chemistry, functionality, and concentration on the extent of oxygen inhibition were considered. As thiol concentration was increased, the degree of oxygen inhibition was greatly reduced because of chain transfer from the peroxy radical to the thiol. When comparing the copolymerization of 1,6‐hexanediol diacrylate with the alkane‐based thiol (1,6‐hexane dithiol) to the copolymerization with the propionate thiol (glycol dimercaptopropionate), it was found that the propionate system was much more reactive and polymerized to a greater extent in the presence of oxygen. In addition, the functionality was considered where the glycol dimercaptopropionate was compared to a tetrafunctional propionate of similar chemistry (pentaerythritol tetrakis(mercaptopropionate)). Given the same thiol concentration, the higher functionality thiol imparted a faster polymerization rate, due to the increased polymer system viscosity, which limited oxygen diffusion and decreased the extent of overall oxygen inhibition. Thus, preliminary insight is provided into how thiol monomer choice affects the extent of oxygen inhibition in thiol–acrylate photopolymerization. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2007–2014, 2006     

Atom transfer radical polymerization directly from poly(vinylidene fluoride): Surface and antifouling properties

The direct preparation of grafting polymer brushes from commercial poly (vinylidene fluoride) (PVDF) films with surface‐initiated atom transfer radical polymerization (ATRP) is demonstrated. The direct initiation of the secondary fluorinated site of PVDF facilitated grafting of the hydrophilic monomers from the PVDF surface. Homopolymer brushes of 2‐(N,N‐dimethylamino)ethyl methacrylate (DMAEMA) and poly (ethylene glycol) monomethacrylate (PEGMA) were prepared by ATRP from the PVDF surface. The chemical composition and surface topography of the graft‐functionalized PVDF surfaces were characterized by X‐ray photoelectron spectroscopy, attenuated total reflectance/Fourier transform infrared spectroscopy, and atomic force microscopy. A kinetic study revealed a linear increase in the graft concentration of poly[2‐(N,N‐dimethylamino)ethyl methacrylate] (PDMAEMA) and poly[poly(ethylene glycol) monomethacrylate] (PPEGMA) with the reaction time, indicating that the chain growth from the surface was consistent with a controlled or living process. The living chain ends were used as macroinitiators for the synthesis of diblock copolymer brushes. The water contact angles on PVDF films were reduced by the surface grafting of DMAEMA and PEGMA. Protein adsorption experiments revealed a substantial antifouling property of PPEGMA‐grafted PVDF films and PDMAEMA‐grafted PVDF films in comparison with the pristine PVDF surface. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3434–3443, 2006     

Synthesis and characterization of poly(dimethylsiloxane‐urethane) elastomers: Effect of hard segments of polyurethane on morphological and mechanical properties

A series of poly(dimethylsiloxane‐urethane) elastomers based on hexamethylenediisocyanate, toluenediisocyanate, or 4,4′‐methylenediphenyldiisocyanate hard segment and polydimethylsiloxane (PDMS) soft segment were synthesized. In this study, a new type of soft‐segmented PDMS crosslinker was synthesized by hydrosilylation reaction of 2‐allyloxyethanol with polyhydromethylsiloxane, using Karstedt's catalyst. The synthesized soft‐segmented crosslinker was characterized by FT‐IR, ¹H, and ¹³C NMR spectroscopic techniques. The mechanical and thermal properties of elastomers were characterized using tensile testing, thermogravimetric analysis, differential scanning calorimetry (DSC), and dynamical mechanical analysis measurements. The molecular structure of poly(dimethylsiloxane‐urethane) membranes was characterized by ATR‐FTIR spectroscopic techniques. Infrared spectra indicated the formation of urethane/urea aggregates and hydrogen bonding between the hard and soft domains. Better mechanical and thermal properties of the elastomers were observed. The restriction of chain mobility has been shown by the formation of hydrogen bonding in the soft and hard segment domains, resulting in the increase in the glass‐transition temperature of soft segments. DSC analysis indicates the phase separation of the hard and soft domains. The storage modulus (E′) of the elastomers was increasing with increase in the number of urethane connections between the hard and soft segments. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2980–2989, 2006     

Mathematical modeling of crystallization analysis fractionation (Crystaf) of polyethylene

Four polyethylene samples (PE) with different molecular weight distributions (MWD) were analyzed by crystallization analysis fractionation (Crystaf) at several cooling rates to investigate the effect of MWD and cooling rate on their Crystaf profiles. Using these results, we developed a mathematical model for Crystaf that considers crystallization kinetic effects, which are ignored in all previous Crystaf models. The Crystaf model we proposed can fit the experimental Crystaf profiles of the 4 polyethylene resins very well. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2749–2759, 2006     

Determination of streptomycin in a pharmaceutical sample based on its degradation by hydrogen peroxide in the presence of copper(II).

The kinetics of streptomycin degradation by hydrogen peroxide at pH 7.4 was investigated. The reaction was catalyzed by traces of Cu(II) ions, and it was followed spectrophotometrically at 322 nm by applying the initial-rate method. The kinetic parameters of the reaction are reported, and a rate equation is suggested. From the dependence of the relative rate constants on the temperature, the activation energy was calculated to be 57.5 kJ/mol. Based on this reaction, a kinetic method for streptomycin determination is proposed. The calibration graph is linear in the ranges 1.94 - 15.48 microg/cm(3) and 0.15 - 1.94 microg/cm(3). The influence of foreign ions and molecules on the accuracy of the determinations was investigated. The proposed kinetic method has high selectivity and good sensitivity, and enabled to determine streptomycin in pharmaceutical samples.     

Thermodynamics of the dissolution of acetoacetylferrocene and 1,1′-bis(acetoacetyl)ferrocene in aqueous ethanol

The solubility of acetoacetylferrocene and 1,1′-bis(acetoacetyl)ferrocene in water and aqueous ethanol at various temperatures is studied over a wide solvent composition range. The solubilities of both compounds increase as the temperature or ethanol concentration is raised, particularly in the case of acetoacetylferrocene. The dissolution of both β-diketones is accompanied by positive changes in enthalpy and entropy.     

Phase equilibria in the Tl-TlBr-S system

The polythermal sections TlBr-Tl₂S, TlBr-Tl₄S₃, TlBr-TlS, and Tl₆SBr₄-Tl; the isothermal section at 300 K of the phase diagram; and the projection of the liquidus surface of the Tl-S-Br system have been investigated in the composition region Tl-TlBr-S by DTA, X-ray powder diffraction analysis, and microhardness measurements. The primary crystallization regions, including that of the only ternary compound (Tl₆SBr₄), have been determined, and the types and coordinates of the invariant and univariant equilibria in the phase diagram are determined.     

Local chemical distribution and electronic structure of Ge1−xTx DMS single crystals (T=Cr,Mn, Fe)

The spatial concentration distribution and local electronic structure of ferromagnetic Ge_1−xT_x (T=Cr, Mn, Fe) DMS single crystals have been investigated by using scanning photoelectron microscopy (SPEM), X-ray absorption spectroscopy (XAS), and photoemission spectroscopy (PES). It is found that doped T ions in Ge_1−xT_x crystals are chemically phase-separated, suggesting that the observed ferromagnetism arises from the phase-separated T-rich phases in Ge_1−xT_x.     

Thermodynamic and surface properties of Sb-Sn and In-Sn liquid alloys

The thermodynamic properties of Sb-Sn and In-Sn liquid alloys have been studied using the quasi-chemical model for compound forming binary alloys and that for simple regular alloys. The concentration fluctuation S _cc(0) and the Warren-Cowley short-range order parameter (α ₁) were determined for the whole concentration range at a temperature of 770 K. The surface tensions of these liquid alloys were determined for the whole concentration range by using energetics determined from thermodynamic calculations. In all calculations, In-Sn manifested properties very close to alloys of ideal mixing, while Sb-Sn showed properties that are asymmetric about equiatomic composition. Our results suggest that a weak complex of the form SbSn₂ could be present in the Sb-Sn alloy at a temperature of about 770 K.