Crystallographic report: catena‐Aqua(2,2′‐bipyrimidine)lithium(I) perchlorate

A lithium(I) coordination polymer has been formed from LiClO₄ and the 2,2′‐bipyrimidine (bpym) ligand in which each square pyramidal lithium(I) atom is coordinated in the basal plane by four nitrogen donor atoms derived from two bpym ligands and one water molecule at the apical position. These are connected into a layer structure via hydrogen‐bonding interactions involving the perchlorate anions. Copyright © 2004 John Wiley & Sons, Ltd.     

Novel,biodegradable, functional poly(ester‐carbonate)s by copolymerization of trans‐4‐hydroxy‐L‐proline with cyclic carbonate bearing a pendent carboxylic group

Water‐soluble poly(ester‐carbonate) having pendent amino and carboxylic groups on the main‐chain carbon is reported for the first time. This article describes the melt ring‐opening/condensation reaction of trans‐4‐hydroxy‐N‐benzyloxycarbonyl‐L ‐proline (N‐CBz‐Hpr) with 5‐methyl‐5‐benzyloxycarbonyl‐1,3‐dioxan‐2‐one (MBC) at a wide range of molar fractions. The influence of reaction conditions such as catalyst concentration, polymerization time, and temperature on the number average molecular weight (M_n) and molecular weight distribution (M_w/M_n) of the copolymers was investigated. The polymerizations were carried out in bulk at 110 °C with 3 wt % stannous octoate as a catalyst for 16 h. The poly(ester‐carbonate)s obtained were characterized by Fourier transform infrared spectroscopy, ¹H NMR, differential scanning calorimetry, and gel permeation chromatography. The copolymers synthesized exhibited moderate molecular weights (M_n = 6000–14,700 g mol^?1) with reasonable molecular weight distributions (M_w/M_n = 1.11–2.23). The values of the glass‐transition temperature (T_g) of the copolymers depended on the molar fractions of cyclic carbonate. When the MBC content decreased from 76 to 12 mol %, the T_g increased from 16 to 48 °C. The relationship between the poly(N‐CBz‐Hpr‐co‐MBC) T_g and the compositions was in approximation with the Fox equation. In vitro degradation of these poly(N‐CBz‐Hpr‐co‐MBC)s was evaluated from weight‐loss measurements and the change of M_n and M_w/M_n. Debenzylation of 3 by catalytic hydrogenation led to the corresponding linear poly(ester‐carbonate), 4 , with pendent amino and carboxylic groups. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2303–2312, 2004     

Synthesis of a soluble pyrrole copolymer with phenetidine

A new series of copolymers was synthesized through the oxidative polymerization of pyrrole (PY) and o‐phenetidine (PHT) with inorganic oxidants in acidic media. The polymerization parameters including the mixing method of the oxidant with the comonomer, the comonomer ratio, the time, the temperature, the oxidant, the organic medium, and the acid were systematically optimized for the synthesis of copolymers with high yields, intrinsic viscosities, and solubility. The resultant copolymers were characterized by elemental analysis, infrared, ultraviolet–visible, solution high‐resolution ¹H NMR and solid‐state high‐resolution ¹³C NMR, circular dichroism spectroscopy, and cyclic voltammetry. The results showed that the PY observed content in the copolymers was much higher than the PY feed content. The regular variation of the polymerization yield, intrinsic viscosity, solubility, macromolecular structure, and electroactivity of the resulting polymers with the comonomer ratio, together with the complete solubility of a PY/PHT (10/90) polymer in highly polar solvents, indicated the formation of real random copolymers containing both PY and PHT units rather than a mixture of two homopolymers. However, the polymers containing more than 59 mol % PY were not homogeneous copolymers consisting of soluble and insoluble parts. A semiquantitative relationship between the polymerization yield or solubility of the copolymers and the polarity index of the organic solvents was examined. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2073–2092, 2004     

Dielectric relaxation analysis of starch oligomers and polymers with respect to their chain length

Starch belongs to the polyglucan group. This type of polysaccharide shows a broad β-relaxation process in dielectric spectra at low temperatures, which has its molecular origin in orientational motions of sugar rings via glucosidic linkages. This chain dynamic was investigated for α(1,4)-linked starch oligomers with well-defined chain lengths of 2, 3, 4, 6, and 7 anhydroglucose units (AGUs) and for α(1,4)-polyglucans with average degrees of polymerization of 5, 10, 56, 70, and so forth (up to 3000; calculated from the mean molecular weight). The activation energy (E_a) of the segmental chain motion was lowest for dimeric maltose (E_a = 49.4 ± 1.3 kJ/mol), and this was followed by passage through a maximum at a degree of polymerization of 6 (E_a = 60.8 ± 1.8 kJ/mol). Subsequently, E_a leveled off at a value of about 52 ± 1.5 kJ/mol for chains containing more than 100 repeating units. The results were compared with the values of cellulose-like oligomers and polymers bearing a β(1,4)-linkage. Interestingly, the shape of the E_a dependency on the chain length of the molecules was qualitatively the same for both systems, whereas quantitatively the starch-like substances generally showed higher E_a values. Additionally, and for comparison, three cyclodextrins were measured by dielectric relaxation spectroscopy. The ringlike molecules, with 6, 7, and 8 α(1,4)-linked AGUs, showed moderately different types of dielectric spectra. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 188–197, 2004     

Isothermal crystallization kinetics of poly(3‐hydroxybutyrate)/layered double hydroxide nanocomposites

Poly(3‐hydroxybutyrate) (PHB)/layered double hydroxides (LDHs) nanocomposites were prepared by mixing PHB and poly(ethylene glycol) phosphonates (PEOPAs)‐modified LDH (PMLDH) in chloroform solution. Both X‐ray diffraction data and TEM micrographs of PHB/PMLDH nanocomposites indicate that the PMLDHs are randomly dispersed and exfoliated into the PHB matrix. In this study, the effect of PMLDH on the isothermal crystallization behavior of PHB was investigated using a differential scanning calorimeter (DSC) and polarized optical microscopy. Isothermal crystallization results of PHB/PMLDH nanocomposites show that the addition of 2 wt % PMLDH into PHB induced more heterogeneous nucleation in the crystallization significantly increasing the crystallization rate and reducing their activation energy. By adding more PMLDH into the PHB probably causes more steric hindrance of the diffusion of PHB, reducing the transportation ability of polymer chains during crystallization, thus increasing the activation energy. The correlation among crystallization kinetics, melting behavior and crystalline structure of PHB/PMLDH nanocomposites can also be discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3337–3347, 2006     

Determination of carbamazepine by chemiluminescence detection using chemically prepared tris(2,2'-bipyridine)ruthenium(III) as oxidant.

A new chemiluminescence method for the determination of carbamazepine (CBZ) has been developed. The method is based on the chemiluminescence produced in the reaction of tris(2,2'-bipyridine)ruthenium(III) and CBZ in an acidic medium. The chemiluminescence intensity was enhanced by organic solvents in the reaction system. Under the optimum experimental conditions, the calibration curve was linear over the range 4.0 x 10(-3)-8.6 x 10(-7) mol/L for CBZ. The detection limit (S/N = 3) was 2.5 x 10(-7) mol/L and the relative standard deviation of six replicate measurements was 2.6% for 4.0 x 10(-4) mol/L of CBZ. The possible reaction mechanism were also discussed. The chemiluminescence method was successfully applied to assay the CBZ contents in pharmaceutical tablets.     

Transition‐metal‐catalyzed reactions of 5‐methylene‐2‐oxazolidinone and 5‐methylene‐1,3‐thiazolidine‐2‐thione with isocyanates

5‐Methylene‐2‐oxazolidinone (1) and 5‐methylene‐1,3‐thiazolidine‐2‐thione (4) react with various isocyanates to give the corresponding urethanes 3 and 5 in high yields in the presence of palladium(0) or palladium(II) catalyst under mild reaction conditions. A mechanism is proposed. Copyright © 2003 John Wiley & Sons, Ltd.     

Synthesis and characterization of white‐light‐emitting polyfluorenes containing orange phosphorescent moieties in the side chain

Two orange phosphorescent iridium complex monomers, 9‐hexyl‐9‐(iridium (III)bis(2‐(4′‐fluorophenyl)‐4‐phenylquinoline‐N,C^2′)(tetradecanedionate‐11,13))‐2,7‐dibromofluorene (Br‐PIr) and 9‐hexyl‐9‐(iridium(III)bis(2‐(4′‐fluorophenyl)‐4‐methylquinoline‐N,C^2′)(tetradecanedionate‐11,13))‐2,7‐dibromofluorene (Br‐MIr), were successfully synthesized. The Suzuki polycondensation of 2,7‐bis(trimethylene boronate)‐9,9‐dioctylfluorene with 2,7‐dibromo‐9,9‐dioctylfluorene and Br‐PIr or Br‐MIr afforded two series of copolymers, PIrPFs and MIrPFs, in good yields, in which the concentrations of the phosphorescent moieties were kept small (0.5–3 mol % feed ratio) to realize incomplete energy transfer. The photoluminescence (PL) of the copolymers showed blue‐ and orange‐emission peaks. A white‐light‐emitting diode with a configuration of indium tin oxide/poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate)/PIr05PF (0.5 mol % feed ratio of Br‐PIr)/Ca/Al exhibited a luminous efficiency of 4.49 cd/A and a power efficiency of 2.35 lm/W at 6.0 V with Commission Internationale de L'Eclairage (CIE) coordinates of (0.46, 0.33). The CIE coordinates were improved to (0.34, 0.33) when copolymer MIr10PF (1.0 mol % feed ratio of Br‐MIr) was employed as the white‐emissive layer. The strong orange emission in the electroluminescence spectra in comparison with PL for these kinds of polymers was attributed to the additional contribution of charge trapping in the phosphorescent dopants. © 2007 Wiley Periodicals, Inc. JPolym Sci Part A: Polym Chem 45: 1746–1757, 2007     

Solvothermal synthesis of TiO2: anatase nanocrystals and rutile nanofibres from TiCl4 in acetone

This work reports a new synthetic approach for single‐phase TiO₂ nanomaterials by solvothermal treatment of titanium tetrachloride in acetone at 80–110 °C. Small, uniform, and yet size‐tunable (5–10 nm) anatase titania nanocrystallites were obtained using a low concentration of TiCl₄ in acetone (i.e., at molar ratios of TiCl₄/acetone ≤ 1:15) in the temperature range of 80–110 °C, while rutile nanofibers were synthesized using a high concentration of TiCl₄ (e.g., TiCl₄/acetone = 1:10) at 110 °C. Copyright © 2007 John Wiley & Sons, Ltd.     

Viscometric properties of dilute polystyrene/dioctyl phthalate solutions

We report viscometric data collected in a Couette rheometry on dilute, single‐solvent polystyrene (PS)/dioctyl phthalate (DOP) solutions over a variety of polymer molecular weights (5.5 × 10⁵ ≤ M_w ≤ 3.0 × 10⁶ Da) and system temperatures (288 K ≤ T ≤ 318 K). In view of the essential viscometric features, the current data may be classified into three categories: The first concerns all the investigated solutions at low shear rates, where the solution properties are found to agree excellently with the Zimm model predictions. The second includes all sample solutions, except for high‐molecular‐weight PS samples (M_w ≥ 2.0 × 10⁶ Da), where excellent time–temperature superposition is observed for the steady‐state polymer viscosity at constant polymer molecular weights. No similar superposition applies at a constant temperature but varied polymer molecular weights, however. The third appears to be characteristic of dilute high‐molecular‐weight polymer solutions, for which the effects of temperature on the viscosity curve are further complicated at high shear rates. The implications concerning the relative importance of hydrodynamic interactions, segmental interactions, and chain extensibility with increasing polymer molecular weight, system temperature, and shear rate are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 787–794, 2006