Dihalodimethyltin(IV) complexes of 2‐(pyrazol‐1‐ylmethyl)pyridine

Reaction of dichloro‐ and dibromodimethyltin(IV) with 2‐(pyrazol‐1‐ylmethyl)pyridine (PMP) afforded [SnMe₂Cl₂(PMP)] and [SnMe₂Br₂(PMP)] respectively. The new complexes were characterized by elemental analysis and mass spectrometry and by IR, Raman and NMR (¹H, ¹³C) spectroscopies. Structural studies by X‐ray diffraction techniques show that the compounds consist of discrete units with the tin atom octahedrally coordinated to the carbon atoms of the two methyl groups in a trans disposition (Sn? C = 2.097(5), 2.120(5) Å and 2.110(6), 2.121(6) Å in the chloro and in the bromo compounds respectively), two cis halogen atoms (Sn? Cl = 2.4908(16), 2.5447(17) Å; Sn? Br = 2.6875(11), 2.7464(9) Å) and the two donor atoms of the ligand (Sn? N = 2.407(4), 2.471(4) Å and 2.360(5), 2.455(5) Å). In both cases, the Sn? N(pyridine) bond length is markedly longer than the Sn? N(pyrazole) distance. Copyright © 2003 John Wiley & Sons, Ltd.     

Temperature‐modulated differential scanning calorimetry studies on the origin of double melting peaks in isothermally melt‐crystallized poly(L‐lactic acid)

In this work, the melting behaviors of nonisothermally and isothermally melt‐crystallized poly(L ‐lactic acid) (PLLA) from the melt were investigated with differential scanning calorimetry (DSC) and temperature‐modulated differential scanning calorimetry (TMDSC). The isothermal melt crystallizations of PLLA at a temperature in the range of 100–110 °C for 120 min or at 110 °C for a time in the range of 10–180 min appeared to exhibit double melting peaks in the DSC heating curves of 10 °C/min. TMDSC analysis revealed that the melting–recrystallization mechanism dominated the formation of the double melting peaks in PLLA samples following melt crystallizations at 110 °C for a shorter time (≤30 min) or at a lower temperature (100, 103, or 105 °C) for 120 min, whereas the double lamellar thickness model dominated the formation of the double melting peaks in those PLLA samples crystallized at a higher temperature (108 or 110 °C) for 120 min or at 110 °C for a longer time (≥45 min). © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 466–474, 2007     

Crystallographic report: Bis(norfloxacin)dilead(II) tetranitrate, [Pb2(H‐Norf)2(ONO2)4]

The centrosymmetric binuclear structure of [Pb₂(H‐Norf)₂(ONO₂)₄]shows the geometry around each lead(II) atom to be distorted trigonal bipyramidal with Pb–O distances ranging from 2.357(3) to 2.769(4) Å. Copyright © 2003 John Wiley & Sons, Ltd.     

Trefftz,collocation, and other boundary methods—A comparison

In this article we survey the Trefftz method (TM), the collocation method (CM), and the collocation Trefftz method (CTM). We also review the coupling techniques for the interzonal conditions, which include the indirect Trefftz method, the original Trefftz method, the penalty plus hybrid Trefftz method, and the direct Trefftz method. Other boundary methods are also briefly described. Key issues in these algorithms, including the error analysis, are addressed. New numerical results are reported. Comparisons among TMs and other numerical methods are made. It is concluded that the CTM is the simplest algorithm and provides the most accurate solution with the best numerical stability. © 2006 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq, 2007     

A nodal coupling of finite and boundary elements

This article presents and analyzes a simple method for the exterior Laplace equation through the coupling of finite and boundary element methods. The main novelty is the use of a smooth parametric artificial boundary where boundary elements fit without effort together with a straight approximate triangulation in the bounded area, with the coupling done only in nodes. A numerically integrated version of the algorithm is also analyzed. Finally, an isoparametric variant with higher order is proposed. © 2003 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 19: 555–570, 2003     

Novel aromatic polyamides bearing pendent diphenylamino or carbazolyl groups

Two new diamines, 2,4‐diaminotriphenylamine ( 3 ) and N‐(2,4‐diaminophenyl)carbazole ( 4 ), were synthesized via the cesium fluoride‐mediated aromatic substitution reactions of 1‐fluoro‐2,4‐dinitrobenzene with diphenylamine and carbazole, followed by palladium‐catalyzed hydrazine reduction. Amorphous and soluble aramids having pendent diphenylamino and carbazolyl groups were prepared by the phosphorylation polycondensation of aromatic dicarboxylic acids with diamines 3 and 4 , respectively. The aramids derived from diamine 3 had sufficiently high molecular weights to permit the casting of flexible and tough films. They exhibited excellent mechanical properties and moderately high softening temperatures in the 221–298 °C range. However, the reactions of diamine 4 with aromatic diacids gave relatively lower molecular weights products that could not afford flexible films. For a comparative purpose, the parent aramids derived from m‐phenylenediamine and aromatic diacids were also prepared and characterized. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3302–3313, 2004     

Poly(phenylene vinylene)‐based copolymers containing 3,7‐phenothiazylene and 2,6‐pyridylene chromophores: Fluorescence sensors for acids,metal ions,and oxidation

A novel copolymer, poly(N‐hexyl‐3,7‐phenothiazylene‐1,2‐ethenylene‐2,6‐pyridylene‐1,2‐ethenylene) ( P3 ), containing N‐hexyl‐3,7‐phenothiazylene and 2,6‐pyridylene chromophores was synthesized to investigate the effect of protonation, metal complexation, and chemical oxidation on its absorption and photoluminescence (PL). Poly(N‐hexyl‐3,8‐iminodibenzyl‐1,2‐ethenylene‐1,3‐phenylene‐1,2‐ethenylene) and poly(N‐hexyl‐3,7‐phenothiazylene‐1,2‐ethenylene‐1,3‐phenylene‐1,2‐ethenylene) ( P2 ), consisting of 1,3‐divinylbenzene alternated with N‐hexyl‐3,8‐iminodibenzyl and N‐hexyl‐3,7‐phenothiazylene, respectively, were also prepared for comparison. Electrochemical investigations revealed that P3 exhibited lower band gaps (2.34 eV) due to alternating donor and acceptor conjugated units (push–pull structure). The absorption and PL spectral variations of P3 were easily manipulated by protonation, metal chelation, and chemical oxidation. P3 displayed significant bathochromic shifts when protonated with trifluoroacetic acid in chloroform. The complexation of P3 with Fe³⁺ led to a significant absorption change and fluorescence quenching, and this implied the coordination of ferric ions with the 2,6‐pyridylene groups in the backbone. Moreover, both phenothiazylene‐containing P2 and P3 showed conspicuous PL quenching with a slight redshift when oxidized with NOBF₄. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1272–1284, 2004     

2‐Cyanoprop‐2‐yl dithiobenzoate mediated reversible addition–fragmentation chain transfer polymerization of acrylonitrile targeting a polymer with a higher molecular weight

The reversible addition–fragmentation chain transfer (RAFT) polymerization of acrylonitrile (AN) mediated by 2‐cyanoprop‐2‐yl dithiobenzoate was first applied to synthesize polyacrylonitrile (PAN) with a high molecular weight up to 32,800 and a polydispersity index as low as 1.29. The key to success was ascribed to the optimization of the experimental conditions to increase the fragmentation reaction efficiency of the intermediate radical. In accordance with the atom transfer radical polymerization of AN, ethylene carbonate was also a better solvent candidate for providing higher controlled/living RAFT polymerization behaviors than dimethylformamide and dimethyl sulfoxide. The various experimental parameters, including the temperature, the molar ratio of dithiobenzoate to the initiator, the molar ratio of the monomer to dithiobenzoate, the monomer concentration, and the addition of the comonomer, were varied to improve the control of the molecular weight and polydispersity index. The molecular weights of PANs were validated by gel permeation chromatography along with a universal calibration procedure and intrinsic viscosity measurements. ¹H NMR analysis confirmed the high chain‐end functionality of the resultant polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1272–1281, 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