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.     

The effect of olefinic terminal chains on the mesomorphic properties of 4,4'-disubstituted diphenyldiacetylenes

New diphenyldiacetylenes of the type with A, B = H and/or F; m = 0, 1; n = 1-4; and X = C n H 2n + 1 , F, CF 3 or CN were synthesized and their mesomorphic properties determined by hot stage polarizing microscopy and DSC. When m = 0, all of these compounds showed only a nematic phase except when X = CF 3 when both nematic and smectic A phases were seen. Both clearing and melting temperatures were higher than those reported for substitution with the corresponding alkyl chains but the much larger increase in clearing temperatures produced considerably wider nematic phases. Eutectic mixtures of a few of these olefins yielded nematic materials also having much wider temperature ranges and higher clearing temperatures than the eutectic mixtures of the alkyl compounds, while retaining their high birefringence and low viscosities. Such materials are of interest for beam-steering devices.

Four of the diacetylenes with m = 1 ( A, B = H) were also prepared ( X = C 6 H 13 , F, n = 2, 3). When X was C 6 H 13 ( n = 2), the nematic range was smaller in the 2- than in the 1-olefin but wider than in the alkyl series. When X = F, either no nematic phase or a monotropic one was observed, whereas the 1-olefins gave a much wider nematic phase. Both transition temperatures were lower than those for the corresponding 1-olefin and alkyl analogues. The compound with X = C 6 H 13 and n = 2 had a melting temperature below room temperature.     

Preparation of enantiomerically pure (R)-2-butyryloxymethylglycidol by lipase-catalyzed asymmetric hydrolysis

Optically active epoxy alcohol, (R)-2-butyryloxymethylglycidol3 which is the precursor of a tert-alcohol chiral building block was obtained in high enantiomeric purity, 98.7% e.e., by lipase-catalyzed asymmetric hydrolysis using a phosphate buffer and organic co-solvent system in 95% of chemical yield.     

Separation of screw-sensed particles in a homogeneous shear field

The Stokes motions of three-dimensional screw-sensed slender particles in a homogeneous shear field are investigated, including the effects of buoyancy. Conclusions are drawn about the possibility of achieving a separation of mixtures of right- and left-handed particles. The linearity of the Stokes equations allows complex flows to be solved by adding the effects of the several terms which describe the flow in which the particle is immersed. The homogeneous shear flow considered here consists of three such terms; solutions for a series of 12 unit motions are sufficient to determine the hydrodynamic resistance tensors. The forces and torques experienced by screw-sensed particles are calculated from these 51 resistance tensors, using slender-filament theory. The results allow an estimate of the range of buoyancy parameters for which gravitational sedimentation can be neglected. The fundamental component of the particle motion is a rotation, at approximately the same angular velocity as that of the fluid. Superimposed on this are variations, of large period, in the particle orientation. A phase plane analysis is used to find the terminal orientations. Very long calculation times are required for the phase portrait. An approximate method based on azimuthally-averaged equations is developed to avoid the requirements for long time integration.     

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