Level Density of the Hénon-Heiles System Above the Critical Barrier Energy

We discuss the coarse-grained level density of the Hénon-Heiles system above the barrier energy, where the system is nearly chaotic. We use periodic orbit theory to approximate its oscillating part semiclassically via Gutzwiller’s semiclassical trace formula (extended by uniform approximations for the contributions of bifurcating orbits). Including only a few stable and unstable orbits, we reproduce the quantum-mechanical density of states very accurately. We also present a perturbative calculation of the stabilities of two infinite series of orbits (R_n and L_m), emanating from the shortest librating straight-line orbit (A) in a bifurcation cascade just below the barrier, which at the barrier have two common asymptotic Lyapunov exponents χ_R and χ_L.     

Facile syntheses of surface-functionalized micelles and shell cross-linked nanoparticles

Block copolymer micelles and shell cross-linked nanoparticles (SCKs) presenting Click-reactive functional groups on their surfaces were prepared using two separate synthetic strategies, each employing functionalized initiators for the controlled radical polymerization of acrylate and styrenic monomers to afford amphiphilic block copolymers bearing an alkynyl or azido group at the α-terminus. The first route for the synthesis of the azide-functionalized nanostructures was achieved via sequential nitroxide-mediated radical polymerization (NMP) of tert-butyl acrylate and styrene, originating from a benzylic chloride-functionalized initiator, followed by deprotection of the acrylic acids, supramolecular assembly of the block copolymer in water and conversion of the benzylic chloride to a benzylic azide. In contrast, the second strategy utilized an alkynyl-functionalized reversible addition fragmentation transfer (RAFT) agent directly for the RAFT-based sequential polymerization of tetrahydropyran acrylate and styrene, followed by selective cleavage of the tetrahydropyran esters to give the α-alkynyl-functionalized block copolymers. These Click-functionalized polymers, with the functionality located at the hydrophilic polymer termini, were then self-assembled using a mixed-micelle methodology to afford surface-functionalized “Clickable” micelles in aqueous solutions. The optimum degree of incorporation of the Click-functionalized polymers was investigated and determined to be ca. 25%, which allowed for the synthesis of well-defined surface-functionalized nanoparticles after cross-linking selectively throughout the shell layer using established amidation chemistry. Functionalization of the chain ends was shown to be an efficient process under standard Click conditions and the resulting functional groups revealed a more “solution-like” environment when compared to the functional group randomly inserted into the hydrophilic shell layer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5203–5217, 2006     

Effect of stoichiometry on liquid crystalline supramolecular polymers formed with complementary nucleobase pair interactions

We report herein studies on the liquid crystalline behavior of a series of supramolecular materials that contain different ratios of two complementary symmetrically-substituted alkoxy-bis(phenylethynyl)benzene AA- and BB-type monomers. One monomer has thymine units placed at either end of the rigid mesogenic core, while the other has N⁶-(4-methoxybenzoyl)-adenine units placed on the ends. Differential scanning calorimetric and polarized optical microscopy studies have been carried out on these systems. These studies show that the material's behavior is strongly dependent on its thermal history. As a result, the materials can exhibit, on heating, either a liquid crystalline phase, a crystalline phase, or the coexistence of crystalline and liquid crystalline regions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5049–5059, 2006     

Heterograft copolymers of poly(ε‐caprolactone) prepared by combination of ATRA “grafting onto” and ATRP “grafting from” processes

This paper aims at reporting on the synthesis of a heterograft copolymer by combining the “grafting onto” process based on atom transfer radical addition (ATRA) and the “grafting from” process by atom transfer radical polymerization (ATRP). The statistical copolymerization of ε‐caprolactone (εCL) and α‐chloro‐ε‐caprolactone (αClεCL) was initiated by 2,2‐dibutyl‐2‐stanna‐1,3‐dioxepane (DSDOP), followed by ATRA of parts of the chlorinated units of poly(αClεCL‐co‐εCL) on the terminal double bond of α‐MeO,ω‐CH₂?CH? CH₂? CO₂‐poly(ethylene oxide) (PEO). The amphiphilic poly(εCL‐g‐EO) graft copolymer collected at this stage forms micelles as supported by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The unreacted pendant chloro groups of poly(εCL‐g‐EO) were used to initiate the ATRP of styrene with formation of copolymer with two populations of randomly distributed grafts, that is PEO and polystyrene. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6015–6024, 2006     

Synthesis and antibacterial activities of water‐soluble methacrylate polymers containing quaternary ammonium compounds

New water‐soluble methacrylate polymers with pendant quaternary ammonium (QA) groups were synthesized and used as antibacterial materials. The polymers with pendant QA groups were obtained by the reaction of the alkyl halide groups of a previously synthesized functional methacrylate homopolymer with various tertiary alkyl amines containing 12‐, 14‐, or 16‐carbon alkyl chains. The structures of the functional polymer and the polymers with QA groups were confirmed with Fourier transform infrared and ¹H and ¹³C NMR. The degree of conversion of alkyl halides to QA sites in each polymer was determined by ¹H NMR to be over 90% in all cases. The number‐average molecular weight and polydispersity of the functional polymer were determined by size exclusion chromatography to be 32,500 g/mol and 2.25, respectively. All polymers were thermally stable up to 180 °C according to thermogravimetric analysis. The antibacterial activities of the polymers with pendant QA groups against Staphylococcus aureus and Escherichia coli were determined with broth‐dilution and spread‐plate methods. All the polymers showed excellent antibacterial activities in the range of 32–256 μg/mL. The antibacterial activity against S. aureus increased with an increase in the alkyl chain length for the ammonium groups, whereas the antibacterial activity against E. coli decreased with increasing alkyl chain length. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5965–5973, 2006     

Synthesis and properties of thermosetting polymers from a phosphorous‐containing fatty acid derivative

A new phosphorous‐containing fatty acid diepoxide was obtained from 10‐undecenoyl chloride and 10‐(2′,5′‐dihydroxyphenyl)‐9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide and crosslinked with 4,4′‐diaminodiphenylmethane and bis(m‐aminophenyl)methylphosphine oxide. The properties of the thermosetting materials were evaluated by differential scanning calorimetry, dynamic mechanical thermal analysis, thermogravimetric analysis, and limiting oxygen index (LOI). Thermal and thermooxidative degradation was studied by gas chromatography/mass spectrometry, FTIR, ³¹P magic angle spinning NMR spectroscopy, and scanning electron microscopy. LOI values indicate good flame‐retardant properties that are related to the formation of a protective phosphorous‐rich layer that slowed down the degradation and prevented it from being total. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5630–5644, 2006     

Synthesis and characterization of poly(arylene ether)s containing 6‐(4‐hydroxyphenyl)pyridazin‐3(2H)‐one or 6‐(4‐hydroxyphenyl)pyridazine moieties

A series of novel soluble pyridazinone‐ or pyridazine‐containing poly(arylene ether)s were prepared by a polycondensation reaction. The pyridazinone monomer, 6‐(4‐hydroxyphenyl)pyridazin‐3(2H)‐one ( 1 ), was synthesized from the corresponding acetophenone and glyoxylic acid in a simple one‐pot reaction. The pyridazinone monomer was successfully copolymerized with bisphenol A (BPA) or 1,2‐dihydro‐4‐(4‐hydroxyphenyl)phthalazin‐1(2H)‐one (DHPZ) and bis(4‐fluorophenyl)sulfone to form high‐molecular‐weight polymers. The copolymers had inherent viscosities of 0.5–0.9 dL/g. The glass‐transition temperatures (T_g's) of the copolymers synthesized with BPA increased with increasing content of the pyridazinone monomer. The T_g's of the copolymers synthesized from DHPZ with different pyridazinone contents were similar to those of the two homopolymers. The homopolymers showed T_g's from 202 to 291 °C by differential scanning calorimetry. The 5% weight loss temperatures in nitrogen measured by thermogravimetric analysis were in the range of 411–500 °C. 4‐(6‐Chloropyridazin‐3‐yl)phenol ( 2 ) was synthesized from 1 via a simple one‐pot reaction. 2 was copolymerized with 4,4′‐isopropylidenediphenol and bis(4‐fluorophenyl)sulfone to form high‐T_g polymers. The copolymers with less than 80 mol % pyridazinone or chloropyridazine monomers were soluble in chlorinated solvents such as chloroform. The copolymers with higher pyridazinone contents and homopolymers were not soluble in chlorinated solvents but were still soluble in dipolar aprotic solvents such as N‐methylpyrrolidinone. The soluble polymers could be cast into flexible films from solution. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3328–3335, 2006     

Synthesis and characterization of polyimides derived from (3‐amino‐2,4,6‐trimethylphenyl)‐(3′‐aminophenyl)methanone and aromatic dianhydrides

A series of new polyimides were prepared via the polycondensation of (3‐amino‐2,4,6‐trimethylphenyl)‐(3′‐aminophenyl)methanone and aromatic dianhydrides, that is, 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), 4,4′‐oxydiphthalic anhydride, 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride, and 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride. The structures of the polyimides were characterized by Fourier transform infrared and NMR measurements. The properties were evaluated by solubility tests, ultraviolet–visible analysis, differential scanning calorimetry, and thermogravimetric analysis. The two different meta‐position‐located amino groups with respect to the carbonyl bridge in the diamine monomer provided it with an unsymmetrical structure. This led to a restriction on the close packing of the resulting polymer chains and reduced interchain interactions, which contributed to the solubility increase. All the polyimides except that derived from BPDA had good solubility in strong aprotic solvents, such as N‐methyl‐2‐pyrrolidinone, N,N′‐dimethylacetamide, N,N‐dimethylformamide, and dimethyl sulfone, and in common organic solvents, such as cyclohexanone and chloroform. In addition, these polyimides exhibited high glass‐transition values and excellent thermal properties, with an initial thermal decomposition temperature above 470 °C and glass‐transition temperatures in the range of 280–320 °C. The polyimide films also exhibited good transparency in the visible‐light region, with transmittance higher than 80% at 450 nm and a cutoff wavelength lower than 370 nm. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1291–1298, 2006     

Cyclolinear polysiloxanes. II. Crosslinking and characterization

The synthesis and characterization of two groups of novel networks prepared from cyclolinear polysiloxanes are described. The first group of networks from cyclolinear polysiloxanes (N‐CLPSs) was synthesized by the hydrosilation of vinyl‐terminated cyclolinear polyorganosiloxanes [prepared from diacetoxydiethyltetramethylcyclotetrasiloxane (D₄Et₂OAc₂) or diacetoxytriethylpentamethylcyclopentasiloxane (D₅Et₃OAc₂)] with a copolymer of dimethylsiloxane and methylhydrosiloxane as the crosslinking agent. Hydrosilation was effected with a platinum carbonyl catalyst with a cyclovinylsiloxane moderator. The second group of networks (N‐eCLPSs) was prepared similarly with extended cyclolinear polysiloxanes. The mechanical properties of the novel networks were comparable to those of polydimethylsiloxane networks (N‐PDMS). The oxygen permeabilities were similar to or slightly higher than that of N‐PDMS. The glass‐transition temperatures of D₄Et₂OAc₂‐ and D₅Et₃OAc₂‐based N‐CLPSs were ?67.8 and ?90.8 °C, respectively, whereas the incorporation of polydimethylsiloxane spacers into similar N‐eCLPSs lowered their glass‐transition temperatures to ?109.7 and ?115.0 °C. Upon heating to 800 °C in air, N‐CLPSs yielded more residue than N‐eCLPSs, which in turn yielded more residue than N‐PDMS. These results may have been due to the presence of T units in the cyclic siloxane units, which may have inhibited chain degradation or the formation of volatile products. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4053–4062, 2006