A novel approach to the characterization of end groups in styrene–methyl methacrylate copolymers by pyrolysis–gas chromatography

The end groups of styrene–methyl methacrylate (St‐MMA) copolymers polymerized radically with 2,2′‐azobisisobutyronitrile (AIBN) as an initiator, which are difficult to characterize even by NMR, were investigated by pyrolysis–gas chromatography. On the resulting pyrograms, characteristic products that formed from the end‐group moiety due to AIBN, such as 2‐cyanopropane, 2‐cyanopropen, and various compounds consisting of an isobutyronitrile group and a monomer unit, were observed together with those from the main chain, such as St and MMA monomers and various dimeric and trimeric products. The relative abundance between the recombination and disproportionation termination reactions in the copolymerization process was estimated from the relative intensities between the characteristic peaks of the end group and those of the main chain. Thus, the estimated abundance for the termination reactions suggested that the polymerization process for this particular copolymer system terminated preferentially by recombination rather than by disproportionation. Furthermore, the relative abundance between the monomer units adjacent to the chain‐end AIBN residues was estimated on the basis of the peak intensities of the products consisting of an isobutyronitrile group and either monomer unit, which reflected the penultimate neighboring structure of the end group in the polymer chain. Thus, the observed results suggested that the isobutyronitrile radical formed by the dissociation of AIBN in the initiation reaction was predominantly adjoined by St monomer rather than by MMA monomer. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1880–1888, 2000     

Preparation,structures, and redox and emission characteristics of the isothiocyanate complexes of hexarhenium(III) clusters [Re6(mu3-E)8(NCS)6]4- (E = S,Se)

Hexarhenium(III) complexes with terminal isothiocyanate ligands, [(n-C(4)H(9))(4)N](4)[Re(6)(mu(3)-S)(8)(NCS)(6)] (1) and (L)(4)[Re(6)(mu(3)-Se)(8)(NCS)(6)] (L(+) = PPN(+) (2a), (n-C(4)H(9))(4)N(+) (2b)), have been prepared by three different methods. Complex 1 was prepared by the reaction of [(n-C(4)H(9))(4)N](4)[Re(6)(mu(3)-S)(8)Cl(6)] with molten KSCN at 200 degrees C, while 2b was obtained by refluxing the chlorobenzene-DMF (2:1 v/v) solution of [Re(6)(mu(3)-Se)(8)(CH(3)CN)(6)](SbF(6))(2) and [(n-C(4)H(9))(4)N]SCN. The [Re(6)(mu(3)-Se)(8)(NCS)(6)](4)(-) anion was also obtained from a mixture of Cs(2)[Re(6)(mu(3)-Se)(8)Br(4)] and KSCN in C(2)H(5)OH by a mechanochemical activation at room temperature for 20 h and isolated as 2a. The X-ray structures of 1 and 2a.4DMF have been determined (1, C(70)H(144)N(10)S(14)Re(6), monoclinic, space group P2(1)/n (No. 14), a = 14.464(7) A, b = 22.059(6) A, c = 16.642(8) A, beta = 113.62(3) degrees, V = 4864(3) A(3), Z = 2; 2a.4DMF, C(162)H(144)N(14)O(4)P(8)S(6)Se(8)Re(6), triclinic, space group P1 (No. 2), a = 15.263(2) A, b = 16.429(2) A, c = 17.111(3) A, alpha = 84.07(1) degrees, beta = 84.95(1) degrees, gamma = 74.21(1) degrees, V = 4098.3(8) A(3), Z = 1). All the NCS(-) ligands in both complexes are coordinated to the metal center via nitrogen site with the Re-N distances in the range of 2.07-2.13 A. The redox potentials of the reversible Re(III)(6)/Re(III)(5)Re(IV) process in acetonitrile are +0.84 and +0.70 V vs. Ag/AgCl for [Re(6)(mu(3)-S)(8)(NCS)(6)](4)(-) and [Re(6)(mu(3)-Se)(8)(NCS)(6)](4)(-), respectively, which are the most positive among the known hexarhenium complexes with six terminal anionic ligands. The complexes show strong red luminescence with the emission maxima (lambda(max)/nm), lifetimes (tau(em)/micros), and quantum yields (phi(em)) being 745 and 715, 10.4 and 11.8, and 0.091 and 0.15 for 1 and 2b, respectively, in acetonitrile. The data reasonably well fit in the energy-gap plots of other hexarhenium(III) complexes. The temperature dependence of the emission spectra and tau(em) of 1 and [(n-C(4)H(9))(4)N](4)[Re(6)(mu(3)-S)(8)Cl(6)] are also reported.     

Reactivity and Structural Properties of a Mechanochemically Treated Ag2O-V2O5 System in Relation to AgVO3 Polymorphs

Formation and chemical properties of amorphous AgVO₃, which was prepared by mechanochemical treatment of an Ag₂O-V₂O₅ mixture, and crystalline AgVO₃ were studied in relation to AgVO₃ polymorphs. A ball-milled sample of the mixture was assigned as a highly deformed β-AgVO₃ rather than the low density phase α-AgVO₃. Crystalline α-AgVO₃ and β-AgVO₃ were converted into deformed β-AgVO₃ by ball milling, which produced a clear change. δ-AgVO₃ is resistant to mechanical treatment and its structure was not markedly affected. The dissolved chemical species from the ball-milled sample precipitates to form α-AgVO₃ without a seeding crystal, but other polymorphs deposit if they are present; i.e., β-AgVO₃ and δ-AgVO₃ grow on the seeding crystal.     

Aurilide, a cytotoxic depsipeptide from the sea hare Dolabella auricularia: isolation, structure determination, synthesis, and biological activity

The bioassay-guided fractionation of the cytotoxic constituents of the Japanese sea hare Dollabella auricularia led to the isolation of aurilide (1), a 26-membered cyclodepsipeptide. The gross structure of 1 was established by spectroscopic analysis including 2D NMR techniques. The absolute stereostructure was determined by chiral HPLC analysis of acid hydrolysates of 1 and by the enantioselective synthesis of a degradation product arising from a dihydroxylated fatty acid portion. The enantioselective synthesis of 1 was achieved in 12% overall yield (16 steps) and confirmed the absolute stereostructure of 1. The cytotoxicity of 1 was evaluated using a synthetic sample, which was found to exhibit potent cytotoxicity against HeLa S₃ cells with an IC₅₀ of 0.011 μg/mL. Further biological and pharmacological studies of 1 have been carried out by using synthetic 1.     

Novel chiral selectors anchored on polydimethylsiloxane as stationary phases for separation of derivatized amino acid enantiomers by capillary gas chromatography

Six chiral selectors of S-(-)-t-Leu-cyclopropylamide, S-(-)-t-Leu-cyclopentylamide, S-(-)-t-Leu-cyclohexylamide, S-(-)-t-Leu-cycloheptylamide, S-(-)-t-Leu-cyclooctylamide, S-(-)-t-Leu-cyclododecylamide have been prepared and anchored individually through amide bonding to a polydimethylsiloxane functionalized with 2,2,2-trifluoroethyl ester groups by way of nucleophilic displacement reaction. The resulting chiral polysiloxanes have been provided as stationary phases for the separation of amino acid enantiomers by capillary GC. Amino acids were derivatized into N(O)-trifluoroacetyl isopropyl esters. Especially, polydimethylsiloxane anchored with S-(-)-t-Leu-cyclooctylamide was found to be efficient for the separation of aspartic acid (Asp) enantiomers. The method was applied to the estimation of ages from the extent of Asp racemization in human dentines.     

Modeling of the elementary gas-phase reaction during chemical vapor deposition of silicon carbide from CH3SiCl3/H2

We established a gas-phase, elementary reaction model for chemical vapor deposition of silicon carbide from methyltrichlorosilane (MTS) and H₂, based on the model developed at Iowa State University (ISU). The ISU model did not reproduce our experimental results, decomposition behavior of MTS in the gas phase in an environment with H₂. Therefore, we made several modifications to the ISU model. Of the reactions included in existing models, 236 were lacking in the ISU model, and thus were added to the model. In addition, we modified the rate constants of the unimolecular reactions and the recombination reactions, which were treated as a high-pressure limit in the ISU model, into pressure-dependent rate expressions based on the previous reports (to yield the ISU+ model), for example, H₂(+M) → H + H(+M), but decomposition behavior remained poorly reproducible. To incorporate the pressure dependencies of unimolecular decomposition rate constants, and to increase the accuracies of these constants, we recalculated the rate constants of five unimolecular decomposition reactions of MTS using the Rice-Ramsperger-Kassel-Marcus method at the CBS-QB3 level. These chemistries were added to the ISU+ model to yield the UT2014 model. The UT2014 model reproduced overall MTS decomposition. From the results of our model, we confirmed that MTS mainly decomposes into CH₃ and SiCl₃ at the temperature around 1000°C as reported in the several studies.     

Roles of metal nanoparticles on organosulfur-conducting polymer composites for lithium battery with high energy density

Ag nanoparticles were added to DMcT-PAn composites to improve charge-discharge performance of the composites as a cathode material for lithium rechargeable batteries. Addition of Ag nanoparticles successfully enhanced the redox activity of the composites, possibly due to electrocatalytic activity of the nanoparticles. Increased conductivity of the composite films could be another possible origin for the enhanced redox activity. UV/vis spectroscopic analysis suggested strong interactions between DMcT and nanoparticles, while only weak interactions were observed between PAn and nanoparticles. XPS measurements further confirmed the interactions between DMcT and Ag nanoparticles based on a signal indicative of a silver-sulfur bond.     

Dynamic headspace analysis of trace volatile components in polymeric materials by wide bore capillary gas chromatography

A novel dynamic headspace gas chromatographic system equipped with a wide bore capillary column was constructed for direct analysis of less volatile components in polymeric materials such as coating paints. With this system, the determination of typical paint additives such as hindered amine light stabilizers and ultraviolet absorbers could be carried out within a short time.     

Solution viscosity behavior of polystyrene-based cationic ionomers. Effects of ion content and solvent

Dilute-solution viscosities of polystyrene-based cationic ionomers containing ammonio or phosphonio groups were measured in several solvents. In polar solvents with dielectric constant (ε_r) beyond 10, the ionomers showed a typical polyelectrolyte behavior, indicating that a large part of ionic groups were dissociated into ions. In nonpolar solvents with low ε_r, the reduced viscosity of the ionomers linearly decreased with a decreasing ionomer concentration. At low polymer concentrations, every ionomer gave a reduced viscosity lower than that of the corresponding chloromethylated polystyrene. With an increasing ion content, the intrinsic viscosity progressively decreased if the nonpolar solvents had a low acceptor number (A_N), such as toluene or tetrahydrofran (THF). In the halogenated solvents with high A_N value, such as chloroform, however, the intrinsic viscosity was hardly dependent on the ion content. This indicates that the intramolecular aggregation among the ionic groups is inhibited in the halogenated solvents due to a strong anion solvation. An addition of a protic solvent to a nonpolar solvent eliminates the aggregation between ionic groups and leads to polyelectrolyte behavior. © 1994 John Wiley & Sons, Inc.