Postmodification of poly(9‐alkyl‐9H‐carbazole‐2,7‐diyl)s as a route to new main‐chain‐functionalized carbazole polymers

The postmodification of poly[9‐(2‐hexyldecyl)‐9H‐carbazole‐2,7‐diyl] ( P1 ) upon its reaction with N‐bromosuccinimide affords exclusive and full bromination of the 3,6‐positions of the carbazole repeat units to yield poly[3,6‐dibromo‐9‐(2‐hexyldecyl)‐9H‐carbazole‐2,7‐diyl] ( P2 ). Brominated polymer P2 can be used as a precursor for further functionalization at the 3,6‐positions with the desired functional group to afford other useful polymers. Polymer P2 has hence been reacted with copper(I) cyanide to afford poly[3,6‐dicyano‐9‐(2‐hexyldecyl)‐9H‐carbazole‐2,7‐diyl] ( P3 ). Full substitution of the bromide groups with nitrile‐functional groups has been achieved. The preparation and structural characterization of polymers P2 and P3 are presented together with studies on their electronic conjugation and photoluminescence properties. Cyclic voltammetry studies on polymer P3 indicate that the new polymer is easier to reduce (n‐dope) but more difficult to oxidize than its unsubstituted counterpart ( P1 ) as a result of the introduction of the electron‐withdrawing nitrile‐functional groups at the 3,6‐positions on the carbazole repeat units on the polymer chains. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3336–3342, 2006     

Synthesis of A2B star block copolymers from a heterotrifunctional initiator

We described the obtention of A₂B star block copolymers through the use of a new heterotrifunctional initiator. That way, well‐defined (PCL)₂‐arm‐PtBuMA and (PCL)₂‐arm‐PS star block copolymers have been synthesized from a heterotrifunctional initiator bearing two hydroxyl groups able to initiate ROP of CL (with AlEt₃ or Sn(Oct)₂ as coinitiator) and a bromide function able to initiate ATRP of tBuMA or styrene. Firstly, we have proceeded using a sequential process (two‐steps), leading to an intermediate macroinitiator. Secondly, attempt to polymerize these two monomers in a simultaneous process (one‐step), that is directly from the mixture of monomers, initiator, coinitiators, and solvent, has been realized and has shown that some interferences between the two polymerizations occurred, leading to an inhibition of ATRP when Sn(Oct)₂ was used and an unexpected increase in control when AlEt₃ was used as catalyst for the ROP (obtention of well‐defined (PCL)₂‐arm‐PtBuMA with pdi of 1.18). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1796–1806, 2006     

Practical syntheses of [1,3,5]‐triazine dendritic molecules on solid supports

A practical and divergent synthesis of supported [1,3,5]‐triazine dendritic molecules on Wang resin, PEGA resin, SynPhase? Lanterns, and silica gel is described. The alkylamine linkers used allow derivatization with functionality for both synthetic (e.g., supported reagent and scavenger activity) and chemical biology applications. The use of supported intermediates allows differentiation of symmetric linkers without the need for protecting group chemistry. The synthetic route uses inexpensive, readily available starting materials in a straightforward and scaleable strategy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2248–2259, 2006     

Random multiblock poly(ester amide)s containing poly(L‐lactide) and cycloaliphatic amide segments: Synthesis and biodegradation studies

Novel multiblock poly(ester amide)s containing poly(L ‐lactide) and cycloaliphatic amide segments were synthesized from telechelic oligomer of α,ω‐hydroxyl terminated poly(L ‐lactide), 1,3‐cyclohexylbis(methylamine), and sebacoylchloride by the “two‐step” interfacial polycondensation method. The blocky nature of PEAs was established by FTIR and ¹H NMR spectroscopies. The effect of relative content of ester and amide segments on the crystallization nature of PEAs was investigated by WAXD and DSC analyses. PEAs having lower content of PLLA, PEA 1 and PEA 2, showed a crystallization pattern analogous to polyamides, whereas PEA 3, having higher content of PLLA, showed two crystalline phases characterized by polyester and polyamide segments. Random nature of PEAs was observed from single T_g values. Biodegradation studies using the enzyme lipase from Candida Cylindracea showed higher degradation rate for PEA 3 than that for PEA 1 and PEA 2. FTIR, ¹H NMR, and DSC analyses of the degraded products indicated the involvement of ester linkages in the degradation process. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3250–3260, 2006     

Effect of excess halide on the palladium‐catalyzed insertion‐triggered radical copolymerization of methyl acrylate and 1‐hexene

[Pd₂(μ‐Cl)₂(C₆F₅)₂(tht)₂] ( 1 ) is a very efficient initiator of the radical polymerization of methyl acrylate, but it is not active in the polymerization of methyl methacrylate or in the copolymerization with 1‐hexene. The addition of an excess of NBu₄Cl to solutions of [Pd₂(μ‐Cl)₂(C₆F₅)₂(tht)₂] ( 1 ) provides an initiator system that copolymerizes methyl acrylate and 1‐hexene by an insertion‐triggered radical mechanism. Random copolymers are obtained with 11% incorporation of 1‐hexene in moderate yields (about 35%). Studies of the decomposition products obtained after the first insertion of methyl acrylate in the Pd? C₆F₅ bond of 1 show that the addition of excess halide in the presence of monomer favors the homolytic cleavage of the Pd? C bond, and the generation of the radicals that are active species in the polymerization, versus alternative evolution pathways. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5682–5691, 2006     

Grafting of silica during the processing of silica‐filled SBR: Comparison between length and content of the silane

The treatment of nanoscopic silica grafted in the blend during the processing of silica‐filled styrene butadiene rubber was performed with silane, introduced at different concentrations, or at a constant concentration with a given length of alkyl chain. From swelling measurements in water and in solvent, the maximum silane content that can be grafted has been calculated as a function of the length of the silane alkyl chains as well as their efficiency to cover the silica surface. The found values are close to the values found in the literature for grafting in solution. Moreover, a direct correspondence between the length of the silane alkyl chains and their concentration has been deduced. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 143–152, 2006     

Metallocene copolymers of propene and 1‐hexene: The influence of the comonomer content and thermal history on the structure and mechanical properties

The relationships between the structure and properties have been established for copolymers of propylene and 1‐hexene synthesized with an isotactic metallocene catalyst system. The most important factor affecting the structure and properties of these copolymers is the comonomer content. The thermal treatment, that is, the rate of cooling from the melt, is also important. These factors affect the thermal properties, the degree of crystallinity, and therefore the structural parameters and the viscoelastic behavior. A slow cooling from the melt favors the formation of the γ phase instead of the α modification. Regarding the viscoelastic behavior, the β relaxation, associated with the glass‐transition temperature, is shifted to lower temperatures and its intensity is increased as the 1‐hexene content raises. The microhardness values are correlated with those of the storage modulus deduced from dynamic mechanical thermal analysis curves, and good linear relations have been obtained between these parameters. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1253–1267, 2006     

Minicolumn field sampling--preconcentration of trace zinc from seawater and its laboratory detection by flow injection flame atomic absorption spectrometry.

A simple field sampling-preconcentration method for zinc determination in seawater is described. Seawater was collected in situ by pumping it through a minicolumn packed with a chelating resin (Chelite P) connected to a field flow preconcentration system (FFPS). These packed minicolumns retain the dissolved zinc, and once are loaded with the analyte, they are returned to the laboratory where they are sequentially inserted into a flow injection system for on-line zinc elution with diluted hydrochloric acid and flame atomic absorption spectrometric detection. A factorial design has been used to optimize the FFPS and the flow injection elution process. The proposed method has a linear calibration range from 0.07 to at least 9.4 microg L(-1) of zinc, with a detection limit of 0.02 microg L(-1) and a throughput of 26 samples h(-1). Validation was carried out against certified reference water samples. This procedure has been successfully applied to the determination of Zn in seawater samples from Galicia (Spain).     

Volumetric and refractive properties of binary mixtures containing 1,3-dioxolane and isomeric chlorobutanes

The relation between refractive index deviations and excess volumes for binary mixtures formed by a cyclic ether and a haloalkane has been tested using several methods: refractive index mixing rules and equations of state. Refractive index deviations, excess volumes and molar refractions have been calculated from experimental data of refractive indices and densities at two temperatures 298.15 and 313.15 K. Results obtained have been discussed in terms of intermolecular interactions. Refractive indices were compared with those predicted by several mixing rules. Excess volumes have also been correlated using several cubic equations of state and finally a relation between parameter b from equations of state and molar refraction has been provided.     

Methods in carbon K-edge NEXAFS: Experiment and analysis

Near-edge X-ray absorption spectroscopy (NEXAFS) is widely used to probe the chemistry and structure of surface layers. Moreover, using ultra-high brilliance polarised synchrotron light sources, it is possible to determine the molecular alignment of ultra-thin surface films. However, the quantitative analysis of NEXAFS data is complicated by many experimental factors and, historically, the essential methods of calibration, normalisation and artefact removal are presented in the literature in a somewhat fragmented manner, thus hindering their integrated implementation as well as their further development. This paper outlines a unified, systematic approach to the collection and quantitative analysis of NEXAFS data with a particular focus upon carbon K-edge spectra. As a consequence, we show that current methods neglect several important aspects of the data analysis process, which we address with a combination of novel and adapted techniques. We discuss multiple approaches in solving the issues commonly encountered in the analysis of NEXAFS data, revealing the inherent assumptions of each approach and providing guidelines for assessing their appropriateness in a broad range of experimental situations.