A post curing strategy toward the feasible covalent adaptable networks in polyacrylate latex films

The implementation of covalent adaptable networks (CANs) in general resin system is becoming attractive. In this work, we propose a simple post-curing strategy based on the core-shell structured acrylate latex for the achievement on both the improved general performance and the CANs characteristics in latex films. The building to the CANs was relied on the introduction of 4,4′-diaminophenyl disulfide as the curing agent, which cured the acetoacetoxy decorated shell polymer through the ketoamine reaction. The metathesis reaction of aromatic disulfides in the crosslinking segments enabled the thermally induced dynamic behavior of the network as revealed in the stress relaxation tests by comparison with other diamine crosslinking agents without the incorporation of disulfide. The synergism of the dynamic crosslinking of the shell polymer and static crosslinking in the core polymer contributed to the improved mechanical strength (15 MPa, strain% = 250%) and the suppressed water adsorption (~1% in 24 h of soaking) of the latex film, which exhibited above 90% of recovery in both strength and strain from a cut-off film damage within 1 h at 80°C. Moreover, the cured latex film could be recycled, and 75% of the mechanical performance was regained after three fragmentation-hot-pressing cycles. These, in addition with the feasible and environmental friendly characteristics, suggest a sustainable paradigm toward the smart thermosetting latex polymers.     

Near-Ultraviolet Circular Dichroism and Two-Dimensional Spectroscopy of Polypeptides

A fully quantitative theory of the relationship between protein conformation and optical spectroscopy would facilitate deeper insights into biophysical and simulation studies of protein dynamics and folding. In contrast to intense bands in the far-ultraviolet, near-UV bands are much weaker and have been challenging to compute theoretically. We report some advances in the accuracy of calculations in the near-UV, which were realised through the consideration of the vibrational structure of the electronic transitions of aromatic side chains.     

Mono-Aryl/Alkylthio-Substituted (Hetero)acenes of Exceptional Thermal and Photochemical Stability by the Thio-Friedel–Crafts/Bradsher Cyclization Reaction

The highly substituted mono-aryl/alkylthio-(hetero)acenes prepared in this study have been found to be thermally more stable (T_decomp.=331–354 °C) than the known di-aryl/alkylthio-substituted acenes by an average of 25 °C. They are also much more photostable at 254 and 365 nm (in both argon and air) than the parent anthracene and other reported anthracenes. The most photostable aryl/alkylthio-anthracenes at 254 nm were found to be 60–70 (in air) and 130 (in argon) times more stable in solution than the unsubstituted anthracene, and much more stable than known EDG/EWG-substituted anthracenes (EDG=electron-donating group, EWG=electron-withdrawing group) with an extended aromatic core. Furthermore, the acenes showed significantly higher photostability at 365 nm in both air and argon. The anthracenes were obtained by the novel thio-Friedel–Crafts/Bradsher cyclization reaction of hitherto unknown [o-(1,3-dithian-2-yl)aryl](aryl)methyl thioethers. The developed approach provides a general access to mono-aryl/alkylthio-substituted (hetero)acene frameworks containing at least three fused (hetero)aromatic rings. The characteristic feature of this approach, which leads to highly substituted acenes, is that the substituents, unlike in other methods, may be introduced at an early stage of the synthesis. DFT and TD-DFT calculations confirmed the stabilizing role of the aryl/alkylthio substituent in the mono-aryl/alkylthio-substituted anthracenes, which are the most stable anthracenes prepared to date. Their high photostability is mainly due to the quenching of singlet oxygen by the acene and the quenching of the acene S₁ state by molecular oxygen.     

Donor-acceptor copolymers from cyclopentannulation polymerizations with dicyclopenta[cd,jk]pyrene and dicyclopenta[cd,lm] perylene acceptors

A series of donor-acceptor copolymers with dicyclopenta[cd,jk]pyrene and dicyclopenta[cd,lm]perylene acceptor units was prepared via palladium catalyzed cyclopenta-annulation reactions. The acceptor units were paired with diethynyl containing donor groups based on benzo[1,2-b:4,5-b’]dithiophene, thieno[3,2-b]thiophene, and 4-octyl-4H-dithieno[3,2-b:2′,3′-d]pyrrole to create six polymer variants. The cyclopentannulation polymerization resulted in copolymers with molecular weights (Mn) of 6–14 kDa and broad light absorption in the visible region with band gaps of 1.38–1.85 eV. The synthetic methodology, as well as optoelectronic properties, including thin-film absorption and cyclic voltammetry, of the donor-acceptor copolymers are presented.     

Preparation of 3-substituted and 2,3-disubstituted-4,4,4-trifluoro-2-butenoic acids—Perkin condensation of activated aromatic ketones

The Perkin reaction of the activated aromatic ketones (2,2,2-trifluoroacetophenone and its 4′-phenyl-derivative) with various condensing agents (acetic anhydride, propionic anhydride, phenylacetic acid/acetic anhydride) gives the title compounds in good or moderate yields, and high E-stereoselectivity. For some derivatives an appreciable amount of the Z isomer was also formed. Several of the resulting butenoic acids and their methyl esters are synthesised and characterised for the first time.     

Magnetic field effect on indole exciplexes: an anomalous dielectric dependence

Individual exciplex formation between various aromatic hydrocarbons, anthracene, pyrene, all-s-trans-1,4-diphenylbuta-1,3-diene and a heteroaromatic amine, 1,2-dimethylindole, was investigated by steady-state fluorescence and magnetic field effect (MFE). A comparative study was carried out with two other exciplex systems 9-cyanophenanthrene-1,2-dimethylindole and 9-cyanophenanthrene-N-methylindole. The extent of charge transfer and dielectric dependence of MFE reveals the potential role of specific interactions related to exciplex geometry.     

Multicyclic polyethers derived from 1,1,1‐tris(4‐hydroxyphenyl)ethane and 2,6‐dihalopyridines

Poly(pyridine ether)s were prepared in two ways: the polycondensation of silylated 1,1,1‐tris(4‐hydroxyphenyl)ethane (THPE) with 2,6‐difluoropyridine (method A) and the polycondensation of free THPE with 2,6‐dichloropyridine (method B). With method A, the THPE/difluoropyridine feed ratio was varied from 1.0:1.0 to 1.0:1.6. Cycles, bicycles, and multicycles were the main reaction products, and crosslinking was never observed. When ideal stoichiometry was used exclusively, multicycles free of functional groups were obtained. These multicycles were detectable in matrix‐assisted laser desorption/ionization time‐of‐flight (MALDI‐TOF) mass spectra up to B₃₈C₇₆ with a mass of approximately 32,000 Da. With method B, the reaction conditions were varied at a fixed feed ratio to achieve an optimum for the preparation of multicyclic polyethers, but because of the lower reactivity of 2,6‐dichloropyridine, a quantitative conversion was not achieved. The reaction products were characterized with MALDI‐TOF mass spectrometry, viscosity measurements, and size exclusion chromatography. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5725–5735, 2004     

Miscible blends of modified poly(aryl ether ketones) with aromatic polyimides

The phase behavior of binary blends of poly(ether ether ketone) (PEEK), sulfonated PEEK, and sulfamidated PEEK with aromatic polyimides is reported. PEEK was determined to be immiscible with a poly(amide imide) (TORLON 4000T). Blends of sulfonated and sulfamidated PEEK with this poly(amide imide), however, are reported here to be miscible in all proportions. Blends of sulfonated PEEK and a poly(ether imide) (ULTEM 1000) are also reported to be miscible. Spectroscopic investigations of the intermolecular interactions suggest that formation of electron donoracceptor complexes between the sulfonated/sulfamidated phenylene rings of the PEEKs and the n-phenylene units of the polyimides are responsible for this miscibility. © 1993 John Wiley & Sons, Inc.     

Feasibility study for the preparation of certified reference materials part I – mineral oil contaminated soils

The international joint project HYCREF (Contract No. G6RD-CT-2002-00854), funded by the European Commission in the 5th Framework programme, aimed to develop methods to prepare homogeneous and stable reference materials of water, soil, and waste contaminated with mineral oil hydrocarbons and to certify the mineral oil content by gas chromatographic methods. The results of a feasibility study for the preparation of three soil reference materials are discussed in this paper, and for the preparation of three waste reference materials in the second part (Koch et al., Accred Qual Assur submitted for publication). The soil materials were selected to represent different soil types and contamination levels. The project plan set three requirements for these reference materials: uncertainty in the mineral oil content resulting from the certification exercise <5%, a sample inhomogeneity of <3% and a minimum long-term stability of 5 years. For the most part, these requirements were met within this project.     

Preparation and catalytic applications of partially fluorinated binaphthol ligands

New partially fluorinated binaphthols were obtained using a copper-catalyzed oxidative coupling. The corresponding enantiomerically pure compounds were prepared by fractional crystallization of the corresponding bis(menthyl)carbamates. Nucleophilic aromatic substitution using oxygen- and carbon-based nucleophiles resulted in functionalized derivatives without concomitant racemization. The titanium(IV) complexes of these ligands are catalytically active in the asymmetric oxidation of sulfides.