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The spontaneous reaction of unsaturated double bonds induced by the fragmentation of ether bonds is presented as a method to obtain a crosslinked polymer material. Poly(1,5‐dioxepan‐2‐one) (PDXO) was synthesized using three different polymerization techniques to investigate the influence of the synthesis conditions on the ether bond fragmentation. It was found that thermal fragmentation of the ether bonds in the polymer main chain occurred when the synthesis temperature was 140 °C or higher. The double bonds produced reacted spontaneously to form crosslinks between the polymer chains. The formation of a network structure was confirmed by Fourier transform infrared spectrometry and differential scanning calorimetry. In addition, the low molar mass species released during hydrolysis of the DXO polymers were monitored by ESI‐MS and MALDI‐TOF‐MS. Ether bond fragmentation also occurred during the ionization in the electrospray instrument, but predominantly in the lower mass region. No fragmentation took place during MALDI ionization, but it was possible to detect water‐soluble DXO oligomers with a molar mass up to approximately 5000 g/mol. The results show that ether bond fragmentation can be used to form a network structure of PDXO. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7258–7267, 2008  相似文献   
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We demonstrate that solid materials can be screened directly and without any pretreatment for their potential liberation of chemicals into the surroundings using a hot (150-250 degrees C) sample cell membrane inlet mass spectrometer with electron ionization. Three very different types of solids were tested: polymers (in this context regarded as a solid), tea leaves and pesticide-contaminated soil. From the polymers phthalates and other additives were liberated; from the tea leaves flavor additives and caffeine were liberated; and from the contaminated soil degradation products of 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) were liberated. In all cases we detected characteristic compounds directly from the untreated sample with an analytical turnover of 8-10 samples per hour. Improved selectivity of compounds penetrating the membrane was achieved either by operating the hot cell at different temperatures or by using variations in the time trend of individual ions following insertion of a piece of the solid material into the hot cell.  相似文献   
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In tandem : Employing a molecular dyad and a cobalt‐based electrolyte gives a threefold‐increase in open‐circuit voltage (VOC) for a p‐type NiO device (VOC=0.35 V), and a fourfold better energy conversion efficiency. Incorporating these improvements in a TiO2/NiO tandem dye‐sensitized solar cell (TDSC), results in a TDSC with a VOC=0.91 V (see figure; CB=conductance band, VB= valence band).

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By taking advantage of “click” chemistry's chemoselective nature, a new platform of bifunctional AB2C dendrimers, having acetylene/azide groups anchored within the interior and hydroxy groups on the periphery, has been realized. In their Communication on page 2126 ff. M. Malkoch and co‐workers reveal a simple synthetic route for two sets of frameworks. To illustrate the utility of AB2C dendrimers they were used in a one‐pot postfunctionalization protocol, in the development of dendritic nanoparticles, and in the formation of hydrogels.

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The synthesis and characterization of a new difunctional coupler (4) based on trimethylolpropane (TMP) are described. The coupler is used to connect biologically active N-acetylglucosamine (GlcNAc) on amino-reactive microtiter plates and on star-shaped poly[(ethylene oxide)-stat-(propylene oxide)] hydrogel layers in microtiter plates. The biological activity of immobilized carbohydrates is determined using an enzyme-linked lectin assay.  相似文献   
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A convenient synthesis of (–)-N-styryl-N-[2-(1,7,7-trimethylbicyclo[2.2.1]hept-2-enyl)ethyl]formamide ( 2 ) was developed starting from natural (+)-camphor ( 3 ) via (–)-2-(bornen-2-yl)ethanol ( 6 ). Cyclization of the N-formylenamine 2 with the aid of 9-borabicyclo[3.3.1]non-9-yl triflate yielded a methanobridged octahydro-1H-benzo[d]azepine derivative.  相似文献   
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Highly oriented pyroelectric liquid-crystalline polymers were prepared by photopolymerization under the influence of a static electric field from binary mixtures of two acrylate monomers exhibiting chiral smectic C mesomorphism. Both monomers contained nitro groups to yield second order nonlinear optical properties (second harmonic generation) and one of the monomers had two functional groups to yield a crosslinked polymer. The room temperature second order nonlinear susceptibility of the polymers showed during the first two hours a 10 % decrease after which it remained constant during the next 48 days. At elevated temperatures there was a significant difference in the nonlinear optical properties over time between crosslinked and uncrosslinked polymers. The uncrosslinked polymer showed a pronounced loss of second order nonlinear optical activity with time at ≥38°C. The crosslinked polymer showed a much smaller and basically a temperature independent decrease rate in the second order nonlinear optical properties at all the ageing temperatures (23-130°C). Both the loss in mesogen order parameter, very evident for the uncrosslinked polymer, and conformational changes occurring within the mesogens (β mechanism), may account for the observations made.  相似文献   
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