X-ray diffraction analysis of four perfluorinated homophthalic (2-carboxymethylbenzoic) acids is carried out. In the crystals of 2-carboxymethyl-3,4,5,6-tetrafluorobenzoic acid (1) the chains (1D architecture) form with the usual dimeric carboxylic C(O)OH
O(HO)C synthon. The aromatic carboxylic group is disordered in the ratio 0.58:0.42 over two positions. In the crystals of 2-(carboxydifluoromethyl)-3,4,5,6-tetrafluorobenzoic (2) and 2-(1-carboxy-2,2,2-trifluoroethyl)-3,4,5,6-tetrafluorobenzoic acids (3) the layers (2D architecture) with dimeric and chain-like synthons C(O)OH...O(HO)C are found. In the crystals of 2-[methoxycarbonyl(difluoromethyl)]-3,4,5,6-tetrafluorobenzoic acid (4) only dimers (0D architecture) form with the chain synthon that incorporates both an ester and a carboxylic group. In the crystals of 1 and 2 intermolecular H-O...π interactions, in the crystals of 4 C-F...π interactions, and in 3 both types of interactions are observed.
Poly (4-styrenesulfonate) (PSS) templated polyaniline-carboxymethyl cellulose blend forming stable aqueous colloidal suspensions was prepared through simple synthesis. Morphology of the spin-coated films obtained from different concentrations of colloidal suspensions was studied through atomic force microscopy (AFM). The AFM images were found to be drastically altered at lower concentrations showing a regular network-like structure. Room-temperature surface resistivity for the network featured spin-coated film showed semiconducting behavior. This indicates the efficacy of dilution as a new design element for network structures, further exhibiting resistivity. 相似文献
Hydrophilic behaviour of carrageenan macroalgae biopolymer, due to hydroxyl groups, has limited its applications, especially for packaging. In this study, macroalgae were reinforced with cellulose nanofibrils (CNFs) isolated from kenaf bast fibres. The macroalgae CNF film was after that treated with silane for hydrophobicity enhancement. The wettability and functional properties of unmodified macroalgae CNF films were compared with silane-modified macroalgae CNF films. Characterisation of the unmodified and modified biopolymers films was investigated. The atomic force microscope (AFM), SEM morphology, tensile properties, water contact angle, and thermal behaviour of the biofilms showed that the incorporation of Kenaf bast CNF remarkably increased the strength, moisture resistance, and thermal stability of the macroalgae biopolymer films. Moreover, the films’ modification using a silane coupling agent further enhanced the strength and thermal stability of the films apart from improved water-resistance of the biopolymer films compared to unmodified films. The morphology and AFM showed good interfacial interaction of the components of the biopolymer films. The modified biopolymer films exhibited significantly improved hydrophobic properties compared to the unmodified films due to the enhanced dispersion resulting from the silane treatment. The improved biopolymer films can potentially be utilised as packaging materials. 相似文献
Hybrid nanocomposites were constructed based on colloidal nanofibrillar hydrogels with interpenetrating supramolecular hydrogels, displaying enhanced rheological yield strain and a synergistic improvement in storage modulus. The supramolecular hydrogel consists of naphthyl‐functionalized hydroxyethyl cellulose and a cationic polystyrene derivative decorated with methylviologen moieties, physically cross‐linked with cucurbit[8]uril macrocyclic hosts. Fast exchange kinetics within the supramolecular system are enabled by reversible cross‐linking through the binding of the naphthyl and viologen guests. The colloidal hydrogel consists of nanofibrillated cellulose that combines a mechanically strong nanofiber skeleton with a lateral fibrillar diameter of a few nanometers. The two networks interact through hydroxyethyl cellulose adsorption to the nanofibrillated cellulose surfaces. This work shows methods to bridge the length scales of molecular and colloidal hybrid hydrogels, resulting in synergy between reinforcement and dynamics. 相似文献
Arsenic is a type 1 carcinogen and its toxicity is critically dependent on chemical speciation. However, after decades of research, the biogenesis of at least fifty naturally occurring arsenic species is still not well understood.Here, based on experimental work, it is proposed a set of pathways for the formation of multiple arsenic species that might help to clarify the present situation.These are focused on the thiol protein arsenic bond and on its interaction with reactive metabolites. In fact, arsenic bound to glutathione interacting with sulfur adenosyl methionine (SAM), MethylCB12 and AdoCB12, forms a number of complexes that might be key intermediates in arsenic biochemistry. These include dimethylarsino glutathione (DMAG) m/z 412 [M + H]+, synthesized non-enzymatically from glutathione and cacodylate. Trimethylarsonio glutathione (TMAG) m/z 426 [M]+ synthesized from DMA, GSH and SAM, apparently by a classical Challenger methylcarbonium attack. Tetramethyl arsonium ion m/z 135 [M]+ is formed in a third step, apparently by carbanion methylation. The presence of trimethylarsine oxide (TMAO) m/z 137 [M + H]+ is attributed to the hydrolysis of TMAG or TMA, or to carbanion methylation of dimethylarsinoyl glutathione (m/z 428 [M]+) formed from cacodylate and GSH. Cantoni type attacks of DMAG on SAM were unsuccessful, eventually due to competition of the trivalent S+ atom of SAM for the AsIII atom attack. The presence of dimethylarsonio diglutathione (DMADG m/z 717 [M]+), is suggested to result from a GS- attack on dimethylarsenoyl glutathione (m/z 428 [M + H]+). The presence of dimethylarsenoyladenosine (m/z 372 [M + H]+), trimethylarsenosugar adenine (m/z 370 [M]+), and dimethylthioarsenosugar adenine (m/z 388 [M + H]+), is explained by the synthesis of the pecursor dimethylarsonio-adenosine glutathione DMAAG (m/z 661 [M]+), a likely source of oxo-and trimethylated arsenosugars, as well as of thio-arsenosugars by the cleavage of its S-C bond. The results gathered suggest that cell vacuoles might play a major role in arsenic metabolism, and that the dominance of oxo-As sugars, in algae extracts, may be supported by a mechanism of synthesis independent of DMAAG (m/z 661).They also offer an explanation for the reason why arsenobetaine, and tetramethylarsonium are loosely bound to biotic tissues. Four arsenic species new to science, to the best of our knowledge, and a number of known arsenic compounds were synthesized in this work, identified by HPLC–ESI-MSn and FTICR–ESI-MS, and suggestions regarding their mechanisms of synthesis were advanced. These results provide a framework for arsenic biochemistry which may explain the origin of a significant part of arsenic known metabolites. 相似文献