Hydrolytic degradation of cellulose was shown to take place during the activation procedure in distilled water during the dissolution procedure of cellulose samples from papers for size-exclusion chromatography analyses in the lithium chloride-N,N-dimethylacetamide (DMAc) solution system. The use of dilute aqueous sodium hydroxide solution in the activation procedure prevents hydrolytic degradation of cellulose during the dissolution procedure, especially in the case of samples of aged papers with low pH. The use of the freeze-drying technique provides samples of cellulose ready-made for dissolution in lithium chloride-N,N-dimethylacetamide solution. 相似文献
Ethylene and different amounts of 1,7-octadiene were copolymerized using the metallocene catalyst system ethylidene-bis(fluorenyl) zirconium dichloride and methylaluminoxane (MAO) at both 50 and 90 °C. The catalyst activity has slightly increased with the addition of low amounts of the diene in relation to the homopolymerization of ethylene. The obtained polymers were characterized according to their melting temperature (Tm) and crystallinity degree (xc) by differential scanning calorimetry (DSC). Weight-average molecular weight (Mw) and polydispersity were determined by gel permeation chromatography (GPC). Diene contents in the copolymer were obtained through the FTIR spectroscopy. The results indicated that at polymerization temperature of 90 °C, crosslinking bonds in the obtained copolymers were low, differently from what was observed at 50 °C. The diene content in the copolymer achieved more than 3 mol% and the comonomer conversion was around 15%. Moreover, the obtained copolymers have Mw around 100,000 and large polydispersity. 相似文献
The synthesis and characterization of two dinuclear ruthenium polypyridyl complexes based on the bridging ligands 5,5'-bis(pyridin-2' '-yl)-3,3'-bis(1H-1,2,4-triazole) and 5,5'-bis(pyrazin-2' '-yl)-3,3'-bis(1H-1,2,4-triazole) and of their mononuclear precursors are reported. The dinuclear compounds have been prepared by a Ni(0) catalyzed coupling of a mononuclear ruthenium(II) polypyridyl complex containing a brominated triazole moiety. Electrochemical and photophysical studies indicate that, in these dinuclear complexes, the protonation state of the bridge may be used to tune the intercomponent interaction between the two metal centers and that these species act as proton driven three-way molecular switches that can be read by electrochemical or luminescence techniques. 相似文献
The non-linear dielectric effect has been studied for acetone and acetophenone, and their solutions in benzene. With the NDE results obtained in this work and the dielectric polarization calculated from literature values of the permittivity, density and refractive index, the mean values of the square and the fourth power of the dipole moment were calculated. Assuming dipolar association of the acetone and acetophenone molecules to be restricted to dimerization, the Gibbs free energy ΔGo of the dimerization process is determined. 相似文献
The sulfonation of polyaniline (PANI) films by nucleophilic addition of sulfite ion has been controlled through the polymer oxidation state under electrochemical control. The process was monitored by in situ electrochemical quartz crystal microbalance (EQCM), and the polymer oxidation was accomplished by electrode potential steps in sulfite aqueous solutions. The nucleophilic addition of sulfite to PANI only takes place on the oxidized polymer. From the ratio of added mass to the injected charge, the degree of sulfonation has been obtained with a yield as high as 50%. It has been observed that the ion-exchange mechanism during the oxidation-reduction process in the resulting sulfonated polymer is analogous to the polymer produced by electrophilic sulfonation of polyaniline or by copolymerization of aniline with aminosulfonic acids, unlike the ionic exchange observed for unmodified PANI. 相似文献
Conformational analysis of nucleosides may have direct applications to the structure–activity relationship (SAR) studies and in the design of new drug candidates. Although conformational analysis may be accessed in many different ways, in this work it was performed using molecular dynamics (MD) simulation in order to study the dynamic behavior of a nucleoside derivative of 1,4-dihydro-4-oxoquinoline-3-carboxylic acid, synthesized by our group as a potential antiviral agent. The MD simulation was carried out during 10 ns in vacuum and in a box of water at two different temperatures (i.e., 300 and 600 K) using the AMBER force field. The in vacuum MD simulation results are in agreement with the crystallographic structure and with the DFT calculations of the nucleoside, revealing the anti conformer as the more stable one. The simulation in water, however, shows that both conformers may exist at 300 K, the temperature of the in vivo and in vitro assays, revealing that both the syn and anti conformers should be considered in a MD simulation study of the inhibitor–enzyme complex. Simulations are also in agreement with the NOE experiment, which shows that the anti conformer is the preferential one in DMSO-d6 solution at 298 K. 相似文献
Tissue furnish optimization plays a key role in enhancing tissue properties, making the process cost-effective. Typically, this furnish is composed of a mixture of hardwood eucalyptus fibers (HW) and softwood (SW) fibers, which ensure strength and tissue machine runnability. However, the tissue paper production with the maximization of eucalyptus fibers achieves softer papers at less cost, since SW fibers are often more expensive than HW fibers. From this perspective, this study aims to investigate the effect of micro/nano-fibrillated cellulose (MFC/NFC) as an additive, on structural, softness, strength, and water absorption properties of tissue papers, promoting partial or total removal of SW fibers to produce 100% eucalyptus materials. MFC/NFC was characterized in terms of morphological, chemical, and water interaction properties. The results showed that MFC/NFC presents a high bonding surface area, high carboxyl group content and, when incorporated into tissue furnishes, it promotes strong inter-fiber bonds. This evidence was also supported by SEM image analysis methods and FTIR. Additionally, laboratory tissue handsheets with low basis weight were produced and used in the characterization assays. Overall, the results indicated that MFC/NFC improved strength, at the expense of bulk, porosity, softness, and absorption properties. Compared to typical industrial furnish mixtures (75%HW?+?25%SW), MFC/NFC enhanced the production of bulkier, porous, and softer structures, but with reduced strength and absorption. It was possible to optimize the furnish composition by using fiber modeling to obtain 3D structure computation simulations with predictive capability. The MFC/NFC proved to be a high-quality additive to improve softness and strength properties.
Pyrroles are powerful nucleophiles in the reaction with dialkyl sulfoxides and trimethylchlorosilane (TMCS) or trimethylbromosilane (TMBS), affording sulfonium salts or halo derivatives, generally in good yields. 相似文献
The conduction mechanism in microcrystalline cellulose (MCC) tablets at varying relative humidity (RH) has been investigated by using the techniques of low frequency dielectric spectroscopy and transient current analysis at room temperature. The dependence on RH on the measured conductivity and charge carrier density indicates that a high-power-law-exponent percolation process of cations being conducted on water molecules occupying available 6-OH units on the cellulose chains is the dominating dc conduction mechanism at RH below 3 wt % of moisture content. The experimentally observed decrease in charge carrier mobility with increasing moisture content shows that protons and H3O+ ions that are being blocked at empty 6-OH sites also contribute to the charge transport process in cellulose at low moisture contents. 相似文献
Androst-4-ene-3,17-dione (1) and 17alpha-methyltestosterone (2) are dimerized in the solid-state by UV radiation. These substances were selected by a search in the CSD among the steroid enones presenting in the crystalline state an intermolecular short contact between a hydrogen alpha to a carbonyl group and the oxygen of an enone system. Dimerization occurs by transfer of the hydrogen to the oxygen and connection between the two involved carbons. Androst-4-ene-3,17-dione (1) affords dimer 3 and trimer 4, both formed by connection of the C-16 of a molecule with the C-3 of a near one. Irradiation of 17alpha-methyltestosterone (2) gives the isomeric trienones 5 and 6. These compounds are reasonably formed by dehydration of unisolated intermediate products 7 and/or 8 obtained by coupling of two molecules through a linkage between the C-2 and the C-3' carbons. The formation mechanisms of the photoproducts are satisfactory explained on the basis of the molecular arrangement of the monomers in the crystal state. Modeling of the dimeric molecules was done using molecular mechanics calculations. A single-crystal X-ray of the dimer of androst-4-ene-3,17-dione confirms the structural interpretation of spectral data. The conformer found in the solid-state agrees well with the results of molecular mechanics calculations. 相似文献