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991.
Ludmila A. Ramos Daniella L. Morgado Omar A. El Seoud Valdinéia C. da Silva Elisabete Frollini 《Cellulose (London, England)》2011,18(2):385-392
The acylation of three cellulose samples by acetic anhydride, Ac2O, in the solvent system LiCl/N,N-dimethylacetamide, DMAc (4 h, 110 °C), has been revisited in order to investigate the dependence of the reaction efficiency
on the structural characteristics of cellulose, and its aggregation in solution. The cellulose samples employed included microcrystalline,
MCC; mercerized cotton linters, M-cotton, and mercerized sisal, M-sisal. The reaction efficiency expresses the relationship
between the degree of substitution, DS, of the ester obtained, and the molar ratio Ac2O/AGU (anhydroglucose unit of the biopolymer); 100% efficiency means obtaining DS = 3 at Ac2O/AGU = 3. For all celluloses, the dependence of DS on Ac2O/AGU is described by an exponential decay equation: DS = DSo − Ae−[(Ac2O/AGU)/B]; (A) and (B) are regression coefficients, and DSo is the calculated maximum degree of substitution, achieved under the conditions of each experiment. Values of (B) are clearly
dependent on the cellulose employed: B(M-cotton) > B(M-sisal) > B(MCC); they correlate qualitatively with the degree of polymerization of cellulose, and linearly with the aggregation number, Nagg, of the dissolved biopolymer, as calculated from static light scattering measurements: (B) = 1.709 + 0.034 Nagg. To our knowledge, this is the first report on the latter correlation; it shows the importance of the physical state of dissolved
cellulose, and serves to explain, in part, the need to use distinct reaction conditions for MCC and fibrous celluloses, in particular Ac2O/AGU, time, temperature. 相似文献
992.
Pham VT Penfold TJ van der Veen RM Lima F El Nahhas A Johnson SL Beaud P Abela R Bressler C Tavernelli I Milne CJ Chergui M 《Journal of the American Chemical Society》2011,133(32):12740-12748
Picosecond and femtosecond X-ray absorption spectroscopy is used to probe the changes of the solvent shell structure upon electron abstraction of aqueous iodide using an ultrashort laser pulse. The transient L(1,3) edge EXAFS at 50 ps time delay points to the formation of an expanded water cavity around the iodine atom, in good agreement with classical and quantum mechanical/molecular mechanics (QM/MM) molecular dynamics (MD) simulations. These also show that while the hydrogen atoms pointed toward iodide, they predominantly point toward the bulk solvent in the case of iodine, suggesting a hydrophobic behavior. This is further confirmed by quantum chemical (QC) calculations of I(-)/I(0)(H(2)O)(n=1-4) clusters. The L(1) edge sub-picosecond spectra point to the existence of a transient species that is not present at 50 ps. The QC calculations and the QM/MM MD simulations identify this transient species as an I(0)(OH(2)) complex inside the cavity. The simulations show that upon electron abstraction most of the water molecules move away from iodine, while one comes closer to form the complex that lives for 3-4 ps. This time is governed by the reorganization of the main solvation shell, basically the time it takes for the water molecules to reform an H-bond network. Only then is the interaction with the solvation shell strong enough to pull the water molecule of the complex toward the bulk solvent. Overall, much of the behavior at early times is determined by the reorientational dynamics of water molecules and the formation of a complete network of hydrogen bonded molecules in the first solvation shell. 相似文献
993.
Thermogravimetric (TG) investigations of organotin(IV) carboxylates with the general formula RmSnL4−m (where R=CH3, C2H5, n‐C4H9, C6H5, cyclo‐C6H11, n‐C8H17, m=2, 3, and L=para‐nitrophenylethanoate anion) have been performed. Derivative thermogravimetry (DTG) and differential thermal analysis (DTA) techniques, Horowitz‐Metzger method and the fundamental thermodynamic relations are used to evaluate the thermokinetic parameters of each thermal degradation pattern. Results reveal that the thermal stability is functional to Sn C and Sn O bonds. In the case of R2SnL2, activation energy, reaction order and pre‐exponential factor associated with the bulk degradation processes increase as the alkane chain length increases. Hence, Oct2SnL2 is thermally more stable than Bu2SnL2, which in turn is more resistant to thermal dissociation than Et2SnL2. The same phenomenon is not observed for R3SnL compounds because their degradation is highly irregular. Furthermore, R2SnL2 has larger values of kinetic parameters than those of corresponding triorganotin(IV) para‐nitrophenylethanotes. Thermodynamic parameters of these compounds also reinforce the above facts. 相似文献
994.
Humayun Ajaz Sajjad Hussain Muhammad Altaf Helen Stoeckli‐Evans Anvarhusein A. Isab Rashid Mahmood Shahnila Altaf Saeed Ahmad 《中国化学》2011,29(2):254-258
Antimony(III) complexes of thioamides [thioamides=thiourea (Tu), N,N′‐dimethylthiourea (Dmtu), tetramethylthiourea (Tmtu), imidazolidine‐2‐thione (Imt) and diazinane‐2‐thione (Diaz)] with the general formulae, Sb(thione)nCl3 (n=1, 2, 2.5, 3) were prepared and characterized by elemental analysis, IR and NMR (1H, 13C) spectroscopic methods. The spectral data of the complexes are consistent with the coordination of the thiones to antimony(III). The crystal structure of one of them, {[Sb(Imt)2Cl2]2(μ2‐Imt)}Cl2 ( 1 ), was determined by X‐ray crystallography, which shows that the complex is dinuclear consisting of two [Sb(Imt)2Cl2] units bridged by an Imt molecule. In 1 , the antimony atom is bonded to two chlorine atoms, two sulfur atoms of coordinated Imt molecules and one sulfur atom of a bridging Imt molecule. The antimony environment can be considered to be distorted octahedral with one Cl? ion weakly bound to antimony. 相似文献
995.
A proton-transfer (charge transfer) complex formed on the reaction between 2,6-diaminopyridine (donor) and picric acid (acceptor) was synthesized and characterized by FTIR, (1)H NMR, thermal and elemental analysis. The crystal structure determined by single-crystal X-ray diffraction indicates that cation and anion are joined together by strong N(+)-H- -O(-) type hydrogen bonds. The hydrogen-bonded charge transfer (HBCT) complex was screened for its pharmacology such as antimicrobial activity against various fungal and bacterial strains and Calf thymus DNA-binding. The results showed that HBCT complex (100μg/ml) exhibited good antibacterial antifungal activity as that of standard antibiotics Tetracycline and Nystatin. A molecular frame work through H-bonding interactions between neighboring moieties is found to be responsible for high melting point of resulting complex. This has been attributed to the formation of 1:1 HBCT complex. 相似文献
996.
A dispersive liquid-liquid microextraction (DLLME) procedure coupled with GC/MS detection is described for preconcentration and determination of some organophosphorus and azole group pesticides from water samples. Experimental conditions affecting the DLLME procedure were optimized by means of an experimental design. A mixture of 60 microL chlorobenzene (extraction solvent) and 750 microL acetonitrile (disperser solvent), 3.5 min extraction time, and 7.5 mL aqueous sample volume were chosen for the best recovery by DLLME. The linear range was 1.6-32 microg/L. The LOD ranged from 48.8 to 68.7 ng/L. The RSD values for organophosphorus and azole group pesticides at spiking levels of 3, 6, and 9 microg/L in water samples were in the range of 1.1-12.8%. The applicability and accuracy of the developed method were determined by analysis of spiked water samples, and the recoveries of the analyzed pesticides from artesian, stream, and tap waters at spiking levels of 3, 6, and 9 microg/L were 89.3-105.6, 89.5-103.0, and 92.0-111.3%, respectively. 相似文献
997.
A. B. Burdukov M. A. Vershinin N. V. Pervukhina S. G. Kozlova I. V. El��tsov Ya. Z. Voloshin 《Russian Chemical Bulletin》2011,60(12):2504-2509
Quantum chemical calculations were performed at the DFT level for the boron-capped dichloro-substituted tris-dioximate iron(II) clathrochelate and cyclohexane and 1,4-dioxane radicals. The 1,4-dioxane and cyclohexane radicals are nucleophiles towards the macrobicyclic precursor studied. The reaction of this clathrochelate with cyclohexane in the presence of a free-radical initiator resulted in substitution of a chlorine atom by a cyclohexyl fragment. The compound obtained was characterized by elemental analysis, IR spectroscopy, 1H and 13C{1H} NMR, and single-crystal X-ray diffraction data. 相似文献
998.
O. S. El’tsov V. S. Mokrushin M. V. Smirnova M. Z. Shafikov 《Russian Chemical Bulletin》2011,60(5):882-888
The reactions of ethyl (5-carbamoyl-3H-imidazol-4-yl)dithiocarbamate with phenacyl bromides afford the S-alkylation products as a mixture of E/Z-isomers, which undergo cyclization to 5-(2-oxo-4-arylthiazol-3-yl)-1H-imidazole-4-carboxamides under the action of a base. 相似文献
999.
A. A. Aleksandrov A. S. Dedeneva M. M. El’chaninov 《Russian Journal of Organic Chemistry》2011,47(5):710-713
By condensation of 1-amino-2-hydroxynaphthalene with furoyl chloride in 1-methyl-2-pyrrolidone 2-(2-furyl)naphtho[1,2-d]oxazole
was synthesized and brought into electrophylic substitution reactions: nitration, bromination, sulfonation, formylation, and
acylation. The substituent commonly was introduced into the position 5 of the furan ring, but at the nitration and bromination electrophilic attack was directed both at the furan ring and the
naphthalene fragment. 相似文献
1000.
Dey GR El Omar AK Jacob JA Mostafavi M Belloni J 《The journal of physical chemistry. A》2011,115(4):383-391
The detailed kinetics of the multistep mechanism of the Au(III) ion reduction into gold clusters have been investigated by radiation chemistry methods in 2-propanol. In particular, a discussion on the steady state radiolysis dose-dependence of the yields concludes to a comproportionation reaction of nascent gold atoms Au(0) with excess Au(III) ions into Au(II) and Au(I). This reaction should be achieved through Au(III) consumption before the coalescence of atoms Au(0) into gold clusters may occur. Then gold clusters catalyze the reduction of Au(I) by 2-propanol. It was also found that a long-lived Au(II) dimer, (Au(II))(2), was transiently formed according to the quantitative analysis of time-resolved absorbance signals obtained by pulse radiolysis. Then the disproportionation of Au(II) is intramolecular in the dimer instead of intermolecular, as usually reported. The yields, reaction rate constants, time-resolved spectra, and molar extinction coefficients are reported for the successive one-electron reduction steps, involving especially the transient species, such as Au(II), (Au(II))(2), and Au(I). The processes are discussed in comparison with other solvents and other metal ions. 相似文献