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11.
Santi Tungprapa Tanarinthorn Puangparn Monchawan Weerasombut Ittipol Jangchud Porntiva Fakum Somsak Semongkhol Chidchanok Meechaisue Pitt Supaphol 《Cellulose (London, England)》2007,14(6):563-575
This paper reports an investigation of the effects of solvent system, solution concentration, and applied electrostatic field
strength (EFS) on the morphological appearance and/or size of as-spun cellulose acetate (CA) products. The single-solvent
systems were acetone, chloroform, N,N
-dimethylformamide (DMF), dichloromethane (DCM), methanol (MeOH), formic acid, and pyridine. The mixed-solvent systems were
acetone–DMAc, chloroform–MeOH, and DCM–MeOH. Chloroform, DMF, DCM, MeOH, formic acid, and pyridine were able to dissolve CA,
forming clear solutions (at 5% w/v), but electrospinning of these solutions produced mainly discrete beads. In contrast, electrospinning of the solution of
CA in acetone produced short and beaded fibers. At the same solution concentration of 5% (w/v) electrospinning of the CA solutions was improved by addition of MeOH to either chloroform or DCM. For all the solvent systems
investigated smooth fibers were obtained from 16% (w/v) CA solutions in 1:1, 2:1, and 3:1 (v/v) acetone–DMAc, 14–20% (w/v) CA solutions in 2:1 (v/v) acetone–DMAc, and 8–12% (w/v) CA solutions in 4:1 (v/v) DCM–MeOH. For the as-spun fibers from CA solutions in acetone–DMAc the average diameter ranged between 0.14 and 0.37 μm
whereas for the fibers from solutions in DCM–MeOH it ranged between 0.48 and 1.58 μm. After submersion in distilled water
for 24 h the as-spun CA fibers swelled appreciably (i.e. from 620 to 1110%) but the physical integrity of the fibrous structure
remained intact. 相似文献
12.
A. M. Pitt S. M. Cramer A. B. Czernicki K. Kalghatgi Cs. Horvath B. A. Solomon 《Applied biochemistry and biotechnology》1983,8(1):55-68
Anisotropic polysulfone membranes were prepared with carboxypeptidase G1 embedded in the polymer structure. The enzymatically active flat and hollow-fiber membranes were obtained by precipitating the polymer from solution in an organic mixture in which an aqueous solution of the enzyme had been dispersed. The process has been found to be particularly suitable for the immobilization of enzymes in anisotropic hollow fibers that exhibited no detectable enzyme leakage upon perfusion. The pH profiles measured with the enzyme in free solution and in the embedded form were similar. Kinetic parameters of multitubular enzyme reactors were investigated by measuring the rate of hydrolysis of glutamate from folic acid or methotrexate at different flow rates and substrate concentrations. The relatively slow mass transfer in such reactors was found to affect strongly the observed kinetics. The results of in vitro experiments with 5000 fiber reactors suggest that hollow fiber cartridges prepared with such membranes have clinical potential for the extracorporeal removal of methotrexate from blood. 相似文献
13.
UV irradiation of phenanthrene and 1,1-dichloro-, 1,2-dichloro-, and 1,1,2-trichloroethenes resulted m [2+2]cycloaddition to give cyclobutane derivatives. Treatment of the 1,2-dichloro-adducts with N-bromosuccinimide resulted in aromatisation to yield cis- and tras-l,2-dichloro-1,2- dihydrocyclobuta[l)phenanthrene, whereas the 1,1-dichloro-adduct resulted in aromatisation and hydrolysis to give cyclobuta[l]phenanthrene-l(2H)-one. The trichloroethene adducts gave 1,2-dichloro-2a,10b-dihydrocyclobuta [l)phenanthrene upon treatment with base, and reaction with N- bromosuccinimide resulted in bromine substitution in the cyclobutane ring. The stereochemistry of the adducts and the stereoselectivity of the bromination reactions are discussed. 相似文献
14.
Pérez-Mendoza M Gonzalez J Wright PA Seaton NA 《Langmuir : the ACS journal of surfaces and colloids》2004,20(18):7653-7658
We have measured the adsorption of methane and ethane to high pressure on SBA-2, a structured mesoporous silica composed of spheres connected by narrow channels. The experimental data were analyzed by carrying out Monte Carlo simulations of adsorption in pore structure models of different complexity and then adjusting the parameters of the models to match the Monte Carlo results to the experimental data. We found that a model based on single-sized spherical cavities was inadequate and that it is necessary to explicitly account for the interconnecting channels. Further, we found that despite the basic regularity of the SBA-2 structure, it is necessary to allow for a distribution of the sizes of both the cavities and the channels. These size distributions were obtained by fitting the parameters of the model to the experimental adsorption data, revealing detailed structural information not previously known for this material. The channels were found to be 5-15 A in diameter, while the cavities were 40-50 A in diameter. There is some evidence that the distribution of channel sizes leads to a percolation effect whereby the pore structure is not equally accessible to all adsorptives. 相似文献
15.
The reaction of a racemic perhydroisoquinolene derivative 9 with the homochiral lithium amide basse 3 in the presence of Me3SiCl in an regiodivergent fashion to give the two non-racemic regioisomeric enol silanes 10 and 11. Conversion of 10 into enone 15, an intermediate useful in the synthesis of the alkaloid (+)-yohimbine, was also possible. 相似文献
16.
Alistair J Usher Nigel T Lucas Simon Petrie Mark G Humphrey Anthony C Willis 《Journal of organometallic chemistry》2004,689(1):50-57
Reaction of WH(CO)3(η-C5Me5) with IrCl(CO)2(4-H2NC6H4Me) affords WIr3(μ-CO)3(CO)8(η-C5Me5) in low yield. A structural study reveals a WIr2-centred plane of bridging carbonyls, in contrast to the crystal structure of WIr3(CO)11(η-C5H5) (all-terminal carbonyl distribution). DFT calculations reveal an increasing proclivity to adopt an all-terminal CO disposition for clusters MIr3(CO)11(η-C5H5) in the gas phase on proceeding from M=Cr to Mo and then W, consistent with structural studies in the solid state for which the tungsten-containing cluster is the only all-terminal example. Increasing electron donation from the ligands in the tungsten system (either from phosphine substitution or cyclopentadienyl permethylation) suffices to impose a plane of bridging carbonyls in the ground state structure. 13C NMR fluxionality studies reveal that CO exchange mechanism(s) for WIr3(CO)11(η-C5H5) and the related tetrahedral cluster W2Ir2(CO)10(η-C5H5)2 are very fast and involve all carbonyls on the clusters. DFT calculations on MIr3(CO)11(η-C5H5) (M=Cr, Mo) substantiate a ‘merry-go-round’ mechanism for carbonyl scrambling in these systems, a result which is consistent with the scrambling behaviour seen in the NMR fluxionality studies on the W-containing congener. 相似文献
17.
Lucas NT Blitz JP Petrie S Stranger R Humphrey MG Heath GA Otieno-Alego V 《Journal of the American Chemical Society》2002,124(18):5139-5153
A systematically varied series of tetrahedral clusters involving ligand and core metal variation has been examined using crystallography, Raman spectroscopy, cyclic voltammetry, UV-vis-NIR and IR spectroelectrochemistry, and approximate density functional theory, to assess cluster rearrangement to accommodate steric crowding, the utility of metal-metal stretching vibrations in mixed-metal cluster characterization, and the possibility of tuning cluster electronic structure by systematic modification of composition, and to identify cluster species resultant upon electrochemical oxidation or reduction. The 60-electron tetrahedral clusters MIr(3)(CO)(11-x)(PMe(3))(x)(eta(5)-Cp) [M = Mo, x = 0, Cp = C(5)H(4)Me (5), C(5)HMe(4) (6), C(5)Me(5) (7); M = W, Cp = C(5)H(4)Me, x = 1 (13), x = 2 (14)] and M(2)Ir(2)(CO)(10-x)(PMe(3))(x)(eta(5)-Cp) [M = Mo, x = 0, Cp = C(5)H(4)Me (8), C(5)HMe(4) (9), C(5)Me(5) (10); M = W, Cp = C(5)H(4)Me, x = 1 (15), x = 2 (16)] have been prepared. Structural studies of 7, 10, and 13 have been undertaken; these clusters are among the most sterically encumbered, compensating by core bond lengthening and unsymmetrical carbonyl dispositions (semi-bridging, semi-face-capping). Raman spectra for 5, 8, WIr(3)(CO)(11)(eta(5)-C(5)H(4)Me) (11), and W(2)Ir(2)(CO)(10)(eta(5)-C(5)H(4)Me)(2) (12), together with the spectrum of Ir(4)(CO)(12), have been obtained, the first Raman spectra for mixed-metal clusters. Minimal mode-mixing permits correlation between A(1) frequencies and cluster core bond strength, frequencies for the A(1) breathing mode decreasing on progressive group 6 metal incorporation, and consistent with the trend in metal-metal distances [Ir-Ir < M-Ir < M-M]. Cyclic voltammetric scans for 5-15, MoIr(3)(CO)(11)(eta(5)-C(5)H(5)) (1), and Mo(2)Ir(2)(CO)(10)(eta(5)-C(5)H(5))(2) (3) have been collected. The [MIr(3)] clusters show irreversible one-electron reduction at potentials which become negative on cyclopentadienyl alkyl introduction, replacement of molybdenum by tungsten, and replacement of carbonyl by phosphine. These clusters show two irreversible one-electron oxidation processes, the easier of which tracks with the above structural modifications; a third irreversible oxidation process is accessible for the bis-phosphine cluster 14. The [M(2)Ir(2)] clusters show irreversible two-electron reduction processes; the tungsten-containing clusters and phosphine-containing clusters are again more difficult to reduce than their molybdenum-containing or carbonyl-containing analogues. These clusters show two one-electron oxidation processes, the easier of which is reversible/quasi-reversible, and the more difficult of which is irreversible; the former occur at potentials which increase on cyclopentadienyl alkyl removal, replacement of tungsten by molybdenum, and replacement of phosphine by carbonyl. The reversible one-electron oxidation of 12 has been probed by UV-vis-NIR and IR spectroelectrochemistry. The former reveals that 12(+) has a low-energy band at 8000 cm(-1), a spectrally transparent region for 12, and the latter reveals that 12(+) exists in solution with an all-terminal carbonyl geometry, in contrast to 12 for which an isomer with bridging carbonyls is apparent in solution. Approximate density functional calculations (including ZORA scalar relativistic corrections) have been undertaken on the various charge states of W(2)Ir(2)(CO)(10)(eta(5)-C(5)H(5))(2) (4). The calculations suggest that two-electron reduction is accompanied by W-W cleavage, whereas one-electron oxidation proceeds with retention of the tetrahedral core geometry. The calculations also suggest that the low-energy NIR band of 12(+) arises from a sigma(W-W) --> sigma*(W-W) transition. 相似文献
18.
Nigel T. Lucas Marie P. Cifuentes Lam T. Nguyen Mark G. Humphrey 《Journal of Cluster Science》2001,12(1):201-221
The new phosphines Ph2PC6H4-4-CCR [R=SiMe3 (1), H (2)] have been used to prepare Ru3(CO)9(Ph2PC6H4-4-CCSiMe3)3 (4) and Ru(CCC6H4-4-PPh2)(PPh3)2(-C5H5) (3), respectively, the latter with a pendent phosphine. Reaction of 4 with carbonate or fluoride affords Ru3(CO)9(Ph2PC6H4-4-CCH)3 (5) with pendent terminal alkynyl groups, the identity of which was confirmed by a structural study. Reaction of 5 with [Ru(NCMe)(PPh3)2(-C5H5)]PF6 or reaction of Ru3(CO)12 with 3 gives Ru3(CO)9{(Ph2PC6H4-4-CC)Ru(PPh3)2(-C5H5)}3 (6). Complexes 3–6 have been studied by cyclic voltammetry. Proceeding from Ru3(CO)12 to 4 or 5 shifts the cluster-centred reduction to more negative potential and affords facile cluster-centred oxidation. Proceeding from 4/5 and 3 to 6 results in similarly-located cluster-centred reduction and peripheral ruthenium-centred oxidation, but results in a lack of observable cluster-centred oxidation. Crystal data for 5·C6H14: space group P¯1, a=12.760(1) Å, b=17.077(1) Å, c=17.924(2) Å, =108.656(5)°, =96.344(5)°, =93.523(5)°, V=3658.4(6) Å3, Z=2, R=0.078, Rw=0.105 for 5008 reflections [I>2.00(I)]. 相似文献
19.
Bogert D Burnstein R Fisk R Fuess S Morfin J Ohska Stutte L Walker JK Bofill J Busza W Eldridge T Friedman JI Goodman MC Kendall HW Kostoulas IG Lyons T Magahiz R Mattison T Mukherjee A Osborne L Pitt R Rosenson L Sandacz A Tartaglia M Taylor FE Verdier R Whitaker S Yeh GP Abolins M Brock R Cohen A Ernwein J Owen D Slate J Weerts H 《Physical review letters》1985,55(6):574-577
20.
Hodgson DM Kirton EH Miles SM Norsikian SL Reynolds NJ Coote SJ 《Organic & biomolecular chemistry》2005,3(10):1893-1904
Organolithium-induced deprotonation of terminal epoxides in the presence of appropriate diamine ligands allows trapping with a range of electrophiles, yielding functionalised di- and tri-substituted epoxides in good yields and with control of stereochemistry at the epoxide. 相似文献