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11.
Irene Yarovsky Marie-Isabel Aguilar Milton T. W. Hearn 《Journal of chromatography. A》1994,660(1-2):75-84
The molecular dynamics method has been applied to investigate the conformations of n-butyl ligands immobilised onto an amorphous silica surface analogous to those utilised with silica-based RP-HPLC sorbents. Three systems were constructed which corresponded to ligand densities of 1.64, 2.67 and 3.69 μmol/m2. A number of parameters related to the structure of the sorbent materials were derived in order to characterise the molecular properties of each system. These parameters included the hydrocarbon layer thickness, the frequency of gauche conformations, the distance distribution for carbon atoms and the diffusion coefficients of individual atoms in the n-butyl ligands. From these properties, the positions of chains with respect to the surface as well as their mobility were estimated. It was found that at higher densities, the n-butyl chains are predominantly perpendicular to the surface while at low density they are highly tilted or lying almost parallel to the surface. The degree of ligand flexibility decreased with increasing surface density. Mobility of individual carbon atoms as well as chain disorder increased with distance from the surface for all ligand densities. The simulated properties of n-butyl chains immobilised to a silica surface correlated well with results obtained by Fourier transform IR and 13C-cross polarisation magic angle spinning NMR experimental methods and statistical predictions of the behaviour of immobilised chains. 相似文献
12.
[reaction: see text] The reaction of o-quinodimethanes (oQDMs) with alkoxy alkynyl Fischer carbene complexes is highly dependent on the carbene complex. Thus, for arylalkynyl carbene complexes, the initial [4 + 2]-cycloadduct evolves opening a new entry to the benzo[b]fluorene skeleton, which is present in many natural products. However, for alkenylalkynyl carbene complexes, the reaction takes place through the double bond, instead of the triple bond, in an unprecedented fashion, leading to new functionalized alkynyl carbene complexes. 相似文献
13.
An extracellular xylanase produced by a Mexican Aspergillus strain was purified and characterized. Aspergillus sp. FP-470 was able to grow and produce extracellular xylanases on birchwood xylan, oat spelt xylan, wheat straw, and corncob, with higher production observed on corncob. The strain also produced enzymes with cellulase, amylase, and pectinase activities on this substrate. A 22-kDa endoxylanase was purified 30-fold. Optimum temperature and pH were 60 degrees C and 5.5, respectively, and isoelectric point was 9.0. The enzyme has good stability from pH 5.0 to 10.0, retaining >80% of its original activity within this range. Half-lives of 150 min at 50 degrees C and 6.5 min at 60 degrees C were found. K(m) and activation energy values were 3.8 mg/mL and 26 kJ/mol, respectively, using birchwood xylan as substrate. The enzyme showed a higher affinity for 4-O-methyl-D-glucuronoxylan with a K(m) of 1.9 mg/mL. The enzyme displayed no activity toward other polysaccharides, including cellulose. Baking trials were conducted using the crude filtrate and purified enzyme. Addition of both preparations improved bread volume. However, addition of purified endoxylanase caused a 30% increase in volume over the crude extract. 相似文献
14.
A novel methodology in on-line pyrolysis-gas chromatography (Py-GC) for the fast analysis of fatty acids in vegetable oils with minimal sample treatment and the use of non-toxic reagents is described. Pyrolysis at 500 degrees C for 10 s of sub-microgram quantity of vegetable oil dissolved in dimethyl carbonate (DMC) and in the presence of nanopowder titanium silicon oxide resulted in the production of fatty acid methyl esters (FAMEs) as unique products. Pyrolysis performed by means of a resistively heated filament pyrolyser interfaced to a GC-MS apparatus enabled the direct analysis of evolved FAMEs. The DMC/Py-GC-MS analysis was tested on soybean, coconut, linseed, walnut and olive oil and the results compared to the classical BF(3)-methanol as reference methodology. The DMC method exhibited a lower precision and was biased towards lower levels of polyunsaturated fatty acids (PUFA) in comparison to the BF(3)-methanol method, but was more advantageous in terms of reduced sample treatment, waste generation and risk factors of employed chemicals. 相似文献
15.
Aguilar CN Favela-Torres E Viniegra-González G Augur C 《Applied biochemistry and biotechnology》2002,102(1-6):407-414
Undesirable protease production by Aspergillus niger Aa-20 in submerged culture and solid-state culture was evaluated using different concentrations of tannic acid as sole carbon
source in a model system designed for tannase production. Protease production was found to be dependent on the culture system
used (submerged culture or solid-state culture) and on the initial tannic acid concentration. Expression of protease activity
in submerged culture was higher (up to 10 times) than activity obtained in solid-state culture, using identical culture medium
composition. In submerged culture, the lowest final protease activity (0.13 IU) was obtained with the highest tannic acid
concentration, while in solid-state culture protease activity was not affected by changes in initial substrate concentration.
Absence of detectable proteolytic activity in solid-state culture is related to high production of tannase enzyme. Hence,
the use of solid-state culture for fungal enzyme production may allow for higher and more stable enzyme titers present in
culture extracts. 相似文献
16.
Buneva VN Kanyshkova TG Vlassov AV Semenov DV Khlimankov DYu Breusova LR Nevinsky GA 《Applied biochemistry and biotechnology》1998,75(1):63-76
Various catalytically active antibodies (Abs), or abzymes, have been detected recently in the sera of patients with autoimmune
pathologies, in whom their presence is probably associated with autoimmunization. Normal humans are generally not considered
to have abzymes, since no obvious immunizing factors are present. Here is shown by different methods that IgG from the milk
of normal females possesses both DNase and RNase activities. The activities were also present in the IgG F(ab′)2 and Fab fragments.
Affinity modification of IgG by the chemically reactive derivative of an oligonucleotide led to preferential modification
of the L chain of IgG. After separation of the subunits by sodium dodecyl sulfate electrophoresis in a gel containing DNA,
an in-gel assay showed DNase activity in the L chain. The L chain separated by affinity chromatography on DNA-cellulose was
catalytically active. These findings speak in favor of the generation of cat alytic Abs by the immune system of healthy mothers.
It is known that the treatment of adults with DNases and RNases offers protection from viral and bacterial diseases. Since
breast milk protects the infants from infec tions until the immune system is developed, this raises the possibility that catalytic
Abs like nucleases, may possess a protective role. 相似文献
17.
Several on-column sample preconcentration modes--large-volume sample stacking using the EOF pump (LVSEP), LVSEP with anion-selective exhaustive injection (LVSEP-ASEI) and field-amplified sample injection with sample matrix removal using the electroosmotic flow (EOF) pump (FAEP)--were used to analyze some nonsteroidal anti-inflammatory drugs (NSAIDs) by capillary electrophoresis, and then compared. Methanol was the background electrolyte solvent to suppress the EOF. The effect of the type and length of the solvent plug, and the sample injection time were investigated in FAEP to determine the conditions that provided the best response. LVSEP, LVSEP-ASEI, and FAEP improved the sensitivity of the peak area by 100-, 1200-, and 1800-fold, respectively. The methodology developed, in combination with solid-phase extraction (SPE), was applied to the analysis of water samples. 相似文献
18.
Meerovich IG Jerdeva V Derkacheva VM Meerovich GA Lukyanets EA Kogan EA Savitsky AP 《Journal of photochemistry and photobiology. B, Biology》2005,80(1):57-64
The photodynamic activity of dibiotinylated aluminum sulfophthalocyanine was studied in vitro and in vivo. Dibiotinylated aluminum sulfophthalocyanine provided enhanced phototoxic action on OAT-75 cell monolayers as compared with the parent drug. Photodynamic therapy of mice with Ehrlich carcinoma using dibiotinylated aluminum sulfophthalocyanine (0.25 mg/kg) resulted in enhanced inhibition of tumor growth, pronounced vascular damage (thrombosis and destruction of vascular walls) and eventual tumor necrosis. 相似文献
19.
20.
Barragán P Errea LF Macías A Méndez L Rabadán I Riera A Lucas JM Aguilar A 《The Journal of chemical physics》2004,121(23):11629-11638
The lowest two ab initio potential energy surfaces (PES), and the corresponding nonadiabatic couplings between them, have been obtained for the H3+ system; the molecular data are compared to those calculated with the diatomic in molecules (DIM) method. The form of the couplings is discussed in terms of the topology of the molecular structure of the triatomic. The method of Baer is employed to generate "diabatic" states and the residual nonadiabatic couplings are calculated. The ab initio results for these are markedly different from the corresponding DIM data, and show the need to consider the third PES. 相似文献