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991.
Structures of tert-butylcarbamate ions in the gas-phase and methanol solution were studied for simple secondary and tertiary carbamates as well as for carbamate-containing products and internal standards for lysosomal enzyme assays used in newborn screening of a α-galactosidase A deficiency (Fabry disease), mucopolysaccharidosis I (Hurler disease), and mucopolysaccharidosis II (Hunter disease). The protonation of simple t-butylcarbamates can occur at the carbonyl group, which is the preferred site in the gas phase. Protonation in methanol solution is more favorable if occurring at the carbamate nitrogen atom. The protonation of more complex t-butylcarbamates occurs at amide and carbamate carbonyl groups, and the ions are stabilized by intramolecular hydrogen bonding, which is affected by solvation. Tertiary carbamates containing aminophenol amide groups were calculated to have substantially greater gas-phase basicities than secondary carbamates containing coumarin amide groups. The main diagnostically important ion dissociation by elimination of 2-methylpropene (isobutylene, i-C(4)H(8)) and carbon dioxide is shown by experiment and theory to proceed in two steps. Energy-resolved collision-induced dissociation of the Hurler's disease enzymatic product ion, which is a coumarin-diamine linker-t-butylcarbamate conjugate (3a(+)), indicated separate energy thresholds for the loss of i-C(4)H(8) and CO(2). Computational investigation of the potential energy surface along two presumed reaction pathways indicated kinetic preference for the migration of a t-butyl hydrogen atom to the carbamate carbonyl resulting in the isobutylene loss. The consequent loss of CO(2) required further proton migrations that had to overcome energy barriers. 相似文献
992.
Heger D Nachtigallová D Surman F Krausko J Magyarová B Brumovský M Rubeš M Gladich I Klán P 《The journal of physical chemistry. A》2011,115(41):11412-11422
A combined experimental-computational approach was used to study the self-organization and microenvironment of 1-methylnaphthalene (1MN) deposited on the surface of artificial snow grains from vapors at 238 K. The specific surface area of this snow (1.1 × 10(4) cm(2) g(-1)), produced by spraying very fine droplets of pure water from a nebulizer into liquid nitrogen, was determined using valerophenone photochemistry to estimate the surface coverage by 1MN. Fluorescence spectroscopy at 77 K, in combination with molecular dynamics simulations, and density functional theory (DFT) and second-order coupled cluster (CC2) calculations, provided evidence for the occurrence of ground- and excited-state complexes (excimers) and other associates of 1MN on the snow grains' surface. Only weak excimer fluorescence was observed for a loading of 5 × 10(-6) mol kg(-1), which is ~2-3 orders of magnitude below monolayer coverage. However, the results indicate that the formation of excimers is favored at higher surface loadings (>5 × 10(-5) mol kg(-1)), albeit still being below monolayer coverage. The calculations of excited states of monomer and associated moieties suggested that a parallel-displaced arrangement is responsible for the excimer emission observed experimentally, although some other associations, such as T-shape dimer structures, which do not provide excimer emission, can still be relatively abundant at this surface concentration. The hydrophobic 1MN molecules, deposited on the ice surface, which is covered by a relatively flexible quasi-liquid layer at 238 K, are then assumed to be capable of dynamic motion resulting in the formation of energetically preferred associations to some extent. The environmental implications of organic compounds' deposition on snow grains and ice are discussed. 相似文献
993.
Čížková M Kolivoška V Císařová I Šaman D Pospíšil L Teplý F 《Organic & biomolecular chemistry》2011,9(2):450-462
A modular approach to the construction of monocationic quaternary N-heteroaromatic frameworks was developed capitalizing on a direct pyridine-type nitrogen quaternization followed by metal-catalyzed [2+2+2] cycloaddition with gaseous acetylene. The flexibility of the route is demonstrated on 12 diverse scaffolds based on pyridinium, quinolinium, thiazolium, benzothiazolium, imidazolium, and pyrimidinium. Electrochemical study revealed a quinolinium redox system with two electrochemically distinct forms that are interconverted by a homogeneous chemical reaction triggered by fast electron transfers (reduction at -0.7 V and oxidation at -0.05 V). 相似文献
994.
The synthesis of the novel nucleotide analogues 5'-deoxynucleoside-5'-S-methylphosphonates, starting from 5'-deoxy-5'-haloribonucleosides, 5'-O-tosylribonucleosides, and 2'-O-triflylnucleosides, is described. The phosphonothiolation of these compounds was achieved using S-(diisopropylphosphonomethyl)isothiouronium tosylate, a new, odourless, and efficient equivalent of mercaptomethylphosphonate. The thiolate anion of mercaptomethylphosphonate was generated in situ from the isothiouronium salt in both protic and aprotic solvents using two equivalents of sodium iso-propoxide. The prepared nucleoside 5'-S-methylphosphonates were deprotected, and the free phosphonic acids were transformed into diphosphoryl derivatives (the NTP analogues). Both mononucleotides and NTP analogues were studied as substrates/inhibitors of several enzymes that are involved in the nucleoside/nucleotide metabolism. 相似文献
995.
The histone deacetylase (HDAC) inhibitor suberoylanilide hydroxamic acid (SAHA) was used to turn on the biosynthesis of EGM-556, a new cyclodepsipeptide of hybrid biosynthetic origin, isolated from the Floridian marine sediment-derived fungus Microascus sp. The absolute configurations of three chiral centers were determined by Marfey's derivatization. EGM-556 represents one of the few examples in which silent biosynthetic genes, encoding a new secondary metabolite, were activated by means of epigenetic manipulation of the fungal metabolome. 相似文献
996.
Gericke M Doliška A Stana J Liebert T Heinze T Stana-Kleinschek K 《Macromolecular bioscience》2011,11(4):549-556
In the present study, blood-compatible PET surfaces were prepared by coating with anticoagulant cellulose sulfates that were synthesized homogeneously in ionic liquids. The adsorption behavior of polysaccharides on PET films was investigated using QCM-D. It was demonstrated that pre-coating with different amino-group-containing polysaccharides improves the affinity toward cellulose sulfate. Moreover, the effect of different degrees of sulfation on the adsorption process was evaluated. Based on these results, several layer-by-layer coated PET foils were prepared that showed significantly improved blood compatibility compared to the initial untreated material. 相似文献
997.
A new simple ultra-high-performance liquid chromatography method with diode array detection (UHPLC-DAD) was developed for
chemical fingerprinting analysis of extracellular metabolites in fermentation broth of Geosmithia spp. The SPE method employing Oasis MCX strong cation-exchange mixed-mode polymeric sorbent was chosen for extraction of
the metabolites. The analyses were performed on an Acquity UPLC BEH C18 column (100 × 2.1 mm i.d.; particle size, 1.7 μm;
Waters) using a gradient elution program with an aqueous solution of trifluoroacetic acid and acetonitrile as the mobile phase.
The applicability of the method was proved by analysis of 38 strains produced by different species and isolated from different
sources (hosts). The results revealed the correlation of obtained UHPLC-DAD fingerprints with taxonomical identity. 相似文献
998.
Lišková M Voráčová I Klepárník K Hezinová V Přikryl J Foret F 《Analytical and bioanalytical chemistry》2011,400(2):369-379
A number of biologically important molecules, such as DNA, proteins, and antibodies, are routinely conjugated with fluorescent
tags for high-sensitivity analyses. Here, the application of quantum dots in the place of bright and size-tunable luminophores
is studied. Several selected bioconjugation reactions via zero-length cross-linkers, long-chain linkers, and oriented methods
for linking of quantum dots with proteins were tested. Anti-ovalbumin, anti-proliferating cell nuclear antigen, anti-hemagglutinin,
and anti-CD3 membrane protein as model antibodies and annexin V were used as high-specificity selectors. The reaction yield
and efficiency of the prepared immunoluminescent probes were tested by capillary zone electrophoresis with laser-induced fluorescence
detection. 相似文献
999.
We study algebraic and topological properties of the convolution semigroup of probability measures on a topological groups
and show that a compact Clifford topological semigroup S embeds into the convolution semigroup P(G) over some topological group G if and only if S embeds into the semigroup exp(G)\exp(G) of compact subsets of G if and only if S is an inverse semigroup and has zero-dimensional maximal semilattice. We also show that such a Clifford semigroup S embeds into the functor-semigroup F(G) over a suitable compact topological group G for each weakly normal monadic functor F in the category of compacta such that F(G) contains a G-invariant element (which is an analogue of the Haar measure on G). 相似文献
1000.
Michal Beneš 《Acta Appl Math》2011,116(3):237-254
We study an initial-boundary-value problem for time-dependent flows of heat-conducting viscous incompressible fluids in channel-like
domains on a time interval (0,T). For the parabolic system with strong nonlinearities and including the artificial (the so called “do nothing”) boundary
conditions, we prove the local in time existence, global uniqueness and smoothness of the solution on a time interval (0,T
∗), where 0<T
∗≤T. 相似文献