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111.
Previous studies demonstrated that lipid membranes attached to a proteinaceous crystalline surface-layer (S-layer) revealed a prolonged lifetime and showed a reduced tendency to rupture in the presence of membrane active molecules. In addition, comparative studies on folded and S-layer-supported lipid membranes (SsLM) revealed an uniform capacitance of 0.64 +/- 0.04 microF/cm(2) for both composite membranes. In the present study, the feasibility to reconstitute the channel-forming protein alpha-hemolysin (alpha HL) into SsLM at single channel resolution was investigated. Single alpha HL channels could be recorded and the intrinsic properties like unitary conductance, current-voltage characteristics, and closure was found to be similar at both membranes. Thus, the tightly attached S-layer allowed complete reconstitution of alpha HL channels in SsLM. 相似文献
112.
The interaction of an excess electron with a polar molecular environment is well known as electron solvation. This process is characterized by an energetic stabilization and by changes of the electronic spatial extent due to screening of the localized charge through molecular rearrangement. At metal–ice interfaces we photo-inject delocalized electrons from the metal substrate into adsorbed ice layers and analyze the ultrafast dynamics of electron transfer, localization and solvation by femtosecond time- and angle-resolved two-photon photoemission spectroscopy. To acquire further understanding of the individual steps of the complex process we vary the interfacial structure. The substrate is changed between Cu(1 1 1) and Ru(0 0 1) and the electron dynamics in ice islands are compared to closed D2O layers. Contrasting crystalline and amorphous ice we found that electron solvation is mediated through electron localization at favorable structural sites, which occurs very efficiently in amorphous ice, but is less likely in a crystalline layer. Next, we find that in an open ice structure like ice islands the energetic stabilization due to electron solvation proceeds at a rate of 1 eV/ps which is three times faster than in a closed ice layer. We attribute this behavior to differences in the molecular coordination, which determines the molecular mobility and, thus, the transfer rate of electronic energy to solvent modes. The substrate’s electronic structure, on the other hand, is important to understand the transfer rates from electrons in ice back to the metal. First experiments on trapped electrons in crystalline ice underline the potential to study electron solvation not only during the equilibration process, but also in quasi-static conditions, where we find that the stabilization continues, although at much weaker rates. 相似文献
113.
Simple binary solids can be found to adopt unprecedented structures when confined into nanometre-sized cavities, such as the inner cylindrical bore of single-walled carbon nanotubes (SWNT). In the case of the discussed Lal(x)@SWNT encapsulation composite, the Lal2 "crystal" fragment adopts the structure of bulk Lal3, with one third of the iodine positions unoccupied. A complete characterisation of the encapsulation composite was achieved using an enhanced digital restoration approach of high-resolution transmission electron microscopy (HRTEM) images. The resulting complex exit surface wave provides information about the precise structural data of both filling material and host SWNT, establishing the SWNT's chirality and thus enabling a prediction of the composite's overall electron-transport properties. 相似文献
114.
Ostash B Rix U Rix LL Liu T Lombo F Luzhetskyy A Gromyko O Wang C Braña AF Méndez C Salas JA Fedorenko V Rohr J 《Chemistry & biology》2004,11(4):547-555
A 3 kb DNA fragment from the Streptomyces globisporus 1912 landomycin E (LaE) biosynthetic gene cluster (lnd) was completely sequenced. Three open reading frames were identified, lndGT4, lndZ4, and lndZ5, whose probable translation products resemble a glycosyltransferase, a reductase, and a hydroxylase, respectively. Studies of generated mutants from disruption and complementation experiments involving the lndGT4 gene allowed us to determine that LndGT4 controls the terminal L-rhodinose sugar attachment during LaE biosynthesis and that LndZ4/LndZ5 are responsible for the unique C11-hydroxylation of the landomycins. Generation of the novel landomycins F, G, and H in the course of these studies provided evidence for the flexibility of lnd glycosyltransferases toward their acceptor substrates and a basis for initial structure-activity relationships within the landomycin family of antibiotics. 相似文献
115.
Klaassen T Kasel D Harlfinger S Fuhr U 《Rapid communications in mass spectrometry : RCM》2004,18(15):1675-1680
A reliable and easy to use liquid chromatography/tandem mass spectrometry (LC/MS/MS) method without the use of sample extraction was developed for the simultaneous quantification of urinary concentrations of mephenytoin, a standard phenotyping substrate for the cytochrome P450 enzyme CYP2C19, and its phase I metabolites 4'-hydroxymephenytoin and nirvanol. Fifty microL of urine were diluted with a buffered beta-glucuronidase solution and incubated at 37 degrees C for 6 h followed by addition of methanol, containing the internal standard 4'-methoxymephenytoin. The chromatographic separation was achieved using a 100 x 3 mm, 5 micro Thermo Electron Aquasil C18 column with a gradient flow, increasing the organic fraction (acetonitrile/methanol 50:50) of the mobile phase from 10 to 90%. Quantification by triple-stage mass spectrometry (TSQ Quantum, Thermo Electron) was accomplished by negative electrospray ionization in the selected reaction monitoring mode. Linearity was observed for all substances in the concentration range 15-10 000 ng/mL. The lower limit of quantification (LLOQ) was 20 ng/mL for 4'-hydroxymephenytoin and 30 ng/mL for nirvanol and mephenytoin, respectively. Intra- and inter-day inaccuracy did not exceed 9.5% for all substances from LLOQ to 10 000 ng/mL. Intra- and inter-day precision were in the range of 0.8-10.5%. The method was validated according to international ICH and FDA guidelines and successfully applied for phenotyping of Caucasian male volunteers who received an oral dose of 50 mg mephenytoin. 相似文献
116.
The cyclization of 1,3-bis-silyl enol ethers or (2,4-dioxobutylidene)triphenylphosphoranes with phthalic dialdehyde allowed a convenient synthesis of a variety of 4,5-benzotropones. The hydrogenation of benzotropones afforded functionalized benzocycloheptanones which were transformed into tricyclic butenolides. 相似文献
117.
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119.
Burlakov VV Arndt P Baumann W Spannenberg A Rosenthal U Parameswaran P Jemmis ED 《Chemical communications (Cambridge, England)》2004,(18):2074-2075
The 2,5-dititanabicyclo[2.2.0]hex-1(4)-ene (bis-titanocene-mu-(Z)-1,2,3-butatriene complex)3 is formed starting from [Cp2Ti(eta2-Me3SiC2SiMe3)] by in situ generated titanocene and 1,4-dichlorobut-2-yne via the 1-titanacyclobut-3-yne (2). 相似文献
120.
Synthesis and derivatization of daptomycin: a chemoenzymatic route to acidic lipopeptide antibiotics
Grünewald J Sieber SA Mahlert C Linne U Marahiel MA 《Journal of the American Chemical Society》2004,126(51):17025-17031
Daptomycin is a branched cyclic nonribosomally assembled acidic lipopeptide, which is the first clinically approved antibiotic of this class. Here we show that the recombinant cyclization domain of the Streptomyces coelicolor calcium-dependent antibiotic (CDA) nonribosomal peptide synthetase (NRPS) is a versatile tool for the chemoenzymatic generation of daptomycin derivatives. Linear CDA undecapeptide thioesters with single exchanges at six daptomycin-specific residues were successfully cyclized by CDA cyclase. Simultaneous incorporation of all six of these residues into the peptide backbone and elongation of the N-terminus of CDA by two residues yielded a daptomycin derivative that lacked only the beta-methyl group of l-3-methylglutamate. Bioactivity studies with several substrate analogues revealed a significant role of nonproteinogenic constituents for antibacterial potency. In accordance with acidic lipopeptides, the bioactivity of the chemoenzymatic assembled daptomycin analogue is dependent on the concentration of calcium ions. Single deletions of the four acidic residues in the peptide backbone suggest that only two aspartic acid residues are essential for antimicrobial potency. These two residues are strictly conserved among other nonribosomal acidic lipopeptides and the EF-motif of ribosomally assembled calmodulin. Based on these findings CDA cyclase is a versatile catalyst that can be used to generate novel daptomycin derivatives that are otherwise difficult to obtain by chemical modification of the parental tridecapeptide to improve further its therapeutic activity. 相似文献