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31.
The 3a,9a-diazaperylenium dication (1) was synthesized for the first time in two steps from p-phenylene diamine. Ab initio calculations show a twisted ground state with a 6.4 degrees tilt between the two quinolizinium building blocks. Dication 1 is photoluminescent in fluid solutions of H(2)O, CH(3)CN, and CH(3)NO(2), but not in rigid matrices of the same solvents. This phenomenon has been attributed to a geometric relaxation of the tilted ground state into an emitting planar lowest singlet excited state. [structure: see text] 相似文献
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Based on structural data of lipid A from Chlamydia trachomatis strains, chemically pure tetra- and pentaacyl 1,4′-bisphosphoryl as well as the related 4′-monophosphoryl derivatives of lipid A were synthesized. (R)-3-Hydroxyicosanoic acid as a chiral constituent was prepared via Noyori-reduction of methyl-3-oxoicosanoic acid. Synthetic intermediates were O-acylated with myristoic acid residues at positions 3 and 3′ and N-acylated with (R)-3-hydroxyicosanoic acid at both glucosamine units. Efficient purification methods for highly hydrophobic long-chain tri-, tetra- and pentaacyl progenitors of lipid A have been developed. Purity and homogeneity of the synthetic target compounds were confirmed by NMR and MS-data as well as a sensitive immunostaining approach. The tetra- and pentaacyl species serve as biomedical probes to investigate the endotoxic potential of chlamydial lipid A and to clarify its role in Chlamydia associated infections. 相似文献
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The bacterial metabolite and potent innate immune modulator d-glycero-β-d-manno-heptose-1,7-bisphosphate (HBP) and its α-configured counterpart d-glycero-α-d-manno-heptose-1,7-bisphosphate were synthesized via stereoselective anomeric phosphorylation of the peracetylated d,d-heptose 7-dibenzylphosphate by exploiting different nucleophilicity of equatorial and axial lactols in the d-manno-series. We also report a novel approach for anomeric phosphorylation using modified Mitsunobu reaction conditions and provide the first full structural characterization of HBP. The first chemical synthesis of HBP offers access to an anomerically pure structurally defined probe for biological studies and to a lead compound operating as a powerful stimulator of intracellular signaling for possible therapeutic immunomodulation. 相似文献
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Synthesis of Chlamydia Lipopolysaccharide Haptens through the use of α‐Specific 3‐Iodo‐Kdo Fluoride Glycosyl Donors 下载免费PDF全文
Barbara Pokorny Prof. Paul Kosma 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):305-313
A scalable approach towards high‐yielding and (stereo)selective glycosyl donors of the 2‐ulosonic acid Kdo (3‐deoxy‐D ‐manno‐oct‐2‐ulosonic acid) is a fundamental requirement for the development of vaccines against Gram‐negative bacteria. Herein, we disclose a short synthetic route to 3‐iodo Kdo fluoride donors from Kdo glycal esters that enable efficient α‐specific glycosylations and significantly suppress the elimination side reaction. The potency of these donors is demonstrated in a straightforward, six‐step synthesis of a branched Chlamydia‐related Kdo‐trisaccharide ligand without the need for protecting groups at the Kdo glycosyl acceptor. The approach was further extended to include sequential iteration of the basic concept to produce the linear Chlamydia‐specific α‐Kdo‐(2→8)‐α‐Kdo‐(2→4)‐α‐Kdo trisaccharide in a good overall yield. 相似文献
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Focusing 12 fs pulses of 800 nm with moderate energy (0.35 mJ) into atmospheric-pressure argon (Ar) gives rise to filamentation (self-focusing) and a supercontinuum with a very broad pedestal, extending to 250 nm. According to the present understanding, the short wavelengths are produced by self-phase modulation in the self-steepened trailing edge of the pulse. Pulses in this spectral range might thus be intrinsically short. Indeed we demonstrate this by extracting the light near the end of the filament, terminating self-focusing by a pressure gradient at a pinhole, beyond which the Ar is pumped away. We obtain pulses of 9.7 fs in the region of 290 nm without the necessity of compression. 相似文献
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Ioannis T. Papadas Chariklia Kosma Yiannis Deligiannakis 《Journal of colloid and interface science》2009,339(1):19-30
Cu2+ binding on γ-Al2O3 is modulated by common electrolyte ions such as Mg2+, , and in a complex manner: (a) At high concentrations of electrolyte ions, Cu2+ uptake by γ-Al2O3 is inhibited. This is partially due to bulk ionic strength effects and, mostly, due to direct competition between Mg2+ and Cu2+ ions for the SO− surface sites of γ-Al2O3. (b) At low concentrations of electrolyte ions, Cu2+ uptake by γ-Al2O3 can be enhanced. This is due to synergistic coadsorption of Cu2+ and electrolyte anions, and . This results in the formation of ternary surface species (SOH2SO4Cu)+, (SOH2PO4Cu), and (SOH2HPO4Cu)+ which enhance Cu2+ uptake at pH < 6. The effect of phosphate ions may be particularly strong resulting in a 100% Cu uptake by the oxide surface. (c) EPR spectroscopy shows that at pH pHPZC, Cu2+ coordinates to one SO− group. Phosphate anions form stronger, binary or ternary, surface species than sulfate anions. At pH pHPZC Cu2+ may coordinate to two SO− groups. At pH pHPZC electrolyte ions and are bridging one O-atom from the γ-Al2O3 surface and one Cu2+ ion forming ternary [γ-Al2O3/elecrolyte/Cu2+] species. 相似文献
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A common approach to finding numerical solutions of the time-dependent incompressible Navier-Stokes equations is considered within the method of lines framework [1]. For the determination of viscous incompressible flows the stream-function formulation for the fourth-order equation [2, 3], an artificial compressibility method [4], and a modified velocity correction method [5] are designed. Some improved and extended results of numerical simulations obtained by the author in the previous works are presented. Test calculations have been done for various flows inside square, triangular and semicircular cavities with one moving wall, the backward-facing step, double bent channels and for the flow around an aerofoil at large angle of attack. An alternative and practical methodology for resolving the Navier-Stokes equations in arbitrarily complex geometries using Cartesian meshes is proposed. Some of complex geometrical configurations can be decomposed into a set of subdomains. The simplest approach for specifying boundary conditions near curved or irregular boundaries is to transfer all the variables from the boundaries to the nearest grid knots. (© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
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By reaction of several N-phenyl-benzamidrazones with SO2F2 2-phenyl-2,5-dihydro-1,2,3,5-thiatriazole-1,1-dioxides2 a–c are formed. By reaction of N,N-diethyl-N-chlorosulfonyl-chloroformamidine8 with hydrazines the corresponding 4-diethylamino-substituted derivatives9 a–d are obtained. Methylation of2 b yields two isomeric products5 and6, whereas by methylation of9 d only one product9 b is obtained. 相似文献