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131.
Pyranoside‐into‐Furanoside Rearrangement: New Reaction in Carbohydrate Chemistry and Its Application in Oligosaccharide Synthesis 下载免费PDF全文
Dr. Vadim B. Krylov Dmitry A. Argunov Dmitry Z. Vinnitskiy Stella A. Verkhnyatskaya Dr. Alexey G. Gerbst Dr. Nadezhda E. Ustyuzhanina Dr. Andrey S. Dmitrenok Prof. Dr. Johannes Huebner Prof. Dr. Otto Holst Prof. Dr. Hans‐Christian Siebert Prof. Dr. Nikolay E. Nifantiev 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(50):16516-16522
Great interest in natural furanoside‐containing compounds has challenged the development of preparative methods for their synthesis. Herein a novel reaction in carbohydrate chemistry, namely a pyranoside‐into‐furanoside (PIF) rearrangement permitting the transformation of selectively O‐substituted pyranosides into the corresponding furanosides is reported. The discovered process includes acid‐promoted sulfation accompanied by rearrangement of the pyranoside ring into a furanoside ring followed by solvolytic O‐desulfation. This process, which has no analogy in organic chemistry, was shown to be a very useful tool for the synthesis of furanoside‐containing complex oligosaccharides, which was demonstrated by synthesizing disaccharide derivatives α‐D ‐Galp‐(1→3)‐β‐D ‐ Galf ‐OPr, 3‐O‐s ‐lactyl‐β‐D ‐ Galf ‐(1→3)‐β‐D ‐Glcp‐OPr, and α‐L ‐ Fucf ‐(1→4)‐β‐D ‐GlcpA‐OPr related to polysaccharides from the bacteria Klebsiella pneumoniae and Enterococcus faecalis and the brown seaweed Chordaria flagelliformis. 相似文献
132.
Physicochemical and adsorption properties of hypercross‐linked polystyrene with ultimate cross‐linking density 下载免费PDF全文
Maria P. Tsyurupa Zinaida K. Blinnikova Yuri A. Borisov Mikhail M. Ilyin Tamara P. Klimova Kiril V. Mitsen Vadim A. Davankov 《Journal of separation science》2014,37(7):803-810
The paper describes unexpected properties of hypercross‐linked polystyrenes with ultimate cross‐linking degrees of 300, 400, and 500%, where three, four, or five methylene links, respectively, could bind each polystyrene phenyl ring to its spacious neighbors. The polymers exhibit a strong electron spin resonance signal, unusual spectra in IR, UV, and visible ranges, and they are not typical dielectrics. The nonfunctionalized hypercross‐linked polymers absorb significant amounts of inorganic acids, salts, and bases due to interactions of protons or other cations with electron‐donating fragments of the aromatic network with the high extent of mutual connectivity and also due to dispersion interactions of anions with the polymer matrix. 相似文献
133.
An efficient and convenient method for the synthesis of aryl hydrazines has been developed via copper-catalyzed cross-coupling of aryl bromides and hydrazine with a readily accessible ligand and water as a solvent. The multigram scale procedure is applicable to aryl bromides bearing both moderately electron-donating and electron-withdrawing substituents in the aromatic nucleus. No column chromatography is required to obtain aryl hydrazine hydrochlorides in good yields. 相似文献
134.
The coordination chemistry of solvated Ag(I) and Au(I) ions has been studied in some of the most strong electron-pair donor solvents, liquid and aqueous ammonia, and the P donor solvents triethyl, tri-n-butyl, and triphenyl phosphite and tri-n-butylphosphine. The solvated Ag(I) ions have been characterized in solution by means of extended X-ray absorption fine structure (EXAFS), Raman, and (107)Ag NMR spectroscopy and the solid solvates by means of thermogravimetry and EXAFS and Raman spectroscopy. The Ag(I) ion is two- and three-coordinated in aqueous and liquid ammonia solutions with mean Ag-N bond distances of 2.15(1) and 2.26(1) A, respectively. The crystal structure of [Ag(NH3)3]ClO4.0.47 NH3 (1) reveals a regular trigonal-coplanar coordination around the Ag(I) ion with Ag-N bond distances of 2.263(6) A and a Ag...Ag distance of 3.278(2) A separating the complexes. The decomposition products of 1 have been analyzed, and one of them, [Ag(NH3)2]ClO4, has been structurally characterized by means of EXAFS, showing [Ag(NH3)2] units connected into chains by double O bridges from perchlorate ions; the Ag...Ag distance is 3.01(1) A. The linear bisamminegold(I) complex, [Au(NH3)2]+, is predominant in both liquid and aqueous ammonia solutions, as well as in solid [Au(NH3)2]BF4, with Au-N bond distances of 2.022(5), 2.025(5), and 2.026(7) A, respectively. The solvated Ag(I) ions are three-coordinated, most probably in triangular fashion, in the P donor solvents with mean Ag-P bond distances of 2.48-2.53 A. The Au(I) ions are three-coordinated in triethyl phosphite and tri-n-butylphosphine solutions with mean Au-P bond distances of 2.37(1) and 2.40(1) A, respectively. 相似文献
135.
Teeters-Kennedy SM Rodriguez KR Rogers TM Zomchek KA Williams SM Sudnitsyn A Carter L Cherezov V Caffrey M Coe JV 《The journal of physical chemistry. B》2006,110(43):21719-21727
The flow of polarized light through a metal film with an array of microchannels is controlled by the phase of an optically active, phospholipid nanocoating, even though the coating does not cover the open area of the microchannels. The molecular details of the assembly (DPPC phospholipid monolayer/bilayer on a hexadecanethiol monolayer on a copper- or nickel-coated microarray) were determined using the infrared, surface-plasmon-mediated, extraordinary transmission of the metal microarrays. Infrared absorption spectra with greatly enhanced absorptions by comparison to literature were recorded and used as a diagnostic for the phase, composition, and molecular geometry of these nanocoatings. This approach presents new tools for nanoscale construction in constricted microspaces, which may ultimately be useful with individual microchannels. 相似文献
136.
Gaspar AB Ksenofontov V Reiman S Gütlich P Thompson AL Goeta AE Muñoz MC Real JA 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(36):9289-9298
The crystal structure of the complex [{Fe(bt)(NCS)(2)}(2)bpym] (1) (bt=2,2'-bithiazoline, bpym=2,2'-bipyrimidine) has been solved at 293, 240, 175 and 30 K. At all four temperatures the crystal remains in the P space group with a=8.7601(17), b=9.450(2), c=12.089(3) A, alpha=72.77(2), beta=79.150(19), gamma=66.392(18) degrees , V=873.1(4) Angstrom(3) (data for 293 K structure). The structure consists of centrosymmetric dinuclear units in which each iron(II) atom is coordinated by two NCS(-) ions in the cis position and two nitrogen atoms of the bridging bpym ligand, with the remaining positions occupied by the peripheral bt ligand. The iron atom is in a severely distorted octahedral FeN(6) environment. The average Fe--N bond length of 2.15(9) Angstrom indicates that compound 1 is in the high-spin state (HS-HS) at 293 K. Crystal structure determinations at 240, 175 and 30 K gave a cell comparable to that seen at 293 K, but reduced in volume. At 30 K, the average Fe--N distance is 1.958(4) Angstrom, showing that the structure is clearly low spin (LS-LS). At 175 K the average Fe--N bond length of 2.052(11) Angstrom suggests that there is an intermediate phase. M?ssbauer investigations of the light-induced excited spin state trapping (LIESST) effect (lambda=514 nm, 25 mW cm(-2)) in 1 (4.2 K, H(ext)=50 kOe) show that the excited spin states correspond to the HS-HS and HS-LS pairs. The dynamics of the relaxation of the photoexcited states studied at 4.2 K and H(ext)=50 kOe demonstrate that HS-HS pairs revert with time to both HS-LS and LS-LS configurations. The HS-LS photoexcited pairs relax with time back to the ground LS-LS configuration. Complex [{Fe(0.15)Zn(0.85)(bt)(NCS)(2)}(2)bpym] (2) exhibits a continuous spin transition centred around 158 K in contrast to the two-step transition observed for 1. The different spin-crossover behaviour observed for 2 is due to the decrease of cooperativity (intermolecular interactions) imposed by the matrix of Zn(II) ions. This clearly demonstrates the role of the intermolecular interactions in the stabilization of the HS-LS intermediate state in 1. 相似文献
137.
Polar Red‐Emitting Rhodamine Dyes with Reactive Groups: Synthesis,Photophysical Properties,and Two‐Color STED Nanoscopy Applications 下载免费PDF全文
Dr. Kirill Kolmakov Dr. Christian A. Wurm M. Sc. Dirk N. H. Meineke Dipl.‐Biol. Fabian Göttfert Prof. Vadim P. Boyarskiy Dr. Vladimir N. Belov Prof. Stefan W. Hell 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(1):146-157
The synthesis, reactivity, and photophysical properties of new rhodamines with intense red fluorescence, two polar residues (hydroxyls, primary phosphates, or sulfonic acid groups), and improved hydrolytic stability of the amino‐reactive sites (NHS esters or mixed N‐succinimidyl carbonates) are reported. All fluorophores contain an N‐alkyl‐1,2‐dihydro‐2,2,4‐trimethylquinoline fragment, and most of them bear a fully substituted tetrafluoro phenyl ring with a secondary carboxamide group. The absorption and emission maxima in water are in the range of 635–639 and 655–659 nm, respectively. A vastly simplified approach to red‐emitting rhodamines with two phosphate groups that are compatible with diverse functional linkers was developed. As an example, a phosphorylated dye with an azide residue was prepared and was used in a click reaction with a strained alkyne bearing an N‐hydroxysuccinimid (NHS) ester group. This method bypasses the undesired activation of phosphate groups, and gives an amphiphilic amino‐reactive dye, the solubility and distribution of which between aqueous and organic phases can be controlled by varying the pH. The presence of two hydroxyl groups and a phenyl ring with two carboxyl residues in the dyes with another substitution pattern is sufficient for providing the hydrophilic properties. Selective formation of a mono‐N‐hydroxysuccinimidyl ester from 5‐carboxy isomer of this rhodamine is reported. The fluorescence quantum yields varied from 58 to 92 % for free fluorophores, and amounted to 18–64 % for antibody conjugates in aqueous buffers. The brightness and photostability of these fluorophores facilitated two‐color stimulated emission depletion (STED) fluorescence nanoscopy of biological samples with high contrast and minimal background. Selecting a pair of fluorophores with absorption/emission bands at 579/609 and 635/655 nm enabled two‐color channels with low cross‐talk and negligible background at approximately 40 nm resolution. 相似文献
138.
Sidorkin VF Belogolova EF Pestunovich VA 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(7):2021-2031
B3LYP and MP2 computations have been performed on a variety of Si,Si'-substituted N,N'-bis(silylmethyl)propylene ureas. According to electron-density atoms-in-molecules (AIM) and electron localization function (ELF) quantum-topological analyses, a transition from the unstable non-chelate forms of these compounds to mono- and bis-chelate forms results in the successive interaction of one and two tetracoordinate silicon atoms with the carbonyl oxygen and the formation, respectively, of one and two covalent, polar Si...O bonds. This previously unknown X-Si<--O-->Si-X type of bonding in isomers possessing an anchor structure may be classified as a five-center, six-electron (5c-6e) bond. The factors that favor the existence of Si,Si'-substituted N,N'-bis(silylmethyl)propylene ureas exclusively in the form of stable, bridged complexes (the size of equatorial ligands and the electronegativity of axial substituents at the silicon atom, change in the donor capability of the carbonyl group, and effect of the polar solvent) are discussed. 相似文献
139.
140.
Soloshonok VA Cai C Yamada T Ueki H Ohfune Y Hruby VJ 《Journal of the American Chemical Society》2005,127(43):15296-15303
This paper describes a systematic study of addition reactions between the chiral Ni(II) complex of the Schiff base of glycine with (S)-o-[N-(N-benzylprolyl)amino]benzophenone and (S)- or (R)-3-[(E)-enoyl]-4-phenyl-1,3-oxazolidin-2-ones as a general and synthetically efficient approach to beta-substituted pyroglutamic acids and relevant compounds. These reactions were shown to occur at room temperature in the presence of nonchelating organic bases and, most notably, with very high (>98% diastereomeric excess (de)) stereoselectivity at both newly formed stereogenic centers. The stereochemical outcome of the reactions was found to be overwhelmingly controlled by the stereochemical preferences of the Michael acceptors, and the chirality of the glycine complex influenced only the reaction rate. Thus, in the reactions of both the (S)-configured Ni(II) complex and the Michael acceptors, the reaction rates were exceptionally high, allowing preparation of the corresponding products with virtually quantitative (>98%) chemical and stereochemical yields. In contrast, reactions of the (S)-configured Ni(II) complex and (R)-configured Michael acceptors proceeded at noticeably lower rates, but the addition products were obtained in high diastereo- and enantiomeric purity. To rationalize the remarkably high and robust stereoselectivity observed in these reactions, we consider an enzyme-substrate-like mode of interaction involving a topographical match or mismatch of two geometric figures. Excellent chemical and stereochemical yields, combined with the simplicity and operational convenience of the experimental procedures, render the present method of immediate use for preparing various beta-substituted pyroglutamic acids and related compounds. 相似文献