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251.
Luigi Lay Francesco Nicotra Luigi Panza Giovanni Russo Elena Adobati 《Helvetica chimica acta》1994,77(2):509-514
The synthesis of the trisaccharide α-L -Fucp-(1 → 2)-β-D -Galp-(1 → 3)-β-D -GalpNAc-1-OPr ( 2 ) is described. The N-acetylgalactosamine 6 was obtained from 4 by an intramolecular displacement of a (trifluoromethyl)sulfonyloxy by a pivaloyloxy group with its concomitant migration from position 3 to position 4 (Scheme 1). The galactosyl donor 9 was obtained from 7 via 8 by regioselective opening of the orthoester function with AcOH/pyridine followed by treatment with CCl3CN and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (Scheme 2). Glycosylation of 6 with 9 in the presence of BF3 · OEt2 gave the disaccharide 10 . Selective deprotection of 10 at O? C(2′) followed by glycosylation with 12 and by standard deprotection afforded the title trisaccharide 2 (Scheme 3). Preliminary biological testing showed that 2 is able to inhibit the binding of the monoclonal antibody MBrl to the target tumor cells MCF7 in a dose-dependent manner. 相似文献
252.
X-ray absorption spectroscopy (XAS) provides a direct means of solving the controversy on Cr oxidation states in nitroso complexes. The first XAS studies of four known Cr-NO complexes, [Cr(NO)(OH(2))(5)](2+), [Cr(NO)(acac)(2)(OH(2))], [Cr(NO)(CN)(5)](3)(-), and [Cr(NO)(NCS)(5)](3)(-), have been performed, in comparison with the related Cr(III) complexes, [Cr(OH(2))(6)](3+), [Cr(acac)(3)], [Cr(CN)(6)](3)(-), and [Cr(NCS)(6)](3)(-). The X-ray absorption near-edge structure (XANES) spectra of the Cr-NO complexes are distinguished from those of the corresponding Cr(III) complexes by increased intensities of pre-edge absorbancies due to the 1s --> 3d transition, as well as with slight shifts (by 0.2-1.0 eV) of the edge positions to lower energies, with no major changes in the edge shape. These features, together with the available structural data on Cr-NO complexes, show that the effective Cr oxidation states in such complexes are close to Cr(III), due to the pi-back-bonding within the Cr-NO moiety. Multiple-scattering fitting of X-ray absorption fine structure (XAFS) spectra of [Cr(NO)(acac)(2)(OH(2))] supported the assignment of this complex as a trans-isomer (Keller, A.; Jezovska-Trzebiatowska, B. Polyhedron 1985, 4, 1847-1852). The first crystal structure of a Cr nitroso-isothiocyanato complex, (Ph(4)P)(3)[Cr(NO)(NCS)(5)].2.4(CH(3))(2)CO, has been determined. 相似文献
253.
Chromium(V) glutathione complexes are among the likely reactive intermediates in Cr(VI)-induced genotoxicity and carcinogenicity. The first definitive structure of one such complex, [Cr(V)O(LH(2))(2)](3)(-) (I; LH(5) = glutathione = GSH), isolated from the reaction of Cr(VI) with excess GSH at pH 7.0 (O'Brien, P.; Pratt, J.; Swanson, F. J.; Thornton, P.; Wang, G. Inorg. Chim. Acta 1990, 169, 265-269), has been determined by a combination of electrospray mass spectrometry (ESMS), X-ray absorption spectroscopy (XAS), EPR spectroscopy, and analytical techniques. In addition, Cr(V) complexes of GSH ethyl ester (gamma-Glu-Cys-GlyOEt) have been isolated and characterized by ESMS, and Cr(III) products of the Cr(VI) + GSH reaction have been isolated and characterized by ESMS and XAS. The thiolato and amido groups of the Cys residue in GSH are responsible for the Cr(V) binding in I. The Cr-ligand bond lengths, determined from multiple-scattering XAFS analysis, are as follows: 1.61 A for the oxo donor; 1.99 A for the amido donors; and 2.31 A for the thiolato donors. A significant electron withdrawal from the thiolato groups to Cr(V) in I was evident from the XANES spectra. Rapid decomposition of I in aqueous solutions (pH = 1-13) occurs predominantly by ligand oxidation with the formation of Cr(III) complexes of GSH and GSSG. Maximal half-lives of the Cr(V) species (40-50 s at [Cr] = 1.0 mM and 25 degrees C) are observed at pH 7.5-8.0. The experimental data are in conflict with a recent communication (Gaggelli, E.; Berti, F.; Gaggelli, N.; Maccotta, A.; Valensin, G. J. Am. Chem. Soc. 2001, 123, 8858-8859) on the formation of a Cr(V) dimer as a major product of the Cr(VI) + GSH reaction, which may have resulted from misinterpretation of the ESMS and NMR spectroscopic data. 相似文献
254.
The reductions of K2Cr2O7 by catecholamines, DOPA, DOPA-beta,beta-d2, N-acetyl-DOPA, alpha-methyl-DOPA, dopamine, adrenaline, noradrenaline, catechol, 1,2-dihydroxybenzoic acid (DHBA), and 4-tert-butylcatechol (TBC), produce a number of Cr(V) electron paramagnetic resonance (EPR) signals. These species are of interest in relation to the potential role of oxidized proteins and amino acids in Cr-induced cancers. With excess organic ligand, all of the substrates yield Cr species with signals at g(iso) approximately 1.972 (Aiso(53Cr) > 23.9 x 10(-4) cm(-1)). These are similar to signals reported previously but have been reassigned as octahedral Cr(V) species with mixed catechol-derived ligands, [CrV(semiquinone)2(catecholate)]+. Experiments with excess K2Cr2O7 show complex behavior with the catecholamines and TBC. Several weak Cr(V) signals are detected after mixing, and the spectra evolve over time to yield relatively stable substrate-dependent signals at g(iso) approximately 1.980. These signals have been attributed to [Cr(O)L2](L = diolato) species, in which the Cr is coordinated to two cyclized catecholamine ligands and an oxo ligand. Isotopic labeling studies with DOPA (ring or side chain deuteration or enrichment with 15N), and simulation of the signals, show that the superhyperfine couplings originate from the side chain protons, confirming that the catecholamine ligands are cyclized. At pH 3.5, a major short-lived EPR signal is observed for many of the substrates at g(iso) approximately 1.969, but the species responsible for this signal was not identified. Several other minor Cr signals are detected, which are attributed (by comparison with isoelectronic V(IV) species) to Cr(V) complexes coordinated by a single catecholamine ligand (and auxiliary ligands e.g. H2O), or to [Cr(O)L2]- (L = diolato) species with a sixth ligand (e.g. H2O). Addition of catalase or deoxygenation of the solutions did not affect the main EPR signals. When the substrates were in excess (pH > 4.5), primary and secondary (cyclized) semiquinones were also detected. Semiquinone stabilization by Zn(II) complexation yielded stronger EPR signals (g(iso) approximately 2.004). 相似文献
255.
Chatterjee D Mitra A Levina A Lay PA 《Chemical communications (Cambridge, England)》2008,(25):2864-2866
[RuIII(edta)(OH2/OH)]1-/2- (edta = ethylenediaminetetraacetate) inhibits protein tyrosine phosphatase (PTP) at physiological pH values in a mechanism that involves binding of the Cys residue of the catalytic domain of the enzyme and similar interactions may be important in the anti-cancer properties of the active forms of many Ru pro-drugs. 相似文献
256.
Torres-Sanchez MI Zaccaria C Buzzi B Miglio G Lombardi G Polito L Russo G Lay L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(23):6623-6635
Neisseria meningitidis type A (MenA) is a Gram-negative encapsulated bacterium that may cause explosive epidemics of meningitis, especially in the sub-Saharan region of Africa. The development and manufacture of an efficient glycoconjugate vaccine against Neisseria meningitidis A is greatly hampered by the poor hydrolytic stability of its capsular polysaccharide, which is made up of (1-->6)-linked 2-acetamido-2-deoxy-alpha-D-mannopyranosyl phosphate repeating units. Since this chemical lability is a product of the inherent instability of the phosphodiester bridges, here we report the synthesis of phosphonoester-linked oligomers of N-acetyl mannosamine as candidates for stabilised analogues of the corresponding phosphate-bridged saccharides. The installation of each interglycosidic phosphonoester linkage was achieved by Mitsunobu coupling of a glycosyl C-phosphonate building block with the 6-OH moiety of a mannosaminyl residue. Each of the synthesised compounds contains an O-linked aminopropyl spacer at its reducing end (alpha- or beta-oriented) to allow for protein conjugation. The relative affinities of the synthetic molecules were investigated by a competitive ELISA assay and showed that a human polyclonal anti-MenA serum can recognise both the phosphonoester-bridged fragments 1-3 and their monomeric subunits, glycosides 20 and 21. Moreover, the biological results suggest that the abilities of these compounds to inhibit the binding of a specific antibody to MenA polysaccharide are dependent on the chain lengths of the molecules, but independent on the orientations of the anomeric linkers. 相似文献
257.
Gidden J Liyanage R Durham B Lay JO 《Rapid communications in mass spectrometry : RCM》2007,21(13):1951-1957
Edible oils consist primarily of triacylglycerols (TAGs). Matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectra of the oils are typically dominated by sodium adducts of these TAGs but also show prominent fragment ions (that do not contain sodium), which can interfere with analytical measurements of other components in oils. The fragments seemingly correspond to the loss of a fatty acid moiety from the sodiated TAGs as a sodium salt: RCOONa. However, a previous study suggested that the fragments actually arise from nearly complete fragmentation of unseen protonated TAGs. These authors suggested that the fragmentation occurs so rapidly and completely that protonated TAGs are not normally observed in the spectra of these oils. In this paper, we present evidence to support their theory and also demonstrate an approach to eliminate these interfering ions from the MALDI-TOF mass spectra via addition of a base to the matrix/sample mixture. The added base does not impede formation of the sodiated TAGs, but does significantly reduce the amount of fragments observed. We propose that this occurs by depleting the H+ ions from the matrix, thus preventing the formation of significant numbers of protonated TAGs in the first place. For measurements by MALDI-TOF, the relative abundances of the fragment ions are related to the strength of the base, and can be almost completely eliminated. However, in longer time-scale experiments such as in post-source decay and Fourier transform mass spectrometry, sodiated and non-sodiated diacylglycerol (DAG)-like fragments are present in spectra, regardless of whether or not a base is added to the sample. 相似文献
258.
Saw CL Olivo M Chin WW Soo KC Heng PW 《Journal of photochemistry and photobiology. B, Biology》2007,86(3):207-218
Formulations of hypericin (HY) with plasma protein have been conventionally used, but to date, no alternative pharmaceutical formulation has been developed for clinical use. Previously, it was reported that formulation of HY containing a biocompatible solvent and penetration enhancer, N-methyl pyrrolidone (NMP) was found to be effective for the delivery of HY across in vivo chick chorioallantoic membrane (CAM). This present study reports further investigations on the HY-NMP formulations in CAM implanted with human bladder cancer cells as a potential fluorescence diagnostic agent of cancer. The conventional formulation of HY (HY-HSA 0.5%) was included as control. The red-to-blue (I(R)/I(B)) intensity ratio of fluorescence images was used as a diagnostic algorithm, to differentiate the uptake of HY between tumor and adjacent regions on CAM. Results indicated that HY-NMP 0.05% was significantly better than HY-HSA 0.5%. The findings of the I(R)/I(B) ratios between tumor and adjacent tissues, indicated the potential of using NMP as an alternative to plasma protein in clinical fluorescence diagnosis with HY. The NMP formulations investigated were able to produce significantly higher contrast for tumor tissues and at earlier time points than was possible with HY-HSA 0.5%. 相似文献
259.
Chromium(III) nutritional supplements are widely used due to their purported ability to enhance glucose metabolism, despite growing evidence on low activity and the potential genotoxicity of these compounds. Reactivities of Cr(III) complexes used in nutritional formulations, including [Cr3O(OCOEt)6(OH2)3](+) (A), [Cr(pic)3] (pic=2-pyridinecarboxylato(-) (B), and trans-[CrCl2(OH2)4](+) (CrCl3.6H2O; C), in a range of natural and simulated biological media (artificial digestion systems, blood and its components, cell culture media, and intact L6 rat skeletal muscle cells) were studied by X-ray absorption near-edge structure (XANES) spectroscopy. The XANES spectroscopic data were processed by multiple linear-regression analyses with the use of a library of model Cr(III) compounds, and the results were corroborated by the results of X-ray absorption fine structure spectroscopy and electrospray mass spectrometry. Complexes A and B underwent extensive ligand-exchange reactions under conditions of combined gastric and intestinal digestion (in the presence of a semisynthetic meal, 3 h at 310 K), as well as in blood serum and in a cell culture medium (1-24 h at 310 K), with the formation of Cr(III) complexes with hydroxo and amino acid/protein ligands. Reactions of compounds A-C with cultured muscle cells led to similar ligand-exchange products, with at least part of Cr(III) bound to the surface of the cells. The reactions of B with serum greatly enhanced its propensity to be converted to Cr(VI) by biological oxidants (H2O2 or glucose oxidase system), which is proposed to be a major cause of both the insulin-enhancing activity and toxicity of Cr(III) compounds (Mulyani, I.; Levina, A.; Lay, P. A. Angew. Chem. Int. Ed. 2004, 43, 4504-4507). This finding enhances the current concern over the safety of consumption of large doses of Cr(III) supplements, particularly [Cr(pic)3]. 相似文献
260.
Patricia Perez Schmidt Dr. Katiuscia Pagano Prof. Dr. Cristina Lenardi Dr. Marta Penconi Ruth Mateu Ferrando Dr. Claudio Evangelisti Prof. Dr. Luigi Lay Dr. Laura Ragona Dr. Marcello Marelli Dr. Laura Polito 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2023,135(1):e202210140
Ultra-small gold nanoparticles (UAuNPs) are extremely interesting for applications in nanomedicine thanks to their good stability, biocompatibility, long circulation time and efficient clearance pathways. UAuNPs engineered with glycans (Glyco-UAuNPs) emerged as excellent platforms for many applications since the multiple copies of glycans can mimic the multivalent effect of glycoside clusters. Herein, we unravel a straightforward photo-induced synthesis of Glyco-UAuNPs based on a reliable and robust microfluidic approach. The synthesis occurs at room temperature avoiding the use of any further chemical reductant, templating agents or co-solvents. Exploiting 1H NMR spectroscopy, we showed that the amount of thiol-ligand exposed on the UAuNPs is linearly correlated to the ligand concentration in the initial mixture. The results pave the way towards the development of a programmable synthetic approach, enabling an accurate design of the engineered UAuNPs or smart hybrid nano-systems. 相似文献