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101.
Optimized conditions for copper-catalyzed N-arylation of methyl pyroglutamate are described. These studies permitted the synthesis of methyl N-naphthylpyroglutamate, which was then cyclized to a ketone. The known dehydration of amidoketones by PPA was extended to this new scaffold to lead to a novel condensed benzo[de]quinoline with potential antioxidative activity. 相似文献
102.
Craig M. Anderson Garrett Brown Matthew W. Greenberg David Yu Nellie Bowen Rahma Ahmed Melissa Yost-Bido Alina Wray 《Tetrahedron letters》2019,60(43):151156
Several thiophene-based N^C ligands were synthesized. Strategically, a bromide was incorporated on the 2-position of the thiophene ring. When allowed to react with the platinum tetramethyl dimer, [Pt2Me4(µ-SMe2)2], platinum(IV) platinacycles were formed by oxidative addition of the C(sp2)-X bond. These platinum(IV) compounds were characterized by NMR and HRMS. The platinum (IV) compounds were subsequently subjected to thermolysis. A series of reactions occurred, including selective C-C reduction elimination and selective C-H oxidative addition, giving mixtures of platinum(II) products with varying degrees of regioselectivity. 相似文献
103.
Chondroitin/dermatan sulfate (CS/DS) chain of decorin (DCN) from human skin fibroblasts (HSk) was released by reductive β-elimination reaction and digested with chondroitin AC I lyase. Enzymatic hydrolysis mixture of CS/DS chains was separated by size-exclusion chromatography (SEC). Collected octasaccharide fraction was subjected to fully automated chip-based nanoelectrospray (nanoESI) quadrupole time-of-flight (QTOF) MS and tandem MS (MS/MS). MS of human skin fibroblasts DCN CS/DS displayed a high complexity due to the large variety of glycoforms, which under chip-nanoESI MS readily ionized to form multiply charged ions. Except for the regularly tetrasulfated octasaccharide, the investigated fraction contained four additional octasaccharides of atypical sulfation status. Two new oversulfated glycoforms and two undersulfated species were identified. Remarkably, the series of decasaccharides discovered in the same SEC pool was found to encompass a trisulfated and a novel hexasulfated [4,5-Δ-GlcAGalNAc(IdoAGalNAc)?] species. MS/MS by collision-induced dissociation (CID) on the [M-4H]? ion corresponding to the previously not reported [4,5-Δ-GlcAGalNAc(IdoAGalNAc)?](5S) corroborated for a novel motif in which three N-acetylgalactosamine (GalNAc) moieties are monosulfated, 4,5-Δ-GlcA and the first IdoA from the non-reducing end bear one sulfate group each, while the second N-acetylgalactosamine from the reducing end is unsulfated. 相似文献
104.
The determination of the content of stable isotopes, 18O and 2H, respectively, in juice water facilitates the distinction between authentic juices and juices made from concentrates by
redilution with tap water. At the same time, the detection of C4 cane or corn-derived sugar syrups in fruit juices which are produced from C3 fruit types is thus facilitated by the characteristic differences in 13C/12C, expressed as δ
13C (‰) values due to photosynthetic CO2 assimilation via the C3−, C4−, and crassulacean acid metabolism pathways. In this study, the quantitative determination of water added to an authentic
juice, on the basis of δ
18O, and δ
2H values, respectively, was successfully performed. Also, the δ
18O, and δ
2H of juice water and δ
13C of the whole juice in 18 samples were also determined. The results obtained provided us with the possibility of distinguishing
between authentic fruit juices and those obtained by redilution of concentrated fruit juices and the detection of C4 type added sugar. 相似文献
105.
Piazza ZA Li WL Romanescu C Sergeeva AP Wang LS Boldyrev AI 《The Journal of chemical physics》2012,136(10):104310
The structures and chemical bonding of the B(21)(-) cluster have been investigated by a combined photoelectron spectroscopy and ab initio study. The photoelectron spectrum at 193 nm revealed a very high adiabatic electron binding energy of 4.38 eV for B(21)(-) and a congested spectral pattern. Extensive global minimum searches were conducted using two different methods, followed by high-level calculations of the low-lying isomers. The global minimum of B(21)(-) was found to be a quasiplanar structure with the next low-lying planar isomer only 1.9 kcal/mol higher in energy at the CCSD(T)/6-311-G* level of theory. The calculated vertical detachment energies for the two isomers were found to be in good agreement with the experimental spectrum, suggesting that they were both present experimentally and contributed to the observed spectrum. Chemical bonding analyses showed that both isomers consist of a 14-atom periphery, which is bonded by classical two-center two-electron bonds, and seven interior atoms in the planar structures. A localized two-center two-electron bond is found in the interior of the two planar isomers, in addition to delocalized multi-center σ and π bonds. The structures and the delocalized bonding of the two lowest lying isomers of B(21)(-) were found to be similar to those in the two lowest energy isomers in B(19)(-). 相似文献
106.
Prof. Dr. Dmitriy M. Volochnyuk Dr. Alina O. Gorlova Prof. Dr. Oleksandr O. Grygorenko 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(62):15277-15326
This review discusses recent advances in the chemistry of saturated boronic acids, boronates, and trifluoroborates. Applications of the title compounds in the design of boron-containing drugs are surveyed, with special emphasis on α-amino boronic derivatives. A general overview of saturated boronic compounds as modern tools to construct C(sp3)−C and C(sp3)-heteroatom bonds is given, including recent developments in the Suzuki-Miyaura and Chan-Lam cross-couplings, single-electron-transfer processes including metallo- and organocatalytic photoredox reactions, and transformations of boron “ate” complexes. Finally, an attempt to summarize the current state of the art in the synthesis of saturated boronic acids, boronates, and trifluoroborates is made, with a brief mention of the “classical” methods (transmetallation of organolithium/magnesium reagents with boron species, anti-Markovnikov hydroboration of alkenes, and the modification of alkenyl boron compounds) and a special focus on recent methodologies (boronation of alkyl (pseudo)halides, derivatives of carboxylic acids, alcohols, and primary amines, boronative C−H activation, novel approaches to alkene hydroboration, and 1,2-metallate-type rearrangements). 相似文献
107.
1,4- and 1,5-disubstituted tetrazoles possess enriched structures and versatile chemistry, representing a challenge for chemists. In the present work, we unravel the fragmentation patterns of a chemically diverse range of 5-allyloxy-1-aryl-tetrazoles and 4-allyl-1-aryl-tetrazolole-5-ones when subjected to electron impact mass spectrometry (EI-MS) and investigate the correlation with the UV-induced fragmentation channels of the matrix-isolated tetrazole derivatives. Our results indicate that the fragmentation pathways of the selected tetrazoles in EI-MS are highly influenced by the electronic effects induced by substitution. Multiple pathways can be envisaged to explain the mechanisms of fragmentation, frequently awarding common final species, namely arylisocyanate, arylazide, arylnitrene, isocyanic acid and hydrogen azide radical cations, as well as allyl/aryl cations. The identified fragments are consistent with those found in previous investigations concerning the photochemical stability of the same class of molecules. This parallelism showcases a similarity in the behaviour of tetrazoles under EI-MS and UV-irradiation in the inert environment of cryogenic matrices of noble gases, providing efficient tools for reactivity predictions, whether for analytical ends or more in-depth studies. Theoretical calculations provide complementary information to articulate predictions of resulting products. 相似文献
108.
Valentina Grumezescu Irina Negut Rodica Cristescu Alexandru Mihai Grumezescu Alina Maria Holban Florin Iordache Mariana Carmen Chifiriuc Roger J. Narayan Douglas B. Chrisey 《Molecules (Basel, Switzerland)》2021,26(12)
Staphylococcus aureus (Gram-positive) and Pseudomonas aeruginosa (Gram-negative) bacteria represent major infectious threats in the hospital environment due to their wide distribution, opportunistic behavior, and increasing antibiotic resistance. This study reports on the deposition of polyvinylpyrrolidone/antibiotic/isoflavonoid thin films by the matrix-assisted pulsed laser evaporation (MAPLE) method as anti-adhesion barrier coatings, on biomedical surfaces for improved resistance to microbial colonization. The thin films were characterized by Fourier transform infrared spectroscopy, infrared microscopy, and scanning electron microscopy. In vitro biological assay tests were performed to evaluate the influence of the thin films on the development of biofilms formed by Gram-positive and Gram-negative bacterial strains. In vitro biocompatibility tests were assessed on human endothelial cells examined for up to five days of incubation, via qualitative and quantitative methods. The results of this study revealed that the laser-fabricated coatings are biocompatible and resistant to microbial colonization and biofilm formation, making them successful candidates for biomedical devices and contact surfaces that would otherwise be amenable to contact transmission. 相似文献
109.
Zamfir AD Lion N Vukelic Z Bindila L Rossier J Girault HH Peter-Katalinic J 《Lab on a chip》2005,5(3):298-307
A thin chip polymer-based microsprayer has been coupled to a hybrid quadrupole time-of-flight mass spectrometer (QTOF MS) and introduced in carbohydrate research. The feasibility of the approach is demonstrated for mapping, sequencing and structural elucidation of glycoconjugates originating from human body fluids and tissues such as a glycopeptide mixture from normal human urine and an isolated and purified GT1 ganglioside fraction from normal adult human brain. The optimization procedure required by each glycoconjugate category is described and the advantages of the system in terms of flexibility and adaptability to QTOF MS, stability of the ESI MS signal, carbohydrate ionization and sequencing, sensitivity, speed of analysis and sample consumption are discussed. 相似文献
110.