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21.
The structures of two saponins, thyonosides A and B, isolated from the holothurian Thyone aurea collected in Namibia, were elucidated by 1D and 2D NMR (1H, 13C, 1H-1H COSY, 1H-1H J-resolved, TOCSY, HMQC, HMBC and NOESY). The two compounds have the same aglycon but different oligosaccharidic chains. Thyonoside A has a 3-O-methyl-β-d-xylopyranosyl-(1→3)-6-O-sodium sulphate-β-d-glucopyranosyl-(1→4)-β-d-quinovopyranosyl-(1→2)-4-O-sodium sulphate-β-d-xylopyranosyl chain, and thyonoside B a 3-O-methyl-β-d-xylopyranosyl-(1→4)-β-d-xylopyranosyl-(1→4)-β-d-quinovopyranosyl-(1→2)-4-O-sodium sulphate-β-d-xylopyranosyl chain. The holostane-type aglycon features an endocyclic double bond at position 7-8, a double bond at position 25-26 and a β-acetoxy group at C16. 相似文献
22.
Copolymerization of an excess of methyl methacrylate (MMA) relative to 2-hydroxyethyl methacrylate (HEMA) was carried out in toluene at 80 °C according to both conventional and controlled Ni-mediated radical polymerizations. Reactivity ratios were derived from the copolymerization kinetics using the Jaacks method for MMA and integrated conversion equation for HEMA (rMMA = 0.62 ± 0.04; rHEMA = 2.03 ± 0.74). Poly(ethylene glycol) α-methyl ether, ω-methacrylate (PEGMA, Mn = 475 g mol−1) was substituted for HEMA in the copolymerization experiments and reactivity ratios were also determined (rMMA = 0.75 ± 0.07; rPEGMA ∼ 1.33). Both the functionalized comonomers were consumed more rapidly than MMA indicating the preferred formation of heterogeneous bottle-brush copolymer structures with bristles constituted by the hydrophilic (macro)monomers. Reactivity ratios for nickel-mediated living radical polymerization were comparable with those obtained by conventional free radical copolymerization. Interactions between functional monomers and the catalyst (NiBr2(PPh3)2) were observed by 1H NMR spectroscopy. 相似文献
23.
Isabelle FavierElisabet Duñach 《Tetrahedron》2003,59(10):1823-1830
Mandelic acid and some aryl substituted derivatives were oxidised under molecular oxygen and a catalytic amount of Bi(0). The corresponding aldehydes and/or the carboxylic acids were obtained selectively depending on the nature of the substituent. Aldehydes and α-keto acids were oxidised under the same Bi(0)/O2 system and α-keto acids were proposed as intermediates in the formation of benzoic acid derivatives. 相似文献
24.
Michael Knorr Isabelle Jourdain Carsten Strohmann 《Journal of organometallic chemistry》2005,690(6):1456-1466
Insertion of hexafluorobutyne into the Pt-H bond of the heterobimetallic complexes [(OC)3Fe{Si(OMe)3}(μ-Ph2PXPPh2)Pt(H)(PPh3)] (1a X = CH2; 1b X = NH) yields the σ-alkenyl complexes [(OC)3Fe{μ-Si(OMe)2(OMe)}(μ-Ph2PXPPh2)Pt{C(CF3)C(H)CF3}] (3a X = CH2; 3b X = NH). This insertion reaction is accompanied by dissociation of the platinum bound PPh3 ligand and saturation of the vacant coordination site by a dative μ−η2-Si-O → Pt interaction. Addition of the Pt-H bond of 1a across the triple bond of 3,3,3-trifluoropropyne affords in a regiospecific manner [(OC)3Fe{μ-Si(OMe)2(OMe)}(μ-dppm)Pt{C(CF3)CH2}] (2) having the trifluoromethyl substituent on the α-carbon. Addition of RNC to 3 affords the isocyanide adducts [(OC)3Fe{Si(OMe)3}(μ-Ph2PXPPh2)Pt(CNR){C(CF3)C(H)CF3}] (4a R = t-Bu, X = CH2; 4b R = 2,6-xylyl, X = CH2; 4c R = 2,6-xylyl, X = NH). In dichloromethane solution 3a is gradually transformed into the C4F6-bridged compound [(OC)3Fe(μ-dppm)(μ-CF3CCCF3)Pt(CO)] 5. The Pt-bound carbonyl ligand of 5 is displaced by xylylisocyanide or trimethylphosphite affording the derivatives [(OC)3Fe(μ-dppm)(μ-CF3CCCF3)Pt(CNxylyl)] 6 and [(OC)3Fe(μ-dppm)(μ-CF3CCCF3)Pt{P(OMe)3}] 7. The molecular structures of 4a, 5 and 6 have been determined by X-ray diffraction studies. 相似文献
25.
Ravindra K. Pandeyi † William R. Potter Isabelle Meunier Adam B. Sumlin Kevin M. Smith 《Photochemistry and photobiology》1995,62(4):764-768
Abstract— A first report on the biological evaluation of a series of isomerically pure benzoporphyrin derivatives ( cis- and frarcs-isomers) as methyl esters is described. In preliminary in vivo studies, the n- bexyl ether analogues of both cis- and trans -isomers of benzoporphyrin derivatives were found to be more active than the industrially prepared benzoporphyrin derivative, a mixture of monocarboxylic acids (BPDMA, Quadralogic Technologies, Vancouver). Further studies with 4-de-vinyl-4-(I-hexyloxyethyl) benzoporphyrin derivative showed that, like BPDMA, it had reduced residual skin phototoxicity compared in mice with Photofrin®. The uptake and clearance characteristics of BPDMA were also compared with the 4-(1-hexyloxyethyl)-derivative by in vivo reflection spectroscopy. 相似文献
26.
Dupont-Gillain CC Jacquemart I Rouxhet PG 《Colloids and surfaces. B, Biointerfaces》2005,43(3-4):179-186
In the last years, adsorbed collagen was shown to form layers with a supramolecular organization depending on the substrate surface properties and on the preparation procedure. If the concentration of collagen and the duration of adsorption are sufficient, fibrillar collagen structures are formed, corresponding to assemblies of a few molecules. This occurs more readily on hydrophobic compared to hydrophilic surfaces. This study aims at understanding the origin of such fibrillar structures and in particular at determining whether they result from the deposition of fibrils formed in solution or from the building of assemblies at the interface. Therefore, type I collagen solutions with an increasing degree of aggregation were prepared, using the “neutral-start” approach, by ageing pH 5.8 solutions at 37 °C for 15 min, 2 or 7 days. The obtained solutions were used to investigate the influence of collagen aggregation in solution on the supramolecular organization of adsorbed collagen layers, which was characterized by X-ray photoelectron spectroscopy and atomic force microscopy. Polystyrene and plasma-oxidized polystyrene were chosen as substrates for the adsorption. The size and the density of collagen fibrils at the interface decreased upon increasing the degree of aggregation of collagen in solution. This is explained by a competitive adsorption process between monomers and aggregates of the solution, turning at the advantage of the monomers. More aggregated solutions, which are thus depleted in free monomers, behave like less concentrated solutions, i.e. lead to a lower adsorbed amount and less fibril formation at the interface. This study shows that the supramolecular fibrils observed in adsorbed collagen layers, especially on hydrophobic substrates, are not formed in the solution, prior to adsorption, but are built at the interface, through the assembly of free segments of adsorbed molecules. 相似文献
27.
Jonas Bruckhuisen Sathapana Chawananon Isabelle Kleiner Anthony Roucou Guillaume Dhont Colwyn Bracquart Pierre Asselin Arnaud Cuisset 《Molecules (Basel, Switzerland)》2022,27(11)
Methylfurans are methylated aromatic heterocyclic volatile organic compounds and primary or secondary pollutants in the atmosphere due to their capability to form secondary organic aerosols in presence of atmospheric oxidants. There is therefore a significant interest to monitor these molecules in the gas phase. High resolution spectroscopic studies of methylated furan compounds are generally limited to pure rotational spectroscopy in the vibrational ground state. This lack of results might be explained by the difficulties arisen from the internal rotation of the methyl group inducing non-trivial patterns in the rotational spectra. In this study, we discuss the benefits to assign the mm-wave rotational-torsional spectra of methylfuran with the global approach of the BELGI-C code compared to local approaches such as XIAM and ERHAM. The global approach reproduces the observed rotational lines of 2-methylfuran and 3-methylfuran in the mm-wave region at the experimental accuracy for the ground v and the first torsional v states with a unique set of molecular parameters. In addition, the and parameters describing the internal rotation potential barrier may be determined with a high degree of accuracy with the global approach. Finally, a discussion with other heterocyclic compounds enables the study of the influence of the electronic environment on the hindered rotation of the methyl group. 相似文献
28.
29.
Baptiste Schindler Agathe Depraz Depland Gina Renois-Predelus Gabriel Karras Bruno Concina Gulabi Celep Jacques Maurelli Vincent Loriot Eric Constant Richard Bredy Christian Bordas Franck Lépine Isabelle Compagnon 《International Journal for Ion Mobility Spectrometry》2017,20(3-4):119-124
An original workflow allowing inline FAIMS separation, electrospray ionization, mass analysis and ion spectroscopy (IRMPD: InfraRed Multiple Photon Dissociation) is presented for multidimensional molecular analysis. This new instrument consists of an ultraFAIMS (Owlstone) device interfaced to a linear ion trap (LTQ XL Thermo Scientific) which was modified for IRMPD spectroscopy. Two modes of operation are demonstrated on an isomeric mixture of paracetamol and 2-phenylglycine. In the first mode a FAIMS (high-Field Asymmetric waveform Ion Mobility Spectrometry) separation of the isomers is performed with a static compensation field for mass- and isomer- selective ion spectroscopy. In the second mode, the compensation field is scanned while the ions are irradiated at a fixed wavenumber. The advantages of this workflow as compared to traditional FAIMS-MS and IRMPD spectroscopy are described. The potential of the two modes for molecular spectroscopy and analytical applications, in particular the new “omics” are discussed. 相似文献
30.
Access to New Endoperoxide Derivatives by Electrochemical Oxidation of Substituted 3‐Azabicyclo[4.1.0]hept‐4‐enes 下载免费PDF全文
Dr. Frédérick Nuter Dr. Abdou Khadre Djily Dimé Dr. Cheng Chen Dr. Lotfi Bounaadja Dr. Elisabeth Mouray Dr. Isabelle Florent Dr. Yvan Six Dr. Olivier Buriez Dr. Angela Marinetti Dr. Arnaud Voituriez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(14):5584-5593
A series of substituted 3‐azabicyclo[4.1.0]hept‐4‐ene derivatives were prepared and analysed by cyclic voltammetry. Preparative aerobic electrochemical oxidation reactions were then carried out. Three original endoperoxides were isolated, characterised and subjected to antimalarial and cytotoxicity activity assays. 相似文献