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471.
Cisse L Djande A Capo-Chichi M Delatre F Saba A Tine A Aaron JJ 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,79(3):428-436
The solvent effects on the electronic absorption and fluorescence emission spectra of several coumarins derivatives, containing amino, N,N-dimethyl-amino, N,N-diethyl-amino, hydroxyl, methyl, carboxyl, or halogen substituents at the positions 7, 4, or 3, were investigated in eight solvents with various polarities. The first excited singlet-state dipole moments of these coumarins were determined by various solvatochromic methods, using the theoretical ground-state dipole moments which were calculated by the AM1 method. The first excited singlet-state dipole moment values were obtained by the Bakhshiev, Kawski-Chamma-Viallet, Lippert-Mataga, and Reichardt-Dimroth equations, and were compared to the ground-state dipole moments. In all cases, the dipole moments were found to be higher in the excited singlet-state than in the ground state because of the different electron densities in both states. The red-shifts of the absorption and fluorescence emission bands, observed for most compounds upon increasing the solvent polarity, indicated that the electronic transitions were of π-π* nature. 相似文献
472.
Ines Ghorbel Aljia Afli Souhir Abid Martine Tessier Rachid El Gharbi Alain Fradet 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(6):433-440
A solution polyaddition procedure was applied to prepare furanic polyacylsemicarbazides based on 2,2′-isopropylidene-bis(5-(2-furoyl) hydrazide) and aliphatic or aromatic diisocyanates. Model compounds were prepared to facilitate the synthesis and the characterization of the polymers. A systematic study of reaction parameters (the nature of the organic phase, the temperature, the reaction time, and the concentration of monomers) was carried out. High MW polymers were obtained after 12 h reaction at 20°C with 0.2 M monomer solutions in dimethylacetamide. In fact, the polyacylsemicarbazides obtained had inherent viscosities ranging from 0.63 to 0.85 dL/g. There showed good solubility in aprotic polar solvents. The 1H and 13C-NMR spectra were consistent with the expected structures. These furan-based polyacylsemicarbazides are thermally stable up to 290°C, but exhibit a complex thermal behavior. This was explained by the cyclohydration of acylsemicarbazide groups into NH-substituted oxadiazoles, resulting in rigid and high melting polymers, less stable, however, than conventional aromatic polyoxadiazoles. 相似文献
473.
Claveranne-Lamolère C Aupiais J Lespes G Frayret J Pili E Pointurier F Potin-Gautier M 《Talanta》2011,85(5):2504-2510
This paper deals with the study of uranium-colloid interactions in a carbonated soil. The work is focused on the immediately available fraction obtained after a leaching process, according to a normalized batch method. In order to characterize the different colloidal carriers, Asymmetrical Flow Field-Flow Fractionation (As-Fl-FFF) coupled to different detectors (UV, Multi Angle Laser Light Scattering (MALLS) and Inductively coupled Plasma-Mass Spectrometry (ICP-MS)) was used. The colloidal carriers are mainly inorganic particles (carbonated particles and clays) mixed with organic substances. Furthermore, dissolved and colloidal uranium species in the leaching solutions were monitored by Capillary Electrophoresis (CE) coupled to ICP-MS, in order to investigate the uranium/colloids interactions. According to the first results, uranium fate in this specific soil is controlled by sorption/desorption phenomena, strongly pH dependent. 相似文献
474.
Renault M Bos MP Tommassen J Baldus M 《Journal of the American Chemical Society》2011,133(12):4175-4177
Multidomain proteins constitute a large part of prokaryotic and eukaryotic proteomes and play fundamental roles in various physiological processes. However, their structural characterization is challenging because of their large size and intrinsic flexibility. We show here that motional-filtered high-resolution solid-state NMR (ssNMR) experiments allow for the observation and structural analysis of very large multidomain membrane proteins that are characterized by different motional time scales. This approach was used to probe the folding of the 790-residue membrane protein BamA, which is the core component of the Escherichia coli outer membrane protein assembly machinery. A combination of dipolar- and scalar-based two-dimensional ssNMR experiments applied to two uniformly (13)C,(15)N-labeled BamA variants revealed characteristic secondary structure elements and distinct dynamics within the BamA transmembrane protein segment and the periplasmic POTRA domains. This approach hence provides a general strategy for collecting atomic-scale structural information on multidomain (membrane) proteins in a native-like environment. 相似文献
475.
Recently, much attention has been given to a noteworthy property of some soft tissues: their ability to grow. Many attempts have been made to model this behavior in biology, chemistry, and physics. Using the theory of finite elasticity, Rodriguez has postulated a multiplicative decomposition of the geometric deformation gradient into a growth-induced part and an elastic one needed to ensure compatibility of the body. In order to fully explore the consequences of this hypothesis, the equations describing thin elastic objects under finite growth are derived. Under appropriate scaling assumptions for the growth rates, the proposed model is of the F?ppl-von Kármán type. As an illustration, the circumferential growth of a free hyperelastic disk is studied. 相似文献
476.
Quanchi Chen Jordi-Amat Cuello-Garibo Ludovic Bretin Liyan Zhang Vadde Ramu Yasmin Aydar Yevhen Batsiun Sharon Bronkhorst Yurii Husiev Nataliia Beztsinna Lanpeng Chen Xue-Quan Zhou Claudia Schmidt Ingo Ott Martine J. Jager Albert M. Brouwer B. Ewa Snaar-Jagalska Sylvestre Bonnet 《Chemical science》2022,13(23):6899
In vivo data are rare but essential for establishing the clinical potential of ruthenium-based photoactivated chemotherapy (PACT) compounds, a new family of phototherapeutic drugs that are activated via ligand photosubstitution. Here a novel trisheteroleptic ruthenium complex [Ru(dpp)(bpy)(mtmp)](PF6)2 ([2](PF6)2, dpp = 4,7-diphenyl-1,10-phenanthroline, bpy = 2,2′-bipyridine, mtmp = 2-methylthiomethylpyridine) was synthesized and its light-activated anticancer properties were validated in cancer cell monolayers, 3D tumor spheroids, and in embryonic zebrafish cancer models. Upon green light irradiation, the non-toxic mtmp ligand is selectively cleaved off, thereby releasing a phototoxic ruthenium-based photoproduct capable notably of binding to nuclear DNA and triggering DNA damage and apoptosis within 24–48 h. In vitro, fifteen minutes of green light irradiation (21 mW cm−2, 19 J cm−2, 520 nm) were sufficient to generate high phototherapeutic indexes (PI) for this compound in a range of cancer cell lines including lung (A549), prostate (PC3Pro4), conjunctival melanoma (CRMM1, CRMM2, CM2005.1) and uveal melanoma (OMM1, OMM2.5, Mel270) cancer cell lines. The therapeutic potential of [2](PF6)2 was further evaluated in zebrafish embryo ectopic (PC3Pro4) or orthotopic (CRMM1, CRMM2) tumour models. The ectopic model consisted of red fluorescent PC3Pro4-mCherry cells injected intravenously (IV) into zebrafish, that formed perivascular metastatic lesions at the posterior ventral end of caudal hematopoietic tissue (CHT). By contrast, in the orthotopic model, CRMM1- and CRMM2-mCherry cells were injected behind the eye where they developed primary lesions. The maximally-tolerated dose (MTD) of [2](PF6)2 was first determined for three different modes of compound administration: (i) incubating the fish in prodrug-containing water (WA); (ii) injecting the prodrug intravenously (IV) into the fish; or (iii) injecting the prodrug retro-orbitally (RO) into the fish. To test the anticancer efficiency of [2](PF6)2, the embryos were treated 24 h after engraftment at the MTD. Optimally, four consecutive PACT treatments were performed on engrafted embryos using 60 min drug-to-light intervals and 90 min green light irradiation (21 mW cm−2, 114 J cm−2, 520 nm). Most importantly, this PACT protocol was not toxic to the zebrafish. In the ectopic prostate tumour models, where [2](PF6)2 showed the highest photoindex in vitro (PI > 31), the PACT treatment did not significantly diminish the growth of primary lesions, while in both conjunctival melanoma orthotopic tumour models, where [2](PF6)2 showed more modest photoindexes (PI ∼ 9), retro-orbitally administered PACT treatment significantly inhibited growth of the engrafted tumors. Overall, this study represents the first demonstration in zebrafish cancer models of the clinical potential of ruthenium-based PACT, here against conjunctival melanoma.A new tris-heteroleptic photoactivated chemotherapy ruthenium complex induces apoptosis upon green light activation in a zebrafish orthothopic conjunctival melanoma xenograft model. 相似文献
477.
Linda Chikh Xavier Arnaud Céline Guillermain Martine Tessier Alain Fradet 《Macromolecular Symposia》2003,199(1):209-222
Hyperbranched aliphatic polyesters of 2,2′-bis-(hydroxymethyl) propanoic acid and hyperbranched aliphatic polyamides obtained from new carboxy- and amino-functionalized caprolactams were studied by NMR spectroscopy and MALDI-TOF mass spectrometry. Ring-chain equilibria taking place through intramolecular hydroxy-ester, carboxy-amide or amine-amide interchanges and leading to the formation of cyclic branches or end-groups were found to exert a predominant influence on the molar mass of these hyperbranched polymers. A number of intra- or intermolecular side reactions, such as the formation of ethers in polyesters and the formation of anhydrides, imides, amidines and secondary amines in polyamides were also detected and resulted in polymer crosslinking on prolonged heating. The existence of such ring-chain equilibria and side-reactions make the control of hyperbranched polymer structure much more difficult than generally accepted. 相似文献
478.
479.
Nicolas Trcera Stphanie Rossano Martine Tarrida 《Journal of Raman spectroscopy : JRS》2011,42(4):765-772
The presence of magnesium in glasses of geological, medical, and technological interests influences their physicochemical and durability properties. However, the understanding of the role of magnesium is dependent on the combined knowledge of the structural environment of magnesium in the glass or melt and of the silicate network connectivity of the studied systems. In this article, we present a Raman spectroscopic study of the network connectivity of 10 ternary silicate glasses in the system Na2O MgO SiO2 and one Mg‐free binary silicate glass Na2O SiO2. Results obtained at constant polymerization suggest the existence of various Qn units according to the nature of the modifying cation. As polymerization decreases for Na2O MgO αSiO2 glasses (labeled as NMSα with α decreasing from 10 to 2), the band associated with Si O Si bending in fully polymerized region disappears being gradually replaced by a band attributed to Si O Si bending in region containing mainly Q2 and Q3 species. For highly polymerized glasses (NMS10‐NMS4), the coexistence of these two bands suggests the presence of two interconnected networks. Concomitantly, the signal associated with Q3 species first increases. For a further decrease of the polymerization, the high wavenumber part of the signal associated with Q3 species decreases, while the intensity of the high wavenumber part of the band related to Q2 species increases. This result strongly suggests that magnesium charge‐balances preferentially Q2 species rather than Q3 species. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
480.
The surface of polyurethane based catheter material or of silicon wafers as model surfaces were modified by spin coating of solutions of poly(ethylene oxide) or poly(vinyl alcohol) in water. For the incorporation of silver ions, silver nitrate was added to some of the solutions or the as-cast surfaces were dipped into AgNO3 solution. Furthermore, samples coated with a thin layer of metallic silver were prepared by deposition of silver vapor in vacuum. The as-prepared surfaces were studied by atomic force microscopy and X-ray photoelectron spectroscopy. During the spin coating of the solutions containing AgNO3, clusters of the silver component were formed. They were well dispersed in a poly(vinyl alcohol) matrix but act as nucleation agents in poly(ethylene oxide) where then large spherulites are formed. The surface compositions of coated samples and the depth profiling were carried out by angle dependent X-ray photoelectron spectroscopy. 相似文献