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991.
The effects of addition of alkanols (ethanol, n-hexanol, and 3-ethyl-3-pentanol) on the micropolarity and microviscosity of the head group region in reverse micelles of AOT-heptane-water have been investigated by fluorescence probing methods (ANS fluorescence yield and TMADPH fluorescence anisotropy), complemented by the use of the solvatochromic probe E(T)(30) in absorption spectroscopy. For all the alkanols considered, ANS fluorescence in AOT reverse micelles (at W=3) is quenched by additive incorporation, being the effect elicited almost independent of the alkanol chain length and topology. As sensed by the E(T)(30) parameter, the micropolarity of the micelle surface increases, remains unmodified, and decreases upon addition of ethanol, 3-ethyl-3-pentanol, and hexanol, respectively. While ethanol barely modifies the fluorescence anisotropy of TMADPH, 3-ethyl-3-pentanol and n-hexanol addition strongly decrease it. The similarity of the tendencies of ANS data to TMADPH anisotropies and the differences between ANS data and E(T)(30) values would indicate that, at least for 3-ethyl-3-pentanol and n-hexanol, microviscosity, rather than micropolarity, must be considered to interpret the effect of the alkanols upon the fluorescent behavior of ANS. 相似文献
992.
Wilhelmsson LM Westerlund F Lincoln P Nordén B 《Journal of the American Chemical Society》2002,124(41):12092-12093
We here report a remarkably slow rearrangement of binding modes for a binuclear ruthenium(II) complex upon interaction with DNA. It has been previously shown that Delta,Delta-[mu-(11,11'-bidppz)(phen)4Ru2]4+ binds to DNA in one of the grooves. However, we find that this is only an initial, metastable, binding mode, which is extremely slowly reorganized into an intercalative binding geometry. The slow rearrangement and dissociation, revealed by flow linear dichroism and fluorescence spectroscopy, are concluded to be a result from the complex being threaded through the DNA, with one of the bridging aromatic dppz ligands intercalated between the base pairs of the DNA, placing one metal center in the minor groove and one in the major groove. A negative LD, a high luminescence quantum yield, and long luminescence lifetimes, similar to the intercalating complex Delta-[Ru(phen)2dppz]2+, indicate intercalation of the bidppz moiety. The unique slow dissociation of the complex in its final DNA-binding mode suggests that this class of threading, partially intercalated binuclear complexes may be interesting in the context of cancer therapy. Also, their unique optical and photophysical properties could make such complexes, either alone or scaffolded by DNA structures, of interest for the development of nanometer-sized molecular optoelectronic devices. 相似文献
993.
Sarrión MN Santos FJ Galceran MT 《Rapid communications in mass spectrometry : RCM》2000,14(23):2271-2281
Headspace solid-phase microextraction combined with gas chromatography/ion trap tandem mass spectrometry (HS-SPME/GC/ITMS/MS) was used for the analysis of 12 halobenzenes from soil samples. For MS/MS optimisation, the experiments were performed by precursor ion selection and software controlled operations. Collision-induced dissociation (CID) can be achieved by two different approaches, resonant and non-resonant excitation modes. Different results were obtained using the two approaches, and the resonant excitation mode was chosen as the best for all halobenzenes. Parameters such as the CID excitation amplitude, excitation RF storage level and CID bandwidth frequency were optimised to maximise the formation of halobenzene product ions. A 100-microm polydimethylsiloxane fibre was used for the isolation and preconcentration of the analytes. The HS-SPME/GC/ITMS/MS method was applied to the analysis of halobenzenes in an agricultural soil sample. The halobenzenes were quantified by standard addition, which led to good reproducibility (RSD between 4.7 and 9.2%) and detection limits in the low pg/g range. The method was validated by comparing the results with those obtained in a European inter-laboratory exercise. 相似文献
994.
Farida Larit Khaled M. Elokely Manal A. Nael Samira Benyahia Francisco Len Stephen J. Cutler Mohammed M. Ghoneim 《Molecules (Basel, Switzerland)》2021,26(4)
The in vitro activity of L. donovani (promastigotes, axenic amastigotes and intracellular amastigotes in THP1 cells) and T. brucei, from the fractions obtained from the hydroalcoholic extract of the aerial part of Hypericum afrum and the isolated compounds, has been evaluated. The chloroform, ethyl acetate and n-butanol extracts showed significant antitrypanosomal activity towards T. brucei, with IC50 values of 12.35, 13.53 and 12.93 µg/mL and with IC90 values of 14.94, 19.31 and 18.67 µg/mL, respectively. The phytochemical investigation of the fractions led to the isolation and identification of quercetin (1), myricitrin (2), biapigenin (3), myricetin (4), hyperoside (5), myricetin-3-O-β-d-galactopyranoside (6) and myricetin-3’-O-β-d-glucopyranoside (7). Myricetin-3’-O-β-d-glucopyranoside (7) has been isolated for the first time from this genus. The chemical structures were elucidated by using comprehensive one- and two-dimensional nuclear magnetic resonance (1D and 2D NMR) spectroscopic data, as well as high-resolution electrospray ionization mass spectrometry (HR-ESI–MS). These compounds have also been evaluated for their antiprotozoal activity. Quercetin (1) and myricetin (4) showed noteworthy activity against T. brucei, with IC50 and IC90 values of 7.52 and 5.71 µM, and 9.76 and 7.97 µM, respectively. The T. brucei hexokinase (TbHK1) enzyme was further explored as a potential target of quercetin and myricetin, using molecular modeling studies. This proposed mechanism assists in the exploration of new candidates for novel antitrypanosomal drugs. 相似文献
995.
Syntheses of 5H-[1,2,4]triazolo[5′,1′:2,3][1,3]thiazino[5,4-c]quinolines 8, 5H-[1,2,4]triazolo[3′,4′:2)3][1,3]thiazino[5,4-c]quinolines 9, 5H-[1,2,4]triazolo[5′,1′:2,3][1,3]thiazino[5,6-c]quinolines 14 and 5H-[1,2,4]triazolo[3′,4′:2,3][1,3]thiazino[5,6-c]quinolines 15 are described starting from 4-chloro-3-chloromethylquinaldine (4) and 1,2,4-triazole-5-thiols 5 taking advantage of different reactivity of the chlorine atoms of 4 under different reaction conditions. The structures of products 8, 9, 14 and 15 and the intermediates leading to them were confirmed by desulfurization, unequivocal syntheses and nmr spectroscopy as well. 相似文献
996.
Estefania Fernandez-Bartolome Arturo Gamonal Jos Santos Saeed Khodabakhshi Eider Rodríguez-Snchez E. Carolina Saudo Nazario Martín Jos Snchez Costa 《Chemical science》2021,12(25):8682
Weak forces can play an essential role in chemical reactions. Controlling such subtle forces in reorganization processes by applying thermal or chemical stimuli represents a novel synthetic strategy and one of the main targets in supramolecular chemistry. Actually, to separate the different supramolecular contributions to the stability of the 3D assemblies is still a major challenge. Therefore, a clear differentiation of these contributions would help in understanding the intrinsic nature as well as the chemical reactivity of supramolecular ensembles. In the present work, a controlled reorganization of an hexakis[60]fullerene-based molecular compound purely governed by the weakest van der Waals interactions known, i.e. the dihydrogen interaction – usually called sticky fingers – is illustrated. This pre-reorganization of the hexakis[60]fullerene under mild conditions allows a further selective hydrogenation of the crystalline material via hydrazine vapors exposure. This unique two-step transformation process is monitored by single-crystal to single-crystal diffraction (SCSC) which allows the direct observation of the molecular movements in the lattice and the subsequent solid–gas hydrogenation reaction.Weak forces play an essential role in chemistry. Controlling these supramolecular interactions will contribute to the creation dynamic absorbent materials with a variety of technological applications as chemosensors and environmental remediation. 相似文献
997.
Although very bulky ligands e.g.(o-MeC6H4)3E or (μ-C10H7)3E (E = P or As) are inert, the normal photochemical or thermal reaction of tertiary phosphines or arsines, L, with [Mn2(CO)10] is CO substitution with the formation of [Mn2(CO)8(L)2] derivatives (I). At elevated temperatures some triarylarsines, R3As, undergo Lambert's reaction with ligand fragmentation to give [Mn2(CO)8(μ-AsR2)2] complexes (II) (R = Ph, p-MeOC6H4, p-FC6H4, or p-CIC6H4) even though, in the absence of [Mn2(CO)10] R3As are stable under the same conditions. Exceptional behaviour is exhibited by (p-Me2NC6H4)3- As which forms a product of type I; by some HN(C6H4)2AsR which give a product of type II as a result of loss of the non-aryl groups R = PhCH2, cyclo-C6H11, or MeO; and by Ph(α-C10H72P which is the only phosphine to form a product of type II, albeit in trace amounts only. The thermal decomposition of a n-butanol solution of [Mn2(CO)8(AsPh3)2] in a sealed tube gives C6H6 and [Mn2(CO)8(α-AsPh2)2], whilst in an open system in the presence of various tertiary phosphines, L, [Mn(H)(CO)3(L)2] are obtained. It is suggested that Lambert's reaction is a thermal fragmentation of [Mn(CO)4(AsR3]* radicals, the first to be recognised. They lose the radical R* which abstracts hydrogen from the solvent. The resulting [Mn(CO)4(AsR2)] moiety dimerises to [Mn2(CO)8-(α-AsR2)2]. the reaction is facilitated by the stability of the departing radical (e.g. PhCH2 or MeO) and, as the crowding about As is relieved, by its size (e.g. Ph, cyclo-C6H11, o-MeC6H4, or α-C10H7). In general, phosphine-substituted radicals [Mn(CO)4(PR)3]* do not undergo this decomposition, probably because the PC bonds are much stronger than AsC. 相似文献
998.
Zusammenfassung Es wurden die elektrochemischen Eigenschaften des Redox-Systems K4[Fe(CN)6]-K3[Fe(CN)6] in Ameisensäure-Wasser-, Essigsäure-Wasser-, Propionsäure-Wasser- und n-Buttersäure-Wasser-Gemischen untersucht. Die Veränderungen des Redoxpotentials, der Leitfähigkeit und der Dielektrizitäts-konstante wurden studiert.Es wurde bewiesen, daß die Potentialveränderung des Redox-Systems bei kleiner Säurekonzentration (n
s<0,6–0,7) vor allem durch die Wasserstoffionen-Konzentration der Lösung bestimmt wird. Mit der Zunahme der H+-Konzentration nimmt die Aktivität des [Fe(CN)6]4– in größerem Maße ab als die des [Fe(CN)6]3–.Bei großer Säurekonzentration beeinflußt dagegen hauptsächlich die Anionsolvatation durch das Lösungsmittelgemisch die Verschiebung des Redoxpotentials. Die Solvatation ruft eine Strukturveränderung hervor, wodurch die Elektronen-population der Lösungsmittelmoleküle in der Nähe der Cyanoferrat-Ionen abnimmt, die Elektronen-Acceptor-Wirkung des Lösungsmittels wächst. Dieser Prozeß bewirkt in bekannter Weise die Zunahme des Redoxpotentials.
Mit 7 Abbildungen 相似文献
The electrochemical behaviour of redox systems in mixed solvents, II.: TheK 4[Fe(CN) 6]-K 3[Fe(CN) 6] system in fatty acid-water mixtures
The electrochemical behaviour of the K4[Fe(CN)6]-K3[Fe(CN)6] system has been investigated in mixtures of water with formic, acetic, propionic and n-butyric acid, resp. The change of the redox potential, the conductivity and the dielectric constant has been studied. It has been proved that the change of the redox potential of the system at low acid concentration (n s<0.6–0.7) is determined by the H+ concentration. Increasing the H+ concentration, the activity of the [Fe(CN)6]4– decreases in a higher extent than the activity of [Fe(CN)6]3–.On the other hand, at high acid concentration the shift in the redox potential is influenced first of all by the anion solvating effect of the solvent. The solvation causes such a change in the structure, that the electron population of the solvent molecules around the [Fe(CN)6]4– ions decreases, the acceptor strength of the solvent increases. It is well known that this process causes an increase in the redox potential.
Mit 7 Abbildungen 相似文献
999.
Carmen Luna Concepción Lloreda Juan F. Almagro Bello Jaime Botella Maria J. Orts Ana Gozalbo 《Mikrochimica acta》2004,145(1-4):121-127
Non-metallic inclusions in steel are formed due to interactions between liquid steel and its environment in the melting shop (refractories and slags). Particles not trapped in the slag remain in the cast steel, impairing steel properties in service. Inclusion composition varies and certified standards covering the whole compositional range are unavailable.The present study describes the preparation of a set of homogeneous, glassy and crystalline standards with a wide compositional range for use in analysing non-metallic steel inclusions. For this, materials were designed based on knowledge of the compositional range of interest in the Al2O3–SiO2–CaO–MgO–CaF2 system, which is the matrix of the most frequent steel inclusions. The composition and microstructural homogeneity of the reference materials was verified. 相似文献
1000.
A simple and fast analytical procedure has been developed for the determination of As, Sb, Se, Te and Bi in milk samples by hydride generation atomic fluorescence spectrometry (HG-AFS). Samples were treated with aqua regia for 10 min in an ultrasound water bath and pre-reduced with KBr for total Se and Te determination or with KI and ascorbic acid for total As and Sb, the determination of Bi being possible in all with or without pre-reduction. Slurries of samples, in the presence of antifoam A, were treated with NaBH4 in HCl medium to obtain the corresponding hydrides, and AFS measurements were processed in front of external calibrations prepared and measured in the same way as samples. Results obtained by the developed procedure compare well with those found after microwave-assisted complete digestion of samples. The proposed method is simple and fast, and only 1 ml of milk is needed. The values obtained for detection limit are 2.5, 1.6, 3, 6 and 7 ng l−1 for As, Sb, Se, Te and Bi respectively in the diluted samples, with average relative standard deviation values of 3.8, 3.1, 1.9, 6.4 and 1.2% for three independent analysis of a series of commercially available samples of different origin. Data found in Spanish market samples varied from 3.2±0.3 to 11.3±0.2 ng g−1 As, from 3.1±0.2 to 11.6±0.4 ng g−1 Sb, from 10.7±0.5 to 25.5±0.4 ng g−1 Se, from 0.9±0.2 to 9.4±0.6 ng g−1 Te and from 11.5±0.1 to 27.7±0.4 ng g−1 Bi. 相似文献