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61.
Summary We outline a theory for the metal-non-metal transition occurring in solutions of alkali metals in molten alkali halides as
governed by a balance between the binding of ionic clusters by localized electrons and the excess free energy of an ionic
assembly screened by metallic electrons. In the model the transition is driven by the composition dependence of the screening
length. The theory is amenable to an analytic solution within the mean spherical approximation when Thomas-Fermi screening
is used and the ions are described by charged hard spheres. 相似文献
62.
De Maria P Fontana A Siani G D'Aurizio E Cerichelli G Chiarini M Angelini G Gasbarri C 《Colloids and surfaces. B, Biointerfaces》2011,87(1):73-78
The aggregation properties of a new sultaine surfactant have been studied in buffered aqueous solution at pH 7.4 under controlled condition of osmolarity. Spontaneously formed sultaine vesicles with a mean diameter of about 1 μm can be observed by optical microscopy. The phase behaviour of the surfactant has been investigated by differential scanning calorimetry (DSC) and Nile Red fluorescence. Two critical vesicular concentrations (CVC(1) and CVC(2)) have been fluorimetrically measured, by using pyrene and Nile Red as the fluorescent probes. The two populations of vesicles behave differently as a consequence of their size. The stability of extruded large unilamellar vesicles (LUV) formed slightly above the CVC(1) has been evaluated in the temperature range 25-75°C by following the rate of spontaneous release of entrapped 5(6)-carboxyfluorescein (CF). The stability of the same vesicles at 70°C has also been investigated under osmotic stress obtained by adding NaCl or sucrose to the bulk solution. At a sultaine concentration above the CVC(2) LUV tend to associate and form stable larger closely packed aggregates as suggested by Dynamic Laser Light Scattering and rheological measurements. 相似文献
63.
Tamboli V Defant A Mancini I Tosi P 《Rapid communications in mass spectrometry : RCM》2011,25(4):526-532
Resveratrol is a polyphenolic compound found in plants and human foods which has shown biological activities including chemoprevention, acting through a mechanism which involves the reduction of Cu(II) species. By electrospray ionization (ESI) mass spectrometry we have produced and detected the resveratrol-copper complexes [Resv+Cu](+), [Resv+Cu+H(2)O](+) and [2Resv+Cu](+) by using a resveratrol/CuSO(4) solution in CH(3)CN/H(2)O. The most stable structures of the detected complexes have been calculated at the B3LYP/6-311G(d) level of theory. Resveratrol interacts with the copper ion through nucleophilic carbon atoms on the aromatic ring and the alkenyl group. The fact that only singly charged ions were observed implies that Cu(II) is reduced to Cu(I) in the ESI process. For investigating the structure-reactivity correlation, we have carried out a similar study on the synthetic analogue dihydroresveratrol (DHResv). For the latter only the [DHResv+Cu](+) complex has been detected. 相似文献
64.
Ambrosi G Formica M Fusi V Giorgi L Macedi E Micheloni M Paoli P Pontellini R Rossi P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(5):1670-1682
Binding properties of 24,29-dimethyl-6,7,15,16-tetraoxotetracyclo[19.5.5.0(5,8).0(14,17)]-1,4,9,13,18,21,24,29-octaazaenatriaconta-Δ(5,8),Δ(14,17)-diene ligand L towards Zn(II) and anions, such as the halide series and inorganic oxoanions (phosphate (Pi), sulfate, pyrophosphate (PPi), and others), were investigated in aqueous solution; in addition, the Zn(II)/L system was tested as a metal-ion-based receptor for the halide series. Ligand L is a cryptand receptor incorporating two squaramide functions in an over-structured chain that connects two opposite nitrogen atoms of the Me(2)[12]aneN(4) polyaza macrocyclic base. It binds Zn(II) to form mononuclear species in which the metal ion, coordinated by the Me(2)[12]aneN(4) moiety, lodges inside the three-dimensional cavity. Zn(II)-containing species are able to bind chloride and fluoride at the physiologically important pH value of 7.4; the anion is coordinated to the metal center but the squaramide units play the key role in stabilizing the anion through a hydrogen-bonding network; two crystal structures reported here clearly show this aspect. Free L is able to bind fluoride, chloride, bromide, sulfate, Pi, and PPi in aqueous solution. The halides are bound at acidic pH, whereas the oxoanions are bound in a wide range of pH values ranging from acidic to basic. The cryptand cavity, abundant in hydrogen-bonding sites at all pH values, allows excellent selectivity towards Pi to be achieved mainly at physiological pH 7.4. By joining amine and squaramide moieties and using this preorganized topology, it was possible, with preservation of the solubility of the receptor, to achieve a very wide pH range in which oxoanions can be bound. The good selectivity towards Pi allows its discrimination in a manner not easily obtainable with nonmetallic systems in aqueous environment. 相似文献
65.
Localized surface plasmon resonance: nanostructures, bioassays and biosensing--a review 总被引:1,自引:0,他引:1
Localized surface plasmon resonance (LSPR) is an optical phenomena generated by light when it interacts with conductive nanoparticles (NPs) that are smaller than the incident wavelength. As in surface plasmon resonance, the electric field of incident light can be deposited to collectively excite electrons of a conduction band, with the result being coherent localized plasmon oscillations with a resonant frequency that strongly depends on the composition, size, geometry, dielectric environment and separation distance of NPs. This review serves to describe the physical theory of LSPR formation at the surface of nanostructures, and the potential for this optical technology to serve as a basis for the development bioassays and biosensing of high sensitivity. The benefits and challenges associated with various experimental designs of nanoparticles and detection systems, as well as creative approaches that have been developed to improve sensitivity and limits of detection are highlighted using examples from the literature. 相似文献
66.
Blangetti M Croce G Deagostino A Mussano E Prandi C Venturello P 《The Journal of organic chemistry》2011,76(6):1814-1820
The direct addition of metalated alkoxydiene 2, obtained from α,β-unsaturated acetal 1 through a LIC-KOR-promoted conjugated elimination reaction, to enantiopure sulfinimines 3 (both R and SN-sulfinyl imines) afforded N-sulfinyl alkoxydienyl amines 4 with high diastereoselectivity. Functionalized enantiopure alkoxydienyl amines 5 were then easily obtained upon the selective removal of the chiral auxiliary under mild conditions. Moreover, the further hydrolysis of the alkoxydienyl moiety gave access to protected enantiopure β-keto amines 7. 相似文献
67.
Diels-Alder reactions of a range of 1-(alkoxy/alkyl-substituted phenyl)buta-1,3-dienes with methyl vinyl ketone and methyl acrylate carried out in ethanol as the reaction medium under 9 kbar pressure were investigated. The use of high pressure as the activating method of the Diels-Alder reactions allows the efficient and endodiastereoselective generation of a series of cis-cyclohexenyl-benzene cycloadducts, which are selectively converted into their trans-epimers. The cis-cyclohexenyl-benzenes and trans-cyclohexenyl-benzenes produced are useful precursors for accessing substituted privileged cis-6a,7,8,10a-tetrahydro-6H-benzo[c]chromene and trans-6a,7,8,10a-tetrahydro-6H-benzo[c]chromene skeletons. The total syntheses of Δ(9)-cis-tetrahydrocannabinol (THC) and Δ(9)-trans-THC, through the use of selected Diels-Alder adducts, are described. Finally, a route for obtaining Δ(9)-trans-THC in both enantiomeric pure forms based on the (S)-(-)-1-amino-2-(methoxymethyl)pyrrolidine (SAMP)-hydrazone method is also reported. 相似文献
68.
69.
Fernando Díaz Andrs Benassi Mariano Quintero Griselda Polla Eleonora Freire Ricardo Baggio 《Acta Crystallographica. Section C, Structural Chemistry》2011,67(7):o222-o225
In the title racemic hemihydrated solvatomorph of carvedilol (carv), C24H26N2O4·0.5H2O, the asymmetric unit contains two independent organic moieties and one water molecule. Within this 2(carv)·H2O unit, the molecular components are strongly linked by hydrogen bonds and the unit acts as the basic building block for the crystal structure. Interactions parallel to (10) generate hydrogen‐bonded layers which are further linked by much weaker C—H...N/O interactions. The conformations of the organic molecules, as well as the hydrogen‐bonding interactions connecting them, are compared with other related structures in the literature. 相似文献
70.
Hrant Yeritsyan Vachagan Harutiunian Volodia Gevorkyan Norair Grigoryan Eleonora Hakhverdyan Sergey Nikoghosyan Aram Sahakyan Rudolf Gevorgyan Hakob Sargisyan Yeghis Keheyan 《Central European Journal of Physics》2005,3(4):623-635
Infrared (IR) absorption and luminescence in chemically and radiation-modified natural Armenian Zeolite (clinoptilolite) samples
have been studied. The luminescence was studied in 390–450 nm and 620–710 nm wavelength bands, and the IR measurements were
carried out in the 400–5400 cm−1 range. It is shown that the luminescence intensity depends on the content of pure clinoptilolite in the samples and, probably
on the distribution of “passive” luminescence centers over Si and Al sites that became “active” under radiation or chemical
treatment. The samples of electron irradiated clinoptilolite have higher luminescence intensity than the chemically and thermally
treated ones. A decrease in the intensity of IR absorption bands at 3550 cm−1 and 3650 cm−1 was found after irradiation. 相似文献