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81.
The first complexes containing both a sulfur atom and a hydroxamate moiety coordinated to a biologically relevant transition metal were synthesized as models for the structure of inhibited peptide deformylases. Two of these [(N(2)S)Zn(hydroxamate)] complexes were characterized by X-ray crystallography. The first contains a thioether and a simple hydroxamate, the second a thiolate and a N-substituted hydroxamate. Isolation of a complex with a thiolate and a simple hydroxamate group was not possible. 相似文献
82.
Giuliana Biagi Irene Giorgi Oreste Livi Clementina Manera Valerio Scartoni 《Journal of heterocyclic chemistry》1999,36(5):1195-1198
Some new 1,2,3-triazolo[4,5-e]-1,2,4-triazolo[3, 4 -c]pyrimidmes were prepared starting from the corresponding 1,2,3-triazolo[4,5-d]pyrimidines via the formation of the 1,2,4-triazole ring. Thus suitable hydrazino derivatives 6 were condensed with triethyl orthoformate, triethyl orthoacetate and triethyl orthobenzoate to give the expected tricyclic derivatives 7 , 8 and 9 . Intramolecular cyclization of the ethoxycarbonylhydrazino derivatives 10 gave the tricyclic compounds 11 bearing an hydroxyl group in the 3 position. The v-triazolo-s-triazolopyrimidine derivatives were tested towards the A1 and A2A adenosine receptors in binding assays, but they did not show any receptor affinity. 相似文献
83.
Serena Staccioli Maria Altamura Gianluca Giorgi Antonio Triolo 《Journal of mass spectrometry : JMS》2009,44(7):1081-1086
Di(hydroxybutyl) ether (DHBE), a liver protecting drug, is composed of a mixture of three regioisomers: 4‐(3‐hydroxybutoxy)‐2‐butanol (1), 3‐(4‐hydroxy‐2‐butoxy)‐1‐butanol (2), and 3‐(3‐hydroxybutoxy)‐1‐butanol (3). Unequivocal differentiation of each regioisomer of DHBE was rapidly obtained without isolation of the single components, using GC‐MS with electron ionization (EI). The mass spectrum of 1 showed a rearrangement ion at m/z 118, characteristic of the 3‐hydroxybutyl chain, deriving from loss of acetaldehyde from the molecular ion, whereas 2 and 3 were characterized by the ion at m/z 117, expected from α‐cleavage of the 4‐hydroxy‐2‐butyl chain. The species at m/z 118, in turn, loses a water molecule via a mechanism involving both alcohol hydrogens, as shown by deuterium exchange experiments. Both this finding and theoretical calculations support a mechanism in which the loss of acetaldehyde in 1 occurs via a cyclic intermediate, stabilized by a strong hydrogen bond between the alcohol oxygen bearing the charge and the other alcohol oxygen, and involves initial hydrogen transfer from the former to the latter. The EI spectrum of 2, having two 4‐hydroxy‐2‐butyl chains, showed the fragmentations expected from classical fragmentation rules of aliphatic ethers and alcohols, whereas the EI spectrum of 3, bearing one 4‐hydroxy‐2‐butyl and one 3‐hydroxybutyl chain, showed essentially the characteristic fragments of both chains. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
84.
Claudio Giorgi 《Milan Journal of Mathematics》2009,77(1):67-100
Phase transitions between two phases are modelled as space regions where a phase-field changes smoothly. The two phases are
separated by a thin transition layer, the so-called diffuse interface. All thermodynamic quantities are allowed to vary inside
this layer, including the pressure and the mass density. A thermodynamic approach is developed by allowing for the nonlocal
character of the continuum. It is based on an extra entropy flux which is proved to be non vanishing inside the transition
layer, only. The phase-field is regarded as an internal variable and the kinetic or evolution equation is viewed as a constitutive
equation of rate type. Necessary and sufficient restrictions placed by thermodynamics are derived for the constitutive equations
and, furthermore, a general form of the evolution equation for the phase-field is obtained within the schemes of both a non-conserved
and a conserved phase-field. Based on the thermodynamic restrictions, a phase-field model for the ice-water transition is
established which allows for superheating and undercooling. A model ruling the liquid-vapor phase transition is also provided
which accounts for both temperature and pressure variations during the evaporation process. The explicit expression of the
Gibbs free enthalpy, the Clausius-Clapeyron formula and the customary form of the vapor pressure curve are recovered. 相似文献
85.
Ambrosi M Fratini E Alfredsson V Ninham BW Giorgi R Lo Nostro P Baglioni P 《Journal of the American Chemical Society》2006,128(22):7209-7214
A bolaform surfactant, 1,12-diascorbyl dodecanedioate (BOLA12), with ascorbic acid units as the polar headgroups was synthesized for the first time. Once dispersed in water above 0.5% w/w, BOLA12 forms hollow nanotubes as revealed by cryo-TEM experiments. These nanostructures transform into clear micellar solutions on heating. X-ray diffraction and SAXS experiments were performed both on the pure solid and on its aqueous dispersions. The critical aggregation concentration and the phase behavior were determined by conductivity and DSC experiments. The latter technique provided also the amount of strongly bound, solvating water molecules that surround the polar headgroups. BOLA12 shows the same reducing properties of ascorbic acid, as indicated by the antioxidant activity evaluated with the DPPH method. This feature was used for the reduction of Pd(II) ions on the surface of the nanoassemblies, which lead to the formation of large bundles homogeneously coated with palladium as observed in SEM micrographs. 相似文献
86.
Buscemi S Pace A Piccionello AP Pibiri I Vivona N Giorgi G Mazzanti A Spinelli D 《The Journal of organic chemistry》2006,71(21):8106-8113
The hydrazinolysis reaction of 5-perfluoroalkyl-1,2,4-oxadiazoles with hydrazine or methylhydrazine as bidentate nucleophiles has been investigated. The reaction occurred through the addition of the bidentate nucleophile to the C(5)-N(4) double bond of the 1,2,4-oxadiazole followed by ring-opening and ring-closure (ANRORC) involving the second nucleophilic site of the reagent. This ring-closure step could involve either the original C(3) of the 1,2,4-oxadiazole (giving a five-to-five membered ring rearrangement) or an additional electrophilic center linked to it (exploiting a five-to-six membered ring rearrangement). An alternative initial nucleophilic attack may involve the additional electrophilic center linked at C(3), that is the carbonyl group, leading to the formation of the hydrazones which undergo the Boulton-Katritzky rearrangement (BKR). The chosen reaction path is a function of the used nucleophile and of the nature of the substituent at C(3). At variance with previous hypotheses, when methylhydrazine was used, the observed regiochemistry always showed the preferred initial attack by the less hindered NH(2) end of the nucleophile on C(5). Moreover, new spectroscopic evidence allowed the assignment of correct structures to the products formed by reaction of 5-perfluoroalkyl-3-phenyl-1,2,4-oxadiazoles with methylhydrazine. 相似文献
87.
V. R. Shaginyan A. Z. Msezane G. S. Japaridze V. A. Stephanovich Y. S. Leevik 《JETP Letters》2018,108(5):335-340
Tunneling differential conductivity (or resistivity) is a sensitive tool to experimentally test the non-Fermi liquid behavior of strongly correlated Fermi systems. In the case of common metals the Landau–Fermi liquid theory demonstrates that the differential conductivity is a symmetric function of bias voltage V. This is because the particle–hole symmetry is conserved in the Landau–Fermi liquid state. When a strongly correlated Fermi system turns out to be near the topological fermion condensation quantum phase transition, its Landau–Fermi liquid properties disappear so that the particle–hole symmetry breaks making the differential tunneling conductivity to be asymmetric function of V. This asymmetry can be observed when a strongly correlated metal is in its normal, superconducting or pseudogap states. We show that the asymmetric part of the dynamic conductance does not depend on temperature provided that the metal is in its superconducting or pseudogap states. In normal state, the asymmetric part diminishes at rising temperatures. Under the application of magnetic field the metal transits to the Landau–Fermi liquid state and the differential tunneling conductivity becomes a symmetric function of V. These findings are in good agreement with recent experimental observations. 相似文献
88.
Merab Gogberashvili Pavle Midodashvili Giorgi Tukhashvili 《General Relativity and Gravitation》2014,46(4):1-12
The new class of the non-stationary solutions to the system of N-dimensional equations for coupled gravitational and massless scalar field is found. The model represents a single (N-1)-brane in a space-time with one large (infinite) and (N-5) small (compact) space-like extra dimensions. In some particular cases the model corresponds to the gravitational and scalar field standing waves bounded by the brane. These braneworlds can be relevant in string and other higher dimensional models. 相似文献
89.
Armentano D De Munno G Di Donna L Sindona G Giorgi G Salvini L Napoli A 《Journal of the American Society for Mass Spectrometry》2004,15(2):268-279
Electrospray tandem mass spectrometry (ESI-MS/MS) is used to evaluate the assembling of cytosine and thymine nucleosides in the gas phase, through the formation of hydrogen bonded supermolecules. Mixtures of cytidine analogues and homologues deliver in the gas phase proton-bound heterodimers stabilized by multiple interactions, as proven by the kinetics of their dissociation into the corresponding protonated monomers. Theoretical calculations, performed on initial structures of methylcytosine homodimers available in the literature, converged to a minimized structure whereby the two pyrimidine rings interact through the formation of three hydrogen bonds of similar energy. The crystallographic data here reported show the equivalency of the two interacting pyrimidines which is attributable to the presence of an inversion center. Thymine and uracil pyrimidyl nucleosides form, by ESI, gaseous proton-bound dimers. The kinetic of their dissociation into the related protonated monomers shows that the nucleobases are weekly interacting through a single hydrogen bond. The minimized structure of the protonated heterodimer formed by thymine and N-1-methylthymine confirmed the existence of mainly one hydrogen bond which links the two nucleobases through the O4 oxygens. No crystallographic data exists on thymine proton-bound species, nor have we been able to obtain these aggregates in the solid phase. The gaseous phase, under high vacuum conditions, seems therefore a suitable environment where vanishing structures produced by ESI can be studied with a good degree of approximation. 相似文献
90.
Dr. Anthony D'Aléo Dr. David Gachet Dr. Vasile Heresanu Dr. Michel Giorgi Prof. Frédéric Fages 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(40):12764-12772
This article describes a series of nine complexes of boron difluoride with 2′‐hydroxychacone derivatives. These dyes were synthesized very simply and exhibited intense NIR emission in the solid state. Complexation with boron was shown to impart very strong donor–acceptor character into the excited state of these dyes, which further shifted their emission towards the NIR region (up to 855 nm for dye 5 b , which contained the strongly donating triphenylamine group). Strikingly, these optical features were obtained for crystalline solids, which are characterized by high molecular order and tight packing, two features that are conventionally believed to be detrimental to luminescence in organic crystals. Remarkably, the emission of light from the π‐stacked molecules did not occur at the expense of the emission quantum yield. Indeed, in the case of pyrene‐containing dye 4 , for example, a fluorescence quantum yield of about 15 % with a fluorescence emission maximum at 755 nm were obtained in the solid state. Moreover, dye 3 a and acetonaphthone‐based compounds 1 b , 2 b , and 3 b showed no evidence of degradation as solutions in CH2Cl2 that contained EtOH. In particular, solutions of brightly fluorescent compound 3 a (brightness: ε×Φf=45 000 M ?1 cm?1) could be stored for long periods without any detectable changes in its optical properties. All together, these new dyes possess a set of very interesting properties that make them promising solid‐state NIR fluorophores for applications in materials science. 相似文献