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排序方式: 共有331条查询结果,搜索用时 265 毫秒
61.
Elsebeth L. Kendix Silvia Prati Edith Joseph Giorgia Sciutto Rocco Mazzeo 《Analytical and bioanalytical chemistry》2009,394(4):1023-1032
In the field of FTIR spectroscopy, the far infrared (FIR) spectral region has been so far less investigated than the mid-infrared
(MIR), even though it presents great advantages in the characterization of those inorganic compounds, which are inactive in
the MIR, such as some art pigments, corrosion products, etc. Furthermore, FIR spectroscopy is complementary to Raman spectroscopy
if the fluorescence effects caused by the latter analytical technique are considered. In this paper, ATR in the FIR region
is proposed as an alternative method to transmission for the analyses of pigments. This methodology was selected in order
to reduce the sample amount needed for analysis, which is a must when examining cultural heritage materials. A selection of
pigments have been analyzed in both ATR and transmission mode, and the resulting spectra were compared with each other. To
better perform this comparison, an evaluation of the possible effect induced by the thermal treatment needed for the preparation
of the polyethylene pellets on the transmission spectra of the samples has been carried out. Therefore, pigments have been
analyzed in ATR mode before and after heating them at the same temperature employed for the polyethylene pellet preparation.
The results showed that while the heating treatment causes only small changes in the intensity of some bands, the ATR spectra
were characterized by differences in both intensity and band shifts towards lower frequencies if compared with those recorded
in transmission mode. All pigments' transmission and ATR spectra are presented and discussed, and the ATR method was validated
on a real case study.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
62.
Collision induced (CI) processes involving hydrogen atoms on a graphite surface are studied quantum mechanically within the rigid, flat surface approximation, using a time-dependent wave packet method. The Eley-Rideal (ER) reaction and collision induced desorption (CID) cross sections are obtained with the help of two propagations which use different sets of coordinates, a "product" and a "reagent" set. Several adsorbate-substrate initial states of the target H atom in the chemisorption well are considered, and CI processes are studied over a wide range of projectile energy. Results show that (i) the Eley-Rideal reaction is the major reactive outcome and (ii) CID cross sections do not exceed 4 A2 and present dynamic thresholds for low values of the target vibrational quantum number. ER cross sections show oscillations at high energies which cannot be reproduced by classical and quasiclassical trajectory calculations. They are related to the vibrational excitation of the reaction products, which is a rather steep decreasing function of the collision energy. This behavior causes a selective population of the low-lying vibrational states and allows the quantization of the product molecular states to manifest itself in a collisional observable. A peak structure in the CID cross section is also observed and is assigned to the selective population of metastable states of the transient molecular hydrogen. 相似文献
63.
Paolo Della Sala Rocco Del Regno Luca Di Marino Carmela Calabrese Carmine Palo Carmen Talotta Silvano Geremia Neal Hickey Amedeo Capobianco Placido Neri Carmine Gaeta 《Chemical science》2021,12(29):9952
Ethyl- and propyl-prism[6]arenes are obtained in high yields and in short reaction times, independent of the nature and size of the solvent, in the cyclization of 2,6-dialkoxynaphthalene with paraformaldehyde. PrS[6]Et or PrS[6]nPr adopt, both in solution and in the solid state, a folded cuboid-shaped conformation, in which four inward oriented alkyl chains fill the cavity of the macrocycle. On these bases, we proposed that the cyclization of PrS[6]Et or PrS[6]nPr occurs through an intramolecular thermodynamic self-templating effect. In other words, the self-filling of the internal cavity of PrS[6]Et or PrS[6]nPr stabilizes their cuboid structure, driving the equilibrium toward their formation. Molecular recognition studies, both in solution and in the solid state, show that the introduction of guests into the macrocycle cavity forces the cuboid scaffold to open, through an induced-fit mechanism. An analogous conformational change from a closed to an open state occurs during the endo-cavity complexation process of the pentamer, PrS[5]. These results represent a rare example of a thermodynamically controlled cyclization process driven through an intramolecular self-template effect, which could be exploited in the synthesis of novel macrocycles.Ethyl- and propyl-prism[6]arenes are obtained by an intramolecular thermodynamic self-template effect: the self-filling of the internal cavity stabilizes their cuboid structure, driving the equilibrium toward their formation. 相似文献
64.
65.
A kinetic study of the crystallization of poly(ethylene oxide) (PEO) and of a blend of PEO+poly(bisphenol A-co-epichlorohydrin)
(PBE) was performed by using DSC in a non-isothermal program at constant cooling rates. The curves obtained were analyzed
by the Kissinger, Ozawa and Friedman methods, with determination of the kinetic parameters in each case. As a consequence
of the presence of PBE, the kinetic parameters were altered, leading to the conclusion that PBE has some influence on the
crystallization of PEO, modifying its mechanism.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
66.
H.O. Di Rocco D.I. Iriarte J.A. Pomarico 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2000,10(1):19-26
In this work we make an experimental and theoretical investigation of transition probabilities (A) and lifetimes of Xe II. Eighteen Aij's corresponding to the 6p-6d array were measured using a Laser Produced Plasma (LPP) as the spectroscopic source. The ab initio (AI) and Least Square Fitting (LSF) approaches were used to calculate the atomic parameters. Relativistic corrections and
Configuration Interaction (CI) effects have been taken into account using the HFR approach described by Cowan. Whereas the
AI parameters corresponding to 6p levels are not very affected by CI effects, several of the 6d levels with J=1/2, 3/2and 5/2 making transitions to the fundamental levels 5p5
are affected by CI effects due to both, discrete nd and continuum states, modifying their lifetimes values. An extensive comparison with other measurements and calculations are made. In particular,
concerned with branching ratio and forbidden transitions.
Received 15 July 1999 相似文献
67.
Sandra Di Rocco 《Mathematische Zeitschrift》1999,231(1):169-188
The notion of a k-convex -support function for a toric variety is introduced. A criterion for a line bundle L to generate k-jets on X is given in terms of the k-convexity of the -support function . Equivalently L is proved to be k-jet ample if and only if the restriction to each invariant curve has degree at least k.
Received October 22, 1997; in final form January 12, 1998 相似文献
68.
G. Fischfeld A. Affranchino A. Di Loreto C. Rocco 《Crystal Research and Technology》2004,39(10):920-925
The results obtained for the r63 electro‐optic coefficient of B‐doped and undoped KDP (KH2PO4) crystals irradiated with neutrons (including thermalized neutrons) produced by scattering of 30 Mev cyclotron protons on a target of Ta201, are presented and compared to those obtained for non‐irradiated doped and undoped crystals. The B‐doped (H3BO3, Na2B4O7 and Li2B4O7) crystals were obtained by the conventional growth method by temperature decrease with 1 wt % dopant concentration in solution. The thermal neutron flux was around ϕ = 1. 1010 n/cm2 s. Pulses of ∼15 μs long, in damped oscillatory mode (V= 8 kV, τ=1.95 μs) were used for the electro‐optic measurements. A Pockels cell, a photomultiplier, a He‐Ne laser (λ=632.8 nm, 5 mW, linearly polarized) and a Tk 720 A oscilloscope complete the experimental setup. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
69.
70.
Rosario Caltabiano Rocco De Pasquale Eliana Piombino Giorgia Campo Ferdinando Nicoletti Eugenio Cavalli Katia Mangano Paolo Fagone 《Molecules (Basel, Switzerland)》2021,26(1)
Discoid Lupus Erythematosus (DLE) is a chronic cutaneous disease of unknown etiology and of immunoinflammatory origin that is characterized by inflammatory plaques and may lead to disfiguring scarring and skin atrophy. Current treatments are limited, with a large proportion of patients either poorly or not responsive, which makes DLE an unmet medical need. Macrophage migration inhibitory factor (MIF) is the prototype of a pleiotropic family of cytokine that also includes the recently discovered homologue D-dopachrome tautomerase (DDT) or MIF2. MIF and DDT/MIF-2 exert several biological properties, primarily, but not exclusively of a proinflammatory nature. MIF and DDT have been suggested to play a key role in the pathogenesis of several autoimmune diseases, such as multiple sclerosis and type 1 diabetes, as well as in the development and progression of certain forms of cancers. In the present study, we have performed an immunohistochemistry analysis for the evaluation of MIF in DLE lesions and normal skin. We found high levels of MIF in the basal layer of the epidermis as well as in the cutaneous appendage (eccrine glands and sebocytes) of normal skin. In DLE lesions, we observed a significant negative correlation between the expression of MIF and the severity of inflammation. In addition, we performed an analysis of MIF and DDT expression levels in the skin of DLE patients in a publicly available microarray dataset. Interestingly, while these in silico data only evidenced a trend toward reduced levels of MIF, they demonstrated a significant pattern of expression and correlation of DDT with inflammatory infiltrates in DLE skins. Overall, our data support a protective role for endogenous MIF and possibly DDT in the regulation of homeostasis and inflammation in the skin and open up novel avenues for the treatment of DLE. 相似文献