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1.
We have studied by ESR and ENDOR spectroscopy the free radicals produced in γ-irradiated inclusion compound formed between the ketone 10-nonadecanone and urea. Only one type of long lived radical is formed by the removal of an α-proton from the ketone. The hyperfine (hf) coupling constants of the α- and β-protons of the radicals have been measured by ESR at different temperatures in the range 110–292 K and at different orientations of the crystals. The hf coupling of the γ-protons of the radical and of the urea protons have been studied by ENDOR. The temperature and angular dependences of the coupling constants have been analyzed in terms of the internal and overall motions of the radical inside the hexagonal channels formed by the urea molecules. It has been found that the radical cannot perform complete reorientations around the long molecular axis, but it undergoes restricted rotational diffusion. This process is explained by assuming a coupling between the rotational and translational degrees of freedom of the radical inside the urea channels. 相似文献
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3.
The surface modification of tire rubber after treatment with saturated NaOH aqueous solution was investigated by HATR infrared analysis, potentiometric titration, and contact angle measurements. Infrared analysis of the powdered treated rubber showed a decrease in absorption at 1540, 1450, and 1395 cm(-1). This decrease is attributed to the removal of zinc stearate, an additive present in tire formulations that often migrates and diffuses to the surface, resulting in poor adhesion between the rubber and other materials. The potentiometric titration of the suspension of powdered rubber in 0.1 M NaCl showed that more hydrochloric acid was consumed by the untreated rubber, most likely a result of the hyrdrolysis of the zinc stearate to the organic acid. Contact angles of flat tire pieces showed an homogeneity enhancement of the treated rubber surface. The decrease of the zinc stearate on the treated rubber surface explains the improvement in the adhesion of this material to the cement matrix, observed in a previous research. The promising results of this study are a starting point for future research on incorporating rubber particles into cementitious materials as a means of successfully utilizing the vast amounts of tire waste currently in landfills. 相似文献
4.
Cecilia Bartolucci Luciano Cellai Concetta Martuccio Andrea Rossi Anna Laura Segre Simona Rizea Savu Luigi Silvestro 《Helvetica chimica acta》1996,79(6):1611-1619
Glycosylrifamycins, a new type of semisynthetic rifamycin derivatives, can be easily obtained by reaction of 3-(2-aminoethylthio)rifamycin SV ( 2 ) with a glycosyl compound carrying a coupling group, such as isothicyanate or carboxy. We prepared O-acetylated and free glucopyranosyl and arabinopyranosyl derivatives of rifamycin S and SV (see 3–10 ). Additionally, derivatives with D -saccharo-1,4-lactone and with shikimic acid were obtained (see 11–15 ). Glycosylrifamycins show an interesting inhibitory power on Gram-positive bacteria (Table). 相似文献
5.
de Oliveira Neto Marçal Pires José M. Giambiagi Mario de Giambiagi Myriam Segre Alvarez Fernando A. 《Structural chemistry》1998,9(5):339-348
Electronic properties of lamotrigine (LTG) and two analogues (A1 and A2) are compared through MOPAC-AM1 calculations. Two stable conformers of LTG are calculated to exist in agreement with X-ray crystallography. In the three compounds and the two conformers for each of them, the more favorable protonation sites are N2 and N4; these should then be the sites appropriate for interaction with a receptor, and group valence reinforces the supposition. The molecular electrostatic potentials show that a region between the two chlorine atoms in LTG could be the site for an electrostatic interaction with a corresponding site in the receptor. The fluorine atom in A1 would play an equivalent role. A simple model for LTG-receptor interaction is proposed. 相似文献
6.
Héctor C. González Myriam Segre de Giambiagi Mario Giambiagi 《Theoretical chemistry accounts》1966,6(3):257-267
Theπ electronic structure of naphtalene is studied, using a semi-empirical approximation for coulombic and resonance integrals; forH andS (H, hamiltonian;S, overlap) the complete matrices are adopted, together withKohlrausch's nuclear effective charges. A non uniform charge distribution is obtained, with charge accumulation at the tertiary carbons. Bond orders between non neighboring atoms indicate contributions to the fundamental state from other structures besides the classical ones. A comparative study of the obtained interatomic distances is carried. It is shown that [H, S]=0 is not a sufficient condition for the identity of the bond orders for the fundamental state calculated with and without overlap. 相似文献
7.
Anna Laura Segre Fulvio Andruzzi Corrado Barone Massimo Paci Pier Luigi Magagnini 《Journal of Polymer Science.Polymer Physics》1985,23(12):2611-2621
The 13C NMR spectra of aromatic comblike polyesters obtained from 1,2-icosanediol and isomeric phthalic acids are reported and discussed. The analysis shows that the most informative spectral regions are those of the carbonyl and quaternary carbon resonances, whose peak multiplicities have been interpreted in terms of dyad and triad sequences. The results indicate that the extent of structural characterization possible for the polymers examined is dependent on the type of isomerism of the aromatic acid involved. 相似文献
8.
S.?VielEmail author D.?Capitani N.?Proietti F.?Ziarelli A.L.?Segre 《Applied Physics A: Materials Science & Processing》2004,79(2):357-361
High and low resolution solid state NMR methods have been applied to characterise a few samples of ancient wood. In an ancient larch wood sample, by applying 1H low resolution NMR methods as a function of the temperature, the average pore size and its distribution have been determined. In addition, high resolution NMR techniques have allowed addressing of the question of the proximity of water pools to cellulose and lignin. In particular, a model can be hypothesized in which water pools are surrounded by thin layers of amorphous cellulose and/or lignin while the crystalline domains of cellulose surround the layers of amorphous cellulose. Preliminary results obtained using a fully non invasive and portable NMR unilateral relaxometer, the Eureka-Mouse10 (EM10), are reported. This instrumentation is shown to be perfectly suitable for characterizing degradation in ancient wood samples. PACS 76.60 k 相似文献
9.
Blümich B Anferova S Sharma S Segre AL Federici C 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2003,161(2):204-209
The NMR-MOUSE is a mobile sensor for single-sided NMR inspection of organic materials which takes advantage of the principles of magnetic resonance and inside-out-NMR. Historical books dating from the 17th century were measured at different points by positioning the NMR-MOUSE on the paper. Different degrees of paper degradation can be discriminated from the regularized inverse Laplace transform of the envelope of the acquired echo signals. For the first time the degradation of historical paper was characterized entirely nondestructively by NMR. As a contribution to current preservation efforts, NMR shows great promise for future use in damage assessment of historical documents. 相似文献
10.
Busico V Van Axel Castelli V Aprea P Cipullo R Segre A Talarico G Vacatello M 《Journal of the American Chemical Society》2003,125(18):5451-5460
The 150 MHz (13)C NMR microstructural analysis of polypropylene samples produced with two representative "oscillating" metallocene catalysts of largely different steric hindrance, namely [(2-(3,5-di-tert-butyl-4-methoxyphenyl)indenyl)(2)ZrP](+) and [(2-phenylindenyl)(2)ZrP](+) (P = polymeryl), and the implications on the origin of the stereocontrol are presented and discussed in detail. The original mechanistic proposal of an "oscillation" between a rac-like (isotactic-selective) and a meso-like (nonstereoselective) conformation cannot explain the observed polymer configuration. The isotactic-stereoblock nature of the polymers obtained with the former catalyst proves unambiguously that the active cation "oscillates" between the two enantiomorphous rac-like conformations at an average frequency that, even at high propene concentration, is only slightly lower than that of monomer insertion. The less-hindered [(2-phenylindenyl)(2)ZrP](+) gives instead a largely stereoirregular polypropylene, which is the logical consequence of a faster ligand rotation; however, depending on the use conditions (in particular, on the nature of the cocatalyst and the polarity of the solvent), the polymerization products may also contain appreciable amounts of a fairly isotactic fraction. The peculiar microstructure of this fraction, with isotactic blocks of the same relative configuration spanned by very short atactic ones, rules out the possibility that the latter are due to an active species in meso-like conformation and points rather to a conformationally "locked" rac-like species with restricted ring mobility. The hypothesis of a stereorigidity induced by the proximity to a counteranion, which would play the role of the interannular bridge in the rac-bis(indenyl) ansa-metallocenes, was tested by computer modeling on a [rac-(2-phenylindenyl)(2)ZrMe(C(3)H(6))][B(C(6)F(5))(4)] ion couple and found viable. 相似文献