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31.
[reaction: see text] A highly regio- and stereoselective bis-stannylation of unsymmetrically substituted butadiyne 3 provides bis-stannane 4. Selective lithiation of the internal tin residue effects a 1,4-retro-Brook rearrangement to afford vinylsilane 5. This was elaborated into the novel diethynylethene 1, which also functions as a masked triyne. 相似文献
32.
33.
Massimiliano Aschi Caterina Fraschetti Antonello Filippi Maurizio Speranza 《Journal of mass spectrometry : JMS》2009,44(7):1038-1046
The nature of the ionic species, formed by electrospray ionization (ESI) of Co(NO3)2/CH3OH solutions with a pair of aminoalcohols W and Y, has been investigated by mass spectrometric and computational methods. Collision induced dissociation (CID) of ions, formally corresponding to the [WYCoNO3]+ structures, yields fragmentation patterns which reflect not only the expected [WYCoNO3]+ connectivity but also that of other isomeric structures. Formation of these latter species is observed only in the presence of a tertiary aminoalcohol, like N‐methylpseudoephedrine. The CID patterns are found to be strongly dependent on the chemical form (whether the free aminoalcohol or its hydrochloride), the configuration, and the relative concentration of the W and Y aminoalcohols. This variability parallels the results of classical MD (molecular dynamics) simulations of the [WYCoNO3]+ adducts which show a drastic alteration of the mechanical–dynamical features of the adducts by simply changing the charge state of W and/or Y, their absolute configuration, or by removing the solvent. The present experimental and computational study confirms the observation of fast stereoselective reactions in ESI nanodroplets before their evaporation and warns against any automatic correlation between the ESI spectrum of an analyte and its structure in solution. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
34.
Giuliano Alagona Caterina Ghio Alessandro Giolitti Susanna Monti 《Theoretical chemistry accounts》1999,101(1-3):143-150
Several histidine-tryptophan complexes (either stacked or T-shaped), derived from the crystal structures available in the
Brookhaven Protein Data Bank, have been examined with molecular mechanics (MM), using the Tripos force field with Gasteiger-Hückel
charges, whose trend was found to be analogous to the AMBER or CHARMM ones. The MM results were compared to the ab initio
MP2 results, with and without counterpoise (CP) correction, previously obtained using extended basis sets on 5-methylimidazole
and indole as model systems. MM seems to underestimate the interaction energy between the two monomers when compared to the
uncorrected MP2 results, while the agreement is much better after including the CP correction at the MP2 level in all cases.
MM was thus used to qualitatively analyse the dependence of the stacking energy on the ring rotation at a variable distance
and ring centroid displacement for these systems, while keeping the rings in parallel planes. An analogous study was carried
out for a T-shaped adduct.
Received: 24 March 1998 / Accepted: 3 September 1998 / Published online: 1 February 1999 相似文献
35.
Caterina Canovaro Irene Calliari Michele Asolati Francesco Grazzi Antonella Scherillo 《Applied Physics A: Materials Science & Processing》2013,112(4):1019-1025
Mixing of different organic charge-transfer-complexes (CT-complexes) might allow the adjustment of the optical and morphological properties of the resulting material system. In this work, a study of two CT-complexes, mixed by thermal coevaporation at different concentrations by substituting only the acceptor molecules, is presented. Electron diffraction patterns, which were collected on samples of the ternary system of the prototypical CT-complexes DBTTF-TCNQ and DBTTF-F4TCNQ do not show any indication of a mixed crystalline phase or novel crystalline order. X-ray diffraction measurements additionally confirm the phase separation in the ternary system. However, upon mixing of the complexes, the degree of crystallinity of the individual phases is reduced. This effect correlates with the mixing ratio of the CT-complexes in the ternary compound. Furthermore, we do not observe a shift or the appearance of new peaks in the infrared spectra of (DBTTF-TCNQ) x :(DBTTF-F4TCNQ)1?x . Hence, there is no indication for a pronounced or novel chemical interaction between the individual CT-complexes in the mixed compound. 相似文献
36.
As management of a national bank wanted to analyze its retail service competition loss probably due to low customer satisfaction, we carried out an empirical study based on a sample of 27,000 retail customers. The survey aimed to analyze retail service weaknesses and to individuate possible recovery actions measuring their effectiveness across different waves (three time lags). We studied a definition of a new dissimilarity measure exploiting a dimension reduction obtained by a three-way factor analysis (TFA). We had previously focused our attention on the limits of this approach related to the geometrical properties of the TFA applied. We introduced a reassessment of the points to adjust the three-way solution according to the quality of representation of the points. This transformation only rescaled the factor scores producing a local adjustment of the point configuration. We then performed a trajectory analysis of the different waves. The results showed the effectiveness of our approach. Therefore, further study of the derivation of a synthetic measure of cluster routes seems appropriate. 相似文献
37.
Giuliano Alagona Caterina Ghio Claudio Pratesi 《Journal of computational chemistry》1991,12(8):934-942
Parameters suitable to describe the conformational behavior of α – β unsaturated aminoacids and peptides in the framework of an existing force field for nucleic acids and proteins (S.J. Weiner, P.A. Kollman, D.A. Case, U. Chandra Singh, C. Ghio, G. Alagona, S. Profeta, Jr., and P. Weiner, J. Am. Chem. Soc., 106 , 765 (1984)) are proposed and tested. Attention is primarily focused on dehydrophenylalanine and dehydroalanine containing peptides. The values of the parameters needed were obtained from experimental measurements available in the literature and from ad hoc quantum mechanical calculations. The selected values have subsequently been adapted and refined through molecular mechanical simulations on model compounds, such as Ac-ΔPhe-NMe, for which it was possible to carry out STO-3G/SCF calculations to check selected points on the ?,ψ conformational map, and Ac-ΔAla-NMe, where the comparison was carried out at the 4-31G level. The newly determined force field was then applied to Ac-ΔPhe-Ala-ΔPhe-NMe, whose minimal energy structures allowed us to explain the different circular dichroism behavior observed in CH2Cl2 and in dioxane. Starting from two minimum energy geometries of this tripeptide, the full optimization with AM1 produced an independent guess to their structure and stability in good agreement with the molecular mechanical one. 相似文献
38.
Giovanni Ricci Aldo Boglia Tiziano Motta Fabio Bertini Antonella Caterina Boccia Lucia Zetta Enrica Alberti Antonino Famulari Paolo Arosio Stefano Valdo Meille 《Journal of polymer science. Part A, Polymer chemistry》2007,45(22):5339-5353
The (E) isomer in mixtures of (E) and (Z) 1,3‐hexadiene was polymerized with the system CoCl2(PiPrPh2)2‐MAO, a highly active and stereospecific catalyst for the preparation of 1,2 syndiotactic polybutadiene. A new crystalline polymer with a melting point of 109 °C was obtained. The polymer was characterized by IR, NMR (13C, 1H in solution and 13C in the solid‐state), X‐ray diffraction, DSC, GPC and it was found to have a trans‐1,2 syndiotactic structure with a 5.18 ± 0.04 Å fiber periodicity. Since only the (E) isomer was polymerized, at the end of the reaction we were able to separate the (Z) isomer, which was ultimately polymerized with CpTiCl3‐MAO at low temperature, obtaining a low molecular weight, stereoregular polymer that, characterized by IR and NMR methods, was found to exhibit a cis‐1,2 syndiotactic structure, never reported before. Molecular mechanics calculations were carried out on the trans‐1,2 syndiotactic polymer and structural models consistent with the X‐ray diffraction data are proposed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5339–5353, 2007 相似文献
39.
We give both a topological and an algebraic definition of the order of a global branch of a variety along a subvariety. Then
we show that these two definitions agree. Finally we compare this order with the orders of the related local branches.
Partially supported by CNR funds. 相似文献
Sunto Diamo due definizioni, una topologica e una algebrica, di ordine di un ramo globale di una varietà lungo una sottovarietà. Poi mostriamo che queste due definizioni coincidono. Infine confrontiamo questo ordine con gli ordini dei relativi rami locali.
Partially supported by CNR funds. 相似文献
40.
Amorati R Attanasi OA Favi G Menichetti S Pedulli GF Viglianisi C 《Organic & biomolecular chemistry》2011,9(5):1352-1355
Hydrogenated cardanol and cardols, contained in industrial grade cardanol oil and obtained by distillation of the raw "cashew nut shell liquid" (CNSL), are easily transformed into efficient 4-thiaflavane antioxidants bearing a long alkyl chain on A ring and a catechol group on B ring. 相似文献