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41.
Gates AJ Kemp GL To CY Mann J Marritt SJ Mayes AG Richardson DJ Butt JN 《Physical chemistry chemical physics : PCCP》2011,13(17):7720-7731
In protein film electrochemistry a redox protein of interest is studied as an electroactive film adsorbed on an electrode surface. For redox enzymes this configuration allows quantification of the relationship between catalytic activity and electrochemical potential. Considered as a function of enzyme environment, i.e., pH, substrate concentration etc., the activity-potential relationship provides a fingerprint of activity unique to a given enzyme. Here we consider the nature of the activity-potential relationship in terms of both its cellular impact and its origin in the structure and catalytic mechanism of the enzyme. We propose that the activity-potential relationship of a redox enzyme is tuned to facilitate cellular function and highlight opportunities to test this hypothesis through computational, structural, biochemical and cellular studies. 相似文献
42.
Gemma L. Ellis V. Elena Ramos S. Barret Kalindjian David J. Tapolczay 《Tetrahedron letters》2007,48(10):1683-1686
Functionalised hydroxylamine derivatives of (S)-proline and (R)-pipecolic acid have been prepared using a Cope elimination. These undergo reverse Cope elimination onto a pendant double bond to give bicyclic lactam and lactone N-oxides containing three contiguous chiral centres, this extends the scope and applicability of the reverse Cope elimination in the synthesis of heterocyclic systems by incorporation of the lactone and lactam structural motifs. 相似文献
43.
Alvarez Ruiz J Kivimäki A Stankiewicz M Melero García E Coreno M Ali S Koperski J Rachlew E Vall-Llosera I Serrano G Feyer V Tuckett R 《Physical chemistry chemical physics : PCCP》2006,8(44):5199-5206
The interaction of SF(5)CF(3) with vacuum-UV radiation has been investigated by photon induced fluorescence spectroscopy. Total fluorescence yield and dispersed fluorescence spectra of SF(5)CF(3) were recorded in the 200-1000 nm fluorescence window. In all cases, the fluorescence spectra resemble those of CF(3)X (X = H, F, Cl, and Br) molecules. At photon energies below 20 eV, the emission is attributed to the excited CF(3) and CF(2) fragments. The threshold for the CF(3) emission is 10.2 +/- 0.2 eV, giving an upper limit estimate for the SF(5)-CF(3) bond dissociation energy of 3.9 +/- 0.3 eV. The excitation functions of the CF(3) and CF(2) emissions were measured in the photon energy range 13.6-27.0 eV. The resonant structures observed in SF(5)CF(3) are attributed to electronic transitions from valence to Rydberg orbitals, following similar assignments in CF(3)X molecules. The photoabsorption spectrum of SF(5)CF(3) shows features at the same energies, indicating a strong contribution from Rydberg excitations. 相似文献
44.
A set of components (CMLReact) for managing chemical and biochemical reactions has been added to CML. These can be combined to support most of the strategies for the formal representation of reactions. The elements, attributes, and types are formally defined as XMLSchema components, and their semantics are developed. New syntax and semantics in CML are reported and illustrated with 10 examples. 相似文献
45.
Braddock DC Cansell G Hermitage SA White AJ 《Chemical communications (Cambridge, England)》2006,(13):1442-1444
Bromoiodinanes--conveniently and directly prepared from iodobenzenecarbinols and N-bromosuccinimide, and characterised for the first time crystallographically--act as electrophilic bromine donors. 相似文献
46.
The aim of this article is to establish, among other results, the asymptotic stability of the depth of the graded pieces of a nonstandard multigraded module. As a corollary, we get the asymptotic stability of the depth of the graded pieces of the multigraded Rees algebra defined by a finite set of ideals and their associated multigraded rings. 相似文献
47.
Gemma Carotenuto Giangiacomo Gerla 《International Journal of Approximate Reasoning》2013,54(8):1066-1086
In this exploratory paper we propose a framework for the deduction apparatus of multi-valued logics based on the idea that a deduction apparatus has to be a tool to manage information on truth values and not directly truth values of the formulas. This is obtained by embedding the algebraic structure V defined by the set of truth values into a bilattice B. The intended interpretation is that the elements of B are pieces of information on the elements of V. The resulting formalisms are particularized in the framework of fuzzy logic programming. Since we see fuzzy control as a chapter of multi-valued logic programming, this suggests a new and powerful approach to fuzzy control based on positive and negative conditions. 相似文献
48.
49.
Gemma M. Locke Dr. Stefan S. R. Bernhard Prof. Dr. Mathias O. Senge 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(18):4590-4647
Nonconjugated hydrocarbons, like bicyclo[1.1.1]pentane, bicyclo[2.2.2]octane, triptycene, and cubane are a unique class of rigid linkers. Due to their similarity in size and shape they are useful mimics of classic benzene moieties in drugs, so-called bioisosteres. Moreover, they also fulfill an important role in material sciences as linear linkers, in order to arrange various functionalities in a defined spatial manner. In this Review article, recent developments and usages of these special, rectilinear systems are discussed. Furthermore, we focus on covalently linked, nonconjugated linear arrangements and discuss the physical and chemical properties and differences of individual linkers, as well as their application in material and medicinal sciences. 相似文献
50.
Stefano Federico Tuhina Khan Nicola Relitti Giulia Chemi Margherita Brindisi Simone Brogi Ettore Novellino Daniela M. Zisterer Giuseppe Campiani Sandra Gemma Stefania Butini 《Tetrahedron letters》2018,59(51):4466-4470
We developed a Jocic-type protocol for the construction of the pyrrolonaphthoxazepine (PNOX) core. After an initial investigation based on the isolation of a trichloromethyl carbinol derivative, we shifted our attention towards a multicomponent single-step protocol. Screening of a variety of bases and solvents led to the identification of the optimum conditions for the preparation of the key α-aryloxy carboxylic acids to undergo intramolecular cyclization. The novel chemical route significantly improved overall yields for the preparation of PNOX-based compounds and was successfully extended to the preparation of 1,4-benzoxazinone-based templates. 相似文献