全文获取类型
收费全文 | 876篇 |
免费 | 30篇 |
国内免费 | 2篇 |
学科分类
数理化 | 908篇 |
出版年
2024年 | 3篇 |
2023年 | 12篇 |
2022年 | 17篇 |
2021年 | 37篇 |
2020年 | 19篇 |
2019年 | 20篇 |
2018年 | 14篇 |
2017年 | 13篇 |
2016年 | 32篇 |
2015年 | 26篇 |
2014年 | 30篇 |
2013年 | 52篇 |
2012年 | 58篇 |
2011年 | 68篇 |
2010年 | 32篇 |
2009年 | 32篇 |
2008年 | 42篇 |
2007年 | 45篇 |
2006年 | 36篇 |
2005年 | 51篇 |
2004年 | 40篇 |
2003年 | 27篇 |
2002年 | 26篇 |
2001年 | 13篇 |
2000年 | 12篇 |
1999年 | 13篇 |
1998年 | 10篇 |
1997年 | 10篇 |
1996年 | 15篇 |
1995年 | 7篇 |
1994年 | 4篇 |
1993年 | 8篇 |
1991年 | 6篇 |
1990年 | 3篇 |
1988年 | 5篇 |
1985年 | 3篇 |
1984年 | 4篇 |
1983年 | 4篇 |
1982年 | 4篇 |
1981年 | 3篇 |
1980年 | 5篇 |
1979年 | 5篇 |
1978年 | 6篇 |
1977年 | 3篇 |
1976年 | 3篇 |
1975年 | 3篇 |
1974年 | 5篇 |
1973年 | 2篇 |
1960年 | 2篇 |
1886年 | 2篇 |
排序方式: 共有908条查询结果,搜索用时 15 毫秒
31.
Nicholas Favalli Gabriele Bassi Tania Zanetti Jrg Scheuermann Dario Neri 《Helvetica chimica acta》2019,102(4)
The construction of DNA‐encoded chemical libraries (DECLs) crucially relies on the availability of chemical reactions, which are DNA‐compatible and which exhibit high conversion rates for a large number of diverse substrates. In this work, we present our optimization and validation procedures for three copper and palladium‐catalyzed reactions (Suzuki cross‐coupling, Sonogashira cross‐coupling, and copper(I)‐catalyzed alkyne‐azide cycloaddition (CuAAC)), which have been successfully used by our group for the construction of large encoded libraries. 相似文献
32.
33.
Camille Descour Tibor Macko Dario Cavallo Matthew Parkinson Gerhard Hubner Anne Spoelstra Maurizio Villani Robbert Duchateau 《Journal of polymer science. Part A, Polymer chemistry》2014,52(10):1422-1434
Stereoblock polypropylenes comprising of iPP and sPP segments are synthesized by polymerization of the following binary system of metallocenes: the Cs‐symmetric [2,7‐t‐Bu2(Flu)2Ph2C(Cp)ZrCl2] and the C2‐symmetric rac‐Me2Si(2‐Me‐4‐Ph‐Ind)2ZrCl2. Blends of samples made either by each catalyst individually (solution blend) with materials obtained with the mixed catalyst system (reactor blend) are compared. The simultaneous presence of MAO and DEZ, enhancing fast and reversible transfer of the growing chains between the two active centers, leads to the formation of a stereoblock microstructure. In this case, low molecular weight polymers are obtained. The junction between the blocks is qualitatively observed in 13C NMR. When made in toluene, the stereoblock material consists of a majority of syndiotactic sequences, whereas the ratio is more equilibrated when the polymerization was conducted in the more polar chlorobenzene. This is confirmed by the results obtained with 13C NMR, CRYSTAF, HT HPLC, DSC, SSA, WAXD, and optical microscopy. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1422–1434 相似文献
34.
Ute Löffelmann Nan Wang Dario Mager Patrick J. Smith Jan G. Korvink 《Journal of Polymer Science.Polymer Physics》2012,50(1):38-46
A new and solvent‐free process for the fabrication of inkjet printed ionic liquid‐polymer gel microstructures with high‐resolution (line widths of ~40 μm), good electrical conductivity (5–30 mS cm?1), optical transparency, and mechanical flexibility is presented. Carrying out the printing and polymerization process in nitrogen atmosphere eliminates the inhibiting influence of oxygen and guarantees homogeneously gelled structures. Careful selection and combination of ionic liquids (ILs) and unsaturated monomers makes it possible to achieve low viscosities which are printable with commercially available inkjet printers and printheads without adding extra solvents. By using different types and amounts of ILs and monomers the resulting properties of the printed IL‐polymer gels can be controlled in terms of ionic conductivity, optical transmission, and mechanical flexibility. Higher conductivities are possible by using a bifunctional instead of a monofunctional monomer, which allows one to lower the amount of monomer without loss in mechanical strength. Cast samples make it possible to obtain data of transmission (~90% for 170‐μm thick films) and mechanical flexibility (E = 0.02–0.23 MPa) of bulk material. Comparing electrical conductivity of printed and cast samples, the higher values of printed samples indicate the conductivity enhancing influence of moisture absorbed from the surrounding atmosphere after the fabrication process. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011 相似文献
35.
Abstract The ability of macrocyclic polyethers to activate enolates has been studied in the alkylation of de-oxybenzoin (1) with butyl derivatives nBuY (Y = Br, I, OMes) catalyzed by crown ether PHDB18C6 (7) or cryptand [2.2.2,C10] (8) under phase-transfer catalysis (PTC) and homogeneous (chlorobenzene) conditions. The enolate reactivity is mainly determined by the ligand (cryptand > crown ether) and solvent (increasing with the polarity, in the order: toluene < chlorobenzene < 1,2dichlorobenzene). Regioselectivity of the reaction is also remarkably affected by ligand and alkylating agent. 相似文献
36.
Dr. Philipp Holtkamp Dario Poier Beate Neumann Dr. Hans-Georg Stammler Prof. Dr. Norbert W. Mitzel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(11):3793-3798
The reactivity of the geminal frustrated Lewis pair (FLP) (F5C2)3SnCH2P(tBu)2 ( 1 ) was explored by reacting it with a variety of small molecules (PhOCN, PhNCS, PhCCH, tBuCCH, H3CC(O)CH=CH2, Ph[C(O)]2Ph, PhN=NPh and Me3SiCHN2), featuring polar or non-polar multiple bonds and/or represent α,β-unsaturated systems. While most adducts are formed readily, the binding of azobenzene requires UV-induced photoisomerization, which results in the highly selective complexation of cis-azobenzene. In the case of benzil, the reaction does not lead to the expected 1,2- or 1,4-addition products, but to the non-stereoselective (tBu)2PCH2-transfer to a prochiral keto function of benzil. All adducts of 1 were characterised by means of multinuclear NMR spectroscopy, elemental analyses and X-ray diffraction experiments. 相似文献
37.
38.
A methodology for the determination of bismuth, based on under-potential deposition-stripping voltammetry (UPD-SV), was investigated. It makes use of mesoporous platinum microelectrodes (Pt-MEs) prepared by a liquid crystal templating technique. The mesoporous microelectrodes, which are characterised by a very high surface area, allowed the accumulation of relatively large amounts of bismuth at under-potential without saturation of the electrode surface. Calibration plots for quantification of bismuth at micromolar levels were constructed by using the charge involved in either the anodic or cathodic peak recoded by cyclic voltammetry that ensued the accumulation of bismuth at the electrode surface. During the anodic scan, the oxidation of metallic bismuth occurred; the cathodic scan involved irreversibly adsorbed bismuth species, which are retained on to the electrode surface. The reproducibility of the proposed UPD-SV procedure (which was within 5 %) was assured by the application to the Pt-MEs of a suitable potential waveform, properly designed to avoid memory effect due to the irreversibly deposited bismuth. The latter phenomenon along with UPD allowed to overcome interference due to copper, which is normally observed when quantification of bismuth is performed by anodic stripping voltammetry at solid electrodes involving bulk metal deposits. The usefulness of the proposed method for the determination of bismuth in real samples was demonstrated by the analysis of a tablet of a pharmaceutical preparation, which is used for curing ulcers. 相似文献
39.
Nikolaus Krall Dr. Jörg Scheuermann Prof. Dario Neri 《Angewandte Chemie (International ed. in English)》2013,52(5):1384-1402
The targeted delivery of potent cytotoxic agents has emerged as a promising strategy for the treatment of cancer and other serious conditions. Traditionally, antibodies against markers of disease have been used as drug‐delivery vehicles. More recently, lower molecular weight ligands have been proposed for the generation of a novel class of targeted cytotoxics with improved properties. Advances in this field crucially rely on efficient methods for the identification and optimization of organic molecules capable of high‐affinity binding and selective recognition of target proteins. The advent of DNA‐encoded chemical libraries allows the construction and screening of compound collections of unprecedented size. In this Review, we survey developments in the field of small ligand‐based targeted cytotoxics and show how innovative library technologies will help develop the drugs of the future. 相似文献
40.
Dr. Sylvain Achelle Dr. Jean‐Pierre Malval Dr. Stéphane Aloïse Dr. Alberto Barsella Dr. Arnaud Spangenberg Dr. Loic Mager Dr. Huriye Akdas‐Kilig Dr. Jean‐Luc Fillaut Prof. Bertrand Caro Prof. Françoise Robin‐le Guen 《Chemphyschem》2013,14(12):2725-2736
The nonlinear properties and the photophysical behavior of two π‐conjugated chromophores that incorporate an electron‐deficient pyrimidine core (A) and γ‐methylenepyrans as terminal donor (D) groups have been thoroughly investigated. Both dipolar and quadrupolar branching strategies are explored and rationalized on the basis of the Frenkel exciton model. Even though a cooperative effect is clearly observed if the dimensionality is increased, the nonlinear optical (NLO) response of this series is moderate if one considers the nature of the D/A couple and the size of the chromophores (as measured by the number of π electrons). This effect was attributed to a disruption in the electronic conjugation within the dyes’ scaffold for which the geometry deviates from planarity owing to a noticeable twisting of the pyranylidene end‐groups. This latter structural parameter also has a strong influence on the excited‐state dynamics, which leads to a very efficient fluorescence quenching. 相似文献