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81.
Jéssica Venância Faria Maurício Silva dos Santos Percilene Fazolin Vegi Julio Cesar Borges Alice M.R. Bernardino 《Tetrahedron letters》2013
In this Letter, we described the synthesis of new 5-(5-amino-1-aryl-1H-pyrazole-4-yl)-1H-tetrazoles 2a–c from 5-amino-1-aryl-1H-pyrazole-4-carbonitriles 1a–c as well as the unexpected 1H-pyrazolo[3,4-d]pyrimidine derivatives 6a–c from 5-amino-1-aryl-3-methyl-1H-pyrazole-4-carbonitriles 4a–c, instead of 5-(5-amino-1-aryl-3-methyl-1H-pyrazole-4-yl)-1H-tetrazoles 5a–c as desired. In an attempt to obtain these tetrazole derivatives containing the methyl group at C3-position in the pyrazole ring, the amino group in 5-amino-1-(4-methoxyphenyl)-3-methyl-1H-pyrazole-4-carbonitrile 4c was protected by the reaction with sodium hydride and di-tert-butyl-dicarbonate (Boc). The tetrazole derivative 5c was synthesized from the protected compound 7c using analogue methodology to obtain 2a–c and 6a–c. 相似文献
82.
83.
Olimpo García-Beltrán Bruce K. Cassels Natalia Mena Marco T. Nuñez Osvaldo Yañez Julio Caballero 《Tetrahedron letters》2014
In this Letter we present a new probe, (E)-7-(diethylamino)-2-oxo-2H-chromene-3-carbaldehyde oxime (JB), which can detect Cu2+ ions in HEPES buffer under physiological conditions. Benesi–Hildebrand and Job plots demonstrate that the stoichiometry of the Cu2+ complex formed is 2:1. Possible interference with other analytes was examined, and the decrease of the fluorescence of JB at 510 nm when it reacts with Cu2+ was shown to be highly selective. This probe accumulates in the plasmalemma of human neuroblastoma SH-SY5Y cells. Molecular dynamics (MD) simulations revealed that JB interacts with the lipid bilayer at the level of the glycerol moieties. 相似文献
84.
Samuel Piña Jr. Diana M. Cedillo Carlos Tamez Nezhueyotl Izquierdo Jason G. Parsons Jose J. Gutierrez 《Tetrahedron letters》2014
Reported here is the reduction of aromatic nitro compounds using sodium borohydride and transition metal sulfides as catalysts. The reaction conditions were optimized using the reduction of nitrobenzene as a model reaction. The catalysts studied were iron sulfide (Fe3S4), copper sulfide (CuS), zinc sulfide (ZnS), cobalt sulfide (Co3S4), and nickel sulfide (NiS). The reduction was monitored using gas chromatography. Quantitative conversions were achieved using Co3S4 and NiS, representing a ten-fold increase in reactivity compared to the non-catalyzed reaction. Fe3S4 and ZnS had no apparent effect on the reduction of nitrobenzene while the reduction using CuS showed a marginal increase. The reduction method was applied to several aryl-nitro derivatives containing either electron-withdrawing or electron-donating groups. Halogen containing aryl-nitro compounds were reduced without dehalogenation. The reduction had no effect on other functional groups such as carboxylic acids, esters, amides, or alkenes, indicating that the reduction is highly chemoselective. 相似文献
85.
86.
Gioria Esteban Signorini Chiara Taleb María C. Thomas Arne Mihályi Magdolna R. Gutierrez Laura 《Cellulose (London, England)》2021,28(14):9135-9147
Cellulose - Palladium was incorporated into carboxymethylated cellulose fibers as a support, thereby becoming an efficient and stable catalyst for low temperature gas phase reaction. Thus, NO was... 相似文献
87.
Gas‐phase elimination kinetics of selected aliphatic α,β‐unsaturated aldehydes catalyzed by hydrogen chloride 下载免费PDF全文
Libia L. Julio José R. Mora Alexis Maldonado Gabriel Chuchani 《Journal of Physical Organic Chemistry》2015,28(4):261-265
The gas‐phase elimination of 2‐methyl‐2‐propenal catalyzed by HCl yields propene and CO gas, while E‐2‐pentenal with the same catalyst gives butene and CO gas. The kinetics determinations were carried out in a static system with the reaction vessels deactivated with allyl bromide and the presence of the free radical inhibitor toluene. Temperature and pressure ranges were 350.0–410.0 °C and 34–76 Torr. The elimination reactions are homogeneous and unimolecular, and follow a first‐order rate law. The rate coefficients for the reactions are expressible by the following Arrhenius equations: Data from the kinetic and thermodynamic parameters of these catalyzed elimination reactions implies a mechanism of a concerted five‐membered cyclic transition state structure for the formation of the corresponding olefin and carbon monoxide. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
88.
89.
Nickel‐Catalyzed Mizoroki–Heck Reaction of Aryl Sulfonates and Chlorides with Electronically Unbiased Terminal Olefins: High Selectivity for Branched Products 下载免费PDF全文
Sarah Z. Tasker Dr. Alicia C. Gutierrez Prof. Timothy F. Jamison 《Angewandte Chemie (International ed. in English)》2014,53(7):1858-1861
Achieving high selectivity in the Heck reaction of electronically unbiased alkenes has been a longstanding challenge. Using a nickel‐catalyzed cationic Heck reaction, we were able to achieve excellent selectivity for branched products (≥19:1 in all cases) over a wide range of aryl electrophiles and aliphatic olefins. A bidentate ligand with a suitable bite angle and steric profile was key to obtaining high branched/linear selectivity, whereas the appropriate base suppressed alkene isomerization of the product. Although aryl triflates are traditionally used to access the cationic Heck pathway, we have shown that, by using triethylsilyl trifluoromethanesulfonate, we can effect a counterion exchange of the catalytic nickel complex, such that cheaper and more stable aryl chlorides, mesylates, tosylates, and sulfamates can be used to yield the same branched products with high selectivity. 相似文献
90.
Aryl‐Copper(III)‐Acetylides as Key Intermediates in CCsp Model Couplings under Mild Conditions 下载免费PDF全文
Mireia Rovira Marc Font Ferran Acuña‐Parés Dr. Teodor Parella Dr. Josep M. Luis Dr. Julio Lloret‐Fillol Dr. Xavi Ribas 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(32):10005-10010
The mechanism of copper‐mediated Sonogashira couplings (so‐called Stephens–Castro and Miura couplings) is not well understood and lacks clear comprehension. In this work, the reactivity of a well‐defined aryl‐CuIII species ( 1 ) with p‐R‐phenylacetylenes (R=NO2, CF3, H) is reported and it is found that facile reductive elimination from a putative aryl‐CuIII‐acetylide species occurs at room temperature to afford the Caryl?Csp coupling species ( IR ), which in turn undergo an intramolecular reorganisation to afford final heterocyclic products containing 2H‐isoindole ( P , P , PHa ) or 1,2‐dihydroisoquinoline ( PHb ) substructures. Density Functional Theory (DFT) studies support the postulated reductive elimination pathway that leads to the formation of C?Csp bonds and provide the clue to understand the divergent intramolecular reorganisation when p‐H‐phenylacetylene is used. Mechanistic insights and the very mild experimental conditions to effect Caryl?Csp coupling in these model systems provide important insights for developing milder copper‐catalysed Caryl?Csp coupling reactions with standard substrates in the future. 相似文献