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261.
Infrared Detection of Criegee Intermediates Formed during the Ozonolysis of β‐Pinene and Their Reactivity towards Sulfur Dioxide
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Jennifer Ahrens Philip T. M. Carlsson Nils Hertl Prof. Dr. Matthias Olzmann Mark Pfeifle Dr. J. Lennard Wolf Dr. Thomas Zeuch 《Angewandte Chemie (International ed. in English)》2014,53(3):715-719
Recently, direct kinetic experiments have shown that the oxidation of sulfur dioxide to sulfur trioxide by reaction with stabilized Criegee intermediates (CIs) is an important source of sulfuric acid in the atmosphere. So far, only small CIs, generated in photolysis experiments, have been directly detected. Herein, it is shown that large, stabilized CIs can be detected in the gas phase by FTIR spectroscopy during the ozonolysis of β‐pinene. Their transient absorption bands between 930 and 830 cm?1 appear only in the initial phase of the ozonolysis reaction when the scavenging of stabilized CIs by the reaction products is slow. The large CIs react with sulfur dioxide to give sulfur trioxide and nopinone with a yield exceeding 80 %. Reactant consumption and product formation in time‐resolved β‐pinene ozonolysis experiments in the presence of sulfur dioxide have been kinetically modeled. The results suggest a fast reaction of sulfur dioxide with CIs arising from β‐pinene ozonolysis. 相似文献
262.
Dr. Sankar Mohan Dr. Philip S. Kerry Nicole Bance Prof. Dr. Masahiro Niikura Prof. Dr. B. Mario Pinto 《Angewandte Chemie (International ed. in English)》2014,53(4):1076-1080
We have previously reported a potent neuraminidase inhibitor that comprises a carbocyclic analogue of zanamivir in which the hydrophilic glycerol side chain is replaced by the hydrophobic 3‐pentyloxy group of oseltamivir. This hybrid inhibitor showed excellent inhibitory properties in the neuraminidase inhibition assay (Ki=0.46 nM ; Ki (zanamivir)=0.16 nM ) and in the viral replication inhibition assay in cell culture at 10?8 M . As part of this lead optimization, we now report a novel spirolactam that shows comparable inhibitory activity in the cell culture assay to that of our lead compound at 10?7 M . The compound was discovered serendipitously during the attempted synthesis of the isothiourea derivative of the original candidate. The X‐ray crystal structure of the spirolactam in complex with the N8 subtype neuraminidase offers insight into the mode of inhibition. 相似文献
263.
Gold‐Catalyzed Cycloisomerization of 1,6,8‐Dienyne Carbonates and Esters to cis‐Cyclohepta‐4,8‐diene‐Fused Pyrrolidines
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Dr. Weidong Rao Sally Stuart Neil Berry Prof. Dr. Philip Wai Hong Chan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(41):13174-13180
A synthetic approach that provides access to cis‐cyclohepta‐4,8‐diene‐fused pyrrolidines efficiently through AuI‐catalyzed cycloisomerization of 1,6,8‐dienyne carbonates and esters at a low catalyst loading of 2 mol % is reported. Starting carbonates and esters with a pendant alkyl group on the terminal alkenyl carbon center were found to favor tandem 1,2‐acyloxy migration/cyclopropanation followed by Cope rearrangement of the resulting cis‐3‐azabicyclo[3.1.0]hexane intermediate. On the other hand, substrates containing a terminal diene or starting materials in which the distal alkene moiety bears a phenyl substituent were observed to undergo competitive but reversible 1,3‐acyloxy migration prior to the nitrogen‐containing bicyclic ring formation. The delineated reaction mechanism also provides experimental evidence for the reversible interconversion between the oft‐proposed organogold intermediates obtained in this step of the tandem process. 相似文献
264.
Jonathan W. Dube Cameron M. E. Graham Prof. Charles L. B. Macdonald Dr. Zachary D. Brown Prof. Philip P. Power Prof. Paul J. Ragogna 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(22):6739-6744
Two unique systems based on low‐coordinate main group elements that activate P4 are shown to quantitatively release the phosphorus cage upon short exposure to UV light. This reactivity marks the first reversible reactivity of P4, and the germanium system can be cycled 5 times without appreciable loss in activity. Theoretical calculations reveal that the LUMO is antibonding with respect to the main group element–phosphorus bonds and bonding with respect to reforming the P4 tetrahedron, providing a rationale for this unprecedented activity, and suggesting that the process is tunable based on the substituents. 相似文献
265.
Stereoelectronic Basis for the Kinetic Resolution of N‐Heterocycles with Chiral Acylating Reagents
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Sheng‐Ying Hsieh Benedikt Wanner Dr. Philip Wheeler Prof. Dr. André M. Beauchemin Prof. Dr. Tomislav Rovis Prof. Dr. Jeffrey W. Bode 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(24):7228-7231
The kinetic resolution of N‐heterocycles with chiral acylating agents reveals a previously unrecognized stereoelectronic effect in amine acylation. Combined with a new achiral hydroxamate, this effect makes possible the resolution of various N‐heterocycles by using easily prepared reagents. A transition‐state model to rationalize the stereochemical outcome of this kinetic resolution is also proposed. 相似文献
266.
Chemical Probing of the Human Sirtuin 5 Active Site Reveals Its Substrate Acyl Specificity and Peptide‐Based Inhibitors
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Claudia Roessler Theresa Nowak Martin Pannek Dr. Melanie Gertz Giang T. T. Nguyen Michael Scharfe Dr. Ilona Born Prof. Dr. Wolfgang Sippl Prof. Dr. Clemens Steegborn Prof. Dr. Mike Schutkowski 《Angewandte Chemie (International ed. in English)》2014,53(40):10728-10732
Sirtuins are NAD+‐dependent deacetylases acting as sensors in metabolic pathways and stress response. In mammals there are seven isoforms. The mitochondrial sirtuin 5 is a weak deacetylase but a very efficient demalonylase and desuccinylase; however, its substrate acyl specificity has not been systematically analyzed. Herein, we investigated a carbamoyl phosphate synthetase 1 derived peptide substrate and modified the lysine side chain systematically to determine the acyl specificity of Sirt5. From that point we designed six potent peptide‐based inhibitors that interact with the NAD+ binding pocket. To characterize the interaction details causing the different substrate and inhibition properties we report several X‐ray crystal structures of Sirt5 complexed with these peptides. Our results reveal the Sirt5 acyl selectivity and its molecular basis and enable the design of inhibitors for Sirt5. 相似文献
267.
Philip Boehm Sven Roediger Alessandro Bismuto Bill Morandi 《Angewandte Chemie (International ed. in English)》2020,59(41):17887-17896
An efficient palladium‐catalyzed chlorocarbonylation of aryl (pseudo)halides that gives access to a wide range of carboxylic acid derivatives has been developed. The use of butyryl chloride as a combined CO and Cl source eludes the need for toxic, gaseous carbon monoxide, thus facilitating the synthesis of high‐value products from readily available aryl (pseudo)halides. The combination of palladium(0), Xantphos, and an amine base is essential to promote this broadly applicable catalytic reaction. Overall, this reaction provides access to a great variety of carbonyl‐containing products through in situ transformation of the generated aroyl chloride. Combined experimental and computational studies support a reaction mechanism involving in situ generation of CO. 相似文献
268.
Nicolas Armanino Julie Charpentier Felix Flachsmann Andreas Goeke Marc Liniger Philip Kraft 《Angewandte Chemie (International ed. in English)》2020,59(38):16310-16344
This review is the sequel to the 2000 report on the recent advances in the chemistry of odorants and it summarizes the developments in fragrance chemistry over the past 20 years. Following the olfactory spectrum set out in that report, trendsetting so‐called captive odorants (patent‐protected ingredients unavailable to the market) are presented according to the main odor families: “fruity”, “marine”, “green”, “floral”, “spicy”, “woody”, “amber”, and “musky”. The design of odorants, their chemical synthesis, and their use in modern perfumery are illustrated with prominent examples. Featured are new fruity odorants that provide signature in the top note, as well as precursor technology. In the green domain, focus is on leafy notes and green pear. New benzodioxepines and benzodioxoles have modernized the marine family and required a revision of the existing olfactophore models. The replacement of Lilial and Lyral kept the industry busy in the floral domain with a plethora of new “muguets”. There was continued activity in the domain of rose odorants, especially in the area of rose ketones. Biotechnology became significant, for example, with Clearwood and Ambrofix, and the principal odorants of vetiver oil in the woody family have been found. Fourth and fifth families of musk odorants were also discovered and populated. Thus, new avenues for further explorations into fragrance chemistry have been opened. 相似文献
269.
Cokes rich in sulphur usually show throughout the high temperature treatment between 1500 and 1800 °C an irreversible dilatation which can be suppressed by additives of inorganic oxides or salts. In brown coal pitch cokes with high content of sulphur and mineral impurities (ash), however, this suphur puffing cannot be observed. Basic ash components (e. g. CaO, Fe2O3, MgO) are responsible for the puffing inhibition. The inhibition is already sufficient if the concerntration of basic ash components equals the suphur conentration. 相似文献
270.
Christopher Glidewell S. Zaka Ahmed Michael Gottfried Philip Lightfoot Brodyck J.L. Royles Jeremy P. Scott Jrg Wonnemann 《Journal of organometallic chemistry》1997,530(1-2):177-185
Ferrocenyl-1,2-diketones FcCOCOR, 3, [Fc = (C5H5)Fe(C5H4)] can be prepared by oxidation of acylferrocenes FcCOCH2R or, more efficiently, by oxidation of the isomeric ketones FcCH2COR, 2. The ketones 2 are in turn readily synthesized from the salt (FcCH2PPh3)+I− via the acylated salts [FcCH(COR)PPh3]+I−. The haloacylferocenes FcCOCClx H3−x (x = 1, 2, 3, of which the x = 2 example is synthetically equivalent to a diketone) are synthesized by Friedel—Crafts acylation of ferrocene using CClxH3−xCOCl/AlCl3, but the reaction proceeds via two parallel pathways, one giving the normal acyl derivatives FcCOCClxH3−x and the other giving the reduced products FcCOCClx−1H4−x. Two diketones FcCOCOFc 3b and FcCOCOC6H4Ph 3c have been structurally characterised by single-crystal X-ray diffraction. 相似文献