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Shoraku Ryu Kazuo Furihata Masanori Koda Feifei Wei Takuya Miyakawa Masaru Tanokura 《Magnetic resonance in chemistry : MRC》2016,54(3):213-221
Japanese persimmon (Diospyros kaki L.) is recognized as an outstanding source of biologically active compounds relating to many health benefits. In the present study, NMR spectroscopy provided a comprehensive metabolic overview of Japanese persimmon juice. Detailed signal assignments of Japanese persimmon juice were carried out using various 2D NMR techniques incorporated with broadband water suppression enhanced through T1 effects (BB‐WET) or WET sequences, and 26 components, including minor components, were identified. In addition, most components were quantitatively evaluated by the integration of signals using conventional 1H NMR and BB‐WET NMR. This is the first detailed analysis combined with quantitative characterization of chemical components using NMR for Japanese persimmon. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
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Regioselective Alkylative Carboxylation of Allenamides with Carbon Dioxide and Dialkylzinc Reagents Catalyzed by an N‐Heterocyclic Carbene–Copper Complex 下载免费PDF全文
Sandeep Suryabhan Gholap Dr. Masanori Takimoto Prof. Dr. Zhaomin Hou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(25):8547-8552
The alkylative carboxylation of allenamide catalyzed by an N‐heterocyclic carbene (NHC)–copper(I) complex [(IPr)CuCl] with CO2 and dialkylzinc reagents was investigated. The reaction of allenamides with dialkylzinc reagents (1.5 equiv) and CO2 (1 atm.) proceeded smoothly in the presence of a catalytic quantity of [(IPr)CuCl] to afford (Z)‐α,β‐dehydro‐β‐amino acid esters in good yields. The reaction is regioselective, with the alkyl group introduced onto the less hindered γ‐carbon, and the carboxyl group introduced onto the β‐carbon atom of the allenamides. The first step of the reaction was alkylative zincation of the allenamides to give an alkenylzinc intermediate followed by nucleophilic addition to CO2. A variety of cyclic and acyclic allenamides were found to be applicable to this transformation. Dialkylzinc reagents bearing β‐hydrogen atoms, such as Et2Zn or Bu2Zn, also gave the corresponding alkylative carboxylation products without β‐hydride elimination. The present methodology provides an easy route to alkyl‐substituted α,β‐dehydro‐β‐amino acid ester derivatives under mild reaction conditions with high regio‐ and stereoselectivtiy. 相似文献
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Dr. Takeshi Matsumoto Risa Yamamoto Dr. Masanori Wakizaka Dr. Akinobu Nakada Prof. Dr. Ho-Chol Chang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(43):9609-9619
The global demand for energy and the concerns over climate issues renders the development of alternative renewable energy sources such as hydrogen (H2) important. A high-spin (hs) FeII complex with o-phenylenediamine (opda) ligands, [FeII(opda)3]2+ (hs- [6R] 2+), was reported showing photochemical H2 evolution. In addition, a low-spin (ls) [FeII(bqdi)3]2+ (bqdi: o-benzoquinodiimine) (ls- [0R] 2+) formation by O2 oxidation of hs- [6R] 2+, accompanied by ligand-based six-proton and six-electron transfer, revealed the potential of the complex with redox-active ligands as a novel multiple-proton and -electron storage material, albeit that the mechanism has not yet been understood. This paper reports that the oxidized ls- [0R] [PF6]2 can be reduced by hydrazine giving ls-[FeII(opda)(bqdi)2][PF6]2 (ls- [2R] [PF6]2) and ls-[FeII(opda)2(bqdi)][PF6]2 (ls- [4R] [PF6]2) with localized ligand-based proton-coupled mixed-valence (LPMV) states. The first isolation and characterization of the key intermediates with LPMV states offer unprecedented molecular insights into the design of photoresponsive molecule-based hydrogen-storage materials. 相似文献
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Dr. Yusuke Imamura Kyohei Takaoka Yuma Komori Dr. Masanori Nagatomo Prof. Dr. Masayuki Inoue 《Angewandte Chemie (International ed. in English)》2023,62(10):e202219114
Taxol is a clinically used drug for the treatment of various types of cancers. Its 6/8/6/4-membered ring (ABCD-ring) system is substituted by eight oxygen functional groups and flanked by four acyl groups, including a β-amino acid side chain. Here we report a 34-step total synthesis of this unusually oxygenated and intricately fused structure. Inter- and intramolecular radical coupling reactions connected the A- and C-ring fragments and cyclized the B-ring, respectively. Functional groups of the A- and C-rings were then efficiently decorated by employing newly developed chemo-, regio-, and stereoselective reactions. Finally, construction of the D-ring and conjugation with the β-amino acid delivered taxol. The powerful coupling reactions and functional group manipulations implemented in the present synthesis provide new valuable information for designing multistep target-oriented syntheses of diverse bioactive natural products. 相似文献
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Prof. Dr. Masanori Yoshida 《Chemical record (New York, N.Y.)》2023,23(7):e202200276
In this personal account, our recent developments on the asymmetric synthesis of a quaternary carbon stereogenic center by organocatalysis using a primary amino acid and its salt as a catalyst are described in three chapters: (1) conjugate addition to nitroalkenes and vinyl ketones, (2) nucleophilic addition to π-allyl palladium complexes, and (3) nucleophilic substitution reactions with allyl and propargyl halides. By these methods, asymmetric α-allylation of α-branched aldehydes and ketones smoothly proceeded to give γ-nitroaldehydes, ketoaldehydes, α-allylated aldehydes, and α-allylated β-ketoesters possessing a quaternary carbon stereogenic center in good yields with high enantioselectivities. 相似文献
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Multicomponent Molecular Orbital–Climbing Image–Nudged Elastic Band Method to Analyze Chemical Reactions Including Nuclear Quantum Effect 下载免费PDF全文
To analyze the H/D isotope effects on hydrogen transfer reactions in XHCHCHCHY?XCHCHCHYH (X, Y=O, NH, or CH2) including the nuclear quantum effect of proton and deuteron, we propose a multicomponent molecular orbital‐climbing image‐nudged elastic band (MC_MO–CI–NEB) method. We obtain not only transition state structures but also minimum‐energy paths (MEPs) on the MC_MO effective potential energy surface by using MC_MO–CI–NEB method. We find that nuclear quantum effect affects not only stationary‐point geometries but also MEPs and electronic structures in the reactions. We clearly demonstrate the importance of including nuclear quantum effects for H/D isotope effect on rate constants (kH/kD). 相似文献
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Supramolecular Polyelectrolyte Complexes of Bone Morphogenetic Protein‐2 with Sulfonated Polyrotaxanes to Induce Enhanced Osteogenic Differentiation 下载免费PDF全文