全文获取类型
收费全文 | 10500篇 |
免费 | 266篇 |
国内免费 | 31篇 |
专业分类
化学 | 7860篇 |
晶体学 | 31篇 |
力学 | 162篇 |
数学 | 1782篇 |
物理学 | 962篇 |
出版年
2020年 | 138篇 |
2019年 | 104篇 |
2018年 | 77篇 |
2017年 | 81篇 |
2016年 | 189篇 |
2015年 | 197篇 |
2014年 | 187篇 |
2013年 | 351篇 |
2012年 | 392篇 |
2011年 | 453篇 |
2010年 | 336篇 |
2009年 | 279篇 |
2008年 | 455篇 |
2007年 | 441篇 |
2006年 | 466篇 |
2005年 | 439篇 |
2004年 | 377篇 |
2003年 | 312篇 |
2002年 | 327篇 |
2001年 | 222篇 |
2000年 | 155篇 |
1999年 | 144篇 |
1998年 | 179篇 |
1997年 | 146篇 |
1996年 | 150篇 |
1995年 | 150篇 |
1994年 | 143篇 |
1993年 | 190篇 |
1992年 | 127篇 |
1991年 | 127篇 |
1990年 | 114篇 |
1989年 | 134篇 |
1988年 | 131篇 |
1987年 | 167篇 |
1986年 | 156篇 |
1985年 | 174篇 |
1984年 | 186篇 |
1983年 | 155篇 |
1982年 | 142篇 |
1981年 | 150篇 |
1980年 | 153篇 |
1979年 | 145篇 |
1978年 | 136篇 |
1977年 | 119篇 |
1976年 | 133篇 |
1975年 | 91篇 |
1974年 | 88篇 |
1973年 | 88篇 |
1971年 | 80篇 |
1970年 | 71篇 |
排序方式: 共有10000条查询结果,搜索用时 12 毫秒
991.
Bai YL Tao J Wernsdorfer W Sato O Huang RB Zheng LS 《Journal of the American Chemical Society》2006,128(51):16428-16429
A novel single-chain magnet, [MnIII3O(Meppz)3(EtOH)4(OAc)] (1), has been successfully synthesized from a secondary building block [MnIII3O(Meppz)3(EtOH)5Cl] (2) with an S = 1 ground state. SCM 1 exhibits both magnetization relaxation and dielectric relaxation properties. 相似文献
992.
An analytical method has been developed for the simultaneous extraction and determination of trace tertiary octylphenol (t-OP), technical nonylphenol isomers (NP), nonylphenol monoethoxylate isomers (NP1EO) and seven phthalates in the atmosphere using gas chromatography-mass spectrometry (GC-MS). High volume samples were collected using a high-volume pump equipped with a PUF/XAD-2 column for air and glass fiber filter for particles. The detection limits of the method for alkylphenols (APs) and the phthalates ranged from 0.0006 to 0.034 ng m−3 in air. The recoveries of t-OP, NP, NP1EO and the phthalates for the entire procedure were satisfactory (>69%). The method was successfully applied to the determination of the analytes in the atmosphere samples collected over land and the ocean. The concentrations of t-OP, NP, NP1EO showed decline trends from land to the open sea, and the phthalates present over land and the North Sea were comparable. It is suggested that the atmosphere is a significant pathway for the transport of alkylphenols and the phthalates in the environment. 相似文献
993.
Iodine(III)‐Catalyzed Rearrangements of Imides: A Versatile Route to α,α‐Dialkylated α‐Hydroxy Carboxylamides 下载免费PDF全文
Anna Ulmer Dr. Maciej Stodulski Stefanie V. Kohlhepp Christoph Patzelt Dr. Alexander Pöthig Dr. Wolfgang Bettray Dr. Tanja Gulder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(4):1444-1448
A tertiary hydroxy group α to a carboxyl moiety comprises a key structural motif in many bioactive substances. With the herein presented metal‐free rearrangement of imides triggered by hypervalent λ3‐iodane, an easy and selective way to gain access to such a compound class, namely α,α‐disubstituted‐α‐hydroxy carboxylamides, was established. Their additional methylene bromide side chain constitutes a useful handle for rapid diversification, as demonstrated by a series of further functionalizations. Moreover, the in situ formation of an iodine(III) species under the reaction conditions was proven. Our findings clearly corroborate that hypervalent λ3‐benziodoxolones are involved in these organocatalytic reactions. 相似文献
994.
Wiebke Germer Timo Stalling Uwe Kramer Wolfgang Saak Jürgen Martens 《Heteroatom Chemistry》2014,25(1):20-27
Starting with thiazolines, an important class of heterocyclic imines, a novel rearrangement reaction of corresponding N‐acyliminium ions is described. Furthermore, a new class of heterobicyclic compounds arylated at a single bridgehead atom is obtained diastereospecifically. 相似文献
995.
Andrea Kunfermann Matthias Witschel Boris Illarionov Ren Martin Matthias Rottmann H. Wolfgang Hffken Michael Seet Wolfgang Eisenreich Hans‐Joachim Knlker Markus Fischer Adelbert Bacher Michael Groll Franois Diederich 《Angewandte Chemie (International ed. in English)》2014,53(8):2235-2239
The enzymes of the non‐mevalonate pathway for isoprenoid biosynthesis have been identified as attractive targets with novel modes of action for the development of herbicides for crop protection and agents against infectious diseases. This pathway is present in many pathogenic organisms and plants, but absent in mammals. By using high‐throughput screening, we identified highly halogenated marine natural products, the pseudilins, to be inhibitors of the third enzyme, IspD, in the pathway. Their activity against the IspD enzymes from Arabidopsis thaliana and Plasmodium vivax was determined in photometric and NMR‐based assays. Cocrystal structures revealed that pseudilins bind to an allosteric pocket by using both divalent metal ion coordination and halogen bonding. The allosteric mode of action for preventing cosubstrate (CTP) binding at the active site was elucidated. Pseudilins show herbicidal activity in plant assays and antiplasmodial activity in cell‐based assays. 相似文献
996.
Zofia M. Wosinska Faye L. Stump Rajeev Ranjan Edward D. Lorance GeNita N. Finley Priya P. Patel Muzamil A. Khawaja Katie L. Odom Wolfgang H. Kramer Ian R. Gould 《Photochemistry and photobiology》2014,90(2):313-328
Irreversible photooxidation based on N–O bond fragmentation is demonstrated for N‐methoxyheterocycles in both the singlet and triplet excited state manifolds. The energetic requirements for bond fragmentation are studied in detail. Bond fragmentation in the excited singlet manifold is possible for ππ* singlet states with energies significantly larger than the N–O bond dissociation energy of ca 55 kcal mol?1. For the nπ* triplet states, N–O bond fragmentation does not occur in the excited state for orbital overlap and energetic reasons. Irreversible photooxidation occurs in the singlet states by bond fragmentation followed by electron transfer. Irreversible photooxidation occurs in the triplet states via bimolecular electron transfer to the donor followed by bond fragmentation. Using these two sensitization schemes, donors can be irreversibly oxidized with oxidation potentials ranging from ca 1.6–2.2 V vs SCE. The corresponding N‐ethylheterocycles are characterized as conventional reversible photooxidants in their triplet states. The utility of these sensitizers is demonstrated by irreversibly generating the guanosine radical cation in buffered aqueous solution. 相似文献
997.
2‐Aminoacetophenone (AAP) was recognized as the key compound for the so‐called untypical aging off‐flavor (UTA) in Vitis vinifera wines. In this study, it was shown that AAP can be formed by photooxidation of free and protein‐bound tryptophan (TRP) in combination with a subsequent storage in model wine. Solutions of TRP and lysozyme were exposed to artificial sunlight both in the presence and in the absence of the photosensitizer riboflavin. Aliquots of the irradiation batches were stored in model wine solutions containing tartaric acid, sulfite and ethanol in different combinations. AAP formation could be identified from both free and bound (lysozyme) TRP, while free TRP resulted in higher yields. The presence of riboflavin during irradiation generally favored the AAP formation. AAP formation increased with increasing irradiation times, but AAP was not detectable, if TRP was directly incubated in model wine. Not only the irradiation time but also the storage time of model wines favored the formation of AAP. Concerning the model wine composition, it became evident that the presence of tartaric acid resulted in the highest AAP formation during storage. 相似文献
998.
Dr. Yukun Zhu Chunxiao Lv Zhuocheng Yin Prof. Jun Ren Prof. Xianfeng Yang Prof. Chung-Li Dong Prof. Hongwei Liu Dr. Rongsheng Cai Yu-Cheng Huang Prof. Wolfgang Theis Prof. Shaohua Shen Prof. Dongjiang Yang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(2):878-883
Red phosphorus is a promising photocatalyst with wide visible-light absorption up to 700 nm, but the fast charge recombination limits its photocatalytic hydrogen evolution reaction (HER) activity. Now, [001]-oriented Hittorf's phosphorus (HP) nanorods were successfully grown on polymeric carbon nitride (PCN) by a chemical vapor deposition strategy. Compared with the bare PCN and HP, the optimized PCN@HP hybrid exhibited a significantly enhanced photocatalytic activity, with HER rates reaching 33.2 and 17.5 μmol h−1 from pure water under simulated solar light and visible light irradiation, respectively. It was theoretically and experimentally indicated that the strong electronic coupling between PCN and [001]-oriented HP nanorods gave rise to the enhanced visible light absorption and the greatly accelerated photoinduced electron–hole separation and transfer, which benefited the photocatalytic HER performance. 相似文献
999.
Henry W. Orton Dr. Jan Stanek Dr. Tobias Schubeis Dylan Foucaudeau Claire Ollier Dr. Adrian W. Draney Dr. Tanguy Le Marchand Dr. Diane Cala-De Paepe Prof. Dr. Isabella C. Felli Prof. Dr. Roberta Pierattelli Prof. Dr. Sebastian Hiller Dr. Wolfgang Bermel Dr. Guido Pintacuda 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(6):2400-2405
1000.
The LiRh-type crystal structure of the equiatomic intermetallic compound IrZn turns out to be a competitor to the otherwise energetically favored CsCl-type structures of congeneric transition metal zinc phases, thus enlightening the structural impact of element-specific factors beyond the Hume-Rothery concept. 相似文献