全文获取类型
收费全文 | 11427篇 |
免费 | 1331篇 |
国内免费 | 424篇 |
专业分类
化学 | 4936篇 |
晶体学 | 25篇 |
力学 | 1079篇 |
综合类 | 38篇 |
数学 | 5153篇 |
物理学 | 1951篇 |
出版年
2023年 | 146篇 |
2022年 | 90篇 |
2021年 | 203篇 |
2020年 | 410篇 |
2019年 | 301篇 |
2018年 | 272篇 |
2017年 | 243篇 |
2016年 | 461篇 |
2015年 | 467篇 |
2014年 | 585篇 |
2013年 | 988篇 |
2012年 | 654篇 |
2011年 | 668篇 |
2010年 | 466篇 |
2009年 | 745篇 |
2008年 | 698篇 |
2007年 | 741篇 |
2006年 | 629篇 |
2005年 | 485篇 |
2004年 | 455篇 |
2003年 | 438篇 |
2002年 | 350篇 |
2001年 | 338篇 |
2000年 | 285篇 |
1999年 | 217篇 |
1998年 | 232篇 |
1997年 | 196篇 |
1996年 | 198篇 |
1995年 | 160篇 |
1994年 | 118篇 |
1993年 | 120篇 |
1992年 | 85篇 |
1991年 | 78篇 |
1990年 | 65篇 |
1989年 | 52篇 |
1988年 | 53篇 |
1987年 | 40篇 |
1986年 | 54篇 |
1985年 | 36篇 |
1984年 | 49篇 |
1983年 | 16篇 |
1982年 | 28篇 |
1981年 | 30篇 |
1980年 | 22篇 |
1979年 | 26篇 |
1978年 | 44篇 |
1977年 | 41篇 |
1976年 | 40篇 |
1975年 | 15篇 |
1974年 | 15篇 |
排序方式: 共有10000条查询结果,搜索用时 171 毫秒
61.
Anwar Jacintomoreno Dr. Hemant K. Sharma Dr. Alejandro Metta-Magaña Prof. Dr. Keith H. Pannell 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(48):11302-11307
The reactions of the Mannich reagent Et3SiOCH2NMe2 ( 1 ) with a variety of anilines (mono-substituted RC6H4NH2, R=H, 4-CN, 4-NO2, 4-Ph, 4-Me, 4-MeO, 4-Me2N; di-substituted R2C6H3NH2, R2=3,5-(CH3)2, 3,5-(CF3)2; tri-substituted R3C6H2NH2, R3=3,5-Me2-4-Br and a “super bulky” aniline (Ar*NH2) [Ar*=2,6-bis(diphenylmethyl)-4-tert-butylphenyl]) led to the formation of a range of products dependent upon the substituent. With electron-withdrawing substituents, previously unknown diamines, RC6H4NH(CH2NMe2) [R=CN ( 2 a ), NO2 ( 2 b )] and R2C6H3NH(CH2NMe2) [R2=3,5-(CF3)2 ( 2 c) ] were formed. Further reaction of 2 a , b , c with 1 yielded the corresponding triamines RC6H4N(CH2NMe2)2 (R=CN ( 3 a ), NO2 ( 3 b ) and R2C6H3N(CH2NMe2)2, R2=3,5-(CF3)2 ( 3 c ). The new polyamines were characterized by NMR spectroscopy, and for 2 a , 2 c , and 3 c , by single crystal XRD. In the case of electron-donating groups, R=4-OMe, 4-NMe2, 4-Me, 3,5-Me2, 3,5-Me2-4-Br, and for R=4-Ph, the reactions with 1 immediately led to the formation of the related 1,3,5-triazines, R=4-MeO ( 5 a ), 4-Me2N ( 5 b ), 4-Me ( 5 c ), 3,5-Me2 ( 5 d ), 3,5-Me2-4-Br ( 5 e ), 4-Ph ( 5 f ), 4-Cl ( 5 g ). The “super bulky” aniline rapidly produced a single product, namely the corresponding imine Ar*N=CH2 ( 4 ) which was also characterized by single crystal XRD. Imine 4 is both thermally and oxidatively stable. All reactions are very fast, thus based upon the presence of Si we are tempted to denote the reactions of 1 as examples of “Silick” chemistry. 相似文献
62.
The use of additive correction schemes to obtain structures and vibrational frequencies of increasingly larger molecules is becoming more common. Such approaches, based on the cubic extrapolation formula applied directly to the quantity of interest, have been successfully validated only at the highest levels of computational accuracy: for coupled cluster methods with comparably large basis sets. Here, a systematic validation of geometries and vibrational frequencies is carried out, including more affordable and relevant levels of theory, such as the Møller-Plesset perturbation theory applied with smaller basis sets. Comparisons of such additive schemes against the more rigorous gradient-based extrapolation are presented. The cbs () routine of the open-source quantum-chemistry package Psi4 has been extended for this purpose. The results confirm that geometries and frequencies of covalently bound species obtained with additive correction schemes are in an excellent agreement with the results of gradient-based extrapolations. However, when applied to systems involving noncovalent interactions, the errors due to such schemes are significantly larger. In general, we propose the application of gradient-based extrapolations, as they incur no extra cost compared to additive schemes. 相似文献
63.
Güllü Canan Hazar Güle 《Mathematical Methods in the Applied Sciences》2019,42(16):5398-5402
By , we denote the set of all sequences such that Σ?nan is summable V whenever Σan is summable U, where U and V are two summability methods. Recently, Sar?göl has characterized the set for k > 1,α > ?1 and arbitrary positive sequences Now, in the present paper, we characterize the sets , k > 1 and , k ≥ 1 for arbitrary positive sequences Hence we extend these results to the range α≥ ? 1. In this way, some open problems in this topic are also completed. 相似文献
64.
Jesús Emmanuel Solís‐Prez Jos Francisco Gmez‐Aguilar Lizeth Torres Ricardo Fabricio Escobar‐Jimnez Juan Reyes‐Reyes 《Mathematical Methods in the Applied Sciences》2019,42(18):7335-7348
In this work, the design of spectral observers for signal reconstruction based on Kalman filters is performed and evaluated. The conformable derivative and the beta‐derivative were used to design the Kalman filters. Both derivatives satisfy the same formulas of the classical derivation, eg, the chain rule. The derivative order, the Ricatti equation parameters, and the observers tuning parameters were optimized using an optimization algorithm based on the bat's echolocation behavior (Bat algorithm). The simulation results showed the advantages of using the proposed observers for the signal reconstruction. 相似文献
65.
Hanghang Wang Haiyan Li Yonggao Zheng Pengcheng Lian Prof. Dr. Xiaobing Wan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(9):2195-2198
In this communication, an unprecedented interception of CnF2n+1(O)SO. radical with a copper-based carbene has been established. Distinguished by wide substrate scopes and mild reaction conditions, this novel radical–carbene coupling reaction (RCC reaction) provides a fundamentally different and mechanistically interesting strategy for the synthesis of perfluoroalkanesulfinate esters. 相似文献
66.
Billy Deng Dr. Xiang Wang Prof. Dr. Suning Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(64):14694-14700
Boron compounds having a conjugated chelate backbone (N,C-chelate or C,C-chelate) and two mesityl substituents on boron have been found to undergo a facile one-pot transformation/reaction with dienophiles, which leads to the dearomatization of one mesityl ring and its [4+2] Diels–Alder addition with the dienophile. Photochemical activation is the key in this transformation of the aryl ring. 相似文献
67.
Wei Yao Zhoufeng Shen Yi Yu Guanghong Ding 《Mathematical Methods in the Applied Sciences》2020,43(4):1555-1564
Acupuncture, a physiotherapy, has been widely accepted all around the world. This study focuses on the influence of membrane structures and explains the acupuncture sensations from the aspect of mechanical properties. By mathematical modeling and numerical simulation, the scientific meaning of the acupuncture depth is investigated and phenomena and theory of acupuncture are discussed. The simulation results show that (a) the fascial structure is the main contributor to the force on the needle, the axial force will gradually increase before piercing the fascial, and suddenly decrease after piercing the fascial; (b) there is an inverse relationship between the needle radius and the maximum radial stress, which indicates that the needle should not be too sharp to cause local stress concentration and piece the fascia layer; and (c) the simulation results of comprehensively considering the static friction and sliding friction is identical with the experiment results. This study proposes a preliminary study of mechanical effects of acupuncture manipulation, clarifies key factors affecting the stress on the needle, and explains the objective requirement of acupuncture depth to effective treatment. 相似文献
68.
Mihály V. Pilipecz Tamás R. Varga Péter Králl Zoltán Vincze Zoltán Mucsi Ruth Deme 《合成通讯》2020,50(11):1712-1723
AbstractThe novel push–pull alkene, the 2-(nitro-nitrosomethylene)-pyrrolidine with numerous aliphatic or aromatic amines as nucleophiles afforded amidoximes. Various substituted oxadiazaborole and oxadiazole derivatives were prepared starting from these amidoximes, widening the synthetic applicability of the push–pull alkenes. Acylation of the amidoximes was also examined. The mechanism of the amidoxime formation was investigated by computational methods. 相似文献
69.
A series of NiMnTi mixed metal oxides (Ni/Mn-TiO2, Mn/NiTi-LDO and TiO2/NiMn-LDO, NiMnTi-LDO) were synthesized via different assembling methods and evaluated in the selective catalytic reduction of NOx with NH3(NH3-SCR). As the results presented, catalysts via diverse assembling methods of LDHs templates afforded different catalytic denitrification (DeNOx) performance, which might be related to the exposure degree of active constituents and the interaction intensity between metal components. Noticeably, compared with Ni/Mn-TiO2, Mn/NiTi-LDO and TiO2/NiMn-LDO catalysts, the NiMnTi-LDO catalyst deriving from one step in-situ method NiMnTi-LDH precursor template exhibited the most desirable performance at temperature window of 150–360 °C in NH3-SCR (above 90% NOx conversion with 95% N2 selectivity). The specific structure and property of samples were correlated by means of a series of characterizations, where the results indicated that NiMnTi-LDO possessed the highest surface area, the strongest redox ability, the most abundant acid amount and the best dispersion. 相似文献
70.
Wenhe Yu Prof. Xiaowen Wu Bohao Cheng Dr. Tianyi Tao Dr. Xin Min Dr. Ruiyu Mi Prof. Zhaohui Huang Prof. Minghao Fang Prof. Yangai Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(11):e202102787
Silicoaluminophosphate zeolite (SAPO-34) has been attracting increasing attention due to its excellent form selection and controllability in the chemical industry, as well as being one of the best industrial catalysts for methanol-to-olefin (MTO) reaction conversion. However, as a microporous molecular sieve, SAPO-34 easily generates carbon deposition and rapidly becomes inactivated. Therefore, it is necessary to reduce the crystal size of the zeolite or to introduce secondary macropores into the zeolite crystal to form a hierarchical structure in order to improve the catalytic effect. In this review, the synthesis methods of conventional SAPO-34 molecular sieves, hierarchical SAPO-34 molecular sieves and nanosized SAPO-34 molecular sieves are introduced, and the properties of the synthesized SAPO-34 molecular sieves are described, including the phase, morphology, pore structure, acid source, and catalytic performance, in particular with respect to the synthesis of hierarchical SAPO-34 molecular sieves. We hope that the review can provide guidance to the preparation of the SAPO-34 catalysts, and stimulate the future development of high-performance hierarchical SAPO-34 catalysts to meet the growing demands of the material and chemical industries. 相似文献