全文获取类型
收费全文 | 1960篇 |
免费 | 53篇 |
国内免费 | 6篇 |
专业分类
化学 | 1396篇 |
晶体学 | 15篇 |
力学 | 19篇 |
数学 | 282篇 |
物理学 | 307篇 |
出版年
2024年 | 3篇 |
2023年 | 11篇 |
2022年 | 30篇 |
2021年 | 41篇 |
2020年 | 38篇 |
2019年 | 45篇 |
2018年 | 39篇 |
2017年 | 26篇 |
2016年 | 68篇 |
2015年 | 60篇 |
2014年 | 68篇 |
2013年 | 144篇 |
2012年 | 138篇 |
2011年 | 157篇 |
2010年 | 109篇 |
2009年 | 106篇 |
2008年 | 147篇 |
2007年 | 114篇 |
2006年 | 119篇 |
2005年 | 97篇 |
2004年 | 86篇 |
2003年 | 54篇 |
2002年 | 62篇 |
2001年 | 23篇 |
2000年 | 18篇 |
1999年 | 22篇 |
1998年 | 15篇 |
1997年 | 14篇 |
1996年 | 20篇 |
1995年 | 17篇 |
1994年 | 7篇 |
1993年 | 11篇 |
1992年 | 14篇 |
1991年 | 8篇 |
1990年 | 5篇 |
1989年 | 6篇 |
1987年 | 5篇 |
1986年 | 5篇 |
1985年 | 5篇 |
1984年 | 4篇 |
1983年 | 4篇 |
1982年 | 11篇 |
1981年 | 4篇 |
1980年 | 12篇 |
1978年 | 5篇 |
1976年 | 2篇 |
1975年 | 4篇 |
1974年 | 3篇 |
1972年 | 2篇 |
1970年 | 4篇 |
排序方式: 共有2019条查询结果,搜索用时 0 毫秒
91.
Pedro Marcos Frugeri Camila Marchioni Ayla Campos do Lago Célio Wisniewski 《Analytical letters》2018,51(10):1492-1504
This work proposes a flow injection analysis system for sulfaguanidine determination in pharmaceutical and food samples. The method was based on the reaction of sulfaguanidine with nitronium ion to produce a colored complex whose absorbance was measured at 545?nm. The flow injection analysis system’s significant parameters were checked by a fractional factorial design 27–2 and optimization by a Doehlert matrix. The flow injection analysis system shows optimum values at 0.28, 2.00, and 0.11% (w/v) for N-naphtil ethylenediamine, ammonium sulfamate, and sodium nitrite concentrations, respectively. The possible interferents present in pharmaceutical and food samples were assessed by a multivariate technique and depicted on probability charts, indicating no significant interferences at the 95% level of confidence interval. The method showed detection and quantification limits of 0.012 and 0.039?mg?L?1, an analytical frequency of 30 readings h?1 and precision always lower than 5.0% expressed as the relative standard deviation. The obtained results were in accordance with those obtained by high-performance liquid chromatography. 相似文献
92.
Olefin Cyclopropanation by Radical Carbene Transfer Reactions Promoted by Cobalt(II)/Porphyrinates: Active‐Metal‐Template Synthesis of [2]Rotaxanes 下载免费PDF全文
Arthur F. P. Alcântara Liniquer A. Fontana Vitor H. Rigolin Yuri F. S. Andrade Dr. Marcos A. Ribeiro Prof. Wdeson P. Barros Prof. Catia Ornelas Prof. Jackson D. Megiatto Jr. 《Angewandte Chemie (International ed. in English)》2018,57(29):8979-8983
A CoII/porphyrinate‐based macrocycle in the presence of a 3,5‐diphenylpyridine axial ligand functions as an endotopic ligand to direct the assembly of [2]rotaxanes from diazo and styrene half‐threads, by radical‐carbene‐transfer reactions, in excellent 95 % yield. The method reported herein applies the active‐metal‐template strategy to include radical‐type activation of ligands by the metal‐template ion during the organometallic process which ultimately yields the mechanical bond. A careful quantitative analysis of the product distribution afforded from the rotaxane self‐assembly reaction shows that the CoII/porphyrinate subunit is still active after formation of the mechanical bond and, upon coordination of an additional diazo half‐thread derivative, promotes a novel intercomponent C?H insertion reaction to yield a new rotaxane‐like species. This unexpected intercomponent C?H insertion illustrates the distinct reactivity brought to the CoII/porphyrinate catalyst by the mechanical bond. 相似文献
93.
Barriga S Fuertes P Marcos CF Miguel D Rakitin OA Rees CW Torroba T 《The Journal of organic chemistry》2001,66(17):5766-5771
We report the synthesis of some new polysulfur-nitrogen heterocyclics by cycloaddition reactions to the thioketo group of readily available tricyclic 1,2-dithiole-3-thiones. Thus treatment of bis[1,2]dithiolo[1,4]thiazine ketothione 1 with diaryl nitrile imines generated from hydrazonoyl chlorides 2a-g gave [1,3,4]thiadiazolylidenyl[1,2]dithiolo[1,4]thiazines 4a-g in high yield. Compounds 4a-f, bearing the same substituents in both aryl groups, were stable but the analogous 4g,h with a p-nitrophenyl group on carbon gave the bis[1,2]dithiolo[1,4]thiazine dione 9, probably by cycloreversion and hydrolysis during chromatography. Treatment of 1, the bis[1,2]dithiolopyrrole ketothione 13, and dithione 12 with ethoxycarbonyl azide 11 gave imines 12 and 15 and bisimine 16, respectively, by an alternative fragmentation of the initial cycloadduct in which the 1,2-dithiole ring is retained. Reaction of 1 with TosMIC gave the imino-1,3-dithietane 17. 相似文献
94.
Urones JG Sexmero MJ Hernandez FA Basabe AB Diez D Marcos IS 《Natural product letters》2001,15(6):387-391
Two new diterpenic acids with an ent-halimane skeleton have been isolated from the aerial parts of Halimium viscosum (Villarino de los Aires chemotype) and separated as methyl esters. These diterpenes were 13-oxo-14, 15-dinor-1(10),11E-ent-halimadien-18-oic acid and 15-hydroxy-1(10),13Z-ent-halimadien-18-oic acid. 相似文献
95.
Current ab initio structure‐prediction methods are sometimes able to generate families of folds, one of which is native, but are unable to single out the native one due to imperfections in the folding potentials and an inability to conduct thorough explorations of the conformational space. To address this issue, here we describe a method for the detection of statistically significant folds from a pool of predicted structures. Our approach consists of clustering and averaging the structures into representative fold families. Using a metric derived from the root‐mean‐square distance (RMSD) that is less sensitive to protein size, we determine whether the simulated structures are clustered in relation to a group of random structures. The clustering method searches for cluster centers and iteratively calculates the clusters and their respective centroids. The centroid interresidue distances are adjusted by minimizing a potential constructed from the corresponding average distances of the cluster structures. Application of this method to selected proteins shows that it can detect the best fold family that is closest to native, along with several other misfolded families. We also describe a method to obtain substructures. This is useful when the folding simulation fails to give a total topology prediction but produces common subelements among the structures. We have created a web server that clusters user submitted structures, which can be found at http://bioinformatics.danforthcenter.org/services/scar. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 339–353, 2001 相似文献
96.
Padeleimon Karafiloglou Enrique Snchez Marcos 《International journal of quantum chemistry》1992,44(3):337-362
This work examines the possibility of finding an electron-hole and an electron-pair simultaneously in a π-system substituted by an electron-donating (NH2) and/or electron-withdrawing (NO2) group. The contributions of various ionic [(+), ( ↑ ↓ )] structures are calculated from ab initio SCF –CI wave functions, using a recently developed general multielectron population analysis. The molecules studied are two monosubstituted ethylenes, aminoethylene and nitroethylene, and a disubstituted ethylene, the 2-nitroethenamine (push–pull ethylene) in its two configurational forms. The influence of the NH2 and/or NO2 group in delocalization and ionic (vs. covalent) character of the C?C double bond are investigated, along with examining the experimental chemist formalism of electron-pair “displacements” in several resonance structures. Analysis of mutual dependence of an electron-hole and an electron-pair, at short and long distances, leads to the conclusion that a push–pull π-system can stimulate the simultaneous existence of an electronhole and an electron-pair even for nonvicinal positions. The relationship between the electronpair distributions and contributions of the corresponding structures are also examined; the effects of electronic correlation are analyzed as well. © 1992 John Wiley & Sons, Inc. 相似文献
97.
Positive ground state of coupled systems of Schrödinger equations in
involving critical exponential growth 下载免费PDF全文
João Marcos do Ó José Carlos de Albuquerque 《Mathematical Methods in the Applied Sciences》2017,40(18):6864-6879
In this paper, we study the existence of a positive ground state solution to the following coupled system of nonlinear Schrödinger equations: where the nonlinearities f1(x,s) and f2(x,s) are superlinear at infinity and have exponential critical growth of the Trudinger‐Moser type. The potentials V1(x) and V2(x) are nonnegative and satisfy a condition involving the coupling term λ(x), namely, λ(x)2<δ2V1(x)V2(x) for some 0<δ<1. For this purpose, we use the minimization technique over the Nehari manifold and strong maximum principle to get a positive ground state solution. Moreover, by using a bootstrap argument and Lq‐estimates, we get regularity and asymptotic behavior. 相似文献
98.
Let (M, g) be a compact Riemannian manifold of dimension n ≥ 2 and 1 < p ≤ 2. In this work we prove the validity of the optimal Gagliardo–Nirenberg inequality
for a family of parameters r, q and θ. Our proof relies strongly on a new distance lemma which holds for 1 < p ≤ 2. In particular, we obtain Riemannian versions of L
p
-Euclidean Gagliardo–Nirenberg inequalities of Del Pino and Dolbeault (J Funct Anal 197:151–161, 2003) and extend the optimal
L
2-Riemannian Gagliardo–Nirenberg inequality of Brouttelande (Proc R Soc Edinb 46:147–157, 2003) in a unified framework. 相似文献
99.
Marcos Petrúcio Cavalcante Heudson Mirandola Feliciano Vitório 《Journal of Geometric Analysis》2014,24(1):205-222
Let $x:M^{m}\to\bar{M}$ , m≥3, be an isometric immersion of a complete noncompact manifold M in a complete simply connected manifold $\bar{M}$ with sectional curvature satisfying $-k^{2}\leq K_{\bar{M}}\leq0$ , for some constant k. Assume that the immersion has finite total curvature in the sense that the traceless second fundamental form has finite L m -norm. If $K_{\bar{M}}\not\equiv0$ , assume further that the first eigenvalue of the Laplacian of M is bounded from below by a suitable constant. We prove that the space of the L 2 harmonic 1-forms on M has finite dimension. Moreover, there exists a constant Λ>0, explicitly computed, such that if the total curvature is bounded from above by Λ then there are no nontrivial L 2-harmonic 1-forms on M. 相似文献
100.
Marcela Cecilia González-Araya Luís Alberto Duncan Rangel Marcos Pereira Estellita Lins Luiz Flávio Autran Monteiro Gomes 《Annals of Operations Research》2002,116(1-4):271-288
This paper presents an application of the UTA method for building utility functions for the evaluation criteria defined by the Staff Evaluation Commission (CAD) of the Rio de Janeiro Federal University (UFRJ). Every year, the CAD-UFRJ gives the staff evaluation results for each Postgraduate Engineering Programme. However, the method used to generate the staff evaluation is assumed unknown. Trying to find the CAD-UFRJ preference structure, the evaluation results supplied by CAD-UFRJ are used to apply the UTA method. Some additional information obtained from the CAD-UFRJ data is incorporated in the optimal solutions analysis. 相似文献