全文获取类型
收费全文 | 9899篇 |
免费 | 250篇 |
国内免费 | 20篇 |
专业分类
化学 | 5795篇 |
晶体学 | 64篇 |
力学 | 206篇 |
数学 | 2161篇 |
物理学 | 1943篇 |
出版年
2023年 | 63篇 |
2021年 | 150篇 |
2020年 | 142篇 |
2019年 | 169篇 |
2018年 | 266篇 |
2017年 | 235篇 |
2016年 | 346篇 |
2015年 | 259篇 |
2014年 | 309篇 |
2013年 | 729篇 |
2012年 | 520篇 |
2011年 | 678篇 |
2010年 | 397篇 |
2009年 | 371篇 |
2008年 | 565篇 |
2007年 | 548篇 |
2006年 | 523篇 |
2005年 | 427篇 |
2004年 | 369篇 |
2003年 | 275篇 |
2002年 | 243篇 |
2001年 | 149篇 |
2000年 | 122篇 |
1999年 | 85篇 |
1998年 | 75篇 |
1997年 | 74篇 |
1996年 | 69篇 |
1995年 | 67篇 |
1994年 | 51篇 |
1993年 | 70篇 |
1992年 | 71篇 |
1991年 | 71篇 |
1990年 | 61篇 |
1989年 | 65篇 |
1988年 | 58篇 |
1987年 | 61篇 |
1986年 | 59篇 |
1985年 | 82篇 |
1984年 | 93篇 |
1983年 | 82篇 |
1982年 | 81篇 |
1981年 | 67篇 |
1980年 | 73篇 |
1979年 | 72篇 |
1978年 | 94篇 |
1977年 | 67篇 |
1976年 | 65篇 |
1975年 | 59篇 |
1974年 | 61篇 |
1973年 | 50篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
Ya-Shan Huang Yuan Xue Prof. Alvaro Muñoz-Castro Prof. Dr. Ivan A. Popov Prof. Dr. Zhong-Ming Sun 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(62):e202202192
During the past two decades, single-atom-centered medium-sized germanium clusters [M@Gen] (M=transition metals, n>12) have been extensively explored, both from theoretical perspectives and experimental gas-phase syntheses. However, the actual structural arrangements of the Ge13 and Ge14 endohedral cages are still ambiguous and have long remained an unresolved problem for experimental implementation. In this work, we successfully synthesize 13-/14-vertex Ge clusters [Nb@Ge13]3− ( 1 ) and [Nb@Ge14]3− ( 2 ), which are structurally characterized and exhibit unprecedented topologies, neither classical deltahedra nor 3-connected polyhedral structures. Theoretical analysis indicates that the major stabilization of the Ge backbones arises due to the substantial interaction of Ge 4p-AOs with the endohedral Nb 4d-AOs through three/four-center two-electron bonds with an enhanced electron density accumulated over the shortest Nb−Ge13 contact in 1 . Low occupancies of the direct two-center two-electron (2c–2e) Nb−Ge and Ge−Ge σ bonds point to a considerable degree of electron delocalization over the Ge cages revealing their electron deficiency. 相似文献
2.
Nonlinear Dynamics - Two types of constitutive equations consisting of instantaneous and power type hereditary contributions are proposed in order to model generalized capacitor (inductor). The... 相似文献
3.
Avramenko Andriy A. Shevchuk Igor V. Dmitrenko Nataliia P. Skitsko Ivan F. 《Journal of Thermal Analysis and Calorimetry》2022,147(22):12709-12719
Journal of Thermal Analysis and Calorimetry - The paper focuses on the analytical analysis of the propagation of a normal shock wave in an adiabatic gas flow with nanoparticles. A modified... 相似文献
4.
Bajuk-Bogdanović Danica Holclajtner-Antunović Ivanka Jovanović Zoran Mravik Željko Krstić Jugoslav Uskoković-Marković Snežana Vujković Milica 《Journal of Solid State Electrochemistry》2019,23(9):2747-2758
Journal of Solid State Electrochemistry - The synergistic effects between two Keggin-type heteropoly acids (HPAs) and carbon surface were examined and elucidated. An improved high rate capability... 相似文献
5.
Kamila B. Muchowska Dominic J. Pascoe Stefan Borsley Ivan V. Smolyar Ioulia K. Mati Catherine Adam Gary S. Nichol Kenneth B. Ling Scott L. Cockroft 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(34):14710-14716
Interactions between carbonyl groups are prevalent in protein structures. Earlier investigations identified dominant electrostatic dipolar interactions, while others implicated lone pair n→π* orbital delocalisation. Here these observations are reconciled. A combined experimental and computational approach confirmed the dominance of electrostatic interactions in a new series of synthetic molecular balances, while also highlighting the distance-dependent observation of inductive polarisation manifested by n→π* orbital delocalisation. Computational fiSAPT energy decomposition and natural bonding orbital analyses correlated with experimental data to reveal the contexts in which short-range inductive polarisation augment electrostatic dipolar interactions. Thus, we provide a framework for reconciling the context dependency of the dominance of electrostatic interactions and the occurrence of n→π* orbital delocalisation in C=O⋅⋅⋅C=O interactions. 相似文献
6.
Daniel Cardenas Anna Turyanskaya Mirjam Rauwolf Arash Panahifar David Cooper Gregory R. Wohl Christina Streli Peter Wobrauschek Ana Pejović-Milić 《X射线光谱测定》2020,49(3):424-433
Strontium-based medications, such as strontium ranelate, have been suggested to have therapeutic effects in patients with osteoporosis. Strontium salts available off-shelf in stores across North America are assumed to provide similar effects as strontium ranelate and thus should lead to similar distributions of elemental strontium incorporated in bone. The objective of this study was to compare the spatial distribution of strontium in animal bones following the administration of strontium ranelate and strontium citrate. Seventeen-week-old Sprague–Dawley rats were split into three groups over 10 weeks and given 625 mg/kg/day of strontium ranelate and 676 mg/kg/day of strontium citrate; the control group received no additional supplementary strontium. The humeri were collected from all animals, and strontium distribution was mapped using 2D micro-XRF and 3D dual energy K-edge subtraction (KES) imaging. 2D and 3D elemental mapping methods demonstrated that strontium delivered during treatment by both salts had the same spatial distribution. 3D elemental strontium maps of treated animal bones showed that strontium was largely observed in the trabecular regions under the epiphyseal (growth) plate. The thickness of the strontium layers in both the strontium ranelate and strontium citrate sample was not significantly different (p = .9201). 2D micro-XRF and 3D dual-energy KES images effectively elucidated the spatial distribution of elemental strontium in calcified tissue. These methods provide a novel approach to evaluating the potential efficacy of strontium supplements in the treatment of osteoporosis. 相似文献
7.
Tanja V. Soldatović Enisa Selimović Nevena Milivojević Milena Jovanović Biljana Šmit 《应用有机金属化学》2020,34(10):e5864
The novel heteronuclear complexes [{cis-PtCl (NH3)(μ-pyrazine)ZnCl (terpy)}](ClO4)2 (Pt-L1-Zn) and [{cis-PtCl (NH3)(μ-4,4′-bipyridyl)ZnCl (terpy)}](ClO4)2 (Pt-L2-Zn) (where terpy = 2,2′:6′,2′′-terpyridine, L1 = pyrazine, L2 = 4,4′-bipyridyl) were synthesized and characterized. The pKa values were determined, and based on them it was established that the π-acceptor ability of the pyrazine bridging ligand is more affective on lower pKa values. The kinetic measurements of the substitution reactions with biologically relevant ligands, such as guanosine-5′-monophosphate (5′-GMP), inosine-5′-monophosphate (5′-IMP) and glutathione (GSH), were studied at pH 7.4. The reactions were followed under pseudo-first-order conditions by UV–Vis spectrophotometry. The order of reactivity of the investigated biomolecules for the first reaction is 5′-GMP > 5′-IMP > GSH, while for the second is 5′-IMP > GSH. Pt-L1-Zn complex is more reactive than Pt-L2-Zn. The cytotoxic activity of heteronuclear Pt-L1-Zn and Pt-L2-Zn complexes was determined on human colorectal cancer cell line (HCT-116) and human breast cancer cell line (MDA-MB-231). Both complexes significantly reduced cell viability on tested cell lines and exerted significant cytotoxic effects, with better effect on HCT-116 cells than cisplatin, especially after 72 hr (IC50 < 0.52 μM). The Pt-L2-Zn complex showed higher activity against human breast cancer cells (MDA-MB-231) than cisplatin after 72 hr. The higher reactivity toward DNA constituent and significant cytotoxic activity may be attributed to the different geometry, Lewis acidity of different metal centers, as well as, to choice of bridging ligands. 相似文献
8.
ABSTRACT We consider the nonsteady flow of a micropolar fluid in a thin (or long) curved pipe via rigorous asymptotic analysis. Germano's reference system is employed to describe the pipe's geometry. After writing the governing equations in curvilinear coordinates, we construct the asymptotic expansion up to a second order. Obtained in the explicit form, the asymptotic approximation clearly demonstrates the effects of pipe's distortion, micropolarity and the time derivative. A detailed study of the boundary layers in space is provided as well as the construction of the divergence correction. Finally, a rigorous justification of the proposed effective model is given by proving the error estimates. 相似文献
9.
This work describes a novel methodology for the recognition of brandies based on direct injection of a raw sample followed by GC-MS analysis. Direct injection was chosen for its simplicity and the fact that the composition of the samples analysed remains unchanged compared to original brandy. The repeatability of the analytical procedure was evaluated by a comparison of the peak areas for randomly selected compounds obtained from 10 parallel measurements. A novel chemometric procedure was investigated in order to separate the samples studied on the basis of their geographical origin, processing technology or maturation time. In this procedure, a principal component analysis was applied to full chromatograms to select the time interval that shows the significant differences between the samples studied. It was shown that the chromatogram recorded at 36–39 min bore the maximal differences, hence it could be used to classify the brandy samples. The chromatographic peaks found within this time interval were identified and their peak areas determined. These compounds could be used as specific markers for determining geographical origin or processing technology. 相似文献
10.