全文获取类型
收费全文 | 340278篇 |
免费 | 9835篇 |
国内免费 | 4640篇 |
专业分类
化学 | 189019篇 |
晶体学 | 3754篇 |
力学 | 14966篇 |
综合类 | 247篇 |
数学 | 40143篇 |
物理学 | 106624篇 |
出版年
2021年 | 2658篇 |
2020年 | 3363篇 |
2019年 | 3214篇 |
2018年 | 3052篇 |
2017年 | 2873篇 |
2016年 | 5380篇 |
2015年 | 4751篇 |
2014年 | 6302篇 |
2013年 | 16394篇 |
2012年 | 13784篇 |
2011年 | 16414篇 |
2010年 | 10346篇 |
2009年 | 10192篇 |
2008年 | 14415篇 |
2007年 | 14385篇 |
2006年 | 13918篇 |
2005年 | 12589篇 |
2004年 | 11187篇 |
2003年 | 9562篇 |
2002年 | 8735篇 |
2001年 | 10277篇 |
2000年 | 7700篇 |
1999年 | 6228篇 |
1998年 | 4921篇 |
1997年 | 4879篇 |
1996年 | 4943篇 |
1995年 | 4802篇 |
1994年 | 4517篇 |
1993年 | 4272篇 |
1992年 | 4734篇 |
1991年 | 4524篇 |
1990年 | 4185篇 |
1989年 | 3938篇 |
1988年 | 4229篇 |
1987年 | 3862篇 |
1986年 | 3724篇 |
1985年 | 5391篇 |
1984年 | 5448篇 |
1983年 | 4403篇 |
1982年 | 4743篇 |
1981年 | 4783篇 |
1980年 | 4509篇 |
1979年 | 4634篇 |
1978年 | 4633篇 |
1977年 | 4601篇 |
1976年 | 4577篇 |
1975年 | 4476篇 |
1974年 | 4334篇 |
1973年 | 4499篇 |
1972年 | 2547篇 |
排序方式: 共有10000条查询结果,搜索用时 156 毫秒
51.
Gribkova N. V. Su J. Zitikis R. 《Annals of the Institute of Statistical Mathematics》2022,74(4):713-735
Annals of the Institute of Statistical Mathematics - Under minimal assumptions, we prove that an empirical estimator of the tail conditional allocation (TCA), also known as the marginal expected... 相似文献
52.
53.
Dr. Zhe Zhang Dr. Xiaofeng Fang Dr. Zhihe Liu Dr. Haichao Liu Dr. Dandan Chen Prof. Shuqing He Prof. Jie Zheng Prof. Bing Yang Prof. Weiping Qin Prof. Xuanjun Zhang Prof. Changfeng Wu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(9):3720-3727
Fluorescence probes in the NIR-IIa region show drastically improved imaging owing to the reduced photon scattering and autofluorescence in biological tissues. Now, NIR-IIa polymer dots (Pdots) are developed with a dual fluorescence enhancement mechanism. First, the aggregation induced emission of phenothiazine was used to reduce the nonradiative decay pathways of the polymers in condensed states. Second, fluorescence quenching was minimized by different levels of steric hindrance to further boost the fluorescence. The resulting Pdots displayed a fluorescence QY of ca. 1.7 % in aqueous solution, suggesting an enhancement of ca. 21 times in comparison with the original polymer in tetrahydrofuran (THF) solution. Small-animal imaging by using the NIR-IIa Pdots exhibited a remarkable improvement in penetration depth and signal to background ratio, as confirmed by through-skull and through-scalp fluorescent imaging of the cerebral vasculature of live mice. 相似文献
54.
The looming global energy crisis and ever-increasing energy demands have catalyzed the development of renewable energy storage systems. In this regard, supercapacitors (SCs) have attracted widespread attention because of their advantageous attributes such as high power density, excellent cycle stability, and environmental friendliness. However, SCs exhibit low energy density and it is important to optimize electrode materials to improve the overall performance of these devices. Among the various electrode materials available, spinel nickel cobaltate (NiCo2O4) is particularly interesting because of its excellent theoretical capacitance. Based on the understanding that the performances of the electrode materials strongly depend on their morphologies and structures, in this study, we successfully synthesized NiCo2O4 nanosheets on Ni foam via a simple hydrothermal route followed by calcination. The structures and morphologies of the as-synthesized products were characterized by X-ray diffraction, scanning electron microscopy, and Brunauer-Emmett-Teller (BET) surface area analysis, and the results showed that they were uniformly distributed on the Ni foam support. The surface chemical states of the elements in the samples were identified by X-ray photoelectron spectroscopy. The as-synthesized NiCo2O4 products were then tested as cathode materials for supercapacitors in a traditional three-electrode system. The electrochemical performances of the NiCo2O4 electrode materials were studied and the area capacitance was found to be 1.26 C·cm-2 at a current density of 1 mA·cm-2. Furthermore, outstanding cycling stability with 97.6% retention of the initial discharge capacitance after 10000 cycles and excellent rate performance (67.5% capacitance retention with the current density from 1 to 14 mA·cm-2) were achieved. It was found that the Ni foam supporting the NiCo2O4 nanosheets increased the conductivity of the electrode materials. However, it is worth noting that the contribution of nickel foam to the areal capacitance of the electrode materials was almost zero during the charge and discharge processes. To further investigate the practical application of the as-synthesized NiCo2O4 nanosheets-based electrode, a device was assembled with the as-prepared samples as the positive electrode and active carbon (AC) as the negative electrode. The assembled supercapacitor showed energy densities of 0.14 and 0.09 Wh·cm-3 at 1.56 and 4.5 W·cm-3, respectively. Furthermore, it was able to maintain 95% of its initial specific capacitance after 10000 cycles. The excellent electrochemical performance of the NiCo2O4 nanosheets could be ascribed to their unique spatial structure composed of interconnected ultrathin nanosheets, which facilitated electron transportation and ion penetration, suggesting their potential applications as electrode materials for high performance supercapacitors. The present synthetic route can be extended to other ternary transition metal oxides/sulfides for future energy storage devices and systems. 相似文献
55.
Nonlinear Dynamics - In this contribution, a modified oscillator of Tamasevicius et al. (Electron Lett 33:542–544, 1997) (referred to as the mTCMNL oscillator hereafter) is introduced with... 相似文献
56.
Three one-dimensional ladder-like coordination polymers consisting of Cd6 metalloring as the building unit, {[Cd4LCl4]·3H2O}n ( 1 ), {[Cd3L(ClO4)(H2O)]ClO4·3H2O}n ( 2 ), and {[Cd6(L)2(NO3)2(CH3OH)(H2O)](NO3)2·2CH3OH·5H2O}n ( 3 ), were solvothermally constructed from a carboxylic functionalized bisazamacrocyclic ligand 4,4′-bis((4,7-bis(2-carboxyethyl)-1,4,7-triazacyclonon-1-yl)methyl)-1,1′-biphenyl (H4L). These compounds dispersed in ethanol show the multiple emissions originating from the monomeric and intramolecularly overlapping biphenyl moieties which could be sensitively quenched by picric acid (PA) and 4-nitrophenol (4-NP) through the effective fluorescence resonance energy transfer process. The differential fluorescent responses of each compound on exposure to PA and 4-NP individually make the convenient ratiometric discrimination of two analytes based on the fluorescent intensity ratio (I320/I360) attainable, and 1 and 2 as ratiometric chemosensors for PA present a broad linear detection range from 4 to 300 μM with detection limits of 0.84 and 0.93 μM, respectively. Furthermore, the blue light emission of 1 under an ultraviolet lamp could be selectively quenched by PA even in the presence of all other interfering nitroaromatic pollutants, which empowers the fast visual detection of PA by naked eye. 相似文献
57.
Qi-Jun Li Ya-Jie Ren Qin Xie Min Wu Hua-Xing Feng Li-Mei Zheng Hua-Xin Zhang Jin-Qiao Long Tian-Shun Wang 《应用有机金属化学》2020,34(10):e5813
Two nickel complexes, [Ni(tpen)](ClO4)2.0.5CH3COCH3 ( 1 ) and [Ni(tpbn)](ClO4)2 ( 2 ), of tetrapyridyl ligands N,N,N′,N′-tetrakis(2-pyridyl-methyl)-1,2-ethanediamine (tpen) and N,N,N′,N′-tetrakis(2-pyridyl-methyl)-1,4-butanediamine (tpbn) were prepared and their catalysis for water oxidation reaction (WOR) studied. In 0.1 M phosphate buffer solution (PBS) of pH 8.0, complex 1 is a homogeneous molecular catalyst with an overpotential of ~440 mV and a Faradaic efficiency of 89%. At pH ≥ 9.0, complex 1 degraded gradually during the catalytic process and formed NiOx composite (nickel oxide with general formula NixOyHz) active for WOR. In contrast, complex 2 deteriorated under measured conditions (pH 8.0–12.0) and formed NiOx composite active for WOR. The NiOx composite derived from 1 in 0.1 M PBS at pH 11.0 showed an activity with an overpotential of ~500 mV, a Tafel slope of ~90 mV/decade and a Faradaic efficiency of 97%. Mechanisms were proposed for water oxidation catalyzed by 1 and 2 . This work revealed that the catalytic activity of the nickel complexes was related to the flexibility of the tetrapyridyl ligands and the adaptability of the coordination sphere of the nickel(II) center. 相似文献
58.
59.
Peter T. Smith Younghoon Kim Dr. Bahiru Punja Benke Prof. Kimoon Kim Prof. Christopher J. Chang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(12):4932-4937
We report a supramolecular strategy for promoting the selective reduction of O2 for direct electrosynthesis of H2O2. We utilized cobalt tetraphenylporphyrin (Co-TPP), an oxygen reduction reaction (ORR) catalyst with highly variable product selectivity, as a building block to assemble the permanently porous supramolecular cage Co-PB-1(6) bearing six Co-TPP subunits connected through twenty-four imine bonds. Reduction of these imine linkers to amines yields the more flexible cage Co-rPB-1(6). Both Co-PB-1(6) and Co-rPB-1(6) cages produce 90–100 % H2O2 from electrochemical ORR catalysis in neutral pH water, whereas the Co-TPP monomer gives a 50 % mixture of H2O2 and H2O. Bimolecular pathways have been implicated in facilitating H2O formation, therefore, we attribute this high H2O2 selectivity to site isolation of the discrete molecular units in each supramolecule. The ability to control reaction selectivity in supramolecular structures beyond traditional host–guest interactions offers new opportunities for designing such architectures for a broader range of catalytic applications. 相似文献