全文获取类型
收费全文 | 96328篇 |
免费 | 3592篇 |
国内免费 | 2662篇 |
专业分类
化学 | 37146篇 |
晶体学 | 945篇 |
力学 | 7738篇 |
综合类 | 118篇 |
数学 | 34403篇 |
物理学 | 22232篇 |
出版年
2024年 | 86篇 |
2023年 | 428篇 |
2022年 | 644篇 |
2021年 | 719篇 |
2020年 | 849篇 |
2019年 | 773篇 |
2018年 | 10958篇 |
2017年 | 10739篇 |
2016年 | 6935篇 |
2015年 | 1785篇 |
2014年 | 1373篇 |
2013年 | 1756篇 |
2012年 | 5390篇 |
2011年 | 12092篇 |
2010年 | 6766篇 |
2009年 | 7045篇 |
2008年 | 7735篇 |
2007年 | 9744篇 |
2006年 | 1172篇 |
2005年 | 2154篇 |
2004年 | 2198篇 |
2003年 | 2544篇 |
2002年 | 1675篇 |
2001年 | 782篇 |
2000年 | 722篇 |
1999年 | 578篇 |
1998年 | 530篇 |
1997年 | 453篇 |
1996年 | 524篇 |
1995年 | 405篇 |
1994年 | 306篇 |
1993年 | 255篇 |
1992年 | 217篇 |
1991年 | 220篇 |
1990年 | 172篇 |
1989年 | 152篇 |
1988年 | 112篇 |
1987年 | 113篇 |
1986年 | 128篇 |
1985年 | 93篇 |
1984年 | 74篇 |
1983年 | 62篇 |
1982年 | 56篇 |
1981年 | 49篇 |
1980年 | 50篇 |
1979年 | 45篇 |
1914年 | 45篇 |
1912年 | 40篇 |
1909年 | 41篇 |
1908年 | 40篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
101.
Xiuxiu Wang Zong-Chang Han Wei Wei Hanshi Hu Pengfei Li Peiqing Sun Xiangzhi Liu Zhijia Lv Feng Wang Yi Cao Zijian Guo Jun Li Jing Zhao 《Chemical science》2022,13(24):7269
Metal clusters, such as iron–sulfur clusters, play key roles in sustaining life and are intimately involved in the functions of metalloproteins. Herein we report the formation and crystal structure of a planar square tetranuclear silver cluster when silver ions were mixed with human copper chaperone Atox1. Quantum chemical studies reveal that two Ag 5s1 electrons in the tetranuclear silver cluster fully occupy the one bonding molecular orbital, with the assumption that this Ag4 cluster is Ag42+, leading to extensive electron delocalization over the planar square and significant stabilization. This bonding pattern of the tetranuclear silver cluster represents an aromatic all-metal structure that follows a 4n + 2 electron counting rule (n = 0). This is the first time an all-metal aromatic silver cluster was observed in a protein.Metal clusters, such as iron–sulfur clusters, play key roles in sustaining life and are intimately involved in the functions of metalloproteins. 相似文献
102.
Tobias Bischof Xueying Guo Ivo Krummenacher Lukas Beßler Zhenyang Lin Maik Finze Holger Braunschweig 《Chemical science》2022,13(25):7492
The synthesis of 9-borafluorene with an electron-withdrawing o-carboranyl substituent and its reactions with a series of alkenes are described. The o-carboranyl substituent is bonded via one of the cluster carbon atoms to the boron atom of the 9-borafluorene moiety. In all cases, the reactions afford partly saturated analogs of borepins (i.e. 6,7-dihydroborepins) by unprecedented alkene insertion into the endocyclic B–C bond of the borole ring. Comparative studies with 9-bromo-9-borafluorene illustrate the superior insertion reactivity of the carboranyl-substituted derivative. A suite of experimental and computational techniques disclose the unique properties of the 9-borafluorene and provide insight into how the 9-carboranyl substituent affects its chemical reactivity.A 9-carboranyl-substituted 9-borafluorene is reported, which is capable of undergoing efficient ring expansion to 6,7-dihydroborepins by a previously unknown alkene insertion. 相似文献
103.
Bingxue Lv Jiahao Ren Yang Chen Siyu Guo Minqian Wu Lijun You 《Molecules (Basel, Switzerland)》2022,27(15)
In this study, a polysaccharide-based hydrogel microsphere (SFP/SA) was prepared using S. fusiforme polysaccharide (SFP) and sodium alginate (SA). Fourier transform infrared spectroscopy (FT-IR) demonstrated that SFP was effectively loaded onto the hydrogel microsphere. Texture profile analysis (TPA) and differential scanning calorimetry (DSC) showed that, with the increase of SFP concentration, the hardness of SFP/SA decreased, while the springiness and cohesiveness of SFP/SA increased, and the thermal stability of SFP/SA improved. The equilibrium adsorption capacity of SFP/SA increased from 8.20 mg/g (without SFP) to 67.95 mg/g (SFP accounted 80%) without swelling, and from 35.05 mg/g (without SFP) to 81.98 mg/g (SFP accounted 80%) after 24 h swelling. The adsorption of crystal violet (CV) dye by SFP/SA followed pseudo-first order and pseudo-second order kinetics (both with R2 > 0.99). The diffusion of intraparticle in CV dye was not the only influencing factor. Moreover, the adsorption of CV dye for SFP/SA (SFP accounted 60%) fit the Langmuir and Temkin isotherm models. SFP/SA exhibited good regenerative adsorption capacity. Its adsorption rate remained at > 97% at the 10th consecutive cycle while SFP accounted for 80%. The results showed that the addition of Sargassum fusiforme polysaccharide could increase the springiness, cohesiveness and thermal stability of the hydrogel microsphere, as well as improve the adsorption capacity of crystal violet dye. 相似文献
104.
Xiaobo Xu Leyu Yan Zhi-Kai Zhang Bingqing Lu Zhuangwen Guo Mengyue Chen Zhong-Yan Cao 《Molecules (Basel, Switzerland)》2022,27(15)
A practical method for the deoxygenation of α-hydroxyl carbonyl compounds under mild reaction conditions is reported here. The use of cheap and easy-to-handle Na2S·9H2O as the reductant in the presence of PPh3 and N-chlorosuccinimide (NCS) enables the selective dehydroxylation of α-hydroxyl carbonyl compounds, including ketones, esters, amides, imides and nitrile groups. The synthetic utility is demonstrated by the late-stage deoxygenation of bioactive molecule and complex natural products. 相似文献
105.
In order to overcome the spectral interference of the conventional Fourier transform in the International Electrotechnical Commission framework, this paper introduces a Bregman-split-based compressive sensing (BSCS) method to estimate the Taylor–Fourier coefficients in a multi-frequency dynamic phasor model. Considering the DDC component estimation, this paper transforms the phasor problem into a compressive sensing model based on the regularity and sparsity of the dynamic harmonic signal distribution. It then derives an optimized hybrid regularization algorithm with the Bregman split method to reconstruct the dynamic phasor estimation. The accuracy of the model was verified by using the cross entropy to measure the distribution differences of values. Composite tests derived from the dynamic phasor test conditions were then used to verify the potentialities of the BSCS method. Simulation results show that the algorithm can alleviate the impact of dynamic signals on phasor estimation and significantly improve the estimation accuracy, which provides a theoretical basis for P-class phasor measurement units (PMUs). 相似文献
106.
Three compounds based on Ge-V-O clusters were hydrothermally synthesized and characterized by IR, UV-Vis, XRD, ESR, elemental analysis and X-ray crystal structural analysis. Both [Cd(phen)(en)]2[Cd2(phen)2V12O40Ge8(OH)8(H2O)]∙12.5H2O (1) and [Cd(DETA)]2[Cd(DETA)2]0.5[Cd2(phen)2V12O41Ge8(OH)7(0.5H2O)]∙7.5H2O (2) (1,10-phen = 1,10-phenanthroline, en = ethylenediamine, DETA = diethylenetriamine) are the first Ge-V-O cluster compounds containing aromatic organic ligands. Compound 1 is the first dimer of Ge-V-O clusters, which is linked by a double bridge of two [Cd(phen)(en)]2+. Compound 2 exhibits an unprecedented 1-D chain structure formed by Ge-V-O clusters and [Cd2(DETA)2]4+ transition metal complexes (TMCs). [Cd(en)3]{[Cd(η2-en)2]3[Cd(η2-en)(η2-μ2-en)(η2-en)Cd][Ge6V15O48(H2O)]}∙5.5H2O (3) is a novel 3-D structure which is constructed from [Ge6V15O48(H2O)]12− and four different types of TMCs. We also synthesized [Zn2(enMe)3][Zn(enMe)]2[Zn(enMe)2(H2O)]2[Ge6V15O48(H2O)]∙3H2O (4) and [Cd(en)2]2{H8[Cd(en)]2Ge8V12O48(H2O)}∙6H2O (5) (enMe = 1,2-propanediamine), which have been reported previously. In addition, the catalytic properties of these five compounds for styrene epoxidation have been assessed. 相似文献
107.
以基于准位相匹配和频与差频级联二阶非线性[X^(2):X^(2)]基础上的全光开关的理论分析作指导,进行了周期极化铌酸锂晶体(PPLN)和退火质子交换光波导(APE)的实验制备,利用所研制的PPLN-APE器件,以自行研制的工作波长为1.54μm的被动调Q掺钴铝酸镁激光器作为控制光源,以工作波长为1.5μm的连续二极管激光器为信号光源进行了级联二阶非线性全光开关实验。当控制光峰值功率为3kw,信号光功率为1mW时,实现13%的开关效率,分析了进一步提高全光开关性能的途径。 相似文献
108.
Faraday-Michelson system for quantum cryptography 总被引:9,自引:0,他引:9
Quantum key distribution provides unconditional security for communication. Unfortunately, current experimental schemes are not suitable for long-distance fiber transmission because of phase drift or Rayleigh backscattering. In this Letter we present a unidirectional intrinsically stable scheme that is based on Michelson-Faraday interferometers, in which ordinary mirrors are replaced with 90 degree Faraday mirrors. With the scheme, a demonstration setup was built and excellent stability of interference fringe visibility was achieved over a fiber length of 175 km. Through a 125 km long commercial communication fiber cable between Beijing and Tianjin, the key exchange was performed with a quantum bit-error rate of less than 6%, which is to our knowledge the longest reported quantum key distribution experiment under field conditions. 相似文献
109.
Lirong Guo Qing Gao Jieqiong Zhu Xiaobao Jin Hui Yin Tao Liu 《Molecules (Basel, Switzerland)》2022,27(9)
Commonly used clinical chemotherapy drugs, such as cyclophosphamide (CTX), may cause injury to the ovaries. Hormone therapies can reduce the ovarian injury risk; however, they do not achieve the desired effect and have obvious side effects. Therefore, it is necessary to find a potential therapeutic candidate for ovarian injury after chemotherapy. N-Benzyl docosahexaenamide (NB-DHA) is a docosahexaenoic acid derivative. It was recently identified as the specific macamide with a high degree of unsaturation in maca (Lepidium meyenii). In this study, the purified NB-DHA was administered intragastrically to the mice with CTX-induced ovarian injury at three dose levels. Blood and tissue samples were collected to assess the regulation of NB-DHA on ovarian function. The results indicated that NB-DHA was effective in improving the disorder of estrous cycle, and the CTX+NB-H group can be recovered to normal levels. NB-DHA also significantly increased the number of primordial follicles, especially in the CTX+NB-M and CTX+NB-H groups. Follicle-stimulating hormone and luteinizing hormone levels in all treatment groups and estradiol levels in the CTX+NB-H group returned to normal. mRNA expression of ovarian development-related genes was positive regulated. The proportion of granulosa cell apoptosis decreased significantly, especially in the CTX+NB-H group. The expression of anti-Müllerian hormone and follicle-stimulating hormone receptor significantly increased in ovarian tissues after NB-DHA treatment. NB-DHA may be a promising agent for treating ovarian injury. 相似文献
110.
基于二代curvelet变换的图像融合研究 总被引:34,自引:0,他引:34
曲波(Curvelet)作为一种新的多尺度分析方法比小波更加适合分析二维图像中的曲线或直线状边缘特征,而且具有更高的逼近精度和更好的稀疏表达能力.将curvelet变换引入图像融合,能够更好地提取原始图像的特征,为融合图像提供更多的信息.第二代curvelet理论的提出也使得其理论更易理解和实现.因此,提出了一种基于第二代curvelet变换的图像融合方法,首先将图像进行curvelet变换,然后在相应尺度上利用融合规则将curvelet系数融合,最后进行重构得到融合结果.对多聚焦图像进行了实验,采用均方误差、偏差指数和相关系数对融合结果进行了客观评价,并与基于小波变换的融合进行了比较,实验结果表明该方法除分解2层时与小波性能相当,取其他分解层数时均获得更好的融合效果. 相似文献