全文获取类型
收费全文 | 4614篇 |
免费 | 662篇 |
国内免费 | 681篇 |
专业分类
化学 | 3506篇 |
晶体学 | 42篇 |
力学 | 380篇 |
综合类 | 28篇 |
数学 | 484篇 |
物理学 | 1517篇 |
出版年
2023年 | 78篇 |
2022年 | 111篇 |
2021年 | 167篇 |
2020年 | 204篇 |
2019年 | 181篇 |
2018年 | 150篇 |
2017年 | 158篇 |
2016年 | 186篇 |
2015年 | 186篇 |
2014年 | 223篇 |
2013年 | 327篇 |
2012年 | 391篇 |
2011年 | 418篇 |
2010年 | 284篇 |
2009年 | 244篇 |
2008年 | 301篇 |
2007年 | 239篇 |
2006年 | 238篇 |
2005年 | 221篇 |
2004年 | 173篇 |
2003年 | 173篇 |
2002年 | 165篇 |
2001年 | 140篇 |
2000年 | 112篇 |
1999年 | 124篇 |
1998年 | 85篇 |
1997年 | 78篇 |
1996年 | 77篇 |
1995年 | 71篇 |
1994年 | 50篇 |
1993年 | 61篇 |
1992年 | 46篇 |
1991年 | 48篇 |
1990年 | 39篇 |
1989年 | 35篇 |
1988年 | 20篇 |
1987年 | 15篇 |
1986年 | 17篇 |
1985年 | 17篇 |
1984年 | 13篇 |
1983年 | 13篇 |
1982年 | 12篇 |
1981年 | 8篇 |
1980年 | 6篇 |
1976年 | 8篇 |
1975年 | 6篇 |
1973年 | 7篇 |
1972年 | 5篇 |
1971年 | 3篇 |
1970年 | 4篇 |
排序方式: 共有5957条查询结果,搜索用时 15 毫秒
61.
Pengzuo Chen Kun Xu Zhiwei Fang Yun Tong Junchi Wu Xiuli Lu Xu Peng Hui Ding Changzheng Wu Yi Xie 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(49):14923-14927
Designing highly efficient electrocatalysts for oxygen evolution reaction (OER) plays a key role in the development of various renewable energy storage and conversion devices. In this work, we developed metallic Co4N porous nanowire arrays directly grown on flexible substrates as highly active OER electrocatalysts for the first time. Benefiting from the collaborative advantages of metallic character, 1D porous nanowire arrays, and unique 3D electrode configuration, surface oxidation activated Co4N porous nanowire arrays/carbon cloth achieved an extremely small overpotential of 257 mV at a current density of 10 mA cm−2, and a low Tafel slope of 44 mV dec−1 in an alkaline medium, which is the best OER performance among reported Co‐based electrocatalysts to date. Moreover, in‐depth mechanistic investigations demonstrate the active phases are the metallic Co4N core inside with a thin cobalt oxides/hydroxides shell during the OER process. Our finding introduces a new concept to explore the design of high‐efficiency OER electrocatalysts. 相似文献
62.
Highly trans‐Selective Arylation of Achmatowicz Rearrangement Products by Reductive γ‐Deoxygenation and Heck–Matsuda Reaction: Asymmetric Total Synthesis of (−)‐Musellarins A–C and Their Analogues 下载免费PDF全文
Zhilong Li Dr. Fanny C. F. Ip Prof. Dr. Nancy Y. Ip Prof. Dr. Rongbiao Tong 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(31):11152-11157
Fully functionalized pyranuloses derived from Achmatowicz rearrangement (AR) are versatile building blocks in organic synthesis. However, access to trans‐2,6‐dihydropyrans from pyranuloses remains underexplored. Herein, we report a new two‐step trans arylation of AR products to access 2,6‐trans‐dihydropyranones. This new trans‐arylation method built on numerous plausible, but unsuccessful, direct arylation reactions, including Ferrier‐type and Tsuji–Trost‐type reactions, was finally enabled by an unprecedented, highly regioselective γ‐deoxygenation of AR products by using Zn/HOAc and a diastereoselective Heck–Matsuda coupling. The synthetic utility of the reaction was demonstrated in the first asymmetric total synthesis of (?)‐musellarins A–C and 12 analogues in 11–12 steps. The brevity and efficiency of our synthetic route permitted preparation of enantiomerically pure musellarins and analogues (>20 mg) for preliminary cytotoxicity evaluation, which led us to identify two analogues with three‐to‐six times greater potency than the musellarins as promising new leads. 相似文献
63.
Yahui Zhang Lingwei Kong Jianbing Shi Bin Tong Junge Zhi Xiao Feng Yuping Dong 《中国化学》2015,33(7):701-704
A new type of AIE molecules based on hexaphenyl‐1,3‐butadienes was reported with respect to the synthesis and characterization. This material exhibited different maximum emission wavelength and enhanced emission intensity at different aggregate state (amorphous and crystalline state). 相似文献
64.
With the aid of Riemann–Liouville fractional calculus theory,fractional order Savitzky–Golay differentiation(FOSGD) is calculated and applied to pretreat near infrared(NIR) spectra in order to improve the performance of multivariate calibrations.Similar to integral order Savitzky–Golay differentiation(IOSGD),FOSGD is obtained by fitting a spectral curve in a moving window with a polynomial function to estimate its coefficients and then carrying out the weighted average of the spectral curve in the window with the coefficients.Three NIR datasets including diesel,wheat and corn datasets were utilized to test this method.The results showed that FOSGD,which is easy to compute,is a general method to obtain Savitzky–Golay smoothing,fractional order and integral order differentiations.Fractional order differentiation computation to the NIR spectra often improves the performance of the PLS model with smaller RMSECV and RMSEP than integral order ones,especially for physical properties of interest,such as density,cetane number and hardness. 相似文献
65.
Visible‐Light‐Promoted Iminyl‐Radical Formation from Acyl Oximes: A Unified Approach to Pyridines,Quinolines, and Phenanthridines 下载免费PDF全文
Heng Jiang Xiaode An Kun Tong Tianyi Zheng Prof. Dr. Yan Zhang Prof. Dr. Shouyun Yu 《Angewandte Chemie (International ed. in English)》2015,54(13):4055-4059
A unified strategy involving visible‐light‐induced iminyl‐radical formation has been established for the construction of pyridines, quinolines, and phenanthridines from acyl oximes. With fac‐[Ir(ppy)3] as a photoredox catalyst, the acyl oximes were converted by 1 e? reduction into iminyl radical intermediates, which then underwent intramolecular homolytic aromatic substitution (HAS) to give the N‐containing arenes. These reactions proceeded with a broad range of substrates at room temperature in high yield. This strategy of visible‐light‐induced iminyl‐radical formation was successfully applied to a five‐step concise synthesis of benzo[c]phenanthridine alkaloids. 相似文献
66.
Tuning the Reactivity of Isocyano Group: Synthesis of Imidazoles and Imidazoliums from Propargylamines and Isonitriles in the Presence of Multiple Catalysts 下载免费PDF全文
Dr. Shuo Tong Dr. Qian Wang Prof. Dr. Mei‐Xiang Wang Prof. Dr. Jieping Zhu 《Angewandte Chemie (International ed. in English)》2015,54(4):1293-1297
The reaction of propargyl amines with tert‐butylisonitrile in the presence of a catalytic amount of both Yb(OTf)3 and AgOTf afforded imidazoles, whereas the same reaction with primary and secondary alkylisonitriles, as well as arylisonitriles, in the presence of three metal salts [Yb(OTf)3/AgOTf/KOTf] resulted in the 1,3,4,5‐tetrasubstituted imidazoliums in excellent yields. Both chiral amines and chiral isonitriles can be used to provide corresponding chiral heterocycles without racemization. In this multiple catalytic system, Yb(OTf)3 catalyzed the insertion of isonitriles to the N? H bond of amines, AgOTf catalyzed the 5‐exo‐dig cyclization of the resulting amidine nitrogen to the tethered triple bond, and KOTf promoted the salt metathesis, thus providing at the same time the counterion to the imidazolium. Against common knowledge, the isocyano group acted in these reactions as a polarized triple bond instead of conventional carbene‐like function. 相似文献
67.
Dr. Xin Fang Ying Tong Di Yu Zhang Dr. Zhi Ping Xu Prof. Yang Lu Qian Qian Chen Prof. Qi Tai Zheng Prof. Dr. Xiao Jiang Hao 《Angewandte Chemie (International ed. in English)》2015,54(19):5592-5595
Perforalactone A ( 1 ), a new 20S quassinoid with a unique cagelike 2,4‐dioxaadamantane ring system and a migrated side chain, was isolated from the plant Harrisonia perforata together with two biosynthetically related new quassinoids. The structures of these natural products were elucidated by NMR spectroscopy, X‐ray diffraction analysis, computational modeling, and the CD excitation chirality method. The compounds exhibited notable biological properties, including insecticidal activity against Aphis medicaginis Koch and antagonist activity at the nicotinic acetylcholine receptor of Drosophila melanogaster. The structural features of these compounds may be related to their promising biological characteristics. Their biosynthesis and an alternative origin of quassinoid‐type natural products are also discussed. 相似文献
68.
研究压电材料双周期裂纹反平面剪切与平面电场作用的问题.运用复变函数方法,获得了该问题严格的闭合解,并由此给出了裂纹尖端应力强度因子和电位移强度因子的精确公式.数值算例显示了裂纹分布特征对材料断裂行为的重要影响.叠间小裂纹能够对主裂纹的应力和电位移场起着屏蔽作用,相反行间小裂纹却起着放大作用,至于钻石形分布裂纹的影响规律则更为复杂.对于某些特殊情形给予了解答并导出一系列有意义的结果。 相似文献
69.
非线性粘弹性拟静态问题与非线性弹性静力问题对应原理 总被引:7,自引:0,他引:7
本文应用多重单边拉氏变换导出了非线性粘弹性拟静态问题与非线性弹性静力问题的对应关系,从而把过去认为只有线性条件下存在的粘弹性——弹性对应原理拓展到了非线性范畴 相似文献
70.
随机振动的一种加权等价线性化方法 总被引:6,自引:0,他引:6
加权等价线性化方法是研究非线性随机振动的一种有效近似方法。关健在于找到一个合适的权函数使之对多数非线性问题都有比较满意的结果。本文提出一种类似峰值概率密度函数的权函数,由此构成一种加权等价线性化方法,借几个各具特点的非线性振动系统进行了可行性验证,表明与一般的等价线性化方法相比,本法所得的均方响应精度有相当程度的改善。 相似文献