全文获取类型
收费全文 | 9083篇 |
免费 | 1493篇 |
国内免费 | 888篇 |
专业分类
化学 | 3987篇 |
晶体学 | 67篇 |
力学 | 842篇 |
综合类 | 49篇 |
数学 | 361篇 |
物理学 | 6158篇 |
出版年
2024年 | 8篇 |
2023年 | 83篇 |
2022年 | 204篇 |
2021年 | 230篇 |
2020年 | 261篇 |
2019年 | 261篇 |
2018年 | 246篇 |
2017年 | 270篇 |
2016年 | 345篇 |
2015年 | 332篇 |
2014年 | 458篇 |
2013年 | 756篇 |
2012年 | 547篇 |
2011年 | 688篇 |
2010年 | 489篇 |
2009年 | 613篇 |
2008年 | 625篇 |
2007年 | 690篇 |
2006年 | 593篇 |
2005年 | 469篇 |
2004年 | 402篇 |
2003年 | 364篇 |
2002年 | 395篇 |
2001年 | 286篇 |
2000年 | 287篇 |
1999年 | 200篇 |
1998年 | 190篇 |
1997年 | 145篇 |
1996年 | 120篇 |
1995年 | 143篇 |
1994年 | 105篇 |
1993年 | 132篇 |
1992年 | 86篇 |
1991年 | 68篇 |
1990年 | 57篇 |
1989年 | 35篇 |
1988年 | 36篇 |
1987年 | 28篇 |
1986年 | 27篇 |
1985年 | 36篇 |
1984年 | 41篇 |
1983年 | 15篇 |
1982年 | 26篇 |
1981年 | 18篇 |
1980年 | 11篇 |
1979年 | 8篇 |
1978年 | 9篇 |
1977年 | 6篇 |
1976年 | 5篇 |
1973年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
51.
Methoxy and Methyl Group Rotation: Solid‐State NMR 1H Spin‐Lattice Relaxation,Electronic Structure Calculations,X‐ray Diffractometry,and Scanning Electron Microscopy 下载免费PDF全文
Prof. Peter A. Beckmann Dr. Clelia W. Mallory Prof. Frank B. Mallory Prof. Arnold L. Rheingold Dr. Xianlong Wang 《Chemphyschem》2015,16(7):1509-1519
We report solid‐state 1H nuclear magnetic resonance (NMR) spin‐lattice relaxation experiments, X‐ray diffractometry, field‐emission scanning electron microscopy, and both single‐molecule and cluster ab initio electronic structure calculations on 1‐methoxyphenanthrene ( 1 ) and 3‐methoxyphenanthrene ( 2 ) to investigate the rotation of the methoxy groups and their constituent methyl groups. The electronic structure calculations and the 1H NMR relaxation measurements can be used together to determine barriers for the rotation of a methoxy group and its constituent methyl group and to develop models for the two coupled motions. 相似文献
52.
Existing selective pulses are mainly constructed in the forms of classically shaped pulses, such as the Gaussian pulses, or generated by using numerical optimization methods. However, all of these pulses are highly sensitive to radiofrequency (RF) intensity variation, which means their performance is highly dependent on the accuracy and stability of the RF intensity. Even a slight RF intensity deviation can cause severe degradation in the excitation profile. To solve this problem, we propose a method for narrow selective excitation by sequential application of a pair of phase‐opposite asymmetric adiabatic pulses, all within two scans. By retaining the adiabatic character, the new method is highly robust to RF intensity variation. Moreover, it has flexible excitation bandwidth, ranging from line‐selective to narrow‐band‐selective pulses. The method is tested both in numerical simulations and solution‐state NMR experiments. 相似文献
53.
Scalar coupling in proton NMR spectra provides important information for the structural analysis. However, the low resolution due to the resulting signal splitting, together with the rather narrow spectral range of hydrogen, often prevents the extraction of J‐coupling information. Here we present a method to achieve real‐time homonuclear J‐downscaling. Thereby, all J‐values are uniformly reduced by an arbitrary scaling factor. In the resulting one‐dimensional spectra, signal overlap is reduced, while scalar coupling information is still available. 相似文献
54.
55.
Study of the forced degradation behavior of prasugrel hydrochloride by liquid chromatography with mass spectrometry and liquid chromatography with NMR detection and prediction of the toxicity of the characterized degradation products 下载免费PDF全文
Dilip Kumar Singh Archana Sahu Tarun Handa Mallikarjun Narayanam Saranjit Singh 《Journal of separation science》2015,38(17):2995-3005
Prasugrel was subjected to forced degradation studies under conditions of hydrolysis (acid, base, and neutral), photolysis, oxidation, and thermal stress. The drug showed liability in hydrolytic as well as oxidative conditions, resulting in a total of four degradation products. In order to characterize the latter, initially mass fragmentation pathway of the drug was established with the help of mass spectrometry/time‐of‐flight, multiple stage mass spectrometry and hydrogen/deuterium exchange data. The degradation products were then separated on a C18 column using a stability‐indicating volatile buffer method, which was later extended to liquid chromatography‐mass spectrometry studies. The latter highlighted that three degradation products had the same molecular mass, while one was different. To characterize all, their mass fragmentation pathways were established in the same manner as the drug. Subsequently, liquid chromatography‐nuclear magnetic resonance (NMR) spectroscopy data were collected. Proton and correlation liquid chromatography with NMR spectroscopy studies highlighted existence of diastereomeric behavior in one pair of degradation products. Lastly, toxicity prediction by computer‐assisted technology (TOPKAT) and deductive estimation of risk from existing knowledge (DEREK) software were employed to assess in silico toxicity of the characterized degradation products. 相似文献
56.
光动力疗法是近年来兴起的一种新型的微创性治疗肿瘤的方法,目前已经成功地应用于临床上多种恶性肿瘤治疗中,并取得了良好的效果。然而,由于生物组织对可见光的吸收和散射,使得光线无法穿透组织到达身体内的目标区域,所以该疗法更适用于浅表肿瘤的治疗。长波长光尤其是近红外光具有良好的组织穿透深度,其在治疗组织深处的肿瘤方面具有显著的优势。基于长波长光激发的光敏剂及载体在实体肿瘤的治疗领域已经取得了丰硕的研究成果。本文将从光敏剂的研发、双光子激光的使用、上转换纳米粒子的引入等方面简要概述近十年来用于光动力治疗中的组装体系,以及长波长激发光在光动力治疗方面的发展趋势。 相似文献
57.
《Angewandte Chemie (International ed. in English)》2017,56(8):2208-2211
To understand the molecular details of O2‐tolerant hydrogen cycling by a soluble NAD+‐reducing [NiFe] hydrogenase, we herein present the first bioinspired heterobimetallic S‐oxygenated [NiFe] complex as a structural and vibrational spectroscopic model for the oxygen‐inhibited [NiFe] active site. This compound and its non‐S‐oxygenated congener were fully characterized, and their electronic structures were elucidated in a combined experimental and theoretical study with emphasis on the bridging sulfenato moiety. Based on the vibrational spectroscopic properties of these complexes, we also propose novel strategies for exploring S‐oxygenated intermediates in hydrogenases and similar enzymes. 相似文献
58.
《Angewandte Chemie (International ed. in English)》2017,56(49):15755-15759
Calmodulin (CaM) binds most of its targets by wrapping around an amphipathic α‐helix. The N‐terminus of Orai proteins contains a conserved CaM‐binding segment but the binding mechanism has been only partially characterized. Here, microscale thermophoresis (MST), surface plasmon resonance (SPR), and atomic force microscopy (AFM) were employed to study the binding equilibria, the kinetics, and the single‐molecule interaction forces involved in the binding of CaM to the conserved helical segments of Orai1 and Orai3. The results consistently indicated stepwise binding of two separate target peptides to the two lobes of CaM. An unparalleled high affinity was found when two Orai peptides were dimerized or immobilized at high lateral density, thereby mimicking the close proximity of the N‐termini in native Orai oligomers. The analogous experiments with smooth muscle myosin light chain kinase (smMLCK) showed only the expected 1:1 binding, confirming the validity of our methods. 相似文献
59.
针对滚动轴承滚珠磨损故障特征难以提取的问题,提出一种基于多脉冲激励法下的Volterra级数核的求解算法.该方法是一种非线性系统模型的“交叉”诊断法,利用轴承系统输入输出的采样信号,建立Volterra非线性辨识系统模型,并运用多脉冲激励Volterra低阶核求解算法,将得到的低阶核通过时域和频域进行对比来判断轴承当前所处的运行状态.该文以无心车床主轴轴承为例进行实验验证,并与传统的小波分析法对比得出:多脉冲激励法能够方便准确地提取轴承的故障特征,该方法对此类故障的诊断具有一定的借鉴意义. 相似文献
60.
本工作借助第一性原理和动力学演化,系统地研究了四个叔丁基-咔唑及吩噻嗪取代的硼-氮化合物(BCz-BN、2PTZ-BN、Cz-PTZ-BN和2Cz-PTZ-BN)的多共振热激活延迟荧光的高效发光机制.结果表明上述分子T1与T2间的内转换速率远大于其它辐射与非辐射速率,同时T2到S1的反向系间窜越速率也高于T1到S1的反向系间窜越速率,因此其多共振热激活延迟荧光过程应遵循T1→T2→S1→S0的路径.进一步动力学演化表明,T1与T2之间的内转换主要发生在演化初期,随着时间的推移,能量逐渐由T2向S1转移,并最终在S1完成荧光发射.上述研究揭示了多共振延迟荧光的微观本质,为未来设计及合成新的多共振热激活延迟荧光分子提供了理论依据. 相似文献