全文获取类型
收费全文 | 8581篇 |
免费 | 1249篇 |
国内免费 | 1207篇 |
专业分类
化学 | 6978篇 |
晶体学 | 98篇 |
力学 | 412篇 |
综合类 | 76篇 |
数学 | 1051篇 |
物理学 | 2422篇 |
出版年
2024年 | 12篇 |
2023年 | 120篇 |
2022年 | 145篇 |
2021年 | 224篇 |
2020年 | 297篇 |
2019年 | 320篇 |
2018年 | 250篇 |
2017年 | 223篇 |
2016年 | 381篇 |
2015年 | 423篇 |
2014年 | 431篇 |
2013年 | 620篇 |
2012年 | 653篇 |
2011年 | 663篇 |
2010年 | 500篇 |
2009年 | 539篇 |
2008年 | 594篇 |
2007年 | 495篇 |
2006年 | 512篇 |
2005年 | 469篇 |
2004年 | 427篇 |
2003年 | 370篇 |
2002年 | 459篇 |
2001年 | 381篇 |
2000年 | 250篇 |
1999年 | 197篇 |
1998年 | 148篇 |
1997年 | 129篇 |
1996年 | 118篇 |
1995年 | 87篇 |
1994年 | 98篇 |
1993年 | 67篇 |
1992年 | 60篇 |
1991年 | 54篇 |
1990年 | 57篇 |
1989年 | 32篇 |
1988年 | 32篇 |
1987年 | 31篇 |
1986年 | 27篇 |
1985年 | 31篇 |
1984年 | 21篇 |
1983年 | 9篇 |
1982年 | 12篇 |
1981年 | 14篇 |
1980年 | 11篇 |
1979年 | 8篇 |
1978年 | 5篇 |
1976年 | 6篇 |
1973年 | 4篇 |
1969年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
Qianqian Fan Zirui Liu Feng Qiu Prof. Yong Mao Prof. Qingju Liu Prof. Longzhou Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(63):e202202700
The artificially accurate design of nonmetal electrocatalysts’ active site has been a huge challenge because no pure active species with the specific structure could be strictly controlled by traditional synthetic methods. Species with a multiconfiguration in the catalyst hinder identification of the active site and the subsequent comprehension of the reaction mechanism. We have developed a novel electro-assisted molecular assembly strategy to obtain a pure pentagon ring on perfect graphene avoiding other reconstructed structures. More importantly, the active atom was confirmed by the subtle passivation process as the topmost carbon atom. Recognition of the carbon-defect electrocatalysis reaction mechanism was first downsized to the single-atom scale from the experimental perspective. It is expected that this innovative electro-assisted molecular assembly strategy could be extensively applied in the active structure-controlled synthesis of nonmetal electrocatalysts and verification of the exact active atom. 相似文献
2.
Haixing Guan Qianwen Zhang Prof. Dr. Patrick J. Walsh Prof. Dr. Jianyou Mao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(13):5210-5215
A unique nickel/organic photoredox co-catalyzed asymmetric reductive cross-coupling between α-chloro esters and aryl iodides is developed. This cross-electrophile coupling reaction employs an organic reductant (Hantzsch ester), whereas most reductive cross-coupling reactions use stoichiometric metals. A diverse array of valuable α-aryl esters is formed under these conditions with high enantioselectivities (up to 94 %) and good yields (up to 88 %). α-Aryl esters represent an important family of nonsteroidal anti-inflammatory drugs. This novel synergistic strategy expands the scope of Ni-catalyzed reductive asymmetric cross-coupling reactions. 相似文献
3.
Paired single residue‐transposed Lys‐N and Lys‐C digestions for label‐free identification of N‐terminal and C‐terminal MS/MS peptide product ions: ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry and tandem mass spectrometry for peptide de novo sequencing 下载免费PDF全文
4.
蛋白质-多糖复合体系作为生物活性物质传递系统的壁材,有着人工合成聚合物或无机物等其他材料不可比拟的多重优势。本文就蛋白质和多糖之间的连接方式及蛋白质-多糖复合体系形成传递系统的多种形式进行了综述,以及对此领域的发展趋势进行了展望。结合蛋白质和多糖的结构特点,二者之间的链接方式分为非共价结合的物理共聚,和共价结合的美拉德偶联、化学交联、酶催化交联等方式,文中分别对各种连接方式的原理和机理,以及其影响因素做了深入阐述。以蛋白质-多糖复合体系为壁材对活性物质的传递形式大体上分成乳化系统、胶束、纳米凝胶、分子复合物以及壳核结构等系统。不同的活性物质的特征和传递需求,可针对性地选择合适结构的蛋白质和多糖种类以及二者的连接方式和传递系统的形式。并且,随着研究的逐步发展和推进,此领域的发展趋势朝着智能化和靶向性的方向进行。目前活性物质的蛋白质-多糖复合体系的传递系统,还依然面临着系统设计、评价和应用等多方面的挑战,这就要求我们在更全面更深入了解认识其对活性物质影响和功效的基础上,安全合理地设计和深入细致地评价活性成分的传递系统。 相似文献
5.
Over the past two decades, advanced materials with hollow interiors have received significant attention in materials research owing to their great application potential across a vast number of technological fields. Though with great difficulty, multi-shelled hollow metal–organic frameworks (MSHMs) have also been successfully synthesized in recent years. Herein, a rational shell-by-shell soft-templating protocol has been devised to fabricate highly uniform multi-shelled hollow cobalt-imidazole-based MOF (ZIF-67). For the first time, it has become possible to endow mesoporosity to this new type of functional material (i.e., mesoporous MOFs). When used as carrier materials in catalytic reactions, in principle, these mesoporous MSHMs with high surface area not only improve the dispersity of metal nanoparticles (NPs), but also efficiently facilitate the mass diffusion of the reactions, resulting in enhanced catalyst activity. Moreover, the obtained MSHMs/M nanocomposites serve as base-metal bifunctional catalysts for one-pot oxidation-Knoevenagel condensation cascade reaction, in which the MSHMs itself serves as a pristine active catalyst in addition to its role of catalyst support. The results demonstrate that excellent multifunctional catalysts can be achieved via preparing intrinsically microporous bulk MOFs into extrinsically mesoporous MSHMs which possess many structural merits that conventional bulk MOFs do not have. 相似文献
6.
Metabolic profiles of dioscin in rats revealed by ultra‐performance liquid chromatography quadrupole time‐of‐flight mass spectrometry 下载免费PDF全文
He Zhu Jin‐Di Xu Qian Mao Hong Shen Ming Kong Jian‐Ping Chen Song‐Lin Li 《Biomedical chromatography : BMC》2015,29(9):1415-1421
Dioscin (DIS), one of the most abundant bioactive steroidal saponins in Dioscorea sp., is used as a complementary medicine to treat coronary disease and angina pectoris in China. Although the pharmacological activities and pharmacokinetics of DIS have been well demonstrated, information regarding the final metabolic fates is very limited. This study investigated the in vivo metabolic profiles of DIS after oral administration by ultra‐performance liquid chromatography quadrupole time‐of‐flight mass spectrometry method. The structures of the metabolites were identified and tentatively characterized by means of comparing the molecular mass, retention time and fragmentation pattern of the analytes with those of the parent compound. A total of eight metabolites, including seven phase I and one phase II metabolites, were detected and tentatively identified for the first time. Oxidation, deglycosylation and glucuronidation were found to be the major metabolic processes of the compound in rats. In addition, a possible metabolic pathway on the biotransformation of DIS in vivo was proposed. This study provides valuable and new information on the metabolism of DIS, which will be helpful for further understanding its mechanism of action. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
7.
8.
Shi-Chun Mao Zhaohui Zhang Jiansen Gao Zhen-Sen Wu 《Waves in Random and Complex Media》2019,29(1):54-62
A solution to the problem of Gaussian beam scattering by an anisotropically coated circular cylinder is presented. The incident Gaussian beam source is expanded as an approximate expression in the simple form with a Tayor’s series. The transmitted field in the anisotropically coated region is expressed as a infinite summation of eigen plane waves with different polar angles. The unknown coefficients of the scattered fields are obtained with the aid of the boundary conditions. The infinite series can be truncated under the prerequisite of achieving the solution convergence. Only the case of transverse-electric polarization is discussed. The similar formulation of transverse-magnetic polarization can be obtained by adopting the similar method. Some numerical results are presented and discussed. The result is in agreement with that available as expected when the Gaussian beam degenerates to a plane wave incidence case. 相似文献
9.
Prof. Jen-Shyang Ni Tianliang Min Yaxi Li Menglei Zha Dr. Pengfei Zhang Prof. Chun Loong Ho Prof. Kai Li 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(25):10265-10271
Planar luminogens have encountered difficulties in overcoming intrinsic aggregation-caused emission quenching by intermolecular π-π stacking interactions. Although excited-state double-bond reorganization (ESDBR) can guide us on designing planar aggregation-induced emission (AIE) luminogens (AIEgens), its mechanism has yet been elucidated. Major challenges in the field include methods to efficiently restrict ESDBR and enhance AIE performance without using bulky substituents (e.g., tetraphenylethylene and triphenylamine). In this study, we rationally developed fluoro-substituent AIEgens with stronger intermolecular H-bonding interaction for restricted molecular motions and increased crystal density, leading to decreased nonradiative decay rate by one order of magnitude. The adjusted ESDBR properties also show a corresponding response to variation in viscosity. Furthermore, their aggregation-induced reactive oxygen species (ROS) generations have been discovered. The application of such planar AIEgen in treating multidrug-resistant bacteria has been demonstrated in a mouse model. The relationship between ROS generation and distinct E/Z-configurational stacking behaviors have been further understood, providing a design principle for synthesizing planar AIEgen-based photosensitizers. 相似文献
10.
采用Agilent 81910A光子全参量测试仪,首次实验研究了InP/In1-xGaxAs1-yPy-MQW(Multiple-Quantum-Well,MQW)材料与衬底间因应力而产生的M-Z型光调制器的PDL影响以及由此引起的由差分群时延(Differential Group Delay,DGD)表征的偏振模色散(Polarization Mode Dispersion,PMD).研究结果表明,半导体MQW光调制器的PDL与DGD是一致的.因此在半导体光器件的制作过程中,应尽可能地减小衬底与波导芯层之间的因残存应力的存在造成对光器件的高速性能的不利影响. 相似文献