全文获取类型
收费全文 | 20408篇 |
免费 | 3362篇 |
国内免费 | 2387篇 |
专业分类
化学 | 14134篇 |
晶体学 | 190篇 |
力学 | 1189篇 |
综合类 | 124篇 |
数学 | 2816篇 |
物理学 | 7704篇 |
出版年
2024年 | 96篇 |
2023年 | 460篇 |
2022年 | 692篇 |
2021年 | 746篇 |
2020年 | 898篇 |
2019年 | 818篇 |
2018年 | 716篇 |
2017年 | 681篇 |
2016年 | 1027篇 |
2015年 | 1002篇 |
2014年 | 1134篇 |
2013年 | 1516篇 |
2012年 | 1743篇 |
2011年 | 1816篇 |
2010年 | 1270篇 |
2009年 | 1146篇 |
2008年 | 1283篇 |
2007年 | 1123篇 |
2006年 | 1009篇 |
2005年 | 919篇 |
2004年 | 724篇 |
2003年 | 623篇 |
2002年 | 687篇 |
2001年 | 550篇 |
2000年 | 446篇 |
1999年 | 442篇 |
1998年 | 348篇 |
1997年 | 312篇 |
1996年 | 332篇 |
1995年 | 299篇 |
1994年 | 240篇 |
1993年 | 171篇 |
1992年 | 169篇 |
1991年 | 164篇 |
1990年 | 127篇 |
1989年 | 99篇 |
1988年 | 54篇 |
1987年 | 57篇 |
1986年 | 71篇 |
1985年 | 49篇 |
1984年 | 32篇 |
1983年 | 26篇 |
1982年 | 15篇 |
1981年 | 11篇 |
1980年 | 4篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1969年 | 1篇 |
1957年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
991.
Youchao Wang Na Tian Weize Sun Boerhan Rena Xusheng Guo Yang Feng Chao Li Xuesong Wang Qianxiong Zhou 《Particle & Particle Systems Characterization》2020,37(5):2000045
Photoactivated chemotherapy (PACT) has appealing merits over traditional chemotherapy as well as photodynamic therapy (PDT) by virtue of its spatial and temporal control on drug activity and oxygen-independent mechanisms of action. However, the short photoactivation wavelengths, e.g., visible light–activated Ru(II)-based PACT agents, limit the clinical application severely. In this work, a facile construction of supramolecular nanoparticles from a poly(ethylene glycol) (PEG)-modified [Ru(dip)2(py-SO3)]+ (abbreviated as Ru-PEG, dip = 4,7-diphenyl-1,10-phenanthroline, py-SO3 = pyridine-2-sulfonate) and 1,3-phenylenebis(pyren-1-ylmethanone) (BP) is shown. While Ru-PEG may undergo photoinduced ligand dissociation and release anticancer species of [Ru(dip)2(H2O)2]2+, BP has extremely large two-photon absorption cross sections (δ2) in the NIR region and intense fluorescence over the wavelengths where Ru-PEG has strong absorption. Thus, two-photon excitation of BP followed by an efficient Förster resonance energy transfer (FRET) from BP to Ru-PEG may lead to a potent inactivation against cisplatin-resistant cancer cells and 3D multicellular tumor spheroids (MCTSs). The residue fluorescence of BP also allows the cellular uptake of the particles to be visualized. This work provides a universal and convenient strategy to realize theranostic PACT in the ideal phototherapeutic window of 650–900 nm. 相似文献
992.
Marie-Claire Giel Dr. Christopher J. Smedley Emily R. R. Mackie Taijie Guo Prof. Dr. Jiajia Dong Dr. Tatiana P. Soares da Costa Prof. Dr. John E. Moses 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(3):1197-1202
The boom in growth of 1,4-disubstituted triazole products, in particular, since the early 2000’s, can be largely attributed to the birth of click chemistry and the discovery of the CuI-catalyzed azide–alkyne cycloaddition (CuAAC). Yet the synthesis of relatively simple, albeit important, 1-substituted-1,2,3-triazoles has been surprisingly more challenging. Reported here is a straightforward and scalable click-inspired protocol for the synthesis of 1-substituted-1,2,3-triazoles from organic azides and the bench stable acetylene surrogate ethenesulfonyl fluoride (ESF). The new transformation tolerates a wide selection of substrates and proceeds smoothly under metal-free conditions to give the products in excellent yield. Under controlled acidic conditions, the 1-substituted-1,2,3-triazole products undergo a Michael addition reaction with a second equivalent of ESF to give the unprecedented 1-substituted triazolium sulfonyl fluoride salts. 相似文献
993.
Mengyi Xiong Zhenglin Yang Ryan J. Lake Junjie Li Shanni Hong Huanhuan Fan Prof. Xiao-Bing Zhang Prof. Yi Lu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(5):1907-1912
Genetically encoded fluorescent proteins (FPs) have been used for metal ion detection. However, their applications are restricted to a limited number of metal ions owing to the lack of available metal-binding proteins or peptides that can be fused to FPs and the difficulty in transforming the binding of metal ions into a change of fluorescent signal. We report herein the use of Mg2+-specific 10–23 or Zn2+-specific 8–17 RNA-cleaving DNAzymes to regulate the expression of FPs as a new class of ratiometric fluorescent sensors for metal ions. Specifically, we demonstrate the use of DNAzymes to suppress the expression of Clover2, a variant of the green FP (GFP), by cleaving the mRNA of Clover2, while the expression of Ruby2, a mutant of the red FP (RFP), is not affected. The Mg2+ or Zn2+ in HeLa cells can be detected using both confocal imaging and flow cytometry. Since a wide variety of metal-specific DNAzymes can be obtained, this method can likely be applied to imaging many other metal ions, expanding the range of the current genetically encoded fluorescent protein-based sensors. 相似文献
994.
Felix Unglaube Paul Hünemörder Xuewen Guo Zixu Chen Dengxu Wang Esteban Mejía 《Helvetica chimica acta》2020,103(12):e2000184
The redox activity of molecular phenazine catalysts has been previously exploited for aerobic oxidative amine homo- and cross-coupling reactions. In this contribution, we have extended the reaction scope of this novel type of organocatalyst and used them in the cross-dehydrogenative aza-Henry coupling of isoquinolines with nitromethane under aerobic conditions. Additionally, we have designed and prepared a novel porous organic polymer by cross-linking of tetrakis(4-bromophenyl)silane and dihydrophenazine through Pd-catalyzed Buchwald-Hartwig cross-coupling. This new type of heterogeneous catalyst, apart from being robust and easily reusable, also showed outstanding catalytic activities and improved selectivity compared to its molecular counterpart. A plausible reaction mechanism was proposed based on spectroscopic and kinetic measurements. 相似文献
995.
Can Li Dr. Zheng Yang Lei Wang Prof. Dr. Yinlong Guo Prof. Dr. Zheng Huang Prof. Dr. Shengming Ma 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(15):6337-6342
An efficient pincer-ligand-based cobalt-complex-catalyzed allene hydroboration affording Z-allylic boronates is described. The reaction demonstrates an excellent regio- as well as Z-stereoselectivity and a wide substrate scope that tolerates many functional groups. Based on solvent-assisted electrospray ionization mass spectrometry (SAESI-MS) studies, a rationale for the cobalt-catalyzed hydroboration involving the highly selective insertion of an allene into the Co−H bond to form Z-allylic cobalt intermediates is proposed. 相似文献
996.
Dr. Yang Li Dr. Xinghua Guo Dr. Xiaofeng Li Dr. Meicheng Zhang Dr. Zhimin Jia Prof. Yun Deng Prof. Yin Tian Prof. Shoujian Li Prof. Lijian Ma 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(10):4197-4204
We report the first example of 2D covalent organic framework nanosheets (Redox-COF1) for the selective reduction and in situ loading of valence-variable, redox-sensitive and long-lived radionuclides (abbreviated as VRL nuclides). Compared with sorbents based on chemical adsorption and physical adsorption, the redox adsorption mechanism of Redox-COF1 can effectively reduce the impact of functional group protonation under the usual high-acidity conditions in chemisorption, and raise the adsorption efficiency from the monotonous capture by pores in physisorption. The adsorption selectivity for UO22+ reaches up to unprecedented ca. 97 % at pH 3, more than for any analogous adsorbing material. 相似文献
997.
998.
Wei Shi Feng Tang Jiwei Ao Qun Yu Junjie Liu Yubo Tang Bofeng Jiang Xuelian Ren Prof. He Huang Prof. Weibo Yang Prof. Wei Huang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(45):20112-20116
Strain-promoted azide–alkyne cycloaddition using dibenzoazacyclooctyne (DBCO) is widely applied in copper-free bioorthogonal reactions. Reported here is the efficient acid-promoted rearrangement and silver-catalyzed amidation of DBCO, which alters its click reactivity robustly. In the switched click reaction, DBCO, as a caged acylation reagent, enables rapid peptide/protein modification after decaging facilitated by silver catalysts, rendering site-specific conjugation of an IgG antibody by a Fc-targeting peptide. 相似文献
999.
1000.
Xinghua Li Yuqin Yang Junjie Miao Zhendong Yin Yijing Zhai Hongmei Shi Zengning Li 《Electrophoresis》2020,41(18-19):1584-1591
In the present research, field-amplified sample injection–CZE (FASI–CZE) coupled with a diode array detector was established to determine trace level sulfa antibiotic. Sulfathiazole, sulfadiazine, sulfamethazine, sulfadimethoxine, sulfamethoxazole, and sulfisoxazole were selected as analytes for the experiments. The background electrolyte solution consisted of 70.0 mmol/L borax and 60.0 mmol/L boric acid (including 10% methanol, pH 9.1). The plug was 2.5 mmol/L borax, which was injected into the capillary at a pressure of 0.5 psi for 5 s. Then the sample was injected into the capillary at an injection voltage of –10 kV for 20 s. The electrophoretic separation was carried out under a voltage of +19 kV. The capillary temperature was maintained at 20˚C throughout the analysis, and six sulfonamides were completely separated within 35 min. Compared with pressure injection-CZE, the sensitivity of FASI-CZE was increased by 6.25–10.0 times, and the LODs were reduced from 0.2–0.5 to 0.02–0.05 μg/mL. The method was applied to the determination of sulfonamides in river water and particulate matter samples. The recoveries were 78.59–106.59%. The intraday and interday precisions were 2.89–7.35% and 2.77–7.09%, respectively. This provides a simpler and faster method for the analysis of sulfa antibiotic residues in environmental samples. 相似文献