全文获取类型
收费全文 | 11480篇 |
免费 | 71篇 |
国内免费 | 32篇 |
专业分类
化学 | 4662篇 |
晶体学 | 14篇 |
力学 | 715篇 |
数学 | 4034篇 |
物理学 | 2158篇 |
出版年
2024年 | 117篇 |
2023年 | 690篇 |
2022年 | 418篇 |
2021年 | 411篇 |
2020年 | 1455篇 |
2019年 | 1067篇 |
2018年 | 926篇 |
2017年 | 754篇 |
2016年 | 733篇 |
2015年 | 563篇 |
2014年 | 737篇 |
2013年 | 2832篇 |
2012年 | 494篇 |
2011年 | 25篇 |
2010年 | 22篇 |
2009年 | 11篇 |
2008年 | 26篇 |
2007年 | 23篇 |
2006年 | 16篇 |
2005年 | 69篇 |
2004年 | 79篇 |
2003年 | 29篇 |
2002年 | 11篇 |
2001年 | 8篇 |
2000年 | 1篇 |
1998年 | 8篇 |
1997年 | 2篇 |
1996年 | 3篇 |
1994年 | 1篇 |
1993年 | 3篇 |
1985年 | 4篇 |
1984年 | 4篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1981年 | 10篇 |
1980年 | 2篇 |
1979年 | 4篇 |
1978年 | 5篇 |
1977年 | 6篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 3篇 |
1973年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 10 毫秒
81.
Dr. Zhen-Zhen Shen Dr. Shuang-Yan Lang Rui-Zhi Liu Dr. Chi Zhou Yao-Zu Zhang Prof. Dr. Bing Liu Prof. Dr. Rui Wen 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2024,136(1):e202316781
Lithium–carbon dioxide (Li–CO2) battery technology presents a promising opportunity for carbon capture and energy storage. Despite tremendous efforts in Li–CO2 batteries, the complex electrode/electrolyte/CO2 triple-phase interfacial processes remain poorly understood, in particular at the nanoscale. Here, using in situ atomic force microscopy and laser confocal microscopy-differential interference contrast microscopy, we directly observed the CO2 conversion processes in Li–CO2 batteries at the nanoscale, and further revealed a laser-tuned reaction pathway based on the real-time observations. During discharge, a bi-component composite, Li2CO3/C, deposits as micron-sized clusters through a 3D progressive growth model, followed by a 3D decomposition pathway during the subsequent recharge. When the cell operates under laser (λ=405 nm) irradiation, densely packed Li2CO3/C flakes deposit rapidly during discharge. Upon the recharge, they predominantly decompose at the interfaces of the flake and electrode, detaching themselves from the electrode and causing irreversible capacity degradation. In situ Raman shows that the laser promotes the formation of poorly soluble intermediates, Li2C2O4, which in turn affects growth/decomposition pathways of Li2CO3/C and the cell performance. Our findings provide mechanistic insights into interfacial evolution in Li–CO2 batteries and the laser-tuned CO2 conversion reactions, which can inspire strategies of monitoring and controlling the multistep and multiphase interfacial reactions in advanced electrochemical devices. 相似文献
82.
83.
The equilibrium solubility of acetaminophen in methanol + water binary mixtures at 298.15 K was determined and correlated with the Jouyban–Acree model. Preferential solvation parameters by methanol (δx1,3) were derived from their thermodynamic solution properties by means of the inverse Kirkwood–Buff integrals method. δx1,3 values are negative in water-rich mixtures but positive in compositions from 0.32 in mole fraction of methanol to pure methanol. It is conjecturable that in the former case, the hydrophobic hydration around non-polar groups plays a relevant role in the solvation. The higher solvation by methanol in mixtures of similar cosolvent compositions and methanol-rich mixtures could be explained in terms of the higher basic behavior of this cosolvent. 相似文献
84.
Suresh Babu Meruva Raghavendra Rao K. Aaseef Mohammed Vilas H. Dahanukar U. K. Syam Kumar P. K. Dubey 《合成通讯》2016,46(2):187-196
A concise and enantioselective syntheses of antileukemic natural products such as (–)-(S)-goniothalamin and (–)-leiocarpin A has been accomplished in excellent yields. By employing reported conditions on suitable substrates via Julia–Kocienski olefination, intramolecular lactonization, and subsequently dehydroxylative olefination, (–)-(S)-goniothalamin was synthesized. Then Sharpless asymmetric dihydroxylation–intramolecular Michael addition on (–)-(S)-goniothalamin provided (–)-leiocarpin A. 相似文献
85.
A discovery that the inexpensive Br2 can serve as a potent Lewis acid catalyst for bis(2-hydroxy-1-naphthyl)methanes synthesis is presented. Under the catalysis of Br2 at room temperature, naphthols reacted smoothly with various aldehydes with high efficiency and broad substrate scope. This reaction used to require highly acidic conditions and/or high temperature and/or pressure, and sometimes featured poor yields. Moreover, theoretical calculations suggested that Br2 is a potent Lewis acid to activate the carbonyl group, yet it was not the primary cause for the remarkable activity of Br2 in the current communication. 相似文献
86.
Pd(OAc)2-catalyzed regioselective C(5)–H arylation of 1,4-disubstituted 1,2,3-triazoles was achieved without ligand under microwave conditions in 1?h, generating 1,4,5-trisubstituted 1,2,3-triazoles with good to excellent yields. The obtained molecules can be easily converted into 4,5-disubstituted 1,2,3-triazoles through the debenzylation process with one-pot manipulation. 相似文献
87.
Ping Zhang Yanhua Chen Meitong Liu Bo Wang Xu Yan Yuan Xu 《International journal of environmental analytical chemistry》2016,96(15):1440-1454
A simple and rapid method based on multi-throughput dynamic microwave-assisted extraction coupled online with salting-out-assisted liquid–liquid extraction was developed for the analysis of chlorpyrifos in soil. First, the chlorpyrifos was extracted with acetonitrile aqueous (50%, v/v) under the action of microwave energy. Then the obtained extract was separated clearly and easily into an acetonitrile phase and an aqueous phase with the assistance of ammonium acetate. The acetonitrile phase containing chlorpyrifos was concentrated and determined by liquid chromatography–tandem mass spectrometry. The effects of parameters on extraction efficiency including microwave power, extraction solvent, volumes and flow rate of extraction solvent, sample pH, types and amount of salt were studied and optimised. To eliminate the matrix effect, validation of the method was carried out using the matrix-based calibration curve. The limits of detection and quantification for chlorpyrifos were 0.17 and 0.5 ng g?1, respectively. The proposed method was applied to analyse chlorpyrifos in five soil samples and verified by the recovery test. The recoveries of chlorpyrifos at three spiked levels (5, 50, 200 ng g?1) were in the range of 90.0–100.5%, with relative standard deviations varying from 1.3% to 5.7%. Compared with the methods reported previously, the proposed method can simplify the operation procedure and reduce solvent consumption in sample pretreatment. 相似文献
88.
The synthesis and anion recognition properties of four novel [2]rotaxane host architectures containing additional alkyl functionality integrated within macrocyclic and axle components to shield the binding cavity from the solvent are described. The rotaxane species containing a tetra(methyl)-functionalised macrocycle component is found to be a weaker anion complexant than the equivalent unfunctionalised receptor, which is likely due to steric hindrance restricting the anion's access to the interlocked cavity. Rotaxane molecules containing tetra(methyl)-functionalised axle components are also investigated, and the additional alkyl functionality serves to enhance anion binding affinity and selectivity when incorporated within the axle's flexible ethylene linkages. Moreover, the equivalent unfunctionalised rotaxane displays a rare preference for oxoanions over chloride guest species. 相似文献
89.
90.
Swetha Parsha Y. Ravindra Kumar M. Ravichander L. Prakash B. Sudharani 《液相色谱法及相关技术杂志》2016,39(4):178-194
A rapid, precise, and reliable liquid chromatography tandem mass spectrometry (LC–MS/MS) method has been developed for the characterization of stressed degradation products of mirabegron. It is used in the treatment of overactive bladder and administered to treat urinary symptoms such as urgency or frequency and incontinence. It also works by relaxing the muscles around bladder.Mirabegron was subjected to hydrolysis (acidic, alkaline, and neutral) and peroxidation, as per ICH-specified conditions. The drug showed degradation under stress conditions. However, it was stable to neutral conditions. A total of seven degradation products were observed and the chromatographic separation of the drug and its degradation products was achieved on X-TerraRP-8 (250 mm × 4.6 mm, i.d., 5 µm) column using 0.01 M ammonium acetate as mobile phase-A and 60:40 ratio of acetonitrile (ACN):water as mobile phase-B. The degradation products were characterized by LC–MS/MS and its fragmentation pathways were proposed. Probable possible structures were drawn based on parent and daughter molecular ions. One peroxide degradant impurity was isolated using preparative LC and characterized using liquid chromatography–mass spectrometry and NMR data. 相似文献