全文获取类型
收费全文 | 2298篇 |
免费 | 346篇 |
国内免费 | 172篇 |
专业分类
化学 | 1229篇 |
晶体学 | 22篇 |
力学 | 269篇 |
综合类 | 47篇 |
数学 | 265篇 |
物理学 | 984篇 |
出版年
2024年 | 8篇 |
2023年 | 67篇 |
2022年 | 219篇 |
2021年 | 208篇 |
2020年 | 130篇 |
2019年 | 99篇 |
2018年 | 80篇 |
2017年 | 88篇 |
2016年 | 107篇 |
2015年 | 79篇 |
2014年 | 92篇 |
2013年 | 185篇 |
2012年 | 127篇 |
2011年 | 96篇 |
2010年 | 73篇 |
2009年 | 111篇 |
2008年 | 87篇 |
2007年 | 114篇 |
2006年 | 97篇 |
2005年 | 75篇 |
2004年 | 91篇 |
2003年 | 86篇 |
2002年 | 55篇 |
2001年 | 42篇 |
2000年 | 51篇 |
1999年 | 52篇 |
1998年 | 37篇 |
1997年 | 31篇 |
1996年 | 27篇 |
1995年 | 35篇 |
1994年 | 30篇 |
1993年 | 22篇 |
1992年 | 23篇 |
1991年 | 10篇 |
1990年 | 10篇 |
1989年 | 10篇 |
1988年 | 5篇 |
1987年 | 4篇 |
1986年 | 3篇 |
1985年 | 10篇 |
1984年 | 5篇 |
1983年 | 3篇 |
1981年 | 6篇 |
1980年 | 2篇 |
1979年 | 3篇 |
1978年 | 5篇 |
1974年 | 4篇 |
1973年 | 3篇 |
1971年 | 2篇 |
1959年 | 2篇 |
排序方式: 共有2816条查询结果,搜索用时 125 毫秒
101.
José Grau Cristian Azorín Juan L. Benedé Alberto Chisvert Amparo Salvador 《Journal of separation science》2022,45(1):210-222
Dispersive liquid-liquid microextraction is one of the most widely used microextraction techniques currently in the analytical chemistry field, mainly due to its simplicity and rapidity. The operational mode of this approach has been constantly changing since its introduction, adapting to new trends and applications. Most of these changes are related to the nature of the solvent employed for the microextraction. From the classical halogenated solvents (e.g., chloroform or dichloromethane), different alternatives have been proposed in order to obtain safer and non-pollutants microextraction applications. In this sense, low-density solvents, such as alkanols, switchable hydrophobicity solvents, and ionic liquids were the first and most popular replacements for halogenated solvents, which provided similar or better results than these classical dispersive liquid-liquid microextraction solvents. However, despite the good performances obtained with low-density solvents and ionic liquids, researchers have continued investigating in order to obtain even greener solvents for dispersive liquid-liquid microextraction. For that reason, in this review, the evolution over the last five years of the three types of solvents already mentioned and two of the most promising solvent alternatives (i.e., deep eutectic solvents and supramolecular solvents), have been studied in detail with the purpose of discussing which one provides the greenest alternative. 相似文献
102.
Li Yang Li-yuan Xie Xuan Chen Xiao-hong Bai Shuang Hu 《Journal of separation science》2022,45(13):2252-2261
A novel solvent terminated microextraction method based on a natural deep eutectic solvent (L-menthol and lactic acid at a molar ratio of 1:2) coupled with high-performance liquid chromatography was proposed, which was utilized for the separation and enrichment of bisdemethoxycurcumin, demethoxycurcumin and curcumin in Curcumae Longae Rhizoma and turmeric tea. The effects of independent parameters on extraction efficiency were optimized by single-factor analysis. Subsequently, four predominated parameters affecting the extraction procedure, including extractant volume, salt concentration, demulsifier consumption, and demulsification time, were further evaluated by a central composite design. Under the optimized conditions, the linear ranges of calibration curves were 0.005–0.5 μg/mL for bisdemethoxycurcumin, 0.004–0.4 μg/mL for demethoxycurcumin, and 0.0045–0.45 μg/mL for curcumin, respectively. In addition, the developed method provided low detection limits (0.1–0.4 ng/mL) and high enrichment factors (279–350). Its intra-day and inter-day precision were carried out by relative standard deviation ranging from 2.2 to 9.2%. Finally, the applicability of this method was assessed by the analysis of Curcumae Longae Rhizoma and turmeric tea samples. The results showed that these samples were detected successfully and the spiked recoveries over the range of 85.3-108.9% with relative standard deviations of 1.6-8.9% were attained, indicating its high relative recoveries with good precision in real sample analysis. 相似文献
103.
Tahereh Sadeghcheh Mohammad Saber Tehrani Hakim Faraji Parviz Aberoomand Azar Masoumeh Helalizadeh 《Journal of separation science》2022,45(7):1362-1373
A sensitive method based on liquid chromatography combined with a diode array detector was developed and validated to simultaneously determine tamoxifen, and its active metabolites N-desmethyltamoxifen, 4-hydroxytamoxifen, and endoxifen in human plasma samples. The green and sustainable vortex-assisted dispersive liquid-phase microextraction technique based on the natural hydrophobic deep eutectic solvent was used for the extraction and preconcentration of the analytes. Chemometrics and multivariate analysis were used to optimize the independent variables including the type and volume of deep eutectic solvent, extraction time, and ionic strength. Under optimal conditions, calibration curves were linear in a suitable range with the lower limits of quantification (0.8–10.0 μg/L), which covered the relevant concentrations of the analytes in plasma samples for a clinical study. Intra- and interday precision evaluated at three concentrations for the analytes were lower than 8.2 and 12.1%, respectively. Accuracy was in the range of 94.9–104.7%. The applicability of the developed method on human plasma samples illustrated the range 45.1–72.8, 98.4–128.3, 0.9–1.2, and 2.7–6.1 μg/L for tamoxifen, N-desmethyltamoxifen, 4-hydroxytamoxifen, and endoxifen, respectively. The validated method can be effective for the pharmacokinetics, pharmacodynamics, and therapeutic drug monitoring studies of tamoxifen and its main metabolites in biological fluids. 相似文献
104.
Single-drop microextraction (SDME) has been recognized as one of the simple miniaturized sample preparation tools for the isolation and preconcentration of several analytes from a complex sample matrix. In this review, we explored the applications of SDME coupled with various analytical techniques (spectroscopy, chromatography, and mass spectrometry) for the analysis of organic molecules, inorganic ions, and biomolecules from various sample matrices including food, environmental, clinical, pharmaceutical, and industrial samples. Also, it summarizes the use of nanoparticles in SDME combined with various analytical tools for the rapid analysis of several trace-level target analytes. An overview of ionic liquids, deep eutectic solvents, and SUPRAS, which improved the selectivity and sensitivity of various analytical techniques toward several analytes, as promising extracting solvent systems in SDME is also included. Finally, discussed the impressive analytical features and future perspectives of SDME in this review article. 相似文献
105.
Natali Rianika Mustafa Vincent Simon Spelbos Geert-Jan Witkamp Robert Verpoorte Young Hae Choi 《Molecules (Basel, Switzerland)》2021,26(9)
Some medicines are poorly soluble in water. For tube feeding and parenteral administration, liquid formulations are required. The discovery of natural deep eutectic solvents (NADES) opened the way to potential applications for liquid drug formulations. NADES consists of a mixture of two or more simple natural products such as sugars, amino acids, organic acids, choline/betaine, and poly-alcohols in certain molar ratios. A series of NADES with a water content of 0–30% (w/w) was screened for the ability to solubilize (in a stable way) some poorly water-soluble pharmaceuticals at a concentration of 5 mg/mL. The results showed that NADES selectively dissolved the tested drugs. Some mixtures of choline-based NADES, acid-neutral or sugars-based NADES could dissolve chloral hydrate (dissociated in water), ranitidine·HCl (polymorphism), and methylphenidate (water insoluble), at a concentration of up to 250 mg/mL, the highest concentration tested. Whereas a mixture of lactic-acid–propyleneglycol could dissolve spironolacton and trimethoprim at a concentration up to 50 and 100 mg/mL, respectively. The results showed that NADES are promising solvents for formulation of poorly water-soluble medicines for the development of parenteral and tube feeding administration of non-water-soluble medicines. The chemical stability and bioavailability of these drug in NADES needs further studies. 相似文献
106.
Andr Delavault Katarina Ochs Olga Gorte Christoph Syldatk Erwann Durand Katrin Ochsenreither 《Molecules (Basel, Switzerland)》2021,26(2)
Glycolipids are non-ionic surfactants occurring in numerous products of daily life. Due to their surface-activity, emulsifying properties, and foaming abilities, they can be applied in food, cosmetics, and pharmaceuticals. Enzymatic synthesis of glycolipids based on carbohydrates and free fatty acids or esters is often catalyzed using certain acyltransferases in reaction media of low water activity, e.g., organic solvents or notably Deep Eutectic Systems (DESs). Existing reports describing integrated processes for glycolipid production from renewables use many reaction steps, therefore this study aims at simplifying the procedure. By using microwave dielectric heating, DESs preparation was first accelerated considerably. A comparative study revealed a preparation time on average 16-fold faster than the conventional heating method in an incubator. Furthermore, lipids from robust oleaginous yeast biomass were successfully extracted up to 70% without using the pre-treatment method for cell disruption, limiting logically the energy input necessary for such process. Acidified DESs consisting of either xylitol or sorbitol and choline chloride mediated the one-pot process, allowing subsequent conversion of the lipids into mono-acylated palmitate, oleate, linoleate, and stearate sugar alcohol esters. Thus, we show strong evidence that addition of immobilized Candida antarctica Lipase B (Novozym 435®), in acidified DES mixture, enables a simplified and fast glycolipid synthesis using directly oleaginous yeast biomass. 相似文献
107.
Zongbo Xie Hongxia Li Bo Wang Zhiwen Wu Zhanggao Le 《Journal of heterocyclic chemistry》2021,58(8):1588-1593
A method for introducing a biologically active heterocycle, 2-methylquinoline into the 4-position of a 2-amino-4H-1-benzopyran skeleton is described. Choline chloride/glucose (1:1 molar ratio) was used as both the solvent and catalyst in the reaction of a salicylaldehyde, methylquinoline, and cyanoacetate to obtain 2-amino-4H-1-benzopyran derivatives in 48%–80% yields after short reaction times. The effects of the deep eutectic solvent type, substrate molar ratio, cosolvent, temperature, and reaction time were examined. The method has the advantages of simple steps, environmental friendliness, mild conditions, and wide substrate applicability. This is the first attempt to synthesize methylquinoline derivatives of 4H-1-benzopyran. 相似文献
108.
Ratan Kotipalli Bart Vermang Viktor Fjällström Marika Edoff Romain Delamare Denis Flandre 《固体物理学:研究快报》2015,9(3):157-160
The benefits of gallium (Ga) grading on Cu(In,Ga)Se2 (CIGS) solar cell performance are demonstrated by comparing with ungraded CIGS cells. Using drive‐level capacitance profiling (DLCP) and admittance spectroscopy (AS) analyses, we show the influence of Ga grading on the spatial variation of deep defects, free‐carrier densities in the CIGS absorber, and their impact on the cell's open‐circuit voltage Voc. The parameter most constraining the cell's Voc is found to be the deep‐defect density close to the space charge region (SCR). In ungraded devices, high deep‐defect concentrations (4.2 × 1016cm–3) were observed near the SCR, offering a source for Shockley–Read–Hall recombination, reducing the cell's Voc. In graded devices, the deep‐defect densities near the SCR decreased by one order of magnitude (2.5 × 1015 cm–3) for back surface graded devices, and almost two orders of magnitude (8.6 × 1014 cm–3) for double surface graded devices, enhancing the cell's Voc. In compositionally graded devices, the free‐carrier density in the absorber's bulk decreased in tandem with the ratio of gallium to gallium plus indium ratio GGI = Ga/(Ga + In), increasing the activation energy, hindering the ionization of the defect states at room temperature and enhancing their role as recombination centers within the energy band. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim) 相似文献
109.
Functionalized Graphene as a Gatekeeper for Chiral Molecules: An Alternative Concept for Chiral Separation
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Andreas W. Hauser Narbe Mardirossian Julien A. Panetier Martin Head‐Gordon Alexis T. Bell Peter Schwerdtfeger 《Angewandte Chemie (International ed. in English)》2014,53(37):9957-9960
We propose a new method of chiral separation using functionalized nanoporous graphene as an example. Computational simulations based on density functional theory show that the attachment of a suitable chiral “bouncer” molecule to the pore rim prevents the passage of the undesired enantiomer while letting its mirror image through. 相似文献
110.
Polydimethylsiloxane: A General Matrix for High‐Performance Chromatographic NMR Spectroscopy
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Shaohua Huang Dr. Jun Gao Rui Wu Prof. Dr. Shengying Li Prof. Dr. Zhengwu Bai 《Angewandte Chemie (International ed. in English)》2014,53(43):11592-11595
The detection and structural characterization of the components of a mixture is a challenging task. Therefore, the development of a facile and general method that enables both the separation and the structural characterization of the components is desired. Diffusion‐ordered NMR spectroscopy (DOSY) with the aid of a matrix is a promising tool for this purpose. However, because the currently existing matrices only separate limited components, the application of the DOSY technique is restricted. Herein we introduce a new versatile matrix, poly(dimethylsiloxane), which can fully separate many mixtures of different structural types by liquid‐state NMR spectroscopy. With poly(dimethylsiloxane), liquid‐state chromatographic NMR spectroscopy could become a general approach for the structural elucidation of mixtures of compounds. 相似文献