全文获取类型
收费全文 | 277篇 |
免费 | 17篇 |
国内免费 | 36篇 |
专业分类
化学 | 305篇 |
晶体学 | 1篇 |
力学 | 2篇 |
综合类 | 7篇 |
数学 | 2篇 |
物理学 | 13篇 |
出版年
2024年 | 3篇 |
2023年 | 4篇 |
2022年 | 16篇 |
2021年 | 18篇 |
2020年 | 12篇 |
2019年 | 11篇 |
2018年 | 13篇 |
2017年 | 10篇 |
2016年 | 15篇 |
2015年 | 17篇 |
2014年 | 17篇 |
2013年 | 45篇 |
2012年 | 16篇 |
2011年 | 12篇 |
2010年 | 11篇 |
2009年 | 16篇 |
2008年 | 12篇 |
2007年 | 18篇 |
2006年 | 11篇 |
2005年 | 13篇 |
2004年 | 9篇 |
2003年 | 4篇 |
2002年 | 3篇 |
2001年 | 7篇 |
2000年 | 4篇 |
1999年 | 1篇 |
1998年 | 1篇 |
1996年 | 1篇 |
1994年 | 3篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1986年 | 1篇 |
1985年 | 1篇 |
排序方式: 共有330条查询结果,搜索用时 31 毫秒
1.
Field-effect transistors (FETs) are one of the most widely-used electronic sensors for continuous monitoring and detection of contaminants such as pharmaceuticals and endocrine-disrupting compounds at low concentrations. FETs have been successfully utilized for the rapid analysis of these environmental pollutants due to their advantageous material properties like the disposability, rapid responses and simplicity. This paper presented an up-to-date overview of applied strategies with different bio-based materials in order to enhance the analytical performances of the designed sensors. Comparison and discussion were made between characteristics of recently engineered FET bio-sensors used for the detection of famous and selected pharmaceutical compounds in the literature. The recent progress in environmental research applications, comments on interesting trends, current challenge for future research in endocrine-disrupting chemicals’ (EDCs) detection using FETs biosensors were highlighted. 相似文献
2.
Peter Esser Bettina Pohlmann Hans-Dieter Scharf 《Angewandte Chemie (International ed. in English)》1994,33(20):2009-2023
The light of the sun can be used directly for changing chemical structures photochemically. Any industrial application must conform to the limitations imposed by the spectral distribution of the photons from the sun, the interruptions to the radiation due to the day/night rhythm, and the weather. In this review, we describe the photochemical potential of the sun, give a fundamental treatment of the concept of photoreactors driven by sunlight (abbreviated to solar photoreactors), and give an account of the realization of this concept in the first pilot plant on the “Plataforma Solar de Almeria” in southern Spain and in other activities in this field. Based on experimental data from photochemical investigations on the pilot plant scale, possibilities, limitations, and the potential growth of solar photochemistry are described. Solar photochemistry, in our opinion, is a technique which could make a contribution to the chemistry of the future because of its photochemical synthesis potential, the avoidance of waste products, and the direct utilization of the sun, not only as a primary energy source, but also as a reaction partner. 相似文献
3.
4.
Certain contaminants at trace concentrations in surface waters can have dramatic effects on the hormonal system of organisms in the aquatic environment. Therefore, immunoanalytical methods at a very low limit of detection (LOD) and a low limit of quantification (LOQ) are becoming more and more important for environmental analysis and especially for monitoring drinking water quality. Environmental monitoring of antibiotics, hormones, endocrine disrupting chemicals, and pesticides in real water samples (e.g. surface, ground or drinking water) with difficult matrices places high demands on chemical analysis. Biosensors have suitable characteristics such as efficiency in allowing very fast, sensitive, and cost-effective detection. Here we describe an assay optimization process with a fully automated immunoassay for estrone which resulted in a LOD below 0.20 ng L−1 and a LOQ below 1.40 ng L−1. In contrast to common analytical methods such as GC-MS or HPLC-MS, the biosensor used requires no sample pre-treatment and pre-concentration. The very low validation parameters for estrone are the result of the continuous optimization of the immunoassay. The basis of our sensitive assay is the antibody with a high affinity constant towards estrone. During the optimization process, we reduced the amount of antibody per sample and improved the chip surface modification. Finally, this proceeding led to a calibration routine with an amount of antibody of only 3.0 ng per sample (sample volume: 1.0 mL). The reduction of the amount of antibody per sample results in better validation parameters (LOD, LOQ, and IC50), but this reduction leads to the current device-related limitation of the River Analyser (RIANA).For some endocrine disrupting compounds, no effect levels (NOELs) in the lower nanogram per liter range are reported. This defines the challenge, which analytical methods have to compete with and our RIANA instrument with its improved sensitivity for the detection of a single hormone in the lower nanogram per liter range is a powerful tool in aquatic analytics in addition to the common analytical methods. 相似文献
5.
6.
The efficient utilization of carbon dioxide (CO2) as a C1 feedstock is of great significance for green and sustainable development. Therefore, the efficient chemical conversion of CO2 into value-added products has recently attracted a lot of research attention in recent years. The transformation of CO2 generally requires high-energy substrates, specific catalysts, and harsh reaction conditions due to its high thermodynamic stability and kinetic inertness. Consequently, several efforts have been dedicated toward the development of high-performance catalysts and new reaction routes for CO2 conversion over the last few decades. To date, many routes of convert CO2 into value-added chemicals have been proposed, together with the development of heterogeneous and homogeneous catalysts. Among the advanced catalysts reported to date, ionic liquids (ILs) have been widely investigated and show great potential for the efficient, selective, and economical conversion of CO2 into highly valuable products under mild conditions, even under ambient conditions. Some task-specific ILs have been designed with unique functional groups (e.g., —OH, —SO3H, —NH2, —COOH, and —C≡N), which can act as the solvent, absorbent, activating agent, catalyst, or cocatalyst to realize the transformation of CO2 under metal-free and mild conditions. In addition, a variety of catalytic systems composed of ILs and metal catalysts have also been reported for the transformation of CO2, in which the combination of the IL and metal catalyst is responsible for CO2 conversion with high efficiency. In this review article, we summarize the recent advances in IL-mediated CO2 transformation into chemicals prepared via C—O, C—N, C—S, C—H, and C—C bond forming processes. ILs that can chemically capture CO2 with high capacity are first introduced, which can activate CO2 via the formation of IL-based carbonates or carbamates, thus realizing the transformation of CO2 under metal-free and mild conditions. Recent progress in IL-mediated CO2 transformations to form carbonates and various kinds of N- and S-containing compounds (e.g., oxazolidinones, ureas, benzimidazolones, formamides, methylamines, benzothiazoles, and other chemicals) as well as CO2 hydrogenation to give formic acid, methane, acetic acid, low-carbon alcohols, and hydrocarbons has been summarized in this review with a focus on the reaction routes, catalytic systems, and reaction mechanism. In these reactions, ILs can simultaneously activate the substrate via strong H-bonding in addition to activating CO2, and the cooperative effects among the ionic and molecular species and metal catalysts accomplish the reactions of CO2 with various kinds of substrates to afford a wide range of value-added chemicals. Finally, the shortcomings and perspectives of ILs are discussed. In short, IL-mediated CO2 transformations provide green and effective routes for the synthesis of high-value chemicals, which may have great potential for a wide range of applications. 相似文献
7.
Kenjiro Hattori Tomoko Takeuchi Mika Ogata Ayumi Takanohashi Katsuhiko Mikuni Katsuyoshi Nakanishi Hideo Imata 《Journal of inclusion phenomena and macrocyclic chemistry》2007,57(1-4):339-342
We obtained the association constants Ka of estrogen (E2) and environmental chemicals by the surface plasmon resonance (SPR) assay using the immobilized mono-6-O-α-maltosyl-β-CD (G2βCD) compared with the immobilized β-CD and the immobilized estrogen receptor (ER). The association behavior of G2βCD was shown as a ER model compound. The calibration curve was determined by the initial rate of association depending on
the various concentrations, and the minimum detectable concentrations in the order of parts per billion were calculated. The
SPR assay has advantages that the pre-treatment of the sample is not necessary and the immobilized ligand is stable and useful
for the repeated measurement. 相似文献
8.
Express detection of nonylphenol in water samples by fluorescence polarization immunoassay 总被引:6,自引:0,他引:6
Yakovleva JN Lobanova AY Shutaleva EA Kourkina MA Mart'ianov AA Zherdev AV Dzantiev BB Eremin SA 《Analytical and bioanalytical chemistry》2004,378(3):634-641
The development of express method for detection of endocrine-disrupting chemicals (EDC) such as alkylphenols is required for ecological monitoring. Several attempts have been made to produce antibodies against 4-nonylphenol (NP) in recent years. This work describes the production of new antibodies against NP and also summarizes the characterization of antibodies obtained earlier. Three approaches used to produce alkylphenol-specific antibodies are compared; these are based on: 1. omega-(4-hydroxyphenyl)nonanoic or omega-(4-hydroxyphenyl)heptanoic acid NP derivatives designed to mimic the linear NP isomer; 2. 4-aminophenol, which potentially mimics various substituted phenolic compounds with different side-chain structures at position 4 of the benzene ring; and 3. a mixture of branched NP isomers, conjugated to the carrier protein via a benzene ring by the Mannich reaction, and expected to be the closest mimic of NP structure by preserving its natural alkyl moiety.Fluorescence polarization immunoassays based on different combinations of antibody and labeled antigen for screening detection of NP were developed and structural aspects of assay sensitivity and specificity were investigated. The assays based on the antisera raised against omega-(4-hydroxyphenyl)nonanoic acid and NP conjugate via Mannich reaction are capable of express detection of NP with detection limit of 7 microg mL(-1 )and assay dynamic range of 18-300 microg mL(-1). 相似文献
9.
Determination of estrogenic steroids in surface water and wastewater by liquid chromatography-electrospray tandem mass spectrometry 总被引:1,自引:0,他引:1
An analytical method is presented which permits trace level determination of 17alpha-ethynylestradiol (EE2), 17beta-estradiol (E2), and estrone (E1). Using this method, the estrogenic steroids were analyzed in drinking water, surface water, and wastewater (sewage influents and effluents) at concentrations down to 0.1 ng/L. Sample volumes between 100 and 500 mL are concentrated using automated solid-phase extraction. Analysis is performed by liquid chromatography with detection by tandem mass spectrometry. Applying simple clean-up procedures and internal standard calibration, recovery losses resulting from matrix-dependent ion suppression during electrospray ionization could be compensated for all of the investigated compounds. Recoveries around 100% were obtained for all analytes after correction using the internal standards. Limits of quantification (LOQ) were between 0.1 and 0.4 ng/L for purified sewage, surface, ground, and drinking water and between 1 and 2 ng/L in the case of raw sewage. Water treatment by wastewater treatment plants (WWTPs) or by a surface water treatment plant affected the removal of all estrogenic steroids. Thus, E1, E2, and EE2 were removed in the municipal WWTPs to the extent of 93%, 93%, and 80%, respectively. In the effluents of the WWTP in Ruhleben (Berlin, Germany), E1, E2, and EE2 were detected at the low ng/L level. E2 and EE2 were, however, not present in the Berlin surface water above the LOQ (0.2 ng/L). E1 was the only compound that could be detected in surface water samples. After additional surface water treatment it was still detectable but only at trace-level concentrations with a mean value of 0.16 ng/L. 相似文献
10.
Paolo Davoli 《Tetrahedron》2005,61(18):4427-4436
The enantioselective total synthesis of the actin-targeting metabolite (−)-microcarpalide is described. Key steps include ring-closing metathesis (RCM) for the final construction of the 10-membered lactone framework and stereoselective homologation of boronic esters for the insertion of all stereocentres with the desired absolute configuration. In particular, the acidic fragment was prepared in seven steps from a suitable chiral bromomethane boronate by means of two sequential stereoselective homologations to install the two stereocentres with the correct final R stereochemistry, employing (−)-pinanediol as the chiral director. Subsequent elaboration to the required C7 backbone entailed nucleophilic displacement with a vinyl Grignard reagent, oxidative cleavage of the boronic scaffold and protection-deprotection manipulations. Interestingly, when the tribenzyloxy diene ester resulting from DCC-mediated coupling of the two key synthons was subjected to RCM in the presence of Grubbs' catalyst, the reaction proceeded stereoselectively to yield the desired trans oxecin-2-one, albeit with poor conversion. 相似文献