全文获取类型
收费全文 | 1584篇 |
免费 | 96篇 |
国内免费 | 2篇 |
专业分类
化学 | 1141篇 |
晶体学 | 8篇 |
力学 | 52篇 |
数学 | 201篇 |
物理学 | 280篇 |
出版年
2024年 | 2篇 |
2023年 | 24篇 |
2022年 | 22篇 |
2021年 | 31篇 |
2020年 | 69篇 |
2019年 | 54篇 |
2018年 | 44篇 |
2017年 | 33篇 |
2016年 | 76篇 |
2015年 | 75篇 |
2014年 | 68篇 |
2013年 | 98篇 |
2012年 | 124篇 |
2011年 | 150篇 |
2010年 | 88篇 |
2009年 | 58篇 |
2008年 | 97篇 |
2007年 | 80篇 |
2006年 | 71篇 |
2005年 | 73篇 |
2004年 | 60篇 |
2003年 | 65篇 |
2002年 | 49篇 |
2001年 | 19篇 |
2000年 | 17篇 |
1999年 | 15篇 |
1998年 | 7篇 |
1997年 | 6篇 |
1996年 | 8篇 |
1995年 | 3篇 |
1994年 | 9篇 |
1993年 | 6篇 |
1992年 | 3篇 |
1991年 | 7篇 |
1990年 | 5篇 |
1989年 | 3篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1986年 | 6篇 |
1985年 | 7篇 |
1984年 | 4篇 |
1983年 | 4篇 |
1982年 | 3篇 |
1981年 | 8篇 |
1980年 | 4篇 |
1979年 | 3篇 |
1978年 | 4篇 |
1977年 | 3篇 |
1976年 | 3篇 |
1975年 | 5篇 |
排序方式: 共有1682条查询结果,搜索用时 0 毫秒
51.
Luis F. F. F. Gonçalves Carlos J. R. Silva Fehmida K. Kanodarwala John A. Stride Maria J. M. Gomes 《Journal of Sol-Gel Science and Technology》2014,71(1):69-78
This paper describes the synthesis and characterization of CdS nanoparticles (NPs) stabilized with poly(N-vinyl-2-pyrrolidone) and their further immobilization on a hybrid organic–inorganic matrix produced by the sol–gel process. The production of the hybrid matrix doped with CdS NPs was carried out in two steps. In the first step a precursor, designated diureasil precursor, was synthesized from the reaction between the terminal amine groups of α,ω-diamine-poly(oxyethylene-co-oxypropylene) and the isocyanate group of 3-isocyanatopropyltriethoxysilane. The next step involved the hydrolysis and condensation reactions of ethoxy groups attached to silicon, this step resulting in the formation of a crosslinked siliceous network linked through urea bonds to a poly(oxyethylene)/poly(oxypropylene) chain. The NPs were added to the diureasil precursor before the gelation process to allow a homogeneous dispersion of the NPs within the matrix. The developed method allowed the transfer of colloidal NPs to a solid matrix without the need of exchange the capping agents or the solvent. The materials were characterized by absorption, steady-state photoluminescence spectroscopy and by TEM. The results obtained showed the presence of CdS NPs with quantum size effect dispersed within the diureasil matrix. The obtained nanocomposites show a high transparency in the visible range accounting for the good dispersion of the NPs within the matrix. The TEM analysis confirmed that the NPs are uniformly dispersed within the diureasil matrix. 相似文献
52.
dos Santos Poli Anne Karoline Hilário Rodrigo Barbosa Gama Adriana Medeiros Baldan Mauricio Ribeiro Gonçalves Emerson Sarmento 《Journal of Solid State Electrochemistry》2019,23(1):33-52
Journal of Solid State Electrochemistry - Polyaniline was electrosynthesized using three voltammetric cycles on carbon fiber felts annealed at 1400, 1600, 2000, and 2300 K. Felts and... 相似文献
53.
Dimerization of Colloidal Particles through Controlled Aggregation for Enhanced Properties and Applications 下载免费PDF全文
Devising syntheses capable of precisely manipulating matter on the nanoscale is central to many areas of research. The underlying motivation is fueled by the fact that at the nanometer scale, the property has a strong correlation with the structure. One such nanostructure that has accrued much attention is the dimer—a structure composed of two colloidal particles separated by a small gap. This Focus Review discusses how colloidal stability can be strategically manipulated to induce dimerization, together with effective purification steps to further improve yields. We conclude the article by providing representative examples for how dimers composed of plasmonic nanoparticles leads to structures with tunable optical properties and strong electric near‐fields, ideal for application in surface‐enhanced Raman spectroscopy. 相似文献
54.
55.
André Coutinho Vieira Mariane Gonçalves Santos 《International journal of environmental analytical chemistry》2017,97(1):29-41
Triazole fungicides are pesticides widely employed in the cultivation of fruits, vegetables and grains. However, their ability to change the steroid hormone biosynthesis may result in endocrine complications for mammals, as well as changes in cholesterol and triglyceride levels and hepatotoxicity. The analysis of the triazole fungicides in superficial waters is important in order to monitor the risk for the biota. However, the use of efficient extraction procedures has been necessary in order to concentrate these pesticides before the analysis. In-disk solid-phase extraction (SPE) can be highlighted as a potential pre-concentration technique, mainly because the possibility to extract the analytes from a large sample volume, increasing the method detectability. Carbon nanotubes (CNTs) have been often used as solid extraction phase due to their high sorption capacity, surface area and internal volume, as well as mechanical, chemical and thermal stability. In this paper, we proposed the preparation of a new SPE disk impregnated with CNTs for the extraction of triazole fungicides from environmental water samples. The disks were obtained by acid corrosion of a cellulose membrane followed by its impregnation with CNTs. The developed method was validated for the analysis of triadimenol, tebuconazole and epoxiconazole, according to international validation protocols. The limits of quantification obtained for triadimenol, tebuconazole and epoxiconazole were 0.1, 0.1 and 0.05 µg L?1, respectively. The linearity ranged from 0.05 to 10.00 µg L?1 for epoxiconazole and from 0.1 to 10.00 µg L?1 for triadimenol and tebuconazole, with correlation coefficients higher than 0.999 for all of them. The precisions, expressed as relative standard deviation, were lower than 12%. The accuracies were within ?12.07% to 17.7% (expressed as relative error). 相似文献
56.
Rafael Dias do Espírito Santo Rosineide Costa Simas Alviclér Magalhães Vanessa Gonçalves dos Santos Thais Regiani Ana Cristina Isler Natiza Graziele Martins Marcos Nogueira Eberlin Eduardo René Pérez González 《Journal of Physical Organic Chemistry》2013,26(4):315-321
Molecules containing the guanidinic nuclei possess several pharmacological applications, and knowing the preferred isomers of a potential drug is important to understand the way it operates pharmacologically. Benzoylguanidines were synthesized in satisfactory to good yields and characterized by NMR, Electrospray Ionization Mass Spectrometry (ESI‐MS) and Fourrier Transform InfraRed Spectroscopy techniques (FTIR). E/Z isomerism of the guanidines was studied and confirmed by NMR analysis in solution (1H‐13C Heteronuclear Single Quantum Coherence (HSQC) and Heteronuclear Multiple‐Bond Correlation (HMBC), 1H‐15N HMBC, 1H‐1H Correlation Spectroscopy (COSY) and Nuclear Overhauser Effect Spectroscopy (NOESY) experiments) at low temperatures. Compounds with p‐Cl and p‐Br aniline moiety exist mainly as Z isomer with a small proportion of E isomer, whereas compounds with p‐NO2 moiety showed a decrease in proportion of isomer Z. The results are important for the application of these molecules as enzymatic inhibitors. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
57.
The 2,5-diketopiperazine (DKP) moiety is a core feature of many natural products and medicinally relevant scaffolds. As part of our efforts directed towards a total synthesis of penicisulfuranol B, we have developed and report herein: (1) the preparation of an N-hydroxy diketopiperazine intermediate accessible via a molybdenum-mediated oxidation of a parent diketopiperazine, and (2) further synthetic studies leading to a novel spirocyclic dihydrobenzofuran-containing diketopiperazine. 相似文献
58.
Apeng Chen Joann J. Lu Congying Gu Min Zhang Kyle B. Lynch Shaorong Liu 《Analytica chimica acta》2015
Toward developing a micro HPLC cartridge, we have recently built a high-pressure electroosmotic pump (EOP). However, we do not recommend people to use this pump to deliver an organic solvent directly, because it often makes the pump rate unstable. We have experimented several approaches to address this issue, but none of them are satisfactory. Here, we develop an innovative approach to address this issue. We first create an abruption (a dead-volume) within a fluid conduit. We then utilize an EOP to withdraw, via a selection valve, a train of eluent solutions having decreasing eluting power into the fluid conduit. When these solutions are further aspirated through the dead-volume, these solutions are partially mixed, smoothening concentration transitions between two adjacent eluent solutions. As these solutions are pushed back, through the dead-volume again, a smooth gradient profile is formed. In this work, we characterize this scheme for gradient formation, and we incorporate this approach with a high-pressure EOP, a nanoliter injection valve, and a capillary column, yielding a micro HPLC system. We then couple this micro HPLC with an electrospray ionization – mass spectrometer for peptide and protein separations and identifications. 相似文献
59.
Rapid and sensitive ultra‐high‐pressure liquid chromatography method for quantification of antichagasic benznidazole in plasma: application in a preclinical pharmacokinetic study 下载免费PDF全文
Marcelo Gomes Davanço Michel Leandro de Campos Rosângela Gonçalves Peccinini 《Biomedical chromatography : BMC》2015,29(7):1008-1015
Benznidazole (BNZ) and nifurtimox are the only drugs available for treating Chagas disease. In this work, we validated a bioanalytical method for the quantification of BNZ in plasma aimed at improving sensitivity and time of analysis compared with the assays already published. Furthermore, we demonstrated the application of the method in a preclinical pharmacokinetic study after administration of a single oral dose of BNZ in Wistar rats. A Waters® Acquity UHPLC system equipped with a UV–vis detector was employed. The method was established using an Acquity® UHPLC HSS SB C18 protected by an Acquity® UHPLC HSS SB C18 VanGuard guard column and detection at 324 nm. The mobile phase consisted of ultrapure water–acetonitrile (65:35), and elution was isocratic. The mobile phase flow rate was 0.55 mL/min, the volume of injection was 1 μL, and the run time was just 2 min. The samples were kept at 25°C until injection and the column at 45°C for the chromatographic separation. The sample preparation was performed by a rapid protein precipitation with acetonitrile. The linear concentration range was 0.15–20 µg/mL. The pharmacokinetic parameters of BNZ in rats were determined and the method was considered sensitive, fast and suitable for application in pharmacokinetic studies. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
60.
Young Jin Sa Chiyoung Park Hu Young Jeong Seok‐Hee Park Zonghoon Lee Kyoung Taek Kim Gu‐Gon Park Sang Hoon Joo 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(16):4186-4190
A facile, scalable route to new nanocomposites that are based on carbon nanotubes/heteroatom‐doped carbon (CNT/HDC) core–sheath nanostructures is reported. These nanostructures were prepared by the adsorption of heteroatom‐containing ionic liquids on the walls of CNTs, followed by carbonization. The design of the CNT/HDC composite allows for combining the electrical conductivity of the CNTs with the catalytic activity of the heteroatom‐containing HDC sheath layers. The CNT/HDC nanostructures are highly active electrocatalysts for the oxygen reduction reaction and displayed one of the best performances among heteroatom‐doped nanocarbon catalysts in terms of half‐wave potential and kinetic current density. The four‐electron selectivity and the exchange current density of the CNT/HDC nanostructures are comparable with those of a Pt/C catalyst, and the CNT/HDC composites were superior to Pt/C in terms of long‐term durability and poison tolerance. Furthermore, an alkaline fuel cell that employs a CNT/HDC nanostructure as the cathode catalyst shows very high current and power densities, which sheds light on the practical applicability of these new nanocomposites. 相似文献