全文获取类型
收费全文 | 9783篇 |
免费 | 262篇 |
国内免费 | 20篇 |
专业分类
化学 | 5789篇 |
晶体学 | 162篇 |
力学 | 270篇 |
数学 | 735篇 |
物理学 | 3109篇 |
出版年
2023年 | 92篇 |
2022年 | 171篇 |
2021年 | 162篇 |
2020年 | 178篇 |
2019年 | 242篇 |
2018年 | 208篇 |
2017年 | 232篇 |
2016年 | 318篇 |
2015年 | 212篇 |
2014年 | 401篇 |
2013年 | 781篇 |
2012年 | 551篇 |
2011年 | 655篇 |
2010年 | 420篇 |
2009年 | 405篇 |
2008年 | 460篇 |
2007年 | 440篇 |
2006年 | 335篇 |
2005年 | 281篇 |
2004年 | 231篇 |
2003年 | 163篇 |
2002年 | 183篇 |
2001年 | 117篇 |
2000年 | 125篇 |
1999年 | 86篇 |
1998年 | 56篇 |
1997年 | 56篇 |
1996年 | 92篇 |
1995年 | 104篇 |
1994年 | 98篇 |
1993年 | 92篇 |
1992年 | 120篇 |
1991年 | 86篇 |
1990年 | 79篇 |
1989年 | 94篇 |
1988年 | 87篇 |
1987年 | 90篇 |
1986年 | 74篇 |
1985年 | 104篇 |
1984年 | 119篇 |
1983年 | 82篇 |
1982年 | 98篇 |
1981年 | 97篇 |
1980年 | 102篇 |
1979年 | 90篇 |
1978年 | 102篇 |
1977年 | 84篇 |
1976年 | 56篇 |
1975年 | 61篇 |
1974年 | 74篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Om Prakash Shiv Kumar Pushkar Singh Volker Deckert S. Chatterjee A.K. Ghosh Ranjan K. Singh 《Journal of Raman spectroscopy : JRS》2016,47(7):813-818
Interest in the synthesis of hybrid substrates for surface‐enhanced Raman scattering (SERS) has surged recently. Hereof, in the present work, a hybrid SERS substrate CuO : Mn/Ag heterojunction has been synthesised. To accomplish this, the nanostructred Ag island film and CuO : Mn nanoparticles are synthesised by vacuum thermal evaporation method and sol–gel method respectively, and thereafter, a heterojunction between the CuO : Mn and Ag is fabricated by adsorption of CuO : Mn (10‐3 m in ethanol) on Ag island film. Further, the SERS sensitivity of CuO : Mn/Ag heterojunctions has been studied by probing methyl orange. We observed that with Mn‐doping in the lattice of CuO, the SERS signal is enhanced considerably because of ferromagnetic ordering in CuO : Mn. DFT/B3LYP/6‐311 G(d, p) method is used to calculate the energy of HOMO and LUMO level of methyl orange. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
992.
An atom economic and facile synthesis of novel dispiro–oxindole–pyrrolidines has been achieved via a three‐component tandem cycloaddition of azomethine ylide generated in situ from isatin and sarcosine by decarboxylative condensation with N‐aryl‐3‐benzylidene‐pyrrolidine‐2,5‐dione derivatives as dipolarophiles. The salient features of synthetic procedure are characterized by the mild reaction conditions, high yields, high regioselectivity and stereoselectivity, one‐pot procedure, and operational simplicity. This regioselectivity was assumed to be under the influence of π–π stacking interactions between the aromatic rings of azomethine ylide and N‐aryl‐3‐benzylidene‐pyrrolidine‐2,5‐diones that further control the exo–endo selectivity of the reaction 1,3‐dipolar cycloaddition. The regiochemistry and structures of the cycloadducts were determined with spectroscopic data. 相似文献
993.
Effect of microhydration on the atmospherically important metastable carbonyl sulfide anion: Structure,energetic, and infrared study
下载免费PDF全文
![点击此处可从《International journal of quantum chemistry》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Saptarsi Mondal Avula Uday Teja Prashant Chandra Singh 《International journal of quantum chemistry》2015,115(12):785-795
Structure, energetics, and vibrational frequency of the microhydrated carbonyl sulfide anion [OCS?? (H2O)n (n = 1–6)] have been explored by the systematic ab initio study to have a comprehensive understanding about the hydration‐induced stabilization phenomenon of OCS?. Water binds with the OCS? in single hydrogen‐bonded (SHB) or double hydrogen‐bonded (DHB) fashion with O? H S and O? H O contacts. Maximum five water molecules can stay in a cyclic water network of these hydrated clusters forming interwater hydrogen bonding (IHB) with each other and out of this, maximum of two water molecules can bind directly to the OCS? in (DHB) arrangement. The stabilization energy values of OCS?? (H2O)n depict that ion–water interaction is significant up to four water molecules and beyond that OCS? is stabilized by IHB between the water molecules. The CO stretching frequency of OCS? gets red shifted, whereas CS stretching frequency gets blue shifted on hydration. Charge analysis of hydrated clusters of OCS? indicates that negative charge moves toward oxygen from sulfur on hydration. © 2015 Wiley Periodicals, Inc. 相似文献
994.
Hydroxylation of the silica in microfabricated thin layer chromatography plates as probed by time‐of‐flight secondary ion mass spectrometry and diffuse reflectance infrared Fourier transform spectroscopy
下载免费PDF全文
![点击此处可从《Surface and interface analysis : SIA》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Supriya S. Kanyal Bhupinder Singh Cody V. Cushman Daniel T. Jankowski Matthew R. Linford 《Surface and interface analysis : SIA》2015,47(3):340-344
Microfabricated silica thin layer chromatography (TLC) plates have previously been prepared on patterned carbon nanotube forests. The high temperatures used in their fabrication reduce the number of hydroxyl groups on their surfaces. Fortunately, silica can be rehydroxylated. In diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), a silanol peak below 3740 cm?1 indicates a well‐hydroxylated silica surface that is fit for chromatography. Hydroxylations of our materials with HF are so effective that it is not possible to discern the position of this peak. In contrast, this signal is discernable when the plates are treated with NH4OH. To find a more convenient method for studying the surfaces of TLC plates, time‐of‐flight secondary ion mass spectroscopy (ToF‐SIMS) was considered. ToF‐SIMS is advantageous because multiple microfabricated TLC plates must be scraped to obtain enough silica for one DRIFT analysis, while static SIMS can be performed on very small regions (500 × 500 µm2 or less) of individual plates. Ratios of the SiOH+ and Si+ ToF‐SIMS signals for microfabricated TLC plates correlated well with ~3740 cm?1 silanol peaks from DRIFT. Thus, SIMS allows direct analysis of all of our treated and untreated plates, including those hydroxylated with HF. The best hydroxylation condition for HF, which was better than any studied for NH4OH, was around 150 ppm at room temperature. The best hydroxylation condition for NH4OH was 50 °C for 72 h. ToF‐SIMS versus DRIFT results of commercial TLC plates were also obtained and evaluated. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
995.
996.
Interaction potential models for bulk Zns,Zns nanoparticle,and Zns nanoparticle‐PMMA from first‐principles
下载免费PDF全文
![点击此处可从《Journal of computational chemistry》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Sadanandam Namsani Nisanth N. Nair Jayant K. Singh 《Journal of computational chemistry》2015,36(15):1176-1186
An ab initio derived transferable polarizable force‐field has been developed for Zinc sulphide (ZnS) nanoparticle (NP) and ZnS NP‐PMMA nanocomposite. The structure and elastic constants of bulk ZnS using the new force‐field are within a few percent of experimental observables. The new force‐field show remarkable ability to reproduce structures and nucleation energies of nanoclusters (Zn1S1‐Zn12S12) as validated with that of the density functional theory calculations. A qualitative agreement of the radial distribution functions of Zn? O, in a ZnS nanocluster‐PMMA system, obtained using molecular mechanics molecular dynamics (MD) and ab initio MD (AIMD) simulations indicates that the ZnS–PMMA interaction through Zn? O bonding is explained satisfactorily by our force‐field. © 2015 Wiley Periodicals, Inc. 相似文献
997.
998.
The influence of poly(methylmethacrylate-co-N-vinyl-2-pyrrolidone), P(MMA-co-VP), on corrosion of carbon steels(J55, N80, P110 SS and C110 steels) in 3.5 wt% NaCl solution saturated with CO2 was evaluated using static high pressure and high temperature(HPHT) autoclave. The surface was further evaluated by X-ray diffraction(XRD), scanning electron microscopy(SEM) and contact angle measurements. Quantum chemical calculations have been used to evaluate the structural, electronic and reactivity parameters of the inhibitor on the steels surface. SEM, XRD and contact angle measurement studies reveal that the surface of metals are quite unaffected after use of inhibitor in 3.5% NaCl solution saturated with CO2. 相似文献
999.
Kaur Jagjeet Dubey Vikas Parganiha Yogita Singh Deepti Suryanarayana N. S. 《Research on Chemical Intermediates》2015,41(6):3597-3621
Research on Chemical Intermediates - In this paper we review the luminescence properties of Pr3+-doped CaTiO3 phosphors, the different methods of sample preparation, and characterization of the... 相似文献
1000.
Combined Experimental and Computational Investigations of Rhodium‐Catalysed CH Functionalisation of Pyrazoles with Alkenes
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Andrés G. Algarra Prof. David L. Davies Dr. Qudsia Khamker Prof. Stuart A. Macgregor Dr. Claire L. McMullin Kuldip Singh Dr. Barbara Villa‐Marcos 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(7):3087-3096
Detailed experimental and computational studies have been carried out on the oxidative coupling of the alkenes C2H3Y (Y=CO2Me ( a ), Ph ( b ), C(O)Me ( c )) with 3‐aryl‐5‐R‐pyrazoles (R=Me ( 1 a ), Ph ( 1 b ), CF3 ( 1 c )) using a [Rh(MeCN)3Cp*][PF6]2/Cu(OAc)2 ? H2O catalyst system. In the reaction of methyl acrylate with 1 a , up to five products ( 2 aa – 6 aa ) were formed, including the trans monovinyl product, either complexed within a novel CuI dimer ( 2 aa ) or as the free species ( 3 aa ), and a divinyl species ( 6 aa ); both 3 aa and 6 aa underwent cyclisation by an aza‐Michael reaction to give fused heterocycles 4 aa and 5 aa , respectively. With styrene, only trans mono‐ and divinylation products were observed, whereas with methyl vinyl ketone, a stronger Michael acceptor, only cyclised oxidative coupling products were formed. Density functional theory calculations were performed to characterise the different migratory insertion and β‐H transfer steps implicated in the reactions of 1 a with methyl acrylate and styrene. The calculations showed a clear kinetic preference for 2,1‐insertion and the formation of trans vinyl products, consistent with the experimental results. 相似文献