全文获取类型
收费全文 | 4394篇 |
免费 | 116篇 |
国内免费 | 39篇 |
专业分类
化学 | 3029篇 |
晶体学 | 67篇 |
力学 | 86篇 |
数学 | 729篇 |
物理学 | 638篇 |
出版年
2021年 | 40篇 |
2020年 | 39篇 |
2019年 | 50篇 |
2018年 | 46篇 |
2017年 | 36篇 |
2016年 | 84篇 |
2015年 | 107篇 |
2014年 | 102篇 |
2013年 | 237篇 |
2012年 | 193篇 |
2011年 | 255篇 |
2010年 | 123篇 |
2009年 | 112篇 |
2008年 | 209篇 |
2007年 | 224篇 |
2006年 | 206篇 |
2005年 | 226篇 |
2004年 | 204篇 |
2003年 | 185篇 |
2002年 | 126篇 |
2001年 | 44篇 |
2000年 | 57篇 |
1999年 | 59篇 |
1998年 | 50篇 |
1997年 | 41篇 |
1996年 | 68篇 |
1995年 | 37篇 |
1994年 | 60篇 |
1993年 | 52篇 |
1992年 | 43篇 |
1991年 | 57篇 |
1990年 | 42篇 |
1989年 | 37篇 |
1988年 | 45篇 |
1987年 | 44篇 |
1986年 | 44篇 |
1985年 | 65篇 |
1984年 | 68篇 |
1983年 | 46篇 |
1982年 | 55篇 |
1981年 | 53篇 |
1980年 | 38篇 |
1979年 | 67篇 |
1978年 | 60篇 |
1977年 | 67篇 |
1976年 | 43篇 |
1975年 | 49篇 |
1974年 | 46篇 |
1973年 | 37篇 |
1972年 | 36篇 |
排序方式: 共有4549条查询结果,搜索用时 140 毫秒
81.
A one-pot synthesis of substituted imidazoles is described. The cornerstone of this methodology involves the thiazolium-catalyzed addition of an aldehyde to an acyl imine to generate the corresponding alpha-ketoamide in situ followed by ring closure to the imidazole in a one-pot sequence. The extension of this methodology to the one-pot synthesis of substituted oxazoles and thiazoles is also described. [reaction: see text] 相似文献
82.
Rudolph Willem Ann Delmotte Inge De Borger Monique Biesemans Marcel Gielen Franois Kayser Edward R. T. Tiekink 《Journal of organometallic chemistry》1994,480(1-2):255-259
The synthesis of (Z)-2-methyl-3-triphenylstannyl-3-pentene-2-ol and its characterization by an X-ray diffraction study and multinuclear NMR are reported. The tin atom exhibits a distorted tetrahedral SnC4 geometry with the four Sn---C bond distances experimentally equivalent. The slight distortion from the ideal tetrahedral geometry is because of the presence of a weak intramolecular HO → Sn interaction of 3.012(3) Å which produces a loose four-membered ring. The title compound was characterized in solution by 1H, 13C and 119Sn NMR, and the persistence of the weak intramolecular HO → Sn coordination in solution was revealed by 13C and 119Sn secondary isotope multiplet of partially labelled entities (SIMPLE-NMR) experiments. 相似文献
83.
The hierarchic organization of cellulose fibrils (microfibrils) was investigated in holocellulose, sulphite pulp and kraft pulp using TEM, XRD, ED and FTIR. There were remarkable differences in both the fibril structure and fibril aggregation between the samples. TEM observations revealed more intimately associated fibrils in the kraft pulp compared to the sulphite pulp and the holocellulose, results in agreement with previous CP/MAS 13C-NMR data [Hult E.-L. et al. (2002) Holzforschung 56: 231–234]. Furthermore, the cellulose crystallinity was higher in the kraft pulp sample. With respect to the cellulose I and I allomorphs, these samples were controversial when different analytical techniques were applied. Due to the small fibril size and the low degree of order of cellulose in these samples, the concept of crystalline triclinic and monoclinic components as determined by diffraction analysis may not be adequate. Instead the fibril can be regarded to have different degrees of lateral order (including paracrystalline ordering) that can be reoriented to I type conformation and packing upon pulping. 相似文献
84.
John M. Kane Christopher R. Dalton Michael A. Staeger Edward W. Huber 《Journal of heterocyclic chemistry》1995,32(1):183-187
Several 1,2,4-triazole derivatives containing a 2-fluorophenyl substituent at either the 3- or 5-position and a methyl group at the 4-position were synthesized. These derivatives exhibit long-range 19F-1H and 19F-13C through-space coupling in their 1H and 13C nmr spectra between the fluorine and the 4-methyl group. The close spatial proximity of these nuclei was confirmed by X-ray analysis and by fluorine irradiated proton observe ({19F}-1H) NOE difference spectroscopy. 相似文献
85.
Edward V. Thompson 《Journal of Polymer Science.Polymer Physics》1966,4(2):199-208
The preparation of five samples of poly(methyl methacrylate) covering a wide range of tacticity and their electron irradiation to produce series of varying molecular weight are described. The glass transition temperature Tg of each polymer was determined by DTA techniques. Plots of Tg and the reciprocal of the molecular weight are well fitted in every case by a straight line. The data are also fitted to the Gibbs-DiMarzio theory and the values of the energy and free-volume parameters obtained are discussed. A method of estimating Tg of pure syndiotactic poly(methyl methacrylate) by extrapolation is presented, the value obtained being 160°C. 相似文献
86.
Quintanar L Yoon J Aznar CP Palmer AE Andersson KK Britt RD Solomon EI 《Journal of the American Chemical Society》2005,127(40):13832-13845
87.
Water-soluble cobalt porphyrin 1Co and imidazole ligand 2 were synthesized. 1Co binds dioxygen in the presence of imidazole ligand 2 in aqueous solution. The formation of the oxygen adduct 2-1Co(O(2)) was studied using UV-vis and EPR spectroscopy. The impact of pH on the kinetic stability of the oxygen adduct was examined. 相似文献
88.
Ion chromatography was used to determine trace anionic contamination on the surface of hard disk drive components. These contaminants can have a detrimental effect on device reliability and yield. Disk drive components were soaked in deionized water and these extracts were analyzed for anions. The anions fluoride, acetate, formate, acrylate, methacrylate, chloride, nitrite, bromide, nitrate, benzoate, sulfate, oxalate, phthalate and phosphate were separated on a high-performance anion-exchange column and determined at concentrations less than 1 microg/l with suppressed conductivity detection. The extract solutions were analyzed either by injecting 1 ml or by preconcentrating 5 ml. We evaluated the performance of both methods. 相似文献
89.
Yongzheng Cong Khatereh Motamedchaboki Santosh A. Misal Yiran Liang Amanda J. Guise Thy Truong Romain Huguet Edward D. Plowey Ying Zhu Daniel Lopez-Ferrer Ryan T. Kelly 《Chemical science》2021,12(3):1001
We report on the combination of nanodroplet sample preparation, ultra-low-flow nanoLC, high-field asymmetric ion mobility spectrometry (FAIMS), and the latest-generation Orbitrap Eclipse Tribrid mass spectrometer for greatly improved single-cell proteome profiling. FAIMS effectively filtered out singly charged ions for more effective MS analysis of multiply charged peptides, resulting in an average of 1056 protein groups identified from single HeLa cells without MS1-level feature matching. This is 2.3 times more identifications than without FAIMS and a far greater level of proteome coverage for single mammalian cells than has been previously reported for a label-free study. Differential analysis of single microdissected motor neurons and interneurons from human spinal tissue indicated a similar level of proteome coverage, and the two subpopulations of cells were readily differentiated based on single-cell label-free quantification.The combination of nanodroplet sample preparation, ultra-low-flow nanoLC, high-field asymmetric ion mobility spectrometry (FAIMS) and latest-generation mass spectrometry instrumentation provides dramatically improved single-cell proteome profiling. 相似文献
90.
Carlo Bruno Eleonora Ussano Gianni Barucca Davide Vanossi Giovanni Valenti Edward A. Jackson Andrea Goldoni Lucio Litti Simona Fermani Luca Pasquali Moreno Meneghetti Claudio Fontanesi Lawrence T. Scott Francesco Paolucci Massimo Marcaccio 《Chemical science》2021,12(23):8048
The presence of non-hexagonal rings in the honeycomb carbon arrangement of graphene produces rippled graphene layers with valuable chemical and physical properties. In principle, a bottom-up approach to introducing distortion from planarity of a graphene sheet can be achieved by careful insertion of curved polyaromatic hydrocarbons during the growth of the lattice. Corannulene, the archetype of such non-planar polyaromatic hydrocarbons, can act as an ideal wrinkling motif in 2D carbon nanostructures. Herein we report an electrochemical bottom-up method to obtain egg-box shaped nanographene structures through a polycondensation of corannulene that produces a new conducting layered material. Characterization of this new polymeric material by electrochemistry, spectroscopy, electron microscopy (SEM and TEM), scanning probe microscopy, and laser desorption-ionization time of flight mass spectrometry provides strong evidence that the anodic polymerization of corannulene, combined with electrochemically induced oxidative cyclodehydrogenations (Scholl reactions), leads to polycorannulene with a wavy graphene-like structure.A bottom-up synthesis of wavy graphene structures obtained through an anodic polymerization process, combined with an electrochemically triggered oxidative cyclodehydrogenation, of the bowl-shaped polyaromatic hydrocarbon corannulene. 相似文献