全文获取类型
收费全文 | 13562篇 |
免费 | 379篇 |
国内免费 | 46篇 |
专业分类
化学 | 10813篇 |
晶体学 | 75篇 |
力学 | 212篇 |
数学 | 1700篇 |
物理学 | 1187篇 |
出版年
2023年 | 108篇 |
2022年 | 451篇 |
2021年 | 518篇 |
2020年 | 291篇 |
2019年 | 335篇 |
2018年 | 257篇 |
2017年 | 214篇 |
2016年 | 437篇 |
2015年 | 451篇 |
2014年 | 423篇 |
2013年 | 847篇 |
2012年 | 872篇 |
2011年 | 988篇 |
2010年 | 599篇 |
2009年 | 587篇 |
2008年 | 835篇 |
2007年 | 806篇 |
2006年 | 691篇 |
2005年 | 627篇 |
2004年 | 532篇 |
2003年 | 444篇 |
2002年 | 436篇 |
2001年 | 163篇 |
2000年 | 132篇 |
1999年 | 111篇 |
1998年 | 114篇 |
1997年 | 99篇 |
1996年 | 127篇 |
1995年 | 88篇 |
1994年 | 86篇 |
1993年 | 77篇 |
1992年 | 61篇 |
1991年 | 76篇 |
1990年 | 54篇 |
1989年 | 72篇 |
1988年 | 62篇 |
1987年 | 49篇 |
1986年 | 52篇 |
1985年 | 63篇 |
1984年 | 82篇 |
1983年 | 45篇 |
1982年 | 67篇 |
1981年 | 58篇 |
1980年 | 55篇 |
1979年 | 47篇 |
1978年 | 54篇 |
1977年 | 38篇 |
1976年 | 32篇 |
1975年 | 24篇 |
1963年 | 20篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
941.
para‐Substituted with electron donating or electron withdrawing groups triphenyl trithioarsenites, (ArS)3As, and octasulfur in refluxing carbon disulfide or chloroform do not give the triaryl tetrathioarsenates, (ArS)3As=S, as was claimed in the literature for tris(4‐methylphenyl) tetrathioarsenate. In some cases oxidative decomposition to As2O3 and disulfides ArSSAr was found. When equivalent amounts of the same esters and octasulfur were heated at 105 or 150 °C no AsV compound was detected or isolated and again some esters decomposed to As2O3 and disulfides. These experiments demonstrated that the aromatic trithioarsenites do not react with octasulfur, probably because they cannot open the octasulfur ring. These esters in solution react with octasulfur in the presence of a catalytic (10—20 mol%) amount of triethylamine giving disulfides, As2O3 and colored solids which could not be characterized. 相似文献
942.
Eleonora Polo Simona Losio Gaetano Zecchi Fabio Bertini Maria Carmela Sacchi 《Macromolecular rapid communications》2004,25(21):1845-1850
Summary: Thanks to the use of a ligand consisting of a saturated ring fused to the cyclopentadienyl moiety, which sensibly increases the stability of titanocenes, it was possible to investigate the oscillating behavior of titanium catalysts in propylene polymerization for the first time. The titanium‐based catalysts yield poly(propylene)s with new and interesting microstructures. Indeed, in spite of the significantly lower isotactic pentad content [mmmm], the average lengths of the isotactic blocks (Niso) are similar or even higher than that obtained with the zirconium‐based homologues. Accordingly, differential scanning calorimetry (DSC) analysis shows melting peaks which are more evident than those obtained with the zirconium homologues. The study of the microstructure of the poly(propylene)s obtained with these catalysts allowed us to participate in the still open discussion on the oscillating mechanism of unbridged metallocenes.
943.
Alesso G Cinellu MA Stoccoro S Zucca A Minghetti G Manassero C Rizzato S Swang O Ghosh MK 《Dalton transactions (Cambridge, England : 2003)》2010,39(42):10293-10304
The first six-membered gold(III) N^C^N pincer complex was obtained in good yield, under very mild conditions, by transmetalation of [Hg(κC-N^C^N)Cl] (N^CH^N = 1,3-bis(pyridin-2-ylmethyl)benzene, HL(1)) with Na[AuCl(4)]. The X-ray crystal structure of [Au(N^C^N)Cl][PF(6)] showed that the fused six-membered metallacycles each exist in a strongly puckered boat conformation. As shown by the (1)H NMR spectra in various solvents, the same structure is also retained in solution: no inversion of the six-membered metallacycles is observed in DMSO up to 95 °C. This correlates well with a reaction barrier of 17.5 kcal/mole, as determined by quantum chemical calculations. The reactivity of the present pincer complex is compared to that of the analogous 1,3-bis(2-pyridyl)benzene, HL(2), derivative, which has five-membered fused metallacycles. Sharp differences are found in the reactions with phosphines, such as PPh(3) and dppe (1,2-bis-diphenylphosphino-ethane), and with silver salts. Theoretical calculations were carried out on the two pincer complexes in order to try to understand these differences, and we found that the gold-chlorine bond is significantly stronger in the case of the complex containing five-membered metallacyclic rings. 相似文献
944.
Dos Santos VA Dos Santos DP Castro-Gamboa I Zanoni MV Furlan M 《Molecules (Basel, Switzerland)》2010,15(10):6956-6973
This work describes the isolation of the secondary metabolites identified as the quinonemethides maytenin (1) and pristimerin (2) from Maytenus ilicifolia extracts obtained from root barks of adult plants and roots of seedlings and their quantification by high performance liquid chromatography coupled to a diode array detector. The electrochemical profiles obtained from cyclic voltammetry and a coulometric detector coupled to high-performance liquid chromatography contributed to the evaluation of their antioxidant capacity. The antioxidant properties of individual components and the crude extracts of the root barks of Maytenus ilicifolia were compared and the possible synergistic associations of quinonemethide triterpenes and phenolic substances were investigated by using rutin as a model phenolic compound. 相似文献
945.
Livraghi S Corazzari I Paganini MC Ceccone G Giamello E Fubini B Fenoglio I 《Chemical communications (Cambridge, England)》2010,46(44):8478-8480
A safe UV filter may be obtained by inhibiting the photo-generation of free radicals through modification of the surface of TiO(2) nanoparticles with carbon. 相似文献
946.
Tosi G Conti C Giorgini E Ferraris P Garavaglia MG Sabbatini S Staibano S Rubini C 《The Analyst》2010,135(12):3213-3219
Fourier transform infrared (FTIR) microspectroscopy has been employed to investigate benign (ordinary dermal and Reed nevi), dysplastic and malignant (invasive melanoma) skin lesions through the analysis of spectral changes of melanocytes as well as in the evaluation of the presence of melanin. Hierarchical cluster analysis and principal component analysis led to a satisfactory separation of malignant from dysplastic and normal melanocytes. Also, on enlarging the clustering with spectra from Reed and dermal nevi, the multivariate analysis segregated well the spectral data into discrete clusters, allowing the obtaining of reliable average spectra for analysis at the molecular level of the main groups or components responsible for the biological and biochemical changes. The most significant spectral characteristics appear to be related to differences in secondary protein structures, in nucleic acid conformation, in intra- and intermolecular bonding. In all cases, supervised and unsupervised spectral analyses resulted in satisfactory agreement with histopathological findings. 相似文献
947.
Zhang L D'Acunzi M Kappl M Imhof A van Blaaderen A Butt HJ Graf R Vollmer D 《Physical chemistry chemical physics : PCCP》2010,12(47):15392-15398
Heat treatment is a standard method to increase the hardness of silica in various applications. Here, we tested the effect of high temperature annealing on the mechanical properties of silica microcapsules by force spectroscopy under point loads applied to the particle shell. The Young's modulus of the shells moderately increases after annealing at temperatures above 500 °C. Temperatures over 850 °C result in a much stronger increase and the Young's modulus is close to that of fused silica after annealing at 1100 °C. NMR analysis revealed that in untreated microcapsules synthesized by seeded growth using the St?ber method only 55% of the silicon atoms form siloxane bonds with four neighbors, whereas the remaining ones only form three or less siloxane bonds each and, thus, a large number of ethoxy and silanol groups still exist. During annealing at 500 °C, these are successively transformed into siloxane bonds through condensation reactions. This process correlates with only a moderate increase in Young's modulus. The strong increase at temperatures above 850 °C was associated with a densification which was associated by a decrease in capsule size and shell thickness while the shells remained homogenous and of spherical shape. The main strengthening of the shells is thus mainly due to compaction by sintering at length scales significantly larger than that of local siloxane bonds. 相似文献
948.
Cantanhêde Silva W Guix M Alarcón Angeles G Merkoçi A 《Physical chemistry chemical physics : PCCP》2010,12(47):15505-15511
Control of molecular and supramolecular properties is used to obtain a new advanced hybrid material based on Prussian blue nanoparticles (PB NPs). This hybrid material is obtained through a self-assembled Layer-by-Layer (LbL) approach combining the advantageous features of β-cyclodextrin (β-CD) polysaccharides, PB NPs and poly(allylamine hydrochloride) from electrostatic interaction between the deposited layers. Transmission electronic microscopy images suggested that PB NPs were protected by β-CD polysaccharides that prevent the aggregation phenomena. In addition, as confirmed by scanning electronic microscopy images, it was found that PB NPs are organized in microcubic supramolecular like structures via a mesoscale self-assembly process. Interestingly, the 3-bilayer {PAH/PB-CD} film exhibited a higher density of microcubic structures and a high electrochemical response with PB sites available for redox reactions at a supramolecular level. By utilizing fewer bilayers and consequently less material deposition, the formed {PAH/PB-CD} multilayer films of a tuneable conductivity can be expected to have interesting future applications for host-guest like dependent electrochemical biosensing designs. 相似文献
949.
Soraa Bouattour Wannes Kallel Ana Maria Botelho do Rego L.F. Vieira Ferreira I. Ferreira Machado Sami Boufi 《应用有机金属化学》2010,24(10):692-699
This work reports on the synthesis of Li‐doped TiO2 nanoparticles using the sol–gel process and solid‐state sintering, and investigates their potential use as a photocatalyst for degradation under sunlight excitation of different organic model compounds in aqueous solution. The structure of the nanocrystals was examined by X‐ray diffraction, UV‐vis ground state diffuse reflectance absorption spectra and X‐ray photoelectron emission spectroscopy. Results showed that samples prepared by sol–gel process and calcined at 400 °C are composed of a mixture of anatase and rutile phases, in contrast to the one prepared by solid‐state sintering, which exhibits an anatase phase with Li being involved in a spinel phase. The photocatalytic degradation of aqueous solutions of different aromatic compounds was successfully achieved under sunlight excitation in presence of Li‐doped TiO2 prepared via sol–gel process. It was shown that the calcination temperature and the preparation mode greatly affect the photocatalytic efficiency. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
950.