全文获取类型
收费全文 | 4547篇 |
免费 | 77篇 |
国内免费 | 34篇 |
专业分类
化学 | 2792篇 |
晶体学 | 38篇 |
力学 | 77篇 |
数学 | 467篇 |
物理学 | 1284篇 |
出版年
2019年 | 34篇 |
2018年 | 21篇 |
2017年 | 24篇 |
2016年 | 67篇 |
2015年 | 43篇 |
2014年 | 57篇 |
2013年 | 182篇 |
2012年 | 179篇 |
2011年 | 227篇 |
2010年 | 95篇 |
2009年 | 87篇 |
2008年 | 207篇 |
2007年 | 223篇 |
2006年 | 201篇 |
2005年 | 201篇 |
2004年 | 190篇 |
2003年 | 167篇 |
2002年 | 151篇 |
2001年 | 140篇 |
2000年 | 129篇 |
1999年 | 69篇 |
1998年 | 61篇 |
1997年 | 47篇 |
1996年 | 89篇 |
1995年 | 72篇 |
1994年 | 94篇 |
1993年 | 105篇 |
1992年 | 99篇 |
1991年 | 58篇 |
1990年 | 56篇 |
1989年 | 80篇 |
1988年 | 56篇 |
1987年 | 51篇 |
1986年 | 59篇 |
1985年 | 73篇 |
1984年 | 56篇 |
1983年 | 34篇 |
1982年 | 56篇 |
1981年 | 54篇 |
1980年 | 57篇 |
1979年 | 49篇 |
1978年 | 55篇 |
1977年 | 66篇 |
1976年 | 44篇 |
1975年 | 43篇 |
1974年 | 50篇 |
1973年 | 49篇 |
1972年 | 31篇 |
1971年 | 26篇 |
1970年 | 24篇 |
排序方式: 共有4658条查询结果,搜索用时 15 毫秒
81.
R. Miller 《Colloid and polymer science》1983,261(5):441-444
Relations are given describing the compression of adsorption layers of soluble surfactants, using models of pure diffusion, pure kinetic, and mixed diffusion-kinetic-controlled adsorption. For the compression of the adsorption layer of a mixture of soluble surfactants all models predict a relativ enrichment of the most surface active substance. 相似文献
82.
C.A. Cody R.C. Levitt R.K. Khanna Philip J. Miller 《Journal of solid state chemistry》1978,26(3):293-309
The infrared and Raman spectra of NaH3(SeO3)2 and NaD3(SeO3)2 have been recorded from 24 to 300°K. The interpretation, assignments, and analysis of the spectral studies are presented on the paraelectric α phase (proton disordered), ferroelectric β phase (proton ordered) and ferroelectric γ phase (proton ordered). A discussion of a newly proposed proton-triggered phase transition mechanism and a possible origin of the hydrogen-bonded OH stretching region of KH2PO4-type ferroelectrics is given. 相似文献
83.
84.
Kenji Maeda Ross A. Miller Ali Shafiee Joseph D. Armstrong III 《Tetrahedron letters》2005,46(9):1545-1549
Highly diastereoselective (>20:1) bromo-lactonization of N-sulfonyl-2-allyl-2-phenylglycine methyl ester (11) was observed. Successive treatment of the chiral lactone with MeONa gave the desired (2S,4R)-4-hydroxy-2-phenylproline derivative in high yield without erosion of the diastereoselectivity. The starting chiral non-racemic compound (5) was prepared from the racemic 2-phenylglycine using a classical kinetic resolution (crystallization), an asymmetric phase transfer alkylation, and an enzyme-catalyzed kinetic resolution. 相似文献
85.
Summary A colorimetric method for the determination of 2,2-dihydroxy-biphenyl in rat urine is described. The ether extract is subjected to thin-layer chromatography on silica gel-G plates in the solvent system benzene-methanol (8020) and spots corresponding to 2,2-dihydroxybiphenyl and its glucuronide derivative are eluted with ethanol. The glucuronide is hydrolysed with HCl and the 2,2-di-hydroxybiphenyl content is determined after colour development with sodium cobaltinitrite, the absorbance being read at 410 nm. The method is sensitive and reproducible. It obeys the Lambert-Beer law in the concentration range 0.7–8.9g/ml.
Eine empfindliche kolorimetrische Methode zur Bestimmung von 2,2 -Dihydroxybiphenyl
Zusammenfassung Eine kolorimetrische Methode zur Bestimmung von 2,2-Dihydroxy-biphenyl in Rattenharn wurde beschrieben. Der ätherische Extrakt wird auf Silikagel-G-Platten dünnschicht-chromatographisch mit dem Lösungsmittelsystem Benzol-Methanol (8020) getrennt. Die dem genannten Stoff und seinem Glucuronid entsprechenden Flecken werden mit äthanol eluiert. Das Glucuronid wird mit Salzsäure hydrolysiert und der Gehalt an 2,2-Di-hydroxybiphenyl nach Ausführung der Farbreaktion mit Natriumkobalti-nitrit und Messung bei 410 nm bestimmt. Das Verfahren ist empfindlich und gut reproduzierbar. Es entspricht dem Lambert-Beerschen Gesetz zwischen 0,7 und 8,9g/ml.相似文献
86.
Abstract —Using semi-empirical analytic formulas for the transmitted and scattered ultraviolet spectral irradiance at the ground (Green, A. E. S., T. Sawada and E. P. Shettle, Photochem. Photobiol. 19 , 251–259, 1974), we calculate erythema dose rates and daily erythema doses. Results are illustrated graphically, and for the purpose of photobiological applications are given in terms of approximate analytic forms, with parameters presented in tabular form. The relative erythema data assembled by W. W. Coblentz and R. Stair (U.S. Bureau of Standards J. Res. 12 , 13–14, 1934), as fit by an analytic form, is taken as a standard spectrum in our calculations. Other forms of erythema spectra are also compared. 相似文献
87.
Three of the main oxygen-containing fragments resulting from 3-methyl-2-butyl trifluoroacetate (11) had been identified previously as the 1-triflnoroacetoxyethyl cation (m/z 141, 12, product of simple cleavage), and the products of single (m/z 142) and double hydrogen transfer (m/z 143, protonated ethyl trifluoroacetate). Collisionally activated dissociation of m/z 142 and the isotopomers resulting from 11-2-d, 11-1-d3, 11-5,6-d6, and 11-18O2 has established that m/z 142 is the oxygen protonated 1-trifluoroacetoxyethyl free radical (17) formed by hydrogen shift irom a γ-methyl group to oxygen in the molecular ion, rather than in a complex (18) between 12 and the 2-propyl free radical, as expected based on a mechanistic model existing in the literature. The second hydrogen transferred originates in the other γ-methyl group; its migration may occur, but does not have to, in the complex between 17 and a molecule of propene, prior to dissociation of the two fragments. Collision-activated dissociation has now shown that the m/z 140 ion observed in the spectrum is the molecular ion of vinyl trifluoroacetate, possibly formed by a hydrogen transfer from 12 to the 2-propyl radical in the complex 18. The hydrogen migration to oxygen exhibits no isotope effect, whereas the transfers to carbon atoms exhibit small primary and α secondary kinetic isotope effects. Exclusive migration of the tertiary hydrogen from C(3) occurs in the formation of 2-methylbutene cation radical (m/z 70) from the molecular ion. The hydrocarbon ion fragments and the heteroatom-containing fragments are formed from 11 by disjoint pathways. 相似文献
88.
Wilkie GD Elliott GI Blagg BS Wolkenberg SE Soenen DR Miller MM Pollack S Boger DL 《Journal of the American Chemical Society》2002,124(38):11292-11294
The scope of intramolecular Diels-Alder and a novel tandem Diels-Alder/1,3-dipolar cycloaddition cascade of 1,3,4-oxadiazoles is disclosed. In the cases examined, the tandem cycloadditions construct three new rings with formation of four new C-C bonds and set all six stereocenters about a central six-membered ring in a single step including three contiguous and four total quaternary centers without a trace of a second diastereomer. 相似文献
89.
Heterogeneous fluorescence immunoassays have been automated using flow injection manifolds incorporating thiophilic gel solid phase reactors to separate antibody-bound and unbound analyte molecules. Antibody elution is achieved by changes in ionic strength, thus allowing the use of pH sensitive fluorescent labels. This facilitates the development of dual analyte systems, in which two competitive immunoassays with separate labels are monitored in parallel. Detection of the fluorophores by high speed synchronous fluorescence scanning while the flow is briefly stopped utilises either one synchronous interval which detects both fluorophores, or two separate scans at different wavelength intervals, one for each fluorophore. Simultaneous analyses of serum albumin and transferrin exemplify these novel approaches. Spectroscopic interferences are very small, analyte recoveries are close to 100%, with a relative standard deviation of 5-6% and a sampling rate of 20 h-1. 相似文献
90.
Miller TA Jeffery JC Ward MD Adams H Pope SJ Faulkner S 《Dalton transactions (Cambridge, England : 2003)》2004,(10):1524-1526
Co-crystallisation of the anionic cyanometallate chromophore [Ru(bipy)(CN)4]2- with Yb(III) provides coordination polymers or oligomers containing Ru-CN-Yb bridges; in [K(H2O)4][Yb(H2O)6][Ru(bipy)(CN)4]2.5H2O Ru-->Yb energy-transfer (k > 5 x 10(6) s(-1)) results in partial quenching of the Ru-based luminescence and sensitised near-IR luminescence from the Yb(III) unit. 相似文献