全文获取类型
收费全文 | 10283篇 |
免费 | 198篇 |
国内免费 | 35篇 |
专业分类
化学 | 5789篇 |
晶体学 | 236篇 |
力学 | 223篇 |
数学 | 1737篇 |
物理学 | 2531篇 |
出版年
2022年 | 163篇 |
2021年 | 190篇 |
2020年 | 118篇 |
2019年 | 168篇 |
2018年 | 169篇 |
2017年 | 190篇 |
2016年 | 302篇 |
2015年 | 249篇 |
2014年 | 331篇 |
2013年 | 772篇 |
2012年 | 485篇 |
2011年 | 568篇 |
2010年 | 437篇 |
2009年 | 414篇 |
2008年 | 497篇 |
2007年 | 484篇 |
2006年 | 418篇 |
2005年 | 358篇 |
2004年 | 346篇 |
2003年 | 313篇 |
2002年 | 270篇 |
2001年 | 199篇 |
2000年 | 177篇 |
1999年 | 133篇 |
1998年 | 140篇 |
1997年 | 127篇 |
1996年 | 129篇 |
1995年 | 139篇 |
1994年 | 96篇 |
1993年 | 92篇 |
1992年 | 101篇 |
1991年 | 76篇 |
1990年 | 100篇 |
1989年 | 97篇 |
1988年 | 85篇 |
1987年 | 79篇 |
1986年 | 84篇 |
1985年 | 131篇 |
1984年 | 153篇 |
1983年 | 88篇 |
1982年 | 88篇 |
1981年 | 104篇 |
1980年 | 101篇 |
1979年 | 79篇 |
1978年 | 80篇 |
1977年 | 98篇 |
1976年 | 76篇 |
1975年 | 67篇 |
1974年 | 59篇 |
1973年 | 51篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
151.
The influence of spent catalyst from catalytic cracking in fluidized bed on the hydration process of cement and the properties
of cement mortars were studied. The spent catalyst was used as an additive to cement in the mortars (10 and 20% of cement).
The samples of mortars kept in water for28 days, then they were placed in sulfate and chloride media for 2 months (the control
samples were kept in water for 3 months). After this time they were subjected to bending strength and compressive strength
determinations. Thermogravimetric and infrared absorption studies were performed and capillary elevation, capability of binding
heavy metals, and changes in mass and apparent density were determined too. The studies disclosed the pozzolana nature of
spent catalyst and its influence on cement mortars being in contact with corrosive media.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
152.
Addition of a phenyl Grignard reagent to a toluene solution of the nickel(II) chloride complex of a dimethylated inverted porphyrin, (2-NCH3-21-CH3CTPP)NiIICl (1), at 203 K results in the formation of a rare paramagnetic (sigma-phenyl)nickel(II) species, (2-NCH3-21-CH3CTPP)NiIIPh (2). The coordination of the sigma-phenyl in 2 is determined by a unique pattern of three sigma-phenyl resonances (ortho 375.0 ppm; meta 108.94 ppm; para 35.68 ppm (at 283 K)) in the 1H NMR and 2H NMR spectra. The (sigma-phenyl)nickel(II) compound 2 is in the high-spin ground electronic state (dxy)2(dxz)2(dyz)2(dz2)1(dx2-y2)1, as confirmed by similarity of the NMR spectra of the equatorial ligand in 1 and 2. Titration of 1 with phenyllithium produces (2-NCH3-21-CH3CTPP)NiIIPh (2). One-electron reduction with excess PhLi yields [(2-NCH3-21-CH3CTPP)NiIIPh]- (3), which can be also generated by independent routes, e.g., by reduction of (2-NCH3-21-CH3CTPP)NiIIPh using lithium triethylborohydride or tetrabutylammonium borohydride. The spectroscopic data indicate that (2-NCH3-21-CH3CTPP)NiIIPh (2) undergoes one-electron reduction without a substantial disruption of the molecular geometry. The presence of two paramagnetic centers in 3, i.e., the high-spin nickel(II) and the carbaporphyrin anion radical, produces remarkable variations in a spectral patterns, such as the upfield and downfield positions of pyrrole resonances (103.78, 96.66, -25.35, -50.97, -92.15, -114.83 ppm (at 253 K)) and sign alternations of the meso-phenyl resonances (ortho -77.81, -79.34 ppm; meta 48.77, 48.04 ppm; para -85.65, -86.46 ppm (at 253 K)). A single species, 4, is detected in the 1H NMR titration of 1 with n-butyllithium. The formation of one- or two-electron-reduced species, [(2-NCH3-21-CH3CTPP)NiBu]- or [(2-NCH3-21-CH3CTPP)NiBu]2-, respectively, is considered to account for the spectroscopic properties of 4 (pyrrole 17.33, 15.45, -5.79, -7.74, -14.62, -58.14 ppm; 21-CH3 3 ppm (at 203 K)). The temperature dependence of the hyperfine shifts of 4 demonstrates pronounced anti-Curie behavior, interpreted in terms of a temperature-dependent spin equilibrium between diamagnetic and paramagnetic states with diamagnetic properties approached as the temperature is lowered. Warming of 2-4 results in complete decomposition via homolytic/heterolytic cleavage of an axial nickel-apical carbon bond. In the case of 2 or 3, the process yields a mixture of two compounds, 5 and 6, which are detected by EPR spectroscopy, demonstrating the anisotropy of the g tensor (5, g1 = 2.237, g2 = 2.092, g3 = 2.090; 6, g1 = 2.115, g2 = 2.030, g3 = 1.940 (in frozen toluene solution at 77 K)). 相似文献
153.
Alicja Wawrzynów Adam Liwo Ewa Kaczmarczyk Lech Chmurzyński 《Journal of solution chemistry》1998,27(5):463-472
Cationic heteroconjugation equilibria of more than ninety systems consisting of substituted pyridines, their N-oxides, and trimethylamine N-oxide, i. e., in systems with mixed hydrogen bridges of type OHN+ (NHO+) were studied in propylene carbonate. Both experimental systems without proton transfer, BH+/B1, and those with proton transfer, B1H+/B, were explored. The stability of the mixed hydrogen bridges, OHN+ (NHO+), is compared with that of the OHC+-type bridges. The influence of the difference in basicity of the conjugate base of the proton donor and the proton acceptor on the presence of the proton transfer equilibria, and, consequently, the possibility of determination of the cationic heteroconjugation constant values is discussed. 相似文献
154.
This work was done while the second author visited Toru. This research was partially supported by the Polish Scientific Grant KBN No. 1222/2/91 相似文献
155.
Summary Multiflorine (1) — a minor lupine alkaloid — treated by methyl lithium or methyl magnesium iodide affords 4S-4-hydroxy-4-methyl-2,3-didehydrosparteine (2) and 2S-2-methyl-4-oxosparteine (3), respectively, as the dominating products. Their steric structure, determined by1H and13C NMR techniques, points to stereospecific preferences of these reactions. The observed nucleophilic 1,2- and 1,4-additions indicate that regiospecificity of the action of MeLi or MeMgI on multiflorine is different from that of the so far known similar alkylation of other enamino ketones.
Die räumliche Struktur von Methylierungsprodukten des Multiflorins
Zusammenfassung Multiflorin (1), ein Lupin-Nebenalkaloid, ergibt bei Umsetzung mit Methyllithium oder Methylmagnesiumiodid 4S-4-Hydroxy-4-methyl-2,3-didehydrospartein (2) und 2S-2-Methyl-4-oxospartein (3) als Hauptprodukte. Ihre NMR-spektroskopisch (1H und13C) aufgeklärte räumliche Struktur weist auf eine Stereoselektivität der erwähnten Reaktionen hin. Die beobachteten nucleophilen 1,2- und 1,4-Additionen zeigen, daß sich die Regiospezifität der Einwirkung von MeLi oder MeMgl auf Multiflorin von jener bis jetzt bekannter Alkylierungen von Enaminoketonen unterscheidet.相似文献
156.
The153/151Eu isotope separation factor (q) for the Eu(II)/Eu(III) chemical exchange in the liquid-liquid extraction system, containing Eu (III) in di (2-ethylhexyl) phosphoric acid (HDEHP) and Eu(II) in water acidified with hydrochloric acid, was found to be 0.9993±0.0002 (2) for the single stage. Some theoretical aspects of separation of the Eu isotopes are discussed. The decisive role of the electron exchange reaction and complexation by the counter-ion in the aqueous phase is emphasized. 相似文献
157.
A. Baranowski M. Dębowska K. Jerie J. Rudzińska-Girulska Z. Paweŀka R. T. Sikorski 《Journal of Radioanalytical and Nuclear Chemistry》1995,190(2):463-467
Results of angular correlation of annihilation radiation (ACAR) and positron annihilation lifetime (PAL) measurements are presented for five styrene copolymers: poly(co-styrene-phenylmaleimide) and its three derivatives with chlorine as well as for one with the OH group substituted at the benzene ring. It occurs that the chlorine substituted at three different positions at the benzene ring poly(co-styrene-o (or-m,-p)-chlorophenylmaleimide) inhibits the formation of the positronium to different extent. The greatest effect is observed in case of the chlorine atom substituted at the benzene ring at the ortho-position towards the nitrogen atom. The two long lifetimes (3 and 4) observed in the lifetime spectra are connected with the bimodal distributions of the free volume radius in the samples. 相似文献
158.
A new, very accurate (definitive) method for the determination of trace amounts of cobalt in biological materials has been devised. The method is based on combination of neutron irradiation with quantitative and selective post-irradiation separation of cobalt from all accompanying radionuclides followed by measurement by -ray spectrometry. Column chromatography in which owing to addition of Co carrier the course of separation can be followed visually is the key element of the separation scheme. Several criteria have been formulated which must be simultaneously fulfilled in order to acknowledge the result as obtained by a definitive method. The high accuracy of the method has been demonstrated by the analysis of several certified reference materials of widely different Co contents. 相似文献
159.
Pyrzyńska K 《Talanta》1994,41(3):381-386
Donnan dialysis enrichment with tubular cation-exchange membrane was used as a preconcentration method prior to determination of gold by flame atomic absorption spectrometry (FAAS). The value of enrichment factor can be controlled for a particular application through adjustment of the membrane tuning length, dialysis time, carrier flow rate, composition of the receiver solution and by addition of complexing ligand to the receiver or the sample solution. For 10 min dialysis enrichment factor above 3 can be achieved. The detection limit (signal-to-noise ratio = 3) of 35 ng/ml was obtained. RSD at 0.2 mug/ml level was 4.7% (n = 6). The results of dialysis of noble metals mixtures are demonstrated. 相似文献
160.
Andrzej Smajdor 《Results in Mathematics》1994,26(3-4):385-389
A set-valued function F defined on a convex cone S in a real vector space X into the set n(Y) of all non-empty subsets of a real vector space Y is said to be the Jensen function iff $${1\over 2}\lbrack F(x)+F(x)\rbrack=F\lbrack{1\over 2}(x+y)\rbrack$$ for all x, y ∈ S. This note deals with iteration semigroups of Jensen set-valued functions on S. 相似文献