全文获取类型
收费全文 | 6283篇 |
免费 | 61篇 |
国内免费 | 9篇 |
专业分类
化学 | 3862篇 |
晶体学 | 69篇 |
力学 | 138篇 |
数学 | 639篇 |
物理学 | 1645篇 |
出版年
2020年 | 47篇 |
2016年 | 63篇 |
2015年 | 67篇 |
2014年 | 75篇 |
2013年 | 244篇 |
2012年 | 201篇 |
2011年 | 206篇 |
2010年 | 124篇 |
2009年 | 126篇 |
2008年 | 205篇 |
2007年 | 219篇 |
2006年 | 200篇 |
2005年 | 241篇 |
2004年 | 201篇 |
2003年 | 156篇 |
2002年 | 151篇 |
2001年 | 86篇 |
2000年 | 71篇 |
1999年 | 86篇 |
1998年 | 49篇 |
1997年 | 82篇 |
1996年 | 111篇 |
1995年 | 105篇 |
1994年 | 69篇 |
1993年 | 72篇 |
1992年 | 60篇 |
1991年 | 66篇 |
1990年 | 63篇 |
1989年 | 59篇 |
1988年 | 70篇 |
1987年 | 83篇 |
1986年 | 53篇 |
1985年 | 69篇 |
1984年 | 74篇 |
1983年 | 64篇 |
1982年 | 75篇 |
1981年 | 64篇 |
1980年 | 82篇 |
1979年 | 59篇 |
1978年 | 78篇 |
1977年 | 70篇 |
1976年 | 64篇 |
1975年 | 70篇 |
1974年 | 48篇 |
1973年 | 45篇 |
1968年 | 43篇 |
1967年 | 40篇 |
1955年 | 59篇 |
1934年 | 43篇 |
1928年 | 38篇 |
排序方式: 共有6353条查询结果,搜索用时 0 毫秒
41.
Jan F. Keij Jan Th . M. Jansen Frank W. Schultz Jan W. M. Visser 《Photochemistry and photobiology》1994,60(5):503-509
Abstract-During the development of a photodamage cell sorter several photosensitizers were tested for their ability to photoinactivate more than 90% of the sensitized cells after a brief irradiation with a fluence of 10 kJ/m2 . In pilot experiments, yeast cells sensitized with 10-dodecyl acridine orange (DAO) were effectively photoinactivated after receiving a fluence of 10 kJ/m2 delivered in 8 s. However, when the same fluence was delivered in 3 μ s during passage through a focused laser beam in the cell sorter, all cells survived.
Computer simulations of the relevant photophysical and chemical reactions inside the irradiated cell were used to investigate the cause of this phenomenon. The results indicated that the absence of photoinactivation by DAO, after flash irradiations, was caused by the combined effects of (1) limited oxygen diffusion into the cell and (2) a reduced number of collisions between photosensitizer triplet and oxygen molecules during the irradiation due to saturation of the intracellular photosensitizer triplet concentration. The contributions of triplet-triplet annihilation and triplet quenching by ground state photosensitizer molecules were found to be minimal and not significant. These findings indicate that Type II photosensitizers are incapable of rapid selective photoinactivation in cell sorters. 相似文献
Computer simulations of the relevant photophysical and chemical reactions inside the irradiated cell were used to investigate the cause of this phenomenon. The results indicated that the absence of photoinactivation by DAO, after flash irradiations, was caused by the combined effects of (1) limited oxygen diffusion into the cell and (2) a reduced number of collisions between photosensitizer triplet and oxygen molecules during the irradiation due to saturation of the intracellular photosensitizer triplet concentration. The contributions of triplet-triplet annihilation and triplet quenching by ground state photosensitizer molecules were found to be minimal and not significant. These findings indicate that Type II photosensitizers are incapable of rapid selective photoinactivation in cell sorters. 相似文献
42.
Zusammenfassung 4-Hydroxy-carbostyrile (1a–c) werden mit Benzylchlorid inDMF bevorzugt zu den 4-Benzyloxy-carbostyrilen (2a–c) alkyliert. In wäßr. NaOH dagegen erhält man aus1a und1c als Hauptprodukt das 3,3-Dibenzyl-2,4-dioxo-1,2,3,4-tetrahydrochinolin (3).
Alkylation of 4-hydroxy-quinol-2-ones (1a–c) with benzyl chloride inDMF in the presence of K2CO3 mainly gives the 4-benzylethers2a–c. However, carbon dialkylation takes place in aqueous NaOH and the main product of the reaction between benzylchloride and1a is 3.3-dibenzyl-2.4-dioxo-1.2.3.4-tetrahydro-quinoline3.相似文献
43.
The molecular energy of the complex (η5-C5H5)2TiCl2 has been calculated for experimental geometry and for several hypothetical forms by a semi-empirical CNDO/2 approach. The energy difference between experimental (quasi-tetrahedral) geometry and a planar geometry is ca. 20 kcal mol?1. This difference is sufficiently high to explain the difficulty of the inversion process. 相似文献
44.
The reaction of the azomethine ylides 2a–c with cyclopropenones 3 and of 2a with methylene cyclopropenes 7 leads via (3+3)-cycloaddition to pyridones-4 5 and 1,4 - dihydro - N - methyl - 4 - methylene - pyridines 8, respectively. The merocyanine systems 8 exhibit marked solvatochromic and thermochromic properties. 相似文献
45.
Zusammenfassung Es werden einstufige Synthesen desGlomerins (2) [1,2-Dimethyl-4(1H)-chinazolinon] und desArborins (3) [1-Methyl-2-benzyl-4(1H)-chinazolinon] bekanntgegeben.
Syntheses of heterocycles, CXXX: Glomerine and arborine
A one step synthesis ofglomerine (2) [1.2-dimethyl-4(1H)-quinazolinone] andarborine (3) [1-methyl-2-benzyl-4(1H)-quinazolinone] is described.相似文献
46.
The oxidation of aldehydes by dicyclohexyl-18-crown-6-potassium permangante complex is presented. Results obtained by this procedure showed that the presence of crown ether (DCC) and the catalyst play an important role in the oxidation of the aldehydes. The stoichiometry found corresponds to 2 μeq of permanganate per 1 μmol of aldehydes in all cases. Alcohols and ketones are not oxidized. Finally, a method for quantitative evaluation of aldehydes is proposed. 相似文献
47.
Zusammenfassung Die Abhängigkeit der Struktur des o-Hydroxymandelsäurelactons von Lösungsmittel und Temperatur wird mit Hilfe IR- und NMR-spektroskopischer Methoden nachgewiesen.
The temperature and solvent dependence of the structures of 2-hydroxymandelic acid lactone and dioxindole have been shown by IR and NMR spectroscopy.相似文献
48.
Metal Complexes with Anionic Ligands of Elements of the Main Group IV. VIII Pentacarbonyltrihalogenostannidometalate(O) Complexes of Chromium, Molybdenum, and Tungsten with Fluorine and Iodine Containing Trihalogenostannido Ligands In methylenechloride [As(C6H5)4][SnF3] readily reacts with the metalhexacarbonyls forming the arsoniumsalts of the pentacarbonyltrifluorostannidometalate(O) complexes, [M(CO)5SnF3]? (M ? Cr, Mo, W). Exclusively by the reaction of the intermediately formed complex Cr(CO)5THF only one pure triiodostannidometalate(O) Complex, [N(C2H5)4][Cr(CO)5SnJ3], could be isolated. The trihalogenostannidometalate(O) complexes [M(CO)5SnClX2]? (X ? F: M ? Cr, Mo, W; X ? J: M ? Cr) could be prepared by SnX2-insertion reactions of the [M(CO)5Cl]? complexes. The bonding properties of the halogenostannide ions are discussed on the bases of the IR spectra of their metalate(O) complexes. 相似文献
49.
Complexation of AlIIIby 8-hydroxyquinoline and fluorescence behavior of the quinolinate(s) were studied in reverse micellar systems at low water content, and compared to aqueous media. Two surfactants were used: one was cationic (CTAC: cetyltrimethylammonium chloride) and the other was anionic (AOT: sodium bis(2-ethylhexyl)sulfosuccinate). The results obtained in the CTAC/dichloromethane system (W= [H2O]/[surfactant] = 0.9) showed that complexation occurred very likely in the oil phase and no micellar effect was observed. On the contrary, in the presence of AOT, specific micellar effects were observed due to the presence of the anionic polar heads: stabilization of the positively charged 1:1 and 1:2 chelates, at the expense of the neutral water-insoluble 1:3 chelate which is formed in aqueous solutions under similar conditions;drastic fluorescence enhancement factorsof 120 and 100 in AOT/heptane (W= 1.5) and AOT/dichloromethane (W= 1.6), respectively. Such factors have never been reported so far in either hydroorganic or direct micellar systems. In return, the length of time for the production of the complex(es) is increased because of the microheterogeneity of the medium and the small sizes of the water pools. 相似文献
50.
R. Demchyna J. P. F. Jemetio Yu. Prots Th. Doert L. G. Akselrud W. Schnelle Yu. Kuz'ma Yu. Grin 《无机化学与普通化学杂志》2004,630(5):635-641
Single crystals of CeAgAs2 have been obtained by chemical transport reactions starting from a pre‐reacted powder sample. The crystal structure was solved using X‐ray diffraction (space group Pmca, No. 57, a = 5.7586(4) Å, b = 5.7852(4) Å, c = 21.066(3) Å, Z = 8) and refined to a residual of R(F) = 0.029 for 46 refined parameters and 1020 reflections. The structure of CeAgAs2 represents a new distorted and ordered variant of the HfCuSi2 type. The characteristic feature of this structure are infinite cis‐trans chains of As atoms with As—As distances of 2.563(1) Å and 2.601(1) Å. CeAgAs2 is paramagnetic (μeff = 2.37 μB, θ = —10.5(2) K), with antiferromagnetic ordering at 5.5(2) K and exhibits a metamagnetic transition starting at 4.6 kOe and T = 1.8 K. 相似文献