全文获取类型
收费全文 | 7214篇 |
免费 | 318篇 |
国内免费 | 79篇 |
专业分类
化学 | 4313篇 |
晶体学 | 221篇 |
力学 | 196篇 |
综合类 | 4篇 |
数学 | 1046篇 |
物理学 | 1831篇 |
出版年
2022年 | 74篇 |
2021年 | 68篇 |
2020年 | 94篇 |
2019年 | 144篇 |
2018年 | 102篇 |
2017年 | 99篇 |
2016年 | 144篇 |
2015年 | 125篇 |
2014年 | 187篇 |
2013年 | 565篇 |
2012年 | 317篇 |
2011年 | 360篇 |
2010年 | 242篇 |
2009年 | 214篇 |
2008年 | 247篇 |
2007年 | 254篇 |
2006年 | 221篇 |
2005年 | 181篇 |
2004年 | 176篇 |
2003年 | 203篇 |
2002年 | 171篇 |
2001年 | 101篇 |
2000年 | 96篇 |
1999年 | 66篇 |
1997年 | 70篇 |
1996年 | 79篇 |
1995年 | 85篇 |
1994年 | 82篇 |
1993年 | 84篇 |
1992年 | 98篇 |
1991年 | 88篇 |
1990年 | 76篇 |
1989年 | 110篇 |
1988年 | 76篇 |
1987年 | 70篇 |
1986年 | 81篇 |
1985年 | 126篇 |
1984年 | 119篇 |
1983年 | 93篇 |
1982年 | 98篇 |
1981年 | 101篇 |
1980年 | 85篇 |
1979年 | 98篇 |
1978年 | 74篇 |
1977年 | 101篇 |
1976年 | 79篇 |
1975年 | 86篇 |
1974年 | 92篇 |
1973年 | 97篇 |
1972年 | 57篇 |
排序方式: 共有7611条查询结果,搜索用时 31 毫秒
251.
Dmitrenok A. S. Radhika P. Anjaneyulu V. Subrahmanyam C. Subba Rao P. V. Dmitrenok P. S. Boguslavsky V. M. 《Russian Chemical Bulletin》2003,52(8):1868-1872
Sphingolipids and glycolipids including previously unknown (2S,3S,4R)-1,3,4-trihydroxy-2-(2-(R)-hydroxyoctadecanoylamino)octadec-8E-ene, (2S,3R)-1,3-dihydroxy-2-octadecanoylamino-4E,8E-hexadecadiene, and (2-hydroxy-3-hexadecyloxypropyl)--L-fucopyranoside were isolated from soft corals collected on the shelf near the Andaman Islands (Indian Ocean). The structures of all compounds were established by spectroscopic methods and chemical analyses. The lipids possessed antibacterial activity against Bacillus subtilis, Bacillus pumilus, Escherichia coli, and Pseudomonas aeruginosa and antifungal activity against Aspergillus niger, Rhizopus oryzae, and Candida albicans. 相似文献
252.
Rao PV Bhaduri S Jiang J Hong D Holm RH 《Journal of the American Chemical Society》2005,127(6):1933-1945
The construction of a synthetic analogue of the A-cluster of carbon monoxide dehydrogenase/acetylcoenzyme synthase, the site of acetylcoenzyme A formation, requires as a final step the formation of an unsupported [Fe(4)S(4)]-(mu(2)-SR)-Ni(II) bridge to a preformed cluster. Our previous results (Rao, P. V.; Bhaduri, S.; Jiang, J.; Holm, R. H. Inorg. Chem. 2004, 43, 5833) and the work of others have addressed synthesis of dinuclear complexes relevant to the A-cluster. This investigation concentrates on reactions pertinent to bridge formation by examining systems containing dinuclear and mononuclear Ni(II) complexes and the 3:1 site-differentiated clusters [Fe(4)S(4)(LS(3))L'](2-) (L' = TfO(-) (14), SEt (15)). The system 14/[{Ni(L(O)-S(2)N(2))}M(SCH(2)CH(2)PPh(2))](+) results in cleavage of the dinuclear complex and formation of [{Ni(L(O)-S(2)N(2))}Fe(4)S(4)(LS(3))]- (18), in which the Ni(II) complex binds at the unique cluster site with formation of a Ni(mu(2)-SR)(2)Fe bridge rhomb. Cluster 18 and the related species [{Ni(phma)}Fe(4)S(4)(LS(3))](3)- (19) are obtainable by direct reaction of the corresponding cis-planar Ni(II)-S(2)N(2) complexes with 14. The mononuclear complexes [M(pdmt)(SEt)]- (M = Ni(II), Pd(II)) with 14 in acetonitrile or Me(2)SO solution react by thiolate transfer to give 15 and [M(2)(pdmt)(2)]. However, in dichloromethane the Ni(II) reaction product is interpreted as [{Ni(pdmt)(mu(2)-SEt)}Fe(4)S(4)(LS(3))](2-) (20). Reaction of Et(3)NH(+) and 15 affords the double cubane [{Fe(4)S(4)(LS(3))}(2)(mu(2)-SEt)](3-) (21). Cluster 18 contains two mutually supportive Fe-(mu(2)-SR)-Ni(II) bridges, 19 exhibits one strong and one weaker bridge, 20 has one unsupported bridge (inferred from the (1)H NMR spectrum), and 21 has one unsupported Fe-(mu(2)-SR)-Fe bridge. Bridges in 18, 19, and 21 were established by X-ray structures. This work demonstrates that a bridge of the type found in the enzyme A-clusters is achievable by synthesis and implies that more stable, unsupported single thiolate bridges may require reinforcement by an additional covalent linkage between the Fe(4)S(4) and nickel-containing components. (LS(3) = 1,3,5-tris((4,6-dimethyl-3-mercaptophenyl)thio)-2,4,6-tris(p-tolylthio)benzene(3-); L(O)-S(2)N(2) = N,N'-diethyl-3,7-diazanonane-1,9-dithiolate(2-); pdmt = pyridine-2,6-methanedithiolate(2-); phma = N,N'-1,2-phenylenebis(2-acetylthio)acetamidate(4-); TfO = triflate.). 相似文献
253.
Thermal decomposition of strontium titanyl oxalate tetrahydrate and calcium titanyl oxalate hexahydrate have been studied employing TG, DTA, gas and chemical analysis. The decompositions proceed through three major steps: dehydration, decomposition of the oxalate to a carbonate and the decomposition of the carbonate to yield the final products, the metatitanates. The intermediates of the oxalate decomposition are found to be Sr2Ti2O4+x(CO3)2-x(CO2)x and Ca2Ti2O4(CO3)2, respectively. The entrapment of carbon dioxide in the former and the presence of non-equivalent carbonate groups in the latter are substantiated by their i.r. spectra. The penultimate solid residues are poorly crystalline Sr2Ti2O5CO3 and amorphous Ca2Ti2O5CO3. Decompositions of these carbonates are accompanied by growth in particle size of the products, SrTiO3 and CaTiO3, respectively. 相似文献
254.
Summary The polarographic behaviour of Cd, Pb, Ni, Tl and U(VI) has been described in 0.1 M isoquinoline formate as base electrolyte. In all cases well defined reversible waves were obtained and determinations are possible in the presence of Mo, Co, Zn, Mn, Te, In, Se, Fe, Cr, V, Th, Zr, As, Sb, Ag, Hg and Cu.
Polarographische Bestimmung von Cadmium, Blei, Nickel, Thallium und Uran(VI) in Isochinolinformiat
Zusammenfassung Das polarographische Verhalten von Cd, Pb, Ni, Th. und U(VI) in 0,1 M Isochinolinformiatlösung wird beschrieben, Bestimmungsmöglichkeiten werden aufgezeigt. In allen Fällen werden gut definierte reversible Stufen erhalten. Folgende Elemente stören nicht: Mo, Co, Zn, Mn, Te, In, Se, Fe, Cr, V, Th, Zr, As, Sb, Ag, Hg, Cu.相似文献
255.
Y. X. Xia J. I. Friese D. A. Moore P. P. Bachelor L. Rao 《Journal of Radioanalytical and Nuclear Chemistry》2007,274(1):79-86
The complexation of plutonium(IV) with sulfate at variable temperatures has been investigated by solvent extraction method.
A NaBrO3 solution was used as holding oxidant to maintain the plutonium(IV) oxidation state throughout the experiments. The distribution
ratio of Pu(IV) between the organic and aqueous phases was found to decrease as the concentrations of sulfate were increased.
Stability constants of the 1:1 and 1:2 Pu(IV)-HSO4
− complexes, dominant in the aqueous phase, were calculated from the effect of [HSO4
−] on the distribution ratio. The enthalpy and entropy of complexation were calculated from the stability constants at different
temperatures using the Van’t Hoff equation. 相似文献
256.
A new chelating polymeric sorbent has been developed using Merrifield chloromethylated resin anchored with quinoline-8-ol (HQ). The modified polymeric resin was characterized by FT-IR spectroscopy and elemental analysis. The HQ anchored resin showed superior binding affinity for U(VI) over Th(IV) and La(III). The influence of various physicochemical parameters on the recovery of U(VI) were optimized by both static and dynamic methods. The phase exchange kinetic studies performed for U(VI) revealed that <5 min was sufficient for reaching equilibrium metal ion sorption. The maximum sorption capacity of HQ anchored resin for U(VI) was found to be 120.30 mg g−1 of resin which is higher than other solid phase extraction sorbents reported so far excepting N,N-dibutyl, N′-benzoyl thiourea sorbed Amberlite XAD-16. The developed HQ anchored polymeric resin is highly selective as none of the extraneous species were found to have any deleterious effect. Solid phase extraction (SPE) studies performed using HQ anchored polymeric resin offered enrichment factor of 100 and the lowest concentration below which recoveries become non-quantitative is 5 μg l−1. The accuracy of the developed SPE method in conjunction with Arsenazo III procedure was tested by analyzing marine sediment (MESS-3) and soil (IAEA–Soil 7) reference materials. Furthermore, the above procedure has been successfully employed for the analysis of real soil and sediment samples. 相似文献
257.
Synthesis and photochemistry of several title compounds 1-3 containing multiple chromophoric systems are described. The Diels-Alder reactions of 2,6,6-trimethylcyclohexa-2,4-dienone (5) with acetylenes 6a-d provided the adducts 7a-d, which upon hydrolysis furnished the desired bicyclo[2.2.2]octenediones 1a-d. Oximes 2a-d were prepared from diones 1a-d by treatment with hydroxylamine hydrochloride in pyridine. 5-Methylenebicyclo[2.2.2]oct-7-en-2-ones 3a-d were obtained via chemoselective Wittig reaction of the corresponding diones 1a-d. Bicyclo[2.2.2]octenediones 1a-c underwent chemoselective oxa-di-pi-methane rearrangement under sensitized conditions and suffered formal ketene extrusion upon direct irradiation. Direct irradiation of 1d afforded 11d via formal ketene extrusion but under sensitization it remained unchanged. Oximes 2a-d suffered ketene extrusion upon direct irradiation and E/Z isomerization under sensitized conditions. On the other hand, 5-methylenebicyclo[2.2.2]oct-7-en-2-ones 3a-d generally underwent 1,3-acyl shift. The plausible courses of all these photochemical processes are discussed. 相似文献
258.
A 1,4-β-d-glucan cellobiohydrolase (EC 3.2.1.91) and l,4-β-d-glucan glucanohydrolase (EC 3.2.1.4) were purified from the culture filtrates ofPenicillium funiculosum by using preparative isoelectric focusing. Both the enzymes were homogeneous on polyacrylamide gel with and without sodium
dodecyl sulphate. The mol wt of the cellobiohydrolase and endoglucanase were 14,400 and 25,000 respectively. The purified
enzymes were free of β-glucosidase activity. Acting in isolation, the cellobiohydrolase had little capacity for solubilizing
Avicel or Walseth cellulose, but showed increased rates of hydrolysis when combined with endoglucanase. Cellobiose inhibition
(50%) was observed in the initial rate of the hydrolysis of Walseth cellulose. It was also observed that cellobiohydrolase
initiates the attack on crystalline cellulose.
† NCL communication no. 3898. 相似文献
259.
Alex. G. Harrison R. Krishna Mohan Rao Kallury 《Journal of mass spectrometry : JMS》1980,15(5):249-256
A study of the electron impact and chemical ionization (H2, CH4, and iso-C4H10) mass spectra of stereoisomeric benzoin oximes and phenylhydrazones indicates that while the former can be distinguished only by their chemical ionization mass spectra the latter are readily distinguishable by both their electron impact and chemical ionization mass spectra. The electron impact mass spectra of the isomeric oximes are practically identical; however, the chemical ionization spectra show that the E isomer forms more stable [MH]+ and [MH? H2O]+ ions than the Z isomer for which both the [MH]+ and [MH? H2O]+ ions are relatively unstable. In electron impact the Z-phenylhydrazone shows a lower [M]+˙ ion abundance and more facile loss of H2O than does the E isomer. This more facile H2O loss also is observed for the [MH]+ ion of the Z isomer under chemical ionization conditions. 相似文献
260.
Some tetracoordinated complexes having the formulae, [AgL4]X (L = Triphenyl-arsine; X = NO, ClO and BrO) and [AgL3X] (L = Triphenyl-arsine/phosphine; X = SCN? and NCO?) have been prepared and characterised by analyses, conductance, magnetic susceptibility and infra-red spectroscopy. 相似文献