全文获取类型
收费全文 | 4802篇 |
免费 | 125篇 |
国内免费 | 16篇 |
专业分类
化学 | 2970篇 |
晶体学 | 14篇 |
力学 | 260篇 |
数学 | 809篇 |
物理学 | 890篇 |
出版年
2023年 | 51篇 |
2022年 | 140篇 |
2021年 | 133篇 |
2020年 | 111篇 |
2019年 | 100篇 |
2018年 | 86篇 |
2017年 | 95篇 |
2016年 | 186篇 |
2015年 | 146篇 |
2014年 | 144篇 |
2013年 | 259篇 |
2012年 | 274篇 |
2011年 | 293篇 |
2010年 | 176篇 |
2009年 | 156篇 |
2008年 | 286篇 |
2007年 | 276篇 |
2006年 | 233篇 |
2005年 | 255篇 |
2004年 | 168篇 |
2003年 | 159篇 |
2002年 | 119篇 |
2001年 | 61篇 |
2000年 | 50篇 |
1999年 | 46篇 |
1998年 | 34篇 |
1997年 | 34篇 |
1996年 | 59篇 |
1995年 | 47篇 |
1994年 | 42篇 |
1993年 | 41篇 |
1992年 | 36篇 |
1991年 | 30篇 |
1990年 | 31篇 |
1989年 | 32篇 |
1988年 | 33篇 |
1987年 | 39篇 |
1986年 | 26篇 |
1985年 | 42篇 |
1984年 | 40篇 |
1983年 | 20篇 |
1982年 | 28篇 |
1981年 | 26篇 |
1980年 | 30篇 |
1979年 | 20篇 |
1978年 | 17篇 |
1977年 | 32篇 |
1975年 | 16篇 |
1974年 | 14篇 |
1858年 | 11篇 |
排序方式: 共有4943条查询结果,搜索用时 31 毫秒
31.
Franco Cristiani Francesco A. Devillanova Gaetano Verani 《Transition Metal Chemistry》1977,2(1):50-52
Summary White crystalline complexes of general formula ML2X2, where M = Zn, Cd, Hg; X = Cl, 13r, I and L = pyrrolidine-2-thione, were prepared and studied by i.r. spectroscopy in the 4000-200 cm–1 range. Evidence for coordination of the ligand to the metal through sulphur was found in each case. The previous assignment of the band present in the ligand at 1110 cm–1 to the(CS) fundamental is discussed.This work was supported by the National Research Council (C.N.R.) of Italy. 相似文献
32.
Corrado Barghigiani Giuliano Colombetti Barbara Franchini Francesco Lenci 《Photochemistry and photobiology》1979,29(5):1015-1019
Abstract—Light-induced behavioral responses of Euglena gracilis have been investigated in single cells by means of a video system coupled to an optical microscope. Light intensity-effect curves at different wavelengths in the near UV and visible range have been determined. From these curves the action spectrum for the step-down photophobic response of Euglena has been calculated. From a comparison with the results obtained using a population method by means of a phototaxigraph, it is concluded that a single photomotile reaction is responsible for cell accumulation, brought about by trapping in the light spot and possibly by phototaxis towards scattered light from organisms already in the light field. 相似文献
33.
Tadini Buoninsegni F Moncelli MR Aloisi G Agostiano A Guidelli R 《Journal of the American Chemical Society》2005,127(7):2231-2237
Monolayers of n-alkanethiols of chain length from C12 to C18 were self-assembled on a hanging mercury drop electrode, and a film of chlorophyllide (Chlide) was adsorbed on top of them. The reduction photocurrents following illumination of the Chlide film were measured over the potential range in which the Chlide is electroinactive in the dark, and their action spectra were determined. Plotting the derivative of the photocurrents with respect to the applied potential against potential yields bell-shaped curves that can be fitted to a Gaussian. The potential of the Gaussian maximum was used to determine the reorganization energy lambda for the Chlide electroreduction process. An increase in the thiol chain length causes lambda to decrease regularly and the photocurrent to decay exponentially with the monolayer thickness, with a decay constant beta of about 0.17 A(-1). 相似文献
34.
Barbieri A Ventura B Flamigni L Barigelletti F Fuhrmann G Bäuerle P Goeb S Ziessel R 《Inorganic chemistry》2005,44(22):8033-8043
The syntheses, structural characteristics, electrochemical behavior, ground-state spectra, photophysical properties, and transient absorption (TA) spectra in CH(3)CN solvent are reported for binuclear [(bpy)(2)Ru(bpy-E(T)(n)()E-bpy)Ru(bpy)(2)](4+) complexes, Ru(bpyT(n)bpy)Ru, where the Ru-based units are connected by alternating 3,4-dibutylthiophene (DBT')/thiophene (T') fragments linked via ethynyl groups (E) to bpy ligands at the 5-position (bpy is 2,2'-bipyridine). The ligand bpyT(3)bpy represents a module containing DBT'/T'/DBT' subunits, and bpyT(5)bpy accounts for a DBT'/T'/DBT'/T'/DBT' pattern. The syntheses and electrochemical and spectroscopic (emission and TA) properties in CH(2)Cl(2) solvent of the bpyT(n)()bpy ligands are likewise reported. The behavior of the Ru(bpyT(n)bpy)Ru dimers has been compared to that of the bpyT(n)bpy ligands and to that of a related mononuclear complex, [(bpy)(2)Ru(bpy-E-DBT')](2+), Ru(bpyDBT'). For the dimeric complexes, the electrochemical results show that the first reduction step takes place at the bpy ligand(s) bearing an ethynylene group, the first oxidation step is thiophene-centered, and further oxidation involves the metal centers, which are only weakly interacting. The photophysical and TA results for the Ru(bpyT(n)bpy)Ru dimers account for the presence of low-lying oligothiophene-centered (3)pi,pi levels, while higher-lying metal-ligand charge transfer ((3)MLCT) levels are thermally accessible only for the case of Ru(bpyT(3)bpy)Ru; the possible role of charge separation (CS) levels (from oxidation at the thiophene bridge and reduction at one of the coordinated bpy's) is also discussed. 相似文献
35.
Francesco A. Devillanova Gaetano Verani D. N. Sathyanarayana 《Journal of heterocyclic chemistry》1978,15(6):945-947
An infrared investigation cm N-methyl-1,3-thiazolidine-2-thione and -2-selone in the range 4000-200 cm?1 is reported. The v CS and v CSe vibrations give contributions to the absorptions around 1000 cm?1 and below 600 cm?1. The assignments are supported by comparison of their ir spectra with those of S- and Se-methiodides. The π-bond orders of the thio- and seleno-ketonic links in these compounds are higher than those found for 1,3-imidazolidine-2-thione and -2-selone. 相似文献
36.
The determination by neutron activation of trace quantities of calcium, strontium and barium in single crystals of alkali halides has been studied. The matrix is eliminated before the irradiation by an ion-exchange procedure. Gamma spectroscopy after radiochemical separation is used to determine strontium and barium. Calcium is determined by measuring the β-activity of 49Sc formed by the decay of 49Ca. Long-lived radioactive tracers are used to determine the chemical yields. 相似文献
37.
Francesco Demartin Fabrizia Fabrizi de Biani Cristina Femoni Maria Carmela Iapalucci Giuliano Longoni Piero Macchi Piero Zanello 《Journal of Cluster Science》2001,12(1):61-74
The [Ni36Pt4(CO)45]6- and [Ni37Pt4(CO)46]6- clusters have been obtained in mixture upon reaction in acetonitrile of [Ni6(CO)12]2- salts with K2PtCl4 in a 2.5:1 molar ratio. The two hexaanions were indistinguishable by spectroscopic techniques. Crystallization of their trimethylbenzylammonium salts led to crystals of composition 0.5[NMe3CH2Ph]6[Ni36Pt4(CO)45]-0.5[NMe3CH2Ph]6[Ni37Pt4(CO)46]·C3H8O, hexagonal,space group P63 (No. 173), a=17.853(9), c=27.127(13) Å, Z=2; final R=0.057. The metal core of the [Ni36Pt4(CO)45]6- anion consists of a Pt4 tetrahedron fully encapsulated in a shell of 36 Ni atoms belonging to a very distorted and incomplete 5 tetrahedron. The [Ni37Pt4(CO)46]6- hexaanion derives from the former by capping the unique triangular face of the metal polyhedron with an additional Ni(CO) fragment. The [Ni36Pt4(CO)45]6--[Ni37Pt4(CO)46]6- mixture is rapidly degraded to the known [Ni9Pt3(CO)21]4- cluster by exposure to carbon monoxide. Its reaction with protic acids initially affords the corresponding [H6-nNi36Pt4(CO)45]n--[H6-nNi37Pt4(CO)46]n- (n=5, 4) derivatives, and eventually leads to rearrangement to the known [H6-n Ni38Pt6(CO)48]n- species. Both [Ni36Pt4(CO)45]6--[Ni37Pt4(CO)46]6- and [HNi36Pt4(CO)45]5--[HNi37Pt4(CO)46]5- mixtures have been chemically and electrochemically reduced to their corresponding [Ni36Pt4(CO)45]n--[Ni37Pt4(CO)46]n- (n=7–9) and [HNi36Pt4(CO)45]n--[HNi37Pt4(CO)46]n- (n=6–8) mixtures. 相似文献
38.
Giuseppe Werber Francesco Buccheri Manlio Gentile 《Journal of heterocyclic chemistry》1977,14(7):1263-1265
The ambident nucleophilic behaviour of some 2-amino-5-H-1,3,4-thiadiazoles in alkylation, acylation and nitrosation reaction has been verified. The structures assigned to the 2-amino-1,3,4-thiadiazoles ( 1a-i ) and to the Δ2-1,3,4-thiadiazolines ( 2a-e ) agree with the spectral data. 相似文献
39.
[reaction: see text] Ytterbium triflate was shown to be an effective catalyst in promoting the synthesis of either isopropyl esters or free alpha-hydroxy-arylacetic acids from substituted aromatic glyoxals and aryl methyl ketones, respectively. The reaction to provide acids starting from differently substituted ketones was carried out by an environmentally friendly method using an aqueous medium as a solvent and giving the adducts in 78-99% yield without any further purification after the usual workup. 相似文献
40.
Attilio Citterio Anna Gentile Francesco Minisci Marco Serravalle Susanna Ventura 《Tetrahedron》1985,41(3):617-620
The homolytic decomposition of hydroxylamine-O-sulphonic acid in alcoholic solvents was investigated in the presence or absence of protonated heteroaromatic bases and Fe(II) salt. The addition of the α-hydroxyalkyl radicals to the base and their oxidation by Fe(III) salt to the corresponding alkyl cyanide were competitive processes. A redox chain process involving the amino radical cation, NH3t., is suggested and the factors affecting the yields of the homolytic substitution are discussed. 相似文献