全文获取类型
收费全文 | 6874篇 |
免费 | 356篇 |
国内免费 | 9篇 |
专业分类
化学 | 4846篇 |
晶体学 | 45篇 |
力学 | 155篇 |
数学 | 948篇 |
物理学 | 1245篇 |
出版年
2023年 | 89篇 |
2022年 | 53篇 |
2021年 | 110篇 |
2020年 | 173篇 |
2019年 | 151篇 |
2018年 | 120篇 |
2017年 | 120篇 |
2016年 | 257篇 |
2015年 | 221篇 |
2014年 | 215篇 |
2013年 | 386篇 |
2012年 | 486篇 |
2011年 | 521篇 |
2010年 | 271篇 |
2009年 | 203篇 |
2008年 | 448篇 |
2007年 | 442篇 |
2006年 | 389篇 |
2005年 | 350篇 |
2004年 | 283篇 |
2003年 | 251篇 |
2002年 | 195篇 |
2001年 | 174篇 |
2000年 | 149篇 |
1999年 | 62篇 |
1998年 | 59篇 |
1997年 | 35篇 |
1996年 | 72篇 |
1995年 | 61篇 |
1994年 | 49篇 |
1993年 | 71篇 |
1992年 | 53篇 |
1991年 | 29篇 |
1990年 | 34篇 |
1989年 | 24篇 |
1988年 | 23篇 |
1987年 | 27篇 |
1986年 | 30篇 |
1985年 | 39篇 |
1984年 | 28篇 |
1983年 | 30篇 |
1982年 | 25篇 |
1981年 | 23篇 |
1980年 | 21篇 |
1979年 | 20篇 |
1978年 | 15篇 |
1977年 | 22篇 |
1976年 | 17篇 |
1975年 | 13篇 |
1934年 | 12篇 |
排序方式: 共有7239条查询结果,搜索用时 31 毫秒
51.
Complexes of TiCl4, VCl4 and SnX4 (X = Cl or Br) with Schiff bases derived from 2-aminobenzimidazole
Agueda Arquero Pilar Souza José A. García-Vázquez José R. Masaguer 《Transition Metal Chemistry》1985,10(11):424-426
Summary The reactions of anhydrous titanium(IV), tin(IV) and vanadium(IV) halides with Schiff bases derived from 2-aminobenzimidazole and 4-methylbenzaldehyde (abimbz) and salicylaldehyde (abisal), yield hexacoordinated complexes M(abimbz)Cl4 and M(abisal)2X4 (M = Ti, Sn or V; X = Cl or Br).The compounds have been characterized by elemental analyses, magnetic measurements, e.p.r., electronic and i.r. spectral studies. I.r. spectra suggest that the Schiff base (abimbz) is coordinated as a bidentate ligand with the metal ion and the (abisal) base acts as a monodentate ligand. 相似文献
52.
Flory-Huggins theory of polymer solutions has been used to express the condition of extrema values in the total sorption, as well as the inversion point in the preferential adsorption parameters for termary polymer systems. Two approaches have been followed, the first considers the binary and ternary interaction parameters independent of polymer concentration and solvent composition. In the second one, this dependence has been introduced. Our attention is focused on the volume fraction of solvent mixture dependence of the above parameters, in order to confirm or not the coincidence between the extrema values and the inversion point. Several cosolvent and cononsolvent ternary polymer systems, have been used to test the validity of the equations obtained. Also, it has been verified, from an experimental point of view, that in cosolvent ternary polymer systems there is coincidence in both compositions while in cononsolvent ternary polymer systems, such coincidence does not appear. 相似文献
53.
Soto-Chinchilla JJ Gámiz-Gracia L García-Campaña AM Imai K García-Ayuso LE 《Journal of chromatography. A》2005,1095(1-2):60-67
The determination of seven sulfonamides by means of HPLC with chemiluminescence detection is proposed for the first time. The analytes are derivatized with fluorescamine, separated and subsequently they participate in the post-column chemiluminescence (CL) peroxyoxalate system using imidazole as a catalyst. Among the different peroxyoxalates tested, bis[4-nitro-2-(3,6,9-trioxadecyloxycarbonyl)phenyl] oxalate provides higher sensitivities and stabilities, avoiding precipitation problems. A rigorous optimization of the significant variables by means of experimental designs has been developed in order to reconcile the chromatographic conditions with the CL reaction. The method provides detection limits in the low microgl(-1) range and has been satisfactorily applied to the analysis of spiked raw milk samples. 相似文献
54.
Piero Pino Felix Oldani Giambattista Consiglio 《Journal of organometallic chemistry》1983,250(1):491-497
In the hydroformylation of ethylene with approximately equimolar H2/D2 mixtures and Rh4(CO)12 or Co2(CO)8 as the catalyst precursor about 50% of propionaldehyde-d1 was formed. The propionaldehyde-d0/d2 ratio was ~ 3 for rhodium and ~ 2.6 for the cobalt catalyst. On the basis of the results and assuming that there is no rapid M(H)2/M(D)2 scrambling, activation of hydrogen through M(H)2 or M(H)2(olefin) complexes can be excluded. 相似文献
55.
Gonzalo Cerruela García Irene Luque Ruiz Miguel Ángel Gómez-Nieto 《Journal of mathematical chemistry》2006,40(3):213-231
In this paper, we propose a new method for clustering of chemical databases based on the representation of measurements of structural similarity onto multidimensional spaces. The proposed method permits the tuning of the clustering process through the selection of the dimension of the projection space, the normal vectors and the sensibility of the projection process. The structural similarity of each element regarding to the database elements is projected onto the defined spaces generating clusters that represent the characteristics and diversity of the database and whose size and characteristics can be easily adjusted. 相似文献
56.
The reactions of [Ru(3)(CO)(12)] with half equivalent of 2-amino-6-methylpyridine (H(2)ampy) or 2-aminopyridine (H(2)apy) in refluxing xylene give the hexanuclear products [Ru(6)(mu(3)-H)(2)(mu(5)-eta(2)-L)(mu-CO)(2)(CO)(14)] (L = ampy, 1; apy, 2). These reactions represent the first high-yield syntheses of hexanuclear complexes with a basal edge-bridged square pyramidal metallic skeleton. Five metal atoms of these complexes are bridged by the N-donor ligand in such a way that the edge-bridging metal atom is attached to the pyridine nitrogen, while the basal atoms of the square pyramid are capped by an imido fragment that arises from the activation of both N-H bonds of the NH(2) group. The reactive sites of these complexes in CO substitution reactions have been determined by studying the reactivity of 1 with triphenylphosphine. Two kinetically controlled monosubstitutions take place on the edge-bridging metal atom in positions cis to the pyridine nitrogen, leading to a mixture of two isomers of formula [Ru(6)(mu(3)-H)(2)(mu(5)-eta(2)-ampy)(mu-CO)(2)(CO)(13)(PPh(3))] (3 and 4). On heating at 80 degrees C, these monosubstituted isomers are transformed, via a dissociative pathway, into the product of thermodynamic control (5), which has the PPh(3) ligand on the apical Ru atom. The di- and trisubstituted derivatives [Ru(6)(mu(3)-H)(2)(mu(5)-eta(2)-ampy)(mu-CO)(2)(CO)(12)(PPh(3))(2)] (6) and [Ru(6)(mu(3)-H)(2)(mu(5)-eta(2)-ampy)(mu-CO)(2)(CO)(11)(PPh(3))(3)] (7) are stepwise formed from 3-5 and PPh(3). Compound 6 has the PPh(3) ligands on the edge-bridging and apical Ru atoms, and compound 7 has an additional PPh(3) ligand on an unbridged basal Ru atom. The compound [Ru(6)(mu(3)-H)(2)(mu(5)-eta(2)-ampy)(mu-CO)(2)(CO)(12)(mu-dppm)] (8), in which a basal and the apical Ru atoms are spanned by the dppm ligand, has been isolated from the reaction of 1 with bis(diphenylphosphino)methane. 相似文献
57.
The present paper describes a procedure that phenols in air were preconcentrated in a membrane cell and their content was determined by adsorptive polarography. First, the phenols in air samples were preconcentrated in a membrane cell using 2.0 M NaOH solution, then in a pH 1.3 buffer solution p-bromophenylamine forms a diazoate with NaNO(2), and into the mixture the collected phenols were added to form azo-compound in a pH 13 buffer solution. The azo-compound can be adsorbed at the mercury electrode and yields a sensitive oscillopolarographic wave. Over the range 2.0x10(-8)-2.0x10(-5) M, the peak currents are linearly proportional to the concentration of phenols. The detection limit is 5.0x10(-9) M. 相似文献
58.
Abstract— The technique of forming bilayer lipid membranes (BLM) has made it possible to study photoreactions of pigments in an environment that is much closer to those in photosynthetic and visual membranes. A pigmented BLM system with Mg2+ -porphyrins as membrane-bound pigments and with ferricyanide and ferrocyanide as the aqueous electron acceptor and donor, respectively, was used to illustrate the photoelectric effects due to coupled interfacial charge transfer reactions.
The steady-state continuous photoresponse was studied by means of the voltage clamp method and a null current method. The independence of the pigment conductance channel and the ionic conductance channel was demonstrated. A tunable voltage clamp method was used to study the transient pulsed photoresponses. Such a measurement permits us to characterize the photosystem in terms of an equivalent circuit model which contains a novel chemical capacitance. Molecular interpretation of this equivalent circuit model was given.
A microscopic model based on the Gouy–Chapman theory and chemical kinetics calculation leads to an equivalent circuit which is also equivalent to the previous one. Generalization of this microscopic model further leads to a physical mechanism of the generation of the early receptor potential (ERP) in visual membranes. Relevance of pigmented BLM research to photosynthesis and other disciplines was also discussed. 相似文献
The steady-state continuous photoresponse was studied by means of the voltage clamp method and a null current method. The independence of the pigment conductance channel and the ionic conductance channel was demonstrated. A tunable voltage clamp method was used to study the transient pulsed photoresponses. Such a measurement permits us to characterize the photosystem in terms of an equivalent circuit model which contains a novel chemical capacitance. Molecular interpretation of this equivalent circuit model was given.
A microscopic model based on the Gouy–Chapman theory and chemical kinetics calculation leads to an equivalent circuit which is also equivalent to the previous one. Generalization of this microscopic model further leads to a physical mechanism of the generation of the early receptor potential (ERP) in visual membranes. Relevance of pigmented BLM research to photosynthesis and other disciplines was also discussed. 相似文献
59.
N. Cutillas J. Gálvez G. García G. López 《Journal of Thermal Analysis and Calorimetry》1982,24(1):67-74
The thermal treatment of the pentafluorophenyl derivativesM(C6F5)2Dxn [M=Pd (n=2, 3) or Pt (n=2); Dx=dioxane] leads to the formation of the new dioxane adducts M(C6F5)2Dx (M=Pd, Pt) and Pt(C6F5)2Dx1.5. Calculations of the order of reaction and the activation energy of some of the decomposition reactions are described. The values were determined by the Coats-Redfern and Freeman-Carroll methods. Structural data on the isolated intermediates were obtained by infrared spectroscopy and magnetic susceptibility measurements.
Zusammenfassung Die thermische Behandlung der PentafluorphenylderivateM(C6F5)2Dxn [M=Pd (n=2, 3) oder Pt (n=2); Dx=Dioxan] führt zu der Bildung der neuen DioxanaddukteM(C6F5)2Dx (M=Pd, Pt) und Pt(C6F5)2Dx1.5. Die Berechnungen der Reaktionsordnung und der Aktivierungsenergie einiger Zersetzungsreaktionen werden beschrieben. Die Werte wurden durch die Methoden von Coats-Redfern und Freeman-Carroll bestimmt. Die Strukturangaben der isolierten Zwischenprodukte wurden durch Infrarotspektroskopie und Messung der magnetischen Suszeptibilität erhalten.
(6F5)2, M=Pd n=2, 3 Pt n=2, - , -M(C6F5)2 (=Pd, Pt) (6F5)21,5. , — —. .相似文献
60.
Summary The reactions of divalent nickel and copper salts with the Schiff base derived from 2-(2-aminophenyl)benzimidazole and benzaldehyde, L, yield complexes of general formulae [CuL2X2] (X=Cl, Br, or ClO4), [CuL(SO4)], [CuL(SO4)] · 4H2O, and NiLX2 (X=Cl, Br, or NCS).All the complexes have been characterized by elemental analyses, magnetic measurements, e.s.r. electronic and i.r. spectral studies. The results show that the Schiff base acts as bidentate ligand through the pyridine-like imine nitrogen of imidazole ring and the azomethine nitrogen. Tentative structures of the complexes are suggested. 相似文献