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121.
Ab initio molecular orbital theory and density functional theory have been used to study nine isomers of N7 ionic clusters with low spin at the HF/6-31G*, MP2/6-31G*, B3LYP/6-31G*, and B3LYP/6-311(+)G* levels of theory. All stationary
points are examined with harmonic vibrational frequency analyses. Four N7
+ isomers and five N7
− isomers are determined to be local minima or very close to the minima on their potential-energy hypersurfaces, respectively.
For N7
+ and N7
−, the energetically low lying isomers are open-chain structures (C
2
v
and C
2
v
or C2). The results are very similar to those of other known odd-number nitrogen ions, such as N5
+, N9
+, and N9
−, for which the open-chain structures are also the global minima. This research suggests that the N7 ionic clusters are likely to be stable and to be potential high-energy-density materials if they could be synthesized.
Received: 16 July 2001 / Accepted: 8 October 2001 / Published online: 21 January 2002 相似文献
122.
A new kinetic-catalytic method by the initial rate procedure for the determination of nanogram level of iron(III) is developed, which is based on its catalytic effect on the oxidative coupling of 3-methyl-2-benzothiazolinone hydrazone (MBTH) with N,N-dimethylaniline (DMA) to form an indamine dye (λmax=590 nm) in the presence of hydrogen peroxide. Iron(II) is also determined, being oxidized to iron(III) by hydrogen peroxide. Calibration graphs obtained by the initial rate method are linear in the range 1–1000 ng ml−1 Fe and as low as 10−8 M Fe(II, III) can easily be determined. The relative standard deviations are 6.6, 2.5 and 1.5% for ten determinations of 1, 20 and 60 ng ml−1 of Fe(III), respectively. The method is applicable to the determination of iron in natural waters without preconcentration and separation. 相似文献
123.
124.
《Electroanalysis》2005,17(23):2129-2136
The investigation of the dissolved iron(III)–nitrilotriacetate–hydroxide system in the water solution (I=0.1 mol L?1 in NaClO4; pH 8.0±0.1) using differential pulse cathodic voltammetry, cyclic voltammetry, and sampled direct current (DC) polarography, was carried out on a static mercury drop electrode (SMDE). The dissolved iron(III) ion concentrations varied from 2.68×10?6 to 6×10?4 mol L?1 and nitrilotriacetate concentrations were 1×10?4 and 5×10?4 mol L?1. By deconvoluting of the overlapped reduction voltammetric peaks using Fourier transformation, four relatively stable, dissolved iron(III) complex species were characterized, as follows: [Fe(NTA)2]3?, mixed ligand complexes [FeOHNTA]? and [Fe(OH)2NTA]2?, showing a one‐electron quasireversible reduction, and binuclear diiron(III) complex [NTAFeOFeNTA]2?, detected above 4×10?4 mol L?1 of the added iron(III) ions, showing a one‐electron irreversible reduction character. The calculations with the constants from the literature were done and compared with the potential shifts of the voltammetric peaks. Fitting was obtained by changing the following literature constants: log β2([Fe(NTA)2]3?) from 24 to 27.2, log β1([FeNTA]?) from 8.9 to 9.2, log β2([Fe(NTA)2]4?) from 11.89 to 15.7 and log β2([Fe(OH)2NTA]3?) from 15.63 to 19. The determination of the electrochemical parameters of the mixed ligand complex [FeOHNTA]?, such as: transfer coefficient (α), rate constant (ks) and formal potential (E°') was done using a sampled DC polarography, and found to be 0.46±0.05, 1.0±0.3×10?3 cm s?1, and ?0.154±0.010 V, respectively. Although known previously in the literature, these four species have now for the first time been recorded simultaneously, i.e. proved to exist simultaneously under the given conditions. 相似文献
125.
A. V. Virovets S. N. Konchenko P. S. Yuferov D. Fenske 《Journal of Structural Chemistry》2004,45(3):496-501
The crystal structures of three cluster compounds: [(µ-H)Fe2Mo(µ3-Te)(CO)8Cp*], [FeMo2(µ3-Te)(CO)7x Cp*2], and [FeMoW(µ3-Te)(CO)7CpCp*], where Cp = 5-C5H5, Cp* = 5-C5 (CH3)5, have been investigated. In the cluster with a tetrahedral {FeMo2Te} core, one can observe positional isomerism of the carbonyl and cyclopentadienyl ligands with respect to the plane through the Fe and Te atoms and the center of the Mo2bond, resulting in two mirror isomers in the racemic crystal. In the cluster with the {FeMoWTe} core, additional chirality causes the formation of four diastereoisomers. Earlier, the structure of the [FeMoW(µ3-Se)(CO)7Cp] cluster with Mo and W atoms coordinated to identical Cp-ligands has been structurally defined. In this crystal, statistical disordering of Mo and W over the metal positions is observed. In the [FeMo(Cp*)W(Cp)(µ3-Te)(CO)7] cluster studied here, the Mo and W atoms are coordinated to different cyclopentadienyl ligands. Due to this, two of four diastereoisomers were isolated as ordered racemic crystals; the other two are nonexistent for steric reasons.Original Russian Text Copyright © 2004 by A. V. Virovets, S. N. Konchenko, P. S. Yuferov, and D. FenskeTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 522–527, May–June 2004. 相似文献
126.
Tarasevich Yu. I. Bondarenko S. V. Zhukova A. I. 《Theoretical and Experimental Chemistry》2004,40(2):125-129
We have used gas chromatography to study the interaction of water and methanol molecules with active hydrophilic centers on the surface of thermally expanded graphite and graphitized thermal carbon black. We have determined the concentration of carboxyl and phenol hydroxyl groups on the surface of the sorbents and the heats of adsorption for adsorption of the studied substances on these groups. We have shown that water molecules are adsorbed as clusters on the hydrophilic centers of the studied sorbents at very low relative pressures, with n = 2 molecules in the cluster. 相似文献
127.
Joel T. Mague 《Journal of Cluster Science》1995,6(2):217-269
The short-bite ligands CH2(PR
2)2 or CH(PR
2)3 (R = Me, Ph),RN(PX
2)2 (R=H, Me, Et;X = F, OR (R= Me, Et, i-Pr, Ph), Ph),RE(CH2
ER2)2 (E = P, As;R = Me, Ph ), Ph2 P(2-C5H4N) and related species are particularly versatile for the synthesis of di- and polynuclear complexes which frequently possess metal-metal bonds. In addition to homometallic products, these ligands often permit the directed synthesis of heterometallic complexes. Selected aspects of the chemistry of these complexes are also reviewed. 相似文献
128.
Stefan Motiu Daniela Dogaru Valentin Gogonea 《International journal of quantum chemistry》2007,107(5):1248-1252
This work puts forth a reaction pathway for the reactivation of exogenous ligand inhibited H‐cluster, the active site of Fe‐only hydrogenases. The H‐cluster is a dimetal complex, Fe–Fe, with the metal centers bridged by di(thiomethyl)amine. Exogenous ligands, H2O, and OH?, are bound to the distal iron (Fed). Density functional theory (DFT) calculations on the native and ruthenium‐modified H‐cluster have been performed using the B3LYP functional with 6‐31+G** and 6‐311+G** basis sets. We have ascertained that there is a thermodynamically favorable pathway for the reactivation of the OH? inhibited H‐cluster, which proceeds by an initial protonation of the Fed–OH? complex. The proposed reaction pathway has all its intermediate reactions ensue exothermically. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
129.
Rodríguez-Cea A de la Campa MR Sanz-Medel A 《Analytical and bioanalytical chemistry》2005,381(2):388-393
Cytochromes P-450 are members of a superfamily of hemoproteins involved in the oxidative metabolism of various physiological and xenobiotic compounds in eukaryotes and prokaryotes. The multiplicity of this group of enzymes has been widely studied by chromatographic techniques, mainly high-performance liquid chromatography (HPLC). Because these enzymes are membrane-bound proteins, sample preparation for chromatographic separation of P-450 enzymes requires a solubilization step. The sample-preparation procedures are critical, because detergents affect not only the efficiency of protein solubilization but also their further chromatographic resolution. Trout liver microsomes have been taken here as a model sample to investigate iron speciation in cytochrome P-450. Trouts were treated intraperitoneally with -naphthoflavone, a potent inducer of some P-450 enzymes, and a microsomal suspension containing 7.4±0.1 nmol mL–1 P-450 enzymes was obtained by ultracentrifugation. Lubrol PX was selected as detergent for solubilization, resulting in about 90% solubilization recovery. The solubilized cytochromes P-450 were further separated by AE–FPLC, with UV detection, or coupled to ICP–MS with an octapole reaction system, ICP–(ORS)MS (monitoring Fe signals at masses 54, 56, and 57). A sampling procedure and chromatographic conditions are developed and were successfully applied to iron speciation in trout liver P-450 enzymes. ICP–(ORS)MS detection of P-450 enzymes is Fe-specific and so will give accurate information on the prosthetic group of the protein, which can constitute an advantageous alternative to classical methods for detection of these hemoproteins. 相似文献
130.
痕量铁的光化学伏安分析法及其应用研究 总被引:1,自引:0,他引:1
在稀硫酸介质中及活化剂草酸存在下,痕量铁(Ⅲ)对结晶紫光化学褪色反应有强烈催化作用,结晶紫的光化学反应产物于-0.70产生一灵敏的2.5次微分级谱波。 相似文献