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951.
A recently proposed perturbational approach to the electron correlation cusp problem 1 is tested in the context of three spherically symmetrical two‐electron systems: helium atom, hydride anion, and a solvable model system. The interelectronic interaction is partitioned into long‐ and short‐range components. The long‐range interaction, lacking the singularities responsible for the electron correlation cusp, is included in the reference Hamiltonian. Accelerated convergence of orbital‐based methods for this smooth reference Hamiltonian is shown by a detailed partial wave analysis. Contracted orbital basis sets constructed from atomic natural orbitals are shown to be significantly better for the new Hamiltonian than standard basis sets of the same size. The short‐range component becomes the perturbation. The low‐order perturbation equations are solved variationally using basis sets of correlated Gaussian geminals. Variational energies and low‐order perturbation wave functions for the model system are shown to be in excellent agreement with highly accurate numerical solutions for that system. Approximations of the reference wave functions, described by fewer basis functions, are tested for use in the perturbation equations and shown to provide significant computational advantages with tolerable loss of accuracy. Lower bounds for the radius of convergence of the resulting perturbation expansions are estimated. The proposed method is capable of achieving sub‐μHartree accuracy for all systems considered here. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003 相似文献
952.
It is difficult to quantify NH4+ by ion chromatography in the presence of high concentrations of Na+ due to peak overlap. The Dionex IonPac CS15 column, which contains phosphonate, carboxylate, and 18-crown-6 functional groups, was originally developed to overcome this problem. We have found that the addition of 18-crown-6 to the eluent promotes improved peak resolution between Na+ and NH4+ even at concentrations as high as 60,000 to 1 using this column. Its use also improves the separation of alkali and alkaline earth metal and amine cations. Mobile phase 18-crown-6 increased the retention times of CH3NH3+, NH4+, and K+, and decreased the retention time of Sr2+. The retention times of Li+, Na+, Mg2+, Ca2+, (CH3)2NH2+, and (CH3)3NH+ were not affected. This method makes possible the direct analysis of ammonia from nitrogenase, the enzyme responsible for biological nitrogen fixation. The resolution of the NH4+ peak from the Na+ and Mg2+ peaks improved from zero resolution to values of 6.19 and 5.65, respectively. This technique considerably reduces the analysis time of NH4+ in the presence of high concentrations of Mg2+ and Na+ over traditional indophenol measurements. 相似文献
953.
《Journal of separation science》2003,26(11):1028-1034
Reversed phase liquid chromatography with diode array detection (DAD) and electrospray mass spectrometric (ESI MSD) methods were developed for the identification of anthraquinone color components of cochineal, lac dye, and madder – red natural dyestuffs. Electrospray mass spectrometry was found to be more suitable than diode array detection for such analysis because of its higher sensitivity (detection limits in the range 30–90 ng mL–1) and selectivity. The developed method permitted unequivocal identification of carminic acid and laccaic acid A as coloring matters in examined preparations of cochineal and lac dye, respectively. In madder more chemical color species were found: alizarin, purpurin, lucidin, ruberythric acid, and also aluminum and calcium alizarin lake. Among the methods recommended so far, the present one allows fast, direct, and unequivocal identification of components of very complicated natural products used in art. 相似文献
954.
Summary A simple and sensitive method has been developed for the liquid chromatographic determination of short-chain aliphatic amines
in water. Analytes are retained in solid-phase extraction (SPE) cartridges, and then derivatized by drawing an aliquot of
the fluorogeneic reagent 9-fluorenylmethyl chloroformate (FMOC) through the cartridges. After a certain reaction time the
derivatives formed are desorbed with acetonitrile. The collected extracts are then chromatographed on a LiChrospher 100 RP18 125 mm×4 mm i.d., 5 μm, column using an acetonitrile-water gradient. The influence of experimental conditions (SPE material,
volume of sample, concentration of FMOC, time of reaction and pH) has been investigated. Optimal results have been obtained
with C18 SPE cartridges using a sample volume of 5.0 mL. For derivatization, 0.25 mL aliquots of 25 mM FMOC have been used, the reaction
time being only 2 min. The method has been applied to the quantification of several aliphatic amines: methylamine, ethylamine,
dimethylamine,n-butylamine,n-pentylamine andn-hexylamine. Under the proposed conditions the percentages of analytes retained plus derivatized were of about 54–107% compared
to those obtained with direct solution derivatization. The method provided good reproducibility, linearity and accuracy within
the 0.050–1.0 mg L−1 concentration range. The limits of detection were in the 0.25–5.0 μg L−1 range. The utility of the described approach has been tested by analysing tap water, river water and industrial waste water. 相似文献
955.
Michael Sax 《Tetrahedron》2005,61(1):205-211
A novel solid phase synthesis of 2-substituted 2,3-dihydropyridin-4(1H)-ones using Rinkamide-polystyrene-resin is described. The key step involves a hetero-Diels-Alder reaction of Danishefsky's diene with solid phase bound imines, which was carefully optimized. Using this method even ketones are transformed into 2,2-disubstituted dihydropyridones. 相似文献
956.
Hydrothermal phase equilibria studies have been carried out in the Ln2O3-H2O systems (Ln = La, Pr, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu) and the stability fields of the phases Ln(OH)3 LnOOH and Ln2O3-C have been established in the pressure-temperature range of 25000 psi and 900° C. The sequioxides Ln2O3-C are stable only in the last four systems of Er to Lu along with the Ln(OH)3 and LnOOH. The systems from Nd to Ho have only Ln(OH)3 and LnOOH as stable phases and those from La to Pr have only Ln(OH)3 as the stable phase. The unit cell parameters of trihydroxides deviate from the values reported in the literature and this
is attributed to the contamination of CO2 in the starting material. 相似文献
957.
Porous polymer spherical particles for column packings in nonaqueous size-exclusion chromatography (SEC) were prepared from 1,2-syndiotactic polybutadiene by suspension and evaporation method. The polymer microbeads obtained were crosslinked by radical reaction between 2-vinyl groups in polybutadiene with ultraviolet radiation, to render them insoluble. These microbeads have wider chromatographic separation width than polystyrene column packings. In addition, the polybutadiene microbeads did not show the excessive retention observed with commercial polystyrene columns for polycyclic aromatic compounds. Therefore, a close correlation between the elution volume and M, for polycyclic aromatic compounds was observed with polybutadiene microbeads columns. 相似文献
958.
A new Schiff base, N,N′-bis-(2-hydroxy-5-bromobenzyl)-2-hydroxy-1,3-diiminopropane, has been synthesized for the very sensitive
determination of iron(III) and iron(II) in natural water samples. It enabled a very selective and rapid method for iron determination
to be developed. The method has also been applied to total iron determination in sediment samples. In the preconcentration
system, the Schiff base reagent is mixed with the samples and chelates containing iron(III). The complexes are then adsorbed
on silica gel within a column system. Elution of the adsorbed chelate from the silica gel was performed with a small volume
of acetone containing 2.5% nitric acid. The iron is measured off-line by flame atomic absorption spectrometry. The method
can be applied to the preconcentration, separation and speciation of iron. The effects of parameters such as pH, sample flow
rate, eluent flow rate, foreign ions and ligand concentration have been investigated. The effect of humic acid that can produce
complexes with metal ions in natural systems has also been investigated. The results obtained indicate that the method is
not affected by the presence of up to 10 ppm humic acid, which would be a very high concentration to be present in natural
systems. The solid phase extraction method developed has been applied to the determination of iron in both natural water samples
and sediment samples. The LOD was found to be 0.17 mg L−1 when no preconcentration was used, although preconcentration factors of 100 could be achieved. The recovery values for spiked
samples were between 100 and 104%. The results were compared statistically with those from the standard 1,10 phenanthroline
method used for iron speciation in water systems. A Student’s t-test indicated no significant difference between the two methods. In addition, this method was applied to the analysis of
a certified sediment sample, LGC 6156. Generally, a 10-fold preconcentration factor was required for the analysis of natural
water samples. 相似文献
959.
Jan Franz 《International journal of quantum chemistry》2006,106(4):773-786
This work presents multi‐state multi‐reference Møller–Plesset second‐order perturbation theory as a variant of multi‐reference perturbation theory to treat electron correlation in molecules. An effective Hamiltonian is constructed from the first‐order wave operator to treat several strongly interacting electronic states simultaneously. The wave operator is obtained by solving the generalized Bloch equation within the first‐order interaction space using a multi‐partitioning of the Hamiltonian based on multi‐reference Møller–Plesset second‐order perturbation theory. The corresponding zeroth‐order Hamiltonians are nondiagonal. To reduce the computational effort that arises from the nondiagonal generalized Fock operator, a selection procedure is used that divides the configurations of the first‐order interaction space into two sets based on the strength of the interaction with the reference space. In the weaker interacting set, only the projected diagonal part of the zeroth‐order Hamiltonian is taken into account. The justification of the approach is demonstrated in two examples: the mixing of valence Rydberg states in ethylene, and the avoided crossing of neutral and ionic potential curves in LiF. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 相似文献
960.
W. Wasiak 《Chromatographia》1987,23(6):423-426
Summary A column packing containing thiol groups chemically bonded to the silica surface was synthesized. The thiol functional groups were used as ligands capable of forming stable complexes with Cu(II). The prepared material was characterized by gas chromatography using unsaturated linear and branched hydrocarbons as well as cyclic and aromatic hydrocarbons. The occurrence of specific metal—olefin interactions resulting from the formation of -complexes during the chromatographic process was observed.Part IV of a series on transition metal complexes in GC. Part III see ref. [1]. 相似文献