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71.
Ammonium acetate was found to catalyze efficiently the selective deprotection of aromatic acetates in the presence of various sensitive functionalities in aqueous methanol under neutral conditions at room temperature to yield the corresponding phenols in excellent yields. The method has been utilized for deprotection of acetates of several naturally occurring bioactive phenolic compounds and for preparation of venkatasin, a natural coumarino-lignan, from the anticancer compound cleomiscosin A. 相似文献
72.
Chakraborty R Das AK Cervera ML De La Guardia M 《Analytical and bioanalytical chemistry》1996,355(1):43-47
The determination of cadmium in different sample types has been carried out by electrothermal atomization atomic absorption spectrometry with D(2)-background correction using a unpyrocoated graphite tube, after pressurized microwave-assisted digestion. Five chemical modifiers [(NH(4))(2)HPO(4), Pd(NO)(3))(2), Ni(NO(3))(2), thiourea and Triton X-100] have been assayed and nickel nitrate has been found to be most effective for an accurate determination of cadmium in mussel tissue, pig kidney and sewage sludge. The characteristic mass of the method is of the order of 1 pg and the limit of detection is lower than 0.1 ng/ml. 相似文献
73.
Summary The synthesis and coordination behaviour of 1-allylbenzotriazole (ABT), containing both -donating heterocyclic ring nitrogen(s) and a -bonding olefinic group, has been studied by complexation with CoII, NiII, CuII, CuI and AgI salts. The solid complexes M(ABT)2X2 (M=Co, Ni or Cu and X=a counterion) and M(ABT)X (M=Cu or Ag and X=Br, I, or NO3) have been characterised by1H-n.m.r. (representative CuI species) and other physical data. Different modes coordination for the title ligand have been proposed based upon i.r. data which indicate the participation of a -donating ring nitrogen only in complexes with bivalent metal salts, and the involvement of both the ring nitrogen and the allylic olefinic component in bonding to a monovalent metal ion.1H-n.m.r. data are qualitatively commensurate with participation of the allyl group in monovalent metal complexes. 相似文献
74.
An atomic-absorption method for determination of tungsten in rocks and minerals is proposed. The method involves sample decomposition by acid digestion or by pyrosulphate fusion, followed by chelate extraction of tungsten by N-benzoylphenylhydroxylamine in toluene. Atomic-absorption measurements are made on the organic phase aspirated into a nitrous oxide-acetylene flame. Quantitative extraction with efficient separation from other elements is achieved in a single extraction from strong acid media. The method is rapid and reliable in terms of precision and accuracy and is applicable to rocks and minerals containing tungsten in the range from 100 ppm to 15%. 相似文献
75.
B. C. Purkayastha Nityaranjan Das 《Journal of Radioanalytical and Nuclear Chemistry》1975,25(1):35-46
The study of homogeneous distribution coefficients in determining the transition temperatures of isomorphologically analogous components and in predicting the existences of some new unstable compounds has been carried out in detail with special references to vitriols of nickel, manganese, zinc, copper and magnesium. In the course of the investigation with NiSO4·7H2O as host and54Mn as guest, the transition temperature of orthorhombic NiSO4·7H2O was shown to be 26.5 °C, and with orthorhombic ZnSO4·7H2O and MgSO4·7H2O as host and copper sulphate as guest, the limits of existences of orthorhombic CuSO4·7H2O and newly predicted CuSO4·6H2O were found to be 13.5° to 44 °C and 44° to 51 °C, respectively. In addition, the transition temperatures of orthorhombic MnSO4·7H2O (10 °C), stable NiSO4·7H2O (30.5±5 °C) and orthorhombic ZnSO4·7H2O (39 °C) were verified. The new method of approach is very simple, reproducible and easily adaptable. 相似文献
76.
Kinetic studies of the aminolysis of [methyl(thiomethyl)carbene]pentacarbonyl chromium(0),(CO)5CrC(CH3)(SCH3) (1-Cr(S)) and [methyl(thiomethyl)carbene]pentacarbonyltungsten(0), (CO)5WC(CH3)(SCH3) (1-W(S)), with morpholine, a secondary amine, in 50% acetonitrile-50% H2O (v/v at 25 °C) is reported. The second-order rate constant (kA in m−1 s−1) increases with amine concentration, giving a linear dependence with an intercept on the rate axis and a tendency towards leveling off at higher amine concentration. The reaction was found to undergo general base catalysis. The mechanism proposed is very similar to those for ester reactions, involving a nucleophilic addition of amine to the substrate to yield a zwitterionic tetrahedral intermediate in the first step, followed by deprotonation to form in the second step, which, in the third step, converted to product by H2O and/or conjugate acid of the base (BH+), assisted MeS− expulsion. The reactivity (k1) of 1-W(S) was found to be higher than that of 1-Cr(S), whereas, comparable , water catalyzed and , BH+ catalyzed, leaving group departure were found for both the carbenes complexes. All these observations have been explained successfully. 相似文献
77.
Kalyan K. Das D. Mukherjee S. P. Bhattacharyya 《International journal of quantum chemistry》1989,35(4):483-494
Structural parameters of a set of five thiocarbonyl molecules in the lowest nπ* states are calculated by using a generalized orbital optimization algorithm (a variant of the orthogonal gradient method) in an INDO MCSCF framework. Transition energies, singlet-triplet splittings, planar inversion barriers, and dipole moments in nπ* states of different spin multiplicities are reported. Predicted structural features agree reasonably well with available experimental or theoretical data. Some interesting trends are noted in the computed inversion barrier heights, singlet-triplet splittings, and dipole moments in nπ* states. 相似文献
78.
S. Gangadharan V. V. Lakshmi M. Sankar Das 《Journal of Radioanalytical and Nuclear Chemistry》1973,15(1):287-304
Correlations between the growth of hair and the trace element profile have been investigated by non-destructive neuron activation
analysis through gamma-ray speetrometry using NaI(Tl) as well as Ge(Li) detectors. After preliminary investigations to establish
the experimental errors, the effect of washing procedures and in-person variations, hair samples belonging to ladies with
known case histories, particularly with regard to dietary habits, health and profession, were examined. Scalp-hair samplex
50–100 cm in length, representing an average time span of ∼5–10 years were collected by combing. Samples in their non-anagen
phase, differentiated by their roots, were analysed in 10 cm sections. The concentrations of the following elements were determined:
Na, Cl, Mn, Co, Cu, Zn, As, Se, Ag, I, Au and Hg. Absolute values for the concentrations are reported for most of the elements,
while for the rest relative values for the various sections are given. The values for the different sections vary by large
factors for many elements although for some elements, like Cu and Mn, the variations are not appreciable. The unusually large
concentrations of elements like Se ang Hg are in broad agreement with the case histories. However, detailed examination of
the results with regard to time-dependent variations seem to pose serious problems in the applications to forensic science. 相似文献
79.
Summary The exchange of Co(NH3)6]3+-ions on amberlite IRC-50 resin has been studied at room temperature. For this exchange process the cations are effective
in the order: Cs+<Rb+<K+<Na+<Li+<NH4
+<Mg2+ <Ca2+<H+ and (C2H5)4N<(CH3)4N+ ≪Cetyltrimethylammonium-ion <Cetylpyridinium-ion.
The logarithm of the selectivity coefficient gives linear graphs when plotted against the radius of the hydrated ions or the
reciprocals of theDebye-Hückel parameter?. 相似文献
80.
Jayaram B McConnell K Dixit SB Das A Beveridge DL 《Journal of computational chemistry》2002,23(1):1-14
Noncovalent association of proteins to specific target sites on DNA--a process central to gene expression and regulation--has thus far proven to be idiosyncratic and elusive to generalizations on the nature of the driving forces. The spate of structural information on protein--DNA complexes sets the stage for theoretical investigations on the molecular thermodynamics of binding aimed at identifying forces responsible for specific macromolecular recognition. Computation of absolute binding free energies for systems of this complexity transiting from structural information is a stupendous task. Adopting some recent progresses in treating atomic level interactions in proteins and nucleic acids including solvent and salt effects, we have put together an energy component methodology cast in a phenomenological mode and amenable to systematic improvements and developed a computational first atlas of the free energy contributors to binding in approximately 40 protein-DNA complexes representing a variety of structural motifs and functions. Illustrating vividly the compensatory nature of the free energy components contributing to the energetics of recognition for attaining optimal binding, our results highlight unambiguously the roles played by packing, electrostatics including hydrogen bonds, ion and water release (cavitation) in protein-DNA binding. Cavitation and van der Waals contributions without exception favor complexation. The electrostatics is marginally unfavorable in a consensus view. Basic residues on the protein contribute favorably to binding despite the desolvation expense. The electrostatics arising from the acidic and neutral residues proves unfavorable to binding. An enveloping mode of binding to short stretches of DNA makes for a strong unfavorable net electrostatics but a highly favorable van der Waals and cavitation contribution. Thus, noncovalent protein-DNA association is a system-specific fine balancing act of these diverse competing forces. With the advances in computational methods as applied to macromolecular recognition, the challenge now seems to be to correlate the differential (initial vs. final) energetics to substituent effects in drug design and to move from affinity to specificity. 相似文献