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101.
Densities have been measured as a function of composition for ternary-pseudobinary mixtures of [(benzene + toluene or methylcyclohexane)
+ (cyclohexane + toluene or methylcyclohexane)] by means of a vibrating-tube densimeter at atmospheric pressure and the temperature
298.15 K. The excess molar volumes, VmE, were calculated from the densities and correlated using the Redlich–Kister equation to estimate the coefficients and standard
errors. The experimental and calculated quantities are used to discuss the mixing behavior of the components. The results
show the third component, toluene and methylcyclohexane, influences the interaction between benzene and cyclohexane. 相似文献
102.
A microfabricated device is reported that has been designed to permit the in situ packing of a section of channel with enzyme immobilised onto controlled pore glass (CPG). It is fabricated from glass and polydimethylsiloxane and to prevent dead volumes, has dedicated channels for packing the reactor. The device has the advantage of being simple in design, the flow through enzyme reactor channel being simply a widened section of the analyte channel. The system is suitable for both hydrodynamic and electro-osmotic pumping, and is designed such that when the packing is exhausted it can be repacked. Controlled pore glass provides a reproducible none swelling, high porosity medium onto which the enzyme could be immobilised. The large particle size meant that it was vital to optimise the immobilisation procedure in order to achieve acceptable enzyme activity. The microfabricated device was developed with two enzymes of different molecular masses; alkaline phosphatase and xanthine oxidase. The pore size of the CPG was found to be very important for xanthine oxidase, where the 697 Å pore size (120-200 mesh) CPG was found to give the highest activity (18-20% activity retained after immobilisation). The microfabricated device was used for the assay of p-nitrophenyl phosphate and hypoxanthine with spectrophotometric detection at 405 and 470 nm, respectively. The limits of detection were 5 and 8 μM, respectively. 相似文献
103.
Immobilized sulfhydryl groups were prepared by partial thiolation of NH2-glass beads. The microenvironment of the immobilized SH groups was varied by different chemical modifications of neighboring
NH2 groups. Introduction of a strong charge in the surroundings of immobilized sulfhydryls results in their dramatic stabilization
against autooxidation. This effect is due to the salting of O2 from the surface microlayer of the thiolated beads. 相似文献
104.
Pentaazadienido Complexes of Zinc, Cadmium, and Mercury. The Crystal Structure of [Cd(EtOC6H4-N5-C6H4OEt)2(py)2] and [Hg(tol-N5-tol)2(py)] The pentaazadienido complexes [M(EtOC6H4N5C6H4OEt)2] (M = Zn ( 1 ), Cd ( 2 )) are formed by the reaction of [M(NH3)4]2+ with [EtOC6H4N5C6H4OEt]? in aqueous ammonia. 2 crystallizes from pyridine as [Cd(EtOC6H4N5C6H4OEt)2py2] ( 3 ) with the triclinic space group P1 and a = 937.2(2); b = 1422.7(2); c = 2085.5(2) pm; α = 75.28(1)°; β = 94.74(1)°; γ = 99.75(1)°; Z = 2. The central Cd2+ ion of 3 exhibits an octahedral coordination by two pyridine ligands in cis arrangement and two (N1, N3)-2+ chelating pentaazadienide ions. The reaction of [HgI4]2 with the 1,5-di(tolyl)pentaazadienide anion in aqueous ammonia affords [Hg(p-tol-N5-tol)2] ( 4 ), which crystallizes from pyridine in form of [Hg(tol-N5-tol)2py] ( 5 ) with the space group P1 and a = 1176.2(4); b = 1203.1(3); c = 1295.6(5) pm; α = 100.77(3)°; β = 110.08(3)°; γ = 94.29(2)°; Z = 2. In 5 the Hg2+ cation is threefold coordinated by two monodentate (N3)-η1 pentaazadienid anions and one pyridine ligand. Within the N5 chains of the pentaazadienid anions of 3 and 5 localized N? N double bonds are found in the positions N1? N2 and N4? N5 with distances between 125 and 129 pm. 相似文献
105.
E. N. Ushakov L. G. Kuz’mina A. I. Vedernikov M. S. Kapichnikova J. A. K. Howard M. Wörner A. M. Braun M. V. Alfimov S. P. Gromov 《Russian Chemical Bulletin》2006,55(1):94-100
The structures of new butadienyl dyes of the benzothiazole series containing the dithia-15-crown-5 (2a) or dithia-18-crown-6 (2b) fragments were established by X-ray diffraction. Complexation of dyes 2a,b with Hg2+, Pb2+, Cd2+, Ag+, Zn2+, and alkaline-earth cations in aqueous-acetonitrile solutions was studied by spectrophotometry. At a high percentage of water
in solutions (P
w ≈ 50%), these dyes have a very low ability to bind Pb2+ cations (logK < 2) and virtually do not bind Cd2+, Zn2+, and alkaline-earth cations. At the same time, these dyes form stable 1: 1 complexes with Hg2+ and Ag+ cations at all P
w. The stability constants of complexes with the Ag+ cation increase with increasing P
w because the free energy of hydration of this cation is much lower than the free energy of solvation in acetonitrile. In the
P
w range from 0 to 75%, the stability constants of the complexes of dyes 2a,b with the Hg2+ cation are larger than those of the corresponding complexes with the Ag+ cation by more than four orders of magnitude.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 90–96, January, 2006. 相似文献
106.
107.
Ignacio López-García Mateo Sánchez-Merlos Manuel Hernández-Córdoba 《Spectrochimica Acta Part B: Atomic Spectroscopy》1997,52(14):378-2092
A graphite furnace atomic absorption spectrometric procedure for the determination of mercury is presented, in which the samples are suspended in a solution containing hydrofluoric and nitric acids. Silver nitrate (4% m/v) and potassium permanganate (3%) are incorporated, in the order specified, and aliquots are directly introduced into the graphite furnace. A fast heating programme with no conventional pyrolysis step is used. The detection limit for mercury in a 125 mg ml−1 suspension is 0.1 μg g−1. Calibration is performed by using aqueous standards. The reliability of the procedure is proved by analysing certified reference materials. 相似文献
108.
Densities and apparent molar volumes of aqueous 2-chloroethanol were determined at temperatures from 15.0 to 34.4°C using digital densimetry. The results of the volumetric measurements have been used to calculate the following thermodynamic quantites at 25°C: V
2
o = 55.05 ± 0.02 cm3-mol–1, (V
2
o/T)p = 0.01486 ± 0.00318 cm3-K–1-mol–1, and (2
V
2
o/T
2)p = 0.02972 ± 0.00318 cm3-K–2-mol–1. Partial molar volumes of transfer from water to 1 mol-dm–3 2-chloroethanol have also been determined for L-glycine, L-alanine, L-serine, L-glutamic acid, and L-aspartic acid at 35.0°C. The transfer results have been explained in terms of the nature of the interactions of the groups in the solute and solvent. Hydration numbers of L-glycine and L-alanine have also been calculated in aqueous 2-chloroethanol. 相似文献
109.
A new theoretical approach of the isothermal crystallization of a thin polymer film is proposed. This model, derived from Evans' theory, is in very good agreement with a previous one, but is much more interesting because it makes it possible to calculate the transformed volume fraction anywhere in the film. The main effects of decreasing thickness are a slower average crystallization of the film and a decrease in the Avrami exponent caused by a slower crystallization of the polymer close to the surfaces.A slight modification of the model allows us to calculate the isothermal crystallization kinetics at any point of the film when it contains two identical transcrystalline regions on its surfaces.All the models are well verified by computer simulations. 相似文献
110.
《Electroanalysis》2006,18(11):1081-1089
This paper describes the voltammetric behavior of As(III) at the hanging mercury drop electrode (HMDE) in the presence of sodium diethyl dithiocarbamate (SDDC) and a new voltammetric method for the determination of As(III) at trace levels. The method is based on the adsorptive deposition of a As(III) complex with SDDC at ?0.45 V (vs. Ag/AgCl) on the HMDE in acidic medium of 0.01 mol L?1 HCl (pH 2.0) and its cathodic stripping during the potential scan (100 mV s?1). The linear range for the determination of As(III) in the presence of SDDC (4 μmol L?1) in water samples was between 1 and 10 μg L?1 for a deposition time of 300 s (r=0.994) and between 10 and 100 μg L?1 for a deposition time of 60 s (r=0.999). For the determination of As(III) in dialysis concentrate samples, the linear range was between 5 and 25 μg L?1 for a deposition time of 180 s (r=0.992) and between 10 and 100 μg L?1 for a deposition time of 60 s (r=0.996). Detection limits of 0.3 and 2.2 μg L?1 in water and dialysis concentrate samples were calculated for the method using a deposition time of 300 and 180 s, respectively. Recovery values between 93.0 and 110.0% for As(III) added to deionized, mineral, seawater (synthetic and real) and dialysis concentrate samples prove the satisfactory accuracy and applicability of the procedure. 相似文献