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81.
A sequential injection analysis (SIA) system was developed with the aim of obtaining an automatic and versatile way to prepare standards needed in the study of systems with higher dimensional sensor signals. To illustrate this, different analytical techniques were used in determinations of several analytes. Automated potentiometric calibrations of different potentiometric sensors, with and without interference, were carried out. Useful determinations of selectivity coefficients with two degrees of freedom were obtained. Simultaneous voltammetric determinations have also been done. Firstly, simultaneous determinations of lead and cadmium, using epoxy-graphite composite as the working electrode, have enabled a separate calibration for each metal to be obtained. Next, a voltammetric electronic tongue was designed and applied to the determination of oxidizable species. The use of artificial neural networks has solved the overlapped signal of ascorbic acid, 4-aminophenol and 4-acetamidophenol (paracetamol). A set of 63 data points was prepared automatically and has facilitated the training of an electronic tongue for these three analytes. Accurate predictions of test solutions, in the range of 12–410 μM for ascorbic acid, 17–530 μM for 4-aminophenol and 10–420 μM for paracetamol, have been achieved with RMSEs lower than 0.10 μM. 相似文献
82.
I. V. Korol’kov A. I. Gubanov K. V. Yusenko I. A. Baidina S. A. Gromilov 《Journal of Structural Chemistry》2007,48(3):486-493
Several non-equilibrium solid solutions belonging to the platinum-osmium systems Os0.9Pt0.1, Os0.8Pt0.2, Os0.5Pt0.5, Os0.7Pt0.3, Os0.75Pt0.25 are prepared and studied. The thermal decomposition of [Pt(NH3)4][OsCl6] in the hydrogen and helium atmosphere is investigated. It is found that the Pt0.5Os0.5 solid solution develops through the formation of (NH4)2[OsCl6] and a metallic phase based on Pt. The crystal structure of a double complex salt [Pt(NH3)4][OsCl6] is studied (X8-APEX Bruker, 1508 independent reflections, R = 2.04%). Crystal data for PtOsN4Cl6H12 are: a = 11.6216(5) Å, b = 11.0016(5) Å, c = 10.3819(5) Å, V = 1327.4(1) Å3, space group Cmca, Z = 4, d x = 3.333 g/cm3. The coordination polyhedron around Os is octahedral: 〈Os-Cl〉 2.357 Å, ∠Cl-Os-Cl 89.5–90.5°, while around Pt it is square-planar: Pt-N 2.046 Å, ∠ N-Pt-N 89.59° and 90.41°. 相似文献
83.
Zhihong Liu 《Analytica chimica acta》2004,519(2):147-153
Two kinds of polymeric pH indicators PPF (phenolphthalein-formaldehyde product) and CPF (o-cresolphthalein-formaldehyde product) immobilized cross-linked poly(vinyl alcohol) membranes (PPF-PVA and CPF-PVA) for optical intermittent determination of high basicity ([OH−] = 1-8 M) based on a kinetic process were developed. In our previous work, we had demonstrated that PPF-PVA and CPF-PVA could perform the determination of high pH values from pH 10.0 to 14.0. Here the discoloring kinetic behaviors of PPF-PVA and CPF-PVA were compared with those of free phenolphthalein, o-cresolphthalein and thymolphthalein. Experimental results and theoretical analysis indicated that the response behaviors of the optodes’ membranes in concentrated NaOH solutions were diffusion-independent and still complied with the pseudo-first-order kinetics. In addition, two data analysis methods for determination were presented. One was directly based on the reduced absorbance; the other was based on the discoloring kinetic constant. It was found that the latter could perform a rapid (60 s) and reliable (relative standard deviation: 2.6%) determination for high basicity. These kinds of optodes can be used repeatedly when they are immersed in low-pH solutions to regain the protonated form after each determination. 相似文献
84.
85.
Raman spectroscopy was applied for the direct non-destructive analysis of amiodarone hydrochloride (ADH), the active ingredient of the liquid formulation Angoron®. The FT-Raman spectra were obtained through the un-broken as-received ampoules of Angoron®. Using the most intense vibration of the active pharmaceutical ingredient (API) at 1568 cm−1, a calibration model, based on solutions with known concentrations, was developed. The model was applied to the Raman spectra recorded from three as-purchased commercial formulations of Angoron® having nominal strength of 50 mg ml−1 ADH. The average value of the API in these samples was found to be 48.56 ± 0.64 mg ml−1 while the detection limit of the proposed technique was found to be 2.11 mg ml−1. The results were compared to those obtained from the application of HPLC using the methodology described in the European Pharmacopoeia and found to be in excellent agreement. The proposed analytical methodology was also validated by evaluating the linearity of the calibration line as well as its accuracy and precision. The main advantage of Raman spectroscopy over HPLC method during routine analysis is that it is considerably faster and no solvent consuming. Furthermore, Raman spectroscopy is non-destructive for the sample. However, the detection limit for Raman spectroscopy is much higher than the corresponding for the HPLC methodology. 相似文献
86.
This research presents the results of an experimental study on the determination of pyrolysis behaviour and kinetics of six
crude oils by differential scanning calorimetry (DSC) and thermogravimetry (TG/DTG). Crude oil pyrolysis indicated two main
temperature ranges where loss of mass was observed. The first region between ambient to 400°C was distillation. The second
region between 400 and 600°C was visbreaking and thermal cracking. Arrhenius-type kinetic model is used to determine the kinetic
parameters of crude oils studied. It was observed that as crude oils gets heavier (°API decreases) cracking activation energy
increases. Activation energy of cracking also show a general trend with asphaltene content.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
87.
Non-destructive in situ determination of pigments in 15th century wall paintings by Raman microscopy
Raman microscopy has been applied to the study of 15th century wall paintings in a chapel of St. Orso Priory palace (Aosta, Italy) in view of their restoration. The use of a transportable instrument has made it possible to work non-destructively in situ without sampling. The main inorganic pigments used by the unknown artist, namely mercury sulphide, azurite, white lead, red and yellow ochre, carbon black and lead tin yellow type I have been identified, and the presence of organic substances and of some decay products (calcium sulphate and oxalate) has been observed. 相似文献
88.
Interaction between octahedrally coordinated Nd3+ and Yd3+ in Cs2NaNd0,4Yb0,6Cl6 reduces the Nd3+ luminescence lifetime by roughly two orders of magnitude with respect to that found in Cs2NaNdCl6– · – Analysis of low temperature absorption and emission spectra reveals that the nonradiative Nd3+–Yb3+ energy transfer has to be assisted by lattice phonon emission, nevertheless the rate of the transfer is high in the 4–300 K temperature region and attains 5.8×105s-1 at room temperature. A phase transition of Cs2NaNd0,4Yb0,6Cl6 between 12 and 13 K is evidenced by abrupt change of both the spectra and lifetimes of Yb3+. Reduction of Yb3+ lifetime from 5.3 ms to 150 μs is at the transition from low symmetry phase to high symmetry phase is supposed to be associated with a three ion interaction which occurs in ordered lattice and disappears in low temperature disordered structure. 相似文献
89.
O. V. Shishkin A. S. Polyakova S. N. Desenko D. V. Orlov S. V. Lindeman Yu. T. Struchkov 《Russian Chemical Bulletin》1995,44(3):470-474
The equilibrium geometry and inversion barriers of 5,6-dihydropyrimidine, 6,7-dihydroazolopyrimidines with node nitrogen atoms and their alkyl (Me, Et, Pri, But) and phenyl derivatives were calculated using a molecular mechanics approach. Annelation with azole cycles and the introduction of substituents have a slight effect on the equilibrium conformation of the dihydrocycle (distorted sofa). Alkyl substutuents at saturated carbons have an essentially equatorial orientation in 5,6-dihydropyridimine derivatives and are axial in the annelated analogs. On the other hand, the equatorial conformers are more stable in phenyl derivatives of dihydroazolopyrimidines. Factors determining the relative stability of conformers were analyzed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 487–491, March, 1995. 相似文献
90.
《Electroanalysis》2004,16(9):697-711
Voltammetric approaches for the determination of arsenic and speciation at trace levels are critically appraised in a review covering the literature from 1970 to 2002. Special attention is devoted to stripping modes and to issues related to the choice of working material and supporting electrolyte. A section is dedicated to the management of real samples and aspects of sample preparation. An extensive compilation, organized by real sample type, gathers essential experimental conditions. Potentiometric stripping analysis is introduced for sake of comparison. The coupling of voltammetric detection or preaccumulation with FIA, chromatography, capillary electrophoresis and ICP techniques is also addressed. 相似文献