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81.
A simple and novel method was developed to successfully synthesize N-succinyl-O-carboxymethylchitosan (NSOCMCS) using N-acylation of chitosan with succinic anhydride. The NSOCMCS structure was characterized by Fourier transform infrared and
1H nuclear magnetic resonance. The aggregation behaviors of NSOCMCS were studied using fluorescence spectroscopy, dynamic light
scattering, and atomic force microscopy techniques. The critical aggregation concentration of NSOCMCS in water was determined
to be 0.2–0.3 mg/ml. The apparent hydrodynamic radium of an NSOCMCS aggregate was dependent on the concentration. The aggregates
demonstrated a much swollen association conformation in aqueous solution. The possible aggregation mechanisms for the NSOCMCS
in water are discussed. Moreover, a driving force to form an open aggregation morphology was revealed in this study. Aggregation
behaviors are important physicochemical properties of NSOCMCS, which impact the potential application in the biomedical field. 相似文献
82.
Horn M Ihringer J Glink PT Stoddart JF 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(17):4046-4054
A template-directed dynamic clipping procedure has generated a library of nine [2]rotaxanes that have been formed from three dialkylammonium salts-acting as the dumbbell-shaped components-and three dynamic, imino bond-containing, [24]crown-8-like macrocycles-acting as the ring-shaped components-which are themselves assembled from three dialdehydes and one diamine. The rates of formation of these [2]rotaxanes differ dramatically, from minutes to days depending on the choice of dialkylammonium ion and dialdehyde, as do their thermodynamic stabilities. Generally, [2]rotaxanes formed by using 2,6-diformylpyridine as the dialdehyde component, or bis(3,5-bis(trifluoromethyl)benzyl)ammonium hexafluorophosphate as the dumbbell-shaped component, assembled the most rapidly. Those rotaxanes containing this particular electron-deficient dumbbell-shaped unit, or 2,5-diformylfuran units in the macroring, were the most stable thermodynamically. The relative thermodynamic stabilities of all nine of the [2]rotaxanes were determined by competition experiments that were monitored by (1)H NMR spectroscopy. 相似文献
83.
The results of NMR-spectroscopy studies of the structure, dynamic stereochemistry, and intermolecular interactions in solutions
of organic derivatives of penta-and hexacoordinated silicon, germanium, and tin containing amidomethyl, lactamomethyl, and
related bidentate ligands are surveyed.
For the series of works “Dynamic stereochemistry of hypervalent compounds of silicon, germanium, and tin,” the author was
awarded the Academia Europea Prize for young scientists from CIS in 1996.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1912–1934. November, 1997. 相似文献
84.
The title sterically crowded di-9-anthrylethyne derivative with 3,5-iPr2-phenyl groups at 1-position showed a barrier to rotation about the acetylenic axis of 18.0 kcal mol−1 based on a dynamic NMR study, which is an extremely high value for acyclic diarylethynes. The mechanism of the dynamic stereochemistry and the substituent effect on the rotational barrier are discussed. 相似文献
85.
Josef Janča 《Mikrochimica acta》1994,112(5-6):197-215
The primary field forces can generate spatially oriented gradient of the effective property of a continuum or pseudo-continuum fluid (carrier liquid). When this gradient is coupled with the action of a secondary field of identical or different nature the isoperichoric focused zones of the dispersed species can appear. Consequently, they can be separated according to differences responding to the property gradient of the carrier liquid. This concept can be applied under static (non-flow) conditions in thin layer focusing as well as under dynamic conditions with the elution due to the carrier liquid flow in focusing field-flow fractionation. The gradient established by the action of the primary field and the concentration distribution of the isoperichoric focused zone formed by the coupled effect of the gradient and of the primary or secondary field are described theoretically. The rigorous relationship describing the shape of the focused zone is compared with the approximate solutions. The performances of the proposed principle were evaluated by model calculations. Potential experimental configurations considering the implementation of the static and dynamic conditions are discussed. The generalized isoperichoric focusing theory can be applied to describe the particular processes operating in analytical and preparative focusing separations of the particles of various, but especially of biological origin. 相似文献
86.
87.
Wojciech Paszkowicz 《Analytica chimica acta》2006,566(1):81-98
Genetic algorithms represent a powerful global-optimisation tool applicable in solving tasks of high complexity in science, technology, medicine, communication, etc. The usual genetic-algorithm calculation scheme is extended here by introduction of a quadratic self-learning operator, which performs a partial local search for randomly selected representatives of the population. This operator is aimed as a minor deterministic contribution to the (stochastic) genetic search. The population representing the trial solutions is split into two equal subpopulations allowed to exhibit different mutation rates (so called asymmetric mutation). The convergence is studied in detail exploiting a crystallographic-test example of indexing of powder diffraction data of orthorhombic lithium copper oxide, varying such parameters as mutation rates and the learning rate. It is shown through the averaged (over the subpopulation) fitness behaviour, how the genetic diversity in the population depends on the mutation rate of the given subpopulation. Conditions and algorithm parameter values favourable for convergence in the framework of proposed approach are discussed using the results for the mentioned example. Further data are studied with a somewhat modified algorithm using periodically varying mutation rates and a problem-specific operator. The chance of finding the global optimum and the convergence speed are observed to be strongly influenced by the effective mutation level and on the self-learning level. The optimal values of these two parameters are about 6 and 5%, respectively. The periodic changes of mutation rate are found to improve the explorative abilities of the algorithm. The results of the study confirm that the applied methodology leads to improvement of the classical genetic algorithm and, therefore, it is expected to be helpful in constructing of algorithms permitting to solve similar tasks of higher complexity. 相似文献
88.
Stern HA 《Journal of computational chemistry》2004,25(5):749-761
We review principles of non-Hamiltonian statistical mechanics and present a new set of equations and integration algorithm for isothermal-isobaric dynamics. The chief advantage of the present scheme is that it is somewhat simpler than previous methods. We perform numerical simulations to test the accuracy of the algorithm and compare its stability to that of a "gold standard," a symplectic integrator for Hamiltonian dynamics of the same system. The stability of the isothermal-isobaric algorithm is comparable to the stability of the symplectic integrator. 相似文献
89.
建立了气相色谱过程的动态数学模型,给出了模型的实用算法,并据此对各种操作条件下的色谱流出曲线进行了动态模拟计算。模拟计算结果表明该模型是有效的,能够用于各种程序控制的色谱过程,可得到色谱分离的优化条件。 相似文献
90.