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101.
《Journal of Chemical Sciences》2005,117(5):525-531
The silicon atom may increase its coordination number to values greater than four, to form pentacoordinated compounds. It
has been observed experimentally that, in general, pentacoordinated compounds show greater reactivity than tetracoordinated
compounds. In this work, density functional theory is used to calculate the global softness and the condensed softness of
the silicon atom for SiH
n
F4−n
and SiH
n
F
5−n
1−
. The values obtained show that the global and condensed softness are greater in the pentacoordinated compounds than in the
tetracoordinated compounds, a result that explains the enhanced reactivity. If the results are analysed through a local version
of the hard and soft acids and bases principle, it is possible to suggest that in nucleophilic substitution reactions, soft
nucleophiles preferably react with SiH
n
F
5−n
1−
, and hard nucleophiles with SiH
n
F4−n
. 相似文献
102.
Rodrigo París José Luis de la Fuente 《Journal of polymer science. Part A, Polymer chemistry》2007,45(16):3538-3549
Different diblock copolymers constituted by one segment of a monomer supporting a reactive functional group, like allyl methacrylate (AMA), were synthesized by atom transfer radical polymerization (ATRP). Bromo‐terminated polymers, like polystyrene (PS), poly(methyl methacrylate) (PMMA), and poly(butyl acrylate) (PBA) were employed as macroinitiators to form the other blocks. Copolymerizations were carried out using copper chloride with N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) as the catalyst system in benzonitrile solution at 70 °C. At the early stage, the ATRP copolymerizations yielded well‐defined linear block copolymers. However, with the polymerization progress a change in the macromolecular architecture takes place due to the secondary reactions caused by the allylic groups, passing to a branched and/or star‐shaped structure until finally yielding gel at monomer conversion around 40% or higher. The block copolymers were characterized by means of size exclusion chromatography (SEC), 1H NMR spectroscopy, and differential scanning calorimetry (DSC). In addition, one of these copolymers, specifically P(BA‐b‐AMA), was satisfactorily modified through osmylation reaction to obtain the subsequent amphiphilic diblock copolymer of P(BA‐b‐DHPMA), where DHPMA is 2,3‐dihydroxypropyl methacrylate; demonstrating the feasibility of side‐chain modification of the functional obtained copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3538–3549, 2007 相似文献
103.
Anatoliy Malyarenko 《Journal of Theoretical Probability》2006,19(2):263-288
We prove a general functional limit theorem for multiparameter fractional Brownian motion. The functional law of the iterated
logarithm, functional Lévy’s modulus of continuity and many other results are its particular cases. Applications to approximation
theory are discussed.
相似文献
104.
In this paper we prove existence results for semilinear neutral functional differential inclusions with finite or infinite
delay in Banach spaces. Our theory makes use of analytic semigroups and fractional powers of closed operators, integrated
semigroups and cosine families.
相似文献
105.
We study the geometry of determinant line bundles associated with Dirac operators on compact odd-dimensional manifolds. Physically, these arise as (local) vacuum line bundles in quantum gauge theory. We give a simplified derivation of the commutator anomaly formula using a construction based on noncyclic trace extensions and associated nonmultiplicative renormalized determinants. 相似文献
106.
107.
Jie Xue Liang Chen Li Zhou Zhifeng Jia Yanping Wang Xinyuan Zhu Deyue Yan 《Journal of Polymer Science.Polymer Physics》2006,44(15):2050-2057
α‐Cyclodextrin (α‐CD) has been complexed with various poly(ethylene glycol) (PEG) derivatives in aqueous solution. It has been found that the end groups of PEG derivatives affect the complexation kinetics greatly, but have only a little influence on the thermodynamic behavior. By increasing the hydrophobicity of end groups, the complexation speeds up rapidly. On the other hand, the bulky end groups slow down the threading of polymeric guests into the cavity of CD. By changing the hydrophobicity and the size of end groups, the complexation rate can be adjusted in the range of several orders of magnitudes, which should be quite useful in the design of new supramolecular systems. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2050–2057, 2006 相似文献
108.
Magnetic properties of Co chain-coated carbon nanotube (CNT) were investigated using a first-principles calculation. Binding energy between Co chain and CNT increased with the coverage ratio, and the adsorption of Co chains on CNT enhanced the conductance channel. Total magnetic moment of Co chains coated on CNT increased with the coverage ratio, while the magnetic moment per Co atom decreased due to spin flip of majority spin states in Co atoms. Spin polarization at the Fermi level of the Co chains was calculated to converge to that of bulk fcc Co. 相似文献
109.
We introduce the notion of n-nuanced MV-algebra by performing a Łukasiewicz–Moisil nuancing construction on top of MV-algebras. These structures extend both MV-algebras and Łukasiewicz–Moisil algebras, thus unifying two important types of structures in the algebra of logic. On a logical level, n-nuanced MV-algebras amalgamate two distinct approaches to many valuedness: that of the infinitely valued Łukasiewicz logic, more related in spirit to the fuzzy approach, and that of Moisil n-nuanced logic, which is more concerned with nuances of truth rather than truth degree. We study n-nuanced MV-algebras mainly from the algebraic and categorical points of view, and also consider some basic model-theoretic aspects. The relationship with a suitable notion of n-nuanced ordered group via an extension of the Γ construction is also analyzed. 相似文献
110.
Simon R. Blackburn 《Journal of Combinatorial Theory, Series A》2006,113(7):1572-1581
The paper contains proofs of the following results. For all sufficiently large odd integers n, there exists a set of 2n−1 permutations that pairwise generate the symmetric group Sn. There is no set of 2n−1+1 permutations having this property. For all sufficiently large integers n with n≡2mod4, there exists a set of 2n−2 even permutations that pairwise generate the alternating group An. There is no set of 2n−2+1 permutations having this property. 相似文献