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1.
Marcelino Maneiro Manuel R. Bermejo M. Isabel Fernndez Ana M. Gonzlez‐Noya Alexei M. Tyryshkin Robin G. Pritchard 《无机化学与普通化学杂志》2003,629(2):285-290
A new MnIII‐Schiff base complex, [MnL(OH2)](ClO4) ( 1 ) (H2L = N, N′‐bis‐(3‐Br‐5‐Cl‐salicylidene)‐1, 2‐diimino‐2‐methylethane), an inorganic model of the catalytic center (OEC, Oxygen Evolving Complex) in photosystem II (PSII), has been synthesized and characterized by elemental analysis, IR and EPR spectroscopy, mass spectrometry, magnetic susceptibility measurement and the study of its redox properties by cyclic and normal pulse voltammetry. This complex mimics reactivity (showing a relevant photolytic activity), and also some structural characteristics (parallel‐mode MnIII EPR signal from partially assembled OEC cluster) of the natural OEC. The complex 1 was found to rearrange in solution into a crystallographically solved square‐pyramidal complex, [MnLL′] ( 2 ) (HL′ = 6‐bromo‐4‐chloro‐2‐cyanophenol), through a process, which probably liberates radical species (detected by EPR), and provokes a C—N bond cleavage in the ligand. A photo‐radical mechanism is discussed to explain this rearrangement. 相似文献
2.
We employ an agent‐based model to show that memory and the absence of an a priori best strategy are sufficient for self‐segregation and clustering to emerge in a complex adaptive system with discrete agents that do not compete over a limited resource nor contend in a winner‐take‐all scenario. An agent starts from a corner of a two‐dimensional lattice and aims to reach a randomly selected site in the opposite side within the shortest possible time. The agent is isolated during the course of its journey and does not interact with other agents. Time‐bound obstacles appear at random lattice locations and the agent must decide whether to challenge or evade any obstacle blocking its path. The agent is capable of adapting a strategy in dealing with an obstacle. We analyze the dependence of strategy‐retention time with strategy for both memory‐based and memory‐less agents. We derive the equality spectrum to establish the environmental conditions that favor the existence of an a priori best strategy. We found that memory‐less agents do not polarize into two opposite strategy‐retention time distributions nor cluster toward a center distribution. © 2004 Wiley Periodicals, Inc. Complexity 9: 41–46, 2004 相似文献
3.
In this paper a cubic lattice L(S) is endowed with a symmetric implication structure and it is proved that L(S) \ {0} is a power of the three-element simple symmetric implication algebra. The Metropolis–Rota’s symmetries are obtained as partial terms in the language of symmetric implication algebras. 相似文献
4.
Lanthanum doped bismuth titanate thin films (Bi3.25La0.75Ti3O12 - BLT) were produced by the polymeric precursor method and crystallized in a domestic microwave oven and in conventional furnace. Using platinum coated silicon substrates configuration, ferroelectric properties of the films were determined with remanent polarization Pr and a coercive field Ec of 3.9 μC/cm2 and 70 kV/cm for the film annealed in the microwave oven and 20 μC/cm2 and 52 kV/cm for the film annealed in conventional furnace, respectively. The films annealed in conventional furnace exhibited excellent retention-free characteristics at low infant periods indicating that BLT thin films can be a promise material for use in non-volatile memories. On the other hand, the pinning of domains wall causes a strong decay at low infant periods for the films annealed in the microwave furnace which makes undesireable the application for future FeRAMS memories. 相似文献
5.
M. Jesús Rodríguez M. Isabel Fernndez Ana M. Gonzlez‐Noya Marcelino Maneiro Rosa Pedrido Miguel Vzquez Bruno Donnadieu Manuel R. Bermejo 《无机化学与普通化学杂志》2005,631(11):2161-2166
M(HL)(H2O)n complexes have been obtained by the electrochemical reaction of Fe, Co, Ni, Cu, Zn and Cd anodes with the potentially pentadentate and trianionic asymmetrical Schiff base 3‐aza‐N‐{2‐[1‐aza‐2‐(5‐nitro‐2‐hydroxylphenyl)‐vinyl]phenyl}‐4‐(5‐nitro‐2‐hydroxyphenyl)but‐3‐enamide (H3L), containing a hard amido donor atom. The complexes have been characterized by elemental analysis, mass spectrometry, IR and 1H NMR spectroscopies, magnetic measurements and molar conductivities. Co(HL)(H2O) ( 2 ) has been found to rearrange in DMF solution into a crystallographically solved octahedral complex, CoL1(H2O)2 ( 7 ) [where H2L1 is the symmetrical Schiff base ligand N,N′‐(1,2‐phenylene)‐bis(5‐nitro‐3‐hydroxysalicylidenimine)]. A hydrolysis mechanism is discussed to explain this rearrangement. 相似文献
6.
M. Zampieri S. R. Lazaro C. A. Paskocimas A. G. Ferreira E. Longo J. A. Varela 《Journal of Sol-Gel Science and Technology》2006,37(1):9-17
Titanium citrate and lead and titanium citrate were prepared by polymeric precursor method in aqueous solution. This citrate
was analyzed by 1H, 13C NMR and gHMBC–NMR (Hetero-nuclear multiple-bond correlation) to investigate the formation of the citrate complexs and influence
of the Pb2+ ion in this complex. These complexs were characterized by interaction between Ti4+ ion and citric acid carboxyls. Quantum mechanic simulations in level ab initio were used to study the electronic structure and natural charges (NBO) to both the complexs. Such techniques indicated the
formation of an octahedral complex with an arrangement similar to Ti atom in the crystalline structure of the PbTiO3. A study using the technique FT-Raman made possible the confirmation of the interaction among the Ti4+ and Pb2+ ions with the citric acid carboxyls. 相似文献
7.
On the basis of Altona's empirical generalization of the Karplus equation, an expression of 3JH,H as function of pseudorotation parameters for five-membered rings, was deduced. The resulting equation was parametrized by means of molecular mechanics calculations for tetrahydrofuran and tetrahydrothiophene. Estimation of 3JH,H for the full pseudorotational itinerary was made. From the best fit between calculated and measured 3JH,H values the preferred conformation of those rings may be established. The procedure was applied for the conformational analysis of 4-thiohexofuranose derivatives, having and β,
-galacto and D- manno, and -
-talo configurations. 相似文献
8.
Maria do Carmo Rangel Varela Milton Francisco de Jesus Filho Fernando Galembeck 《Hyperfine Interactions》1994,83(1):159-167
Mössbauer spectroscopy was used to follow the aging of ferrihydrite with different amounts of acetate, to achieve more crystalline products. Mössbauer spectra of fresh samples did not show any magnetic components. After two years aging, the solids presented crystalline fractions. Hematite formation was inhibited as acetate content increased in solids. For an acetate/iron molar ratio equal to 0.63 goethite was formed instead of hematite. X-ray diffraction confirmed these results. This work shows that synthetic samples can be used for elucidating the anti-hematitic effect of organic matter already detected in soils. 相似文献
9.
LetA be a von Neumann algebra and a faithful normal state. ThenO
= {
ºAd(g
1) :g G
A
}andU
= {
ºAd(u
*) :u U
A
are homogeneous reductive spaces. IfA is aC
* algebra,e
the Jones projection of the faithful state viewed as a conditional expectation, then we prove that the similarity orbit ofe
by invertible elements ofA can be imbedded inAA in such a way thate
is carried to 1 1 and the orbit ofe
to a homogeneous reductive space and an analytic submanifold ofAA. 相似文献
10.
2-Acetoxy-3,4-di-O-acetyl-D-arabinal (6), similar to its D-xylo analogue 4, reacted with benzyl alcohol by the tin(IV) chloride-promoted glycosylation to produce optically active (S)-2-benzyloxy-2H-pyran-3(6H)-one (8a). The L-arabinal derivative (5) gave 9a, the dihydropyranone enantiomer of 8a. These results indicated that the configuration of the C-4 stereocenter in the starting glycal defines the configuration of the new chiral center in the resulting dihydropyranone. The influence of other catalysts (BF(3) or iodine) employed for the glycosylation on the optical purity of the dihydropyranone was studied. Enantiomerically pure dihydropyranones 8b and 9c were obtained using chiral alcohols ((R)- and (S)-2-octanol, respectively) as glycosylating agents. Compounds 8a,b and 9a,c proved to be reactive dienophiles in thermal and Lewis acid-promoted Diels-Alder reactions. The addition of 2,3-dimethylbutadiene, cyclopentadiene, and 1,3-cyclohexadiene to the beta-pyranones 8a,b led to the corresponding adducts 10a,b, 12a,b, and 16a,b as major products. Enantiomeric cycloadducts were synthesized from the alpha-pyranones 9a,c. The main products were formed by highly facial-diastereoselective addition of dienes to the pyranone ring, guided by the sterical hindrance of the alkoxy substituent of the C-2 stereocenter. As cycloadditions with cycloalkadienes were also highly endo diastereoselective, these reactions gave access to pure tetrahydrobenzopyranones that carry a multitude of stereogenic centers installed in a predictable way. 相似文献