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211.
Zhou XP Xu Z He J Zeller M Hunter AD Clérac R Mathonière C Chui SS Che CM 《Inorganic chemistry》2010,49(21):10191-10198
This paper aims to illustrate the rich potential of the thioether-carboxyl combination in generating coordination networks with tunable and interesting structural features. By simply varying the ratio between Cu(NO(3))(2) and the bifunctional ligand tetrakis(methylthio)benzenedicarboxylic acid (TMBD) as the reactants, three coordination networks can be hydrothermally synthesized in substantial yields, which present a distinct evolution with regard to metal-ligand interactions. Specifically, Cu(TMBD)(0.5)(H(2)TMBD)(0.5)·H(2)TMBD (1) was obtained with a relatively small (1:1) Cu(NO(3))(2)/TMBD ratio, and crystallizes as an one-dimensional (1D) coordination assembly based on Cu(I)-thioether interactions, which is integrated by hydrogen-bonding to additional H(2)TMBD molecules to form a three-dimensional (3D) composite network with all the carboxylic acid and carboxylate groups remaining uncoordinated to the metal ions. A medium (1.25:1) Cu(NO(3))(2)/TMBD ratio leads to compound Cu(2)TMBD, in which Cu(I) ions simultaneously bond to the carboxylate and thioether groups, while an even higher (2.4:1) Cu(NO(3))(2)/TMBD ratio produced a mixed-cation compound Cu(II)(2)OHCu(I)(TMBD)(2)·2H(2)O (2), in which the carboxylic groups are bonded to (cupric) Cu(II) ions, and the thioether groups to Cu(I). Despite the lack of open channels in 2, crystallites of this compound exhibit a distinct and selective absorption of NH(3), with a concomitant color change from green to blue, indicating substantial network flexibility and dynamics with regards to gas transport. 相似文献
212.
213.
214.
Allen JJ Hamilton CE Barron AR 《Dalton transactions (Cambridge, England : 2003)》2010,39(47):11451-11468
The aryl-functionalized pyridylamine 2-(i)PrC(6)H(4)N(H)py (1) and bis(2-pyridyl)amines of the type ArN(py)(2) for Ar = Mes (2), 2,6-Et(2)C(6)H(3) (3), 2-(i)PrC(6)H(4) (4), 2,6-(i)Pr(2)C(6)H(3) (5), and 1-naph (6), have been prepared by the palladium-catalyzed cross-coupling of substituted anilines with 2-bromopyridine, and have been characterized by (1)H and (13)C NMR NMR, FTIR, MS, and TGA. Complexes of these new N-aryl bis(2-pyridyl)amines have been prepared for the acid salts [H{ArN(py)(2)}]BF(4) where Ar = Mes (7) and 2-(i)PrC(6)H(4) (8), and the dimeric bridged complexes [Cu{ArN(py)(2)}(μ-X)(Y)](2) where X/Y = Cl(-) and Ar = Ph (9), 2-(i)PrC(6)H(4) (10), and 1-naph (11), in addition to X = OH(-), Y = H(2)O and Ar = Mes (12). The olefin complexes [Cu(Ar-dpa)(styrene)]BF(4) for Ar = Ph (13), Mes (14), 2-(i)PrC(6)H(4) (15), and 1-naph (16), in addition to the norborylene complexes of Ar = Mes (17) and 2-(i)PrC(6)H(4) (18) have been prepared and characterized by (1)H and (13)C NMR, FTIR, and TGA. The crystal structures have been determined for compounds 1-17. Secondary amine 1 crystallizes in hydrogen-bonded head-to-tail dimers, while the N-aryl bis(2-pyridyl)amines 2-6 crystallize in a three-bladed propellar conformation, having nearly planar geometries about the amine nitrogen. The geometry about copper centers in the dimeric complexes 9-12 is distorted trigonal bypyramidal, with the axial positions occupied by one of the two pyridyl nitrogens and one of the bridging ligands (i.e., Cl or OH). The copper atoms in each of the olefin complexes 13-17 are coordinated to the two pyridine nitrogen atoms and the appropriate olefin; consistent with a pseudo three-coordinate Cu(I) cation. Distortion of pyridyl ring geometries about the copper centers, and concomitant bending of the aryl groups away from the CuN(amine) vectors were found to correlate with the steric bulk of the aryl group present in both dimeric and olefin complexes. Such distortion is also observed to a lesser extent in the acid salts as well. The (1)H and (13)C NMR spectra of [Cu(Ar-dpa)(olefin)]BF(4) exhibit an upfield shift in the olefin signal as compared to free olefin. A good correlation exists between the (1)H and (13)C NMR Δδ values and olefin dissociation temperatures, confirming that the shift of the olefin NMR resonances upon coordination is associated with the binding strength of the complex. 相似文献
215.
Wenhui Zhang Allen G. Oliver Anthony S. Serianni 《Acta Crystallographica. Section C, Structural Chemistry》2010,66(11):o557-o560
3‐Deoxy‐3‐fluoro‐d ‐glucopyranose crystallizes from acetone to give a unit cell containing two crystallographically independent molecules. One of these molecules (at site A) is structurally homogeneous and corresponds to 3‐deoxy‐3‐fluoro‐β‐d ‐glucopyranose, C6H11FO5, (I). The second molecule (at site B) is structurally heterogeneous and corresponds to a mixture of (I) and 3‐deoxy‐3‐fluoro‐α‐d ‐glucopyranose, (II); treatment of the diffraction data using partial‐occupancy oxygen at the anomeric center gave a high‐quality packing model with an occupancy ratio of 0.84:0.16 for (II):(I) at site B. The mixture of α‐ and β‐anomers at site B appears to be accommodated in the lattice because hydrogen‐bonding partners are present to hydrogen bond to the anomeric OH group in either an axial or equatorial orientation. Cremer–Pople analysis of (I) and (II) shows the pyranosyl ring of (II) to be slightly more distorted than that of (I) [θ(I) = 3.85 (15)° and θ(II) = 6.35 (16)°], but the general direction of distortion is similar in both structures [ϕ(I) = 67 (2)° (BC1,C4) and ϕ(II) = 26.0 (15)° (C3TBC1); B = boat conformation and TB = twist‐boat conformation]. The exocyclic hydroxymethyl (–CH2OH) conformation is gg (gauche–gauche) (H5 anti to O6) in both (I) and (II). Structural comparisons of (I) and (II) to related unsubstituted, deoxy and fluorine‐substituted monosaccharides show that the gluco ring can assume a wide range of distorted chair structures in the crystalline state depending on ring substitution patterns. 相似文献
216.
For a graph G of order |V(G)| = n and a real-valued mapping
f:V(G)?\mathbbR{f:V(G)\rightarrow\mathbb{R}}, if S ì V(G){S\subset V(G)} then f(S)=?w ? S f(w){f(S)=\sum_{w\in S} f(w)} is called the weight of S under f. The closed (respectively, open) neighborhood sum of f is the maximum weight of a closed (respectively, open) neighborhood under f, that is, NS[f]=max{f(N[v])|v ? V(G)}{NS[f]={\rm max}\{f(N[v])|v \in V(G)\}} and NS(f)=max{f(N(v))|v ? V(G)}{NS(f)={\rm max}\{f(N(v))|v \in V(G)\}}. The closed (respectively, open) lower neighborhood sum of f is the minimum weight of a closed (respectively, open) neighborhood under f, that is, NS-[f]=min{f(N[v])|v ? V(G)}{NS^{-}[f]={\rm min}\{f(N[v])|v\in V(G)\}} and NS-(f)=min{f(N(v))|v ? V(G)}{NS^{-}(f)={\rm min}\{f(N(v))|v\in V(G)\}}. For
W ì \mathbbR{W\subset \mathbb{R}}, the closed and open neighborhood sum parameters are NSW[G]=min{NS[f]|f:V(G)? W{NS_W[G]={\rm min}\{NS[f]|f:V(G)\rightarrow W} is a bijection} and NSW(G)=min{NS(f)|f:V(G)? W{NS_W(G)={\rm min}\{NS(f)|f:V(G)\rightarrow W} is a bijection}. The lower neighbor sum parameters are NS-W[G]=maxNS-[f]|f:V(G)? W{NS^{-}_W[G]={\rm max}NS^{-}[f]|f:V(G)\rightarrow W} is a bijection} and NS-W(G)=maxNS-(f)|f:V(G)? W{NS^{-}_W(G)={\rm max}NS^{-}(f)|f:V(G)\rightarrow W} is a bijection}. For bijections f:V(G)? {1,2,?,n}{f:V(G)\rightarrow \{1,2,\ldots,n\}} we consider the parameters NS[G], NS(G), NS
−[G] and NS
−(G), as well as two parameters minimizing the maximum difference in neighborhood sums. 相似文献
217.
Paul T. Allen Lars Andersson Alvaro Restuccia 《Communications in Mathematical Physics》2011,301(2):383-410
In this paper we consider the classical initial value problem for the bosonic membrane in light cone gauge. A Hamiltonian
reduction gives a system with one constraint, the area preserving constraint. The Hamiltonian evolution equations corresponding
to this system, however, fail to be hyperbolic. Making use of the area preserving constraint, an equivalent system of evolution
equations is found, which is hyperbolic and has a well-posed initial value problem. We are thus able to solve the initial
value problem for the Hamiltonian evolution equations by means of this equivalent system. We furthermore obtain a blowup criterion
for the membrane evolution equations, and show, making use of the constraint, that one may achieve improved regularity estimates. 相似文献
218.
Çapoğlu İR White CA Rogers JD Subramanian H Taflove A Backman V 《Optics letters》2011,36(9):1596-1598
Rigorous numerical modeling of optical systems has attracted interest in diverse research areas ranging from biophotonics to photolithography. We report the full-vector electromagnetic numerical simulation of a broadband optical imaging system with partially coherent and unpolarized illumination. The scattering of light from the sample is calculated using the finite-difference time-domain (FDTD) numerical method. Geometrical optics principles are applied to the scattered light to obtain the intensity distribution at the image plane. Multilayered object spaces are also supported by our algorithm. For the first time, numerical FDTD calculations are directly compared to and shown to agree well with broadband experimental microscopy results. 相似文献
219.
Radosevich AJ Mutyal NN Turzhitsky V Rogers JD Yi J Taflove A Backman V 《Optics letters》2011,36(24):4737-4739
In this Letter, we describe an easy to implement technique to measure the spatial backscattering impulse-response at length scales shorter than a transport mean free path with resolution of better than 10 μm using the enhanced backscattering phenomenon. This technique enables spectroscopic measurements throughout the visible range and sensitivity to all polarization channels. Through a combination of Monte Carlo simulations and experimental measurements of latex microspheres, we explore the various sensitivities of our technique to both intrinsic sample properties and extrinsic instrumental properties. We conclude by demonstrating the extraordinary sensitivity of our technique to the shape of the scattering phase function, including higher order shape parameters than the anisotropy factor (or first moment). 相似文献
220.
R. J. Ball G. C. Allen G. Starrs W. J. McCarter 《Applied Physics A: Materials Science & Processing》2011,105(3):739-751
The conduction and dielectric behaviour of two different grades of natural hydraulic lime is presented over the frequency
range 1 Hz–1 MHz, with measurements taken over the initial six months after gauging with water. Samples containing embedded
electrodes were exposed to both a natural atmosphere (20°C and 65% relative humidity) and a natural atmosphere with a carbon
dioxide concentration maintained at 400 ppm which was used to accelerate the carbonation process. A decrease in relative dielectric
permittivity and rise in conductivity, with increasing frequency, was observed at all stages over the time-scale presented.
When plotted in the complex plane, the impedance featured a bulk response comprising two depressed semicircles and a low frequency
spur, the latter being associated with the electrode/sample interface. The complex impedance plot, together with the application
of an equivalent circuit model, indicated a dual arc feature with carbonation and hydration contributing to bulk impedance
response. This study demonstrates the applicability of electrical property measurements to monitor the combined processes
of hydration and carbonation in this group of materials. 相似文献