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171.
Electrically-induced optical storage effects in smectic polysiloxanes A variable transmission device
Abstract Changes in the optical transmission induced by electric fields have been studied in a smectic side-chain polysiloxane liquid crystal. The transmission varied from effectively zero, for a highly scattering (opaque) texture, to total, for a homeotropic texture, on increasing the applied voltage across the material. The field-induced textures were durably stored in the smectic phase, enabling the order parameter of the side groups to be studied by dielectric relaxation measurements. For the highly transparent texture, a side group order parameter of 0-92 has been observed. 相似文献
172.
Two new pyrrole amide–crown ether conjugates have been synthesised and their anion complexation properties studied in the absence and presence of stoichiometric quantities of sodium or caesium cations. Certain anions are sequestered by the metal cation in DMSO-d 6 (0.5% water), however, in one case a 4.7 fold increase in the fluoride affinity of the receptor was observed upon addition of caesium cations. 相似文献
173.
Simon J. Coles Philip A. Gale Mark E. Light Colin N. Warriner 《Supramolecular chemistry》2013,25(7):469-486
A variety of furan and thiophene amide and thioamide cleft type anion receptors have been synthesised and crystallographically characterised. Unlike 2,5-diamidopyrrole anions, analogous 2,5-diamidofurans and thiophenes do not interlock in the solid state. The anion binding properties of these receptors have been investigated in DMSO/0.5% water solution using 1H NMR titration techniques. Solution studies and solid-state evidence suggests that the thiophene receptors may utilise a thiophene CH hydrogen atom for hydrogen bond formation to anions with a 2,4-diamidothiophene showing similar anion binding affinities to a 2,5-diamidopyrrole. 相似文献
174.
Mohammed A. Altahan Simon J. Coles Peter N. Horton 《Phosphorus, sulfur, and silicon and the related elements》2020,195(11):952-956
Abstract[Cu(en){B6O7(OH)6}].3H2O (1) (en = 1,2-diaminoethane), obtained as a crystalline solid in low yield (31%) after prolonged standing of an aqueous solution initially containing [Cu(en)2](OH)2 and B(OH)3 (1:7 ratio), was characterized by thermal analysis (TGA/DSC), 11B NMR and IR spectroscopy, powder XRD, and single-crystal XRD studies, and magnetic susceptibility measurements. The single-crystal X-ray diffraction revealed that the oxidoborate complex is a 1D coordination polymer with the hexaborate(2-) ligand bridging two hexacoordinate Cu(II) centers, in an alternating a fac-tridentate (κ3-O) and monodentate (κ1-O) arrangement. Cu-O coordination bonds and extensive H-bonding networks promote and stabilize the self-assembly of [Cu(en){B6O7(OH)6}].3H2O from the Dynamic Combinatorial Libraries of available reactants. [Cu(en){B6O7(OH)6}].3H2O is thermally decomposed to CuB6O10 in air at 700?°C. 相似文献
175.
Nakanishi W Hayashi S Pitak MB Hursthouse MB Coles SJ 《The journal of physical chemistry. A》2011,115(42):11775-11787
The structure of 2-(2-pyridylimino)-2H-1,2,4-thiadiazolo[2,3-a]pyridine (NSN) indicates that the molecule has a planar geometry with a linear N···S···N linkage, creating a tetracyclic structure of the formal C(2v) symmetry. To clarify the nature of the NSN σ(3c-4e) bonding, together with the related NSeN and NTeN, the dynamic and static behaviors are investigated by applying atoms-in-molecules (AIM) dual functional analysis to both the fully optimized and perturbed structures. The structures were optimized computationally, retaining C(2v) symmetry. All bond critical points are detected as expected and exhibited on both sides of the N···Z···N moiety which supports the formation of NZN σ(3c-4e). It is confirmed that N···S···N is of the covalent nature close to Me(2)S(+)-?-Cl or Me(2)Se(+)-?-Br, whereas N···Se···N and N···Te···N have the (regular) CS nature close to the CT adducts of Me(2)S(-?-Cl)(2) (TBP) and Me(2)Se-?-Br(2) (MC), respectively. An experimental high-resolution charge density determination has been performed on NSN, which thoroughly supports the theoretical results. Very similar results are obtained in the analogous pyrimidyl derivatives for N···S···N, N···Se···N, and N···Te···N. AIM dual functional analysis, as validated by experimental high-resolution charge densities, is thus confirmed to be an excellent method to elucidate the nature of these interactions. 相似文献
176.
Beşli S Coles SJ Davies DB Kılıç A Shaw RA 《Dalton transactions (Cambridge, England : 2003)》2011,40(19):5307-5315
Cyclotriphosphazene derivatives containing a P-NHR group in the side-chain react in the presence of a strong base to form stable intermolecular bridged products. Reaction of sodium hydride with mono-spiro cyclophosphazene derivatives having a P-NH group, N(3)P(3)Cl(4)[O(CH(2))(3)NH], (1a) or N(3)P(3)Cl(4)[CH(3)N(CH(2))(3)NH], (1b) leads to formation of bis-cyclophosphazenes bridged with an eight-membered cyclophosphazene ring in an ansa arrangement (2a, 2b) whereas reaction of sodium hydride with mono-amino cyclophosphazene derivatives [N(3)P(3)Cl(5)(NHR), R = n-hexyl, 3a; i-Pr, 3b; Ph, 3c] give bis-cyclophosphazenes bridged with a four-membered cyclophosphazane ring in a spiro arrangement (4a-c). In the latter reaction P-O-P bridged compounds (5a-c) were also obtained as a result of hydrolysis reactions associated with the amount of moisture in the solvent tetrahydrofuran. In addition, it was found that reaction of a mixture of cyclotriphosphazene with either mono spiro compound, (1a) or (1b), in the presence of sodium hydride lead to formation of the first examples of asymmetrically-bridged cyclophosphazenes (6a-b). 相似文献
177.
Dr. Annalisa Mancini Dr. M. Carla Aragoni Dr. Ann L. Bingham Dr. Carlo Castellano Dr. Susanne L. Coles Prof. Francesco Demartin Prof. Michael B. Hursthouse Prof. Francesco Isaia Prof. Vito Lippolis Dr. Giuseppe Maninchedda Dr. Anna Pintus Dr. Massimiliano Arca 《化学:亚洲杂志》2013,8(12):3071-3078
The reactions of 1,3,8,10‐tetrakis(4′‐fluorophenyl)‐4,5,6,7‐tetrathiocino[1,2‐b:3,4‐b′]diimidazolyl‐2,9‐dithione ( 4 ) and molecular diiodine afforded spoke adducts with stoichiometries 4·I2 and 4? 3I2, isolated in the compound 4? 3I2 ? xCH2Cl2 ? (1?x)I2 (x=0.70), and characterized by single‐crystal XRD and FT–Raman spectroscopy. The nature of the reaction products was investigated under the prism of theoretical calculations carried out at the DFT level. The structural data, FT–Raman spectroscopy, and quantum mechanical calculations agree in indicating that the introduction of fluorophenyl substituents results in a lowering of the Lewis basicity of this class of bis(thiocarbonyl) donors compared with alkyl‐substituted tetrathiocino donors and fluorine allows for extended interactions that are responsible for solid‐state crystal packing. 相似文献
178.
Abstract Recently there has been much interest in the electroclinic effect due to its potential application in high speed optical modulators and grey scale displays. In present materials, however, the electroclinic effect is very dependent on temperature and falls off rapidly with increasing temperature. This limits the useful device operating range. In this paper the electroclinic behaviour of new, side chain polymer doped, low molar mass ferroelectic liquid crystal mixtures is reported. By measuring the rate of change of the electroclinic coefficient with temperature it is shown that the temperature range over which the electroclinic effect exists increases with polymer concentration. Data are also presented on electroclinic response times. 相似文献
179.
Natalie E. Mansfield Martyn P. Coles Peter B. Hitchcock 《Phosphorus, sulfur, and silicon and the related elements》2013,188(11):2685-2702
Two novel lithium compounds containing either the phosphorus-chalcogenide anions [Ph 2 PS]? or [Cy 2 PS 2 ]? were isolated as decomposition products in the attempted formation of phospha(V)guanidinate anions. Lithium diphenylthiophosphinite was structurally characterized as the dimeric TMEDA adduct [Li(Ph 2 PS)(TMEDA)] 2 (1), in which a rare example of the κ 1 -S bonding mode was observed for the anion. The dicyclohexyldithiophosphinate anion was incorporated into an aggregated structure with molecular formula [Li 5 (Cy 2 PS 2 ) 4 (OH)] 2 (2). DFT calculations were performed on the isolated [R 2 PS]? and [R 2 PS 2 ]? anions (R = Ph, Cy), indicating delocalization of electron density into the P-S bonds for each model, in agreement with bond-lengths taken from crystallographic data. 相似文献
180.
Coles MP Hitchcock PB Khvostov AV Lappert MF Maron L 《Dalton transactions (Cambridge, England : 2003)》2011,40(12):3047-3052
Reduction at ambient temperature of each of the lithium benzamidinates [Li(L(1))(tmeda)] or [{Li(L(2))(OEt(2))(2)}(2)] with four equivalents of lithium metal in diethyl ether or thf furnished the brown crystalline [Li(3)(L(1))(tmeda)] (1) or [Li(thf)(4)][Li(5)(L(2))(2)(OEt(2))(2)] (2), respectively. Their structures show that in each the [N(R(1))C(R(3))NR(2)](3-) moiety has the three negative charges largely localised on each of N, N' and R = Aryl); a consequence is that the "aromatic" 2,3- and 5,6-CC bonds of R(3) approximate to being double bonds. Multinuclear NMR spectra in C(6)D(6) and C(7)D(8) show that 1 and 2 exhibit dynamic behaviour. [The following abbreviations are used: L(1) = N(SiMe(3))C(Ph)N(SiMe(3)); L(2) = N(SiMe(3))C(C(6)H(4)Me-4)N(Ph); tmeda = (Me(2)NCH(2)-)(2); thf = tetrahydrofuran.] This reduction is further supported by a DFT analysis. 相似文献