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31.
The complexes [Te(etu)4][SiF6] (1), [Te(etu)4][SiF6] · H2O (2), [Te(trtu)4][SiF6] (3), [Te(etu)4][GeF6] · H2O (4), [Te(trtu)4][GeF6] (5) and [Te(etu)4][SnF6] (6) (etu = ethylenethiourea, trtu = trimethylenethiourea) have been prepared and their crystal structures determined by X-ray crystallographic methods. The crystals of 1, 3 and 5 are tetragonal; space groups P4cc (No. 103) with Z = 4 for 1, P4nc (No. 104) with Z = 2 for 3, and I4 (No. 79) with Z = 2 for 5. The crystals of 2, 4 and 6 are orthorhombic, space group Pccn (No. 56) with Z = 8 for 2 and 4 and Z = 4 for 6; those of 2 and 4 being isomorphous. The cations contain square planar or slightly distorted square planar TeS4 coordination groups. In 1, 3 and 5 the Te atoms are located on fourfold rotation axes; the cations have fourfold rotational symmetry and the four thiourea ligands extend to the same side of the TeS4 plane. These are the first examples of [TeL4]2+ conformers of this type. In 2 and 4 the Te atoms lie on general positions; the cations are distorted versions of those in 1, and also in these the four ligands extend to the same side of the TeS4 plane. In 6 the Te atoms are located on twofold rotation axes, the conformation of the cations corresponds to the point group C2 with two neighbouring ligands extending to one side of the coordination plane and the remaining two to the opposite side. In 1–5 each of the four ligands forms a N–HF bond to the same F atom in the counter ion. The crystals of 1–5 are red, and those of 6 are yellow. The red colour is attributed to interactions of Te and S lone electron pairs caused by ligand TeS4/TeSC tilt angles markedly different from 90°. 相似文献
32.
Meijler MM Arad-Yellin R Cabantchik ZI Shanzer A 《Journal of the American Chemical Society》2002,124(43):12666-12667
Synthetic iron chelators based on the natural siderophore ferrichrome have previously been shown to bind Fe(III) with high affinity (pKf > 27) and have shown no toxicity to mammalian cell cultures in vitro. A new class of lipophilic ferrichrome analogues carrying acetoxymethyl ester moieties has been synthesized. We have shown that these molecules penetrate rapidly through cell membranes and turn highly hydrophilic while inside the cells, upon esterase mediated hydrolysis of the lipophilic termini. The intracellular retention was visualized by labeling these analogues with a fluorescent naphthalic diimide probe. The prohydrophilic iron chelators have been shown to inhibit the metal-catalyzed intracellular formation of reactive oxygen species with high effectivity, and preliminary results suggest these molecules to be potent antimalarial agents. 相似文献
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Microwave induced delayed phosphorescence (MIDP) measurements have been performed in the 00 bands of the phosphorescence spectrum of benzene dissolved in two phases of cyclohexane. From the relative radiative rates for decay of the three zero-field levels it is concluded that on the average the symmetry of the electronic structure is lower than D2h. In the monoclinic low temperature stable phase of cyclohexane (phase II) the structure is approximately antiquinoidal, and in the metastable phase III it is approximately quinoidal. 相似文献
35.
Crystals of Ba5Fe5−xPtxClO13 and Ba5Co5−yPtyClO13 were prepared for x=1.31, 1.51, 1.57, 1.59 and y=0, 0.97 and 1.08 in a BaCl2 flux and investigated by X-ray diffraction methods. These compounds adopt a 10H perovskite structure built from the stacking of BaO3 and BaOCl layers in the sequence (BaO3)4(BaOCl) with space group P63/mmc. The cation sites within the trimeric unit of face-sharing octahedra are occupied by Co or Fe and Pt ions, while the tetrahedral sites formed between BaO3 and BaOCl layers are only occupied by Fe or Co. Moreover, oxygen stoichiometry indicates an average oxidation state for Co and Fe higher than +III, indicating the stabilization of Co4+ and Fe4+. 相似文献
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38.
Philip Wormald Kristina Wickholm Per Tomas Larsson Tommy Iversen 《Cellulose (London, England)》1996,3(1):141-152
An investigation into the effects of mechanical treatment and hydration on the order of cellulose substrates (microcrystalline cellulose and Cladophora cellulose) was performed by the use of ball milling followed by cyclic wetting and drying. The results, monitored by13C-CP/MAS NMR-spectroscopy, were evaluated by calculation of the crystallinity indices and principal component analysis of the NMR data acquired. The results showed that a large part of the disorder induced by the mechanical treatment of cellulose by ball milling is reversible and reordering upon hydration leads to the cellulose I form initially present. The C4 signals corresponding to the reversibly disordered cellulose chains are observed in the amorphous region between 79 and 86 ppm in the13C-CP/MAS NMR-spectra together with signals from cellulose chains on the surface of ordered regions. The peak cluster which contains the C2, C3 and C5 ring carbons can be divided into two specific spectral regions; one between 74 and 77 ppm largely originates from ring carbons within disordered cellulose structures, and one between 70 and 74 ppm contains larger contributions from ordered cellulose. The behaviour of the celluloses upon milling is in accordance with a concept of ordered cellulose fibrils containing amorphous cellulose mainly as surface layers and induced reversible lattice distortions. 相似文献
39.
The crystal and molecular structure of [2.2](2,5)furano(1,4)naphthalenophane (1) was determined by X-ray crystallography. The molecule exists in the anti-conformation and the study represents the first instance in which the structural features of a naphthalenoid ring within a cyclophane were determined. Crystals of cyclophane 1 are orthorhombic, space group Pbca, with a = 7.859(2). b = 11.482(3) and c = 28.818(8) Å. While the nonbridged portion of the naphthalenoid ring is planar, the portion which is bridged to the furanoid ring through its 1 and 4 C atoms is puckered and boat-shaped. These C atoms are positioned 14° out of the plane of the other four C atoms of this ring. The furanoid ring is essentially planar but is not parallel to the naphthalenoid ring. It is inclined 22° to the least squares plane of the bridged portion of the naphthalenoid ring. This angle of inclination staggers the atoms of the furanoid and bridged naphthalenoid ring and positions the 3 and 4 C atoms, the 2 and 5 C atoms and the 0 atom of the furanoid ring 3.4. 2.9 and 2.6 Å. respectively, from the least squares plane of the bridged portion of the naphthalenoid ring. While the internal angles around the bridging C atoms α- to the naphthalenoid ring are 109°, those α- to the furanoid ring are 113°. In addition unusually large bond angles (137°) at the 2 and 5 C atoms of the furanoid ring, external to the ring, are also observed. The distortions are considered with respect to the strain within the cyclophane macrocycle and are compared with other similar systems. 相似文献
40.
The carbenoid or carbene derived from undergoes dimerization or trapping with DPIBF. The allene mechanism previously proposed was made doubtful by the finding that stereoisomeric carbenes and give stereoisomeric products without crossover. 相似文献