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831.
Eight new terpenoids ( 1 – 8 ) were isolated from the bark of Jatropha neopauciflora, together with eight known compounds. The new isolates include the sesquiterpenoids (1R,2R)‐diacetoxycycloax‐4(15)‐ene ( 1 ); (1R,2R)‐dihydroxycycloax‐4(15)‐ene ( 2 ), (2R)‐δ‐cadin‐4‐ene‐2,10‐diol ( 3 ), (2R)‐δ‐cadina‐4,9‐dien‐2‐ol ( 4 ), (1R,2R)‐dihydroxyisodauc‐4‐en‐14‐ol ( 5 ) and its acetonide 6 (artifact), as well as the two triterpenoids (3β,16β)‐16‐hydroxylup‐20(29)‐en‐3‐yl (E)‐3‐(4‐hydroxyphenyl)prop‐2‐enoate ( 7 ) and (3β,16β)‐16‐hydroxyolean‐18‐en‐3‐yl (E)‐3‐(4‐hydroxyphenyl)prop‐2‐enoate ( 8 ). The structures of these compounds were established by extensive 1D‐ and 2D‐NMR spectroscopic methods, and their absolute configurations were determined by circular‐dichroism (CD) experiments, and by X‐ray crystallographic analysis (compound 7 ; Fig. 3). A plausible biosynthesis of the sesquiterpenoids 1 – 5 is proposed (Scheme), starting from (?)‐germacrene D as the common biogenetic precursor. 相似文献
832.
Reactions of N-methyliminobis(methylenephosphonic acid), CH(3)N(CH(2)PO(3)H(2))(2) (H(4)L), with divalent metal acetates under different conditions result in metal diphosphonates with different structures. Mn(H(3)L)(2).2H(2)O (complex 1) with a layer structure was prepared by a layering technique. It is triclinic, P1 macro with a = 9.224(3) A, b = 9.780(3) A, c = 10.554(3) A, alpha = 82.009(6) degrees, beta = 74.356(6) degrees, gamma = 89.853(6) degrees, Z = 2. The Mn(II) ion is octahedrally coordinated by six phosphonate oxygen atoms from four ligands, two of them in a bidentate and two in a unidentate fashion. Each MnO(6) octahedron is further linked to four neighboring MnO(6) octahedra through four bridging phosphonate groups, resulting in a two-dimensional metal phosphonate (002) layer. These layers are held together by strong hydrogen bonds between uncoordinated phosphonate oxygen atoms. The zinc complex Zn(3)(HL)(2) (complex 2) was synthesized by hydrothermal reactions (4 days, 438 K, autogenous pressure). It is monoclinic, P2(1)/n with a = 7.7788(9) A, b = 17.025(2) A, c = 13.041(2) A, beta = 94.597(2) degrees, Z = 4. The structure of complex 2 features a 3D network built from ZnO(4) tetrahedra linked together by bridging phosphonate groups. Each zinc cation is tetrahedrally coordinated by four phosphonate oxygen atoms from four ligands, each of which connects with six zinc atoms, resulting in voids of various sizes. Magnetic measurements for the manganese complex shows an antiferromagnetic interaction at low temperature. The effect of the extent of deprotonation of phosphonic acids on the type of complex formed is discussed. 相似文献
833.
Hisahiro Sasabe G. Abraham Rajkumar Nobuhiro Kihara Kazuhiko Mizuno Toshikazu Takata 《Tetrahedron》2006,62(9):1988-1997
Synthesis of [60]fullerene (C60)-functionalized rotaxanes via Diels-Alder reactions with C60 is described. Diels-Alder reaction of C60 and sulfolene moiety as masked diene attached on the wheels of rotaxanes results in high yields of C60 incorporation. Rotaxanes are prepared by tin-catalyzed urethane-forming end-capping reaction with isocyanate of pseudorotaxane having the wheel carrying C60 functionality as introduced by the Diels-Alder reaction. The Diels-Alder reaction was accomplished as end-capping reaction between C60 and pseudorotaxane bearing sultine moiety as masked diene on the axle terminal. A variety of C60-containing [2]rotaxanes was prepared in moderate to good yields by these Diels-Alder protocols. 相似文献
834.
[structure: see text] Partition coefficients of single ions in the octanol/water system (log P(oct)) have been assigned on the (Ph4As+, Ph4P+) = Ph4B- assumption. The log P(oct) values of Cl-, Br-, and I- ions are then used to obtain the partition coefficients of cations from partition coefficients of the neutral combination of anion and cation. Partition coefficients of 544 cations derived from 585 organic salts from the MedChem database have been studied. The contributions of the aliphatic charge N+ and aromatic charge n+ in these cations have been investigated. The results show that the contributions of N+ and n+ in different homologous series are affected by the attached functional groups and are not constant, although the effect of the central cation is constant along any given homologous series. The latter can be accounted for qualitatively and semiquantitatively by the electrostatic theory of ionic solvation of Abraham and Liszi. A number of regression equations have been established between partition coefficients of ions and partition coefficients of the corresponding neutral species. These equations can be used to estimate octanol/water partition coefficients for additional cations to about 0.5 log unit. 相似文献
835.
Design of microfluidic channel geometries for the control of droplet volume, chemical concentration, and sorting 总被引:10,自引:0,他引:10
Passive microfluidic channel geometries for control of droplet fission, fusion and sorting are designed, fabricated, and tested. In droplet fission, the inlet width of the bifurcating junction is used to control the range of breakable droplet sizes and the relative resistances of the daughter channels were used to control the volume of the daughter droplets. Droplet fission is shown to produce concentration differences in the daughter droplets generated from a primary drop with an incompletely mixed chemical gradient, and for droplets in each of the bifurcated channels, droplets were found to be monodispersed with a less than 2% variation in size. Droplet fusion is demonstrated using a flow rectifying design that can fuse multiple droplets of same or different sizes generated at various frequencies. Droplet sorting is achieved using a bifurcating flow design that allows droplets to be separated base on their sizes by controlling the widths of the daughter channels. Using this sorting design, submicron satellite droplets are separated from the larger droplets. 相似文献
836.
It is well-known that a bulk, symmetric, A-b-B diblock copolymer forms a lamellar morphology, with period L, below an order-disorder transition (T(ODT)) temperature, for chiN < 10.5; chi is the Flory-Huggins interaction parameter and N is the degree of polymerization of the copolymer. The ordering temperatures of poly(styrene-b-methyl methacrylate) (PS-b-PMMA) thin film diblock copolymers of thickness h = 2L, supported by SiO(x)/Si substrates, in vacuum environments, are shown to increase beyond the bulk, and estimates of the temperature shifts indicate that small changes of chiN are associated with unusually large shifts of the transition temperature. Further, we find that in compressed CO(2) environments, these films are ordered at temperatures where the films are disordered in vacuum (or air) environments. This latter observation is of particular significance because small molecule diluents, including compressed CO(2), are known to decrease the ODT of the bulk (enhanced miscibility). 相似文献
837.
Components for integrated poly(dimethylsiloxane) microfluidic systems 总被引:11,自引:0,他引:11
This review describes the design and fabrication of microfluidic systems in poly(dimethylsiloxane) (PDMS). PDMS is a soft polymer with attractive physical and chemical properties: elasticity, optical transparency, flexible surface chemistry, low permeability to water, and low electrical conductivity. Soft lithography makes fabrication of microfluidic systems in PDMS particularly easy. Integration of components, and interfacing of devices with the user, is also convenient and simpler in PDMS than in systems made in hard materials. Fabrication of both single and multilayer microfluidic systems is straightforward in PDMS. Several components are described in detail: a passive chaotic mixer, pneumatically actuated switches and valves, a magnetic filter, functional membranes, and optical components. 相似文献
838.
Doi TR Yoshinaga F Tormena CF Rittner R Abraham RJ 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(9):2221-2230
The solvent dependence of the 13C NMR spectra of chloroacetone (CA), bromoacetone (BA) and iodoacetone (IA) are reported and the 3J(CH) couplings analysed using ab initio calculations and solvation theory. In CA the energy difference (E(cis) - E(gauche)) between the cis (Cl-C-C=O 0 degrees) and gauche (Cl-C-C=O 155 degrees) conformers is 1.7 kcal mol(-1) in the vapour, decreasing to 0.8 kcal mol(-1) in CCl4 solution and to -1.0 kcal mol(-1) in the pure liquid. The conformational equilibrium, in BA, is between the more polar cis (Br-C-C=O 0 degrees) and gauche (Br-C-C=O 132 degrees) conformations. The energy difference (E(cis) - E(gauche)) is 1.8 kcal mol(-1) in the vapour, decreasing to 0.9 kcal mol(-1) in CCl4 solution and to -0.4 kcal mol(-1) in the pure liquid. The energy difference (E(cis) - E(gauche)), in IA, between the cis (I-C-C=O 0 degrees) and gauche (I-C-C=O 104 degrees) conformers is 1.1 kcal mol(-1) in the vapour phase, decreasing to 0.5 kcal mol(-1) in CCl4 solution and to -0.5 kcal mol(-1) in the pure liquid. The vapour state energy difference for BA [1.4 kcal mol(-1) at B3LYP/6-311++G(d,p)] and for IA [1.6 kcal mol(-1) at B3LYP/6-311++G(d,p)/LANL2DZ)] are in very good agreement with the above values. For CA the agreement is also satisfactory [1.4 kcal mol(-1) at B3LYP/6-311++G(d,p)]. 相似文献
839.
Reaction of copper salts with 1,4-phenylenebis(phosphonic acid) yielded a conventional layered compound, Cu(2)[(O(3)PC(6)H(4)PO(3))(H(2)O)(2)], while a similar reaction with 4,4'-biphenylenebis(phosphonic acid) resulted in a new lamellar structure with composition Cu[HO(3)P(C(6)H(4))(2)PO(3)H]. The structures of these compounds were solved ab initio by using X-ray powder diffraction data. The crystals of the phenylenebis(phosphonate) compound are monoclinic, space group C2/c, with a = 18.8892(4) ?, b = 7.6222(2) ?, c = 7.4641(2) ?, beta = 90.402(2) degrees, and Z = 4. The layer structure in this case is similar to that in copper phenylphosphonate, Cu[O(3)PC(6)H(5)]. The metal atoms display a distorted square pyramidal geometry where four of the coordination sites are occupied by the phosphonate oxygens. The remaining site is filled by an oxygen atom of the water molecule. Adjacent metal-O(3)PC layers are covalently pillared by the phenyl group of the phosphonates to create a 3-dimensional structure. Cu[HO(3)P(C(6)H(4))(2)PO(3)H] is triclinic, space group P&onemacr;, with a = 4.856(2) ?, b = 14.225(5) ?, c = 4.788(2) ?, alpha = 97.85(1) degrees, beta = 110.14(1) degrees, gamma = 89.38(1) degrees, and Z = 1. The structure in this case, ideally consists of linear chains of copper atoms. The copper atoms are bridged by centrosymmetrically related phosphonate groups utilizing two of their oxygen atoms. This binding mode leads to square planar geometry for the copper atoms. The third oxygen atom of the phosphonate is protonated and is involved in linking adjacent linear chains through hydrogen bonds. At the same time, these hydroxyl oxygens interact weakly (Cu-O = 3.14 ?) with the copper atoms of the adjacent chain. Considering these long Cu-O interactions, the geometry of the copper atom may be described as distorted square bipyramidal. As in the phenylphosphonate structure, the biphenyl groups covalently link the Cu-O(3)PC networks in the perpendicular direction. 相似文献
840.