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991.
Woiterski L Britt DW Käs JA Selle C 《Langmuir : the ACS journal of surfaces and colloids》2012,28(10):4712-4722
We report on attenuated total reflection Fourier-transform infrared (ATR FTIR) spectroscopic measurements on oriented lipid multilayers of N,N-dimethyl-N,N-dioctadecyl-ammonium halides (DODAX, X = F, Cl, Br, I). The main goal of this study is the investigation of the structure and spectroscopic properties of water absorbed to these model membranes. Intensities of the water stretch absorptions were used to determine the amount of bound water. At high water activity, DODAF membranes bind ~11 water molecules/lipid while DODAC and DODAB adsorb 1-2 water/lipid and DODAI was hydrophobic. By adjustment of DODAF hydration to ~2 water molecules, stretching absorptions from water of the first hydration shell were accessible for the fluoride, chloride, and bromide analogs. The polarized measurements demonstrate highly confined and oriented water with infrared (IR) order parameters ranging from 0.2 to -0.4. Resolved IR water band components are attributed to different hydrogen-bonded populations. Complementary molecular dynamics simulations of DODAB strongly support the existence of differently hydrogen-bonded and oriented water within DODAB multilayers. A combination of both techniques was used for an assignment of water stretch band components to structures. The described cationic lipid systems are a prototype for a bottom-up approach to understand the IR spectroscopy of structured water at biological interfaces since they permit a defined increase of hydrophilic water-anionic interactions leading to extended water networks at membranes. 相似文献
992.
993.
Michal Ilavsk Karel Bouchal Helena Valentovä František Lednick Antonín Sikora Josef Baldrian 《Journal of Macromolecular Science: Physics》2013,52(5):645-666
Synthesis of the liquid crystalline (LC) diol 6,6′-[ethylenebis(l,4-phenylene-oxy)]-dihexanol (I) is described. The structure of polyurethanes prepared from diol I and 4,4′-methylenedi(phenyl isocyanate) (MDI), 4,4′-methylenedi(cyclohexyl isocyanate) (HMDI), or 2(4)-methyl-l,3-phenylene diisocyanate (TDI) at 1:1 molar ratios of isocyanate and hydroxy groups is studied by dynamic mechanical spectroscopy, differential scanning calorimetry (DSC), polarizing microscopy, and x-ray scattering. The polymer prepared from HMDI and the diol (I/HMDI) shows, on cooling, thermal behavior typical of amorphous polymers. A frequency-temperature superposition could be applied to the mechanical data, and the horizontal shift factor satisfied the Williams-Landel-Ferry (WLF) equation. A more-complex thermal behavior was found for I/HMDI polymer during subsequent heating; above 70°C, the formation of an ordered structure takes place, and this structure melts at about 120°C. Complex thermal behavior is exhibited by I/TDI polymer. On cooling its melt, the polymer forms a nematic phase at about 80°C, which freezes into the LC glassy state. On heating, the mesophase melts, and. subsequently, a better-ordered smectic phase is formed at 95°C, which melts at 120°C. This structure buildup is accompanied by a rapid increase in storage modulus G′, and the sample shows thermorheologically complex mechanical behavior. The polymer formed from the diol and MDI (I/MDI) exhibits a most-complex thermal behavior. On cooling and heating, four transitions can be detected in its thermal mechanical behavior, and the structure of the polymer is strongly dependent on its thermal history. 相似文献
994.
995.
The spin dipole–spin dipole and spin–orbit coupling contributions to the zero-field splitting parameters D and E of [CH3–N–CH3]+, [CH3–P–CH3]+, and [CH3–As–CH3]+ have been calculated from CASSCF(14,14)/cc-pVTZ wave functions and the Breit–Pauli Hamiltonian at T1 B3LYP/cc-pVTZ optimized geometries. The spin–orbit coupling contributions represent a minor correction for the dimethylnitrenium cation, which has a triplet ground state. They dominate the spin–spin terms by an order of magnitude in the dimethylphosphenium cation and by more than two orders of magnitude in the dimethylarsenium cation, both of which have a singlet ground state. The properties of all these biradicaloids follow expectations based on the simple algebraic 2-in-2 model of biradical structure. 相似文献
996.
997.
Josef Brody Stanley H. Erlwanger 《International Journal of Mathematical Education in Science & Technology》2013,44(4):645-659
This paper extends the themes on the computational approach discussed in Parts 1 and 2 to the differentiation of functions. One theme is that constructing diagrams for programs using a calculator helps students to visualize processes and thus acquire the concepts involved. The ability to construct diagrams for a given problem is identical to that of programming a calculator to solve the problem. However, in this case constructing the diagram for derivatives from the diagram of the function also represents the ability to teach a calculator how to perform formal differentiation. A second theme is that the approach promotes sequential or procedural thinking which is important in both programming and mathematics. A third theme is that the approach permits the generation of many subproblems, thereby encouraging one to pose questions rather than merely to solve those set by others. Consequently, it becomes clear that the approach has wider applications in the learning of mathematics. 相似文献
998.
In this paper, we show that one can interrelate pluriharmonic maps with para-pluriharmonic maps by means of the loop group method. As an appendix, we give examples for the interrelation between pluriharmonic maps and para-pluriharmonic maps. Moreover, we investigate the relation among CMC-surfaces by use of such maps. 相似文献
999.
Lunkenbein T Kamperman M Li Z Bojer C Drechsler M Förster S Wiesner U Müller AH Breu J 《Journal of the American Chemical Society》2012,134(30):12685-12692
Nanostructured inverse hexagonal polyoxometalate composite films were cast directly from solution using poly(butadiene-block-2-(dimethylamino)ethyl methacrylate) (PB-b-PDMAEMA) diblock copolymers as structure directing agents for phosphomolybdic acid (H(3)[PMo(12)O(40)], H(3)PMo). H(3)PMo units are selectively incorporated into the PDMAEMA domains due to electrostatic interactions between protonated PDMAEMA and PMo(3-) anions. Long solvophilic PB chains stabilized the PDMAEMA/H(3)PMo aggregates in solution and reliably prevented macrophase separation. The choice of solvent is crucial. It appears that all three components, both blocks of the diblock copolymer as well as H(3)PMo, have to be soluble in the same solvent which turned out to be tetrahydrofuran, THF. Evaporation induced self-assembly resulted in highly ordered inverse hexagonal nanocomposite films as observed from transmission electron microscopy and small-angle X-ray scattering. This one-pot synthesis may represent a generally applicable strategy for integrating polyoxometalates into functional architectures and devices. 相似文献
1000.
Šardzík R Green AP Laurent N Both P Fontana C Voglmeir J Weissenborn MJ Haddoub R Grassi P Haslam SM Widmalm G Flitsch SL 《Journal of the American Chemical Society》2012,134(10):4521-4524
O-mannosyl glycans are known to play an important role in regulating the function of α-dystroglycan (α-DG), as defective glycosylation is associated with various phenotypes of congenital muscular dystrophy. Despite the well-established biological significance of these glycans, questions regarding their precise molecular function remain unanswered. Further biological investigation will require synthetic methods for the generation of pure samples of homogeneous glycopeptides with diverse sequences. Here we describe the first total syntheses of glycopeptides containing the tetrasaccharide NeuNAcα2-3Galβ1-4GlcNAcβ1-2Manα, which is reported to be the most abundant O-mannosyl glycan on α-DG. Our approach is based on biomimetic stepwise assembly from the reducing end and also gives access to the naturally occurring mono-, di-, and trisaccharide substructures. In addition to the total synthesis, we have developed a "one-pot" enzymatic cascade leading to the rapid synthesis of the target tetrasaccharide. Finally, solid-phase synthesis of the desired glycopeptides directly on a gold microarray platform is described. 相似文献