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61.
A. M. Gaspar M. Alves Marques M. I. Cabao M. I. de Barros Marques T. Buslaps V. Honkimaki 《Journal of Molecular Liquids》2004,110(1-3):15-22
Concentrated aqueous solutions of calcium chloride and calcium bromide have been investigated by X-ray diffraction. In the diffraction patterns of aqueous chloride solutions of different concentrations, a maximum of intensity is observed in the region 0.6–1.1 Å−1, while in the investigated aqueous bromide solution no maximum is observed in that region. This pre-peak suggests the existence of positional correlations in solution beyond direct contact. The interpretation is similar to the one proposed by the authors in previous investigations, and is supported by the calculations based on ad hoc molecular models. The influence of the anion is discussed. 相似文献
62.
63.
The paper reports the first chemical study of the porostome nudibranch Doriopsilla pelseneeri collected off the Portuguese coast (Atlantic Ocean). Two new furanosesquiterpene alcohols, pelseneeriol-1 (1) and pelseneeriol-2 (2), have been isolated together with known compounds, 15-acetoxy-ent-pallescensin-A (5), and dendocarbin-A (6), from the mantle of the nudibranch, whereas euryfuran (3) and drimane ester mixture 4 were identified in the extract of the internal glands. The structures of 1 and 2 have been determined by extensive spectroscopic studies as well as by comparison with literature model compounds. In order to assess the relative stereochemistry of 1 and 2, full NMR assignment of related sponge metabolite microcionin-2 (8) and of co-occurring sesquiterpenes 9-11, that have been re-isolated from the Mediterranean sponge Fasciospongia cavernosa, has been also conducted. In particular, the relative stereochemistry of tricyclic sesquiterpene microcionin-1 (9) has now been rigorously assigned by detailed analysis of NOE difference experiments. 相似文献
64.
Niel V Muñoz MC Gaspar AB Galet A Levchenko G Real JA 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(11):2446-2453
Low-spin, high-spin and spin-transition behaviours have been observed for the doubly interpenetrating three-dimensional bimetallic compounds (FeII(pz)[Ag(CN)2]2).pz (pz = pyrazine), (FeII(4,4'-bipy)2[Ag(CN)2]2) (4,4'-bipy = 4,4'-bipyridine), and (FeII(bpe)2[Ag(CN)2]2) (bpe = bispyridylethylene), respectively. The single crystals of the bpe derivative undergo a spin transition with a large hysteresis loop at about 95 K. After several warming and cooling cycles, the single crystals become a microcrystalline powder with 50% spin transition. Influence of pressure--as well as light-induced excited spin-state trapping (LIESST) on the thermal 50% spin transition of the microcrystalline sample has also been investigated. Thermal spin-transition behaviour has also been induced at pressures higher than 1 bar for the 4,4'-bipy derivative. Both the 4,4'-bipy and bpe derivatives show strong pressure dependence of the spin state at 300 K. 相似文献
65.
McIntire TM Scott Lea A Gaspar DJ Jaitly N Dubowski Y Li Q Finlayson-Pitts BJ 《Physical chemistry chemical physics : PCCP》2005,7(20):3605-3609
Self-assembled monolayers (SAMs) of vinyl-terminated 3- and 8-carbon compounds were generated on Si substrates and reacted at room temperature with approximately 1 ppm gaseous O(3). A combination of atomic force microscopy (AFM), scanning electron microscopy (SEM), Auger electron spectroscopy (AES) and time-of-flight secondary ion mass spectrometry (TOF-SIMS) was used to study the surface composition and morphology after oxidation. A distribution of large ( approximately 0.1-10 microm) organic aggregates was formed, while the surrounding substrate became depleted of carbon compared to the unreacted SAM. This highly unusual result establishes that the mechanism of ozonolysis of alkene SAMs must have a channel that is unique compared to that in the gas phase or in solution, and may involve polymerization induced by the Criegee intermediate (CI). Oxidation at 60% RH led to the formation of a number of smaller aggregates, suggesting water intercepted the CI in competition with aggregate formation. The uptake of water, measured using transmission FTIR, was not increased upon oxidation of these films. In conjunction with literature reports of polymer formation from VOC-NO(x) photooxidations, these results suggest that formation of aggregates and polymers in the atmosphere is much more widespread than previously thought. The implications for the ozonolysis of alkenes on surfaces, for the transformation of organics in the atmosphere, and for the reactions and stability of unsaturated SAMs, are discussed. 相似文献
66.
67.
Adriano D'Addio Juraj Malinčik Dr. Olaf Fuhr Prof. Dr. Dieter Fenske Prof. Dr. Daniel Häussinger Prof. Dr. Marcel Mayor 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(56):e202201678
Orthogonal joints, understood as connections with an angle of 90°, were introduced in the design of the “Geländer” model compounds 1 and 2 . The banister, consisting of a conjugated carbazole dimer linked by either 1,3-butadiyne ( 2 ) or a single thiophene ( 1 ), wraps around an axis composed of a phthalimide dimer due to the dimensional mismatch of both subunits, which are interconnected by phenylene rungs. The “Geländer” structure was assembled from a monomer comprising the 1,4-diaminobenzene rung with one amino substituent as part of a 4-bromo phthalimide subunit forming the orthogonal junction to the axis, and the other as part of a masked 2-ethynyl carbazole as orthogonal joint to the banister. The macrocycle was obtained by two sequential homocoupling steps. A first dimerization by a reductive homocoupling assembled the axis, while an oxidative acetylene coupling served as ring-closing reaction. The formed butadiyne was further derivatized to a thiophene, rendering all carbons of the model compound sp2 hybridized. Both helical structures were fully characterized and chirally resolved. Assignment of the enantiomers was achieved by simulation of chiroptical properties and enantiopure synthesis. 相似文献
68.
69.
Eric Sidler Dr. Patrick Zwick Charlotte Kress Ksenia Reznikova Dr. Olaf Fuhr Prof. Dr. Dieter Fenske Prof. Dr. Marcel Mayor 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(53):e202201764
The synthetic access to macrocyclic molecular topologies with interesting photophysical properties has greatly improved thanks to the successful implementation of organic and inorganic corner units. Based on recent reports, we realized that pseudo-meta [2.2]paracyclophanes (PCPs) might serve as optimal corner units for constructing 3D functional materials, owing to their efficient electronic communication, angled substituents and planar chirality. Herein, we report the synthesis, characterization and optical properties of four novel all-carbon enantiopure macrocycles bearing three to six pseudo-meta PCPs linked by 1,3-butadiyne units. The macrocycles were obtained by a single step from enantiopure, literature-known dialkyne pseudo-meta PCP and were unambiguously identified and characterized by state of the art spectroscopic methods and in part even by x-ray crystallography. By comparing the optical properties to relevant reference compounds, it is shown that the pseudo-meta PCP subunit effectively elongates the conjugated system throughout the macrocyclic backbone, such that already the smallest macrocycle consisting of only three subunits reaches a polymer-like conjugation length. Additionally, it is shown that the chiral pseudo-meta PCPs induce a remarkable chiroptical response in the respective macrocycles, reaching unprecedented high molar circular dichroism values for all-carbon macrocycles of up to 1307 L mol−1 cm−1. 相似文献
70.
C.B.P. Ligiero T.S. Fernandes D.L. D'Amato F.V. Gaspar P.S. Duarte M.A. Strauch J.G. Fonseca L.G.R. Meirelles P. Bento da Silva R.B. Azevedo G. Aparecida de Souza Martins B.S. Archanjo C.D. Buarque G. Machado A.M. Percebom C.M. Ronconi 《Materials Today Chemistry》2022
Due to the unprecedented and ongoing nature of the coronavirus outbreak, the development of rapid immunoassays to detect severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) and its highly contagious variants is an important and challenging task. Here, we report the development of polyclonal antibody-functionalized spherical gold nanoparticle biosensors as well as the influence of the nanoparticle sizes on the immunoassay response to detect the SARS-CoV-2 spike protein by dynamic light scattering. By monitoring the increment in the hydrodynamic diameter (ΔDH) by dynamic light scattering measurements in the antigen–antibody interaction, SARS-CoV-2 S-protein can be detected in only 5 min. The larger the nanoparticles, the larger ΔDH in the presence of spike protein. From adsorption isotherm, the calculated binding constant (KD) was 83 nM and the estimated limit of detection was 13 ng/mL (30 pM). The biosensor was stable up to 90 days at 4 °C. Therefore, the biosensor developed in this work could be potentially applied as a fast and sensible immunoassay to detect SARS-CoV-2 infection in patient samples. 相似文献