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71.
Serrano I López MI Ferrer Í Poater A Parella T Fontrodona X Solà M Llobet A Rodríguez M Romero I 《Inorganic chemistry》2011,50(13):6044-6054
The synthesis of a family of new Ru complexes containing the facial tridentate ligand with general formula [Ru(II)(T)(D)(X)](n+) (T = trispyrazolylmethane (tpm); D = ((4S,4'S)-(-)-4,4',5,5'-tetrahydro-4,4'-bis(1-methylethyl)-2,2'-bioxazole) (iPr-box-C) or N-(1-hydroxy-3-methylbutan-(2S)-(-)-2-yl)-(4S)-(-)-4-isopropyl-4,5-dihydrooxazole-2-carbimidate (iPr-box-O); X = Cl, H(2)O) has been described. All complexes have been spectroscopically characterized in solution through (1)H NMR and UV-vis techniques, and the redox properties of complexes have also been studied by means of cyclic voltammetry (CV). Furthermore, the chloro complexes presented here have been characterized in the solid state through monocrystal X-ray diffraction analysis. The oxazolinic iPr-box-C ligand undergoes a Ru-assisted hydrolysis reaction generating the corresponding amidate anionic ligand iPr-box-O, that keeps coordinated to the Ru metal center and that produces a strong σ-donation effect over it. The reactivity of the Ru-OH(2) complexes described in this paper together with other similar ones, previously synthesized by us, has been tested with regard to the epoxidation of different olefins. Complexes [Ru(II)(R-box-C)(tpm)OH(2)](BF(4))(2), R = Bz, 3'c/iPr, 3c, show high stereoselectivity in the epoxidation of cis-β-methylstyrene, with the exclusive formation of the cis-epoxide. However, there is a significant difference in regioselectivity between the two catalysts in the epoxidation of 4-vinylcyclohexene; complex 3'c leads to the regioselective oxidation at the ring alkene position, whereas complex 3c leads to the oxidation at the terminal position. Computational calculations indicate only small energy differences between the two possible products of 4-vinylcyclohexene epoxidation, but the energy barriers for the interaction of the catalytic systems with the alkene groups of 4-vinylcyclohexene agree with the reactivity differences found for the two catalysts having isopropyl or benzyl as substituent of the oxazole ligand. Computed local Fukui functions help to explain the observed reactivity trends. 相似文献
72.
73.
Niko Guskos Janusz Typek Aleksander Guskos Grzegorz Zolnierkiewicz Pawel Berczynski Diana Dolat Barbara Grzmil Antoni Morawski 《Central European Journal of Chemistry》2013,11(12):1996-2004
Nanoparticles of nitrogen-modified TiO2 (N-doped TiO2) calcined at 300°C and 350°C, have been prepared with and without water rinsing. Samples were characterized by x-ray diffractrometry (XRD) and optical spectroscopy. The electron paramagnetic resonance (EPR) spectra from centers involving oxygen vacancies were recorded for all samples. These could be attributed to paramagnetic surface centers of the hole type, for example to paramagnetic oxygen radicals O?, O2 ? etc. The concentration of these centers increased after water rising and it further increased for samples annealed at higher temperature. Additionally, for samples calcined at 300°C, and calcined at 350°C and rinsed, the EPR spectra evidenced the presence of magnetic clusters of Ti3+ ions. The photocatalytic activity of samples was studied towards phenol decomposition under unltraviolet-visible (UV-Vis) irradiation. It was found that, in comparison to the starting materials, the rinsed materials showed increased photocatalytic activity towards phenol oxidation. The light absorption (UV-Vis/DRS) as well as surface Fourier transform infrared/diffuse reflectance spectroscopy (FTIR/DR) studies confirmed a significantly enhanced light absorption and the presence of nitrogen groups on the photocatalysts surfaces, respectively. A significant increase of concentration of paramagnetic centers connected with oxygen vacancies after water rising has had an essential influence on increasing their photocatalytic activity. 相似文献
74.
The pressure-temperature phase diagram of n-octyl-isothiocyanato-biphenyl (8BT) in the pressure range up to 250 MPa (2.5 kbar) and the temperature range 250-400 K was established with the aid of DTA. At 1 atm the substance exhibits exclusively CrE polymorphism. At pressures above 190 MPa, the clearing line splits showing an additional phase which is not yet identified. Dielectric relaxation measurements on the CrE phase of 8BT were performed in the pressure range 0.1-120 MPa and the temperature range 304-345 K. A Debye-type relaxation process was observed in the frequency range 100 Hz-1 MHz. The longitudinal relaxation time τ, characterizing the molecular reorientations around the short axis, was analysed with respect to the pressure and temperature, yielding the activation volume, Δ# V = RT(? ln τ/?p)T, and activation enthalpy, Δ# H = R(? ln τ/? T-1)p, respectively. The results are compared with analogous data obtained recently for similar compounds having other liquid crystalline phases (N, SmA). 相似文献
75.
Electric field modulation in tissue electroporation with electrolytic and non-electrolytic additives
Electroporation, cell membrane permeabilization with short electrical field pulses, is used in tissue for in vivo gene therapy, drug therapy and minimally invasive tissue ablation. For the electroporation to be successful, the electrical field that develops during the application of the pulses needs to be precisely controlled. In this study we investigate the use of electrolytic and non-electrolytic gels to generate the precise electrical fields required for controlled electroporation, in heterogeneous and irregular tissues, in vivo. Finite element computer simulations are used to illustrate various applications, such as the treatment of irregularly shaped organs and interior cavities. The feasibility of the concept is demonstrated experimentally in vivo with a rat liver subjected to irreversible electroporation. 相似文献
76.
An automatic system based on multisyringe flow injection analysis (MSFIA) and lab-on-valve (LOV) flow techniques for separation and pre-concentration of 226Ra from drinking and natural water samples has been developed. The analytical protocol combines two different procedures: the Ra adsorption on MnO2 and the BaSO4 co-precipitation, achieving more selectivity especially in water samples with low radium levels. 相似文献
77.
Consumption of non-steroidal anti-inflammatory drugs (NSAIDs) is increasing and with it the danger of environmental pollution
by pharmaceutical residues. Publications regarding NSAIDs in the environment not only show that they are toxic to many animal
species, but also highlight the need for robust analytical methods for monitoring the level of such contaminants in environmental
matrices. In our study we selected the four most widely used NSAIDs in Slovenia and Central Europe, ibuprofen, naproxen, ketoprofen
and diclofenac, and studied their extraction from sediment samples. We examined several extraction techniques (ultrasonic
extraction, Soxhlet extraction, pressurized liquid extraction, supercritical fluid extraction and microwave-assisted extraction)
using a spiked sediment sample and determined optimal extraction conditions. After extraction we applied a clean-up step,
derivatisation of the analytes and gas chromatography with mass spectrometric detection (GC-MSD) and selected the most appropriate
extraction procedure. The optimised analytical method chosen for analysis of sediment samples consisted of microwave-assisted
extraction, clean-up of the extract with SPE, derivatisation with MSTFA and determination with GC-MSD. The optimised procedure
was applied to the analysis of two environmental river samples taken from the vicinity of Novo mesto, the biggest town in
the south eastern part of Slovenia with 62,000 inhabitants, a hospital and a pharmaceutical factory in its vicinity. While
analysis of the sample taken upstream of the town showed no detectable amounts of NSAIDs, analysis of samples taken downstream
showed quantifiable levels of two of the studied NSAIDs (naproxen and ketoprofen). Besides these two NSAIDs, river water samples
sampled at the same time and location on the River Krka also showed the presence of diclofenac. Sampling on the River Krka
and other Slovene rivers will in the future be repeated at different sampling points in order to track down the main sources
of pollution. 相似文献
78.
Leszek Wachowski Antoni Grodzicki Piotr Piszczek Monika Richert Magdalena Hofman 《Reaction Kinetics and Catalysis Letters》2007,91(1):93-99
Hydrogenation of styrene has been applied as a test reaction to study the catalytic activity of TiO2 deposited by the CVD (chemical vapour deposition) method on the surface of a carbonaceous material enriched in nitrogen (CN). 相似文献
79.
Isidoro Lpez Mehmed Z. Ertem Somnath Maji Jordi Benet‐Buchholz Anke Keidel Uwe Kuhlmann Peter Hildebrandt Christopher J. Cramer Victor S. Batista Antoni Llobet 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(1):209-213
The homogeneous catalysis of water oxidation by transition‐metal complexes has experienced spectacular development over the last five years. Practical energy‐conversion schemes, however, require robust catalysts with large turnover frequencies. Herein we introduce a new oxidatively rugged and powerful dinuclear water‐oxidation catalyst that is generated by self‐assembly from a mononuclear catalyst during the catalytic process. Our kinetic and DFT computational analysis shows that two interconnected catalytic cycles coexist while the mononuclear system is slowly and irreversibly converted into the more stable dinuclear system: an extremely robust water‐oxidation catalyst that does not decompose over extended periods of time. 相似文献
80.
Masllorens E Rodríguez M Romero I Roglans A Parella T Benet-Buchholz J Poyatos M Llobet A 《Journal of the American Chemical Society》2006,128(16):5306-5307
Three new Ru-aqua complexes containing a mixed carbene and pyridylic ligands with general formulas [Ru(CNC)(bpy)(H2O)](PF6)2 (1) (CNC is 2,6-bis(butylimidazol-2-ylidene)pyridine; bpy is 2,2'-bipyridine) and cis-/trans-[Ru(CNC)(nBu-CN)(H2O)](PF6)2 (cis-2 and trans-2) (nBu-CN is 2-(butylimidazol-2-ylidene)pyridine) have been prepared and structurally characterized both in the solid state (monocrystal X-ray diffraction analysis for 1 and for the related complex trans-[Ru(Br)(CNC)(nBu-CN)](PF6)) and in solution (for all of them) through NMR. The electrochemical properties of these three Ru-aqua complexes have been investigated by cyclic voltammetry, differential pulse voltammetry and Coulombimetric techniques. It is found that, for complex 1 at pH 7, the difference between the IV/III and the III/II redox couples (DeltaE1/2) is 50 mV, which is the smallest ever reported for this type of complex. On the other hand, for complexes cis-2 and trans-2, the oxidation state III is unstable with respect to disproportionation to II and IV. The reactivity of their Ru=O species has been tested toward cis-beta-methylstyrene oxidation, and it has been compared to [Ru(O)(trpy)(bpy)]2+. An inverse correlation between the degree of cis/trans-epoxide isomerization and DeltaE1/2 is found. In particular, for complexes cis-2 and trans-2, which have a DeltaE1/2 < 0, the epoxidation is highly stereoselective, yielding only cis-epoxide. 相似文献