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91.
Wojciech Dmowski Jolanta Ignatowska Krystyna Piasecka-Maciejewska 《Journal of fluorine chemistry》2004,125(7):1147-1151
Sodium dithionite effectively promotes the addition of 1-bromo-1-chloro-2,2,2-trifluoroethane to the exocyclic double bond of β-pinene. The reaction proceeded in an MeCN/H2O system to give almost quantitatively a 1:1 mixture of diastereoisomers of 4-(2-bromoisopropyl)-1-(2-chloro-3,3,3-trifluoropropyl)-cyclohexene (1). Dehydrobromination of 1 with pyridine gave a mixture of regioisomeric dienes 2 and 3, while treatment with DBU at elevated temperature resulted in total dehydrohalogenation to give trienes 4 and 5. Reduction of 1 with Bu3SnH gave 1-(2-chloro-3,3,3-trifluoropropyl)-4-(isopropyl)cyclohexene (6) which on dehydrochlorination with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) afforded conjugated diene, 4-isopropyl-1-(trans-3,3,3-trifluoropropenyl)-cyclohexene (7), with 50% overall yield. All the transformations proceeded with the retention of configuration at the carbon atom C-4 and the final compound 7 exhibited high optical activity. 相似文献
92.
Speed of sound and density of 1-propanol + heavy water were measured in the whole concentration range at temperatures from 293 to 313 K. Isentropic compressibility was calculated from the Laplace formula. The partial molar volume of 1-propanol reaches a minimum at the mole fraction of 1-propanol x
1 0.03. At the same concentration, the compressibility isotherms intersect one another. These features of the investigated system are similar to those of 1-propanol + H2O, that points to essential similarity of the two mixtures. A clathrate-like structure was suggested to explain the experimental results for dilute solutions of the alcohol. Somewhat more pronounced hydrophobic hydration in D2O than in H2O is manifested by an effect similar to that resulting from the elongation of the alcohol molecule. 相似文献
93.
Mirkin MV Nogala W Velmurugan J Wang Y 《Physical chemistry chemical physics : PCCP》2011,13(48):21196-21212
This Perspective is an update to our more extensive survey of scanning electrochemical microscopy (SECM) published in 2007. During this time, the SECM field retained its momentum by expanding into new areas and meeting the emerging scientific and technological challenges. Here we focus on most prominent developments such as high-resolution imaging, investigation of structures and processes on the nanoscale, alternative energy applications, and new approaches to solving "real world" problems. The fabrication of novel SECM probes and related theoretical advances are also discussed. 相似文献
94.
Kaczmarek P Jezowska-Bojczuk M Gatner K Bal W 《Dalton transactions (Cambridge, England : 2003)》2005,(11):1985-1988
Redox properties of Cu(II) complexes of the terminally blocked hexapeptide -TESHHK- and a series of its alanine substituted analogs: -TASHHK-, -TEAHHK-, -TESAHK-, -TESHAK-, were investigated in their reactions with hydrogen peroxide in solution and by cyclic voltammetry in a broad range of pH. The formation of reactive oxygen species was followed with the use of spectrophotometric indicators, NDMA and NBT. The results indicate that the ability of these complexes to generate hydroxyl-like radicals correlates with the formation of active Cu(III) complexes resulting from the oxidation of Cu(II) by H2O2, which interact with further H2O2 molecules specifically. 相似文献
95.
Thioridazine is a well-known dopamine-antagonist drug with a wide range of pharmacological properties ranging from neuroleptic to antimicrobial and even anticancer activity. Thioridazine is a critical component of a promising multi-drug therapy against M. tuberculosis. Amongst the various proposed mechanisms of action, the cell membrane-mediated one is peculiarly tempting due to the distinctive feature of phenothiazine drug family to accumulate in selected body tissues. In this study, we employ long-scale molecular dynamics simulations to investigate the interactions of three different concentrations of thioridazine with zwitterionic and negatively charged model lipid membranes. Thioridazine partitions into the interfacial region of membranes and modifies their structural and dynamic properties, however dissimilarly so at the highest membrane-occurring concentration, that appears to be obtainable only for the negatively charged bilayer. We show that the origin of such changes is the drug induced decrease of the interfacial tension, which ultimately leads to the significant membrane expansion. Our findings support the hypothesis that the phenothiazines therapeutic activity may arise from the drug–membrane interactions, and reinforce the wider, emerging view of action of many small, bioactive compounds. 相似文献
96.
Water‐Stable Zirconium‐Based Metal–Organic Framework Material with High‐Surface Area and Gas‐Storage Capacities 下载免费PDF全文
Dr. Oleksii V. Gutov Dr. Wojciech Bury Dr. Diego A. Gomez‐Gualdron Dr. Vaiva Krungleviciute Dr. David Fairen‐Jimenez Dr. Joseph E. Mondloch Dr. Amy A. Sarjeant Salih S. Al‐Juaid Prof. Dr. Randall Q. Snurr Prof. Dr. Joseph T. Hupp Prof. Dr. Taner Yildirim Prof. Dr. Omar K. Farha 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(39):12389-12393
We designed, synthesized, and characterized a new Zr‐based metal–organic framework material, NU‐1100 , with a pore volume of 1.53 ccg?1 and Brunauer–Emmett–Teller (BET) surface area of 4020 m2g?1; to our knowledge, currently the highest published for Zr‐based MOFs. CH4/CO2/H2 adsorption isotherms were obtained over a broad range of pressures and temperatures and are in excellent agreement with the computational predictions. The total hydrogen adsorption at 65 bar and 77 K is 0.092 g g?1, which corresponds to 43 g L?1. The volumetric and gravimetric methane‐storage capacities at 65 bar and 298 K are approximately 180 vSTP/v and 0.27 g g?1, respectively. 相似文献
97.
Dr. Nico Röder Dr. Tomasz Marszalek Daniel Limbach Prof. Wojciech Pisula Prof. Heiner Detert 《Chemphyschem》2019,20(3):463-469
π-Conjugated molecules with the shape of St. Andrew′s cross have been synthesized via fourfold Huisgen reaction. Four 2,5-diaryl-1,3,4-oxadiazol arms are attached to a central pyrazine nucleus. These fluorescent stars, when decorated with a rim of eight alkoxy side chains are discotic liquid crystals. Depending on the substitution pattern, the width of the liquid phase varies within a broad range of 25 °C to 250 °C. In their liquid crystalline phase, the molecules assemble in a typical hexagonal columnar supramolecular arrangement. 相似文献
98.
Fijalkowski KJ Genova RV Filinchuk Y Budzianowski A Derzsi M Jaroń T Leszczyński PJ Grochala W 《Dalton transactions (Cambridge, England : 2003)》2011,40(17):4407-4413
We describe the successful synthesis of the first mixed-cation (pseudoternary) amidoborane, Na[Li(NH(2)BH(3))(2)], with theoretical hydrogen capacity of 11.1 wt%. Na[Li(NH(2)BH(3))(2)] crystallizes triclinic (P1) with a = 5.0197(4) ?, b = 7.1203(7) ?, c = 8.9198(9) ?, α = 103.003(6)°, β = 102.200(5)°, γ = 103.575(5)°, and V = 289.98(5) ?(3) (Z = 2), as additionally confirmed by Density Functional Theory calculations. Its crystal structure is topologically different from those of its orthorhombic LiNH(2)BH(3) and NaNH(2)BH(3) constituents, with distinctly different coordination spheres of Li (3 N atoms and 1 hydride anion) and Na (6 hydride anions). Na[Li(NH(2)BH(3))(2)], which may be viewed as a product of a Lewis acid (LiNH(2)BH(3))/Lewis base (NaNH(2)BH(3)) reaction, is an important candidate for a novel lightweight hydrogen storage material. The title material decomposes at low temperature (with onset at 75 °C, 6.0% mass loss up to 110 °C, and an additional 3.0% up to 200 °C) while evolving hydrogen contaminated with ammonia. 相似文献
99.
Magdalena Kurdziel Elżbieta Szczepaniec-Cięciak Barbara Dąbrowska Wojciech Nitek Katarzyna Paliś Edyta Ślusarska 《Journal of solution chemistry》2003,32(7):601-615
The solubilities of solid 2,3-dimethylbutane and cyclopentene in liquid argon at a temperature of 87.3 K and in liquid nitrogen at 77.4 K have been measured by the filtration method. The hydrocarbon contents in solutions were determined using gas chromatography. GC–MS was used to identify impurities in solutes. The experimental value of the mole fraction solubility of solid 2,3-dimethyl-butane in liquid argon at 87.3 K is (8.26 ± 1.60) × 10–6 and (2.77 ± 0.94) × 10–8 in liquid nitrogen at 77.4 K. The experimental value of the mole fraction solubility of solid cyclopentene in liquid argon at 87.3 K is (5.11 ± 0.44) × 10–6 and (4.60 ± 0.76) × 10–8 in liquid nitrogen at 77.4 K. The Preston–Prausnitz method was used for calculation of the solubilities of solid hydrocarbons in liquid argon in the temperature range 84.0–110.0 K and in liquid nitrogen from 64.0 to 90.0 K. The solvent–solute interaction parameters l
12 were also calculated. At 90.0 K liquid argon is a better solvent for investigated solid hydrocarbons than is liquid nitrogen. 相似文献
100.
Owczarek E Kwiatkowski W Lemieszewski M Mazur A Rostkowski M Paneth P 《The Journal of organic chemistry》2003,68(21):8232-8235
Nitrogen, deuterium, halogen, and carbon kinetic isotope effects have been modeled for the Menshutkin reaction between methyl halides and substituted N,N-dimethylaniline at the HF/6-31G(d) level of theory augmented by the C-PCM continuum solvent model for several solvents. Systematic changes in geometries of the transition states and Gibbs free energies of activation have been found with phenyl ring substituents, solvent, and the leaving group. Kinetic isotope effects also change systematically; however, these changes are predicted to be small, inside the usual precision of the experimental measurements. On the contrary, no correlation has been found between the kinetic isotope effects and the Hammett constants for para substituents. Thus opposite to previous assumptions, our results indicate that kinetic isotope effects on the Menshutkin reaction cannot be used to predict the position of the transition state on the reaction coordinate. 相似文献