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91.
Mirosław Dors Helena Nowakowska Mariusz Jasiński Jerzy Mizeraczyk 《Plasma Chemistry and Plasma Processing》2014,34(2):313-326
Results of chemical kinetics modeling in methane subjected to the microwave plasma at atmospheric pressure are presented in this paper. The reaction mechanism is based on the methane oxidation model without reactions involving nitrogen and oxygen. For the numerical calculations 0D and 1D models were created. 0D model uses Calorimetric Bomb Reactor whereas 1D model is constructed either as Plug Flow Reactor or as a chain of Plug Flow Reactor and Calorimetric Bomb Reactor. Both models explain experimental results and show the most important reactions responsible for the methane conversion and production of H2, C2H2, C2H4 and C2H6 detected in the experiment. Main conclusion is that the chemical reactions in our experiment proceed by a thermal process and the products can be defined by considering thermodynamic equilibrium. Temperature characterizing the methane pyrolysis is 1,500–2,000 K, but plasma temperature is in the range of 4,000–5,700 K, which means that methane pyrolysis process is occurring outside the plasma region in the swirl gas flowing around the plasma. 相似文献
92.
Mariusz Krupiński Beata Krupińska Krzysztof Labisz Zbigniew Rdzawski Wojciech Borek 《Journal of Thermal Analysis and Calorimetry》2014,118(2):1361-1367
In this study, the change of the cooling rate in the range of about 0.1–1 °C s?1 and the addition of Sr on the crystallization kinetics of the cast zinc alloys of the ZnAlCu type, as well as its relation to the microstructure were also investigated. Therefore, the aim of the rapid crystallisation is the achievement of materials with better properties, which can be obtained by refinement of the dendritic or eutectic microstructure, elimination of segregation, or creation of metastable phases and their morphology changes. In the investigated alloys, the change of cooling rate of 1 °C s?1 has caused microstructure’s refinement as well as increase in hardness. Increase in the cooling rate causes also morphology changes of the η + α eutectic, and makes generally a global overcooling of the alloy as well as change in the temperatures at the beginning of crystallization T DN and of the alloy crystallization T S. The presented investigations concerning the electron microscopy methods, including transmission electron microscopy, allow revealing the crystallographic structure, based on the d-spacing changes, as well as the diffraction method used for phase determination, which is a helpful tool for the explanation of the important points in the thermo-derivative analysis curve, where the relation between the amount of phase and the occurrence of new phases can be determined. 相似文献
93.
We have analyzed the character of B═B and B≡B bonds in the neutral molecules of general form: LHB═BHL (2-L) and LB≡BL (3-L), for various ancillary ligands L attached to the boron center, based on a recently developed method that combines the extended transition state scheme with the theory of natural orbitals for chemical valence (ETS-NOCV). In the case of molecules with the B═B bond, 2-L, we have included L = PMe(3), PF(3), PCl(3), PH(3), C(3)H(4)N(2)═C(NHCH)(2), whereas for molecules containing the B≡B connection, 3-L, the following ligands were considered L = CO, PMe(3), PCl(3), (Me(2)NCH(2)CH(2)O)(2)Ge. The results led us to conclude that use of phosphorus ligands leads to strengthening of the B═B bond by 6.4 kcal/mol (for 2-PMe(3)), by 4.4 (for 2-PF(3)) and by 9.2 (for 2-PH(3)), when compared to a molecule developed on the experimental basis, 2-C(3)H(4)N(2) (ΔE(total) = -118.3 kcal/mol). The ETS scheme has shown that all contributions, that is, (i) orbital interaction ΔE(orb), (ii) Pauli repulsion ΔE(Pauli), and (iii) electrostatic stabilization ΔE(elstat), are important in determining the trend in the B═B bond energies, ΔE(total). ETS-NOCV results revealed that both σ(B═B) and π(B═B) contributions are responsible for the changes in ΔE(orb) values. All considered molecules of the type LB≡BL, 3-L, exhibit a stronger B≡B bond when compared to a double B═B connection in 2-L (|ΔE(total)| is lower by 11.8-42.5 kcal/mol, depending on the molecule). The main reason is a lower Pauli repulsion contribution noted for 3-CO, 3-PMe(3), and 3-PCl(3) molecules. In addition, in the case of 3-PMe(3) and 3-PCl(3), the orbital interaction term is more stabilizing; however, the effect is less pronounced compared to the drop in the Pauli repulsion term. In all of the systems with double and triple boron-boron bonds, the electronic factor (ΔE(orb)) dominates over the electrostatic contribution (ΔE(elstat)). Finally, the strongest B≡B connection was found for 3-Ge [L = (Me(2)NCH(2)CH(2)O)(2)Ge], predominantly as a result of the strongest σ- and π-contributions, despite the highest destabilization originating from the sizable bulkiness of the germanium-containing ligand. The data on energetic stability of multiple boron-boron bonds (relatively high values of bond dissociation energies |ΔE(total)|), suggest that it should be possible to isolate experimentally the novel proposed systems with double B═B bonds, 2-PMe(3), 2-PF(3), 2-PCl(3), and 2-PH(3), and those with triple B≡B connections, 3-PMe(3), 3-Ge, and 3-PCl(3). 相似文献
94.
Karel Procházka Pavel Matějíček Mariusz Uchman Miroslav Štěpánek Jana Humpolíčková Martin Hof Milena Špírková 《Macromolecular Symposia》2008,273(1):95-102
Summary: The self-assembled core-shell nanoparticles based on fluorescently double-tagged high-molar-mass polystyrene-block-poly(methacrylic acid), PS-PMA, were prepared in aqueous buffers by dialysis from 1,4-dioxane – water mixtures. The conformations of shell-forming PMA chains were studied using nonradiative excitation energy transfer measurements. The study shows that two populations of distinctly different conformations (collapsed and stretched) coexist in the shell and their ratio depends on pH. 相似文献
95.
Bollermann T Schwedler I Molon M Freitag K Gemel C Seidel RW Fischer RA 《Dalton transactions (Cambridge, England : 2003)》2011,40(46):12570-12577
The reactions of heteroleptic GaCp*/CO containing transition metal complexes of iron and cobalt, namely [(CO)(3)M(μ(2)-GaCp*)(m)M(CO)(3)] (Cp* = pentamethylcyclopentadienyl; M = Fe, m = 3; M = Co, m = 2) and [Fe(CO)(4)(GaCp*)], with ZnMe(2) in toluene and the presence of a coordinating co-solvent were investigated. The reaction of the iron complex [Fe(CO)(4)(GaCp*)] with ZnMe(2) in presence of tetrahydrofurane (thf) leads to the dimeric compound [(CO)(4)Fe{μ(2)-Zn(thf)(2)}(2)Fe(CO)(4)] (1). Reaction of [(CO)(3)Fe(μ(2)-GaCp*(3))Fe(CO)(3)] with ZnMe(2) and stoichiometric amounts of thf leads to the formation of [(CO)(3)Fe{μ(2)-Zn(thf)(2)}(2)(μ(2)-ZnMe)(2)Fe(CO)(3)] (2) containing {Zn(thf)(2)} as well as ZnMe ligands. Using pyridine (py) instead of thf leads to [(CO)(3)Fe{μ(2)-Zn(py)(2)}(3)Fe(CO)(3)] (3) via replacement of all GaCp* ligands by three{Zn(py)(2)} groups. In contrast, reaction of [(CO)(3)Co(μ(2)-GaCp*)(2)Co(CO)(3)] with ZnMe(2) in the presence of py or thf leads in both cases to the formation of [(CO)(3)Co{μ(2)-ZnL(2)}(μ(2)-ZnCp*)(2)Co(CO)(3)] (L = py (4), thf (5)) via replacement of GaCp* with {Zn(L)(2)} units as well as Cp* transfer from the gallium to the zinc centre. All compounds were characterised by NMR spectroscopy, IR spectroscopy, single crystal X-ray diffraction and elemental analysis. 相似文献
96.
Maślanka A Krzek J Stolarczyk M Walczak M Głogowska A 《Journal of AOAC International》2011,94(6):1791-1799
Stability of clonazepam, diazepam, haloperidol, and doxepin was determined in acidic solutions. In addition, determination of the kinetic and thermodynamic properties of this stability was carried out. Reaction rate constants (k), half-life times (t(0.1) and t(0.5)), and activation energy (Ea) were estimated for the drugs, which differed in polarity expressed with log P values. It was observed that estimated Ea values increased from 42.13 to 125.03 kJ/mol with an increase of lipophilicity (log P) beginning from the most hydrophilic drug (clonazepam, 2.70 log P) to the most lipophilic drug (doxepin, 4.10 log P). All degradation products were studied using an HPLC/electrospray ionization-MS technique in the positive ionization mode. 相似文献
97.
Bollermann T Freitag K Gemel C Molon M Seidel RW von Hopffgarten M Jerabek P Frenking G Fischer RA 《Inorganic chemistry》2011,50(20):10486-10492
The synthesis, structural characterization, and bonding situation analysis of a novel, all-zinc, hepta-coordinated palladium complex [Pd(ZnCp*)(4)(ZnMe)(2){Zn(tmeda)}] (1) is reported. The reaction of the substitution labile d(10) metal starting complex [Pd(CH(3))(2)(tmeda)] (tmeda = N,N,N',N'-tetramethyl-ethane-1,2-diamine) with stoichiometric amounts of [Zn(2)Cp*(2)] (Cp* = pentamethylcyclopentadienyl) results in the formation of [Pd(ZnCp*)(4)(ZnMe)(2){Zn(tmeda)}] (1) in 35% yield. Compound 1 has been fully characterized by single-crystal X-ray diffraction, (1)H and (13)C NMR spectroscopy, IR spectroscopy, and liquid injection field desorption ionization mass spectrometry. It consists of an unusual [PdZn(7)] metal core and exhibits a terminal {Zn(tmeda)} unit. The bonding situation of 1 with respect to the properties of the three different types of Zn ligands Zn(R,L) (R = CH(3), Cp*; L = tmeda) bonded to the Pd center was studied by density functional theory quantum chemical calculations. The results of energy decomposition and atoms in molecules analysis clearly point out significant differences according to R vs L. While Zn(CH(3)) and ZnCp* can be viewed as 1e donor Zn(I) ligands, {Zn(tmeda)} is best described as a strong 2e Zn(0) donor ligand. Thus, the 18 valence electron complex 1 nicely fits to the family of metal-rich molecules of the general formula [M(ZnR)(a)(GaR)(b)] (a + 2b = n ≥ 8; M = Mo, Ru, Rh; Ni, Pd, Pt; R = Me, Et, Cp*). 相似文献
98.
Roles of steroid hormones, and compounds that can influence their levels in cells, are of increasing interest in e.g. cancer research, partly because resistance to hormone therapies often complicates treatment. To elucidate the processes involved, the hormones and related compounds need to be accurately measured. Reversed-phase liquid chromatography with dynamic multiple reaction monitoring mass spectrometric detection in electrospray mode is capable of providing such measurements. Therefore, LC-MS/MS was developed for sensitive, selective analysis of 11 steroid hormones, cholesterol and two prostaglandins. The effects of the tissue matrix, and solid-phase extraction (SPE) sample clean-up, on the LC-MS/MS signals of the hormones were also investigated. The results show that the developed LC-MS/MS method, following SPE clean-up to reduce matrix interference, can detect selected steroids in extracts of mouse tissues. The method provides linear measurements of the steroids at concentrations up to few ng/μL, and limits of detection in the range 0.03-0.2 pg/μL (for some compounds lower than those of previously reported methods). 相似文献
99.
Molon M Bollermann T Gemel C Schaumann J Fischer RA 《Dalton transactions (Cambridge, England : 2003)》2011,40(40):10769-10774
Treatment of [Mo(N(2))(PMe(3))(5)] with two equivalents GaCp* (Cp* = η(5)-C(5)(CH(3))(5)) leads to the formation of cis-[Mo(GaCp*)(2)(PMe(3))(4)] (1), while AlCp* did not react with this precursor. In addition, [Ni(GaCp*)(2)(PPh(3))(2)] (2a), [Ni(AlCp*)(2)(PPh(3))(2)] (2b), [Ni(GaCp*)(2)(PCy(3))(2)] (3a), [Ni(GaCp*)(2)(PMe(3))(2)] (3b), [Ni(GaCp*)(3)(PCy(3))] (4) and [Ni(GaCp*)(PMe(3))(3)] (5) have been prepared in high yields by a direct synthesis from [Ni(COD)(2)] and stoichiometric amounts of the ligands PR(3) and ECp* (E = Al, Ga), respectively. All compounds have been fully characterized by (1)H, (13)C, and (31)P NMR spectroscopy, elemental analysis and single crystal X-ray diffraction studies. 相似文献
100.
The preparation of 1,4-dihydro-4-oxo-3′-alkylthio-3,4′-diquinolinyl sulfides 3 or 1,4-dihydro-4-oxo-3-(alkylthio)quinolines 4 by acid catalysed hydrolysis of 4-methoxy-3′-alkylthio-3,4′-diquinolinyl sulfides 1 or 4-methoxy-3-(alkylthio)-quinolines 2 is described. The reactions of 4-methoxy-3′-alkylthio-3,4′-diquinolinyl sulfides 1 or 1,4-dihydro-4-oxo-3′-alkylthio-3,4′-diquinolinyl sulfides 3 with phosphoryl chloride in DMF afforded 4-chloro-3′-alkylthio-3,4′-diquinolinyl sulfides 5 . Treatment of the title compounds 1 or 3 with boiling phosphoryl chloride systems:leads to 4-chloro-3-(alkylthio)quinolines 6 and thioquinanthrene but those of alkoxy- or oxo-quinolines 2 or 4 lead to 4-chloro-3-(alkylthio)quinolines 6 . The reactions of N-methyl-4(1H)-quinolinones 3n and 4n with phosphoryl chloride directed to 4-chloro-3-(alkylthio)quinolines 6 were studied as well. 相似文献