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81.
Hanford KL Mitchem L Reid JP Clegg SL Topping DO McFiggans GB 《The journal of physical chemistry. A》2008,112(39):9413-9422
Aerosol optical tweezers are used to simultaneously characterize and compare the hygroscopic properties of two aerosol droplets, one containing inorganic and organic solutes and the second, referred to as the control droplet, containing a single inorganic salt. The inorganic solute is either sodium chloride or ammonium sulfate and the organic component is glutaric acid. The time variation in the size of each droplet (3-7 microm in radius) is recorded with 1 s time resolution and with nanometre accuracy. The size of the control droplet is used to estimate the relative humidity with an accuracy of better than +/-0.09%. Thus, the Kohler curve of the multicomponent inorganic/organic droplet, which characterizes the variation in equilibrium droplet size with relative humidity, can be determined directly. The measurements presented here focus on high relative humidities, above 97%, in the limit of dilute solutes. The experimental data are compared with theoretical treatments that, while ignoring the interactions between the inorganic and organic components, are based upon accurate representations of the activity-concentration relationships of aqueous solutions of the individual salts. The organic component is treated by a parametrized fit to experimental data or by the UNIFAC model and the water activity of the equilibrium solution droplet is calculated using the approach suggested by Clegg, Seinfeld and Brimblecombe or the Zdanovskii-Stokes-Robinson approximation. It is shown that such an experimental strategy, comparing directly droplets of different composition, enables highly accurate measurements of the hygroscopic properties, allowing the theoretical treatments to be rigorously tested. Typical deviations of the experimental measurements from theoretical predictions are shown to be around 1% in equilibrium size, comparable to the variation between the theoretical frameworks considered. 相似文献
82.
Blanco-Rodríguez AM Ronayne KL Zalis S Sýkora J Hof M Vlcek A 《The journal of physical chemistry. A》2008,112(16):3506-3514
Excited-state dynamics of [Re(Etpy)(CO)3(bpy)]+ was studied in three imidazolium ionic liquids by time-resolved IR and emission spectroscopy on the picosecond to nanosecond time scale. Low-lying excited states were characterized by TD-DFT calculations, which also provided molecular dipole moment vectors in the relevant electronic states. TRIR spectra in ionic liquids show initial populations of two excited states: predominantly bpy-localized 3IL and 3MLCT, characterized by nu(CO) bands shifted to lower and higher frequencies, respectively, relative to the ground state. Internal conversion of 3IL to the lowest triplet 3MLCT occurred on a time scale commensurate with solvent relaxation. The nu(CO) IR bands of the 3MLCT state undergo a dynamic shift to higher wavenumbers during relaxation. Its three-exponential kinetics were determined and attributed to vibrational cooling (units of picoseconds), energy dissipation to the bulk solvent (tens of picoseconds), and solvent relaxation, the lifetime of which increases with increasing viscosity: [EMIM]BF4 (330 ps) < [BMIM]BF4 (470 ps) < [BMIM]PF6 (1570 ps). Time-resolved phosphorescence spectra in [BMIM]PF6 show a approximately 2 ns drop in intensity due to the 3IL --> 3MLCT conversion and a dynamic Stokes shift to lower energies with a lifetime decreasing from 1.8 ns at 21 degrees C to 1.1 ns at 37 degrees C, due to decreasing viscosity of the ionic liquid. It is proposed that solvent relaxation predominantly involves collective translational motions of ions. It drives the 3IL --> 3MLCT conversion, increases charge reorganization in the lowest excited-state 3MLCT, and affects vibrational anharmonic coupling, which together cause the dynamic shift of excited-state IR bands. TRIR spectroscopy of carbonyl-diimine complexes emerges as a new way to investigate various aspects of solvation dynamics, while the use of slowly relaxing ionic liquids offers new insight into the photophysics of Re(I) carbonyl polypyridyls. 相似文献
83.
Easun TL Alsindi WZ Towrie M Ronayne KL Sun XZ Ward MD George MW 《Inorganic chemistry》2008,47(12):5071-5078
The dyad RuLRe contains (Re(bpy)(CO)3Cl) and (Ru(bpy)(bpyam)2)2+ termini (bpy = 2,2'-bipyridine; bpyam = 4,4'-diethylamido-2,2'-bipyridine) separated by a flexible ethylene spacer. Luminescence studies reveal the expected Re --> Ru photoinduced energy transfer, with partial quenching of Re(I)-based triplet metal-to-ligand charge-transfer (3MLCT) luminescence and consequent sensitization of the Ru(II)-based 3MLCT luminescence, which has a component with a grow-in lifetime of 0.76 (+/-0.2) ns. The presence of IR-active spectroscopic handles on both termini [CO ligands directly attached to Re(I) and amide carbonyl substituents on the bpy ligands coordinated to Ru(II)] allowed the excited-state dynamics to be studied by time-resolved IR (TRIR) spectroscopy in much more detail than allowed by luminescence methods. A combination of picosecond- and nanosecond-time-scale TRIR studies revealed the presence of at least three distinct Re --> Ru energy-transfer processes, with lifetimes of ca. 20 ps and 1 and 13 ns. This complex behavior occurs because of a combination of two different Ru-based 3MLCT states (Ru --> L and Ru --> bpyam), which are sensitized by energy transfer from the Re(I) donor at different rates; and the presence of at least two conformers of the flexible molecule RuLRe, which have different Re...Ru separations. 相似文献
84.
85.
Leaching test for calcined kaolinite and kaolinite/TiO<Subscript>2</Subscript> photoactive composite
Michaela Tokarčíková Kateřina Mamulová Kutláková Jana Seidlerová 《Chemical Papers》2016,70(9):1253-1261
Kaolinite is a suitable material for fixing TiO2 nanoparticles in a composite form. The kaolinite/TiO2 composite has promising photoactive properties which are as important as is the possible impact of the composite on the environment. Accordingly, the stability of the kaolinite/TiO2 composite dried at 105°C (KTI1) and calcined at 600 °C (KTI6) and the stability of the original kaolinite treated at various temperatures (105–800 °C) were studied by the leaching test in accordance with European standard BS EN 12457-2:2002 (British Standards Institution, 2002). The stability was evaluated on the basis of elements leached from the materials to extraction agents. Atomic emission spectrometry with inductively coupled plasma was used for determining the concentration of elements. In order to better understand the process of calcination and the structure changes in the kaolinite/TiO2 composite and calcined kaolinite, the materials were evaluated using X-ray powder diffraction and infrared spectroscopy with Fourier transformation. The processes of kaolinite dehydroxylation and metakaolinite formation were observed. Kaolinite is an appropriate carrier for composite preparation due to its stability even after its treatment at high temperatures. The experiments confirmed the TiO2 nanoparticles to be very strongly bound to the kaolinite surface. On the other hand, the experiments demonstrated that the presence of TiO2 on the kaolinite surface caused the release of Al in high concentrations to the final extracts, especially after kaolinite/TiO2 composite calcination. 相似文献
86.
87.
Bateman KP Castro-Perez J Wrona M Shockcor JP Yu K Oballa R Nicoll-Griffith DA 《Rapid communications in mass spectrometry : RCM》2007,21(9):1485-1496
Metabolite identification studies involve the detection and structural characterization of the biotransformation products of drug candidates. These experiments are necessary throughout the drug discovery and development process. The use of high-resolution chromatography and high-resolution mass spectrometry together with data processing using mass defect filtering is described for in vitro and in vivo metabolite identification studies. Data collection was done using UPLC coupled with an orthogonal hybrid quadrupole time-of-flight mass spectrometer. This experimental approach enabled the use of MS(E) data collection (where E represents collision energy) which has previously been shown to be a powerful approach for metabolite identification studies. Post-acquisition processing with a prototype mass defect filtering program was used to eliminate endogenous interferences in the study samples, greatly enhancing the discovery of metabolites. The ease of this approach is illustrated by results showing the detection and structural characterization of metabolites in plasma from a preclinical rat pharmacokinetic study. 相似文献
88.
Tull EJ Bartlett PN Ryan KR 《Langmuir : the ACS journal of surfaces and colloids》2007,23(14):7859-7873
Site-selective assembly of 5 microm amine-functionalized glass spheres from aqueous suspensions onto gold surfaces patterned with carboxylic acid and methyl-terminated thiols has been achieved through the introduction of a variable tilt flow cell. In situ microscope imaging has been employed to study the four phases of assembly independently, and the relative roles of electrostatic attraction and capillary emersion have been explored. In contradiction to the commonly recognized electrostatic assembly model, detailed theoretical analysis and experimental evidence are presented to support a mechanism where patterning occurs at the point of meniscus contact. Control of pattern quality is demonstrated through the comparison of results obtained from a variety of experiments, and the best conditions for the assembly of monolayer features are identified. Finally, evidence for the extension of this assembly method to the production of singlet sphere arrays is discussed. 相似文献
89.
Steven C. Smith Shane M. Peper Matthew Douglas Kate L. Ziegelgruber Erin C. Finn 《Journal of Radioanalytical and Nuclear Chemistry》2009,282(2):617-621
Bench scale experiments were conducted to determine the dissolution characteristics of UO2, U3O8, and UO3 in aqueous peroxide-containing carbonate solutions. The experimental parameters investigated included carbonate countercation
(NH4
+, Na+, K+, and Rb+) and H2O2 concentration. The carbonate countercation had a dramatic influence on the dissolution behavior of UO2 in 1 M carbonate solutions containing 0.1 M H2O2, with the most rapid dissolution occurring in (NH4)2CO3 solution. The initial dissolution rate (y) of UO2 in 1 M (NH4)2CO3 increased linearly with peroxide concentration (x) ranging from 0.05 to 2 M according to: y = 2.41x + 1.14. The trend in initial dissolution rates for the three U oxides under study was UO3 ≫ U3O8 > UO2. 相似文献
90.
Shani Sperinck Thomas Becker Kate Wright William R. Richmond 《Journal of inclusion phenomena and macrocyclic chemistry》2009,65(1-2):89-95
A solvothermal method has been used to prepare hybrid inorganic–organic composites with a lamellar structure in which layers of wurtzite ZnS are separated by intercalated diamine molecules. A hybrid composite prepared with diethylenetriamine has been isolated and characterised and its structure and properties compared with those of the composite prepared using ethylenediamine. Comparative structural and morphological studies of the two lamellar hybrid composites are described on the basis of powder XRD, electron and scanning probe microscopies and thermal analysis of the materials. 相似文献