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181.
Kalenius E Beyeh NK Jänis J Rissanen K 《Chemical communications (Cambridge, England)》2011,47(9):2649-2651
Pyrogallarene shows concentration-dependent instability in dilute solutions resulting in elimination of two ketene molecules and formation of pyrogallarene lactones. This unexpected phenomenon, which is not observed with resorcinarenes, highlights the significance of the four hydroxyl groups at 2-position for the molecular characteristics of pyrogallarenes. 相似文献
182.
Yang S Pelton R Raegen A Montgomery M Dalnoki-Veress K 《Langmuir : the ACS journal of surfaces and colloids》2011,27(17):10438-10446
This is the first report describing a new technology where hydrophobic nanoparticles adsorb onto much larger, hydrophilic mineral particle surfaces to facilitate attachment to air bubbles in flotation. The adsorption of 46 nm cationic polystyrene nanoparticles onto 43 μm diameter glass beads, a mineral model, facilitates virtually complete removal of the beads by flotation. As little as 5% coverage of the bead surfaces with nanoparticles promotes high flotation efficiencies. The maximum force required to pull a glass bead from an air bubble interface into the aqueous phase was measured by micromechanics. The pull-off force was 1.9 μN for glass beads coated with nanoparticles, compared to 0.0086 μN for clean beads. The pull-off forces were modeled using Scheludko's classical expression. We propose that the bubble/bead contact area may not be dry (completely dewetted). Instead, for hydrophobic nanoparticles sitting on a hydrophilic surface, it is possible that only the nanoparticles penetrate the air/water interface to form a three-phase contact line. We present a new model for pull-off forces for such a wet contact patch between the bead and the air bubble. Contact angle measurements of both nanoparticle coated glass and smooth films from dissolved nanoparticles were performed to support the modeling. 相似文献
183.
Taesch J Heitz V Topić F Rissanen K 《Chemical communications (Cambridge, England)》2012,48(42):5118-5120
A large covalent cage incorporating two porphyrins attached by four long and flexible polyether chains each bearing two 3-pyridyl ligands was synthesized from a DABCO-templated olefin metathesis reaction. The X-ray structure of the cage with the DABCO coordinated inside the cavity to the two zinc(II) porphyrins reveals a highly symmetric structure. 相似文献
184.
Vehkamäki H McGrath MJ Kurtén T Julin J Lehtinen KE Kulmala M 《The Journal of chemical physics》2012,136(9):094107
The critical cluster is the threshold size above which a cluster will be more likely to grow than to evaporate. In field and laboratory measurements of new particle formation, the number of molecules of a given species in the critical cluster is commonly taken to be the slope of the log-log plot of the formation rate versus the concentration of the species. This analysis is based on an approximate form of the first nucleation theorem, which is derived with the assumption that there are no minima in the free energy surface prior to the maximum at the critical size. However, many atmospherically relevant systems are likely to exhibit such minima, for example, ions surrounded by condensable vapour molecules or certain combinations of acids and bases. We have solved numerically the birth-death equations for both an electrically neutral one-component model system with a local minimum at pre-critical sizes and an ion-induced case. For the ion-induced case, it is verified that the log-log slope of the nucleation rate versus particle concentration plot gives accurately the difference between the cluster sizes at the free energy maximum and minimum, as is expected from the classical form of the ion-induced nucleation rate. However, the results show that applying the nucleation theorem to neutral systems with stable pre-nucleation clusters may lead to erroneous interpretations about the nature of the critical cluster. 相似文献
185.
Pekka J. Korhonen Kari Silvennoinen Jyrki Wallenius Anssi Öörni 《Annals of Operations Research》2013,211(1):565-578
We investigate the connection between weights, scales, and the importance of criteria, when a linear value function is assumed to be a suitable representation of a decision maker’s preferences. Our considerations are based on a simple two-criteria experiment, where the participants were asked to indicate which of the criteria was more important, and to pairwise compare a number of alternatives. We use the participants’ pairwise choices to estimate the weights for the criteria in such a way that the linear value function explains the choices to the extent possible. More specifically, we study two research questions: (1) is it possible to find a general scaling principle that makes the rank order of the importance of criteria consistent with the rank order of the magnitudes of the weights, and (2) how good is a simple, direct method of asking the decision maker to “provide” weights for the criteria compared to our estimation procedure. Our results imply that there is reason to question two common beliefs, namely that the values of the weights would reflect the importance of criteria, and that people could reliably “provide” such weights without estimation. 相似文献
186.
Peljo P Murtomäki L Kallio T Xu HJ Meyer M Gros CP Barbe JM Girault HH Laasonen K Kontturi K 《Journal of the American Chemical Society》2012,134(13):5974-5984
Oxygen reduction catalyzed by cofacial metalloporphyrins at the 1,2-dichlorobenzene-water interface was studied with two lipophilic electron donors of similar driving force, 1,1'-dimethylferrocene (DMFc) and tetrathiafulvalene (TTF). The reaction produces mainly water and some hydrogen peroxide, but the mediator has a significant effect on the selectivity, as DMFc and the porphyrins themselves catalyze the decomposition and the further reduction of hydrogen peroxide. Density functional theory calculations indicate that the biscobaltporphyrin, 4,5-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]-9,9-dimethylxanthene, Co(2)(DPX), actually catalyzes oxygen reduction to hydrogen peroxide when oxygen is bound on the "exo" side ("dock-on") of the catalyst, while four-electron reduction takes place with oxygen bound on the "endo" side ("dock-in") of the molecule. These results can be explained by a "dock-on/dock-in" mechanism. The next step for improving bioinspired oxygen reduction catalysts would be blocking the "dock-on" path to achieve selective four-electron reduction of molecular oxygen. 相似文献
187.
Winkler PM Vrtala A Steiner G Wimmer D Vehkamäki H Lehtinen KE Reischl GP Kulmala M Wagner PE 《Physical review letters》2012,108(8):085701
First order phase transitions involve nucleation, formation of nanoscale regions of a new phase within a metastable parent phase. Using the heterogeneous nucleation theorem we show how clusters formed by nucleation on single molecules evolve from the gas phase and determine the critical size beyond which condensation starts to form aerosol particles. Our experiments reveal the activation of molecules into droplets to happen via formation of critical clusters substantially larger than the seed molecule. The nanosized critical clusters were found to be well predicted by the Kelvin-Thomson relation pointing directly to the key step in the phase transition. 相似文献
188.
Dirk C. de Graaf Wolfgang Ritter Frans J. Jacobs Marleen Brunain Hein Imberechts Koen Mintiens Yves Van der Stede Bart Verheyden Aud Kari Fauske Patrick Boujon Gabriela Chioveanu Daniel Dezmirean Giovanni Formato Franco Mutinelli Hendrik-Jan Roest Dalibor Titĕra Stephen F. Pernal Katia Knapen 《Accreditation and quality assurance》2009,14(5):273-276
We report on the first proficiency test in the context of honey bee disease testing on a broad international scale. Honey
samples were distributed to 12 participating laboratories for isolation and identification of spores of the etiological agent
of American foulbrood, Paenibacillus larvae. Of the 11 laboratories responding to this proficiency testing event, only 6 (54%) provided data that were in full agreement
with the previously determined status of the honey samples; eight (72%) laboratories fell within the threshold for qualification
as defined a priori in this proficiency test (=level of agreement of at least 90%). Some lessons can now be drawn from the
organizational point of view and will certainly improve new initiatives to be taken. 相似文献
189.
Zhiyan Song Kari J. Parker Idorenyin Enoh Hua Zhao Olarongbe Olubajo 《Analytical and bioanalytical chemistry》2009,395(5):1453-1459
We conducted 31P NMR kinetic studies and 1H-diffusion measurements on myosin-catalyzed hydrolysis of adenosine triphosphate (ATP) under varied conditions. The data
elucidate well the overall hydrolysis rate and various factors that significantly impact the reaction. We found that the enzymatic
hydrolysis of ATP to adenosine diphosphate (ADP) was followed by ADP hydrolysis, and different nucleotides such as ADP and
guanosine triphosphate acted as competitors of ATP. Increasing ATP or Mg2+ concentration resulted in decreased hydrolysis rate, and such effect can be related to the decrease of ATP diffusion constants.
Below 50 °C, the hydrolysis was accelerated by increasing temperature following the Arrhenius’ law, but the hydrolysis rate
was significantly lowered at higher temperature (~60 °C), due to the thermal–denaturation of myosin. The optimal pH range
was around pH 6–8. These results are important for characterization of myosin-catalyzed ATP hydrolysis, and the method is
also applicable to other enzymatic nucleotide reactions. 相似文献
190.
A 2,6‐dibutoxylnaphthalene‐based tetralactam macrocycle was designed and synthesized. This macrocycle shows highly selective recognition to phenazine – a well‐known secondary metabolite in bacteria and an emerging disinfection byproduct in drinking water. In contrast, the macrocycle shows no binding to the structurally similar dibenzo‐1,4‐dioxin. It was revealed that hydrogen bonding, π‐π and σ‐π interactions are the major driving forces between phenazine and the new tetralactam macrocycle. A perfect complementarity in electrostatic potential surfaces may explain the high selectivity. In addition, the macrocycle shows fluorescent response to phenazine, demonstrating its potential in fluorescent detection of phenazine. 相似文献