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71.
A bicomponent coextrusion process is modelled using a 3-D finite element formulation. The layer uniformity problem in coextrusion is addressed by examining the effects of the polymer melt/polymer melt/die wall contact line boundary condition. It has been observed that the less viscous polymer layer will tend to displace the more viscous polymer layer near the die wall. The behaviour of the contact lisle is considered to be either a stick or slip boundary condition. In the stick boundary condition, the contact line does not move from its original position after the two polymer layers meet, A slip boundary condition allows the contact line to move along the die wall. The calculated interfaces which result from different contact line assumptions are determined. Results show that if a stick boundary condition is appropriate for a given fluid/fluid/solid contact line, then a very thin entrained layer of the more viscous polymer melt will be trapped between the less viscous polymer melt and the die wall. Slip boundary conditions would allow complete displacement of the contact line along the die wall. Both slip and stick boundary conditions produce similar interface profiles far away from the die wall for small viscosity ratios. In certain eases, the displacement of the more viscous material by the less viscous material will cease and a static interface structure is produced regardless of die length. Experimental work with polycarbonate melts is compared with the numerical simulations.A. Torres on leave from Investigación y Desarrollo,, C.A. (INDESCA), P.O. Box 10319, Complejo Petroquímico El Tablazo, Maracaibo, 4001, Venezuela. 相似文献
72.
Stefanopoulos KL Romanos GE Vangeli OC Mergia K Kanellopoulos NK Koutsioubas A Lairez D 《Langmuir : the ACS journal of surfaces and colloids》2011,27(13):7980-7985
Small-angle neutron scattering (SANS), contrast-matching SANS, and nitrogen adsorption have been utilized to investigate the confined ionic liquid (IL) [bmim][PF(6)] phase in ordered mesoporous silica MCM-41 and SBA-15. The results suggest that the pores of SBA-15 are completely filled with IL whereas a small fraction of the pore volume, the pore "core", of MCM-41 is empty. The contrast-matching SANS measurements confirm the enhanced solubility of water in IL. In addition, they provide strong evidence that water does not enter the empty pore core of MCM-41, possibly because of the preferred orientation of the IL molecules in the adsorbed layer. 相似文献
73.
Mtei RP Lyashenko G Stein B Rubie N Hille R Kirk ML 《Journal of the American Chemical Society》2011,133(25):9762-9774
The electronic structure of a genuine paramagnetic des-oxo Mo(V) catalytic intermediate in the reaction of dimethyl sulfoxide reductase (DMSOR) with (CH(3))(3)NO has been probed by electron paramagnetic resonance (EPR), electronic absorption, and magnetic circular dichroism (MCD) spectroscopies. EPR spectroscopy reveals rhombic g- and A-tensors that indicate a low-symmetry geometry for this intermediate and a singly occupied molecular orbital that is dominantly metal centered. The excited-state spectroscopic data were interpreted in the context of electronic structure calculations, and this has resulted in a full assignment of the observed MCD and electronic absorption bands, a detailed understanding of the metal-ligand bonding scheme, and an evaluation of the Mo(V) coordination geometry and Mo(V)-S(dithiolene) covalency as it pertains to the stability of the intermediate and electron-transfer regeneration. Finally, the relationship between des-oxo Mo(V) and des-oxo Mo(IV) geometric and electronic structures is discussed relative to the reaction coordinate in members of the DMSOR enzyme family. 相似文献
74.
Farhad Haghjoo Nick Barnes Robin Pritchard 《Acta Crystallographica. Section C, Structural Chemistry》2011,67(7):o219-o221
In the crystal structure of the title compound, 2C22H24P+·I82−, the I82− anion is located on a crystallographic inversion centre and consists of two tri‐iodide anions linked by di‐iodine at angles of 89.92 (4)° to form a planar `Z'‐shaped dianion. The octaiodides are linked via long‐range interactions [3.877 (11) Å] into infinite polyiodide ribbons. This is the first example of a structure containing an [(o‐tolyl)3PMe]+ cation, and the CMe—P—C—CMe torsion angles of −54.0 (11), −51.3 (11) and −48.2 (11)° indicate that the configuration is exo3. 相似文献
75.
We give a new Esakia-style duality for the category of Sugihara monoids based on the Davey-Werner natural duality for lattices with involution, and use this duality to greatly simplify a construction due to Galatos-Raftery of Sugihara monoids from certain enrichments of their negative cones. Our method of obtaining this simplification is to transport the functors of the Galatos-Raftery construction across our duality, obtaining a vastly more transparent presentation on duals. Because our duality extends Dunn's relational semantics for the logic R-mingle to a categorical equivalence, this also explains the Dunn semantics and its relationship with the more usual Routley-Meyer semantics for relevant logics. 相似文献
76.
Nick Schiavon Tilde De Caro Alemayehu Kiros Ana Teresa Caldeira Isabella Erica Parisi Cristina Riccucci Giovanni Ettore Gigante 《Applied Physics A: Materials Science & Processing》2013,113(4):843-854
A multianalytical approach combining Optical Microscopy (OM), Backscattered Variable Pressure Scanning Electron Microscopy + Energy Dispersive X-ray Spectroscopy (VP-BSEM + EDS), Powder X-ray Diffractometry (PXRD), Raman Spectroscopy, and Microbiological techniques has been applied to characterize decay products and processes occurring at the surface of two rock-hewn churches (Bete Gyorgis and Bete Amanuel) at the UNESCO’s World Heritage site of Lalibela, Northern Ethiopia. The two churches were carved into volcanic scoria deposits of basaltic composition. In their geological history, the Lalibela volcanic rocks underwent late to post-magmatic hydrothermal alteration together with partial laterization and are therefore characterized by a decay-prone highly vesicular microtexture with late stage to post-magmatic precipitation of secondary mineral phases (calcite–zeolite–smectite). The main objective of the study was to gain a better insight into the weathering products and mechanisms affecting the surface of the stone monuments and to assess the relative contribution of natural “geological” weathering processes versus biological/salt attack in stone decay at this unique heritage site. Results indicate that while the main cause of bulk rock deterioration and structural failure could be related to the stone inherited “geological” features, biological attack by micro- (bacteria) and/or macro- (lichens) organisms is currently responsible for severe stone surface physical and chemical weathering leading to significant weakening of the stone texture and to material loss at the surface of the churches walls. A prompt and careful removal of the biological patinas with the correct biocidal treatment is therefore recommended. 相似文献
77.
Possible mechanisms for degrading chloromethylmercury (CH(3)HgCl) and dimethylmercury [(CH3)2Hg] involving thiol and ammonium residues were investigated by DFT and atoms-in-molecules (QTAIM) calculations. Using H2S and HS- as models for thiol and thiolate groups RSH and RS-, respectively, we obtained transition states and energy barriers for possible decomposition routes to Hg(SH)2 based on a model proposed by Moore and Pitts (Moore, M. J.; Distefano, M. D.; Zydowsky, L. D.; Cummings, R. T.; Walsh, C. T. Acc. Chem. Res. 1990, 23, 301. Pitts, K. E.; Summers, A. O. Biochemistry 2002, 41, 10287). Demethylation was found to be a multistep process that involved initial substitution of Cl- by RS-. We found that successive coordination of Hg with thiolates leads to increased negative charge on the methyl group and facilitates the protonolysis of the Hg-C bond by H-SH. This was also found to be the case for (CH3)2Hg. We found that NH4(+) readily protonolyzes the Hg-C bond of these thiolate complexes, suggesting that ammonium residues of protonated amino acids might also act as effective proton donors. 相似文献
78.
Wen J Chowdhury P Wills NJ Wannemuehler Y Park J Kesavan S Carpenter S Kraus GA Petrich JW 《Photochemistry and photobiology》2002,76(2):153-157
The synthesis of a molecule containing hypericin and luciferin moieties joined by a tether is reported. The light-induced (in vitro) antiviral activity as well as the photophysical properties of this new compound are measured and compared with those of the parent compounds, hypericin and pseudohypericin. This tethered molecule exhibits excited-state behavior that is very similar to that of its parent compounds and antiviral activity that is identical, within experimental error, to that of its more closely related parent compound, pseudohypericin. The implications for a photodynamic therapy that is independent of external light sources are discussed. 相似文献
79.
Nick Alexandrou Murray Smith Richard Park Kevin Lumb Ken Brice 《International journal of environmental analytical chemistry》2013,93(4):257-280
Abstract The Accelerated solvent extraction (ASE) of PAHs (23 2- to 6-ring species) spiked onto glass fibre filters (GFFs) was studied as a function of variable extraction solvents, pressure, temperature and extraction times. Acceptable recoveries (85% ± 15%) were obtained for certain combinations of conditions and a tentative method (1500 psi, 150°C, 70:30 hexane:acetone mixture, 7 min heat-up time, 5 min static extraction time, 60% flush volume, 2 static cycles was selected for further testing. However, this method did not prove as effective as the traditional Soxhlet method of extraction when these parameters were used to extract native PAHs from ambient atmospheric particulate matter collected on a GFF by Integrated Atmospheric Deposition Network (IADN) sampling protocols. The extraction recovery study for spiked GFFs was repeated using slightly different extraction conditions: 2000 psi, 100°C, 70:30 hexane:acetone, 5 min heat-up time, 5 min static extraction time, 150% flush volume, 3 static cycles. When this method was applied to the extraction of native PAHs from ambient atmospheric particulate matter collected on GFFs, the results showed equivalent or better recoveries to that of the Soxhlet method. The total time of extraction was 25 min requiring only 30 mL of solvent. This ASE method is presently used to quantitatively determine PAHs in IADN particle-phase samples. 相似文献
80.
Gielen E Smisdom N De Clercq B Vandeven M Gijsbers R Debyser Z Rigo JM Hofkens J Engelborghs Y Ameloot M 《Journal of fluorescence》2008,18(5):813-819
Many membrane proteins and lipids are partially confined in substructures ranging from tens of nanometers to micrometers in
size. Evidence for heterogeneities in the membrane of oligodendrocytes, i.e. the myelin-producing cells of the central nervous
system, is almost exclusively based on detergent methods. However, as application of detergents can alter the membrane phase
behaviour, it is important to investigate membrane heterogeneities in living cells. Here, we report on the first investigations
of the diffusion behavior of the myelin-specific protein MOG (myelin oligodendrocyte glycoprotein) in OLN-93 as studied by
the recently developed RICS (raster-scanning image correlation spectroscopy) technique. We implemented RICS on a standard
confocal laser-scanning microscope with one-photon excitation and analog detection. Measurements on FITC-dextran were used
to evaluate the performance of the system and the data analysis procedure.
Ellen Gielen and Nick Smisdom contributed equally to this work. 相似文献