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排序方式: 共有165条查询结果,搜索用时 15 毫秒
1.
We prove that a random change of variable in general improves convergence properties of the Fourier expansions, and we give
a precise quantitative estimate of the phenomenon.
Submitted: December 1997, final version: May 1998 相似文献
2.
3.
Theodorus J.M. de Bruin Karoly Vekey Yves Gimbert Anne Milet 《Journal of organometallic chemistry》2006,691(20):4281-4288
The influence of carbon-carbon triple bond polarization on the regiochemistry of the Pauson-Khand reaction has been studied with the B3LYP functional. The regiochemistry determining step of this reaction, i.e., olefin insertion leading to cobaltacycle formation, has been examined with ethylene as the olefin and propyne, methyl 2-butynoate, and methyl propiolate as the acetylenes. From this study, it has been concluded that, in absence of overwhelming steric effects of an acetylene substituent, the regiochemistry is influenced by the polarization of the acetylenic bond, which arises from the different substituents. The initial C-C bond is preferentially formed with the acetylenic carbon that has the greater electron density: with propyne, this leads to a cyclopentenone having the methyl group in the α-position; with methyl 2-butynoate, to a cyclopentenone with the CO2Me in the β-position; with methyl propiolate, which is virtually unpolarized in the complex, to a cyclopentenone with the CO2Me in the α-position (a result of steric effects). These theoretical results are concordant with those observed experimentally with norbornene. The question of axial versus equatorial reactive positions for the coordinated olefin is also addressed and a kinetic simulation is presented. 相似文献
4.
P. Kozma P. Bém B. P. Ad'yasevich V. G. Antonenko 《Czechoslovak Journal of Physics》1985,35(10):1118-1127
The parametrization of polarization observables in terms of (l, s, J) matrix elements is given for2H(d, p)3H and2H(d, n)3He reactions at low energies. It is shown that transverse polarizations of outgoing nucleons are to be measured in order to obtain a complete set of cross-section, analysing powers, spin-correlation and polarization transfer experiments. 相似文献
5.
Kassai Cs. Illés R. Pokol G. Sztatisz J. Fogassy E. Kozma D. 《Journal of Thermal Analysis and Calorimetry》2000,62(3):647-655
The resolution of three chiral alcohols with O,O'-dibenzoyl-(2R,3R)-tartaric acid (DBTA) via diastereoisomeric supramolecular
compound formation was investigated with thermoanalytical methods. On the basis of TG measurements the DBTA:chiral alcohol
molar ratio in the compounds is 1:1 which agrees with the results of single-crystal X-ray diffraction analysis. The DBTA –
chiral alcohol supramolecular compounds have different supramolecular structure than the DBTA – achiral alcohol supramolecular
compounds. The supramolecular compounds containing cyclohexanols have higher thermal stability than the compounds containing
acyclic aliphatic alcohols. The amount of unreacted DBTA monohydrate in the solid phase can be determined both with DSC and
with TG measurements.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
6.
Karoly Vkey Jzsef Tams Arpd Somogyi Antonella Bertazzo Carlo Costa Graziella Allegri Roberta Seraglia Piero Traldi 《Journal of mass spectrometry : JMS》1992,27(11):1216-1219
Structural studies of a synthetic melanin, obtained by means of performic acid oxidation of tryptophan, were carried out by pyrolysis gas chromatography/mass Spectrometry (Py-GC/MS). To identify the best pyrolysis conditions, both Curie-point pyrolysis and filament pyrolysis were employed and the effects of pyrolysis temperatures and times were studied. Using the first approach, various compounds were identified: toluene, ethylbenzene, styrene, indole, methylindole, ethylindole, phenol, cresol and ethylphenol. Using filament pyrolysis some interesting differences could be observed. Whereas toluene, ethylbenzene, phenol, cresol and methylindole were found, neither indole nor ethylindole was detected. Instead, new pyrolysis products were evident, such as methylpyrrole and indolin-2-one. Hence filament pyrolysis seems to activate different thermal decomposition pathways of the melanin under study. It is suggested that tryptophan melanin is a polymer containing indole and hydroxyindole derivatives as subunits. 相似文献
7.
8.
Wei Xu Dr. Karoly Kozma Tianxiang Sha Yi-Jen Wu Prof. May Nyman Prof. Michael M. Lerner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(36):8101-8104
The alkaline earth metals (M=Mg, Ca, Sr, and Ba) exhibit a +2 oxidation state in nearly all known stable compounds, but MI dimeric complexes with M−M bonding, [M2(en)2]2+, (en=ethylenediamine) of all these metals can be stabilized within the galleries of donor-type graphite intercalation compounds (GICs). These metals can also form GICs with more conventional metal (II) ion complexes, [M(en)2]2+. Here, the facile interconversion between dimeric-MI and monomeric-MII intercalates upon the addition/removal of en are reported. Thermogravimetry, powder X-ray diffraction, and pair distribution function analysis of total scattering data support the presence of either [M2(en)2]2+ or [M(en)2]2+ guests. This phase conversion requires coupling graphene and metal redox centers, with associated reversible M−M bond formation within graphene galleries. This chemistry allows the facile isolation of unusual oxidation states, reveals M0→M2+ reaction pathways, and present new opportunities in the design of hybrid conversion/intercalation materials for applications such as charge storage. 相似文献
9.
Coordination Chemistry of Cyclopropenylidene‐Stabilized Phosphenium Cations: Synthesis and Reactivity of Pd and Pt Complexes 下载免费PDF全文
Ágnes Kozma Tobias Deden Dr. Javier Carreras Christian Wille Dr. Jekaterina Petuškova Jörg Rust Dr. Manuel Alcarazo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(8):2208-2214
A straightforward synthesis of cyclopropenylidene‐stabilized phosphenium cations 1 a – g through the reaction of [(iPr2N)2C3+Cl]BF4 with secondary phosphines is described. Their donor ability was evaluated by analysis of the CO stretching frequency in Rh complexes [RhCl(CO)L2](BF4)2 and electrochemical methods. The cyclopropenium ring induces a phosphite‐type behavior that can be tuned by the other two substituents attached to the phosphorus atom. Despite of the positive charge that they bear, phosphenium cations 1 a – g still act as two‐electron donor ligands, forming adducts with PdII and PtII precursors. Conversely, in the presence of Pd0 species, an oxidative insertion of the Pd atom into the Ccarbene–phosphorus bond takes place, providing dimeric structures in which each Pd atom is bonded to a cyclopropenyl carbene while two dialkyl/diaryl phosphide ligands serve as bridges between the two Pd centers. The catalytic performance of the resulting library of PtII complexes was tested; all of the cationic phosphines accelerated the prototype 6‐endo‐dig cyclization of 2‐ethynyl‐1,1′‐biphenyl to afford pentahelicene. The best ligand 1 g was used in the synthesis of two natural products, chrysotoxene and epimedoicarisoside A. 相似文献
10.
Jens Moons Dr. Francisco de Azambuja Jelena Mihailovic Karoly Kozma Dr. Katarina Smiljanic Mehran Amiri Prof. Tanja Cirkovic Velickovic Prof. May Nyman Prof. Tatjana N. Parac-Vogt 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(23):9179-9186
The selective hydrolysis of proteins by non-enzymatic catalysis is difficult to achieve, yet it is crucial for applications in biotechnology and proteomics. Herein, we report that discrete hafnium metal-oxo cluster [Hf18O10(OH)26(SO4)13⋅(H2O)33] ( Hf18 ), which is centred by the same hexamer motif found in many MOFs, acts as a heterogeneous catalyst for the efficient hydrolysis of horse heart myoglobin (HHM) in low buffer concentrations. Among 154 amino acids present in the sequence of HHM, strictly selective cleavage at only 6 solvent accessible aspartate residues was observed. Mechanistic experiments suggest that the hydrolytic activity is likely derived from the actuation of HfIV Lewis acidic sites and the Brønsted acidic surface of Hf18 . X-ray scattering and ESI-MS revealed that Hf18 is completely insoluble in these conditions, confirming the HHM hydrolysis is caused by a heterogeneous reaction of the solid Hf18 cluster, and not from smaller, soluble Hf species that could leach into solution. 相似文献