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81.
Limbach HH Pietrzak M Sharif S Tolstoy PM Shenderovich IG Smirnov SN Golubev NS Denisov GS 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(20):5195-5204
In this paper, equations are proposed which relate various NMR parameters of OHN hydrogen-bonded pyridine-acid complexes to their bond valences which are in turn correlated with their hydrogen-bond geometries. As the valence bond model is strictly valid only for weak hydrogen bonds appropriate empirical correction factors are proposed which take into account anharmonic zero-point energy vibrations. The correction factors are different for OHN and ODN hydrogen bonds and depend on whether a double or a single well potential is realized in the strong hydrogen-bond regime. One correction factor was determined from the known experimental structure of a very strong OHN hydrogen bond between pentachlorophenol and 4-methylpyridine, determined by the neutron diffraction method. The remaining correction factors which allow one also to describe H/D isotope effects on the NMR parameters and geometries of OHN hydrogen bond were determined by analysing the NMR parameters of the series of protonated and deuterated pyridine- and collidine-acid complexes. The method may be used in the future to establish hydrogen-bond geometries in biologically relevant functional OHN hydrogen bonds. 相似文献
82.
A. Szyczewski R. Krzyminiewski S. Lis J. Pietrzak M. Elbanowski 《Radiation Physics and Chemistry》1995,45(6):935-938
The gadolinium chelates with: acetylacetone—Gd(acac)3 · 3H2O, thenoyltrifluoroacetone—Gd(TTA)3 · 2H2O, benzoylacetone—Gd(BAC)3 · 2H2O, ethylenediaminetetraacetate Gd(EDTA) and diglycolate Gd(DGA)3 have been chosen for EPR study (X band). The EPR spectra of these complexes were obtained in the form of badly separated signals and thus were difficult to interpret. In order to improve the spectra resolution a computer analysis based on Fourier transform was applied. This analysis permitted a considerable increase in resolution of the spectra and revealed the fine structure of Gd3+ ion in the condensed phase. 相似文献
83.
The synthesis and binding properties of resorcinarene-based cavitands functionalized with N-acylthiourea moieties towards different cations are described. Extraction studies with metal (Pb2+, Cu2+, Ag+, Hg2+, Cd2+, Eu3+, Fe3+, K+, Na+, and Ca2+) picrates and the incorporation in ion selective electrodes (ISEs), show that there is more than a 40% increase of the Ag+ extraction for N-acylthiourea ionophores (2, 3, and 8) in comparison with N-benzoyl-N′-benzylthiourea (9). Ionophore 8, which has a C3 chain between the platform and the ionophore, extracts two times more Cu2+ than the more rigid one (2). Stoichiometry studies showed for ligand 2 a ligand/metal ratio of 1:1, while for model compound 9 a ratio of 1:2 was found. Potentiometric studies of electrodes revealed that cavitands 2, 3, and 8 induce a significantly different selectivity pattern compared to the cation-exchanger used, as well as model compound 9. Especially, a considerable enhancement of the selectivity towards Ag+ and Pb2+ over K+, Ca2+, and Na2+ ions was observed. 相似文献
84.
Novel aluminum(III)- and zirconium(IV)-tetraphenylporhyrin (TPP) derivatives are examined as fluoride-selective ionophores for preparing polymer membrane-based ion-selective electrodes (ISEs). The influence of t-butyl- or dichloro-phenyl ring substituents as well as the nature of the metal ion center (Al(III) versus Zr(IV)) on the anion complexation constants of TPP derivative ionophores are reported. The anion binding stability constants of the ionophores are characterized by the so-called “sandwich membrane” method. All of the metalloporphyrins examined form their strongest anion complexes with fluoride. The influence of plasticizer as well as the type of lipophilic ionic site additive and their amounts in the sensing membrane are discussed. It is shown that membrane electrodes formulated with the metalloporphyrin derivatives and appropriate anionic or cationic additives exhibit enhanced potentiometric response toward fluoride over all other anions tested. Since selectivity toward fluoride is enhanced in the presence of both anionic and cationic additives, the metalloporphyrins can function as either charged or neutral carriers within the organic membrane phase. In contrast to previously reported fluoride-selective polymeric membrane electrodes based on metalloporphyrins, nernstian or near-nernstian (−51.2 to −60.1 mV decade−1) as well as rapid (t < 80 s) and fully reversible potentiometric fluoride responses are observed. Moreover, use of aluminum(III)-t-butyltetraphenylporphyrin as the ionophore provides fluoride sensors with prolonged (7 months) functional lifetime. 相似文献
85.
Pietrzak M Shibl MF Bröring M Kühn O Limbach HH 《Journal of the American Chemical Society》2007,129(2):296-304
The 1H and 2H NMR spectra of porphycene (1), 2,3,6,7,12,13,16,17-octaethylporphycene (2), 2,7,12,17-tetra-n-propylporphycene (3), and 2,7,12,17-tetra-(tert-butyl)-3,6-13,16-dibenzo[cde;mno]porphycene (4) partially deuterated in the mobile proton sites are reported. These compounds exhibit two intramolecular NHN hydrogen bonds of increasing strength representing models of the concerted HH transfer in the parent compound, porphycene. The 1H chemical shifts of the mobile protons are correlated with the difference of the energies of the amino- and imino-N1s orbitals reported by Ghosh A.; Moulder J.; Br?ring M.; Vogel E. Angew. Chem., Int. Ed. 2001, 113, 445-448. The chemical shifts of 4 indicate a reduced contribution of the aromatic ring current as compared to the other compounds which is associated to the nonplanarity of this molecule. The primary H/D isotope effects on the chemical shifts give information about the primary, secondary, and vicinal geometric isotope effects of the two inner hydrogen bonds of porphycenes. The vicinal effects indicate a cooperative coupling of the two hydrogen bonds which may favor a concerted double proton-transfer mechanism. 相似文献
86.
Marek Pietrzak Marek Józefowicz Agnieszka Bajorek Janina R. Heldt 《Journal of fluorescence》2017,27(2):537-549
Newly synthesized, differently substituted chalcones (1,3-diaryl-2-propen-1-ones) have been studied using steady-state and time-resolved techniques combined with quantum-chemical modelling. To explore spectroscopic structure - property relationships the substituent (acceptor moiety) was chosen according to systematic variation in the Hammett parameter. It was shown that photophysical properties of the studied donor-acceptor (D-A) molecules can be predicted in terms of a simple model from the properties of individual chromophores (composite-model of decoupled moieties: donor (D) and acceptor (A)). The results of spectroscopic measurements also indicate that for investigated D-A fluorophores in medium-polar solvent, the initially populated, locally excited (LE) state (where the fundamental role plays donor moiety (D*-A)) reacts further to produce intramolecular charge transfer (ICT) state. Additionally, the experimental absorption (M ge ) and fluorescence (M eg ) transition dipole moments were calculated on the basis of spectroscopic data and compared with results of our quantum-chemical calculations. The absorption transition dipole moment was found to vary linearly with the Hammett substituent coefficient (σ). 相似文献
87.
ABSTRACT The hybrid numbers are generalization of complex, hyperbolic and dual numbers. In this paper, we introduce and study the Fibonacci and Lucas hybrinomials, i.e. polynomials, which are a generalization of the Fibonacci hybrid numbers and the Lucas hybrid numbers, respectively. 相似文献
88.
Mesoporous carbon of regular structure was subjected to oxidation by ammonium persulfate at 30, 60 or 100 °C. The mesostructure and pore evolution were characterised by XRD, TEM, and N2 sorption techniques. The functional groups present on the surface of the carbon materials were identified by FTIR and thermogravimetric studies. It was established that the micropores and small mesopores could be blocked by the surface oxides attached under mild oxidation. High densities of surface oxygen complexes, especially carboxylic groups, were generated on the surface of mesoporous carbons. All materials obtained were tested for the removal of Auramine-O from aqueous solution. Adsorption experiments were carried out as batch studies at different contact time, pH and initial dye concentration. Removal of this cationic dye in basic solutions was more effective than in acidic solutions. The highest sorption capacity towards Auramine-O was obtained for the carbon sample oxidised by ammonium persulfate solution at 100 °C. Fitting equilibrium data to Langmuir and Freundlich isotherms showed that Langmuir model was more suitable to describe the Auramine-O adsorption. The changes in standard enthalpy (ΔH0), standard entropy (ΔS0) and Gibbs free energy (ΔG0) were analysed. Thermodynamic study showed that the adsorption of Auramine-O was a spontaneous and exothermic process. 相似文献
89.
Tadeusz Biedroń Łukasz Pietrzak Przemysław Kubisa 《Journal of polymer science. Part A, Polymer chemistry》2011,49(24):5239-5244
Medium molecular weight poly(L ,L ‐lactide)s (PLA) containing at one chain end ionic group derived from imidazolium ionic liquid (IL) were synthesized by cationic polymerization using hydroxylated IL as initiator. matrix assisted laser desorption/ionization time‐of‐flight analysis confirmed the structure of products (PLA‐IL). Carbon nanotubes (CNT) were dispersed in solution of PLA‐IL in 1,4‐dioxane and significant improvement of stability of suspension was observed by measurements of suspension absorbance. Similar effect was, however, observed also for solutions of PLA which did not contain terminal IL group. CNT samples treated with PLA‐IL and PLA were isolated, thoroughly washed with 1,4‐dioxane and stability of suspensions was again measured. Sample treated with PLA after washing behave similarly to untreated CNT. Stability of suspension of CNT treated with PLA‐IL after washing was considerably higher than that of untreated CNT and the presence of polymer bound to CNT was clearly detectable in scanning electron microscopy images. Results indicate that there is indeed an interaction between end‐group derived from IL and CNT surface as postulated earlier but to observe solely this effect an excess of polymer should be removed, otherwise factors such as increase of viscosity of solution or weak interactions of PLA ester groups with CNT may obscure results. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
90.
Anetta Bajer Jon F. Carlson 《Proceedings of the American Mathematical Society》1999,127(12):3445-3449
In this paper we give a sufficient condition for a restricted enveloping algebra to be quasi-elementary. We also prove that every finite dimensional -nilpotent Lie algebra can be embedded in a finite dimensional -nilpotent quasi-elementary Lie algebra.