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181.
I. Glaser 《Optics Communications》1982,40(3):161-163
The standard halftone screen methods of nonlinear processing are usually nonadaptive; the system response curve with these methods is usually input-independent and predetermined for a specific system. However, some image processing operations, usually implemented digitally require response curves that depend on some input image characteristics. In this work we propose a method of implementing input-dependent nonlinear image processing optically. 相似文献
182.
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184.
S. Ebel E. Glaser M. Richter und P. Surmann 《Fresenius' Journal of Analytical Chemistry》1981,305(3):204-208
Zusammenfassung Die rechnerunterstützte Polarographie setzt eine mit mathematischen Kriterien beschreibbare Ermittlung der Basislinien voraus. Es werden zwei Modellfunktionen beschrieben, die sich für diesen Zweck eignen: eine Exponentialfunktion mit drei Parametern und ein Polynom 3. Grades. Bei Festlegung geeigneter Nebenbedingungen ist das Polynom 3. Grades unempfindlicher gegenüber numerischen Problemen und besitzt zudem den Vorteil wesentlich kürzerer Rechenzeiten. An verschiedenen Beispielen wird dieses Verfahren diskutiert.
Computerized polarography2. Evaluation of baseline
Summary In the computer controlled evaluation in polarography one problem is to find mathematical criteria to approximate the baseline. Two modell functions are described in this paper: a three-parametric exponential function and the third-degree polynomial. It is possible to give some conditions for using the polynomial. The advantages are in this case the shorter timer required for all calculations and the higher stability towards numerical problems. Some examples are given to discuss the proposed method.
Der Deutschen Forschungsgemeinschaft danken wir für die großzügige Unterstützung dieser Arbeiten durch Personal- und Sachmittel, dem Fonds der Chemischen Industrie für eine Sachbeihilfe. 相似文献
185.
We present an optimized method for compound-specific stable carbon isotope (delta(13)C) analysis of n-alkanes. For sample preparation, the traditionally used Soxhlet extraction was replaced by accelerated solvent extraction (ASE). delta(13)C values of individual n-alkanes--measured using gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS)--were first drift-corrected with regularly discharged pure CO(2) pulses as reference gas and, secondly, corrected for the amount dependence of the delta(13)C values by co-analyzing standards with varying analyte concentrations. Finally, the delta(13)C values were calibrated against two internal standards. The improved method was applied to selected sediment samples from a palaeoenvironmental study in subtropical NE Argentina. The measured delta(13)C values of all long-chain n-alkanes (nC(27), nC(29), nC(31) and nC(33)), representing biomarkers for terrestrial plants, correlate significantly with the delta(13)C of bulk organic matter (delta(13)C(TOC)). The latter is hence corroborated as a proxy for C3-C4 vegetation changes. Furthermore, the delta(13)C variations reveal higher amplitudes for nC(31) and nC(33) than for nC(27) and nC(29), indicating that the former n-alkanes mainly derive from C3 and/or C4 grasses, whereas the latter homologues mainly derive from C3 plants (trees and shrubs). Except for the lowermost part of the sediment core, the delta(13)C values of the mid-chain alkanes nC(23) and nC(25) do not reflect the terrestrial delta(13)C pattern, thus indicating that they are probably mainly of lacustrine origin. 相似文献
186.
Glaser T Heidemeier M Strautmann JB Bögge H Stammler A Krickemeyer E Huenerbein R Grimme S Bothe E Bill E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(33):9191-9206
A series of trinuclear Cu(II) complexes with the tris(tetradentate) triplesalen ligands H(6)talen, H(6)talen(tBu(2) ), and H(6)talen(NO(2) ), namely [(talen)Cu(II) (3)] (1), [(talen(tBu(2) ))Cu(II) (3)] (2), and [(talen(NO(2) ))Cu(II) (3)] (3), were synthesized and their molecular and electronic structures determined. These triplesalen ligands provide three salen-like coordination environments bridged in a meta-phenylene arrangement by a phloroglucinol backbone. The structure of [(talen)Cu(II) (3)] (1) was communicated recently. The structure of the tert-butyl derivative [(talen(tBu(2) ))Cu(II) (3)] (2) was established in three different solvates. The molecular structures of these trinuclear complexes show notable differences, the most important of which is the degree of ligand folding around the central Cu(II)-phenolate bonds. This folding is symmetric with regard to the central phloroglucinol backbone in two structures, where it gives rise to bowl-shaped overall geometries. For one solvate two trinuclear triplesalen complexes form a supramolecular disk-like arrangement, hosting two dichloromethane molecules like two pearls in an oyster. The FTIR spectra of these complexes indicate the higher effective nuclear charge of Cu(II) in comparison to the trinuclear Ni(II) complexes by the lower C--O and higher C=N stretching frequencies. The UV/Vis/NIR spectra of 1-3 reflect the stronger ligand folding in the tert-butyl complex 2 by an intense phenolate-to-Cu(II) LMCT. This absorption is absent in 1 and is obscured by the nitro chromophore in 3. The more planar molecular structures cause orthogonality of the Cu(II) d(x(2)-y(2) ) orbital and the phenolate O p(z) orbital, which leads to small LMCT dipole strengths. Whereas 1 and 3 exhibit only irreversible oxidations, 2 exhibits a reversible one-electron oxidation at +0.26 V, a reversible two-electron oxidation at +0.59 V, and a reversible one-electron oxidation at +0.81 V versus Fc(+)/Fc. The one-electron oxidized form 2(+) is strongly stabilized with respect to reference mononuclear salen-like Cu complexes. Chemical one-electron oxidation of 2 to 2(+) allows the determination of its UV/Vis/NIR spectrum, which indicates a ligand-centered oxidation that can be assigned to the central phloroglucinol unit by analogy with the trinuclear Ni triplesalen series. Delocalization of this oxidation over three Cu(II)-phenolate subunits causes the observed energetic stabilization of 2(+). Temperature-dependent magnetic susceptibility measurements reveal ferromagnetic couplings for all three trinuclear Cu(II) triplesalen complexes. The trend of the coupling constants can be rationalized by two opposing effects: 1) electron-withdrawing terminal substituents stabilize the central Cu(II)-phenolate bond, which results in a stronger coupling, and 2) ligand folding around the central Cu(II)-phenolate bond opens a bonding pathway between the magnetic Cu(II) d(x(2)-y(2) ) orbital and the phenolate O p(z) orbital, which results in a stronger coupling. Density functional calculations indicate that both spin-polarization and spin-delocalization are operative and that slight geometric variations alter their relative magnitudes. 相似文献
187.
Qian M Yang S Wu H Majumdar P Leigh N Glaser R 《Journal of the American Society for Mass Spectrometry》2007,18(11):2040-2057
The results are reported of mass-spectrometric studies of the nucleobases adenine 1h (1, R = H), guanine 2h, and cytosine 3h. The protonated nucleobases are generated by electrospray ionization of adenosine 1r (1, R = ribose), guanosine 2r, and deoxycytidine 3d (3, R = deoxyribose) and their fragmentations were studied with tandem mass spectrometry. In contrast to previous EI-MS studies of the nucleobases, NH(3) elimination does present a major path for the fragmentations of the ions [1h + H](+), [2h + H](+), and [3h + H](+). The ion [2h + H - NH(3)](+) also was generated from the acyclic precursor 5-cyanoamino-4-oxomethylene-dihydroimidazole 13h and from the thioether derivative 14h of 2h (NH(2) replaced by MeS). The analyses of the modes of initial fragmentation is supported by density functional theoretical studies. Conjugate acids 15-55 were studied to determine site preferences for the protonations of 1h, 2h, 3h, 13h, and 14h. The proton affinity of the amino group hardly ever is the substrate's best protonation site, and possible mechanisms for NH(3) elimination are discussed in which the amino group serves as the dissociative protonation site. The results provide semi-direct experimental evidence for the existence of the pyrimidine ring-opened cations that we had proposed on the basis of theoretical studies as intermediates in nitrosative nucleobase deamination. 相似文献
188.
Dr. Stephan Walleck Prof. Dr. Mihail Atanasov Prof. Dr. Jürgen Schnack Dr. Eckhard Bill Anja Stammler Dr. Hartmut Bögge Prof. Dr. Thorsten Glaser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(61):15240-15251
The first confacial pentaoctahedron comprised of transition metal ions namely ZnIIFeIIIAFeIIIBFeIIIAZnII has been synthesized by using a dinucleating nonadentate ligand. The face-sharing bridging mode enforces short ZnII⋅⋅⋅FeIIIA and FeIIIA⋅⋅⋅FeIIIB distances of 2.83 and 2.72 Å, respectively. Ab-initio CASSCF/NEVPT2 calculations provide significant negative zero-field splittings for FeIIIA and FeIIIB with |DA|>|DB| with the main component along the C3 axis. Hence, a spin-Hamiltonian comprised of anisotropic exchange, zero-field, and Zeeman term was employed. This allowed by following the boundary conditions from the theoretical results the simulation in a theory-guided parameter determination with Jxy=+0.37, Jz=−0.32, DA=−1.21, EA=−0.24, DB=−0.35, and EB=−0.01 cm−1 supported by simulations of high-field magnetic Mössbauer spectra recorded at 2 K. The weak but ferromagnetic FeIIIAFeIIIB interaction arises from the small bridging angle of 84.8° being at the switch from anti- to ferromagnetic for the face-sharing bridging mode. 相似文献
189.
In future the model quality will have an increasing priority in the industrial context and suitable techniques and methods to quantify them have to be developed. In this paper we want to focus on the challenge of selecting the most informative measurement data for a time-dependent simulation model to infer parameter distributions. Sobol indices are used to give a estimate about the global sensitivity of those parameters and they are illustrated for the given benchmark problem. In this context the gained knowledge on the parameters is used to define a Likelihood function for the Bayes' rule. (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
190.
Glaser C Faber S Eckstein F Fischer H Springer V Heudorfer L Stammberger T Englmeier KH Reiser M 《Magnetic resonance imaging》2001,19(2):177-185
In view of follow up, survey and development of therapeutic strategies for osteoarthritis where cartilage deterioration plays an important role, a non invasive, reliable and quantitative assessment of the articular cartilage is desirable. The currently available high resolution T(1)-weighted (T1-w) 3D FLASH pulse sequences with frequency selective fat suppression are very time consuming. We have 1) optimized a high resolution T1-w 3D FLASH water excitation (WE) sequence for short acquisition time and cartilage visualization, and 2) validated this sequence for cartilage volume and thickness quantification. The spectral fat presaturation was replaced by selective water excitation. The flip angle of the WE sequence was optimized for the contrast to noise (C/N(cart)) ratio of cartilage. Sagittal datasets (voxel size: 0.31 x 0.31 x 2 mm(3)) of the knees of nine healthy volunteers were acquired both, with the 3D FLASH WE (17.2/6.6/30 degrees ) sequence (WE) and a previously validated 3D FLASH fat saturated (42/11/30 degrees ) sequence (FS). For validation of the WE sequence, cartilage volume, mean and maximal cartilage thickness of the two sequences were compared. Reproducibility was assessed by calculating the coefficient of variation (COV %) of 4 consecutive WE data sets in the volunteers. The acquisition time was reduced from 16'30" (FS) down to 7'14" for the WE sequence. Image contrast and visualization of the cartilage was very similar, but delineation of the basal layer of the cartilage was slightly improved with the WE sequence. A flip angle of 30 degrees provided the best C/N(cart) ratios (WE). Reproducibility (COV) was between 1.9 and 5.9%. Cartilage volume and thickness agreed within 4% between FS and WE sequence. The WE sequence allows for rapid, valid and reproducible quantification of articular cartilage volume and thickness, prerequisites for follow-up examinations. The reduced acquisition time (50% of FS) enables routine clinical application and thus may contribute to a broader assessment of osteoarthritis. 相似文献