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排序方式: 共有147条查询结果,搜索用时 31 毫秒
91.
Anna Lewandowska‐Andralojc Franciszek Kazmierczak Gordon L. Hug Gerald Hörner Bronislaw Marciniak 《Photochemistry and photobiology》2013,89(1):14-23
The reactions of ketone/methionine systems are widely used as efficient and selective sources of biorelevant radical species. In this study, we address intramolecular variants of this couple with respect to its photosynthetic utility and as a mechanistic model of underlying elementary reaction steps of biological importance, especially with respect to the study of photoinitiated electron transport in complex peptides. The outcomes of this study are two‐fold: (1) steady‐state irradiation of sterically constrained benzophenone/methionine dyads afforded stable photocyclization products with high yield and product selectivity. (2) Mechanistic insights into the triplet‐triggered product formation were obtained from an analysis of the flash photolysis results and the molecular structure of the stable product formed upon irradiation. Time‐resolved experiments identified (net) hydrogen‐atom transfer from the methionine as the mechanism of the triplet quenching and the resulting biradicals as the major precursor of the isolated stable product. Both the analyses of triplet quenching and stable‐product formation in the diastereomeric pairs point to effects of chiral center configuration, i.e., significant stereoselectivity is observed for all elementary steps. The underlying stereochemical restraints were quantitatively addressed by means of molecular dynamics simulations. 相似文献
92.
Tomasz uk Franciszek Rakowski Jan P. Radomski 《Computational Biology and Chemistry》2009,33(4):339-343
The spread efficiency of influenza virus is significantly affected by several environmental parameters. However, neither the underlying reasons, nor the exact character and magnitude of the phenomena involved are sufficiently well understood. Here we present a probabilistic approach to the virus transmission events. For a sample ensemble, we construct a model of the infectivity as a function of the ambient conditions, and we determine its parameter values on the basis of the available experimental data. 相似文献
93.
Adam Rakowski 《Colloid and polymer science》1912,11(6):269-272
Ohne Zusammenfassung 相似文献
94.
A. Dumanski M. Tschapek E. W. Rakowski T. M. Poljakowa und N. Pjawtschenko 《Fresenius' Journal of Analytical Chemistry》1937,111(1):46
Ohne Zusammenfassung 相似文献
95.
Zbigniew Gregorowicz Zdzisaw Klima Ewa liwa und Franciszek Buhl 《Fresenius' Journal of Analytical Chemistry》1965,214(1):25-27
Zusammenfassung Eine gravimetrische Methode zur Bestimmung von Wismut(III) als Bi(C12H8N2)2(SCN)3 wurde ausgearbeitet. Das Verfahren eignet sich zur Bestimmung von kleinen Wismutmengen (5–20 mg). Ein Vergleich der nach der Oxidjodidmethode erhaltenen Ergebnisse mit denen der Phenanthrolinmethode zeigt, daß letztere genauere Resultate liefert. Der Einfluß von Fremdionen wurde geprüft.
Summary A gravimetric method for the determination of bismuth as Bi(C12H8N2)2(SCN)3 has been described. The method can be applied to the gravimetric determination of small amounts (5–20 mg) of bismuth. A comparison of results obtained by the oxide iodide method and those obtained by the phenanthroline method revealed that the latter one yields more accurate values. The influence of foreign ions has been investigated.相似文献
96.
Manfred Mö ller Franciszek Hugon Szafraniec 《Proceedings of the American Mathematical Society》2008,136(6):2165-2176
In this paper we discuss diverse aspects of the mutual relationship between adjoints and formal adjoints of unbounded operators bearing a matrix structure. We emphasize the behaviour of row and column operators as they turn out to be the germs of an arbitrary matrix operator, providing most of the information about the latter as it is the troublemaker.
97.
Wilson AD Newell RH McNevin MJ Muckerman JT Rakowski DuBois M DuBois DL 《Journal of the American Chemical Society》2006,128(1):358-366
Highly efficient electrocatalysts for both hydrogen evolution and hydrogen oxidation have been designed, synthesized, and characterized. The catalysts in their resting states are air-stable, mononuclear nickel(II) complexes containing cyclic diphosphine ligands with nitrogen bases incorporated into the ligand backbone. X-ray diffraction studies have established that the cation of [Ni(P(Ph)(2)N(Ph)(2))(2)(CH(3)CN)](BF(4))(2), 6a, (where P(Ph)(2)N(Ph)(2) is 1,3,5,7-tetraphenyl-1,5-diaza-3,7-diphosphacyclooctane) is a trigonal bipyramid with bonds to four phosphorus atoms of the two bidentate diphosphine ligands and the nitrogen atom of an acetonitrile molecule. Two of the six-membered rings formed by the diphosphine ligands and Ni have boat conformations with an average Ni- - -N distance to the two pendant bases of 3.4 A. The cation of [Ni(P(Cy)(2)N(Bz)(2))(2)](BF(4))(2), 6b, (where Cy = cyclohexyl and Bz = benzyl) is a distorted square planar complex. For 6b, all four six-membered rings formed upon coordination of the diphosphine ligands to the metal are in the boat form. In this case, the average Ni- - -N distance to the pendant base is 3.3 A. Complex 6a is an electrocatalyst for hydrogen production in acidic acetonitrile solutions, and compound 6b is an electrocatalyst for hydrogen oxidation in basic acetonitrile solutions. It is demonstrated that the high catalytic rates observed with these complexes are a result of the positioning of the nitrogen base so that it plays an important role in the formation and cleavage of the H-H bond. 相似文献
98.
Makowska J Bagiñska K Makowski M Jagielska A Liwo A Kasprzykowski F Chmurzyñski L Scheraga HA 《The journal of physical chemistry. B》2006,110(9):4451-4458
We compared the ability of two theoretical methods of pH-dependent conformational calculations to reproduce experimental potentiometric titration curves of two models of peptides: Ac-K5-NHMe in 95% methanol (MeOH)/5% water mixture and Ac-XX(A)7OO-NH2 (XAO) (where X is diaminobutyric acid, A is alanine, and O is ornithine) in water, methanol (MeOH), and dimethyl sulfoxide (DMSO), respectively. The titration curve of the former was taken from the literature, and the curve of the latter was determined in this work. The first theoretical method involves a conformational search using the electrostatically driven Monte Carlo (EDMC) method with a low-cost energy function (ECEPP/3 plus the SRFOPT surface-solvation model, assumming that all titratable groups are uncharged) and subsequent reevaluation of the free energy at a given pH with the Poisson-Boltzmann equation, considering variable protonation states. In the second procedure, molecular dynamics (MD) simulations are run with the AMBER force field and the generalized Born model of electrostatic solvation, and the protonation states are sampled during constant-pH MD runs. In all three solvents, the first pKa of XAO is strongly downshifted compared to the value for the reference compounds (ethylamine and propylamine, respectively); the water and methanol curves have one, and the DMSO curve has two jumps characteristic of remarkable differences in the dissociation constants of acidic groups. The predicted titration curves of Ac-K5-NHMe are in good agreement with the experimental ones; better agreement is achieved with the MD-based method. The titration curves of XAO in methanol and DMSO, calculated using the MD-based approach, trace the shape of the experimental curves, reproducing the pH jump, while those calculated with the EDMC-based approach and the titration curve in water calculated using the MD-based approach have smooth shapes characteristic of the titration of weak multifunctional acids with small differences between the dissociation constants. Nevertheless, quantitative agreement between theoretically predicted and experimental titration curves is not achieved in all three solvents even with the MD-based approach, which is manifested by a smaller pH range of the calculated titration curves with respect to the experimental curves. The poorer agreement obtained for water than for the nonaqueous solvents suggests a significant role of specific solvation in water, which cannot be accounted for by the mean-field solvation models. 相似文献
99.
Franciszek Grabowski 《Physica A》2010,389(16):3081-1286
The paper is concerned with the new logistic equation of arbitrary order which describes the performance of complex executive systems X vs. number of tasks N, operating at limited resources K, at non-extensive, heterogeneous self-organization processes characterized by parameter f. In contrast to the classical logistic equation which exclusively relates to the special case of sub-extensive homogeneous self-organization processes at f=1, the proposed model concerns both homogeneous and heterogeneous processes in sub-extensive and super-extensive areas. The parameter of arbitrary order f, where −∞<f<+∞, depends on both the coefficient of external resource utilization u=N/K, where 0<u<1, and the internal microscopic character of realized processes related to the depth of feedback β. The coefficient β directly influences self-organization of processes by the change of microscopic parameters Vi, Si, i and Z, where Vi is the number of references (visit) to the ith component of the system during the service of each task, Si is the time of serving the task by the ith component, and Z is the think time of a given process. In the general case of complex system, parameters Vi, Si, i and Z can have values in the range from 0 to +∞. In this way the new equation includes all possible cases of a complex executive system’s operation. Furthermore, it allows us to define the optimal matching point between X and N with f as the parameter. It also helps to balance the load in complex systems and to equip artificial systems with self-optimization mechanisms similar to those observed in natural systems. 相似文献
100.
A. Bartnik H. Fiedorowicz R. Jarocki J. Kostecki R. Rakowski M. Szczurek 《Applied physics. B, Lasers and optics》2008,91(1):21-24
Extreme ultraviolet (EUV) radiation is absorbed in a thin surface layer of any material. Irradiation of material samples with
intense EUV pulses may cause different surface changes. Some of them, especially connected with material desorption, can be
clearly visible using an optical or electron microscope. Other changes concerning crystal structure or chemical composition
may not be visible under the microscope. They can however be detected using the EUV radiation itself. In this paper a new
method of measurement of surface changes by irradiation with a laser-plasma EUV source is presented. The radiation was collected
and focused on a material surface using a specially designed multifoil collector. Radiation scattered or excited in the material
was detected with the use of a Wolter-type mirror coupled to a back-illuminated CCD camera. Depending on material samples,
images with different intensity distributions were registered. For some samples, the intensity distributions of the images
obtained before and after irradiation were slightly different. The intensity differences in such cases allowed us to obtain
differential images. The appearance of such images was assumed to be evidence of surface changes.
PACS 42.62.-b; 61.80.-x; 52.25.Os 相似文献