全文获取类型
收费全文 | 619篇 |
免费 | 20篇 |
国内免费 | 3篇 |
专业分类
化学 | 318篇 |
晶体学 | 2篇 |
力学 | 15篇 |
数学 | 137篇 |
物理学 | 170篇 |
出版年
2020年 | 6篇 |
2019年 | 5篇 |
2018年 | 6篇 |
2016年 | 8篇 |
2015年 | 11篇 |
2014年 | 10篇 |
2013年 | 28篇 |
2012年 | 16篇 |
2011年 | 24篇 |
2010年 | 15篇 |
2009年 | 16篇 |
2008年 | 16篇 |
2007年 | 21篇 |
2006年 | 21篇 |
2005年 | 12篇 |
2004年 | 18篇 |
2003年 | 16篇 |
2002年 | 13篇 |
2001年 | 13篇 |
2000年 | 12篇 |
1999年 | 6篇 |
1994年 | 8篇 |
1993年 | 14篇 |
1989年 | 8篇 |
1988年 | 5篇 |
1987年 | 8篇 |
1986年 | 6篇 |
1985年 | 8篇 |
1984年 | 5篇 |
1983年 | 5篇 |
1980年 | 5篇 |
1979年 | 10篇 |
1978年 | 7篇 |
1977年 | 10篇 |
1975年 | 6篇 |
1973年 | 5篇 |
1968年 | 6篇 |
1967年 | 6篇 |
1959年 | 5篇 |
1936年 | 5篇 |
1932年 | 12篇 |
1931年 | 6篇 |
1930年 | 5篇 |
1928年 | 9篇 |
1927年 | 6篇 |
1926年 | 5篇 |
1896年 | 4篇 |
1895年 | 4篇 |
1893年 | 13篇 |
1892年 | 4篇 |
排序方式: 共有642条查询结果,搜索用时 0 毫秒
1.
Under idealized conditions, electroconvection in a nematic liquid crystal sets in at a well-defined threshold of the driving ac voltage. Fluctuating convection rolls of a small amplitude below that threshold have been observed recently. The measurement of the amplitude of these fluctuations is described in detail in this paper. It is based on averaging the light intensity signals using the structure function and a quantitative analysis of the light deflection. 相似文献
2.
The paper presents a new formulation of the integral boundary element method (BEM) using subdomain technique. A continuous approximation of the function and the function derivative in the direction normal to the boundary element (further ‘normal flux’) is introduced for solving the general form of a parabolic diffusion‐convective equation. Double nodes for normal flux approximation are used. The gradient continuity is required at the interior subdomain corners where compatibility and equilibrium interface conditions are prescribed. The obtained system matrix with more equations than unknowns is solved using the fast iterative linear least squares based solver. The robustness and stability of the developed formulation is shown on the cases of a backward‐facing step flow and a square‐driven cavity flow up to the Reynolds number value 50 000. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
3.
Elie Leopold 《Numerical Algorithms》2007,44(4):347-366
In this paper, we give some new explicit relations between two families of polynomials defined by recurrence relations of
all order. These relations allow us to analyze, even in the Sobolev case, how some properties of a family of orthogonal polynomials
are affected when the coefficients of the recurrence relation and the order are perturbed. In a paper we have already given
a method which allows us to study the polynomials defined by a three-term recurrence relation. Also here some generalizations
are given. 相似文献
4.
We investigate function spaces of generalised smoothness of Besov and Triebel–Lizorkin type. Equivalent quasi-norms in terms
of maximal functions and local means are given. An atomic decomposition theorem for this type of spaces is proved.
Mathematics Subject Classification (2000) 46E35 相似文献
5.
Martinho M Banse F Bartoli JF Mattioli TA Battioni P Horner O Bourcier S Girerd JJ 《Inorganic chemistry》2005,44(25):9592-9596
The green complex S=1 [(TPEN)FeO]2+ [TPEN=N,N,N',N'-tetrakis(2-pyridylmethyl)ethane-1,2-diamine] has been obtained by treating the [(TPEN)Fe]2+ precursor with meta-chloroperoxybenzoic acid (m-CPBA). This high-valent complex belongs to the emerging family of synthetic models of Fe(IV)=O intermediates invoked during the catalytic cycle of biological systems. This complex exhibits spectroscopic characteristics that are similar to those of other models reported recently with a similar amine/pyridine environment. Thanks to its relative stability, vibrational data in solution have been obtained by Fourier transform infrared. A comparison of the Fe=O and Fe=(18)O wavenumbers reveals that the Fe-oxo vibration is not a pure one. The ability of the green complex to oxidize small organic molecules has been studied. Mixtures of oxygenated products derived from two- or four-electron oxidations are obtained. The reactivity of this [FeO]2+ complex is then not straightforward, and different mechanisms may be involved. 相似文献
6.
Yan B Collins N Wheatley J Irving M Leopold K Chan C Shornikov A Fang L Lee A Stock M Zhao J 《Journal of combinatorial chemistry》2004,6(2):255-261
We have developed a high-throughput purification system to purify combinatorial libraries at a 50-100-mg scale with a throughput of 250 samples/instrument/day. We applied an accelerated retention window method to shorten the purification time and targeted one fraction per injection to simplify data tracking, lower QC workload, and simplify the postpurification processing. First, we determined the accurate retention time and peak height for all compounds using an eight-channel parallel LC/UV/MS system, and calculated the specific preparative HPLC conditions for individual compounds. The preparative HPLC conditions include the compound-specific gradient segment for individual compounds with a fixed gradient slope and the compound-specific UV or ELSD threshold for triggering a fraction collection device. A unique solvent composition or solvent strength was programmed for each compound in the preparative HPLC in order to elute all compounds at the same target time. Considering the possible deviation of the predicted retention time, a 1-min window around the target time was set to collect peaks above a threshold based on UV or ELSD detection. Dual column preparative instruments were used to maximize throughput. We have purified more than 500 000 druglike compounds using this system in the past 3 years. We report various components of this high-throughput purification system and some of our purification results. 相似文献
7.
Zusammenfassung In der vorliegenden Arbeit wird das Sedimentationsgleichgewicht der Systeme Na6[H2W12O40]—NaCI—H2O und Na6[H2W12O40]—NaClO4— H2O untersucht. Die scheinbare molare Masse Mapp des Natriummetawolframats wird in beiden Systemen als Funktion der Natriummetawolfrarnat-Anfangspartialdichte
0
PX
z gemessen. Durch lineare Extrapolation der Funktion Mapp = Mapp (PP,, ) auf die Polymerelektrolyt-Anfangspartialdichte Null können die Grenzwerte der scheinbaren molaren Masse (Mapp)o ermittelt werden. Aus den (Mapp)o-Werten wird die Abhängigkeit der Größe (ln
PXz
/m
BX
)
mPXz von der NaCI- bzw. NaClO4-Molalität berechnet.Die Bestimmung der molaren Masse und der (stöchiometrischen) Ladungszahl eines Polymerelektrolyten aus den experimentell ermittelten (Mapp)o-Werten unter Anwendung der Lamm-Williams-Gleichung wird diskutiert. Zur Ermittlung der beiden Größen müssen mehrere Versuchsreihen mit zwei verschiedenen Fremdelektrolyten durchgeführt werden. Externe Messungen sind nicht erforderlich.Man erhält auf diese Weise verläßliche Werte so-wohl der molaren Masse als auch der (stächiometrischen) Ladungszahl.
Mit 5 Abbildungen und 3 Tabellen 相似文献
Summary The sedimentation equilibria of the systems sodium metatungstate-sodium chloride-water and sodium metatungstate-sodium perchlorate-water are investiated. In both systems the apparent molecular mass Mapp of sodium metatungstate (PX z) is measured in dependence on partial density 0 PX z before centrifugation. By linear extrapolation of the function Mapp = Mapp ( 0 PX z the limiting value (Mapp)o for 0 PX z = 0 is obtained. The variation with sodium chloride and sodium perchlorate molality of the quantity (ln PX z m BX )mPXz is calculated from (Mapp)o data.The determination of the molecular mass and the algebraic valency of a polymeric ion by means of the (Mapp)o values calculated by Lamm-Williams equation is discussed. In order to obtain these two quantities at least two series of experiments are required, each of which using a different supporting electrolyte. External measurements are not necessary. In this way reliable values for the molecular mass as well as for the stoichiometric valency are obtained.
Mit 5 Abbildungen und 3 Tabellen 相似文献
8.
Zusammenfassung In der vorliegenden Arbeit wird das Sedimentations-gleichgewicht des Systems Na6[H2W12O40]-NaClO4-H2O bei 25 °C untersucht. Die scheinbare Ladungszahl des Natriummetawolframats wird als Funktion der NaClO4-MolalitätmNaClO4 ermittelt. Aus dieser Abhängigkeit kann für die summarische Dissoziation des NatriummetawolframatsNa2[H2W12O4o] 6Na+ + [H2W12O40]6– die DissoziationskonstanteK in Gegenwart von NaClO4 als Fremdelektrolyt zuK=0,08 mol6·kg–6 bestimmt werden.Der Kreuzdifferentialquotient
(
PXz
, ist der Trace-Aktivitätskoeffizient des Natriummetawolframats) wird ebenfalls als Funktion der NaClO4-Molalität ermittelt.Die Konzentrationsabhängigkeit des Trace-Aktivitätskoeffizienten zeigt einen Verlauf, wie er unseres Wissens nach noch nicht von anderen Autoren beobachtet wurde.
Mit 5 Abbildungen und 1 Tabelle 相似文献
Summary An ultracentrifugal study of the sedimentation equilibrium of the system Na2[H2W12O40]-NaClO4-H2Oat 25 °C is presented. The dependency of the apparent charge of the sodium metatungstate on NaClO4-molality is investigated. From these data the dissociation constant for the dissociation of the sodium metatungstate in the presence of NaClO4 according to the equationNa[H2W12O40] 6Na+ + [H2W12O40]6– is calculated toK=0.08 mol6·kg–6. The cross differential quotient ( PXz is the trace activity coefficient of the sodium metatungstate) shows a behavior in its dependence on NaClO4-molality which to our knowledge has not yet been reported by other authors.
Mit 5 Abbildungen und 1 Tabelle 相似文献
9.
H. Horner 《Zeitschrift für Physik B Condensed Matter》1984,58(1):39-48
The ground state of the holmium ion in ferromagnetic HoAl2 is discussed in the light of available experimental evidence, including hitherto unpublished NMR measurements on165Ho. The measured quadrupole splitting is not consistent with the ground state derived from neutron form factor experiments, but is compatible with exchange and crystal field parameters derived from magnetization measurements and neutron spectroscopy in the context of the conventional three-parameter mean-field model. A more detailed analysis of the NMR data indicates that the exchange interaction in HoAl2 is over 20% stronger than that derived, using mean-field theory, from the Curie temperature. Using the revised exchange constant and a weighted average of published crystal field parameters, we obtain = (9.39 ± 0.05)
B
for the moment on the Ho3+ ion atT =0. The contribution of orbitally polarized conduction electrons to the hyperfine field at the holmium nucleus is estimated to be (–1.4±2.0) T. 相似文献
10.
Carboxylate-substituted radicals from phenylselenide derivatives. Designs on models for coenzyme B12-dependent enzyme-catalyzed rearrangements 总被引:1,自引:0,他引:1
Miranda N Daublain P Horner JH Newcomb M 《Journal of the American Chemical Society》2003,125(18):5260-5261
Laser flash photolysis (266 nm) of alpha- and beta-phenylselenyl esters, carboxylic acids, and carboxylates in aqueous acetonitrile media gave the corresponding radicals by homolytic cleavage of the phenylselenyl groups. In the beta-substituted systems, acid and carboxylate radicals reacted in intramolecular reporter reactions with approximately equal rate constants. For the alpha-substituted systems, an ester- and carboxylic acid-substituted radical reacted in an intramolecular reporter reaction with the same rate constants, but the analogous alpha-carboxylate radical, a radical anion, reacted an order of magnitude less rapidly and with an activation energy that is 3 kcal/mol greater than that found for analogues. A kinetic titration of the equilibrating alpha-acid and alpha-carboxylate radicals gave pKa = 4.6. The results indicate that alpha-ester and alpha-carboxylic acid radicals are unlikely to be appropriate models for alpha-carboxylate radicals, the intermediates formed in a large subset of coenzyme B12-dependent enzyme-catalyzed reactions. 相似文献