全文获取类型
收费全文 | 2885篇 |
免费 | 55篇 |
国内免费 | 11篇 |
专业分类
化学 | 1857篇 |
晶体学 | 25篇 |
力学 | 59篇 |
数学 | 262篇 |
物理学 | 748篇 |
出版年
2019年 | 20篇 |
2016年 | 39篇 |
2015年 | 39篇 |
2014年 | 39篇 |
2013年 | 93篇 |
2012年 | 133篇 |
2011年 | 121篇 |
2010年 | 72篇 |
2009年 | 70篇 |
2008年 | 109篇 |
2007年 | 79篇 |
2006年 | 114篇 |
2005年 | 91篇 |
2004年 | 83篇 |
2003年 | 76篇 |
2002年 | 67篇 |
2001年 | 64篇 |
2000年 | 58篇 |
1999年 | 44篇 |
1998年 | 47篇 |
1997年 | 52篇 |
1996年 | 56篇 |
1995年 | 58篇 |
1994年 | 59篇 |
1993年 | 47篇 |
1992年 | 53篇 |
1991年 | 49篇 |
1990年 | 40篇 |
1989年 | 30篇 |
1988年 | 46篇 |
1987年 | 31篇 |
1986年 | 34篇 |
1985年 | 47篇 |
1984年 | 45篇 |
1983年 | 24篇 |
1982年 | 37篇 |
1981年 | 63篇 |
1980年 | 37篇 |
1979年 | 35篇 |
1978年 | 58篇 |
1977年 | 46篇 |
1976年 | 44篇 |
1975年 | 44篇 |
1974年 | 37篇 |
1973年 | 33篇 |
1972年 | 18篇 |
1970年 | 33篇 |
1967年 | 20篇 |
1966年 | 17篇 |
1965年 | 18篇 |
排序方式: 共有2951条查询结果,搜索用时 15 毫秒
91.
H. H. Deubler K. Lekkas P. Sperr K. Dietrich 《Zeitschrift für Physik A Hadrons and Nuclei》1978,284(2):237-244
The process of instantaneous fission in deep inelastic collisions is investigated in a classical model. Kinetic energies and angular distributions of the fragments are calculated for the proposed reaction Pb+U atE cm inc =750 MeV; an experimental setup for the separation of the fragments originating from instantaneous fission from the fragments of thermal fission is explained. We also discuss fusion following instantaneous fission as a mechanism for the production of superheavy elements and arrive at rather promising estimates. 相似文献
92.
Victoria V. Lipson Irina V. Ignatenko Sergey M. Desenko Svetlana V. Shishkina Oleg V. Shishkin Sergey A. Komykhov Natalya V. Logvinenko Valery D. Orlov Herbert Meier 《Journal of heterocyclic chemistry》2003,40(6):1081-1086
The reaction of 5,7‐diphenyl‐4,7‐dihydro‐1,2,4‐triazolo[1,5‐a]pyrimidine ( 1 ) with α,β‐unsaturated carbonyl compounds 2a‐f led to the formation of the alkylated heterocycles 3a‐f (Figure 1). However, the reaction of 5‐methyl‐7‐phenyl‐4,7‐dihydro‐1,2,4‐triazolo[1,5‐a]pyrimidine ( 5 ) with 2a‐c yielded under the same conditions the triazolo[5,1‐b]quinazolines 6a‐c (Figure 3). In this case, the alkylation is followed by a cyclocondensation. The structure elucidation of the products is based on ir, ms, 1H and 13C nmr measurements and on an X‐ray diffraction study. 相似文献
93.
94.
The large number of known stable compounds in which phosphorus has a low coordination number makes it clear that such compounds can no longer be regarded as “exotic” in main group chemistry. While the rich chemistry of P? C multiply bonded systems makes clear their affinity to their organic congeners, iminophosphanes in particular are also of increasing importance. The linkage of a phosphinidine fragment with an imine fragment via a multiple bond gives rise to a class of compounds with an unusually wide range of structural types. This in turn leads to a broad spectrum of chemical behavior which makes iminophosphanes extremely useful synthetic building blocks in organoelement chemistry. 相似文献
95.
Eberhard Bothe Man Nien Schuchmann Dietrich Schulte-Frohlinde Clemens von Sonntag 《Photochemistry and photobiology》1978,28(4-5):639-643
Abstract— In aqueous solutions α-hydroxyalkylperoxyl radicals undergo a spontaneous and a base catalysed HO2 elimination. From kinetic deuterium isotope effects, temperature dependence, and the influence of solvent polarity it was concluded that the spontaneous reaction occurs via an HO2 elimination followed by the dissociation of the latter into H+ and O2 - . The rate constant of the spontaneous HO2 elimination increases with increasing methyl substitution in α-position ( k (CH2 (OH)O2 ) < 10s-1 k (CH3 CH(OH)O2 ) = 52s-1 k ((CH3 )2 C(OH)O2 ) = 665 s-1 ). The OH- catalysed reaction is somewhat below diffusion controlled. The mixture of peroxyl radicals derived from polyhydric alcohols eliminate HO2 at two different rates. Possible reasons for this behaviour are discussed. The mixture of the six peroxyl radicals derived from d -glucose are observed to eliminate HO2 with at least three different rates. The fastest rate is attributed to the HO2 elimination from the peroxyl radical at C-l ( k > 7000s-1 ). Because of the HO2 eliminations the peroxyl radicals derived from d -glucose do not undergo a chain reaction in contrast to peroxyl radicals not containing an α-OH group. In competition with the first order elimination reactions the α-hydroxylalkylperoxyl radicals undergo a bimolecular decay. These reactions are briefly discussed. 相似文献
96.
Meier H Gerold J Kolshorn H Mühling B 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(2):360-370
Four OPV series 1-4 (a-d) with a terminal dialkylamino group as electron donor were prepared by Wittig-Horner reactions. To study the influence of the push-pull effect on the long-wavelength absorption, three of the four series contained terminal acceptor groups (CN, CHO, NO(2)). The length of the chromophores strongly affects the intramolecular charge transfer (ICT)-an effect which superimposes upon the extension of the conjugation. Increasing numbers n of repeat units cause an overall bathochromic shift for the purely donor-substituted series 1 a-4 a and the series 1 b-4 b with CN as weak acceptor. The two effects annihilate each other in the series 1 c-4 c with terminal CHO groups, so that the absorption maxima are almost independent of the length of the chromophore. A hypsochromic shift is observed for the series 1 d-4 d, which contains the strong acceptor group NO(2). This anomaly disappears on protonation of the dialkylamino group because the push-pull effect disappears in the ammonium salts. The results can be explained by semiempirical quantum mechanics (AM1, INDO/S). The HOMO-LUMO transition, which is mainly responsible for the ICT, becomes less important in the electron transitions S(0)-->S(1) when the distance between donor and acceptor is increased. The commonly used VB model, which contains an electroneutral and a zwitterionic resonance structure, is contrasted with a MO model with dipole segments at both ends of the OPV chains. The latter model turned out to be more appropriate-at least for donor-acceptor-substituted OPVs with n >/= 2. 相似文献
97.
Losod, a new type of crystalline hydrated sodium aluminosilicate, Na12Al12Si12O48 · q H2O, has been prepared from reaction mixtures containing bulky quaternary alkylammonium ions, particularly azonia-spiro[4.4]nonane, besides sodium ions. Losod crystallizes from batches with a low sodium content (Na/Al ≤ 1 and Si/Al ≈? 1). The quaternary ammonium hydroxide primarily serves as a source of hydroxide ions and is not incorporated into the zeolite crystals. These bulky bases provide a useful means for controlling the alkalinity of the system independently of the concentration of the necessary cations built into the zeolite. The crystals of Losod are hexagonal (a = 12.91 and c = 10.54 Å) and the proposed framework structure shows a polytypic relationship to sodalite and cancrinite. Losod has reversible sorption and ion exchange properties typical of a small-pore zeolite and in essential agreement with the proposed structure. 相似文献
98.
H. Meier E. Zimmerhackl W. Albrecht D. ßösche W. Hecker P. Menge A. Ruckdeschel E. Unger G. Zeitler 《Mikrochimica acta》1970,58(4):733-743
Zusammenfassung Die hochspannungselektrophoretische Wanderung der Halogenokomplexe der Platinmetalle und weiterer anorganischer Ionen wird bei Anwendung von Polycarbonsäuren (Oxalsäure, Bernsteinsäure, Apfelsäure, Weinsäure und Zitronensäure) als Elektrolyt untersucht und der Einfluß des pH-Werts und der Konzentration der Substanzen auf die Wanderung geprüft. Es wird festgestellt, daß die auf die abgestufte Komplexbildungstendenz der Polycarbonsäuren (Zitronensäure > Weinsäure Apfelsäure > Bernsteinsäure) rückführbaren Unterschiede der Wanderungsgeschwindigkeiten für die Trennung anorganischer Gemische gut einzusetzen sind. Für die Chlorokomplexe der Platinmetalle wird eine Abstufung der Beweglichkeiten in der Reihe Ir Pt Os > Rh > > Pd > Ru (> Rh) gefunden.
The high voltage electrophoretic separation of inorganic ions with special consideration of the platinum metals
Summary The high voltage eleetrophoretic migration of the halogen complexes of the platinum metals and other inorganic ions was studied with the employment of the polycarboxylic acids (oxalic, succinic, malic, tartaric, citric) as electrolyte, and the influence of the pH-value and the concentration of the substances on the migration investigated. It was found that the differences in the migration velocities, which may be traced back to the graded complex-forming tendency of the polycarboxylic acids (citric > tartaric malic > > succininic) can be used to good advantage in the separation of inorganic mixtures. With respect to the chlorocomplexes of the platinum metals, a decrease in the mobilities was discovered in the series Ir > Pt > Os > > Rh > Pd > Ru (>Rd).相似文献
99.
H. Meier E. Zimmerhackl W. Albrecht D. Bösche W. Hecker P. Menge A. Ruckdeschel E. Unger G. Zeitler 《Mikrochimica acta》1970,58(3):553-563
Zusammenfassung Die hochspannungselektrophoretische Wanderung der Halogenokomplexe der Platinmetalle und einer Reihe weiterer anorganischer Ionen wird mit Nitrilotriessigsäure und Äthylendiamintetraessigsäure als Elektrolyt in Abhängigkeit von verschiedenen Versuchsparametern (Elektrolytkonzentration,ph-Wert und Substanzmenge) untersucht. Die Wanderungsgeschwindigkeiten der verschiedenen Metallionen bzw.-komplexe zeigen charakteristische Abstufungen, die sich mit den für die hochspannungselektrophoretische Wanderung gültigen Gesetzmäßigkeiten erklären lassen. Beispielsweise beobachtet man eine Abnahme der Beweglichkeit bei Ersatz von Chlorid- durch Bromidionen (Masseneinfluß), Auswirkungen der vomph bzw. der Elektrolytkonzentration abhängigen unterschiedlichen Komplexierungen zwei- und dreiwertiger Ionen, Einflüsse der auf Hydrolyse zurückgehenden Änderungen der Ligandenzusammensetzung sowie Unterschiede der Wanderungsgeschwindigkeiten als Folge der Komplexierung mit NTE oder AeDTE.Durch die unter bestimmten Bedingungen erreichbare Abstufung der Beweglichkeiten können verschiedene Gemische, unter anderem auch die Chlorokomplexe der meisten Platinmetalle in der Reihenfolge Ir > Os Pt > Rh Pd > Ru (> Rh), getrennt werden. NTE ist dabei für Trennungen besser als AeDTE geeignet.
The high tension electrophoretic separation of inorganic ions with special reference to the platinum metals. I
Summary The high tension electrophoretic migration of the halogeno complexes of the platinum metals and several other inorganic ions was investigated with nitrilotriacetic acid and ethylenediaminetetraacetic acid as electrolytes in relation to the various experimental parameters (electrolyte concentration,ph-value, and amount of substance). The migration velocities of the various metal ions or complexes exhibit characteristic gradations that may be explained on the basis of the regularities that are valid for the high tension electrophoretic migration. Instances are: a decrease was observed in the mobility when chloride was replaced by bromide ions (mass effect), influence of different complexing of di- and trivalent ions that are related to changes in theph or electrolyte concentration, or influences of the changes due to hydrolysis in the composition of the ligands or alterations in the migration rates resulting from complexing with nitrolotriacetic acid or EDTA.The gradation of the mobility obtained under certain conditions are employed as the basis of a procedure for separating various mixtures, including also the chloro complexes of most of the platinum metals in the succession Ir > Os Pt > Rh Pd > Ru (> Rh). It has been found that NTE is better for separations than EDTA.相似文献
100.
It is shown that azulenium cations in the first electronically excited state S1 are stronger acids than in the ground state S0. Their apparent pK″*, obtained from the H0-dependence of the quenching of the azulenium cation S1 → S0 fluorescence does not correspond to a true acid-base equilibrium in the electronically excited state S1. The pK″* values are kinetically controlled, the rate of reprotonation of azulene in the S1 state being too low to compete with the internal conversion to S0. 相似文献