全文获取类型
收费全文 | 4156篇 |
免费 | 74篇 |
国内免费 | 14篇 |
专业分类
化学 | 2799篇 |
晶体学 | 25篇 |
力学 | 64篇 |
数学 | 855篇 |
物理学 | 501篇 |
出版年
2019年 | 36篇 |
2016年 | 53篇 |
2015年 | 49篇 |
2014年 | 54篇 |
2013年 | 137篇 |
2012年 | 104篇 |
2011年 | 111篇 |
2010年 | 81篇 |
2009年 | 112篇 |
2008年 | 141篇 |
2007年 | 115篇 |
2006年 | 113篇 |
2005年 | 131篇 |
2004年 | 121篇 |
2003年 | 102篇 |
2002年 | 95篇 |
2001年 | 81篇 |
2000年 | 72篇 |
1999年 | 45篇 |
1998年 | 47篇 |
1997年 | 64篇 |
1996年 | 61篇 |
1995年 | 47篇 |
1994年 | 65篇 |
1993年 | 59篇 |
1992年 | 67篇 |
1991年 | 50篇 |
1990年 | 54篇 |
1989年 | 70篇 |
1988年 | 77篇 |
1987年 | 81篇 |
1986年 | 41篇 |
1985年 | 69篇 |
1984年 | 65篇 |
1983年 | 38篇 |
1982年 | 55篇 |
1981年 | 60篇 |
1980年 | 82篇 |
1979年 | 60篇 |
1978年 | 63篇 |
1977年 | 40篇 |
1976年 | 39篇 |
1975年 | 55篇 |
1974年 | 46篇 |
1973年 | 55篇 |
1972年 | 36篇 |
1971年 | 39篇 |
1970年 | 38篇 |
1967年 | 32篇 |
1932年 | 34篇 |
排序方式: 共有4244条查询结果,搜索用时 93 毫秒
101.
Plasma modeling and diagnostics commonly involve solution of rate equations for the population densities of impurity ions in their excited and charge states. Construction of the rate equations requires a complete set of atomic transition rates for all the charge and excited states involved. However, the rates are themselves affected by the host plasma ions and electrons. The ionic and electronic effects in a two-component plasma are intimately interconnected, especially when the rate equations are simplified for computational purpose in the determination of ionization balance. We formulate a coherent approach to the problem of the plasma density effect, and apply it to carbon impurities in a hydrogen plasma. Both the plasma field distortion of atomic states and the corresponding rates by the plasma ions and stochastic plasma collisional transitions caused by the plasma electrons are included. The latter effect is estimated by constructing an effective collisional transition operator, and the electron-ion recombination processes are explicitly evaluated. It is shown that, these two effects of the ionic field distortions and electronic collisions tend to cancel each other, resulting in many cases in reducing the overall effect of the plasma density on the ionization. 相似文献
102.
C.A. Henry P.K. Diwakar D.W. Hahn 《Spectrochimica Acta Part B: Atomic Spectroscopy》2007,62(12):1390-1398
The role of helium addition on the analyte signal enhancement in laser-induced breakdown spectroscopy for analysis of pure gaseous systems was examined using carbon and hydrogen atomic emission lines. Increased analyte response, as measured by peak-to-base and signal-to-noise ratios, was observed with increasing helium addition, with maximum enhancement approaching a factor of 7. Additional measurements revealed a significant decrease in plasma electron density with increasing helium addition. To explore the mechanisms of analyte signal enhancement, the helium emission lines were also examined and found to be effectively quenched with nitrogen addition. In consideration of the data, it is concluded that the role of metastable helium is not as important as the overall changes in plasma properties, namely electron density and laser-plasma coupling. Helium addition is concluded to affect the electron density via Penning ionization, as well as to play a role in the initial plasma breakdown processes. 相似文献
103.
Lakshman MK Ngassa FN Bae S Buchanan DG Hahn HG Mah H 《The Journal of organic chemistry》2003,68(15):6020-6030
Single-electron oxidation of the carcinogenic hydrocarbon benzo[a]pyrene (BaP) is thought to result in a radical cation intermediate and this species has been proposed to cause alkylation at the nitrogens of the purine nucleobases. Although several different nucleoside adducts have been isolated as arising from this mode of metabolic activation, there are no selective, total syntheses of the stable exocyclic amino group adducts formed by the single-electron oxidation of any hydrocarbon with the purine 2'-deoxynucleosides to date. In this paper we disclose the synthesis of the model adducts N(6)-(1-pyrenyl)-2'-deoxyadenosine and N(2)-(1-pyrenyl)-2'-deoxyguanosine as well as the first synthesis of the carcinogen-linked nucleoside derivatives N(6)-(6-benzo[a]pyrenyl)-2'-deoxyadenosine and N(2)-(6-benzo[a]pyrenyl)-2'-deoxyguanosine via a palladium-mediated C-N bond formation. Two different coupling strategies were attempted: coupling of an aryl bromide with a suitably protected nucleoside and the coupling of an arylamine with a suitable halonucleoside. The former had somewhat limited applicability in that only N(6)-(1-pyrenyl)-2'-deoxyadenosine was prepared by this method; on the other hand, the latter was more general. However, there are noteworthy differences in the amination reactions at the C-6 and C-2 positions. Reactions at the C-6 resulted in the competing formation of a 1:2 amine-nucleoside adduct in addition to the desired monoaryl nucleoside. Such a dimer formation was not observed at the C-2. The C-2 adducts, however, displayed an interesting conformational behavior. 相似文献
104.
The electrochemical oxidation of methanol was investigated on a Pt–Ru–Mo catalyst with an in situ infrared reflectance spectroscopy. The electrocatalysts were prepared by an electrochemical deposition and dispersed in a conducting three-dimensional matrix of polyaniline (PAni). We observed that CO2 is produced from methanol oxidation at 350 mV vs. RHE on PAni/Pt–Ru–Mo, which is 100 mV less negative than on PAni/Pt–Ru and 200 mV less than on PAni/Pt. The results suggest that Pt–Ru–Mo is less sensitive to COADS poisoning than Pt–Ru and much more sensitive than Pt. Large differences are observed concerning the average wavenumber of ADS between Pt–Ru–Mo, Pt–Ru, and Pt. 相似文献
105.
Contributions to the Chemistry of Phosphorus. 167. Constitutional and Configurational Isomers of Pentaphosphane(7), P5H7 Phosphane mixtures containing 10—15 P-% of pentaphosphane(7), P5H7, are obtained by thermolysis of diphosphane, P2H4, or as residue from distillation of crude diphosphane [3]. According to the complete analysis of the 31P{1H}-NMR spectrum on the basis of selective population transfer experiments, P5H7 exists as a mixture of three diastereomers of n-P5H7 — 1a (erythro, erythro), 1b (erythro, threo), 1c (threo, threo) — and of the constitutional isomer 2-phosphinotetraphosphane 2 (iso-P5H7, largest relative isomeric abundance). The correlation between the diastereomers and the observed spin systems results from the preferred gauche orientation of neighboring free electron pairs, the dependence of 1J(PP) on dihedral angles, and the 3J(PP) long range couplings. From the 31P-NMR data of the phosphane molecules PnHn+2 with n = 1—5 general relationships for the δ(31P) values and the 1J(PP) coupling constants of chain-type phosphorus hydrides as a function of their structural parameters are derived. 相似文献
106.
Zusammenfassung Mercaptosubstituierte Ionen von Schwefelheterocyclen, die iso--elektronisch mit dem Mercaptotropyliumion sind, zeigen mehrere charakteristische Absorptionsmaxima im Ultravioletten, die sich mehr oder weniger von den Absorptionen der unsubstituierten Heterocyclen unterscheiden. Diese Verbindungen werden durch Protonierung iso--elektronischer Thiotropene erhalten. Halbempirische SCF-LCI-Rechnungen mit früher abgeleiteten Parametern geben die experimentellen Ergebnisse gut wieder. Der Einfluß einer Methylsubstitution am exocyclischen Schwefel läßt sich durch eine Änderung des Parameters U
s abschätzen.
19. Mitteilung: Hartmann, H., u. J. Fabian (im Druck). 相似文献
MO-LCAO-calculations on sulfur containing -electron systemsXX. PPP-calculations on the mercapto-tropylium ion and iso--electronic sulfur-heterocycles
Iso--electronic thiotropones are converted by means of protonisation into mercaptosubstituted ions of the analogous heterocycles. These ions show various characteristic absorption maxima in the UV-region. Semiempirical SCF-LCI-calculations using parameters derived formerly reflect the experimental results satisfactory. By appropriate adjustment of the parameter U s it is possible to estimate the influence of methyl substitution on the exocyclic sulfur atom.
Résumé Des thiotropones isolélectroniques sont par protonation converties en ions mercapto-substitués des hétérocycles correspondants. Ces ions présentent différents maxima d'absorption caractéristiques dans le spectre U.V. Des calculs semi-empiriques SCF-LCI, utilisant des paramètres précédemment obtenus, reflètent d'une manière satisfaisante les résultats expérimentaux. Par un ajustement convenable du paramètre U s il est possible d'estimer l'influence de la substitution méthylique sur l'atome de soufre exocyclique.
19. Mitteilung: Hartmann, H., u. J. Fabian (im Druck). 相似文献
107.
Horst Pietzner und Hans Werner 《Fresenius' Journal of Analytical Chemistry》1966,221(1):186-194
Zusammenfassung Es wird eine Goldbestimmung an sulfidischen Erzen für den Bereich von 0,05–5 ppm bei 20 g Einwaage beschrieben. Das Gold wird durch Salpetersäurebehandlung von den übrigen Metallen getrennt, mit Salzsäure/ Salpetersäure gelöst und mit Selen als innerem Standard und Tellur als Spurenfänger mittels Zinn(II)-chlorid gefällt. Der Niederschlag wird auf ein Membranfilter aufgezogen. Die Goldbestimmung erfolgt über den Impulsratenquotienten der Gold L- und Selen K-Linien. Die störende Molybdän K-Strahlung und die Comptonstreuung werden durch ein Zirkoniumblech auf dem Röhrenfenster unterdrückt. Der Variationskoeffizient beträgt 20% für 0,2–5 ppm und 53,6% für 0,05 ppm.
Herrn Prof. Dr.-Ing. habil. J. Hesemann zum 65. Geburtstag gewidmet. 相似文献
Summary A method is described for the determination of gold in sulphide ores within the concentration range of 0.05–5 ppm with sample weights of 20 g. Gold is separated from the other metals by treatment with nitric acid, dissolved by hydrochloric acid, containing some nitric acid, and is finally precipitated by stannous chloride applying selenium as internal standard and tellurium as collecting agent. The precipitate is mounted on a diaphragm filter and the determination of gold is carried out by X-ray analysis suppressing the disturbing Mo K radiation and compton scattering by a zirconium sheet-metal on the X-ray tube. The pulse rate quotient of the lines Au L /Se K is a function of the concentration of gold. The variation coefficient is 20% for 0.2–5 ppm and 53.6% for 0.05 ppm.
Herrn Prof. Dr.-Ing. habil. J. Hesemann zum 65. Geburtstag gewidmet. 相似文献
108.
Horst J. Klepp 《Zeitschrift für Angewandte Mathematik und Physik (ZAMP)》1980,31(5):657-662
Zusammenfassung Ein autonomer und konservativer Verband mit einem Freiheitsgrad wird betrachtet. Die potentielle Energie des Verbandes wird mit Hilfe der Heaviside Funktion ausgedrückt und ihre Ableitungen besitzen Unstetigkeitsstellen. Mit der potentiellen EnergieU wird eine DistributionU gebildet und die ersten zwei Ableitungen dieser Distribution bestimmt. In den DistributionenU undU erscheinen Funktionen und Werte welche mitV, K undR bezeichnet werden und welche es erlauben die Natur der Unstetigkeitsstellen zu bestimmen. In einer Ebene mit den Achsen OV und OR werden die Bereiche der stabilen und instabilen Gleichgewichtslagen dargestellt. Dir kritischen Fälle an den Grenzen der Bereiche werden mit Hilfe vonK untersucht. Abschließend wird ein Beispiel gebracht.
Summary An undamped autonomous system with one degree of freedom is considered. The potential energy of the system is expressed with the help of the Heaviside function and its derivatives possess points of discontinuity. With the potential energyU a distributionU is determined and the first and second differentiation of the distributionU are calculated. In the distributionsU andU appear functions and values denoted byV, K, R which permit to establish the nature of the points of discontinuity. In a plane with the axes OV and OR the regions of stable and instable equilibrium positions are represented. Critical cases on the boundaries between the different regions are analysed with the help ofK. An example is also considered.相似文献
109.
Alkynylxenon(II) fluorides, RCC(triple bond)XeF, have been prepared from the reactions of the corresponding trimethyl(alkynyl)silanes, Me3(-)SiC(triple bond)CR, and XeF2 in the presence of [NMe4F in common organic solvents at low temperature. The existence of the linear unit C(triple bond)C-Xe-F was proved for PhC(triple bond)CXeF by the 19F-13C NMR correlation method using the HMBC pulse sequence. 相似文献
110.
FTIR-spectroscopic investigations of catalytic reactions yield detailed information about the interaction of adsorbed molecules with the catalyst and kinetic data of the surface reaction, if the participating molecules show vibrations whose position and intensity in the IR-spectrum depend on the sorption state and the quantity adsorbed. In this paper, the possibilities and limitations of the method are represented by two examples. 相似文献