全文获取类型
收费全文 | 48818篇 |
免费 | 15853篇 |
国内免费 | 131篇 |
专业分类
化学 | 58806篇 |
晶体学 | 80篇 |
力学 | 1217篇 |
数学 | 2617篇 |
物理学 | 2082篇 |
出版年
2024年 | 423篇 |
2023年 | 4264篇 |
2022年 | 1456篇 |
2021年 | 2470篇 |
2020年 | 4788篇 |
2019年 | 2347篇 |
2018年 | 2435篇 |
2017年 | 664篇 |
2016年 | 5698篇 |
2015年 | 5622篇 |
2014年 | 5083篇 |
2013年 | 5434篇 |
2012年 | 3475篇 |
2011年 | 1521篇 |
2010年 | 3591篇 |
2009年 | 3491篇 |
2008年 | 1491篇 |
2007年 | 1172篇 |
2006年 | 627篇 |
2005年 | 554篇 |
2004年 | 455篇 |
2003年 | 357篇 |
2002年 | 395篇 |
2001年 | 204篇 |
2000年 | 203篇 |
1999年 | 175篇 |
1998年 | 179篇 |
1997年 | 193篇 |
1996年 | 204篇 |
1995年 | 240篇 |
1994年 | 220篇 |
1993年 | 315篇 |
1992年 | 179篇 |
1991年 | 168篇 |
1985年 | 157篇 |
1984年 | 156篇 |
1982年 | 176篇 |
1981年 | 175篇 |
1980年 | 180篇 |
1979年 | 190篇 |
1978年 | 182篇 |
1977年 | 241篇 |
1976年 | 268篇 |
1975年 | 245篇 |
1974年 | 248篇 |
1973年 | 165篇 |
1972年 | 194篇 |
1971年 | 157篇 |
1970年 | 234篇 |
1968年 | 154篇 |
排序方式: 共有10000条查询结果,搜索用时 12 毫秒
31.
Rudzevich Y Vysotsky MO Bohmer V Brody MS Rebek Jr J Broda F Thondorf I 《Organic & biomolecular chemistry》2004,2(21):3080-3084
The dimerization of tetratolyl- and tetratosyl-urea derivatives 1 and 2, derived from a tetrapentoxy calix[4]arene in the cone conformation and of the corresponding tetra-urea derivatives 3 and 4, in which the cone conformation is rigidified by the two crown-3 tethers, have been studied. All six possible equimolar mixtures were examined by 1H NMR using CDCl3 and CD2Cl2 as solvents. While no heterodimers are found for the combinations 1/3 and 2/4 in either solvent, all remaining combinations lead to the (exclusive) formation of heterodimers in CD2Cl2. In CDCl3 heterodimers are only observed for the combinations of 3 with 2 or 4. These results are discussed in terms of entropic and enthalpic contributions and compared with MD-simulations in a box of chloroform solvent molecules. 相似文献
32.
33.
Charles E. Carraher D'Orsay Winthers Frank Millich 《Journal of polymer science. Part A, Polymer chemistry》1969,7(10):2763-2773
The stirred interfacial polycondensation of phenylphosphonic dichloride and 1,6-hexanediamine has been studied as a function of several reaction variables. The reaction is rapid, being completed in less than 1 min. When organic solvent is varied and reactant molar ratio is varied with an excess of the acid chloride, yield is constant. When reactant molar ratio is varied polymer yield increases with increase in amine concentration. When reactant concentration is increased yield increases. With the addition of a soluble salt in the aqueous phase yield is increased. The above indicates that the diffusion of the amine to the reaction zone is of primary importance in determining polymerization rate and that the diffusion of the acid chloride is relatively unimportant. Polymer yield was found to be dependent on the pH of the amine in the aqueous phase. The observed trend is related to the apparent solubility of the amine in the aqueous phase such that the greater the apparent solubility of the amine, the less the polymer yield. Polymer molecular weight is found to be independent of reaction variables tested. Polymer was also formed from the condensation of phenylphosphonic dichloride with p-phenylenediamine, H2N-D-NH2 (where D is a 36-carbon hydrocarbon chain), 1,3-di-4-piperidylpropane, and 4-aminomethylpiperidine; phenyl phosphorodichloridate with 1,6-hexanediamine; chloromethyl phosphonic dichloride with 1,6-hexanediamine. 相似文献
34.
Alfred Trautwein Yutaka Maeda Frank E. Harris Helmuth Formanek 《Theoretical chemistry accounts》1974,36(1):67-76
Experimental Mössbauer spectra of the Fe57-enriched CO complex of sperm whale myoglobin (MbCO) at T= 4.2 K with and without applied magnetic field (H⊥γ) were measured to derive the sign of the electric field gradient (EFG), the quadrupole splitting ΔE Q, and the isomer shift δ of the heme iron. We find a positive EFG, δE Q = 0.363 mm/sec, and δ + 0.266 mm/sec. Molecular orbital calculations were carried out to obtain theoretical estimates of EFG and ΔE Q for several steric arrangements of the CO ligand relative to the heme group. Our results are most consistent with the conclusion that the iron is situated in the heme plane, and that a bent geometry with a Fe-C-O angle of about 135 ° is more favorable than a more symmetric structure with a linear Fe-C-O geometry. 相似文献
35.
The low temperature spectra of TcO
4
–
and ReO
4
–
both show two band systems with pronounced vibrational structures. The bands are identified as1
A
11
T
2 transitions. No other bands are observed with certainty. It seems likely that the KClO4 crystals contain KReO4 crystallites. They are therefore not pure mixed crystals. It is concluded that the virtual orbital (2e) used in the construction of the low lying states resembles an atomic nd orbital more and more when going from n=3, Mn to n=5, Re.
Nachwuchsstipendiat, Schweizerischer Nationalfonds. 相似文献
Zusammenfassung Die Tieftemperaturspektren von TcO 4 – und ReO 4 – zeigen beide zwei Bandensysteme mit ausgeprägten Schwingungsstrukturen. Die Banden werden als 1 A 11 T 2-Übergänge identifiziert. Keine anderen Banden werden mit Sicherheit beobachtet. Es scheint wahrscheinlich, daß die KClO4-Kristalle KReO4-Kristallite enthalten und deswegen keine reinen Mischkristalle sind. Es wird geschlossen, daß das virtuelle Orbital (2e), welches zur Konstruktion der tiefliegenden Zustände gebraucht wird, in der Reihe n=3, Mn bis n=5, Re immer weitgehender einem nd-Atomorbital ähnelt.
Nachwuchsstipendiat, Schweizerischer Nationalfonds. 相似文献
36.
Frank W. Harris Steve O. Norris 《Journal of polymer science. Part A, Polymer chemistry》1973,11(9):2143-2151
A series of phenylated polydihydrophthalimides has been synthesized by the Diels-Alder reactions of 3,3′-(oxydi-p-phenylene)bis(2,4,5-triphenylcyclopentadienone) and 3,3′-(p-phenylene)bis(2,4,5-triphenylcyclopentadienone) with N,N′-o-, -m-, and -p-phenylenedimaleimide. The polydihydrophthalimides were soluble in dimethylformamide (DMF) and had intrinsic viscosities that ranged from 0.33 to 1.01, the polymers were dehydrogenated thermally and chemically to afford the corresponding phenylated polyphthalimides. The totally aromatic polyimides were also soluble in DMF but had intrinsic viscosities only as high as 0.41. The thermogravimetric analyses of the polyphthalimides showed breaks near 530°C in air and in nitrogen atmospheres. 相似文献
37.
Zusammenfassung Es wird eine für alle Stromführungen einheitliche Näherungsgleichung mit drei oder vier anpaßbaren Parametern zur Berechnung des Korrekturfaktors für die mittlere logarithmische Temperaturdifferenz angegeben. Die anpaßbaren Parameter wurden für etwa 50 verschiedene Stromführungen durch Ausgleichsrechnung bestimmt. Die Genauigkeit der Gleichung ist für die Berechnung im praktisch wichtigen Bereich mehr als ausreichend.
Formelzeichen A Übertragungsfläche - a, b, c, d Parameter der Näherungsgleichung - Wärmekapazitätsstrom - F Korrekturfaktor für die logarithmische mittlere Temperaturdifferenz - k Wärmedurchgangskoeffizient - m, n Zahl der Durchgänge oder Einzelapparate - NTU Anzahl der Übertragungseinheiten (number of transfer units); NTUi=kA/ i - P dimensionslose Temperaturänderung - R Wärmekapazitätsstromverhältnis;R 1=1/2;R 2=2/1 - relativer Fehler - Mittelwert von NTU1 und NTU2 Indizes 1, 2 Stoffstrom 1, 2 - G Gegenstrom - s Schätzwert Herrn Prof. Dr.-Ing. E.h. K. Stephan zum 65. Geburtstag gewidmet. 相似文献
New approximate equation for uniform heat exchanger design
An approximate equation with three or four empirical parameters for the uniform calculation of the LMTD-correction factor of all heat exchanger configurations is proposed. The empirical parameters have been determined for about 50 different flow configurations using least squares estimation. The accuracy of the equation is more than sufficient for practical design purposes.
Formelzeichen A Übertragungsfläche - a, b, c, d Parameter der Näherungsgleichung - Wärmekapazitätsstrom - F Korrekturfaktor für die logarithmische mittlere Temperaturdifferenz - k Wärmedurchgangskoeffizient - m, n Zahl der Durchgänge oder Einzelapparate - NTU Anzahl der Übertragungseinheiten (number of transfer units); NTUi=kA/ i - P dimensionslose Temperaturänderung - R Wärmekapazitätsstromverhältnis;R 1=1/2;R 2=2/1 - relativer Fehler - Mittelwert von NTU1 und NTU2 Indizes 1, 2 Stoffstrom 1, 2 - G Gegenstrom - s Schätzwert Herrn Prof. Dr.-Ing. E.h. K. Stephan zum 65. Geburtstag gewidmet. 相似文献
38.
B. Aspacher W. Frank P. Kizler K. Maier 《Applied Physics A: Materials Science & Processing》1994,59(4):339-348
In previous Perturbed-Angular-Correlation (PAC) studies of the - emission of 111In probe nuclei in cold-worked or particle-irradiated nickel, it has been found that thermal annealing in the temperature regime of recovery stage III leads to the formation of so-called C-defects (Cubic defects). This is indicated by the occurrence of a new frequency of about 80 Mrad/s, in addition to the frequency (200 Mrad/s) that is due to 111In on substitutional sites. Obviously, the C-defects are complexes consisting of 111In and the intrinsic point-defect species that migrates freely in recovery stage III. Therefore, they have played an important rôle in the long-standing controversy on whether the recovery-stage-III defects are vacancies (one-interstitial model) or self-interstitials (two-interstitial model). The present paper reports on a novel experimental effort to reveal the nature of the C-defects by combining PAC studies on nickel samples differently pretreated in a systematic way, investigations of the Extended X-ray Absorption Fine Structure (EXAFS) on In-doped nickel, and measurements of the decay rate of 111In nuclei in the Electron-Capture-Induced Decay (ECID). On the basis of the results of these experiments it is concluded that the defects trapped by substitutional 111In atoms (Ins) in recovery stage III are self-interstitials (I), as expected according to the two-interstitial model. Moreover, there is evidence that the C-defects are In interstitials on tetrahedral sites (Ini) that form exclusively in the vicinity of the specimen surface from Ins – I pairs via the reaction Ins+I Ini. 相似文献
39.
Directionality of incident space radiation is a significant factor in spacecraft shielding and astronaut dosimetry in low Earth orbit (LEO). Particle directionality of GCR and trapped protons were measured on LDEF with plastic nuclear track detectors (PNTD) from the P0006 west-side experiment. This experiment consisted of a thick detector stack and is described more fully in a companion article (Benton et al., 1996). The anisotropy of the trapped protons produced maximum intensity for protons arriving from the west. The fluences of the eastward directed trapped protons have been measured by selection of the particles on the basis of range in the PNTDs. The measured fluences are compared with the model calculations of Armstrong and Colborn (1993). 相似文献
40.