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141.
1,3-Dimethylated hydrocarbon segments occur frequently as structural elements in polyketide natural products. The (13)C NMR chemical shifts of a series of model compounds containing such segments can be well reproduced by a combination of molecular mechanics and SOS-DFPT/IGLO calculations. (13)C NMR chemical shifts are calculated on MM3 geometries and are Boltzmann weighted according to the MM3 energies. On the basis of the resulting thermally averaged chemical shifts, all diastereomers of the model compounds can be unequivocally distinguished. Significant differences in chemical shifts occur at methyl groups and methylene groups that are adjacent to a single stereogenic center. The method is applied to predict the relative configuration of two stereocenters in the side chains of two natural products, sambutoxin and the bradykinin inhibitor L-755,897. 相似文献
142.
Mass-selected gas-phase UV spectra of laser-desorbed molecules at room temperature have been measured via resonance-enhanced multiphoton ionisation (REMPI) and time-of-flight mass selection. The wavelength range of 260 to 320 nm is optimal for detection of polycyclic aromatic hydrocarbons (PAHs) using REMPI-mass spectrometry. A new laser desorption/laser ionisation source has been used which features a compact size and thermal equilibrium of the desorbed molecules. 16 PAHs have been investigated which have been selected by the US Environmental Protection Agency (EPA). These 16 EPA-PAHs are commonly used world-wide to characterise the PAH-load of environmental samples. 相似文献
143.
Ulrich Felgner 《Monatshefte für Mathematik》1984,98(3):185-191
Using Eisenstein's law of cubic reciprocity we investigate cases in whichx
3=y
2+k is unsolvable in the ring of rational integers In particular we show, that for all primesp ± 1 (mod 9),p3, the equationx
3=y
2+3p(p±9) has no solutions in . 相似文献
144.
Prof. Dr. Ulrich Krengel 《Monatshefte für Mathematik》1978,86(1):3-6
Given any ergodic invertible measure preserving transformation τ of [0,1] and any null-sequence (α N ) of positive reals, there exists a continuousf such that $$\lim \sup \alpha _{\rm N}^{ - 1} \left| {N^{ - 1} \sum\limits_{k = 0}^{N - 1} {f \circ \tau ^k - \smallint f} } \right| = \infty a. e.,$$ i.e. there is no “speed of convergence” in the ergodic theorem for any τ. The analogous result holds also for norm-convergence. 相似文献
145.
B. T. Ulrich 《Zeitschrift für Angewandte Mathematik und Physik (ZAMP)》1978,29(2):359-361
A voltmeter of sensitivity
is based on direct conversion of the voltage to be measured into a frequency according to the Josephson voltage-frequency relation. Selfpumped parametric amplification in a d.c. biased loop containing two Josephson junctions and a measuring resistanceR
s=4.7×10–9 amplifies the femptovolt level voltages acrossR
s to microvolt levels that can be observed with a room temperature amplifier. The sensitivity of the femptovoltmeter is determined by Johnson-Nyquist noise voltages at 4.2 K in the 4.7×10–9 resistance. 相似文献
146.
A. Hochrainer S. Hellweger W. Silhan Ulrich Schmidt 《Monatshefte für Chemie / Chemical Monthly》1968,99(6):2153-2156
Zusammenfassung Die Reaktion von 1,3-Bis-dimethylamino-1,3-dienen mit Säurechloriden zu substituierten 1,3-Diaminbenzolen wird beschrieben.
Herrn Prof. Dr.L. Schmid zum 70. Geburtstag in Verehrung gewidmet.
4. Mitt.:Ulrich Schmidt undM. Schwochau, Tetrahedron Letters 1967, 4491. 相似文献
The reaction of 1,3-bis-dimethylamino-1,3-dienes with acyl chlorides to substituted 1,3-diaminobenzenes is described.
Herrn Prof. Dr.L. Schmid zum 70. Geburtstag in Verehrung gewidmet.
4. Mitt.:Ulrich Schmidt undM. Schwochau, Tetrahedron Letters 1967, 4491. 相似文献
147.
Robert F. Kirchner Gilda H. Loew Ulrich T. Mueller-Westerhoff 《Theoretical chemistry accounts》1976,41(1):1-6
An iterative extended Hückel molecular orbital calculation was used to obtain wave functions for the ground state of ferrocene and several low lying states of the ferrocenium ion. Photoemission spectra in terms of relative ionization potentials and the electric field gradient at the iron nucleus were calculated for ferrocene andg values and the electric field gradient were calculated for the ferrocenium ion. These values are in good agreement with experiment. The nature of the molecular orbitals was compared with results of previous semi-empirical andab initio calculations. 相似文献
148.
Mono- and Binuclear Dinitrosyl Complexes of Molybdenum and Tungsten. Crystal Structures of (PPh3Me)2[WCl4(NO)2], (PPh3Me)2[MoCl3(NO)2]2, and (PPh3Me)2[WCl3(NO)2]2 The complexes (PPh3Me)2[MCl4(NO)2] (M = Mo, W), and (PPh3Me)2[MCl3(NO)2]2, respectively, are prepared by reactions of the polymeric compounds MCl2(NO)2 with triphenylmethylphosphonium chloride in CH2Cl2, forming green crystals. According to the IR spectra the nitrosyl groups are in cis-position in all cases. The tungsten compounds as well as (PPh3Me)2[MoCl3(NO)2]2 were characterized by structure determinations with X-ray methods. (PPh3Me)2[WCl4(NO)2]: space group C2/c, Z = 4. a = 1874, b = 1046, c = 2263 pm, β = 119.99°. Structure determination with 3492 independent reflexions, R = 0.057. The compound consists of PPh3Me⊕ ions, and anions [WCl4(NO)2]2? with the nitrosyl groups in cis-position (symmetry C2v). (PPh3Me)2[WCl3(NO)2]2: Space group C2/c, Z = 4. Structure determination with 2947 independent reflexions, R = 0.059. (PPH3Me)2[MoCl3(NO)2]2: Space group P1 , Z = 1. a = 989, b = 1134, c = 1186 pm; α = 63.25°, β = 80.69°, γ = 69.94°. Structure determination with 3326 independent reflexions, R = 0.046. The compounds consist of PPh3Me⊕ ions, and centrosymmetric anions [MCl3(NO)2]22?, in which the metal atoms are associated via MCl2M bridges of slightly different lengths. One of the NO groups is in an axial position, the other one in equatorial position (symmetry C2h). 相似文献
149.
Ulrich Vgeli Wolfgang von Philipsborn Kuppuswamy Nagarajan Mohan D. Nair 《Helvetica chimica acta》1978,61(2):607-617
Heterocyclic compounds obtained by addition of acetylenedicarboxylic acid esters to thioureas, cyclic amidines and o-difunctionalized aromatic systems have been studied by 13C-NMR. In particular, C, H-spin-coupling constants over two and three bonds were used to differentiate between the various constitutional isomers and to establish the configuration of trisubstituted exocyclic C, C-double bonds. The configurational significance and diagnostic value of vicinal cis and trans C,H-spin coupling is again demonstrated in the present series. 相似文献
150.
Dieter Seebach Paola E. Ciceri Mark Overhand Bernhard Jaun Dario Rigo Lukas Oberer Ulrich Hommel Ren Amstutz Hans Widmer 《Helvetica chimica acta》1996,79(8):2043-2066
Structural prerequisites for the stability of the 31 helix of β-peptides can be defined from inspection of models (Figs. 1 and 2): lateral non-H-substituents in 2- and 3-position on the 3-amino-acid residues of the helix are allowed, axial ones are forbidden. To be able to test this prediction, we synthesized a series of heptapeptide derivatives Boc-(β-HVal-β-HAla-β-HLeu-Xaa-β-HVal-β-HAla-β-HLeu)-OMe 13–22 (Xaa = α- or β-amino-acid residue) and a β-depsipeptide 25 with a central (S)-3-hydroxybutanoic-acid residue (Xaa = –OCH(Me)CH2C(O)–) (Schemes 1 3). Detailed NMR analysis (DQF-COSY, HSQC, HMBC, ROESY, and TOCSY experiments) in methanol solution of the β-hexapeptide H(-β-HVal-β-HAla-β-HLeu)2-OH ( 1 ) and of the β-heptapeptide H-β-HVal-β-HAla-β-HLeu-(S,S)-β-HAla(αMe)-β-HVal-β-HAla- β-HLeu-OH ( 22 ), with a central (2S,3S)-3-amino-2-methylbutanoic-acid residue, confirm the helical structure of such β-peptides (previously discovered in pyridine solution) (Fig.3 and Tables 1–5). The CD spectra of helical β-peptides, the residues of which were prepared by (retentive) Arndt-Eistert homologation of the (S)- or L -α-amino acids, show a trough at 215 nm. Thus, this characteristic pattern of the CD spectra was taken as an indicator for the presence of a helix in methanol solutions of compounds 13–22 and 25 (including partially and fully deprotected forms) (Figs.4–6). The results fully confirm predicted structural effects: incorporation of a single ‘wrong’ residue ((R)-β-HAla, β-HAib, (R,S)-β-HAla(α Me), or N-Me-β-HAla) in the central position of the β-heptapeptide derivatives A (see 17, 18, 20 , or 21 , resp.) causes the CD minimum to disappear. Also, the β-heptadepsipetide 25 (missing H-bond) and the β-heptapeptide analogs with a single α-amino-acid moiety in the middle ( 13 and 14 ) are not helical, according to this analysis. An interesting case is the heptapeptide 15 with the central achiral, unsubstituted 3-aminopropanoic-acid moiety: helical conformation appears to depend upon the presence or absence of terminal protection and upon the solvent (MeOH vs. MeOH/H2O). 相似文献