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91.
The metal-binding site of a Helicobacter pylori ATPase 439 (heli(WT)-tag) was successfully used as a new fusion peptide for immobilized metal ion affinity chromatography (IMAC). It produced higher yields than the frequently used his6-tag. Due to stronger binding of the peptide to metal ions, harsher elution conditions were, however, necessary. This undesired side-effect was overcome by modifying the heli(WT)-tag by polymerase chain reaction-directed mutagenesis. The modified tags were screened by an automated high-throughput IMAC system, leading to a heliM14-tag peptide that could be eluted under conditions similar to those of the his6-tag but at the same time produced 20% higher yields of the desired protein. 相似文献
92.
Hans Jürgen Rosenkranz Barbara Winkler-Lardelli Hans-Jürgen Hansen Hans Schmid 《Helvetica chimica acta》1974,57(3):887-916
It is shown that treatment of indolines like 4a-methyl-1,2,3,4,4a,9a-hexahydrocarbazole ( 1 ) and even indoline-alkaloids like 5 or 6 (cf. scheme 1) with KMnO4 in boiling acetone solution leads to the indolenines 10, 29 and 33 , respectively, and, in relatively high yields, to N,N′- or C,N-coupling products (cf. schemes 2 and 5). The results of the oxidation of 6- or 8-methoxy-indolines are shown in schemes 3 and 4, respectively. Analogous ‘dimeric’ dehydrogenation products are observed when tetrahydroquinolines ( 8 and 9 , resp.) are treated with KMnO4 (cf. schemes 7 and 8, resp.). The formation of the bis-compounds is almost certainly due to the coupling of two intermediate indolenyl or tetrahydroquinolyl radicals. The cleavage of the hydrazine derivatives 11 or 17 (scheme 9) also leads to ‘dimeric’ C,N-coupling products. By heating the hydrazine derivative 17 with aqueous HCl, a complete cleavage into indoline 2 and the indolenines 16 and 20 is observed. The reaction is rationalized in scheme 10. So far no naturally occurring alkaloids related to the above mentioned C,N-coupling products have been found. 相似文献
93.
K. Jurkschat B. Schmid M. Dybiona U. Baumeister H. Hartung A. Tzschach 《无机化学与普通化学杂志》1988,560(1):110-118
Structure and Reactivity of Stannylated Propyl Amines and Propyl Sulfides. Crystal and Molecular Structure of Bis(3-chlorodimethylstannylpropyl)sulfide S(CH2CH2CH2SnMe2Cl)2 The synthesis and reactivity of stannylated propyl amines and propyl sulfides, respectively, E(CH2CH2CH2SnMe3)2 ( 1 , E ? NMe; 2 E ? S) and N(CH2CH2CH2SnMe3)3 3 are reported. 1 and 3 react with dimethyl dichlorostannane under thermal cyclisation to 1,5-dimethyl-5-chloro-1aza-5-stannabicyclo[3.3.01,5]octane Me(Cl)Sn(CH2CH2CH2)2NMe 4 and 5-chloro-1-aza-5-stannatricyclo[3.3.3.01,5]-undecane ClSn(CH2CH2CH2)3N 5 , respectively. The reaction of 2 with dimethyl dichlorostannane leads to the formation of bis(3-chloro-dimethylstannylpropyl)sulfide S(CH2CH2CH2SnMe2Cl)2 6 , whereas the treatment of 2 with tin tetrachloride yields the bis(3-di-chloro-methylstannylpropyl)sulfide S(CH2CH2CH2SnMeCl2)2 7 . The 1H, 13C, and 119Sn NMR data are discussed. 6 crystallizes in the ortho-rhombic space group Pna21 with the unit cell parameters a = 2275.0(1), b = 733.6(2), c = 1062.0(4) pm, V = 1.77273 nm3, Z = 4. The structure was refined to a final R value of 0.041. Both tin atoms adopt distorted trigonal bipyramidal configurations as a result of intramolecular interactions with the bridging sulphur. The sulphur and the chlorine atoms occupy the apical positions. The Sn? S distances amount to 309.7(4) and 311.8(4) pm. 相似文献
94.
Reisner E Arion VB Rufińska A Chiorescu I Schmid WF Keppler BK 《Dalton transactions (Cambridge, England : 2003)》2005,(14):2355-2364
Reaction of the antitumor complex trans-[Ru(III)Cl4(Hind)2]- (Hind = indazole) with an excess of dimethyl sulfoxide (dmso) in acetone afforded the complex trans,trans,trans-[Ru(II)Cl2(dmso)2(Hind)2] (1). Two other isomeric compounds trans,cis,cis-[Ru(II)Cl2(dmso)2(Hind)2] (2) and cis,cis,cis-[Ru(II)Cl2(dmso)2(Hind)2] (3) have been obtained on refluxing cis-[Ru(II)Cl(2)(dmso)(4)] with 2 equiv. of indazole in ethanol and methanol, respectively. Isomers 1 and 2 react with acetonitrile yielding the complexes trans-[Ru(II)Cl2(dmso)(Hind){HN=C(Me)ind}].CH3CN (4.CH3CN) and trans,cis-[Ru(II)Cl2(dmso)2{HN=C(Me)ind}].H2O (5.H2O), respectively, containing a cyclic amidine ligand resulting from insertion of the acetonitrile C triple bond N group in the N1-H bond of the N2-coordinated indazole ligand in the nomenclature used for 1H-indazole. These are the first examples of the metal-assisted iminoacylation of indazole. The products isolated have been characterized by elemental analysis, IR spectroscopy, UV-vis spectroscopy, electrospray mass-spectrometry, thermogravimetry, differential scanning calorimetry, 1H NMR spectroscopy, and solid-state 13C CP MAS NMR spectroscopy. The isomeric structures of 1-3 and the presence of a chelating amidine ligand in 4 and 5 have been confirmed by X-ray crystallography. The electrochemical behavior of 1-5 and the formation of 5 have been studied by cyclic voltammetry. 相似文献
95.
Photochemie von tricyclischen β, γ-γ′, δ′-ungesättigten Ketonen. 50. Mitteilung über Photoreaktionen
Photochemistry of tricyclic β, γ-γ′, δ′-unsaturated ketones The easily available tricyclic ketone 1 (cf. Scheme 1) with a homotwistane skeleton yielded upon direct irradiation the cyclobutanone derivative 3 by a 1,3-acyl shift. Further irradiation converted 3 into the tricyclic hydrocarbon 4 . However, acetone sensitized irradiation of 1 gave the tetracyclic ketone 5 by an oxa-di-π-methane rearrangement. Again with acetone as a sensitizer the ketone 5 was quantitatively converted to the pentacyclic ketone 6 . The conversion 5 → 6 represents a novel photochemical 1,4-acyl shift. The possible mechanisms are discussed (see Scheme 7). The tricyclic ketone 2 underwent similar types of photoreactions as 1 (Scheme 2). Unlike 5 the tetracyclic ketone 9 did not undergo a photochemical 1,4-acyl shift. The epoxides 10 and 14 derived from the ketones 1 and 2 , respectively, underwent a 1,3-acyl shift upon irradiation followed by decarbonylation, and the oxa-di-π-methane rearrangement (Schemes 3 and 4). The diketone 18 derived from 1 behaved in the same way (Scheme 5). The tetracyclic diketone 21 cyclized very easily to the internal aldol product 22 under the influence of traces of base (Scheme 5). Upon irradiation the γ, δ-unsaturated ketone 24 underwent only the Norrish type I cleavage to yield the aldehyde 25 (Scheme 6). 相似文献
96.
Hermann Schmid 《Monatshefte für Chemie / Chemical Monthly》1968,99(5):1932-1942
The mechanism of the ionisation of weak acids was elucidated according to the interpretation of the acid—base-catalysis of the mutarotation of α-glucose by the author. The primary elementary reaction of the ionisation of weak acids is the exothermic formation of the hydrogen bridge of the acid with the polar solvent. The secondary reaction is the endothermic total transfer of the proton to the solvent. The thermodynamic values of both elementary reactions were determined for the ionisation of different weak acids in aqueous solution and in this way a contribution was made to the thermodynamics of intermediate reactions which was propagated by the autorh. The formation of hydrogen bridge at the acid—base-catalysis of the mutarotation of α-glucose is discussed from the point of view of the mechanism of ionisation of weak acids. Furthermore the limits of the validity of theBrönsted equation for the acid—base-catalysis of the mutarotation of α-glucose were demonstrated. 相似文献
97.
98.
Rudolf Schmid Marco Cereghetti Bernd Heiser Peter Schnholzer Hans-Jürgen Hansen 《Helvetica chimica acta》1988,71(4):897-929
The axially dissymmetric diphosphines (?)-(R)- and (+)-(S)-(6-6′-dimethylbiphenyl-2,2′-diyl)bis(diphenyl-phosphine) ((?)-(R)- 10 and (+)-(S)- 10 ; ‘BIPHEMP’) have been synthesized, starting from (R)- and (S)-6,6′-dimethylbiphenyl-2,2′-diamine ((R)- and(S)- 16 ), respectively, via Sandmeyer reaction, liathiation, and phosphinylation. Moreover, racemic 4,4′- dimethyl- and 4,4′-bis(dimethylamino)-substituted analogues 11 and 12 respectively, and the 6,6′-bridged analogues 1,11-bis(diphenylphosphino)-5,7-dihydrodibenz[c,e]oxepin (13) were synthesized and resolved into optically pure (R)- and(S)-enantiomers via complexation with di-μ-chlorob is {(R)-2-[1-(dimethylamino)ethyl]pheny-C? N}dipalladium(II) ((R)- 18 ). The molecular structures of the diphosphines (S)- 10 and (R)- 13 and of two derived cationic Rh(I) complexes,[Rh((S)- 10 )(nbd)]BF4 and [Rh((R)- 13 )(nbd)]BF 4 were determined by x-ray analyses. Absolute configurations were established for (+)-(S)- 10 by X-ray analyses of both the free diphosphine and of the derived Rh(I) complex, and for (?)-(R)- 13 by X-ray analysis of the derived Rh(I) complex. Configurational assignments for the substituted BIPHEMP analogues 11 12 were achieved by means of 1H-NMR comparisons. The BIPHEMP ligand 10 and analogues 11 , 12 and 13 are the first examples of optically active bis(triaylphosphines) containing the axially dissymmetric biphenyl moiety. All these new diphosphines proved to be excellent asymmetry-inducing ligands in Rh(I)-catalyzed isomerizations of N,N-diethylnerylamine affording citronellat enamine of 98-99% ee. 相似文献
99.
100.
B. Schmid B. Dorner D. Visser M. Steiner 《Zeitschrift für Physik B Condensed Matter》1992,86(2):257-262
The magnetic excitations in CsFeBr3 have been measured with inelastic scattering of cold neutrons to high precision at 80 mK. The fact that the lowest frequency mode softens with decreasing temperature but stabilizes at 0.11 THz below 2.5 K is the indication that CsFeBr3 remains a SGS system forT0.From dispersion curves measured earlier in a magnetic field along the chain axis experimental intensities were derived and in turn correlation lengths. Correlation lengths were also calculated using the new parameters for exchange and anisotropy. The experimental results and the calculations both show that the correlation lengths increase for increasing magnetic field, flatten off around the phase transformation at 4.1 Tesla with a maximum of about 35 Å and then decrease again for higher fields. No critical phenomena connected with this phase transformation could be detected.The Mirror Mode published earlier was found to be of spurious origin due to double scattering. It does not exist. 相似文献