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21.
A determination of ethanol is described, which is based on a purging system in conjunction with a photoionization detector. With that system a fast and reliable determination of ethanol in aqueous solutions is possible. The system has been used for the analysis of wine. The 3delta-detection limit has been 0.005% ethanol, the relative standard deviation 4.8 to 6.0% and the time constant of the entire analytical system 20 s. The photoionization detector has been also applied to the analysis of artificial and genuine human breath. A comparison with gas-chromatography and non-dispersive IR-detection has been proven the reliability of results. 相似文献
22.
Monodisperse Linear and Cyclic Oligo[(R)-3-hydroxybutanoates] Containing up to 128 Monomeric Units Using benzyl ester/(tert-butyl)diphenylsilyl ether protection, (COCl)2/pyridine esterification conditions, and a fragment-coupling strategy (with H2/Pd-C debenzylation and HF · pyridine desilylation), linear oligomers of (R)-3-hydroxybutanoic acid (3-HB) containing up to 128 3-HB building blocks (mol. weight > 11 000 Da) are assembled (Schemes 1,2,5, and 6). In contrast to the previously employed protecting-group combination, and due to the low-temperature esterifying conditions, this procedure leads to monodisperse oligomers: all steps occur without loss of single 3-HB units. The product oligomers with two, one, and no terminal protecting groups (mostly prepared in multi-gram amounts) are characterized by all standard spectroscopic methods, especially by mass spectroscopy (Figs. 2 and 3), by their optical activity, and by elemental analyses. Cyclization of the oligo[(R)-3-hydroxybutanoic acids] with up to 32 3-HB units, using thiopyridine activation and CuBr2 for the ring closure, produces oligolides consisting of up to 128 ring atoms (Scheme 7). Mixed oligolides containing 3-HB and (R)-3-hydroxypentanoic units are prepared from the corresponding linear trimers, using Yamaguchi's method for the ring closure (Scheme 8 and Fig.4 (X-ray crystal structures of two folded conformers)). Comparisons of melting points (Table 1), of [α] values (Tables 2 and 3), of 1H-NMR coupling constants (Table 3), and of molecular volume/hydroxyalkanoate unit (Table 4) of linear and cyclic oligomer derivatives and of the high-molecular-weigh polymer show that the monodisperse oligomers appear to be surprisingly good models for the polymer. Besides this insight, our synthesis is supplying the samples to further test the role of P(3-HB) (ca. 140 units) as a component of complexes forming channels through cell-wall phospholipid bilayers. 相似文献
23.
Investigations on Lithiation and Substitution of HP[Si(t-Bu)2]2PH HP[Si(t-Bu)2]2PH 1 is monolithiated by reaction with LiPH2 · DME or LiBu in toluene. The crystalline compound HP[Si(t-Bu)2]2PLi · 2 DME 2 can be isolated in DME. Reaction of 2 with Me2SiCl2 leads to HP[Si(t-Bu)2]2P? SiMe2Cl 4 , ClMe2Si? P[Si(t-Bu)2]2P? SiMe2Cl 5 , HP[Si(t-Bu)2]2P? SiMe2? P[Si(t-Bu)2] 2PH 6 . Isomerization by Li/H migration between 4 and 2 leads to the formation of 5 . Reaction of Li(t-Bu) with 1 or 2 yields LiP[Si(t-Bu)2]2PLi 3 by further lithiation. 3 could not be obtained purely, only in a mixture with 2 . These compounds favourably generate with t-BuPCl2 in hexane Cl(t-Bu)P? P[Si(t-Bu)2]2P? P(t-Bu)Cl 9 , in THF HP[Si(t-Bu)2]2P? P(t-Bu)? P[Si(t-Bu)2]2 PH 12 (main product), 9 , H(t-Bu)P? P[Si(t-Bu)2]2P? P(t-Bu)Cl 10 , H(t-Bu)P? P[Si(t-Bu)2]2P? P(t-Bu)H 11 as well as HP[Si(t-Bu)2]2P? P(t-Bu)H 13 and HP[Si(t-Bu)2]2P? P(t-Bu)2 14 . 相似文献
24.
Title compound 1 was synthesized by a published route which had to be modified (seven steps from readily obtainable starting materials). Characterization of 1 was achieved by spectroscopic means (FAB-MS, 1H-NMR, including 2D-COSY). Furthermore, commercially available reference material purchased for comparison, was unequivocally established to be 10 , i.e. incompletely deprotected 1 . 相似文献
25.
Lukin O Müller WM Müller U Kaufmann A Schmidt C Leszczynski J Vögtle F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(15):3507-3517
The readily available in gram quantities tris(allyloxy)knot of the amide-type 5 (knotane) can be completely and partially deprotected with nBu(3)SnH in the presence of a palladium catalyst resulting in hydroxyknotanes 7-9. These, in turn, react with diethylchlorophosphate giving rise to knotanes equipped with between one and three phosphoryl groups. Sulfonylation of bis(allyloxy)monohydroxyknotane 8 with p-toluenesulfonyl chloride and, following removal of one or two allyl groups from the intermediate monosulfonate 13, give rise to sulfonyloxy-allyloxy-hydroxy- and sulfonyloxy-dihydroxy-knotanes 15 and 14, respectively. This provides a convenient method for the preparation of knotanes with any substitution pattern. All new knotanes have been isolated in preparative amounts and as highly pure substances with an exception of allyloxy-dihydroxyknotane 9. This compound could only be obtained as a mixture with the corresponding monohydroxy-derivative 8. The structures of all synthesized compounds were established by means of FAB and MALDI TOF mass spectrometry, (1)H and (31)P NMR spectroscopy. The triphosphorylated knotane 10 exhibits high solubility in alcohols, allowing its complete enantiomeric resolution with a commercially available chiral HPLC column. (1)H,(1)H DQF-COSY correlation spectroscopy along with H/D exchange experiments and ab initio calculations provided the first detailed (1)H NMR signal assignments of knotanes in [D(6)]DMSO solution. The combination of variable temperature (1)H and (31)P NMR spectroscopy and molecular modeling has been applied to study the conformational behavior of the new knotanes in different solvents. It has been shown that in DMSO solution at room temperature knotanes exist in a relatively rigid nonsymmetrical conformation similar to that found in the solid state while faster conformational exchange leading to the average D(3) symmetrical structure was detected in a number of other solvents. 相似文献
26.
Transition Metal Complexes of the Hexamethyl-trisila-tetraphospha-nortricyclene P4 (Sime 2) 3 P4(Sime2)3 1 reacts with Mo(CO)6, Cr(CO)5THF, and Mn(η-C5H5)(CO)2THF to give crystalline complexes in which 1 functions as a monodentate ligand. In each compound one phophorus atom of the cyclotriphosphane ring coordinates to the metal atom. Using Mn(η-C5H5)(CO)2THF, two different P atoms of the P3 Cr(CO)4 norbornadiene and 1 react, yielding the dimeric, red, crystalline compound (CO) 4Cr[μ-P4(Sime2)3]2Cr(CO)4. In this complex the two molecules of 1 are both bonded by two P atoms of the P 3 ring to the two Cr(CO)4 Units, forming a six-memered (CrP2)2ring. 相似文献
27.
Gert Brandl Fritz Kastner Rainer Fritsch Herbert Zinner Albrecht Mannschreck 《Monatshefte für Chemie / Chemical Monthly》1992,123(11):1059-1069
Summary A procedure is described which serves to measure circular dichrograms () on line during stops of flow in liquid chromatography. Since the concentration of substrate in the spectrometer cell during the stop is not known, the differential absorption coefficients are calculated from the experimental differential absorbances A by means of UV absorption (i. e. photomultiplier voltage) data. Verifications of the procedure are obtained by its application to three substrates (Table 1), the () spectra of which were known. The present on-line technique is compared with a corresponding off-line method.The N,N-dimethylthiobenzamides1 and2 as well as the 9,10-phenanthrenequinone7 consist of interconvertible enantiomers because their planar states are destabilized by steric overcrowding of groups. The unknown dichrograms () of1, 2 and7 are obtained (Figs. 2 and 4) and discussed with reference to the helicities of these molecules.In memory of the late Professor Dr. Dr. h. c. Günther Snatzke. 相似文献
28.
Tanaka K Mori M Xu Q Helaleh MI Ikedo M Taoda H Hu W Hasebe K Fritz JS Haddad PR 《Journal of chromatography. A》2003,997(1-2):127-132
In this study, an aqueous solution consisting of benzoic acid with low background conductivity and beta-cyclodextrin (beta-CD) of hydrophilic nature and the inclusion effect to benzoic acid were used as eluent for the ion-exclusion chromatographic separation of aliphatic carboxylic acids with different pKa values and hydrophobicity on a polymethacrylate-based weakly acidic cation-exchange resin in the H+ form. With increasing concentration of beta-cyclodextrin in the eluent, the retention times of the carboxylic acids decreased due to the increased hydrophilicity of the polymethacrylate-based cation-exchange resin surface from the adsorption of OH groups of beta-cyclodextrin. Moreover, the eluent background conductivity decreased with increasing concentration of beta-cyclodextrin in 1 mM benzoic acid, which could result in higher sensitivity for conductimetric detection. The ion-exclusion chromatographic separation of carboxylic acids with high resolution and sensitivity was accomplished successfully by elution with a 1 mM benzoic acid-10 mM cyclodextrin solution without chemical suppression. 相似文献
29.
Fritz Theil 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》1992,104(7):943-944
30.
A new thiosemicarbazone was prepared, characterized, and used as a complexing reagent for the chromatographic separation and determination of metal complexes by reverse-phase HPLC. The reagent was sufficiently soluble in methanol-water solutions for metal ions to be complexed in this aqueous organic phase, without need for extraction. Many variables affected the retention times of the metal complexes. Several metals were determined selectively by complexation with the reagent and chromatographic separation of the complexes. Interference effects from other metal ions were also investigated. 相似文献