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71.
S. Unterricker Kim Jung Ho W. Stolz D. Degering 《Journal of Radioanalytical and Nuclear Chemistry》1988,122(2):271-278
The underground radiation conditions in the mining district of Freiberg and in a rock salt environment of the Werra district were investigated. In a salt mine a very low natural activity level can be found. For selection of proper shielding materials a low-level -spectrometer and an optimum sample geometry must be used. The photopeak differences between sample and blank are small in most cases. Considerable differences can be found in the continuous background below 0.7 MeV. 相似文献
72.
Fauhl C Wittkowski R Lofthouse J Hird S Brereton P Versini G Lees M Guillou C 《Journal of AOAC International》2004,87(5):1179-1188
The aim of the present study was to provide the official wine control authorities with an internationally validated method for the determination of 3-methoxy-1,2-propanediol (3-MPD) and cyclic diglycerols (CycDs)-both of which are recognized as impurities of technical glycerol-in different types of wine. Because glycerol gives a sweet flavor to wine and contributes to its full-body taste, an economic incentive is to add glycerol to a wine to mask its poor quality. Furthermore, it is known that glycerol, depending on whether it is produced from triglycerides or petrochemicals, may contain considerable amounts of 3-MPD in the first case or CycDs in the second. However, because these compounds are not natural wine components, it is possible to detect glycerol added to wine illegally by determining the above-mentioned by-products. To this end, one of the published methods was adopted, modified, and tested in a collaborative study. The method is based on gas chromatographic/mass spectrometric analysis of diethyl ether extracts after salting out with potassium carbonate. The interlaboratory study for the determination of 3-MPD and CycDs in wine was performed in 11 laboratories in 4 countries. Wine samples were prepared and sent to participants as 5 blind duplicate test materials and 1 single test material. The concentrations covered ranges of 0.1-0.8 mg/L for 3-MPD and 0.5-1.5 mg/L for CycDs. The precision of the method was within the range predicted by the Horwitz equation. HORRAT values obtained for 3-MPD ranged from 0.8 to 1.7, and those obtained for CycDs ranged from 0.9 to 1.3. Average recoveries were 104 and 109%, respectively. 相似文献
73.
The reactions of 3-phenylsydnonyllithium with a variety of ketones to afford tertiary carbinols 4a-4i and their subsequent dehydration to 4-(3-phenylsydnonyl) alkenes 5a-5i are discussed. Among the alkenes, 2-[4-(3-phenylsydnonyl)]propene ( 5b ) and 1-[4-(3-phenylsydnonyl)]-1-cyclohexene ( 5i ) were photochromic. A Wittig reaction between ethyl-4-(3-phenylsydnonyl)-ketone and methylenetriphenylphosphorane afforded the photochromic 2-[4-(3-phenylsydnon-yl)]-1-butene(5j). 相似文献
74.
Andr Darchen Pascal Berthelot Claude Vaccher M. Nazareth Viana Michel Debaert Jean Louis Burgot 《Journal of heterocyclic chemistry》1986,23(5):1603-1607
Two-electron reduction of some substituted 1,2-dithiole-3-thiones 1 followed by alkylation of the dianionic intermediates leads through electrosynthesis to mixture of Z and E isomers of the corresponding substituted alkyl-(3-thioalkyl)-2-propenedithioates 2, 3 in satisfactory yield. The structure of those products was established by 13C and 1H nmr and mass spectroscopy. The isomers ratios were determined by nmr spectroscopy. 相似文献
75.
Cheikhousman R Zude M Bouveresse DJ Léger CL Rutledge DN Birlouez-Aragon I 《Analytical and bioanalytical chemistry》2005,382(6):1438-1443
The potential of fluorescence spectroscopy for characterizing the deterioration of extra virgin olive oil (EVOO) during heating was investigated. Two commercial EVOO were analysed by HPLC to determine changes in EVOO vitamin E and polyphenols as a result of heating at 170°C for 3 h. This thermal oxidation of EVOO caused an exponential decrease in hydroxytyrosol and vitamin E (R2=0.90 and 0.93, respectively) whereas the tyrosol content was relatively stable. At the same time, amounts of preformed hydroperoxides (ROOH), analysed by an indirect colorimetric method, decreased exponentially during the heating process (R2=0.94), as a result of their degradation into secondary peroxidation products. Fluorescence excitation spectra with emission at 330 and 450 nm were recorded to monitor polyphenols and vitamin E evolution and ROOH degradation, respectively. Partial least-squares calibration models were built to predict these indicators of EVOO quality from oil fluorescence spectra. A global approach was then proposed to monitor the heat charge from the overall fluorescence fingerprint. Different data pretreatment methods were tested. This study indicates that fluorescence spectroscopy is a promising, rapid, and cost-effective approach for evaluating the quality of heat-treated EVOO, and is an alternative to time-consuming conventional analyses. In future work, calibration models will be developed using a wide range of EVOO samples. 相似文献
76.
Characterization of Two Light-Harvesting Subunits Isolated from the Brown Alga Pelvetia canaliculata: Heterogeneity of Xanthophyll Distribution 总被引:1,自引:0,他引:1
Alessandra De Martino Dominique Douady Bernard Rousseau Jean Claude Duval Lise Caron 《Photochemistry and photobiology》1997,66(2):190-197
The main light-harvesting fraction from Pelvetia canaliculata was isolated on a sucrose density gradient from digitonin-solubilized chloroplasts. After further solubilization by dodecyl maltoside, the bulk fraction was separated into two subunits by preparative isoelectric focusing. The more acidic brown fraction was mainly composed of 22 kDa polypeptides having an apparent pI of 4.55. Its pigment composition was very simple, containing chlorophyll (Chi) a, Chi c and fucoxanthin. The in vivo spectral properties of fucoxanthin, namely a shift in light absorption to the green and efficient energy transmission to Chi a, were conserved in this subunit. No xanthophyll associated with photoprotection was found in this band, even when obtained from photoinhibited thalli. The less acidic green band contained predominantly 22 kDa polypeptides that were resolved into numerous components by denaturing isoelectric focusing. Its pigment composition was more complex, containing, in addition, pigments of the so-called xanthophyll cycle. In photoinhibited thalli, about half of the violaxanthin was converted into antheraxanthin and zeaxanthin. All the pigments of the xanthophyll cycle were specifically associated with this subunit, and it may thus have a central role in the thermal dissipation of the absorbed light energy as postulated for light-harvesting complex II isolated from green plants. 相似文献
77.
Further studies on dppm-stabilized mixed-metal clusters: X-ray structure of PdPtCoCl(CO)3(μ-dppm)2
1
Pierre Braunstein Claude de Bellefon Yves Dusausoy Daniel Bayeul 《Journal of Cluster Science》1995,6(1):175-185
The metalloligated mixed-metal cluster [PdPtCo2(CO)7(-dppm)2] (2) (dppm = -Ph2PCH2PPh2) possesses numerous potential reaction centers (e.g., metal(s), metal-metal bonds, CO, and dppm ligands) and this has previously led to an investigation of the site selectivity of reactions with nucleophiles. The exocyclic CO(CO)4 fragment was substituted with a chloride ligand and the resulting chiral, triangular cluster PdPtCoCl(CO)3(-dppm)2 (4) has been structurally characterized. The Pd-Co and Pt-Co edges of this almost equilateral triangle are bridged by a dppm ligand, and two of the three carbonyls borne by the Co atom are semi-triply bridging above and below the plane of the metals. The Co(CO)3P fragment behaves as an anionic 4-electron donor organometallic bridging group toward thed
9-d
9 Pd(I)-Pt(I) unit. Crystal data for4, monoclinic space groupP21/n with Z=4 in a unit cell of dimensionsa=12.291(3),b=19.321(4),c=23.680(5) Å,=100.05(2)°. The structure has been solved from diffractometer data by Patterson, Fourier methods and refined by full-matrix least squares on the basis of 3512 observed reflections (l>3) toR(F) andR
w(F) values of 0.059 and 0.061.Dedicated to Professor L. F. Dahl on the occasion of his 65th birthday, with our sincere congratulations and best wishes. 相似文献
78.
Cavé C Desmaële D d'Angelo J Riche C Chiaroni A 《The Journal of organic chemistry》1996,61(13):4361-4368
The Michael-type addition of chiral imines, derived from racemic alpha-substituted cyclanones and optically active 1-phenylethylamine, to electrophilic alkenes, in neutral conditions, constitutes one of the most efficient methods for the stereocontrolled construction of quaternary carbon centers. In order to create an additional stereogenic center at the alpha- or beta-position to the quaternary one, the behavior of a variety of alpha- and beta-substituted alkenyl acceptors was examined. In general, these additions are highly regioselective, the alkylation taking place predominantly, if not exclusively, at the more substituted alpha-side of the imine function; however, in some cases (electrophilic alkenes 28 and 49), significant amounts (10-15%) of regioisomeric adducts were obtained. With the exception of methyl propiolate 52, a remarkable control of the absolute configuration of the adducts were always observed with these Michael acceptors. According to the general rule we have previously proposed, the alkylation process takes place preferentially on the less hindered pi-face of the more substituted secondary enamine, in tautomeric equilibrium with the starting imine. An excellent diastereocontrol was always obtained by using the present alpha- and beta-substituted alkenes. These stereochemical outcomes can be interpreted by invoking that the reaction proceeds through a compact approach of the reactants, the hydrogen atom at the nitrogen center of the enamine being transferred to the alpha-vinylic carbon atom of the acceptor, concertedly with the creation of the C-C bond. In this respect the "endo-approach" 58, in which the electron-withdrawing group of the acceptor faced to the nitrogen atom of the enamine (case of acceptors 10, methyl methacrylate, 24, 28, 43, 47, and 49) largely prevails over the "exo-approach" 59 (case of acceptor 38). This predominant "endo-preference" can be reasonably interpreted in terms of a cooperative effect between steric and stereoelectronic factors. 相似文献
79.
Thi Thanh-Tâm Nguyên Claude Delseth Jean-Pierre Kintzinger Pierre-Alain Carrupt Pierre Vogel 《Tetrahedron》1980,36(19):2793-2797
Natural-abundance 17O-NMR spectra of 7-oxanorbornane exo-3-oxatricyclo [3.2.1.02.4]octane and their unsaturated derivatives (endo cyclic and exocyclic double bonds) have been measured. Linear correlation laws were observed for of these ethers/corresponding hydrocarbons. The “cyclization shifts” for δo in ethers were not correlated by the “cyclization shifts” for δc of the corresponding hydrocarbons. 相似文献
80.
Zusammenfassung In unpolaren Lösungsmitteln kondensieren sich monomeres und dimeres Malonitril mit Dimethylamino-phenyl-propenon zu linearen Dienen bzw. Trienen. 2-Cyan-5-dimethylamino-3-phenyl-2,4-pentadienamid (4) kann als Zwischenprodukt für die Bildung von Pyridonen aus Enaminoketonen und Cyanacetamid aufgefaßt werden, da in saurem Medium die Cyclisierung zum 2-Oxo-4-phenyl-1,2-dihydro-pyridin-3-carbonitril bzw. dem Carbonsäureamid gelingt.
Herrn Prof.O. Hromatka zum 65. Geburtstag gewidmet. 相似文献
Syntheses with nitriles, XXIX: The linear condensation products from dimethylaminophenyl propenone with malononitrile
Monomeric and dimeric malononitrile condense in nonpolar solvents with dimethylamino phenyl propenone to form linear dienes and trienes, resp. 2-Cyano-5-dimethylamino-3-phenyl-2,4-pentadienamide (4) represents an intermediate in the formation of pyridones from enamine ketones and cyanoacetamide. It is cyclised in acidic medium to 2-oxo-4-phenyl-1,2-dihydropyridine-3-carbonitrile (8) (or-3-carboxamide,9).
Herrn Prof.O. Hromatka zum 65. Geburtstag gewidmet. 相似文献