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101.
Ernst Pittenauer Günter Allmaier 《Journal of the American Society for Mass Spectrometry》2009,20(6):1037-1047
Triacylglycerols were analyzed as cationized species (Li+, Na+, K+) by high-energy CID at 20 keV collisions utilizing MALDI-TOF/RTOF mass spectrometry. Precursor ions, based on [M+Li]+-adduct ions exhibited incomplete fragmentation in the high and low m/z region whereas [M+K]+-adducts did not show useful fragmentation. Only sodiated precursor ions yielded product ion spectra with structurally diagnostic
product ions across the whole m/z range. The high m/z region of the CID spectra is dominated by abundant charge-remote fragmentation of the fatty acid substituents. In favorable
cases also positions of double bonds or of hydroxy groups of the fatty acid alkyl chains could be determined. A-type product
ions represent the end products of these charge-remote fragmentations. B- and C-type product ions yield the fatty acid composition
of individual triacylglycerol species based on loss of either one neutral fatty acid or one sodium carboxylate residue, respectively.
Product ions allowing fatty acid substituent positional determination were present in the low m/z range enabling identification of either the sn-1/sn-3 substituents (E-, F-, and G-type ions) or the sn-2 substituent (J-type ion). These findings were demonstrated with synthetic triacylglycerols and plant oils such as cocoa
butter, olive oil, and castor bean oil. Typical features of 20 keV CID spectra of sodiated triacylglycerols obtained by MALDI-TOF/RTOF
MS were an even distribution of product ions over the entire m/z range and a mass accuracy of ±0.1 to 0.2 u. One limitation of the application of this technique is mainly the insufficient
precursor ion gating after MS1 (gating window at 4 u) of species separated by 2 u. 相似文献
102.
Schwizer D Patton JT Cutting B Smieško M Wagner B Kato A Weckerle C Binder FP Rabbani S Schwardt O Magnani JL Ernst B 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(5):1342-1351
A new class of N-acetyl-D-glucosamine (GlcNAc) mimics for E-selectin antagonists was designed and synthesized. The mimic consists of a cyclohexane ring substituted with alkyl substituents adjacent to the linking position of the fucose moiety. Incorporation into E-selectin antagonists led to the test compounds 8 and the 2'-benzoylated analogues 21, which exhibit affinities in the low micromolar range. By using saturation transfer difference (STD)-NMR it could be shown that the increase in affinity does not result from an additional hydrophobic contact of the alkyl substituent with the target protein E-selectin, but rather from a steric effect stabilizing the antagonist in its bioactive conformation. The loss of affinity found for antagonists 10 and 35 containing a methyl substituent in a remote position (and therefore unable to support to the stabilization of the core) further supports this hypothesis. Finally, when a GlcNAc mimetic containing two methyl substituents (52 and 53) was used, in which one methyl was positioned adjacent to the fucose linking position and the other was in a remote position, the affinity was regained. 相似文献
103.
Albert A. Smith Matthias Ernst Sereina Riniker Beat H. Meier 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(28):9483-9488
Nuclear magnetic resonance (NMR) relaxation data and molecular dynamics (MD) simulations are combined to characterize the dynamics of the fungal prion HET‐s(218‐289) in its amyloid form. NMR data is analyzed with the dynamics detector method, which yields timescale‐specific information. An analogous analysis is performed on MD trajectories. Because specific MD predictions can be verified as agreeing with the NMR data, MD was used for further interpretation of NMR results: for the different timescales, cross‐correlation coefficients were derived to quantify the correlation of the motion between different residues. Short timescales are the result of very local motions, while longer timescales are found for longer‐range correlated motion. Similar trends on ns‐ and μs‐timescales suggest that μs motion in fibrils is the result of motion correlated over many fibril layers. 相似文献
104.
Ernst Vidic 《Fresenius' Journal of Analytical Chemistry》1952,135(1):81-98
Zusammenfassung Der nephelometrische Nachweis des Morphins und Dilaudids nach Deckert ist für die Anzeige von Eukodal, Dicodid, Codein, Acedicon, Narcotin, Papaverin und Cocain nicht anwendbar, wenn diese Alkaloide, wie dies in der Praxis der Urinkontrolle suchtverdächtiger Personen fast ausschließlich der Fall ist, nur in geringeren Konzentrationen (unter 75g je 10 ml oder 7,5 mg je Liter) im Harn enthalten sind.Um möglichst alle Opiate und deren Derivate durch eine kurze Voruntersuchung auch in geringsten Mengen nachweisbar zu machen und dadurch eine rasche Entscheidung über die weitere Untersuchung möglich zu machen bzw. einwandfrei negativ reagierende Urine ausscheiden zu können, wurde eine neue Schnellmethode entwickelt. Diese Methode kann in einfacher, zeitsparender Weise mit der Prüfung nach Deckert verbunden werden und beruht auf charakteristischen Trübungsreaktionen mit den Halogenen Brom und Jod. Bei der Durchführung der Reaktionen in essigsaurem Medium wird durch Anwendung von Brom- und Jodlösungen bestimmter Zusammensetzung, je nachdem, ob dieselben einzeln oder zugleich den nach Deckert hergestellten Extraktlösungen hinzugefügt werden, nicht nur eine zuverlässige Anzeige, sondern auch eine gewisse Differenzierung der einzelnen Alkaloide ermöglicht. Die Empfindlichkeit der Reaktionen ist ausreichend groß, so daß mit einer Urinmenge von 20 ml — bzw. 10 ml bei allgemeiner Opiatanzeige mit beiden Halogenen zugleich — das Auslangen gefunden wird.Mit normalen, opiatfreien Urinen werden einwandfreie Blindproben erhalten, welche sich auch von den schwach positiven Befunden deutlich unterscheiden und dadurch eine große Sicherheit in der Anzeige geringster Opiatgehalte bedingen.Bei der Überprüfung des Verhaltens einer größeren Zahl von Arzneistoffen konnte festgestellt werden, daß eine Vortäuschung von Opiaten durch diese Stoffe nicht zu befürchten ist. Die als Störsubstanzen in Betracht kommenden Analgetica Polamidon, Dolantin und mit Einschränkung auch Cliradon sind ebenso wie Chinin leicht und rasch durch die Reaktion mit Bromkresolgrün zu erkennen. Die Halogenmethode besitzt demnach einen bedeutenden Grad von Spezifität. 相似文献
105.
106.
Wolfgang Scherer Prof. Dr. Christoph Hauf Dipl.‐Phys. Manuel Presnitz Dipl.‐Phys. Ernst‐Wilhelm Scheidt Dr. Georg Eickerling Dr. Volker Eyert Dr. Rolf‐Dieter Hoffmann Dr. Ute C. Rodewald Dipl.‐Ing. Adrienne Hammerschmidt Dr. Christian Vogt Dr. Rainer Pöttgen Prof. Dr. 《Angewandte Chemie (International ed. in English)》2010,49(9):1578-1582
107.
108.
Dr. Michael Peter Mercer Sam Affleck Dr. Edgardo Maximiliano Gavilán-Arriazu Dr. Alana Aragón Zülke Dr. Philip A. Maughan Shivam Trivedi Prof. Maximilian Fichtner Dr. Anji Reddy Munnangi Prof. Ezequiel P. M. Leiva Prof. Harry Ernst Hoster 《Chemphyschem》2022,23(5):e202100748
Sodium-ion batteries (NIBs) utilize cheaper materials than lithium-ion batteries (LIBs) and can thus be used in larger scale applications. The preferred anode material is hard carbon, because sodium cannot be inserted into graphite. We apply experimental entropy profiling (EP), where the cell temperature is changed under open circuit conditions. EP has been used to characterize LIBs; here, we demonstrate the first application of EP to any NIB material. The voltage versus sodiation fraction curves (voltage profiles) of hard carbon lack clear features, consisting only of a slope and a plateau, making it difficult to clarify the structural features of hard carbon that could optimize cell performance. We find additional features through EP that are masked in the voltage profiles. We fit lattice gas models of hard carbon sodiation to experimental EP and system enthalpy, obtaining: 1. a theoretical maximum capacity, 2. interlayer versus pore filled sodium with state of charge. 相似文献
109.
Michael I. Bruce Ernst Horn Janis G. Matisons Michael R. Snow 《Journal of organometallic chemistry》1985,286(2):271-287
The reactions of Os3(μ-H)2(CO)10 with a series of Group IB metal acetylide-tertiary phosphine complexes are described. Whereas the compounds M(C2C6F5)(PPh3) (M = Cu, Ag, Au) afforded the complexes MOs3(μ-CHCHC6F5)(CO)10(PPh3) cleanly and in high yield, complex mixtures of products were obtained from reactions of the analogous phenylacetylides. The complexes MOs3(μ-CHCHPh)(CO)10(PPh3), MOs3(μ-CHCHPh)(CO)9(PPh3)2 and MOs3(μ-H)(CO)10(PPh3) (of known structure), and MOs3(μ-CHCHPh)(CO)9(PPh3)2 and HMOs3(CHCPh)(CO)8 (of unknown structure) were characterised; Au(C2Ph)(PMe3) afforded similar derivatives. The reactions proceed by oxidative-addition and hydrogen migration steps; MP bond cleavage reactions also occur to a small extent. The molecular structures of AuOs3(μ-CHCHC6R5)(CO)10(PPh3) (R = F or H) were determined by X-ray analyses. For R = F, crystals are triclinic, space group P with a 9.081(2), b 13.291(2), c 17.419(2) Å, α 84.49(1), β 76.20(2), γ 75.81(2)° and Z = 2; 4622 observed data [I > 2.5σ(I)] were refined to R = 0.027, RW = 0.031. For R = H, crystals are triclinic, space group P, with a 9.403(4), b 13.448(3), c 13.774(4) Å, α 83.34(2), β 88.66(3), γ 70.21(3)°, and Z = 2; 4405 observed data [I > 2.5σ(I)] were refined to R = 0.030, RW = 0.033. The two molecules differ in the orientation of the Ph rings of the PPh3 groups, but are otherwise similar to Os3(μ-H)(μ-CHCHBut)(CO)10 with the μ-H ligand replaced by the isolobal μ-Au(PPh3) group. 相似文献
110.
Computerized quantification of components under overlapping chromatographic peaks is done by calibration of chromatograms against component mixtures. For conventional (single-channel) detectors, the limitations of earlier methods based on ordinary multiple regression, can be circumvented by data reduction with the aid of principal component analysis with the partial least-squares approach. Simulation studies show that the method can be applied even when there is severe peak overlap, unstable baseline, noisy chromatograms or non-linear detector response. Advantages in the quantification of fused peaks by means of multichannel detectors are outlined. Present limitations on the quantitative evaluation of several overlapping component peaks from a single spectro-chromatogram by means of the partial least-squares method combined with multiple regression on the pure component spectra, are discussed with respect to practical high-performance liquid chromatography. 相似文献