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341.
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344.
An attempted synthesis of the tricyclic peptidomimetic 1, designed to imitate a beta-turn tripeptide in tendamistat, afforded instead the 6,6,8-ring system of 2. The key step in the synthesis entailed acylation of the hindered alpha,alpha'-disubstituted morpholine 4.2, which was approached by acylative ring opening of the 3,6-oxazabicyclo[4.2.0]octane 4.3. However, transannular rather than exocyclic cleavage occurred, giving the 1,6-oxazacyclooctane isomer 4.5. Subsequent ring closures to form the bi- and tricyclic intermediates 7.3 and 8.5 were difficult because of the strain being built into the ring systems. After completion of the synthesis, the structures of the intermediates and final product were elucidated by NMR, with three-bond, heteronuclear multiple-bond correlation experiments providing unambiguous evidence for the ring connectivity, and by molecular modeling, which allowed assignment of the stereochemistry. Compound 2 is a modest inhibitor of the target enzyme alpha-amylase (K(i) = 170 &mgr;M in 5% DMSO/water), binding with similar affinity to the tripeptide Ac-Trp-Arg-Tyr-OMe. Although the side-chain attachment points in the ring system of 2 correspond closely to the relative Calpha-positions in tendamistat (rmsd = 0.24 ?), the alignment of the Calpha-Cbeta bonds is poor, illustrating the importance of side-chain orientation in a peptidomimetic. 相似文献
345.
Marisa Mena 《Tetrahedron》2005,61(34):8264-8270
Syntheses of enantiopure 3-acetoxy-2-methyldecahydroquinolines are accomplished by coupling cyclohexenyllithium 3 with α-amino epoxides and an aminocyclization of 2-(3-aminoalkyl)cyclohexenones (i.e., 5 and 9) as the key steps. The procedure allows the incorporation of alkyl substituents at C(5) to give enantiopure 2,3,5-trisubstitued decahydroquinolines. 相似文献
346.
Baldini M Belicchi-Ferrari M Bisceglie F Dall'aglio PP Pelosi G Pinelli S Tarasconi P 《Inorganic chemistry》2004,43(22):7170-7179
New alpha-ketoglutaric acid thiosemicarbazone (H(3)ct) derivatives and their copper complexes were synthesized and characterized by analytical and spectroscopic (IR and NMR) methods. For two of the ligands, Me-H(3)ct and Allyl-H(3)ct, and for a complex, [Cu(Me-Hct)(OH(2))](n) x 2nH(2)O, the X-ray structures were also determined. In the latter the copper atom shows a 4 + 1 pyramidal coordination, a water oxygen appears in the apical position, and three of the basal positions are occupied by the SNO tridentate ligand and the fourth by a carboxylic oxygen of an adjacent molecule that gives rise to a polymeric chain. DNA binding constants were determined, and studies of thermal denaturation profiles and nuclease activity were also performed. Tests in vitro on human leukemia cell line U937 were carried out on cell growth inhibition, cell cycle, and apoptosis induction. 相似文献
347.
Marisa Scrocco 《Chemical physics letters》1979,61(3):453-456
Satellite structure has been observed at about 3.1, 5.4, 6.4 and 14.5 eV below the main peaks in the X-ray photoelectron spectra of the Ti and O levels of TiO2. These satellites arise from transitions, accompanying primary photoemission, between predominantly O2p states of the ligand and various excited states in the conduction band. The energies found fit the transitions calculated by Daude et al. for an electronic band structure calculated by a combined tight-binding and pseudopotential method. 相似文献
348.
349.
Giuliano Alagona Renzo Cimiraglia Eolo Scrocco Jacopo Tomasi 《Theoretical chemistry accounts》1972,25(1):103-119
The conformation energies for monohydrated associates M · H2O, where M stands for oxirane, aziridine, oxaziridine and cyclopropene, have been obtained by using an electrostatic method, tested in a preceding paper, which relies on SCF molecular potentials calculated exactly. Stable associates have been found in the heterogroup region as well as near the bent bonds (single or double).A discussion is made on the errors in calculating thermodynamic properties for such associates in gas phase by using a priori calculations. As a numerical example the free energy change in the association process is compared for two monohydrated associates of aziridine.
Zusammenfassung Die Konformationsenergien für Anlagerungsverbindung M · H2O, wobei M für Oxiran, Aziridin, Oxaziridin und Cyclopropen steht, werden mit einer elektrostatischen Methode berechnet. Dieses Verfahren wurde in einer vorhergehenden Veröffentlichung getestet und beruht auf exakt berechneten SCF-Molekülpotentialen. Stabile Anlagerungsverbindungen wurden für Konformationen gefunden, bei denen das Wassermolekül in der Nähe der Heterogruppe oder der gezogenen Einfach- oder Doppelbindung liegt. Die Fehler bei der Berechnung thermodynamischer Eigenschaften für derartige Anlagerungsverbindungen in der Gasphase werden abgeschätzt. Als ein numerisches Beispiel wird die Differenz der freien Energie bei der Anlagerung für zwei Anlagerungsverbindungen von Aziridin und Molekül Wasser verglichen.相似文献
350.
Fontana José D. Joerke Cassandra G. Baron Madalena Maraschin Marcelo Ferreira Antonio G. Torriani Iris Souza A. M. Soares Marisa B. Fontana Milene A. Guimaraes Manoel F. 《Applied biochemistry and biotechnology》1997,(1):327-338
Since natural substances like pseudoxanthins exert a positive effect on the cellulogenic ability ofAcetobacter xylinum when producing cellulosic pellicles suitable for skin burn therapy, new defined and complex modulators were sought. Ca2+ and Mg2+ (4 mM) were strongly stimulatory. Na+ had no effect and K+ was inhibitory. Ammonium dihydrogen phosphate (0.12 g/L) ensured the same nitrogen supply as the same concentration of yeast
extract as measured by cellomembrane dry wt./yield albeit higher yeast extract supplies produced thicker membranes. Corn steep
liquor (CSL) was also progressively beneficial from 0.125 to 0.5 mL/L, and this yield could be further improved by the combination
of CSL with a tea infusion (source of caffeine). Uridine (precursor for UDP-Glc, sugar donor in cellulose biosynthesis), guanine,
guanosine, and its butirylated derivatives (precursors for the positive modulator of cellulose synthetase, di-cGMP) resulted
in only moderate stimulation. Sodium phytate and betaine were also slightly stimulatory. The fibrilar product from a newAcetobacter isolate (Ax-M) was characterized as cellulose by comparison with the solid-state13C-NMR of algal cellulose. Its X-ray diffractogram was a confirmatory analysis. After incorporation of tamarind xyloglucan
to previously air-dried cellulosic pellicles, diffractometry displayed only slight differences. Mercerized (5M NaOH) fresh
cellulosic biofilms underwent drastic size reduction (3.5-fold), turning compact nut still flexible if maintained wet. 相似文献