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11.
Lakshman MK Ngassa FN Bae S Buchanan DG Hahn HG Mah H 《The Journal of organic chemistry》2003,68(15):6020-6030
Single-electron oxidation of the carcinogenic hydrocarbon benzo[a]pyrene (BaP) is thought to result in a radical cation intermediate and this species has been proposed to cause alkylation at the nitrogens of the purine nucleobases. Although several different nucleoside adducts have been isolated as arising from this mode of metabolic activation, there are no selective, total syntheses of the stable exocyclic amino group adducts formed by the single-electron oxidation of any hydrocarbon with the purine 2'-deoxynucleosides to date. In this paper we disclose the synthesis of the model adducts N(6)-(1-pyrenyl)-2'-deoxyadenosine and N(2)-(1-pyrenyl)-2'-deoxyguanosine as well as the first synthesis of the carcinogen-linked nucleoside derivatives N(6)-(6-benzo[a]pyrenyl)-2'-deoxyadenosine and N(2)-(6-benzo[a]pyrenyl)-2'-deoxyguanosine via a palladium-mediated C-N bond formation. Two different coupling strategies were attempted: coupling of an aryl bromide with a suitably protected nucleoside and the coupling of an arylamine with a suitable halonucleoside. The former had somewhat limited applicability in that only N(6)-(1-pyrenyl)-2'-deoxyadenosine was prepared by this method; on the other hand, the latter was more general. However, there are noteworthy differences in the amination reactions at the C-6 and C-2 positions. Reactions at the C-6 resulted in the competing formation of a 1:2 amine-nucleoside adduct in addition to the desired monoaryl nucleoside. Such a dimer formation was not observed at the C-2. The C-2 adducts, however, displayed an interesting conformational behavior. 相似文献
12.
The O2–N2 and O2–Ar negative-ion chemical ionization mass spectra of aromatic amines show a series of unusual ions dominated by an addition appearing at [M + 14]?˙. Other ions are observed at [M – 12]?˙, [M + 5]?˙, [M + 12]?˙, [M + 28]?˙ and [M + 30]?˙. Ion formation was studied using a quadrupole instrument equipped with a conventional chemical ionization source and a Fourier transform ion cyclotron resonance (FTICR) mass spectrometer. These studies, which included the examination of ion chromatograms, measurement of positive-ion chemical ionization mass spectra, variation of ion source temperature and pressure and experiments with 18O2, indicate that the [M + 14]?˙ ion is formed by the electron-capture ionization of analytes altered by surfaceassisted reactions involving oxygen. This conversion is also observed under low-pressure conditions following source pretreatment with O2. Experiments with [15N]aniline, [2,3,4,5,6-2H5] aniline and [13C6]aniline show that the [M + 14]?˙ ion corresponds to [M + O ? 2H]?˙, resulting from conversion of the amino group to a nitroso group. Additional ions in the spectra of aromatic amines also result from surface-assisted oxidation reactions, including oxidation of the amino group to a nitro group, oxidation and cleavage of the aromatic ring and, at higher analyte concentrations, intermolecular oxidation reactions. 相似文献
13.
Tapan Kumar Lal John F. Richardson Mark S. Mashuta Robert M. Buchanan Rabindranath Mukherjee 《Polyhedron》1997,16(24):1248-4336
Synthesis and characterization of a nitrite-bound copper(II) compound [CuL4)2(ONO)]ClO4 have been achieved (L4 = 2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine]. The bidentate ligand L4 provides a pyridine and a pyrazole donor site; however, they are separated by a methylene spacer. The complex has been structurally characterized and it belongs to only a handful of complexes having nitrito-bound mononuclear copper(II) centre. The metal atom has a distorted square pyramidal geometry with the copper atom displaced from the equatorial plane by 0.25 Å. In MeCN solution the green complex exhibits a broad ligand-field transition at 655 nm with a shoulder at 675 nm and in dichloromethane-toluene glass (80 K) it exhibits an EPR spectral feature characteristic of the unpaired electron in the dx2−y2 orbital. Variable-temperature (80–300 K) magnetic susceptibility measurements in the solid state as well as room temperature measurement in MeCN solution reveal mononuclear magnetically dilute copper(II) centre. When examined by cyclic voltammetry (MeCN solution) it displays electrochemically irreversible CuII---CuI response [cathodic peak potential, Epc (V vs saturated calomel electrode (SCE)): −0.32]. An oxidative response is observed at 1.14 V, probably due to bound-nitrite oxidation and is partially removed to generate a solvated complex at the electrode surface. The latter species gives rise to reversible CuII---CuI redox response [
]. 相似文献
14.
Mark S. Mashuta Lionel Cheruzel Robert M. Buchanan 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(10):o629-o631
Cocrystallization of a polyimidazole compound with boric acid results in the formation of the title compound, C15H21N7·B(OH)3, which has an extensive hydrogen‐bonding network. The O?N(im) separations (im is imidazole) range from 2.6991 (15) to 2.7914 (14) Å, with O—H?N angles ranging from 170.6 (18) to 175 (2)°. In addition, symmetry‐related boric acid molecules form intermolecular hydrogen bonds, with an O?O distance of 2.7582 (14) Å, and symmetry‐related imidazole groups form π–π stacks, with a centroid‐to‐centroid separation of 3.533 Å. 相似文献
15.
A. Breakstone C. D. Buchanan R. Campanini H. B. Crawley M. Cuffiani G. M. Dallavalle M. M. Deninno K. Doroba D. Drijard F. Fabbri A. Firestone H. G. Fischer H. Flöge H. Frehse W. M. Geist L. Gesswein G. Giacomelli R. Gokieli M. Gorbics M. Gorski P. Hanke M. Heiden D. Isenhower E. E. Kluge J. W. Lamsa T. Lohse R. Mankel W. T. Meyer T. Nakada M. Panter A. Putzer K. Rauschnabel B. Rensch F. Rimondi M. Schmelling G. P. Siroli J. Skeens R. Sosnowski M. Szczekowski O. Ullaland D. Wegener R. Yeung 《Zeitschrift fur Physik C Particles and Fields》1991,52(4):551-557
16.
Bobette D. Nourse Robert L. Hettich Michelle V. Buchanan 《Journal of the American Society for Mass Spectrometry》1993,4(4):296-305
Analytical Chemistry Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA Differentiation of the seven isomers of methyl guanine has been accomplished by monitoring gas-phase hydrogen/deuterium (H/D) exchange reactions of the protonated molecular ions with deuterium oxide (D2O) in a Fourier transform mass spectrometer. In each case a distinctive reaction rate for the first H/D exchange was observed, and exchanges of up to three deuterium atoms occurred with characteristic ion abundances that could be used to differentiate the isomers. O6-Methyl guanine, for example, showed only one slow H/D exchange with D2O, whereas l-methyl guanine exchanged two hydrogen atoms at a significantly faster rate. On comparison of the possible resonance structures of each protonated isomer with the experimental information about the number and rate of H/D exchanges observed, a reaction mechanism involving a concerted proton abstraction-deuterium cation donation was proposed. 相似文献
17.
Middleton CT Buchanan LE Dunkelberger EB Zanni MT 《The journal of physical chemistry letters》2011,2(18):2357-2361
We report that the waiting time delay in 2D IR pulse sequences can be used to suppress signals from structurally disordered regions of amyloid fibrils. At a waiting time delay of 1.0 ps, the random coil vibrational modes of amylin fibrils are no longer detectable, leaving only the sharp excitonic vibrational features of the fibril β-sheets. Isotope labeling with (13)C(18)O reveals that structurally disordered residues decay faster than residues protected from solvent. Since structural disorder is usually accompanied by hydration, we conclude that the shorter lifetimes of random-coil residues is due to solvent exposure. These results indicate that 2D IR pulse sequences can utilize the waiting time to better resolve solvent-protected regions of peptides and that local mode lifetimes should be included in simulations of 2D IR spectra. 相似文献
18.
Acid treatment of 2-(β-Benzoylethyl)-cyclopentanone (III) leads directly to a phenylcycloheptene carboxylic acid (VII) and the related lactone (XI), via a bicyclic intermediate. 相似文献
19.
Sporolides A and B: structurally unprecedented halogenated macrolides from the marine actinomycete Salinispora tropica 总被引:4,自引:0,他引:4
Buchanan GO Williams PG Feling RH Kauffman CA Jensen PR Fenical W 《Organic letters》2005,7(13):2731-2734
[structure: see text] Analysis of the fermentation broth of a strain of the marine actinomycete Salinispora tropica has led to the isolation of two unprecedented macrolides, sporolides A (1) and B (2). The structures and absolute stereochemistries of both metabolites were elucidated using a combination of NMR spectroscopy and X-ray crystallography. 相似文献
20.
A.B. Weerasekara M.B.M. Rinzan S.G. Matsik A.G.U. Perera M. Buchanan H.C. Liu G. von Winckel A. Stintz S. Krishna 《Infrared Physics & Technology》2007,50(2-3):194-198
Terahertz detection capability of an n-type heterojunction interfacial work function internal photoemission (HEIWIP) detector is demonstrated. Threshold frequency, f0, of 3.2 THz (93 μm) was obtained by using n-type GaAs emitter doped to 1 × 1018 cm−3 and Al0.04Ga0.96As single barrier structure. The detector shows a broad spectral response from 30 to 3.2 THz (10–93 μm) with peak responsivity of 6.5 A/W at 7.1 THz under a forward bias field of 0.7 kV/cm at 6 K. The peak quantum efficiency and peak detectivity are 19% and 5.5 × 108 Jones, respectively under a bias field of 0.7 kV/cm at 6 K. In addition, the detector can be operated up to 25 K. 相似文献