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51.
52.
R C Chloupek R J Harris C K Leonard R G Keck B A Keyt M W Spellman A J Jones W S Hancock 《Journal of chromatography. A》1989,463(2):375-396
Two high-resolution tryptic maps have been developed for recombinant tissue plasminogen activator (rt-PA) that separate the expected 51 tryptic peptides. The trypsin digestion was performed after reduction and S-carboxymethylation of the protein. The high-performance liquid chromatographic separation of the tryptic peptides used a Nova-Pak C18 (5 microns) column with a mobile phase that contained 0.1% aqueous trifluoroacetic acid (TFA) or 50 mM sodium phosphate (pH 2.85) and a linear gradient of acetonitrile. A TFA solvent system was also used for re-purification and for characterization of the peptides isolated from the phosphate-based separation. All of the isolated peptides had compositions consistent with the sequence proposed for rt-PA. The identities of the glycopeptides were confirmed by lectin chromatography on concanavalin A-Sepharose. The mixture of tryptic peptides was also treated with endo-beta-N-acetylglucosaminidase H and peptide:N-glycosidase F to locate the position of either high mannose or complex oligosaccharides. These studies demonstrated that a high mannose oligosaccharide is attached to Asn-117 while complex carbohydrate side-chains are attached to Asn-184 and Asn-448. The residue Asn-184 is the site of optional glycosylation that results in the formation of two rt-PA variants that contain either two or three oligosaccharides. 相似文献
53.
Recent measurements show substantial differences in levels of Reynolds stress in otherwise nominally similar separations. No explanation for these differences is know, but it appears they are not associated with end effects. End effects appear to be significant only for unexpectedly small flow width. 相似文献
54.
Peroxy-benzoic acid residues have been attached to polystyrene resins with nominal crosslink ratios of 5–40%, and also to various commercially available silicas and aluminas. Chemical modification of the resins becomes increasingly difficult as the crosslink ratio is increased, although resistance to oxidative degradation by hydrogen peroxide in methanesulphonic acid is simultaneously enhanced. Two different linkages were employed for the binding of peroxy-acid groups to the inorganic oxide supports, one involving a direct silicon aromatic bond and the other with an ethylene bridge interposed. In both cases, the introduction of peroxy-acid groups proceeded with ease and without any apparent degradation although the loadings achieved were somewhat lower than with the resins, as anticipated. All the supported peroxyacids functioned as oxidants for tetrahydrothiophene, the 5% crosslinked species being the most effective of the resin bound acids. One macroreticular resin displayed partial selectivity in oxidizing the thioether to its sulphoxide rather than sulphone. The best of the inorganic oxide supported oxidants approached closely to the reactivity shown by the 5% crosslinked resin; a mixed silica/alumina support showed the highest selectivity for sulphoxide formation in the case when its bound peroxy-acid was attached by a direct silicon aromatic bond. 相似文献
55.
J. S. Morris M. F. Smith R. E. Morrow E. D. Heimann J. C. Hancock T. Gall 《Journal of Radioanalytical and Nuclear Chemistry》1982,69(1-2):473-494
Interest in the element selenium with respect to its biological significance has been steadily increasing for the last ten
years. Neutron activation analysis has long been used for the accurate determination of selenium in biological samples usually
via75Se. More recently activation analysts having access to high flux reactors with rapid delivery pneumatic tube facilities; have
successfully employed77mSe. This approach, which is much faster, is particularly well suited to the Missouri University Research Reactor (MURR). The
specific interest concerning bulls has to do with the involvement of selenium in the reproductive system. Selenium analysis
methodology and data on plasma, semen and 22 tissues from both beef and dairy bulls are presented. 相似文献
56.
57.
Magnetic fields were used to fashion permanently aligned microtubule arrays allowing formation of highly ordered platforms for assembly, separation, and single molecule motor studies. 相似文献
58.
[reaction: see text] Ortho-lithiation of (2R,4S,5R)-3,4-dimethyl-2-ferrocenyl-5-phenyl[1,3,2]oxazaphospholidine 2-oxide 2 was carried out with diastereoselectivity of >99%, affording a new and efficient way for introducing planar chirality into the ferrocene backbone. Various electrophiles were used to quench the lithiated species, showing the wide applicability of the new ortho-directing group and its potential to generate ligands for use in asymmetric catalysis. 相似文献
59.
Romain Bénéteau Anne Boussonnière Jean‐Christophe Rouaud Prof. Dr. Jacques Lebreton Dr. Jérôme Graton Prof. Dr. Denis Jacquemin Dr. Muriel Sebban Prof. Dr. Hassan Oulyadi Ghanem Hamdoun Dr. Amber N. Hancock Prof. Dr. Carl H. Schiesser Dr. Fabrice Dénès 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(14):4809-4824
α‐Bromo aluminium acetals are suitable substrates for Ueno–Stork‐like radical cyclisations affording γ‐lactols and acid‐sensitive methylene‐γ‐lactols in high yields. The mechanistic study herein sets the scope and limitation of this reaction. The influence of the halide (or chalcogenide) atom X (X=Cl, Br, I, SPh, SePh) in the precursors α‐haloesters, as well as influence of the solvent and temperature was studied. The structure of the aluminium acetal intermediates resulting from the reduction of the corresponding α‐haloesters has been investigated by low‐temperature 13C‐INEPT diffusion‐ordered NMR spectroscopy (DOSY) experiments and quantum calculations, providing new insights into the structures of these thermally labile intermediates. Oxygen‐bridged dimeric structures with a planar Al2O2 ring are proposed for the least hindered aluminium acetals, while monomeric structures seem to prevail for the most hindered species. A comparison against the radical cyclisation of aluminium acetals derived from allyl and propargyl alcohols with the parent Ueno–Stork has been made at the BHandHLYP/6‐311++G(d,p) level of theory, highlighting mechanistic similarities and differences. 相似文献
60.
Hancock G Horrocks SJ Ritchie GA Helden JH Walker RJ 《The journal of physical chemistry. A》2008,112(40):9751-9757
This paper demonstrates how a quantum cascade laser (QCL) in its intrapulse mode can provide a simple method for probing the products of a photolysis event. The system studied is the 266 nm photodissociation of CF3I with the CF3 fragments subsequently detected using radiation at approximately 1253 cm(-1) generated by a pulsed QCL. The tuning range provided by the frequency down-chirp of the QCL operated in its intrapulse mode allows a approximately 1 cm(-1) segment of the CF3 nu3 band to be measured following each photolysis laser pulse. Identification of features within this spectral region allows the CF3 ( v = 0) number density to be calculated as a function of pump-probe delay, and consequently the processes which populate and deplete this quantum state may be examined. Rate constants for the population cascade from higher vibrational levels into the v = 0 state, k 1, and for the recombination of the CF3 radicals to form C2F6, k2, are measured. The returned values of k1 = (2.3 +/- 0.34) x 10(-12) cm(3) molecule(-1) s(-1) and k2 = (3.9 +/- 0.34) x 10(-12) cm(3) molecule(-1) s(-1) are found to be in good agreement with reported literature values. 相似文献