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81.
Garnick Kelly Wetherby Anthony E. Sweeney Brian Scott Thomas A. Wei Cong 《Journal of Radioanalytical and Nuclear Chemistry》2021,330(3):979-984
Journal of Radioanalytical and Nuclear Chemistry - A rapid analytical method for quantifying 90Sr in infant formula prior to secular equilibrium is presented. The approach is dependent on the use... 相似文献
82.
Campbell Keri Judge Elizabeth J. Dirmyer Matthew R. Kelly Dan Czerwinski Ken 《Journal of Radioanalytical and Nuclear Chemistry》2017,313(1):197-206
Journal of Radioanalytical and Nuclear Chemistry - We report a study of a fast radiochemical method to determine the activity of 131I via the radiochemical recovery obtained with a 129I tracer.... 相似文献
83.
Chong Han Sean M. Kelly Theresa Cravillion Scott J. Savage Tina Nguyen Francis Gosselin 《Tetrahedron》2019,75(32):4351-4357
An efficient synthesis of PI3K inhibitor GDC-0077, featuring two consecutive Cu-catalyzed CN coupling reactions, is reported. The described synthetic route involves a chemoselective Ullmann-type coupling of a chiral difluoromethyl-substituted oxazolidinone, a Cu-catalyzed N-arylation of l-alanine with high stereochemical integrity, and a high-yielding final amide bond formation step to produce GDC-0077 in >99.5 area % HPLC purity. 相似文献
84.
85.
The rate of reduction of nitrite by trimethylamine-borane was followed by observing the decrease in nitrite absorbance under pseudo-first-order conditions. The reaction is acid-catalyzed and exhibits a first-order dependence on both amine-borane and total nitrite concentration. The molar equivalence of NaNO(2) to (CH(3))(3)NBH(3) = 2:1. Equimolar amounts of hydrogen and nitrous oxide are formed, and the molar ratio of nitrite reacted to N(2)O produced is 2:1. In concentrated HCl or H(2)SO(4), a correlation of rate with the Hammett acidity function, h(o), is observed. The reaction is subject to a pronounced inversesolvent isotope effect (k(D)()2(O)/k(H)()2(O) approximately 2.7) and a modest normal substrate effect (k((CH)()3())()3(N.BH)()3/k((CH)()3())()3(N.BD)()3 approximately 1.4). The reaction is first-order in H(3)O(+) in the region pH 0.7-2.7, but a second-order dependence is observed above pH 4 with the transition occurring at pH approximately pK(a) for HNO(2). Results are consistent with a mechanistic model involving preequilibration protonation of molecular nitrous acid followed by rate-limiting hydride attack on H(2)ONO(+) or free NO(+) to produce nitrosyl hydride as a reactive intermediate. 相似文献
86.
Simon J. Coles Michael B. Hursthouse David G. Kelly Andrew J. Toner Neil M. Walker 《Journal of organometallic chemistry》1999,580(2):11367
[TiCl2(salen)] (1) reacts with AlMe3 (1:2) to give the heterometallic Ti(III) and Ti(IV) complexes [Ti{(μ-Cl)(AlMe2)}{(μ-Cl)(AlMe2X)}(salen)] (X=Me or Cl) (2) and [TiMe{(μ-Cl)(AlCl2Me)}(salen)] (3). Addition of diethyl ether to 3 affords [Ti(Me)Cl(salen)] (4). The analogous reaction of [TiBr2(salen)] (5) gives the crystallographically characterised [Ti{(μ-Br)(AlMe2)}{(μ-Br)(AlMe2X)}(salen)] (X=Me or Br) (6) and [Ti(Me)Br(salen)] (7) in a single step, whilst the comparable reaction of [TiCl2{(3-MeO)2salen}] (8) with AlMe3 yields [Ti(Me)Cl{(3-MeO)2salen}] (9) with no evidence of titanium(III) species. Reactivity of both halide and methyl groups of 4 has been probed using magnesium reduction, SbCl5 and AgBF4 halide abstraction and SO2 insertion reactions. Hydrolysis of [Ti(Me)X(L)] complexes affords μ-oxo species [TiX(L)]2(μ-O) [X=Cl, L=salen (13); X=Br, L=salen (14); X=Cl, L=(3-MeO)2salen (15)]. 相似文献
87.
M R Winchester W R Kelly J L Mann W F Guthrie B S MacDonald G C Turk 《Fresenius' Journal of Analytical Chemistry》2001,370(2-3):234-240
The S mass fractions of coal SRMs 2682b, 2684b, and 2685b are certified by direct comparison with coal SRMs 2682a, 2684a, and 2685a, respectively, using high-temperature combustion analysis with infrared (IR) absorption detection. The S mass fractions of the "a" materials used for calibration were previously determined by means of isotope-dilution thermal-ionization mass spectrometry (ID-TIMS). Therefore, the comparisons performed with the combustion-IR absorption method establish direct traceability links to accurate and precise ID-TIMS measurements. The expanded uncertainties associated with the certified S mass fractions are of approximately the same magnitude as would be expected for the ID-TIMS methodology. An important aspect of these certifications is that each "b" material is essentially identical with the corresponding "a" material, because both were produced from the same bulk, homogenized coal. As a test of the efficacy of the new certification approach when calibrant and unknown are not identical, the S mass fraction of coal SRM 2683b has been determined by direct comparison to coal SRM 2683a. These two coals, which have both previously been analyzed with ID-TIMS, are different in terms of S content and other properties. Whereas the S mass fraction for SRM 2683b determined with the new methodology agrees statistically with the ID-TIMS value, there is reason for caution in such cases. In addition to the usefulness of the alternative approach for certification activities within NIST, this approach might also be an excellent way of establishing NIST traceability during the value assignment process for reference materials not issued by NIST. Further research is needed, however, to understand better the scope of applicability. 相似文献
88.
R Kaul A R Angeles M J?ger E T Powers J W Kelly 《Journal of the American Chemical Society》2001,123(22):5206-5212
To probe the conformational requirements of loop 1 in the Pin1 WW domain, the residues at the i + 2 and i + 3 positions of a beta-turn within this loop were replaced by dPro-Gly and Asn-Gly, which are known to prefer the conformations required at the i + 1 and i + 2 positions of type II' and type I' beta-turns. Conformational specificity or lack thereof was further examined by incorporating into the i + 2 and i + 3 positions a non-alpha-amino acid-based beta-turn mimetic (4-(2'-aminoethyl)-6-dibenzofuran propionic acid residue, 1), which was designed to replace the i + 1 and i + 2 positions of beta-turns. All these Pin WW variants are monomeric and folded as discerned by analytical ultracentrifugation, NMR, and CD. They exhibit cooperative two-state transitions and display thermodynamic stability within 0.5 kcal/mol of the wild-type WW domain, demonstrating that the acquisition of native structure and stability does not require a specific sequence and, by extension, conformation within loop 1. However, it could be that these loop 1 mutations alter the kinetics of antiparallel beta-sheet folding, which will be addressed by subsequent kinetic studies. 相似文献
89.
Kelly SD Heaton KD Brereton P 《Rapid communications in mass spectrometry : RCM》2001,15(15):1283-1286
A rapid continuous-flow technique for quantitative determination of hydrogen isotope ratios in water and organic materials at natural abundance levels is described. Water and organic samples were reduced in a helium stream at temperatures in excess of 1000 degrees C over chromium metal. delta(2)H per thousand values of water and organic samples were determined by calibration against International Atomic Energy Agency reference materials V-SMOW and SLAP water. The accuracy of the method was demonstrated through the analysis of the intermediate water standard GISP and IAEA water intercomparison materials OH-1, OH-2 and OH-3. Values obtained using this technique compared well with reference values (maximum difference 2.2 per thousand). The precision of water analyses was less than 2.3 per thousand (1 sigma or 1 standard deviation) in all cases. No apparent memory effect was observed when measuring samples at the natural abundance level. The application of the technique to organic molecules and the salts of organic acids was successfully demonstrated by measuring the delta(2)H per thousand values of an n-hexadecane laboratory reference and anhydrous calcium formate versus water calibration materials. Copyright Crown copyright 2001. Reproduced with permission of the Controller of Her Majesty's Stationery Office. Published by John Wiley & Sons, Ltd. 相似文献
90.
Zhou J Kelly WL Bachmann BO Gunsior M Townsend CA Solomon EI 《Journal of the American Chemical Society》2001,123(30):7388-7398
Using a single ferrous active site, clavaminate synthase 2 (CS2) activates O(2) and catalyzes the hydroxylation of deoxyguanidinoproclavaminic acid (DGPC), the oxidative ring closure of proclavaminic acid (PC), and the desaturation of dihydroclavaminic acid (and a substrate analogue, deoxyproclavaminic acid (DPC)), each coupled to the oxidative decarboxylation of cosubstrate, alpha-ketoglutarate (alpha-KG). CS2 can also catalyze an uncoupled decarboxylation of alpha-KG both in the absence and in the presence of substrate, which results in enzyme deactivation. Resting CS2/Fe(II) has a six-coordinate Fe(II) site, and alpha-KG binds to the iron in a bidentate mode. The active site becomes five-coordinate only when both substrate and alpha-KG are bound, the latter still in a bidentate mode. Absorption, CD, MCD, and VTVH MCD studies of the interaction of CS2 with DGPC, PC, and DPC provide significant molecular level insight into the structure/function correlations of this multifunctional enzyme. There are varying amounts of six-coordinate ferrous species in the substrate complexes, which correlate to the uncoupled reaction. Five-coordinate ferrous species with similar geometric and electronic structures are present for all three substrate/alpha-KG complexes. Coordinative unsaturation of the Fe(II) in the presence of both cosubstrate and substrate appears to be critical for the coupling of the oxidative decarboxylation of alpha-KG to the different substrate oxidation reactions. In addition to the substrate orientation relative to the open coordination position on the iron site, it is hypothesized that the enzyme can affect the nature of the reactivity by further regulating the binding energy of the water to the ferrous species in the enzyme/succinate/product complex. 相似文献