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21.
A new tricarborane building block based on pentaerythritol was prepared for applications in boron neutron capture therapy (BNCT). Its X-ray single-crystal structure revealed a high degree of steric congestion. To enable the attachment of the building block to other moieties, a succinimidyl linker has been introduced at the focal point, and a generation-2 hexacarborane-containing dendron carrying 60 boron atoms has been prepared using a 2,2-bis(hydroxymethyl)propionic acid core. 相似文献
22.
Olga V. Dorofeeva Inna N. Kolesnikova Ilya I. Marochkin Oxana N. Ryzhova 《Structural chemistry》2011,22(6):1303-1314
Gas-phase enthalpies of formation of 122 relatively large organic molecules with up to 15 non-hydrogen atoms have been calculated
at the Gaussian-4 (G4) level of theory using the atomization reaction procedure. The calculated values were compared with
experimental data published mainly last years. Particular attention has been given to nitro compounds and nitrogen, oxygen,
and sulfur containing heterocyclic compounds. The expected accumulation of systematic errors as the molecular size increases
was not observed with increasing the number of non-hydrogen atoms from 6 to 15. The largest mean absolute deviation between
experimental and G4 enthalpies of formation, 10.7 kJ/mol, was revealed for nitro compounds. All theoretical values for nitro
compounds were underestimated by 5–15 kJ/mol. The best agreement with experiment with mean absolute deviation of 4.5 kJ/mol
was observed for compounds which types were widely presented in the original test set of G4 method. The mean absolute deviations
for nitrogen heterocycles (6.8 kJ/mol) and oxygen and sulfur heterocycles (9.1 kJ/mol) are noticeably larger. Experimental
enthalpies of formation of four compounds (N,N-dinitromethanamine, 2,3,5,6-tetrachloronitrobenzene, 2-methyl-2H-tetrazole, and proline) were suggested to be unreliable from comparison with the G4 values calculated from atomization energies
and isodesmic reactions. 相似文献
23.
Ilya V. Mishakov Ekaterina V. Ilyina Alexander F. Bedilo Aleksey A. Vedyagin 《Reaction Kinetics and Catalysis Letters》2009,97(2):355-361
Nanocrystalline aerogel VOx/MgO catalysts for the oxidative dehydrogenation of propane with high surface area and uniform vanadium distribution were
synthesized by co-gelation followed by supercritical drying. The catalysts were shown to have superior performance compared
to nanocrystalline VOx/MgO catalysts prepared by impregnation. 相似文献
24.
Dmitri V. Konarev Alexey V. Kuzmin Salavat S. Khasanov Alexey A. Goryunkov Victor A. Brotsman Ilya N. Ioffe Akihiro Otsuka Hideki Yamochi Hiroshi Kitagawa Rimma N. Lyubovskaya 《化学:亚洲杂志》2019,14(11):1958-1964
Radical anion salt {cryptand[2.2.2] (K+)}2(bispheroid)2??3.5C6H4Cl2 ( 1 ) of the double‐caged fullerene C60 derivative, in which fullerene cages are linked by a cyclobutane bridging cycle and additionally by a pyrrolizidine moiety, was obtained. Each fullerene cage in this derivative accepts one electron on reduction, thus forming the (bispheroid)2? dianions with two interacting S=1/2 spins on the neighboring cages. Low‐temperature magnetic measurements reveal a singlet ground state of the bispheroid dianions whereas triplet contributions prevail at increased temperature. An estimated exchange interaction between two spins J/kB=?78 K in 1 indicates strong magnetic coupling between them, nearly two times higher than that (J/kB=?44.7 K) in previously studied (C60?)2 dimers linked via a cyclobutane bridge only. The enhancement of magnetic coupling in 1 can be explained by a shorter distance between the fullerene cages and, possibly, an additional channel for the magnetic exchange provided by a pyrrolizidine bridge. Quantum‐chemical calculations of the lowest electronic state of the dianions by means of multi‐configuration quasi‐degenerate perturbation theory support the experimental findings. 相似文献
25.
Bhatt AI May I Volkovich VA Collison D Helliwell M Polovov IB Lewin RG 《Inorganic chemistry》2005,44(14):4934-4940
The reduction of selected lanthanide cations to the zerovalent state in the room-temperature ionic liquid [Me3N(n)Bu][TFSI] is reported (where TFSI = bistriflimide, [N(SO2CF3)2]-). The lanthanide cations were introduced to the melt as the TFSI hydrate complexes [Ln(TFSI)3(H2O)3] (where Ln = La(III), Sm(III) or Eu(III)). The lanthanum compound [La(TFSI)3(H2O)3] has been crystallographically characterized, revealing the first structurally characterized f-element TFSI complex. The lanthanide in all three complexes was shown to be reducible to the metallic state in [Me3N(n)Bu][TFSI]. For both the Eu and Sm complexes, reduction to the metallic state was achieved via divalent species, and there was an additional observation of the electrodeposition of Eu metal. 相似文献
26.
Gridnev ID Alberico E Gladiali S 《Chemical communications (Cambridge, England)》2012,48(16):2186-2188
The mechanism of asymmetric hydrogenation catalyzed by [Rh(NBD)((R)-PhenylBinepine)(2)]SbF(6)1 has been studied by NMR experiments and DFT computations. Either the low-temperature hydrogenation of the catalyst-substrate adduct 4 or the reaction of solvate dihydride 6 with MAC produced the hydrogenation product with over 99% ee (S). 相似文献
27.
Structures of Chlorinated Fullerenes,IPR C96Cl20 and Non‐classical C94Cl28 and C92Cl32: Evidence of the Existence of Three New Isomers of C96 下载免费PDF全文
Prof. Dr. Shangfeng Yang Tao Wei Song Wang Dr. Ilya N. Ioffe Prof. Dr. Erhard Kemnitz Prof. Dr. Sergey I. Troyanov 《化学:亚洲杂志》2014,9(11):3102-3105
Chlorination of various HPLC fractions of C96 with a mixture of VCl4 and SbCl5 at 340–360 °C and single‐crystal X‐ray diffraction study of the products led to the identification of three new IPR isomers of C96. The C96(175) isomer forms a stable chloride, C96(175)Cl20, while chlorides of two other new isomers, C96(114) and C96(80), undergo cage shrinkage yielding C94(NC1)Cl28 and C96(NC2)Cl32 with non‐classical (NC) cages. These two NC chlorides contain, respectively, one and two heptagons flanked by pairs of fused pentagons and are stabilized by chlorine attachment to the emerging pentagon–pentagon junctions. Thus, the number of the experimentally confirmed C96 isomers has reached nine, which corroborates the empirical rule that the C6n fullerenes exhibit particularly rich isomerism. 相似文献
28.
Irena Pankratov Sara Elhanany Sharona Henig Shunit Zaritsky Ivan Ostapenko Ilya Kuselman 《Accreditation and quality assurance》2010,15(8):459-466
A proficiency testing (PT) scheme was developed for a limited number of analytical laboratories participating in the analysis
of natural water in Israel. Three fit-for-intended-use reference materials (RMs) were prepared for a pilot PT from natural
water: RM-blank and two in-house reference materials (IHRMs) with seven analytes fortified to achieve different levels of
analyte concentrations. The measurands for the PT participants were the traceable spike values certified in the IHRMs, i.e.,
added mass concentrations of the analytes. The RM-blank and IHRMs were found to be homogeneous and stable over 11 days, the
time necessary for the experimental part of the PT. The RMs were distributed to the PT participants as unknown test items
similar to routine samples. The test results were evaluated using their deviations from the IHRM-certified values. Eight Israeli
laboratories took part in the interlaboratory comparison. Individual laboratory performance and metrological compatibility
of the PT results of the participants, as a local group of laboratories, were evaluated for every analyte. 相似文献
29.
30.
Konstantin N. Gavrilov Alexei A. Shiryaev Ilya V. Chuchelkin Sergey V. Zheglov Eugenie A. Rastorguev Vadim A. Davankov Armin Börner 《Tetrahedron: Asymmetry》2012,23(14):1052-1057
New P,P-bidentate diastereomeric diphosphoramidite chiral ligands with mixed stereogenic elements and a C1 backbone symmetry have been prepared from (Sa)- and (Ra)-1,1′-binaphthyl-2,2′-diol (BINOL) and (S)-N-benzyl-1-(pyrrolidin-2-yl)methanamine and are fully characterized. The use of these ligands provides up to 84% ee in the Pd-catalyzed asymmetric allylic substitution of (E)-1,3-diphenylallyl acetate and up to 95% ee in the Rh-catalyzed asymmetric hydrogenation of α-dehydrocarboxylic acid esters. The results indicate that the catalytic performance is highly affected by the axial chirality of the binaphthyl moieties of the ligand and the nature of the solvent. 相似文献