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81.
Dr. Aaron R. Finney Dr. Sébastien Lectez Dr. Colin L. Freeman Prof. John H. Harding Dr. Stephen Stackhouse 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(37):8725-8740
A better understanding of the solution chemistry of the lanthanide (Ln) salts in water would have wide ranging implications in materials processing, waste management, element tracing, medicine and many more fields. This is particularly true for minerals processing, given governmental concerns about lanthanide security of supply and the drive to identify environmentally sustainable processing routes. Despite much effort, even in simple systems, the mechanisms and thermodynamics of LnIII association with small anions remain unclear. In the present study, molecular dynamics (MD), using a newly developed force field, provide new insights into LnCl3(aq) solutions. The force field accurately reproduces the structure and dynamics of Nd3+, Gd3+ and Er3+ in water when compared to calculations using density functional theory (DFT). Adaptive-bias MD simulations show that the mechanisms for ion pairing change from dissociative to associative exchange depending upon cation size. Thermodynamics of association reveal that whereas ion pairing is favourable, the equilibrium distribution of species at low concentration is dominated by weakly bound solvent-shared and solvent-separated ion pairs, rather than contact ion pairs, reconciling a number of contrasting observations of LnIII–Cl association in the literature. In addition, we show that the thermodynamic stabilities of a range of inner sphere and outer sphere coordination complexes are comparable and that the kinetics of anion binding to cations may control solution speciation distributions beyond ion pairs. The techniques adopted in this work provide a framework with which to investigate more complex solution chemistries of cations in water. 相似文献
82.
[reaction: see text] Glucuronyl iodide 1 has been studied in detail as a "disarmed" glycosyl donor. In a model reaction, using N-iodosuccinimide (NIS) as a promoter and 2-phenylethanol as acceptor, best results were obtained using NIS with I(2), followed by trimethylsilyltrifluoromethanesulfonate (TMSOTf). When a series of primary and secondary alcohols was glycosylated using these conditions, yields of 60-83% of beta-glucuronides were obtained. Various "nonheavy" metal salts also effectively catalyzed the model reaction but led to significant amounts of alpha-product with less reactive secondary alcohols. 相似文献
83.
Duncan A. J. Harding Eric G. Hope Gregory A. Solan John Fawcett 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(7):m321-m322
The reaction between carbonyl fluoride and [Ir(COD)(PPh3)2]BF4 (COD is cycloocta‐1,5‐diene) in dichloromethane solution affords the novel title iridium salt, [IrCl2(C18H15P)2(CO)2]BF4. The cation lies across a twofold rotation axis in the space group P21212 and its structure confirms the presence in a cis relationship of two metal‐bound chlorides, while the phosphine ligands occupy a trans pair of sites. The anion also lies across a twofold rotation axis, and the F atoms are disordered over two sets of sites. 相似文献
84.
I. Romanski I. Berkes D. E. Brown M. De Jesus R. Eder I. S. Grant E. Hagn P. Harding P. Herzog B. Hinfurtner B. Kastelein H. Postma J. Prinz P. Richards K. Schlösser N. J. Stone L. Vanneste E. Zech Nicole Isolde 《Hyperfine Interactions》1992,75(1-4):457-470
The methods of time-resolved and time-integral on-line nuclear orientation have been applied to study short lived nuclei with
the NICOLE facility (Nuclear Implantation into Cold On-Line Equipment) at ISOLDE-3 in CERN using beams of182–186Hg. The half-lives in these decay chains are of the order of seconds and therefore comparable to the spin-lattice relaxation
times of the nuclei in iron. As the relaxation rate depends strongly on the g-factor, g-factors of nuclei in the decay chains
can be deduced from the observation of the time evolution of γ-ray anisotropy. Using this technique the existence of an isomer
in184Au has been found and the g-factors of184Au,184mAu and182Au have been determined. Accurate half-lives have been extracted from the data.
Time-integral nuclear orientation has been observed for short lived as well as longer lived isotopes of the Hg decay chains.
From these measurements, after proper correction for incomplete relaxation, the magnetic moments of183mPt,183Ir and182Ir have been derived.
The applicability of the time-resolved nuclear orientation technique for nuclei far from stability and its possible limitations
is discussed. 相似文献
85.
86.
We show that the variety of ortholattices has the strong amalgamation property and that the variety of orthomodular lattices has the strong Boolean amalgamation property, i.e. that two orthomodular lattices can be strongly amalgamated over a common Boolean subalgebra. We give examples to show that the variety orthomodular lattices does not have the amalgamation property and that the variety of modular ortholattices does not even have the Boolean amalgamation property. We further show that no non-Boolean variety of orthomodular lattices which is generated by orthomodular lattices of bounded height can have the Boolean amalgamation property. 相似文献
87.
Ditopic symmetrical bis(pyridyl) ligands incorporating the chiral dibenzobicyclo[b,f][3.3.1]nona-5a,6a-diene-6,12-dione cleft have been synthesised and characterised by NMR spectroscopy, mass spectrometry and X-ray crystallography. The ligands, which incorporate pyridyl groups directly connected to the carbocyclic cleft core or via alkyne or phenyl linkers were accessed from palladium-catalysed coupling reactions of 2,8-dibromodibenzobicyclo[b,f][3.3.1]nona-5a,6a-diene-6,12-dione. X-ray crystal analyses show the interplanar angles between the two cleft aromatic rings in these molecules, which range from 97.80(3) to 109.80(4)°. 相似文献
88.
Lester MI Pond BV Marshall MD Anderson DT Harding LB Wagner AF 《Faraday discussions》2001,(118):373-85; discussion 419-31
A hydrogen-bonded complex composed of the OH and CO reactants has been identified along the OH + CO-->HOCO reaction pathway. IR action spectroscopy in the OH overtone region has been used to examine the vibrational modes of the linear OH-CO complex, including intermolecular bending modes that probe portions of the reaction path leading to HOCO. The spectroscopic measurements have accessed highly excited intermolecular levels, with energies up to 250 cm-1 above the zero-point level, which lie in close proximity to the transition state for reaction. The OH-CO binding energy, D0 < or = 430 cm-1, has also been established from the quantum state distribution of the OH fragments following vibrational predissociation of the OH-CO complex. Complementary electronic structure calculations have been performed to characterize the OH-CO and OH-OC complexes, the transition state for HOCO formation, and the direct reaction path that connects the experimentally observed OH-CO complex to the HOCO intermediate. 相似文献
89.
Barry CS Bushby N Harding JR Hughes RA Parker GD Roe R Willis CL 《Chemical communications (Cambridge, England)》2005,(29):3727-3729
Trapping intermediates on the Prins cyclisation pathway with carbon-based nucleophiles has given further insight into factors affecting the acid-mediated reactions of homoallylic alcohols with aldehydes, enabling the design of efficient syntheses of 4-hydroxy-2,6-disubstituted tetrahydropyrans. 相似文献
90.
Leeuwenburgh MA Litjens RE Codee JD Overkleeft HS van der Marel GA van Boom JH 《Organic letters》2000,2(9):1275-1277
[formula: see text] Tributyltin radical mediated cyclization of carbohydrate-derived beta-(alkynyloxy)acrylates leading to highly functionalized cis- and trans-fused bicyclic ethers of various ring sizes is described. The efficacy of the radical cyclization is nicely illustrated in the iterative construction of a trans-fused tricyclic tetrahydropyran. 相似文献