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31.
This study reports magnitudes and the orientation of the (13)C(alpha) chemical shift anisotropy (CSA) tensors of peptides obtained using quantum chemical calculations. The dependency of the CSA tensor parameters on the energy optimization of hydrogen atom positions and hydrogen bonding effects and the use of zwitterionic peptides in the calculations are examined. Our results indicate that the energy optimization of the hydrogen atom positions in crystal structures is necessary to obtain accurate CSA tensors. The inclusion of intermolecular effects such as hydrogen bonding in the calculations provided better agreement between the calculated and experimental values; however, the use of zwitterionic peptides in calculations, with or without the inclusion of hydrogen bonding, did not improve the results. In addition, our calculated values are in good agreement with tensor values obtained from solid-state NMR experiments on glycine-containing tripeptides. In the case of peptides containing an aromatic residue, calculations on an isolated peptide yielded more accurate isotropic shift values than the calculations on extended structures of the peptide. The calculations also suggested that the presence of an aromatic ring in the extended crystal peptide structure influences the magnitude of the delta(22) which the present level of ab initio calculations are unable to reproduce. 相似文献
32.
Renee J. Soukup-Hein Jeff Schneiderheinze Paul Mehelic Daniel W. Armstrong 《Chromatographia》2007,66(7-8):461-468
Previous work on the LC separation of peptides had shown that macrocyclic glycopeptide stationary phases to be selective for
peptides of five to thirteen amino acids in length. In this work, the selectivity of the teicoplanin stationary phase is compared
to that of a C18 stationary phase for seven diastereomeric enkephalin peptides. The teicoplanin stationary phase separated
all seven diastereomeric enkephalin peptides in a single chromatographic run. The insertion of d-amino acids into the primary enkephalin sequence produced areas of hydrophobicity that influenced retention order on the
C18 stationary phase. However, analogous trends are not observed on the teicoplanin stationary phase, which is more polar
and structurally diverse. Optimization of the mobile phase and the use of a step-gradient for the enkephalin separation on
the teicoplanin stationary phase is discussed. Also, the selectivity of macrocyclic glycopeptide stationary phases for peptides
of 14, 28, 30, and 36 amino acids also is investigated and compared to separation on a C18 stationary phase. A method for
eluting peptides with multiple basic amino acids, which tend to be strongly retained on the macrocyclic glycopeptide stationary
phases, is presented. 相似文献
33.
The electrochemical and spectroscopic properties of [Mn2(tpp)2(SO4)] (H2tpp=tetraphenylporphyrin=5,10,15,20‐tetraphenyl‐21H,23H‐porphine) were studied to characterize the stability of this compound as a function of solvent, redox state, and sulfate concentration. In non‐coordinating solvents such as 1,2‐dichloroethane, the dimer was stable, and two cyclic voltammetric waves were observed in the region for MnIII reduction. These waves correspond to reduction of the dimer to [MnII(tpp)] and [MnIII(tpp)(OSO3)]?, and reduction of [MnIII(tpp)(OSO3)]? to [MnII(tpp)(OSO3)]2?, respectively. In the coordinating solvent DMSO, [Mn2(tpp)2(SO4)] was unstable and dissociated to form [MnIII(tpp)(DMSO)2]+. A single voltammetric wave was observed for MnIII reduction in this solvent, corresponding to formation of [MnII(tpp)(DMSO)]. In non‐coordinating solvent systems, addition of sulfate (as the bis(triphenylphosphoranylidene)ammonium (PPN+) salt) resulted in dimer dissociation, yielding [MnIII(tpp)(OSO3)]?. Reduction of this monomer produced [MnII(tpp)(OSO3)]2?. In DMSO, addition of SO led to displacement of solvent molecules forming [MnIII(tpp)(OSO3)]?. Reduction of this species in DMSO led to [MnII(tpp)(DMSO)]. 相似文献
34.
35.
The multicanonical basin hopping (MUBH) method, which uses a multicanonical weight in the basin hopping (BH) Monte Carlo method, was found to be very efficient for global optimization of large-scale systems such as Lennard-Jones clusters containing more than 150 atoms. We have implemented an asynchronous parallel version of the MUBH method using the message passing interface (MPI) to take advantage of the full usage of multiprocessors in either a homogeneous or heterogeneous computational environment. Based on the intrinsic properties of the Monte Carlo method, this MPI implementation used the task parallelism to minimize interthread data communication. For a Co nanocluster consisting of N atoms, we have applied the asynchronous multicanonical basin hopping (AMUBH) method (for 181 < N < or = 200), together with BH (for 2 < or = N < 150) and MUBH (for 150 < or = N < or = 180), to search for the molecular configuration of the global energy minimum. AMUBH becomes the only practical computational scheme for locating the energy minimum within realistic computational time for a relatively large cluster. 相似文献
36.
Jeff Kahn 《Combinatorica》1992,12(4):417-423
Letn(k) be the least size of an intersecting family ofk-sets with cover numberk, and let
k
denote any projective plane of orderk–1.Theorem There is a constant A such that ifH is a random set ofm Aklogk lines from
k
then Pr(H<)0(k).Corollary
If there exists a
k
thenn(k)=O(klogk). These statements were conjectured by P. Erds and L. Lovász in 1973.Supported in part by NSF-DMS87-83558 and AFOSR grants 89-0066, 89-0512 and 90-0008 相似文献
37.
Rajendiran TM Kirk ML Setyawati IA Caudle MT Kampf JW Pecoraro VL 《Chemical communications (Cambridge, England)》2003,(7):824-825
Binuclear manganese complexes Mn2(III/IV)(dtsalpn)2DCBI, 1, Mn2(III/III)(dtsalpn)2HDCBI, 2, containing the ligand dicarboxyimidazole (DCBI) have been prepared in order to address the issue of imidazole bridged and ferromagnetically coupled Mn sites in high oxidation states of the OEC in Photosystem II (PS II). Temperature dependent magnetic susceptibility studies of 1 indicates that the interaction between the two Mn(III)/Mn(IV) ions is ferromagnetic (J = +1.4 cm(-1)). Variable temperature EPR spectra of 1 shows that a g = 2 multiline is as an excited state signal corresponding to S = 1/2. 相似文献
38.
Marcantonio KM Frey LF Liu Y Chen Y Strine J Phenix B Wallace DJ Chen CY 《Organic letters》2004,6(21):3723-3725
[reaction: see text] The palladium-catalyzed cyanation reaction is known to be sensitive to dissolved cyanide. Investigation into some causes of high levels of dissolved cyanide is presented here, along with a robust solution to this problem. 相似文献
39.
Giacalone F Segura JL Martín N Ramey J Guldi DM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(16):4819-4834
A series of donor-acceptor arrays (C60-oligo-PPV-exTTF; 16-20) incorporating pi-conjugated oligo(phenylenevinylene) wires (oligo-PPV) of different length between pi-extended tetrathiafulvalene (exTTF) as electron donor and C60 as electron acceptor has been prepared by multistep convergent synthetic approaches. The electronic interactions between the three electroactive species present in 16-20 were investigated by UV-visible spectroscopy and cyclic voltammetry (CV). Our studies clearly show that, although the C60 units are connected to the exTTF donors through a pi-conjugated oligo-PPV framework, no significant electronic interactions are observed in the ground state. Interestingly, photoinduced electron-transfer processes over distances of up to 50 Angstroms afford highly stabilized radical ion pairs. The measured lifetimes for the photogenerated charge-separated states are in the range of hundreds of nanoseconds (approximately 500 ns) in benzonitrile, regardless of the oligomer length (i.e., from the monomer to the pentamer). A different lifetime (4.35 micros) is observed for the heptamer-containing array. This difference in lifetime has been accounted for by the loss of planarity of the oPPV moiety that increases with the wire length, as established by semi-empirical (PM3) theoretical calculations carried out with 19 and 20. The charge recombination dynamics reveal a very low attenuation factor (beta = 0.01 +/- 0.005 Angstroms(-1)). This beta value, as well as the strong electron coupling (V approximately 5.5 cm(-1)) between the donor and the acceptor units, clearly reveals a nanowire behavior for the pi-conjugated oligomer, which paves the way for applications in nanotechnology. 相似文献
40.
Markus Follmann Nils Griebenow Michael G. Hahn Ingo Hartung Franz‐Josef Mais Joachim Mittendorf Martina Schfer Hartmut Schirok Johannes‐Peter Stasch Friederike Stoll Alexander Straub Peter Jeschke Ralf Nauen Michael Edmund Beck Hans‐Wilhelm Engels Hans‐Georg Pirkl Reinhard Albers Rolf W. Albach Jens Krause Andreas Hoffmann Holger Casselmann Jeff Dormish 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2013,125(36):9503-9503