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101.
Prof. Dr. Oliver S. Wenger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(24):6043-6052
Ruthenium complexes with polypyridine ligands are very popular choices for applications in photophysics and photochemistry, for example, in lighting, sensing, solar cells, and photoredox catalysis. There is a long-standing interest in replacing ruthenium with iron because ruthenium is rare and expensive, whereas iron is comparatively abundant and cheap. However, it is very difficult to obtain iron complexes with an electronic structure similar to that of ruthenium(II) polypyridines. The latter typically have a long-lived excited state with pronounced charge-transfer character between the ruthenium metal and ligands. These metal-to-ligand charge-transfer (MLCT) excited states can be luminescent, with typical lifetimes in the range of 100 to 1000 ns, and the electrochemical properties are drastically altered during this time. These properties make ruthenium(II) polypyridine complexes so well suited for the abovementioned applications. In iron(II) complexes, the MLCT states can be deactivated extremely rapidly (ca. 50 fs) by energetically lower lying metal-centered excited states. Luminescence is then no longer emitted, and the MLCT lifetimes become much too short for most applications. Recently, there has been substantial progress on extending the lifetimes of MLCT states in iron(II) complexes, and the first examples of luminescent iron complexes have been reported. Interestingly, these are iron(III) complexes with a completely different electronic structure than that of commonly targeted iron(II) compounds, and this could mark the beginning of a paradigm change in research into photoactive earth-abundant metal complexes. After outlining some of the fundamental challenges, key strategies used so far to enhance the photophysical and photochemical properties of iron complexes are discussed and recent conceptual breakthroughs are highlighted in this invited Concept article. 相似文献
102.
Dr. James Jennings Dr. Erik J. Cornel Dr. Matthew J. Derry Dr. Deborah L. Beattie Dr. Matthew J. Rymaruk Oliver J. Deane Prof. Anthony J. Ryan Prof. Steven P. Armes 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(27):10940-10945
Polymerization-induced self-assembly (PISA) enables the scalable synthesis of functional block copolymer nanoparticles with various morphologies. Herein we exploit this versatile technique to produce so-called “high χ–low N” diblock copolymers that undergo nanoscale phase separation in the solid state to produce sub-10 nm surface features. By varying the degree of polymerization of the stabilizer and core-forming blocks, PISA provides rapid access to a wide range of diblock copolymers, and enables fundamental thermodynamic parameters to be determined. In addition, the pre-organization of copolymer chains within sterically-stabilized nanoparticles that occurs during PISA leads to enhanced phase separation relative to that achieved using solution-cast molecularly-dissolved copolymer chains. 相似文献
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Thomas Tennant Matthew C. Hulme Thomas B.R. Robertson Oliver B. Sutcliffe Ryan E. Mewis 《Magnetic resonance in chemistry : MRC》2020,58(12):1151-1159
Piperazine-based drugs, such as N-benzylpiperazine (BZP), became attractive in the 2000s due to possessing effects similar to amphetamines. Herein, BZP, in addition to its pyridyl analogues, 2-, 3-, and 4-pyridylmethylpiperidine (2-PMP, 3-PMP, and 4-PMP respectively) was subjected to the hyperpolarisation technique Signal Amplification By Reversible Exchange (SABRE) in order to demonstrate the use of this technique to detect these piperazine-based drugs. Although BZP was not hyperpolarised via SABRE, 2-PMP, 3-PMP, and 4-PMP were, with the ortho- and meta-pyridyl protons of 4-PMP showing the largest enhancement of 313-fold and 267-fold, respectively, in a 1.4-T detection field, following polarisation transfer at Earth's magnetic field. In addition to the freebase, 4-PMP.3HCl was also appraised by SABRE and was found not to polarise, however, the addition of increasing equivalents of triethylamine (TEA) produced the freebase, with a maximum enhancement observed upon the addition of 3 equivalents of TEA. Further addition of TEA led to a reduction in the observed enhancement. SABRE was also employed to polarise 4-PMP.3HCl (~20% w/w) in a simulated tablet to demonstrate the forensic application of the technique (138-fold enhancement for the ortho-pyridyl protons). The amount of 4-PMP.3HCl present in the simulated tablet was quantified via NMR using D2O as a solvent and compared well to complimentary gas chromatography–mass spectrometry data. Exchanging D2O for CD3OD as the solvent utilised for analysis resulted in a significantly lower amount of 4-PMP.3HCl being determined, thus highlighting safeguarding issues linked to drug abuse in relation to determining the amount of active pharmaceutical ingredient present. 相似文献
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The chemisorption of CO on W(100) at ~ 100K has been studied using a combination of flash desorption and electron stimulated desorption (ESD) techniques. This is an extension of a similar study made for CO adsorption on W(100) at temperatures in the range 200–300K. As in the 200–300 K CO layer, both α1-CO and α2-CO are formed in addition to more strongly bound CO species upon adsorption at ~ 100K; the α-CO states yield CO+ and O+ respectively upon ESD. At low CO coverages, the α1 and α2-CO states are postulated to convert to β-CO or other strongly bound CO species upon heating. At higher CO coverages, α1-CO converts to α2-CO upon thermal desorption or electron stimulated desorption. There is evidence for the presence of other weakly-bound states in the low temperature CO layer having low surface concentration at saturation. The ESD behavior of the CO layer coadsorbed with hydrogen on W(100) is reported, and it is found that H(ads) suppresses either the concentration or the ionic cross section for α1 and α2-CO states. 相似文献
109.
S.R. Bare K. Griffiths P. Hofmann D.A. King G.L. Nyberg N.V. Richardson 《Surface science》1982,120(2):367-375
Using both synchrotron and HeII radiation the electronic and geometric structure of Pt{110}-(2×1)p1g1 CO was examined. The shape resonance for the 4σ orbital of CO is found to be peaked at 38 eV, while that for the 5σ orbital is peaked at 28 eV. No shape resonance is observed from the 1π orbital. The ordering is reversed from that of gas phase CO. Further evidence, from the polar intensity variation of the non-bonding 4σ orbital, is presented for the tilted CO structure proposed previously. 相似文献
110.
Oliver Jenkinson 《Proceedings of the American Mathematical Society》2008,136(3):1023-1027
For an irrational number , let denote its -th continued fraction inverse complete quotient, obtained by deleting the first partial quotients. For any positive real number , we establish the optimal linear bound on the sum of the -th powers of the first complete quotients. That is, we find the smallest constants such that for all and all irrationals .