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101.
102.
Fabio Cesar Gozzo Marcos N. Eberlin 《Journal of the American Society for Mass Spectrometry》1995,6(7):554-563
Ion-molecule reactions of the mass-selected distonic radical cation +CH2-O-CH 2 · (1) with several heterocyclic compounds have been investigated by multiple stage mass spectro- metric experiments performed in a pentaquadrupole mass spectrometer. Reactions with pyridine, 2-, 3-, and 4-ethyl, 2-methoxy, and 2-n-propyl pyridine occur mainly by transfer of CH 2 +· to the nitrogen, which yields distonic N-methylene-pyridinium radical cations. The MS3 spectra of these products display very characteristic collision-induced dissociation chemistry, which is greatly affected by the position of the substituent in the pyridine ring. Ortho isomers undergo a δ-cleavage cyclization process induced by the free-radical character of the N-methylene group that yields bicyclic pyridinium cations. On the other hand, extensive CH 2 +· transfer followed by rapid hydrogen atom loss, that is, a net CH+ transfer, occurs not to the heteroatoms, but to the aromatic ring of furan, thiophene, pyrrole, and N-methyl pyrrole. The reaction proceeds through five- to six-membered ring expansion, which yields the pyrilium, thiapyrilium, N-protonated, and N-methylated pyridine cations, respectively, as indicated by MS3 scans. Ion 1 fails to transfer CH 2 +· to tetrahydrofuran, whereas a new α-distonic sulfur ion is formed in reactions with tetrahydrothiophene. Unstable N-methylene distonic ions, likely formed by transfer of CH 2 +· to the nitrogen of piperidine and pyrrolidine, undergo rapid fragmentation by loss of the α-NH hydrogen to yield closed-shell immonium cations. The most thermodynamically favorable products are formed in these reactions, as estimated by ab initio calculations at the MP2/6-31G(d,p)//6-31G(d,p) + ZPE level of theory. 相似文献
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Marcos Juanes Rizalina Tama Saragi Cristbal Prez Luca Evangelisti Lourdes Enríquez Martín Jaraíz Alberto Lesarri 《Molecules (Basel, Switzerland)》2022,27(8)
Weakly-bound intermolecular clusters constitute reductionist physical models for non-covalent interactions. Here we report the observation of the monomer, the dimer and the monohydrate of 2-adamantanol, a secondary alcohol with a bulky ten-carbon aliphatic skeleton. The molecular species were generated in a supersonic jet expansion and characterized using broadband chirped-pulse microwave spectroscopy in the 2–8 GHz frequency region. Two different gauche-gauche O-H···O hydrogen-bonded isomers were observed for the dimer of 2-adamantanol, while a single isomer was observed for the monomer and the monohydrate. The experimental rotational parameters were compared with molecular orbital calculations using density functional theory (B3LYP-D3(BJ), B2PLYP-D3(BJ), CAM-B3LYP-D3(BJ), ωB97XD), additionally providing energetic and electron density characterization. The shallow potential energy surface makes the dimer an interesting case study to benchmark dispersion-corrected computational methods and conformational search procedures. 相似文献
105.
Dayanne Cristiane Mozaner Bordin Marcela Nogueira Rabelo Alves Eduardo Geraldo de Campos Bruno Spinosa De Martinis 《Journal of separation science》2016,39(6):1168-1172
Disposable pipette tips extraction consists of a solid‐phase extraction in which the sorbent is poorly dispersed in a pipette tip, which allows a quick and dynamic contact between the aspirated analyte from the sample and the solid phase. It is a technique used particularly in food and forensic analysis, since it requires a small amount of sample and solvent. This article highlights the principles, advantages and disadvantages of the disposable pipette tips extraction method and reviews recent applications. 相似文献
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Lana Mara Rodrigues dos Santos Philippe Michelon Marcos Nereu Arenales Ricardo Henrique Silva Santos 《Annals of Operations Research》2011,190(1):165-180
In this article we propose a 0-1 optimization model to determine a crop rotation schedule for each plot in a cropping area.
The rotations have the same duration in all the plots and the crops are selected to maximize plot occupation. The crops may
have different production times and planting dates. The problem includes planting constraints for adjacent plots and also
for sequences of crops in the rotations. Moreover, cultivating crops for green manuring and fallow periods are scheduled into
each plot. As the model has, in general, a great number of constraints and variables, we propose a heuristics based on column
generation. To evaluate the performance of the model and the method, computational experiments using real-world data were
performed. The solutions obtained indicate that the method generates good results. 相似文献
108.
da Silva Jussara Vieira Madurro Ana Graci Brito Madurro João Marcos 《Journal of Solid State Electrochemistry》2017,21(7):2129-2139
Journal of Solid State Electrochemistry - This paper reports a new platform for oligonucleotide hybridization, prepared by electropolymerization of 3-hydroxyphenylacetic acid onto gold electrode... 相似文献
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