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991.
992.
The aggregation behavior of C60 fullerenes and C60 fullerenes with six symmetrically tethered poly(ethylene oxide) oligomers [(PEO)-6-C60] in aqueous solutions has been studied using implicit solvent molecular dynamics simulations. Our simulations reveal that while the attraction between two (PEO)-6-C60 fullerenes in aqueous solution is stronger and longer range than that between two bare C60 fullerenes, the (PEO)-6-C60 fullerenes do not phase-separate in water but rather aggregate in chain-like clusters at concentrations where unmodified fullerenes completely phase-separate. 相似文献
993.
Four fulvic acid dietary supplement samples were obtained for this study with the intention of investigating the elemental composition and association of fulvic acids found in fulvic acid supplements. This was achieved by coupling size-exclusion chromatography (SEC) sequentially with UV-vis and inductively coupled plasma mass spectrometric (ICP-MS) detectors. The combination of UV and ICP-MS offered highly sensitive and selective detection. This technique was used in the present study to initially investigate the chemical association of several different elements including, Cr, Co, Ca, Fe, I, Mg, Zn, Se, Cu, Mn, Mo, As, Hg, Pb, and Ag, by observing the elution profile of the fulvic acids obtained with UV detection and matching their retention times with the peaks measured with ICP-MS. The results found based on this type of analysis suggest that there was some association of the elements to the fulvic acids. It was also of interest to observe the stability of these complexes upon human digestion; therefore a gastric digestion was mimicked. In the fulvic acid dietary supplement samples studied, fulvic acids were present in the samples and there was elemental association based on the retention time overlap in the UV as well as the ICP-MS. The fulvic complexes found in the samples were of a low molecular weight As a result of the digestion the SEC-ICP-MS chromatographic profile in some of the samples changed, which may infer that the elemental association had changed. 相似文献
994.
Grant D.W. Anderson Malcolm L.H. Green Ino C. Vei 《Journal of organometallic chemistry》2004,689(24):4407-4419
Reactions between [Fe(η-C5H5)(MeCO)(CO)(L)], L = PPh3 (1), PMe3 (2), PPhMe2 (3), PCy3 (4), CO (5), and B(C6F5)3 give new complexes [Fe(η-C5H5){MeCOB(C6F5)3}(CO)(L)] L = PPh3 (7), PMe3 (8), PPhMe2 (9), PCy3 (10), CO (11), where B(C6F5)3 coordinates selectively to the O-acyl groups. Hydrolysis of 7 gives [Fe(η-C5H5){HOB(C6F5)3}(CO)(PPh3)] (6). The X-ray structures of 6, 8 and 11 have been determined. Calculations, using density functional theory, demonstrate that the charge transfer to the acyl group on Lewis acid coordination is more significant in the σ than the π system. Both effects lead to a lengthening of the acyl C-O bond thus π populations cannot be inferred from the distance changes. 相似文献
995.
High resolution mass spectrometry, metastable defocusing and deuterium labeling of trimethylsilyl (TMS) ethers have been used to study the electron-impact induced fragmentations of o-, m- and p-hydroxyalkylphenones and their TMS ether derivatives. These derivatives have proven useful in contrasting the fragmentation patterns of singly- and doubly-charged ions because of the competing fragmentations: α-cleavage and a McLafferty rearrangement from the ketone moiety and methyl cleavage from the TMS group. A proximity effect was responsible for a markedly increased methyl radical loss from the o-TMS ether. This fragmentation was minor with the m- and p-isomers. Significantly intense doubly-charged ions were formed from ketonic cleavage and by the loss of a TMS methyl radical. The sequence of fragmentation depended on the size of the alkyl group attached to the ketone carbonyl. There was no evidence found for a McLafferty rearrangement occurring from the doubly-charged molecular ion of the TMS ethers of the hydroxyalkylphenones but the rearrangement occurred from the doubly-charge molecular ion of bis-3-(1-oxopentyl)-4-hydroxy-phenyl-methane and, of course, from the singly charged [M]+. The bis-p-hydroxyphenylmethane derivatives were studied in an effort to increase the intensity of the doubly-charged ions as it was expected that the charges would be separated by a longer distance. 相似文献
996.
Michelle A. Meierhoefer S. Patrick Dunn Laela M. Hajiaghamohseni Matthew J. Walters Mildred C. Embree Sally P. Grant Jennifer R. Downs Jessica D. Townsend Clyde R. Metz Charles F. Beam William T. Pennington Donald G. VanDerveer N. Dwight Camper 《Journal of heterocyclic chemistry》2005,42(6):1095-1099
Select C(α), N‐phenylhydrazones were dilithiated in excess lithium diisopropylamide followed by condensation with methyl 2‐(aminosulfonyl)benzoate and acid cyclization to afford new pyrazol‐benzenesul‐fonamides, 2‐(1‐phenyl‐1H‐pyrazol‐5‐yl)benzenesulfonamides. 相似文献
997.
Grant SA Pierce ME Lichlyter DJ Grant DA 《Analytical and bioanalytical chemistry》2005,381(5):1012-1018
A novel optical biosensor technique is being developed for the early detection of myocardial infarction by utilizing the distance-dependent chemical transduction method of fluorescence resonance energy transfer (FRET). The FRET process requires two fluorophores termed the donor and the acceptor. When in close proximity, the donor absorbs energy from the excitation source and non-radiatively transfers the energy to the acceptor, which in turn emits fluorescent energy. This distance-dependent property was utilized to detect conformational changes when antibodies combine with their respective antigens. The fluorophores were conjugated to an antibody–Protein A complex and then immobilized via silanization to the distal ends of optical fibers. Three different antibody–Protein A complexes were immobilized: generic IgG, cardiac Troponin T (cTnT), and cardiac Troponin I (cTnI). Results showed that upon the addition of the specific antigens, the antibodies underwent a conformational change, reducing the distance between the FRET fluorophores. The generic IgG responded to 233 nM antigens, whereas the cTnT biosensor had a limit of detection of 75 nM, and the cTnI biosensors had a limit of detection of 94 nM. 相似文献
998.
Diurnal fluxes and the isotopomer ratios of N(2)O in a temperate grassland following urine amendment
Yamulki S Toyoda S Yoshida N Veldkamp E Grant B Bol R 《Rapid communications in mass spectrometry : RCM》2001,15(15):1263-1269
There is an urgent need to provide an accurate, up-to-date estimate of N(2)O fluxes in order that national policies can be developed to reduce emissions of N(2)O from soils. There are only limited data on temporal and diurnal patterns of N(2)O fluxes to the atmosphere, mainly due to constraints in the measurement techniques. In this paper we present the first terrestrial source values of N(2)O isotopomers and have measured and quantified the temporal and diurnal variability in N(2)O fluxes following urine addition to a grassland system in the UK. The experiment was carried out over a 2-week period on an artificially drained grassland system at the Institute of Grassland and Environmental Research (IGER), North Wyke, UK. Duplicate samples of urine, each of 2 L, were collected from dairy cows and applied to chambers (of area 0.16 m(2)). The N(2)O diurnal fluxes from urine and control (no urine) plots were measured by an automatic closed chamber technique. The isotopomers of N(2)O were obtained by analysing the gas samples collected during a peak emission phase. Soil and meteorological data were also collected. The results showed strong diurnal variations in N(2)O fluxes with minimum fluxes generally occurring between 7:00 and 14:00 hrs. The total cumulative flux of N(2)O for the whole experimental period was higher by a factor of >2 compared with estimates based on the daytime (between 10.00-16.00 hrs) measurements only. Therefore, measurements of N(2)O fluxes based on daily single exposure and expressed on a 24-h basis could impose a considerable bias and inaccuracy to the emission estimates, depending on when it was taken. The measured site preference values (difference between the centre (delta(15)Nalpha) and the end (delta(15)Nbeta) N atom of the N(2)O molecule) for soil-emitted N(2)O measured during our study were always lower than the tropospheric value. This work confirms that the enhanced tropospheric N(2)O site preference value could be the result of the back injection from the stratosphere. The intramolecular isotope ratios of nitrogen (delta(15)N) and oxygen (delta(18)O) and the site preference of the emitted N(2)O indicated that there was a shift of processes during the measurement period. 相似文献
999.
1000.
Krow GR Lin G Rapolu D Fang Y Lester WS Herzon SB Sonnet PE 《The Journal of organic chemistry》2003,68(13):5292-5299
The reactions of N-(alkoxycarbonyl)-2-azabicyclo[2.2.0]hex-5-enes 5 with halonium ion electrophiles were studied in polar and nonpolar aprotic solvents and also in protic media with the aim of controlling nitrogen neighboring group participation. Specifically, for bromonium ions nitrogen participation is facilitated by the polar aprotic solvent nitromethane and by the poorly nucleophilic protic solvent acetic acid. Alkene 5b and bromine/nitromethane afford only the rearranged anti,anti-5,6-dibromo-2-azabicyclo[2.1.1]hexane 6b, and NBS/acetic acid gives an 8:1 mixture favoring rearranged 5-bromo-6-acetate 6f. Conversely, pyridinium bromide perbromide/CH(2)Cl(2) is selective for only unrearranged 5,6-dibromide 7. Iodonium and phenylselenonium ions react with alkenes 5 to give only unrearranged 1,2-addition products 9 and 10, regardless of solvent. Chloronium and fluoronium ions react with alkenes 5 to give 4-aminomethyl-3-hydroxycyclobutene 11, derived by ring cleavage. 相似文献