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71.
72.
We have provided a model to interpret the non-quadratic-intensity dependence behavior commonly observed in the two-photon fluorescence (TPF) experiment excited with high laser intensity. The model also provides one with a different technique to measure the two-photon absorption cross section of an organic chromophore in solution. In contrast to the commonly used low intensity technique that depends on the quadratic-intensity law, the present technique is based on the non-quadratic-intensity dependence of two-photon fluorescence. Auxiliary data such as two-photon quantum efficiency and fluorescence collection efficiency, essential in the low intensity method, are not required in the present technique. TPF measurements of Rhodamine B in methanol are carried out to demonstrate the validity of the present method. The method is used to determine the two-photon absorption cross section of a new chromophore attached with tricyano-derivatized furan as the electron acceptor. The two-photon absorption cross section measured using this method is also compared with that using a conventional transmission technique. 相似文献
73.
[reaction: see text] Ester-containing nitrones, including 5-tert-butoxycarbonyl-5-methyl-1-pyrroline N-oxide 5, have been reported to be robust spin traps for superoxide (O2*-). Using a chiral column, we have been able to isolate the two enantiomers of nitrone 5. With enantiomerically pure nitrone 5a and 5b we explored whether one of these isomers was solely responsible for the EPR spectrum of aminoxyl 6. Data obtained demonstrate that the spin trapping of O2*- by nitrone 5a and nitrone 5b affords the identical EPR spectra and lifetimes in homogeneous aqueous solution and exhibits the same ratio of cis and trans isomers. Quantum chemical modeling in vacuo also finds no difference, aside from the expected optical activity, arising from the difference in stereochemistry. 相似文献
74.
We report the separation of polycyclic aromatic hydrocarbons (PAHs) using 0.1% poly(ethylene oxide) (PEO) in micellar electrokinetic chromatography (MEKC). In the presence of PEO, adsorption of PAHs on the capillary wall was reduced, leading to better resolution and reproducibility. Effects of tetrapentylammonium iodide (TPAI), dextran sulfate (DS), methanol, and sodium lauryl sulfate (SDS) on the separation of PAHs were elucidated. In terms of resolution and speed, DS, compared to TPAI, is a better additive for separation of PAHs. When using 0.1% PEO solution containing 45% methanol, 50 mM SDS, and 0.02% DS, separation of 10 PAHs containing 2 to 5 benzene rings was accomplished in less than 12 min at 15 kV in a commercial CE system. The method has also been tested for separating seven PAHs with high quantum yields when excited at 325 nm using a He-Cd laser. Unfortunately, separation of the seven PAHs was not achieved and sensitivity diminished under the same conditions. To optimize sensitivity, resolution and speed, a stepwise technique in MEKC has been proposed. The seven PAHs were resolved in 35 min at 15 kV when separation was performed in 0.1% PEO solution containing 35 mM SDS, 40% methanol and 0.02% DS for 2 min, and subsequently in 0.1% PEO solution containing 20 mM SDS, 50% methanol, and 0.02% DS. 相似文献
75.
Synthesis and photochemistry of several title compounds 1-3 containing multiple chromophoric systems are described. The Diels-Alder reactions of 2,6,6-trimethylcyclohexa-2,4-dienone (5) with acetylenes 6a-d provided the adducts 7a-d, which upon hydrolysis furnished the desired bicyclo[2.2.2]octenediones 1a-d. Oximes 2a-d were prepared from diones 1a-d by treatment with hydroxylamine hydrochloride in pyridine. 5-Methylenebicyclo[2.2.2]oct-7-en-2-ones 3a-d were obtained via chemoselective Wittig reaction of the corresponding diones 1a-d. Bicyclo[2.2.2]octenediones 1a-c underwent chemoselective oxa-di-pi-methane rearrangement under sensitized conditions and suffered formal ketene extrusion upon direct irradiation. Direct irradiation of 1d afforded 11d via formal ketene extrusion but under sensitization it remained unchanged. Oximes 2a-d suffered ketene extrusion upon direct irradiation and E/Z isomerization under sensitized conditions. On the other hand, 5-methylenebicyclo[2.2.2]oct-7-en-2-ones 3a-d generally underwent 1,3-acyl shift. The plausible courses of all these photochemical processes are discussed. 相似文献
76.
Hou-Jen Tsai Shyi-Chen Wu 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):191-204
Abstract Treatment of ethyl oxalyl chloride or methyl oxalyl chloride with lithium diisopropyl(carboethoxyfluoromethyl)phosphonate[(i-PrO)2P(O)CFCO2Et]?Li+ 2 followed by in siru nucle-ophilic addition with methylmagnesium iodide or vinyl magnesium bromide affords with exclusive E-stereoselectivity formation of diethyl-2-fluoro-3-methyl fumarate (CH3)(C02Et)C[dbnd]CFCO2Et 4 or 75% of the E-isomer of a-fluoro-P-vinyl-a,P-unsaturated diester (E,Z)-(CH2[dbnd]CH)(CO2C2H5)C[dbnd]CFCO2Et 5, respectively. However, direct reaction of ethyl pyruvate with 2 gives the fluoro-olefin (CH3)(CO2Et)C[dbnd]CFCO2Et 4 with 79% E-stere-oselectivity. The E/Zratio of (CH2[dbnd]CH)(CO2Et)C[dbnd]CFCO2Et 5 depends on the HMFT or DMPU cosolvents present in the reaction mixture. 相似文献
77.
Ronald G. Cavell Chih Y. Wong Robert McDonald 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4)
Abstract Neutral hexacoordinate phosphorus(V) compounds of a number of univalent bidentate ligands are known.l,2 The silylated forms of tridentate, dianionic Schiff base ligands: N-(2-hydroxyphenyl)salicylideneamine H2LI, N-(4-tert-butyl-2-hydroxyphenyl)-salicylideneamine H2LII, N-(2-hydroxy-4-nitrophenyl)salicylidene-amine H2LIII, and 2,2′-azodiphenol H2LIV gave, with halogeno- and (trifluoromethyl)halogenophosphoranes, neutral hexa-coordinate derivatives with bis-chelate structures. The ligands form bicyclic five- and six-membered chelate rings in a meridional conformation, with two P-O bonds and one N→P donor bond. Hexacoordinate structures were evidenced by high-field 31P NMR chemical shifts (-136 to -148 ppm), characteristic J PF coupling patterns and was further substantiated by crystal structures of Cl3LII (A) and F3PLII (B). 相似文献
78.
C. L. Kuo T. L. Tsai A. C. Chiang K. S. Chang-Liao J. H. Chao 《Journal of Radioanalytical and Nuclear Chemistry》2013,298(1):465-473
The purpose of this study is to develop a neutron activation method to determine trace amounts of 129I in cement-solidified radwastes. The radwaste samples were alkaline fused using KOH and then 129I and iodine carrier were chemically separated by solvent extraction before and after neutron irradiation. Both stable iodine (127I) and 129I can be activated by neutrons through 127I (n, 2n) 126I and 129I (n, γ) 130I reactions; their activated radionuclides were counted together with a high-purity germanium detector. The chemical recovery yields ranged from 30 to 60 %, and it was found that more than 99.9 % of interfering radionuclides can be removed using solvent extraction after neutron irradiation. The minimum detectable amounts can be lowered to less than 1 mBq g?1, which is superior to low energy γ-ray spectrometry by a factor of >102, on average. The established technique can be applied to re-evaluation of 129I content in radwastes that can be re-classified to lower classes, and the cost for designing a final disposal facility can be significantly reduced. 相似文献
79.
Two fused-ring structures, 6-decyloxy-2-naphthoic acid C10ONA (3) and 6-dodecyloxyisoquinoline IS (8), were synthesized and utilized as proton donor and acceptor moieties to construct a series of simple mesogenic supramolecules. The other complementary hydrogen-bonded (H-bonded) moieties are benzoic acids, thiophenecarboxylic acid and pyridines containing different alkyl chain lengths connected by ether and ester linkages, i.e. 4-alkoxybenzoic acid C n OBA (1), terephthalic acid monoalkyl ester C n COOBA (2), 2,5-thiophenedicarboxylic acid monodecyl ester C10COOTHA (4), 4-alkoxypyridine C n OP (6) and isonicotinic acid alkyl ester C n COOP (7). Several series of simple mesogenic supramolecular dimers were constructed from 1:1 molar ratios of proton donors (C n OBA, C n COOBA, C10ONA and C10COOTHA) and proton acceptors (IS, C n OP and C n COOP), though the proton acceptor C n COOP induced phase separation in all complexes. In order to investigate their fused-ring and linking group effects on the mesogenic properties of the H-bonded complexes, analogous simple supramolecular structures are compared. Supramolecular architecture and the distinct mesomorphism of these simple H-bonded liquid crystalline materials were confirmed by polarizing optical microscopy, DSC and powder X-ray diffraction experiments. 相似文献
80.
Cheng‐Hua Lee Meng‐Rong Tsai Yen‐Tzu Chang Prof. Dr. Long‐Li Lai Dr. Kuang‐Lieh Lu Dr. Kung‐Lung Cheng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(32):10573-10579
Three unconventional dendrimers that contained rigid NH? triazine linkages and peripheral tert‐butyl moieties were prepared by using a convergent approach and characterized by 1H and 13C NMR spectroscopy, mass spectrometry, and elemental analysis. Based on a thermogravimetric analysis study, these dendrimers were observed to display thermal stability at about 300 °C. The NH? triazine moiety, which possessed protonated and proton‐free nitrogen sites (like the imidazole unit), displayed the capture of polarizable CO2 molecules through hydrogen‐bond and/or dipole–quadrupole interactions. In addition, the adsorption of various amounts of CO2 and N2 at different pressures suggests that the dendritic pores, which arise from the stacking of the middle co‐planar and rim protuberant dendrimers, G n ‐N~N‐G n (n=1–3), either swell or shrink at high pressure, thus indicating that these dendrimers may have a breathing ability. 相似文献