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131.
Ramírez-Arizmendi LE Heidbrink JL Guler LP Kenttämaa HI 《Journal of the American Chemical Society》2003,125(8):2272-2281
Reactions of differently substituted phenyl radicals with components of nucleic acids have been investigated in the gas phase. A positively charged group located meta with respect to the radical site was employed to allow manipulation of the radicals in a Fourier-transform ion cyclotron resonance mass spectrometer. All of these electrophilic radicals react with sugars via exclusive hydrogen atom abstraction, with adenine and uracil almost exclusively via addition (likely at the C8 and C5 carbons, respectively), and with the nucleoside thymidine by hydrogen atom abstraction and addition at C5 in the base moiety (followed by elimination of (*)CH(3)). These findings parallel the reactivity of the phenyl radical with components of nucleic acids in solution, except that the selectivity for addition is different. Like HO(*), the electrophilic charged phenyl radicals appear to favor addition to the C5-end of the C5-C6 double bond of thymine and thymidine, whereas the phenyl radical preferentially adds to C6. The charged phenyl radicals do not predominantly add to thymine, as the neutral phenyl radical and HO(*), but mainly react by hydrogen atom abstraction from the methyl group (some addition to C5 in the base followed by loss of (*)CH(3) also occurs). Adenine appears to be the preferred target among the nucleobases, while uracil is the least favored. A systematic increase in the electrophilicity of the radicals by modification of the radicals' structures was found to facilitate all reactions, but the addition even more than hydrogen atom abstraction. Therefore, the least reactive radicals are most selective toward hydrogen atom abstraction, while the most reactive radicals also efficiently add to the base. Traditional enthalpy arguments do not rationalize the rate variations. Instead, the rates reflect the radicals' electron affinities used as a measure for their ability to polarize the transition state of each reaction. 相似文献
132.
Nelsen SF Konradsson AE Weaver MN Guzei IA Goebel M Wortmann R Lockard JV Zink JI 《The journal of physical chemistry. A》2005,109(48):10854-10861
Photolysis into the longest wavelength absorption band of 2-tert-butyl-2,3-diazabicyclo[2.2.2]oct-3-yl hydrazine (Hy) substituted naphthalenes causes aryl group reduction electron transfer to give (+)Hy-Ar(-). Electrooptical absorption measurements characterize the charge separation properties from these bands. Emission studies demonstrate that the separation between absorption and emission maxima for symmetrically disubstituted compounds is smaller than that for monosubstituted compounds, which is attributed to excited-state intervalence. The excited-state diabatic surfaces may be described as a Hy(+)-NA(- )-Hy(0), Hy(0)-NA(-)-Hy(+) pair, for which electronic interaction produces a double minimum that qualitatively resembles that in the ground state of the disubstituted intervalence radical cations. 相似文献
133.
Reactions of 1,3-Thiazole-5(4H)-thiones with Grignard- and Organolithium Compounds: Carbophilic and Thiophilic Additions Organolithium compounds and 1,3-thiazole-5(4H)-thiones 9 reacted via thiophilic addition on the exocyclic S-atom. The intermediate anion E has been trapped by protonation to give 12 and by alkylation to yield 16 , respectively (Schemes 5 and 6). In competition with protonation of E , a fragmentation to benzonitrile and a dithioester 14 was observed (Scheme 5). In some cases, the alkylation of E led to the formation of dithioacetals 17 instead of 16 (Scheme 6). Methyl, ethyl, and isopropyl Grignard reagents and 9 in THF underwent again a thiophilic addition yielding 4,5-dihydro-1,3-thiazoles of type 12 (Scheme 3). In contrast to this result, MeMgI reacted with 9a in Et2O via carbophilic addition to 11 . Again a carbophilic attack at C(5) of 9 was observed with allylmagnesium and 2-propynylmagnesium bromide, respectively, in Et2O. 相似文献
134.
Justin C. Wedal Jeffrey M. Barlow Joseph W. Ziller Jenny Y. Yang William J. Evans 《Chemical science》2021,12(24):8501
Electrochemical measurements on tris(cyclopentadienyl)thorium and uranium compounds in the +2, +3, and +4 oxidation states are reported with C5H3(SiMe3)2, C5H4SiMe3, and C5Me4H ligands. The reduction potentials for both U and Th complexes trend with the electron donating abilities of the cyclopentadienyl ligand. Thorium complexes have more negative An(iii)/An(ii) reduction potentials than the uranium analogs. Electrochemical measurements of isolated Th(ii) complexes indicated that the Th(iii)/Th(ii) couple was surprisingly similar to the Th(iv)/Th(iii) couple in Cp′′-ligated complexes. This suggested that Th(ii) complexes could be prepared from Th(iv) precursors and this was demonstrated synthetically by isolation of directly from UV-visible spectroelectrochemical measurements and reactions of with elemental barium indicated that the thorium system undergoes sequential one electron transformations.Electrochemical determination of the reduction potentials for a variety of tris(cyclopentadienyl)uranium and thorium complexes, including data on U(ii) and Th(ii) complexes. 相似文献
135.
Charles W. Bock George D. Markham Amy K. Katz Jenny P. Glusker 《Theoretical chemistry accounts》2006,115(2-3):100-112
Structural features of clusters involving a metal ion (Li+, Na+, Be2+, Mg2+, Zn2+, Al3+, or Ti4+) surrounded by a total of 18 water molecules arranged in two or more shells have been studied using density functional theory.
Effects of the size and charge of each metal ion on the organization of the surrounding water molecules are compared to those
found for a Mg[H2O]62+• [H2O]12 cluster that has the lowest known energy on the Mg2+• [H2O]18 potential energy surface (Markham et al. in J Phys Chem B 106:5118–5134, 2002). The corresponding clusters with Zn2+ or Al3+ have similar structures. In contrast to this, clusters with a monovalent Li+ or Na+ ion, or with a very small Be2+ ion, differ in their hydrogen-bonding patterns and the coordination number can decrease to four. The tetravalent Ti4+ ionizes one inner-shell water molecule to a hydroxyl group leaving a Ti4+(H2O)5 (OH−) core, and an H3O+• • • H2O moiety dissociates from the second shell of water molecules. These observations highlight the influence of cation size and
charge on the local structure of hydrated ions, the high-charge cations causing chemical changes and the low-charge cations
being less efficient in maintaining the local order of water molecules.
Electronic Supplementary Material: Supplementary material is available for this article at http://dx.doi.org/10.1007/S00214-005-0056-2. 相似文献
136.
Pfennig BW Mordas CJ McCloskey A Lockard JV Salmon PM Cohen JL Watson DF Bocarsly AB 《Inorganic chemistry》2002,41(17):4389-4395
The synthesis, characterization, electrochemical, photophysical, and photochemical properties of two hexanuclear mixed-valence compounds are reported. Each supramolecular species consists of two cyano-bridged [(NC)(5)Fe(II)-CN-Pt(IV)(NH(3))(3)L-NC-Fe(II)(CN)(5)] triads that are linked to each other through a Pt(IV)-L-Pt(IV) bridge, where L = 4,4'-dipyridyl (bpy) or 3,3'-dimethyl-4,4'-dipyridyl (dmb). The major difference between the two compounds is the electronic nature of the bridging ligand between the two Pt atoms. Both species exhibit a broad Fe(II) --> Pt(IV) intervalent (IT) absorption band at 421 nm with an oscillator strength that is approximately four times that for [(NC)(5)Fe(II)-CN-Pt(IV)(NH(3))(5)] and twice that for [(NC)(5)Fe(II)-CN-Pt(IV)(NH(3))(4)-NC-Fe(II)(CN)(5)].(4-) When L = bpy, the resonance Raman spectrum obtained by irradiating the IT band at 488 nm exhibits several dipyridyl ring modes at 1604, 1291, and 1234 cm(-1) which are not present in the spectrum when L = dmb. In addition, femtosecond pump-probe spectroscopy performed at 400 nm yields a transient bleach of the IT absorption band with a single exponential decay of 3.5 ps for L = bpy, compared with only 1.8 ps for L = dmb and 2.1 ps for [(NC)(5)Fe(II)-CN-Pt(IV)(NH(3))(4)-NC-Fe(II)(CN)(5)].(4-) Last, prolonged irradiation of the complexes at 488 nm leads to the formation of 4 equiv of ferricyanide with a quantum efficiency of 0.0014 for L = bpy and 0.0011 for L = dmb. The transient absorption, resonance Raman, and photochemical data suggest that the degree of excited electronic coupling in these compounds is tunable by changing the electronic nature of the Pt-L-Pt bridging ligand. 相似文献
137.
This paper describes the development of two different capillary-based heterogeneous competitive flow immunoassay formats (capillary flow injection immunoassay (CFIIA) and capillary sequential injection immunoassay (CSIIA)) for the determination of 2,4,6-trichlorophenol (2,4,6-TCP). The assays are based on the competition between the analyte and an analyte derivative labelled with the enzyme beta-galactosidase, for an anti-TCP antibody, followed by the injection of the mixture at equilibrium into a flow stream, where separation between the fractions bound and unbound to the antibody is performed in a glass capillary containing immobilised protein A. The antibody-tracer fraction retained inside the protein A capillary was measured by injection of 4-aminophenyl- beta- D-galactoside (4-APG), followed by amperometric detection of the enzymatically generated 4-aminophenol (4-AP), leading to a negative correlation between the signal and the analyte concentration.The two immunoassay formats were compared in terms of sensitivity and speed, giving IC(50) values of 1.41+/-0.03 and 1.64+/-0.07 micro g L(-1), detection limits of 0.2 and 0.4 micro g L(-1), and sample throughputs of 6 and 4 h(-1) for the CFIIA and CSIIA system, respectively.The influence of different interfering chlorophenolic compounds in the assay was minor, with only one exception (i.e. 2,4-dichlorophenol). In addition, different water matrices were tested (surface, tap, and rain water), showing that the matrix influence was negligible, except for rainwater, which resulted in a 30% increase in sensitivity. As a conclusion, the assay is suitable for the fast screening of TCP present at low concentration levels in water samples. 相似文献
138.
Taylor F Mcaloon AJ Craig JC Yang P Wahjudi J Eckhoff SR 《Applied biochemistry and biotechnology》2001,94(1):41-49
The Quick-Germ process developed at the University of Illinois at Urbana-Champaign is a way to obtain corn oil, but with lower
capital costs than the traditional wet-milling process. Quick-Germ has the potential to increase the coproduct credits and
profitability of the existing dry-grind fuel ethanol process, but the fermentability of the corn remaining after oil recovery
has not been tested. Therefore, a series of pilot scale (50 L) fermentations was carefully controlled and monitored with unique
methods for standard inoculation and automatic sampling. It was found that the concentration of suspended solids was significantly
reduced in the Quick-Germ fermentations. When compared at the same concentration of fermentable sugars, the fermentation rate
and yield were not statistically different from controls. When Quick-Germ was integrated into a state-of-the-art dry-grind
fuel ethanol process, computer simulation and cost models indicated savings of approx $0.01/L of ethanol ($0.04/gal) with
the Quick-Germ process. Additional savings associated with the lower suspended solids could not be quantified and were not
included. However, the savings are sensitive to the price of corn oil.
Mention of brand or firm name does not constitute an endorsement by the U.S. Department of Agriculture over others of a similar
nature not mentioned. 相似文献
139.
140.
T. Jenny W. von Philipsborn J. Kronenbitter A. Schwenk 《Journal of organometallic chemistry》1981,205(2):211-222
57Fe NMR spectra of 35 organoiron complexes predominantly of the type [Fe(CO)3(diene)] have been measured by direct detection at 2.9 MHz and at natural isotope abundance (2.2%). The 57Fe chemical shift range so far observed is 3000 ppm, corresponding to about 9 KHz. The majority of the resonances are at higher frequency than that of Fe(CO)5, which is proposed as a secondary standard. The 57Fe resonance frequencies are also reported as ratios relative to the 73Ge frequency of GeCl4.The 57Fe shielding is discussed qualitatively in terms of charge distribution in the complexes, very large deshielding effects being observed for cationic olefinic ligands. For η4-diene complexes, the shielding also depends upon ligand geometry and decreases with increasing ring size or CCC bond angle. Two types of ferrocenylcarbenium ions may be distinguished, indicated by high- or low-frequency shifts relative to ferrocene. For a number of [Fe(CO)3(olefin)] complexes 1J(57Fe, 13C) coupling constants involving the carbonyl carbon are also reported. 相似文献