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111.
1,1-Dialkylethenes are readily prepared in good yields from vinyltrialkylborates derived from trialkylboranes and trisylhydrazones of methyl ketones by treatment with iodine. 相似文献
112.
Munetaka Nakata Tsutomu Fukuyama Kozo Kuchitsu Harutoshi Takeo Chi Matsumura 《Journal of Molecular Spectroscopy》1980,83(1):118-129
The microwave spectra of eight isotopic species of COCl2 have been observed, and the following rotational constants have been obtained: An analysis of the rotational constants has resulted in the rs and rm structures. The equilibrium structure, re, has been estimated by combining the rm parameters derived according to Watson's method and the re bond distances estimated in our recent electron-diffraction and spectroscopic studies to be , , ∠eClCCl = 111.79 ± 0.24°. 相似文献
113.
Hamao Watanabe Kazuaki Higuchi Tomoko Goto Tsutomu Muraoka Jun Inose Masaaki Kageyama Yasuko Iizuka Masakatsu Nozaki Yoichiro Nagai 《Journal of organometallic chemistry》1981,218(1):27-39
In the presence of a catalytic amount of sodium methoxide, sym-dimethoxytetramethyldisilane was converted into α,ω-dimethoxypermethylpolysilanes, MeO(SiMe2)nOMe where n ? 3, at room temperature. On the other hand, similar treatment of the disilane in THF solution gave cyclic polysilanes, (Me2Si)n where n = 5–7. Decomposition of the disilane in the presence of diphenylacetylene afforded a trisilacyclopentene derivative under similar conditions. This compound was obtained also by the reaction between α,ω-dimethoxypermethylpolysilanes and diphenylacetylene in the presence of sodium methoxide. These cyclic products most likely were formed via permethyl polysilyl anion intermediates derived from α,ω-dimethoxypermethylpolysilanes. Also, the formation of α,ω-dimethoxypermethylpolysilanes could be elucidated in terms of the mechanism involving the base-assisted, concerted nucleophilic substitution or stepwise substitution by silyl anions, rather than the successive dimethylsilylene (Me2Si:) insertion reaction. 相似文献
114.
Summary Polymer-supported and polymeric chiral guanidines carrying an imidazolidine skeleton are designed as polymer-based base catalysts.
Thus, (R)-2-[(S)-1-hydroxymethyl-2-phenylethylimino]-4-phenylimidazolidine was newly prepared from (R)-phenylglycine as the key functional unit of these guanidines. Application of the polymer-based chiral guanidines to the
asymmetric Michael reaction of t-butyl diphenyliminoacetate with MVK led to expected asymmetric induction in the Michael adduct with moderate enantioselectivity
in the use of the latter polymeric chiral guanidines. 相似文献
115.
Nishioka H Kimura A Yamato T Kawatsu T Kakitani T 《The journal of physical chemistry. B》2005,109(32):15621-15635
Developing the quantum transition rate theory of Prezhdo and Rossky (J. Chem. Phys. 1997, 107, 5863), we produced a new non-Condon theory of the rate of electron transfer (ET) which happens through a protein medium with conformational fluctuation. The new theory is expressed by a convolution form of the power spectrum for the autocorrelation function of the electronic tunneling matrix element T(DA)(t) with quantum correction and the ordinary Franck-Condon factor. The new theory satisfies the detailed balance condition for the forward and backward ET rates. The ET rate formula is divided into two terms of elastic and inelastic tunneling mechanisms on the mathematical basis. The present theory is applied to the ET from Bph(-) to Q(A) in the reaction center of Rhodobacter sphaeroides. Numerical calculations of T(DA)(t) were made by a combined method of molecular dynamics simulations and quantum chemistry calculations. We showed that the normalized autocorrelation function of T(DA)(t) is almost expressed by exponential forms. The calculated energy gap law of the ET rate is nearly Marcus' parabola in most of the normal region and around the maximum region, but it does not decay substantially in the inverted region, which is called the anomalous inverted region. We also showed that the energy gap law at the high uphill energy gap in the normal region is elevated considerably from the Marcus' parabola, which is called the anomalous normal region. Those anomalous energy gap laws are due to the inelastic tunneling mechanism which works actively at the energy gap far from zero. We presented an empirical formula for easily calculating the non-Condon ET rate, which is usable by many researchers. We provided experimental evidence for the anomalous inverted region which was basically reproduced by the present theory. The present theory was extensively compared with the previous non-Condon theories. 相似文献
116.
In this paper we consider the Schrödinger operator on the hyperbolic plane , where is the hyperbolic Laplacian and V is a scalar potential on . It is proven that, under an appropriate condition on V at ‘infinity’, the number of eigenvalues of HV less than λ is asymptotically equal to the canonical volume of the quasi-classically allowed region as λ→∞. Our proof is based on the probabilistic methods and the standard Tauberian argument as in the proof of Theorem 10.5 in Simon (Functional Integration and Quantum Physics, Academic Press, New York, 1979). 相似文献
117.
118.
119.
Luminescence channels of manganese-doped spinel 总被引:1,自引:0,他引:1
Ayana Tomita Kensuke Tanaka Masanobu Shirai Kouichirou Tanaka Eiichi Hanamura 《Journal of luminescence》2004,109(1):19-24
Two independent luminescence channels are observed from manganese-doped spinel Mn:MgAl2O4. The luminescence around 520 nm is assigned to transition from the lowest electronic excited state 4T1 to the ground state 6A1 of Mn2+ (3d)5 ion by analyzing the excitation spectrum and electron spin resonance measurement. The emission at 650 nm is triggered by the band edge excitation and is assigned similarly to the charge-transfer process associated with the manganese ion. 相似文献
120.
Suzuki M Nakajima Y Yumoto M Kimura M Shirai H Hanabusa K 《Organic & biomolecular chemistry》2004,2(8):1155-1159
Organogels are formed through a conventional organogelation involving a heating process and an in situ organogelation at room temperature. The conventional organogelation is carried out by dissolution of gelators by heating, while the in situ organogelation is performed by mixing of highly reactive methyl 2,6-diisocyanatohexanoate (LDI) or 2-isocyanatoethyl 2,6-diisocyanatohexanoate (LTI) and alkylamines. The in situ organogelation produced the organogels within several seconds after mixing. The organogels prepared by the in situ organogelation showed quite similar FT-IR spectra and SEM photographs to those formed by conventional organogelation. Moreover, the in situ organogelation using LTI and octylamine as well as dodecylamine produced organogels of acetone, ethyl acetate, and acetonitrile that gelators 5 and 6 cannot gel through conventional organogelation. 相似文献