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11.
Yoshitaka Gotoh Yutaka Kohno Wakichi Fukuda Masao Tomoi 《Journal of polymer science. Part A, Polymer chemistry》1994,32(8):1543-1550
Soluble polystyrenes with crown ether structures and hydroxyl groups adjacent to the macrorings were prepared by the reaction of epoxide-containing polystyrenes with monoaza-15-crown-5 or monoaza-18-crown-6. Rate of formation of the polymer-bound alkali cation-crown alkoxide ion pair from the soluble polystyrenes and aqueous NaOH or KOH depended on the loading of crown ether and hydroxyl units and on the size of the macroring. The elimination of HCl from less reactive 2-chloroethylbenzene with aqueous NaOH or KOH in the presence of the soluble polystyrene catalysts under two-phase conditions was limited mainly by the intrinsic reaction rate. The elimination of HBr from more reactive 2-bromoethylbenzene in the presence of the less (11%) ring-substituted polymer catalyst with 18-crown unit was limited by the alkoxide formation rate. © 1994 John Wiley & Sons, Inc. 相似文献
12.
Yoshitaka Ogiwara Hitoshi Kubota Yuji Kimura 《Journal of polymer science. Part A, Polymer chemistry》1978,16(11):2865-2873
The influence of ferric acetylacetonate [Fe(acac)3] on the photodegradation of model compounds of polyethylene (PE) was examined. By studying electron-spin-resonance (ESR) spectra of photoirradiated compounds such as 1-octene and 1,7-octadiene, which contain carbon double bonds, Fe(acac)3 was found to accelerate the formation of allyl radical by contact with them. On the other hand, Fe(acac)3 suppressed the radical formation based on Norrish type I reaction in a carbonyl group of compounds such as 2-octanone and 3-octanone. Based on the study of ultraviolet (UV) spectra as well as ESR spectra on photoirradiated samples, the influence of Fe(acac)3 on the photodecomposition of model compounds of PE was discussed. Finally, the discussion turned to the mechanism of photodecomposition of PE in the presence of ferric salt. 相似文献
13.
A cationic CpRu(II) complex in combination with quinaldic acid shows high reactivity and chemoselectivity for the catalytic deprotection of hydroxyl groups protected as allyl ethers. The catalyst operates in alcoholic solvents without the need for any additional nucleophiles, satisfying the practical requirements of operational simplicity, safety, and environmental friendliness. The wide applicability of this deprotection strategy to a variety of multifunctional molecules, including peptides and nucleosides, may provide new opportunities in protective group chemistry. [structure: see text] 相似文献
14.
Yoshikatsu Ito Meng Ji-Ben Shin Suzuki Yoshitaka Kusunaga Teruo Matsuura Keiichi Fukuyama 《Tetrahedron letters》1985,26(17):2093-2096
In contrast to simple imidazoles, 1-methy1–2,4,5-triphenylimidazole () produced stable oxetane photoadducts - with good efficiency upon irradiation in the presence of benzophenone derivatives - in acetonitrile solution. Irradiation in the solid-phase was also studied. The oxetanes - readily underwent cycloreversion by acid catalysis or by heating. 相似文献
15.
The α,β-unsaturated γ,δ-epoxyketone 7 is isomerized almost exclusively to the δ-diketone 9 both upon irradiation in the n → π* absorption band with light of wavelengths above 310 nm (in anhydrous dioxane or benzene solutions) and upon triplet sensitization using acetophenone in benzene. The reaction may be formulated by the cleavage of the Cγ? O oxide bond and the shift of the δ-hydrogen to the γ-position, and thus bears a formal “double bond homology” to the photochemical α,β-epoxyketone rearrangement. Excitation in the π → π* absorption band of 7 with light of wavelength 253,7 nm (in anhydrous dioxane solution) leads to the formation of product 10 as well as to the triplet rearrangement to 9 . With this result a novel partial synthesis of O-acetyl-B-nortestosterone has been accomplished, which has the advantages of fewer steps and higher product yield ( 7 → 10 : ~30% yield) than previously published syntheses. On the basis of the presently available experiments, the mechanism of the transformation 7 → 10 , which constitutes one of the still few examples of enone photoreactions induced selectively from the π,π* excited singlet, remains unknown. 相似文献
16.
17.
[reaction: see text] The Sc(OTf)3/FERRODIOL (2) complex was prepared at -78 degrees C in CH2Cl2 in the presence of 2,6-lutidine and MS 4A. The chiral scandium Lewis acid-catalyzed asymmetric Diels-Alder reaction of cyclopentadiene (3) with 3-acyloxazolidin-2-ones (4) effectively produced the adduct (5) in a high yield with good selectivity, i.e., endo/exo = 90:10 up to 91% ee (endo). 相似文献
18.
The nature of the complex europium carbonate ion in concentrated carbonate solution was studied polarographically. A polarographic method for the determination of micro amounts of europium ion in the presence of diverse ions (and especially lanthanides) was developed. 相似文献
19.
Yoshitaka Watanabe Hiroshi Kashiwagi 《International journal of quantum chemistry》1983,23(5):1739-1752
Ab initio SCF MO calculations have been carried out on benzene + TCNE (tetracyanoethylene) and naphthalene + TCNE complexes with the STO -3G, STO -3G π-split (STO -3G for π orbitals and a split basis for π orbitals), and 4–31G basis sets. The interaction energy, gross charges, dipole moment, and the electron density in the middle plane of the complexes have also been evaluated. The STO -3G π-split basis set is appropriate for the calculation of large π–π stacking complexes from two points of view, production of reliable results and ease of computations. The approximation scheme based on the semiorthogonalized orgitals is revealed to be very efficient to save CPU time and storage in such calculations. The stable conformation and the charge-transfer interaction of the two complexes are discussed on the basis of the calculated quantities. 相似文献
20.
Porous Al2O3 presenting a specific surface area of SBET = 105 m2 g(-1) was coated with 3-N-propylpyridinium chloride silsesquioxane polymer. The ion exchange capacity of this polymer grafted onto an Al2O3 surface, resulting in a material designated as AlSiPy(+)Cl-, was 1.09 mmol g(-1). Furthermore, a cobalt(II) tetrasulfophthalocyanine anionic complex was immobilized on the chemically modified surface by an ion exchange reaction with a yield of 40 micromol g(-1) (the surface density of the electroactive species is 3.80 x 10(-11) mol cm(-2)). The electrochemical properties of the material obtained, AlSiPy/CoTsPc, were tested for the catalytic oxidation of oxalic acid at 0.77 V vs SCE in 1.0 mol l(-1) KCl solution. Furthermore, a chronoamperometric technique was used with the electrode to test its potential use as a sensor for oxalic acid. The electrode response to oxalic acid concentrations between 1.0 and 3.5 mmol l(-1) was linear with an estimated detection limit of 0.5 mmol l(-1). The charge transfer resistance of the material, measured using the electrochemical impedance spectroscopy technique, was 43 Omega cm2. 相似文献