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81.
Goto T Ikehata A Morisawa Y Higashi N Ozaki Y 《Physical chemistry chemical physics : PCCP》2012,14(22):8097-8104
The first electronic transition (?←X?) of liquid water was studied from the perspective of the hydration of cations by analyzing the attenuated total reflection far-ultraviolet (ATR-FUV) spectra of the Group I, II, and XIII metal nitrate electrolyte solutions. The ?←X? transition energies of 1 M electrolyte solutions are higher (Li(+): 8.024 eV and Cs(+): 8.013 eV) than that of pure water (8.010 eV) and linearly correlate with the Gibbs energies of hydration of the cations. The increases in the ?←X? transition energies are mostly attributable to the hydrogen bond formation energies of water molecules in the ground state induced by the presence of the cations. The deviation from the linear relation was observed for the high charge density cations, H(+), Li(+), and Be(2+), which reflects that the electronic energies in the excited states are also perturbed. Quantum chemical calculations show that the ?←X? transition energies of the water-cation complexes depend on the hydration structures of the cations. The calculated ?←X? transition energies of the water molecules hydrating high charge density cations spread more widely than those of the low charge density cations. The calculated transition energy spreads of the water-cation complexes directly correlate with the widths of the ?←X? transition bands measured by ATR-FUV spectroscopy. 相似文献
82.
Yokoi T Kato H Kim IY Kikuta K Kamitakahara M Kawashita M Ohtsuki C 《Dalton transactions (Cambridge, England : 2003)》2012,41(9):2732-2737
Octacalcium phosphates (OCPs) co-incorporated with various molar ratios of succinate and suberate ions were synthesized by wet processing. The interplanar spacings of the (100) planes (d(100)) of OCPs formed in the presence of succinic acid (Suc) or suberic acid (Sub) were larger than those of OCPs formed without addition of a dicarboxylic acid to the reaction solvent. The increases in the interplanar spacings of the (100) planes were caused by substitution of HPO(4)(2-) by dicarboxylate ions. The OCPs with co-incorporated succinate and suberate ions, i.e. solid solutions of OCP with incorporated Suc and Sub, were formed by reactions in the presence of Suc and Sub. When the Suc/(Suc + Sub) values in the starting compositions were in the range 0.45-1.0, Suc was preferentially incorporated into the OCP. In contrast, when the Sub/(Suc + Sub) values in the starting compositions were in the range 0.60-1.0, Sub was preferentially incorporated into the OCP crystals. 相似文献
83.
Shoji T Higashi J Ito S Okujima T Yasunami M Morita N 《Organic & biomolecular chemistry》2012,10(12):2431-2438
Arylethynyl-2H-cyclohepta[b]furan-2-ones reacted with 7,7,8,8-tetracyanoquinodimethane (TCNQ) in a formal [2 + 2] cycloaddition reaction, followed by ring opening of the initially formed cyclobutene derivatives, to afford the corresponding dicyanoquinodimethane (DCNQ) chromophores in excellent yields. The intramolecular charge-transfer (ICT) interactions between the 2H-cyclohepta[b]furan-2-one ring and DCNQ acceptor moiety were investigated by UV/Vis spectroscopy and theoretical calculations. The redox behavior of the novel DCNQ derivatives was examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their multistep electrochemical reduction properties depended on the number of DCNQ units in the molecule. Moreover, a significant color change was observed by visible spectroscopy under electrochemical reduction conditions. 相似文献
84.
I D Gridnev M Yasutake N Higashi T Imamoto 《Journal of the American Chemical Society》2001,123(22):5268-5276
The asymmetric hydrogenation of aryl- and alkyl-substituted enamides catalyzed by Rh-BisP complex affords optically active amides with very high ee values. The Rh-MiniPHOS catalyst gives somewhat less satisfactory results. Hydrogenation of the aryl-substituted enamides with (S,S)-BisP-Rh catalyst gives R-amides, whereas the t-Bu- and 1-adamantyl-substituted enamides give S-products with 99% ee. Reaction of [Rh(BisP)(CD(3)OD)(2)]BF(4) (11) with CH(2)=C(C(6)H(5))NHCOCH(3) (5) gives two diastereomers of the catalyst-substrate complex (12a,b), which interconvert reversibly by both intra- and intermolecular pathways as shown by EXSY data. Only one isomer in equilibrium with solvate complex 11 was detected for each of the catalyst-substrate complexes 17 and 18 obtained from CH(2)=C(t-Bu)NHCOCH(3) (6) or CH(2)=C(1-adamantyl)NHCOCH(3) (7). Hydrogenation of these equilibrium mixtures at -100 degrees C gave monohydride intermediates 19 and 20, respectively. In these monohydrides the Rh atom is bound to the beta-carbon. A new effect of the significant decrease of ee was found for the asymmetric hydrogenation of CH(2)=C(C(6)H(4)OCH(3)-o)NHCOCH(3) (21), when H(2) was substituted for HD or D(2). 相似文献
85.
In this paper, we establish a stronger version of Artemov's arithmetical completeness theorem of the Logic of Proofs . Moreover, we prove a version of the uniform arithmetical completeness theorem of . 相似文献
86.
Morita Kentato Motoyama Keiichi Kuramoto Ayako Onodera Risako Higashi Taishi 《Journal of inclusion phenomena and macrocyclic chemistry》2021,100(3-4):169-175
Journal of Inclusion Phenomena and Macrocyclic Chemistry - In recent years, functional materials using cyclodextrin (CD)-based polyrotaxanes have attracted considerable attention, and... 相似文献
87.
KazutakeShimada TatsuyaHigashi KunikoMitamura 《色谱》2003,21(6):632-637
Steroids comprise a large group of natural substances that must frequently be monitored in various biological materials. Due to the metabolic versatility of steroid molecules, extremely complex mixtures are often encountered, necessitating the use of a chromatographic procedure prior to measurement. In this article we present our work, that is, the development of analyses of biological steroids (especially vitamin D compounds and neurosteroids) using gas chromatography/mass spectrometry, high-performance liquid chromatography (including inclusion chromatography using cyclodextrin) and liquid chromatography/mass spectrometry. 相似文献
88.
Yuki Marubashi Tatsuro Higashi Shoichiro Hirakawa Seiji Tani Tomoki Erata Mitsuo Takai Jun Kawamata 《Optical Review》2004,11(6):385-387
The molecular chain orientation of mercerized cellulose II was examined by optical second harmonic generation (SHG) measurements. The SHG intensities of several kinds of mercerized cellulose II were found to be much larger than those expected for a structural model with an antiparallel molecular chain orientation as proposed by X-ray studies. This result suggests that the orientation of mercerized cellulose II is parallel as suggested by molecular dynamics simulation. © 2004 The Optical Society of Japan 相似文献
89.
90.
A method is presented for characterizing the family of overall systems reconstructable from a given possibilistic structure system. The technique is elaborated in terms of fuzzy relation equations.It is demonstrated that the reconstruction family of a given structure system is equivalent to the set of solutions of a special type of fuzzy relation equation. The solution set is partially ordered, and contains both minimal solutions and a unique maximum solution. When these elements are identified, all members of the reconstruction family are determined.Another characteristic of the reconstruction family is its reconstruction uncertainty, a measure of which is also developed in this paper. This measure is used to define an identifiability quotient that expresses the degree of confidence with which we may identify a single overall system given a particular structure system. 相似文献