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441.
Teruya Shinjo 《Hyperfine Interactions》1994,90(1):159-170
Recent topics in multilayer studies are the giant magnetoresistance phenomena and interlayer exchange couplings between magnetic layers through non-magnetic intervening layers. Several measurements have been carried out concerning these problems, utilizing197Au,119Sn and57Fe as Mössbauer probes. In this article, experimental results are described and the use of Mössbauer spectroscopy for these problems is discussed. 相似文献
442.
443.
The identification of the stage of ionization for various kinds of one-center electron repulsion integrals, occurring when nonbonding or lone-pair electrons are considered explicitly as well as π-electrons, is discussed for conjugated organic molecules containing heteroatoms N. It is concluded that the value for the negative ions should be used for (πCπC | πCπC) in all the states but for (πNπN | πNπN) only in the π-π states. In the n-π states, the appropriate value of (πNπN | πNπN) is that of the neutral atom if the molecule contains only one N atom. If more than one N atom is involved in the molecule, some weighted mean of the values for the negative ion and for the neutral atom should be used. The value for the neutral atom is most adequate for one-center repulsion integrals other than the (ππ | ππ) type in both the π-π and the n-π states. The method of determining these integrals is also discussed. It is concluded that they are to be determined from the consideration of appropriate electron-transfer reactions except for exchange integrals. The exchange integrals are shown to have to be determined from the Slater–Condon parameters derived from the analysis of the experimental atomic energy levels. Illustrative calculations are given for the lower singlet levels of the formaldehyde, pyrazine, pyridine, and the p-benzoquinone molecule. It is found that the calculated energies of the n-π transitions become much too low unless the (ππ | ππ) values of the heteroatoms in the molecule are chosen differently in the n-π states and in the π-π states as pointed out theoretically in this article. 相似文献
444.
Kenta?Fujii Yasuhiro?Umebayashi Ryo?Kanzaki Daisuke?Kobayashi Ryoko?Matsuura Shin-ichi?IshiguroEmail author 《Journal of solution chemistry》2005,34(7):739-753
Chloride complexation of cobalt(II), nickel(II) and zinc(II) ions has been studied by calorimetry and spectrophotometry in N-methylformamide (NMF) containing 1.0 mol-dm− 3 (n-C4H9)4NClO4 as an ionic medium at 298 K. A series of mononuclear complexes, MCln(2 -n) + (M=Co, Ni and Zn) with n = 1, 3 and 4 for cobalt(II), n = 1 for nickel(II), and n = 1–4 for zinc(II), are formed and their formation constants, enthalpies and entropies were obtained. It revealed that complexation is suppressed significantly in NMF relative to that in N,N-dimethylformamide (DMF) in all metal systems examined. The suppressed complexation in NMF is mainly ascribed to the smaller formation entropies in NMF reflecting that the solvent–solvent interaction or solvent structure in the bulk NMF is much stronger than that in the bulk DMF. Formation entropies, Δ S1o, of the monochloro complex in DMF, dimethyl sulfoxide and NMF are well correlated with the Marcus’ solvent parameter, Δ Δv So/R, according to Δ S1o/R = aΔ Δv So/R+b. The a value is negative and similar in all metal systems examined, whereas the b value depends on the metal system. When a gaseous ion is introduced into a solvent, the ionic process of solvation is divided into two stages: the ion destroys the bulk solvent structure to isolate solvent molecules at the first stage and the ion then coordinates a part of isolated solvent molecules around it at the second stage. We propose that the a and b values may reflect the changes in the freedom of motion of solvent molecules at the first and second stages, respectively, of the ionic process of solvation. 相似文献
445.
Hagiwara H Hamano K Nozawa M Hoshi T Suzuki T Kido F 《The Journal of organic chemistry》2005,70(6):2250-2255
[reaction: see text] The neo-trans-clerodane natural product, (-)-methyl barbascoate 1, has been synthesized for the first time starting from the known ketone 6 derived from (R)-(-)-Wieland-Miescher ketone analogue 5. 相似文献
446.
Yue Zhang Natsumi Watanabe Yuuko Miyawaki Yutaka Mune Kenta Fujii Yasuhiro Umebayashi Shin-ichi Ishiguro 《Journal of solution chemistry》2005,34(12):1429-1443
Aprotic N,N-dimethylpropionamide (DMPA) and N,N,N′,N′-tetramethylurea (TMU) are both strong donor solvents and coordinate to metal ions through the carbonyl oxygen atom. These
solvents show a different conformational aspect in the bulk phase, i.e., DMPA exists as either a planar cis or a nonplanar staggered conformer, while TMU exists in a single planar cis conformer. It has been established that the manganese(II) ion is solvated by five molecules in both solvents. Interestingly,
although the planar cis conformer of DMPA is more favorable than the nonplanar staggered one in the bulk phase, the reverse is the case in the coordination
sphere of the metal ion, i.e., a conformational change occurs upon solvation. To reveal the thermodynamic aspect of this conformational change, the complexation
of Mn(II) with bromide ions in DMPA and TMU has been studied by titration calorimetry at 298 K. It was found that the Mn(II)
ion forms mono-, di- and tri-bromo complexes in both solvents, and their formation constants, enthalpies and entropies were
obtained. The Δ H∘1 value for MnBr+ strongly depends on the solvent, i.e., it is positive (19.4 kJ-mol−1) in DMPA and negative (−8.7 kJ-mol−1) in TMU, whereas the Δ H^∘2 and Δ H∘3 values for the stepwise formation of MnBr2 and MnBr3− are both small and negative. The enthalpy of transfer ΔtH∘ from DMPA to TMU, which is evaluated on the basis of the extrathermodynamic TATB assumption, is 25.5 kJ-mol−1 for Mn2+ and −3.6 kJ-mol−1 for MnBr+. These values indicate that the difference between the formation enthalpy of MnBr+ in the two solvents, Δ H^∘1 (DMPA) – Δ H∘1 (TMU), is mainly ascribed to the value of ΔtH∘(Mn2+). It is found that the metal ion is also five-coordinated in the monobromo complex, MnBr(DMPA)4+ . The enthalpy for the conformational change of DMPA from its planar cis to the nonplanar staggered form is evaluated to be −11 and −5.5 kJ-mol−1 for Mn(DMPA)52 + and MnBr(DMPA)4+, respectively. Note that these values are significantly smaller than the corresponding value (5.0 kJ-mol−1) in the bulk phase. We thus conclude that, although steric hindrance among solvent molecules is reduced by replacing one
DMPA of Mn(DMPA)52 + with the relatively small bromide ion, DMPA molecules are still sterically hindered in the MnBr(DMPA)4+ complex. 相似文献
447.
Watanabe K Suzuki Y Aoki K Sakakura A Suenaga K Kigoshi H 《The Journal of organic chemistry》2004,69(23):7802-7808
The construction of strained carbon skeletons by ring-closing olefin metathesis (RCM) was investigated. With well-designed diene 4, RCM was found to be applicable to the formation of a highly strained inside-outside bicyclo[4.4.1]undecane skeleton of ingenol, a bioactive diterpenoid, and formal total synthesis of optically active ingenol (1) was achieved. The key features of this synthesis are construction of an A-ring by spirocyclization of the ketone with an allylic chloride unit, 26, and ring closure of a B-ring by olefin metathesis. Starting from Funk's keto ester 6, the key intermediate aldehyde 9 in Winkler's total synthesis was synthesized in eight steps in 12.5% overall yield. This strategy of direct cyclization of a strained inside-outside skeleton provided the first easy access to optically active ingenol. 相似文献
448.
Kenta Itahashi Satoshi Itoh Nobuhisa Fukunishi Hans Geissel Ryugo S. Hayano Satoru Hirenzaki Masahiko Iwasaki Paul Kienle Rie Kimura Karl Lindberg Chiara Nociforo Hiroaki Ohnishi Shinji Okada Naoya Ono Haruhiko Outa Masaharu Sato Ken Suzuki Takatoshi Suzuki Hideyuki Tatsuno Per–Erik Tegnér Masanori Wakasugi Helmut Weick Junko Yamagata–Sekihara Toshimitsu Yamazaki Yasushige Yano Irina Zartova 《Hyperfine Interactions》2009,193(1-3):27-31
We are preparing for a high resolution spectroscopy of the 1s and 2s pionic states of 121Sn in the 122Sn(d,3He) reaction at the incident deuteron energy of ~500 MeV. The measurement will provide accurate information on the strong interaction between the pion and the nucleus, which leads to quantitative determination of the magnitude of the quark condensate at the normal nuclear density. 相似文献
449.
Kenta Kokado Yoshiki Chujo 《Journal of polymer science. Part A, Polymer chemistry》2008,46(11):3749-3755
Anionic poly(p‐phenylene‐ethynylene) (PPE) incorporated polymer hybrids were synthesized from the PPE and tetramethoxysilane together with the organic polymers such as poly(vinylpyrrolidone) via a sol–gel method. Up to 10 wt % of the anionic PPE could be dispersed homogeneously in the resulting polymer hybrid matrix. The obtained polymer hybrids exhibited controllable photoluminescence properties by the modification of the internal environment of organic–inorganic polymer hybrids by changing the organic/inorganic ratios. The photoluminescence of the anionic PPE surrounded by the polymer hybrid matrix was reinforced against the thermal irradiation. Moreover, the photoluminescence of the obtained organic–inorganic polymer hybrids was also tuned by utilizing ionic interactions between the anionic PPE and the inorganic matrix. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3749–3755, 2008 相似文献
450.
Numerical verification methods, so-called Nakao's methods, on existence or uniqueness of solutions to PDEs have been developed by Nakao and his group including the authors. They are based on the error estimation of approximate solutions which are mainly computed by FEM. 相似文献