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71.
Dr. Pengfei Wu Prof. Dr. Adriana Pietropaolo Dr. Mariagrazia Fortino Dr. Masayoshi Bando Prof. Dr. Katsuhiro Maeda Dr. Tatsuya Nishimura Shuhei Shimoda Dr. Hiroyasu Sato Prof. Dr. Naofumi Naga Prof. Dr. Tamaki Nakano 《Angewandte Chemie (International ed. in English)》2023,62(29):e202305747
Optically active, hyperbranched, poly(fluorene-2,4,7-triylethene-1,2-diyl) [poly(fluorenevinylene)] derivatives bearing a neomenthyl group and a pentyl group at the 9-position of the fluorene backbone at various ratios acted as a chirality donor (host polymers) efficiently included naphthalene, anthracene, pyrene, 9-phenylanthracene, and 9,10-diphenyanthracene as a chirality acceptor (guest molecules) in their interior space in film as well as in solution, with the guest molecules exhibiting intense circular dichroism through chirality transfer with chirality amplification. The efficiency of the chirality transfer was much higher with higher-molar-mass polymers than lower-molar-mass ones as well as with hyperbranched polymers compared to the analogous linear ones. The hyperbranched polymers include the small molecules in their complex structure without any specific interactions at various stoichiometries. The included molecules may have ordered intermolecular arrangement that may be somewhat similar to those of liquid crystals. Naphthalene, anthracene, and pyrene included in the polymer exhibited efficient circularly polarized luminescence, where the chirality was remarkably amplified in excited states, and anthracene exhibited especially high anisotropies in the emission on the order of 10−2. 相似文献
72.
Cover Picture: Nucleobase‐Modified PNA Suppresses Translation by Forming a Triple Helix with a Hairpin Structure in mRNA In Vitro and in Cells (Angew. Chem. Int. Ed. 3/2016) 下载免费PDF全文
73.
74.
Kenichiro Tamaki 《Journal of multivariate analysis》2007,98(3):638-659
We consider the second order asymptotic properties of an efficient frequency domain regression coefficient estimator proposed by Hannan [Regression for time series, Proc. Sympos. Time Series Analysis (Brown Univ., 1962), Wiley, New York, 1963, pp. 17-37]. This estimator is a semiparametric estimator based on nonparametric spectral estimators. We derive the second order Edgeworth expansion of the distribution of . Then it is shown that the second order asymptotic properties are independent of the bandwidth choice for residual spectral estimator, which implies that has the same rate of convergence as in regular parametric estimation. This is a sharp contrast with the general semiparametric estimation theory. We also examine the second order Gaussian efficiency of . Numerical studies are given to confirm the theoretical results. 相似文献
75.
We propose a new scheme for quantum dynamics control of multilevel system using intense lasers. To do so, we apply intense CW lasers to create a strongly coupled subsystem with which one can make the complementary space effectively isolated, and we apply the established control schemes to the isolated subsystem. We have also obtained an effective Hamiltonian for the target subsystem with the help of the second-order perturbation theory. Numerical demonstrations on model systems show that the present decomposition scheme effectively works for population dynamics control. It is also found that relaxation processes can be suppressed under the proposed scheme. 相似文献
76.
Yoshimura F Lear MJ Ohashi I Koyama Y Hirama M 《Chemical communications (Cambridge, England)》2007,(29):3057-3059
In advanced studies directed toward the total synthesis of the kedarcidin chromophore, we have successfully achieved the late-stage installation of the nine-membered diyne ring in the presence of the highly functionalised ansamacrocyclic bridge. 相似文献
77.
78.
Masakuni Tako Takeshi Teruya Yukihiro Tamaki Teruko Konishi 《Colloid and polymer science》2009,287(12):1445-1454
The 1H-nuclear magnetic resonance spectrum showed that the l-rhamnosyl residues of native gellan gum were coinvolved in both a small number of 4C1-pyranose conformations and a large number of 1C4-pyranose conformations, whereas for deacylated polymer, almost of the residues were involved in 4C1-pyranose conformation. The flow curves of native gellan gum showed plastic behavior above 0.2%. The elastic modulus stayed
at a constant value with increase in temperature up to 40 °C, then decreased rapidly. The elastic modulus increased with addition
of CaCl2 (6.8 mM) and stayed constant value with increase in temperature up to 65 °C, then decreased rapidly. The stronger elastic
modulus was observed in deacylated gellan gum with addition of CaCl2. The elastic modulus of native gellan gum showed larger value than that in aqueous solution in the presence of urea (4.0 M).
Intra- and intermolecular associations of native gellan gum molecules in the presence of Ca+2 were proposed. 相似文献
79.
Takashi Tamaki Midue Nagata Masato Ohashi Dr. Sensuke Ogoshi Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(39):10083-10091
Cyclopropanecarboxaldehyde ( 1 a ), cyclopropyl methyl ketone ( 1 b ), and cyclopropyl phenyl ketone ( 1 c ) were reacted with [Ni(cod)2] (cod=1,5‐cyclooctadiene) and PBu3 at 100 °C to give η2‐enonenickel complexes ( 2 a – c ). In the presence of PCy3 (Cy=cyclohexyl), 1 a and 1 b reacted with [Ni(cod)2] to give the corresponding μ‐η2:η1‐enonenickel complexes ( 3 a , 3 b ). However, the reaction of 1 c under the same reaction conditions gave a mixture of 3 c and cyclopentane derivatives ( 4 c , 4 c′ ), that is, a [3+2] cycloaddition product of 1 c with (E)‐1‐phenylbut‐2‐en‐1‐one, an isomer of 1 c . In the presence of a catalytic amount of [Ni(cod)2] and PCy3, [3+2] homo‐cycloaddition proceeded to give a mixture of 4 c (76 %) and 4 c′ (17 %). At room temperature, a possible intermediate, 6 c , was observed and isolated by reprecipitation at ?20 °C. In the presence of 1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene (IPr), both 1 a and 1 c rapidly underwent oxidative addition to nickel(0) to give the corresponding six‐membered oxa‐nickelacycles ( 6 ai , 6 ci ). On the other hand, 1 b reacted with nickel(0) to give the corresponding μ‐η2:η1‐enonenickel complex ( 3 bi ). The molecular structures of 6 ai and 6 ci were confirmed by X‐ray crystallography. The molecular structure of 6 ai shows a dimeric η1‐nickelenolate structure. However, the molecular structure of 6 ci shows a monomeric η1‐nickelenolate structure, and the nickel(II) 14‐electron center is regarded as having “an unusual T‐shaped planar” coordination geometry. The insertion of enones into monomeric η1‐nickelenolate complexes 6 c and 6 ci occurred at room temperature to generate η3‐oxa‐allylnickel complexes ( 8 , 9 ), whereas insertion into dimeric η1‐nickelenolate complex 6 ai did not take place. The diastereoselectivity of the insertion of an enone into 6 c having PCy3 as a ligand differs from that into 6 ci having IPr as a ligand. In addition, the stereochemistry of η3‐oxa‐allylnickel complexes having IPr as a ligand is retained during reductive elimination to yield the corresponding [3+2] cycloaddition product, which is consistent with the diastereoselectivity observed in Ni0/IPr‐catalyzed [3+2] cycloaddition reactions of cyclopropyl ketones with enones. In contrast, reductive elimination from the η3‐oxa‐allylnickel having PCy3 as a ligand proceeds with inversion of stereochemistry. This is probably due to rapid isomerization between syn and anti isomers prior to reductive elimination. 相似文献
80.
Yuko Hasegawa Shuhei Saitou Sayaka Tamaki Hirofumi Yajima Makoto Tadokoro 《Helvetica chimica acta》2009,92(11):2565-2575
The UV, excitation, and luminescence spectra of tris(pivaloyltrifluoroacetonato)europium(III) ([Eu(pta)3]; Hpta=1,1,1‐trifluoro‐5,5‐dimethylhexane‐2,4‐dione=HA) were measured in the presence of bis(salicylidene)trimethylenediamine (H2saltn), bis[5‐(tert‐butyl)salicylidene]trimethylenediamine (H2(tBu)saltn), or bis(salicylidene)cyclohexane‐1,2‐diyldiamine (H2salchn), and the corresponding ZnII complexes [ZnB] (B=Schiff base). The excitation and luminescence spectra of the solution containing [Eu(pta)3] and [Zn(salchn)] exhibited much stronger intensities than those of solutions containing the other [ZnB] complexes. The introduction of a tBu group into the Schiff base was not effective in sensitizing the luminescence of [Eu(pta)3]. The luminescence spectrum of [ZnB] showed a band around 450 nm. The intensity decreased in the presence of [Eu(pta)3], reflecting complexation between [Eu(pta)3] and [ZnB]. On the basis of the change in intensity against the concentration of [ZnB], stability constants were determined for [Eu(pta)3Zn(saltn)], [Eu(pta)3Zn{(tBu)saltn}], and [Eu(pta)3Zn(salchn)] as 4.13, 4.9 and 5.56, respectively (log , where =[[Eu(pta)3ZnB]]([[Eu(pta)3]][[ZnB]])?1). The quantum yields of these binuclear complexes were determined as 0.15, 0.11, and 0.035, although [Eu(pta)3Zn(salchn)] revealed the strongest luminescence at 613 nm. The results of X‐ray diffraction analysis for [Eu(pta)3Zn(saltn)] showed that ZnII had a coordination number of five and was bridged with EuIII by three donor O‐atoms, i.e., two from the salicylidene moieties and one from the ketonato group pta. 相似文献