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61.
62.
Yamagiwa N Qin H Matsunaga S Shibasaki M 《Journal of the American Chemical Society》2005,127(38):13419-13427
The full details of a catalytic asymmetric aza-Michael reaction of methoxylamine promoted by rare earth-alkali metal heterobimetallic complexes are described, demonstrating the effectiveness of Lewis acid-Lewis acid cooperative catalysis. First, enones were used as substrates, and the 1,4-adducts were obtained in good yield (57-98%) and high ee (81-96%). Catalyst loading was successfully reduced to 0.3-3 mol % with enones. To broaden the substrate scope of the reaction to carboxylic acid derivatives, alpha,beta-unsaturated N-acylpyrroles were used as monodentate, carboxylic acid derivatives. With beta-alkyl-substituted N-acylpyrroles, the reaction proceeded smoothly and the products were obtained in high yield and good ee. Transformation of the 1,4-adducts from enones and alpha,beta-unsaturated N-acylpyrroles afforded corresponding chiral aziridines and beta-amino acids. Detailed mechanistic studies, including kinetics, NMR analysis, nonlinear effects, and rare earth metal effects, are also described. The Lewis acid-Lewis acid cooperative mechanism, including the substrate coordination mode, is discussed in detail. 相似文献
63.
Noriyuki Inoue 《Mathematical Thinking and Learning》2013,15(1):36-67
Studies report that students often fail to consider familiar aspects of reality in solving mathematical word problems. This study explored how different features of mathematical problems influence the way that undergraduate students employ realistic considerations in mathematical problem solving. Incorporating familiar contents in the word problems was found to have only a limited impact. Instead, removing contextual constraints from the problem goal was found to motivate students to validate their problem solving in terms of their everyday experiences. Based on these findings, what determines the authenticity and relevance of a mathematical problem seems to be whether the problem allows students to freely reconstruct the problem situation by making use of their imagination and everyday experiences. In short, the basic principle seems to be “less is more”; that is, fewer constraints in problem goals could function to help students personally associate problem solving with their everyday experiences. 相似文献
64.
Kosuke Takeda Kazushi Fujimoto Noriyuki Yoshii Susumu Okazaki 《Journal of computational chemistry》2019,40(31):2722-2729
Molecular dynamics calculations of a mixed micelle composed of sodium dodecyl sulfate (SDS) and octaethylene glycol monododecyl ether (C12E8) were performed for six compositions (SDS/C12E8 = 100/0, 80/20, 60/40, 40/60, 20/80, and 0/100) to investigate the composition dependence of the mixed micelle structure and solubilization of cyclohexane, benzene, and phenol molecules by the micelle. The radial density distribution of the hydrophilic polyoxyethylene (POE) group of C12E8 as a function of distance from the micelle center is very sharp for micelles with high SDS content because the POE group captures a Na+ ion in solution and wraps around it to form a compact crown-ether-like complex. The hydrophobic dodecyl groups of SDS and C12E8 were separately distributed in the mixed micelle core. ΔG(r) evaluated for each solute showed that despite the structural changes of the micelle the binding strength of the solute molecules to the micelle did not change significantly. © 2019 Wiley Periodicals, Inc. 相似文献
65.
Mariko Kitajima Tomomi Yanagisawa Mari Tsukahara Yasuka Yamaguchi Noriyuki Kogure Ruri Kikura-Hanajiri Yukihiro Goda Osamu Iida Yasushi Sugimura Nobuo Kawahara Hiromitsu Takayama 《Tetrahedron》2018,74(4):441-452
Three new biphenyl ether quinolizidine lactone alkaloids (1–3) and 13 new biphenyl quinolizidine lactone alkaloids (4–16) were isolated from Heimia salicifolia (Lythraceae) together with seven known alkaloids. Their structures were determined by spectroscopic analyses and chemical conversions. 相似文献
66.
Heteroisotope and heteroatom tagging with [34S]-enriched methionine (Met), selenomethionine (SeMet), and telluromethionine (TeMet) was applied to in vitro translation.
Green fluorescent protein (GFP) and JNK stimulatory phosphatase-1 (JSP-1) genes were translated with wheat germ extract (WGE)
in the presence of Met derivatives. GFPs containing Met derivatives were subjected to HPLC coupled with treble detection,
i.e., a photodiode array detector, a fluorescence detector, and an inductively coupled plasma mass spectrometer (ICP-MS).
The activities of JSP-1-containing Met derivatives were also measured. GFP and JSP-1 containing [34S]-Met and SeMet showed comparable fluorescence intensities and enzyme activities to those containing naturally occurring
Met. TeMet was unstable and decomposed in WGE, whereas SeMet was stable throughout the experimental period. Thus, although
Te was the most sensitive to ICP-MS detection among S, Se, and Te, TeMet was less incorporated into the proteins than Met
and SeMet. Finally, the potential of heteroisotope and heteroatom tagging of desired proteins in in vitro translation followed
by ICP-MS detection was discussed.
Figure TeMet was less incorporated into GFP than Met and SeMet due to its instability in WGE 相似文献
67.
The authors have demonstrated the Hf(OTf)4-doped Me3SiCl system-catalyzed aminomethylation of electron-rich aromatic compounds, such as indoles and anilines, with new types of N,O-acetals having a variety of functional groups, such as cyano, ester, bis(trimethylsilyl)amino, diallylamino, and cyclic amino moieties, for the preparation of non-natural aromatic amino acid derivatives. Aminomethylation using an N,O-acetal with a bis(trimethylsilyl)amino group was particularly successful in the direct preparation of an N-unsubstituted α-indolylglycine derivative, which required only a standard aqueous workup. 相似文献
68.
Ohishi Y Kimura K Yamaguchi M Uchida N Kanayama T 《The Journal of chemical physics》2008,128(12):124304
We report the formation of icosahedral B(12)H(8) (+) through ion-molecule reactions of the decaborane ion [B(10)H(x)(+) (x=6-14)] with diborane (B(2)H(6)) molecules in an external quadrupole static attraction ion trap. The hydrogen content n of B(12)H(n)(+) is determined by the analysis of the mass spectrum. The result reveals that B(12)H(8)(+) is the main product. Ab initio calculations indicate that B(12)H(8)(+) preferentially forms an icosahedral structure rather than a quasiplanar structure. The energies of the formation reactions of B(12)H(14)(+) and B(12)H(12)(+) between B(10)H(x)(+) (x=6,8) ions, which are considered to be involved in the formation of B(12)H(n)(+), and a B(2)H(6) molecule are calculated. The calculations of the detachment pathway of H(2) molecules and H atoms from the product ions, B(12)H(14)(+) and B(12)H(12) (+), indicate that the intermediate state has a relatively low energy, enabling the detachment reaction to proceed owing to the sufficient reaction energy. This autodetachment of H(2) accounts for the experimental result that B(12)H(8)(+) is the most abundant product, even though it does not have the lowest energy among B(12)H(n)(+). 相似文献
69.
Magnetically Alignable Bicelles with Unprecedented Stability Using Tunable Surfactants Derived from Cholic Acid 下载免费PDF全文
Ryoichi Matsui Dr. Noriyuki Uchida Dr. Masataka Ohtani Kuniyo Yamada Arisu Shigeta Prof. Dr. Izuru Kawamura Prof. Dr. Takuzo Aida Dr. Yasuhiro Ishida 《Chemphyschem》2016,17(23):3916-3922
Five novel surfactants were prepared by modifying the three hydroxy groups of sodium cholate with triethylene glycol chains endcapped with an amide ( SC‐C1 , SC‐ n C4 , and SC‐ n C5 ) or a carbamoyl group ( SC‐O n C4 and SC‐O t C4 ). The phase behavior of aqueous mixtures of these surfactants with 1,2‐dimyristoyl‐sn‐glycero‐3‐phosphatidylcholine (DMPC) was systematically studied by 31P NMR spectroscopy. The surfactants endcapped with carbamate groups ( SC‐O n C4 and SC‐O t C4 ) formed magnetically alignable bicelles over unprecedentedly wide ranges of conditions, in terms of temperature (from 21–23 to >90 °C), lipid/surfactant ratio (from 5 to 8), total lipid content (5–20 wt %), and lipid type [DMPC, 1,2‐dilauroyl‐sn‐glycero‐3‐phosphatidylcholine (DLPC), or 1‐palmitoyl‐2‐oleoyl‐sn‐glycero‐3‐phosphatidylcholine (POPC)]. In conjunction with appropriate phospholipids, the carbamate‐endcapped surfactants afforded unique bicelles, characterized by exceptional thermal stabilities (from 0 to >90 °C), biomimetic lipid compositions (DMPC/POPC=25:75 to 50:50), and extremely large 2H quadrupole splittings (up to 71 Hz). 相似文献
70.
Asymmetric hydrogenation of various alpha-chloro aromatic ketones with Ru(OTf)(TsDPEN)(eta6-arene) (TsDPEN = N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine) produces the chiral chlorohydrins in up to 98% ee. This reaction can be conducted even on a 206-g scale. The hydrogenation of an alpha-chloro ketone with a phenol moiety has been utilized for the synthesis of (R)-norphenylephrine without protection-deprotection operations. [reaction: see text]. 相似文献