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51.
Spiros Tzavalas Dionysis E. Mouzakis Vasilis Drakonakis Vasilis G. Gregoriou 《Journal of Polymer Science.Polymer Physics》2008,46(7):668-676
PET‐nanotube composite samples were manufactured by mixing neat PET with a PET‐multiwall carbon nanotube masterbatch. Fourier transform infrared (FTIR) spectroscopy was utilized to monitor the gauche and trans conformations of the polymeric chains with respect to the nanotube content. The crystallinity as well as the crystallization behavior of the polymer were studied via differential scanning calorimetry (DSC). An increase of the trans conformations and crystallinity was recorded at low NT contents followed by a sharp decrease at 1 wt % of nanotubes, further addition of nanotubes led once again to increase of the trans conformations and crystallinity. This behavior was attributed to the aggregations formation which as shown via transmission electron microscopy (TEM) was initiated at concentrations above 0.5 wt %. Discordance between the FTIR and DSC results in the case of the PET sample showed that the later bears relatively more trans non‐crystalline conformers than the nanocomposite samples. Thus it appears that the nanotubes incorporate the trans non‐crystalline segments into the crystalline phase. This work has shown that even a minor addition of carbon nanotubes (even 0.1 wt %) alters the crystallization behavior of the polymer dramatically, yielding a novel nanocomposite material rather than a simple mixture of two ingredients. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 668–676, 2008 相似文献
52.
Fuzhou Wang Ryo Tanaka Zhengguo Cai Yuushou Nakayama Takeshi Shiono 《Macromolecular rapid communications》2016,37(16):1375-1381
α‐Diimine nickel complexes bearing bulky ortho‐sec‐phenethyl groups (bis{[N,N′‐(4‐methyl‐2,6‐di‐sec‐phenethylphenyl)imino]‐1,2‐dimethylethane}dibromonickel ( 1 ), bis{[N,N′‐(4,6‐dimethyl‐2‐sec‐phenethylphenyl)imino]‐1,2‐dimethylethane}dibromonickel ( 2 ), bis{[N,N′‐(4‐methyl‐2‐sec‐phenethylphenyl)imino]‐1,2‐dimethylethane}dibromonickel ( 3 )) and {bis[N,N′‐(2,4,6‐trimethylphenyl)imino]‐1,2‐dimethylethane}dibromidonickel ( 4 ) are used as a precatalyst for the polymerization of trans‐4‐octene upon activation with modified methylaluminoxane. These catalysts conduct chain‐walking polymerization of trans‐4‐octene to give polymers possessing propyl and butyl branches with high molecular weight and narrow molecular weight distribution. The branching structure depends on the nickel complex as well as the polymerization temperature, and the ratio of propyl branch was increased with increasing the bulkiness of the ligand and decreasing the polymerization temperature. Consequently, the most bulky 1 among the complexes used is found to polymerize trans‐4‐octene with high 1,5‐regioselectivity at −20 °C to give poly(1‐propylpentan‐1,5‐diyl).
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The Acceptor Properties of the Metal—Metal Unit in the Dinuclear Complexes cis-M2(O2CCH3)2Cl4L2, M = Tc, Re; L = neutrale Base The weakly bound H2O molecules in axial positions of the dimetalates cis-M2(O2CCH3)2Cl4L2, M = Tc, Re, are easily substituted on reaction with stronger donor bases. With increasing donor number DN or donor strength DS of the axial ligands, the metal—metal stretching frequency v1 is lowered. The linearity between v1 and the hard DN scale shows, that the M2 unit acts as a hard Lewis acid in the axial direction, according to the observation that no coordination of soft donor bases takes place. The trans influence of the metal—metal multiple bond is estimated from the ratio of the shifts observed for v1 and the equatorial metal-ligand stretching modes after formation of adducts. The ratio is about 5: 1 in the ditechnetates and thus considerable higher than in the dirhenates with about 2: 1. 相似文献
56.
Drahomír Výprachtický Věra Cimrová Ivan Kmínek Petra Pavlačková 《Macromolecular Symposia》2010,295(1):94-99
Summary: By the Suzuki coupling reaction of 9,9-dioctyl-2,7-bis(1,3,2-dioxaborinan-2-yl)fluorene ( I ) and 3,5-di-tert-butylphenyl 2,5-dibromobenzenesulfonate ( II ) the alternating poly{[9,9-dioctylfluoren-2,7-diyl]-alt-[2-(3,5-di-tert-butyl-phenoxysulfonyl)-1,4-phenylene]} ( III ) was synthesized. Alkaline hydrolysis of III gave a conjugated polyelectrolyte carrying sulfonic acid groups ( IV ). Monomers 2,5-dibromo-3-[2-(pyren-1-yl)vinyl]thiophene and 2,5-dibromo-3-[2-(quinolin-4-yl)vinyl)thiophene were prepared and copolymerized with I to afford poly{[9,9-dioctylfluoren-2,7-diyl]-alt-[3-(2-(pyren-1-yl)vinyl)thiophen-2,5-diyl]} ( V ) and poly{[9,9-dioctylfluoren-2,7-diyl]-alt-[3-(2-(quinolin-4-yl)-vinyl)thiophen-2,5-diyl] ( VI ), respectively. Conjugated backbone of V contains the conjugated pyrene unit in the side chain. Similarly the side chain of VI contains the conjugated quinoline structure unit which can be for instance protonated. By the Suzuki polycondensation reaction of I and of the prepared methyl 3-(2,7-dibromocarbazole-9-yl)propionate ( VII ) the new poly{[9,9-dioctylfluorene-2,7-diyl]-alt-[9-(2-methoxycarbonylethyl)carbazole-2,7-diyl]} ( VIII ) was synthesized and characterized. 相似文献
57.
Danni Wu Kathleen Joyce D. Carillo Shen‐Long Tsai Jiun‐Jie Shie Der‐Lii M. Tzou 《中国化学会会志》2019,66(10):1318-1326
The neurosteroid trans‐dehydroandrosterone (DHEA) and its analogs with slightly different modifications in the side chain attached to C17, that is, (3S)‐acetoxypregn‐5‐en‐20‐one ( 1 ) and (3S,20R)‐acetoxypregn‐5‐en‐20‐ol ( 2 ), have been synthesized to investigate DHEA–cation interactions. In this study, we applied solid‐state 1H/13C cross‐polarization/magic‐angle spinning (CP/MAS) nuclear magnetic resonance (NMR) spectroscopy to a series of DHEA analog/Mg2+ mixtures at different Mg2+ concentrations. The high‐resolution 13C NMR spectra of 1 /Mg2+ mixtures exhibit two distinct 13C spectral patterns, one attributable to 1 free from Mg2+, and the other attributable to 1 with bound Mg2+. For 2 , the 13C NMR spectra exhibit three distinct spectral patterns; besides that of the free form, the other two can be assigned to Mg2+‐bound forms. Based on the analysis of the chemical shift deviations (CSDs), we conclude that both 1 and 2 might be subject to a cation–π interaction via the C5–C6 double bond, in contrast to that observed previously for DHEA. As demonstrated, DHEA possesses two Mg2+ binding sites, that is, C17–O and C5–C6 double bond, in which the binding affinity of the former is at least three times stronger than that of the latter. The solid‐state 13C NMR investigation allows better understanding of the underlying cation binding effects of neurosteroid molecules in vitro. 相似文献
58.
Chikao Onogi Michiyo Motoyama Hiro‐o Hamaguchi 《Journal of Raman spectroscopy : JRS》2008,39(5):555-556
High concentration trans form unsaturated lipids have been found in a HeLa cell by Raman microspectroscopy. Two CC stretch bands are observed simultaneously at 1669 cm−1 (trans form) and at 1656 cm−1 (cis form) in a Raman spectrum obtained from a small area (1 µm in diameter) in a HeLa cell. The intensity ratio 1669/1656 indicates that the concentration of the trans form is as high as that of the cis. It is demonstrated that Raman microspectroscopy provides a powerful and unique means for in situ and noninvasive structural characterization of unsaturated lipids in a living cell. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
59.
Werner Uhl Prof. Dr. Michael Claesener Sima Haddadpour Beate Jasper Ines Tiesmeyer Sarina Zemke 《无机化学与普通化学杂志》2008,634(15):2889-2896
Hydrogallation Reactions Involving the Monoalkynes H5C6‐C≡C‐SiMe3 and H5C6‐C≡C‐CMe3 – cis/trans Isomerisation and Substituent Exchange Phenyl‐trimethylsilylethyne, H5C6‐C≡C‐SiMe3, reacted with different dialkylgallium hydrides, R2Ga‐H (R = Me, Et, nPr, iPr, tBu), by the addition of one Ga‐H bond to its C≡C triple bond (hydrogallation). The gallium atoms attacked selectively those carbon atoms, which were also attached to trimethylsilyl groups. The cis arrangement of Ga and H across the resulting C=C double bonds resulted only for the sterically most shielded di(tert‐butyl)gallium derivative, while in all other cases spontaneous cis/trans rearrangement occurred with the quantitative formation of the trans addition products. The diethyl compound Et2Ga‐C(SiMe3)=C(H)‐C6H5 ( 2 ) gave by substituent exchange the secondary products EtGa[C(SiMe3)=C(H)‐C6H5]2 ( 7 , Z,Z) and Ga[C(SiMe3)=C(H)‐C6H5]3 ( 8 ). Interestingly, compound 8 has two alkenyl groups with a Z configuration, while the third C=C double bond has the cis arrangement of Ga and H (E configuration). The reversibility of the cis/trans isomerisation of hydrogallation products was observed for the first time. tert‐Butyl‐phenylethyne gave the simple addition product, R2Ga(C6H5)=C(H)‐CMe3 ( 9 ), only with di(n‐propyl)gallium hydride. 相似文献
60.
Ea S Aubert C Giacometti S Ciccolini J Siv C Bun H 《Biomedical chromatography : BMC》2008,22(2):125-130
A simple HPLC method with ultraviolet detection has been developed and validated for the simultaneous determination of haplamine and its metabolites (trans/cis-3,4-dihydroxyhaplamine) in rat. A liquid-liquid extraction was used to extract the compounds from rat plasma. The analysis was performed on a C(18) Nucleosil Nautilus column. The mobile phase consisted of water (A) and a mixture of methanol and acetonitrile (85:15; v/v) (B) used in gradient mode (38-40% B for 10 min, 40-58% B for 49 min, 58-38% B for 1 min, and 38% for 5 min) pumped at 1 mL/min. The calibration curves showed good linearity with correlation coefficients greater than 0.999 for the analytes in the investigated concentration range. The lower limit of detection was 0.007, 0.008 and 0.009 microg/mL and the lower limit of quantification was 0.014, 0.017 and 0.018 microg/mL for haplamine, and trans/cis-3,4-dihydroxyhaplamine, respectively. The method was applied to a preliminary pharmacokinetic study in rats. This method proved to meet fully the standards required of experimental pharmacokinetic studies and should be used in further preclinical investigation. 相似文献