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91.
The regioselectivity of the metal-catalyzed ring opening of unsymmetrical 1,2-dioxines to cis-gamma-hydroxyenones was investigated using two different Co(II) salen complexes. Regioselectivity was determined by direct examination of the enone ratios and by derivitization with a stabilized phosphorus ylide. The steric influence of the substituents on the 1,2-dioxine was the primary influence on regioselectivity. Temperature played little role; however, solvent and selection of Co(II) complex could be used to mildly influence the outcome of the rearrangement for selected substrates. The origins of the selectivity for the reaction are discussed. 相似文献
92.
Structure of microemulsions with gemini surfactant studied by solvatochromic probe and diffusion NMR
Ben Moshe M Magdassi S Cohen Y Avram L 《Journal of colloid and interface science》2004,276(1):221-226
The structure of microemulsions prepared by the anionic gemini surfactant didodecyl diphenyl ether disulfonate (C12-DADS) was investigated by a solvatochromic probe and nuclear magnetic resonance (NMR) diffusion measurements. The NMR measurements indicate the presence of bicontinuous and oil-in-water microemulsions depending on microemulsion composition. The absorbance spectra of the solvatochromic probe, Nile red, indicate the solubilization of the probe in different sites, in agreement with the NMR findings. It was also found that the microemulsions were capable of dissolving the hydrophobic probe, Nile red, up to four times better than expected if it were simply dissolved in the toluene phase. 相似文献
93.
Yiru Zhang Jianlei Shen Rong Hu Xiujuan Shi Xianglong Hu Benzhao He Anjun Qin Ben Zhong Tang 《Chemical science》2020,11(15):3931
Surface immobilization provides a useful platform for biosensing, drug screening, tissue engineering and other chemical and biological applications. However, some of the used reactions are inefficient and/or complicated, limiting their applications in immobilization. Herein, we use a spontaneous and catalyst-free amino-yne click bioconjugation to generate activated ethynyl group functionalized surfaces for fast immobilization of native proteins and cells. Biomolecules, such as bovine serum albumin (BSA), human IgG and a peptide of C(RGDfK), could be covalently immobilized on the surfaces in as short as 30 min. Notably, the bioactivity of the anchored biomolecules remains intact, which is verified by efficiently capturing target antibodies and cells from the bulk solutions. This strategy represents an alternative for highly efficient surface biofunctionalization.Fast surface immobilization of native bioconjugates through a spontaneous amino-yne click reaction is realized. 相似文献
94.
The ability of templated uranium sulfate fluorides to adopt diverse inorganic architectures is demonstrated in six novel materials. The inorganic structures present in [N2C6H16][UO2F2(SO4)](USFO-2), [N2C6H16][UO2F(SO4)]2(USFO-3), [N2C3H12][UO2F(SO4)]2.H2O (USFO-4), [N2C5H14][UO2F(H2O)(SO4]2(USFO-5), [N2C6H18]2[UO2F(SO4)]4.H2O (USFO-6) and [N2C3H12][UO2F(SO4)]2.H2O (USFO-7) range from infinite chains to five different layer topologies. The chain, and two of the five layers, have unprecedented structure types. These compounds illustrate the structural diversity within this new family of materials, arising from the varied coordination of the U6+ centres. Each material was synthesised under hydrothermal conditions, through reaction of uranyl acetate, sulfuric acid, HF(aq), water, and the respective organic template. 相似文献
95.
Zhai HJ Yang X Wang XB Wang LS Elliott B Boldyrev AI 《Journal of the American Chemical Society》2002,124(23):6742-6750
Although neutral and ionic O4(0/-/+) species have been observed experimentally and considered for energetic materials, O4(2-) and O5(2-) dianions have not yet been explored. O4(2-) is valent isoelectronic to the well-known ClO3- and SO3(2-) anions, and O5(2-) is valent isoelectronic to ClO4- and SO4(2-). All are stable, common anions in solutions and inorganic salts. In this article, we explore the possibility of making covalently bound O4(2-) and O5(2-) species stabilized in the forms of M+O4(2-) and M+O5(2-) (M = Li, Na, K, Cs) in the gas phase. Laser vaporization experiments using M-containing targets and an O2-seeded carrier gas yielded very intense mass peaks corresponding to MO4- and MO5-. To elucidate the structure and bonding of the newly observed MO4- and MO5- species, we measured their photoelectron spectra and then compared them with ab initio calculations and the spectra of ClO3-, Na+SO3(2-), ClO4-, and Na+SO4(2-). Careful analyses of the experimental and ab initio results showed, however, that the observed species are of the forms, O2-M+O2- and O2-M+O3-. The more interesting M+O4(2-) and M+O5(2-) species were found to be higher-energy isomers, but they are true minima on the potential energy surfaces, which suggests that it might be possible to synthesize bulk materials containing covalently bound tetra- and pentatomic oxygen building blocks. 相似文献
96.
本文研究了乙酰基香豆素及其衍生物与吲哚的混晶在微环境影响下的固相光反应,并用固体紫外光谱、固体荧光光谱和X-射线粉末衍射技术考察了混晶的特征。实验结果表明,3-乙酰基香豆素及其7-乙酰氧基、7-苯甲酰氧基、5,6-苯并和6-溴衍生物与吲哚的固相光反应分别得到1:2缩合产物1~5,而6-硝基衍生物与吲哚的固相光反应却得到开环脱羰加成产物6。通过IR、MS、^1H NMR和元素分析结果确定了这六个新产物的结构。固体光谱的测试结果表明,取代乙酰基香豆素与吲哚间混晶的形成,分子间存在相互作用,使分子所处的微环境条件发生了变化。 相似文献
97.
A modified version of the first generation unidirectional molecular motor showed >99% stereoselectivity in photo-induced isomerizations in both directions, thus functioning as a perfect chiroptical molecular switch. 相似文献
98.
Greig MJ Bolaños B Quenzer T Bylund JM 《Rapid communications in mass spectrometry : RCM》2003,17(24):2763-2768
Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) was coupled with atmospheric pressure photoionization (APPI) for the first time and used for the analysis of several corticosteroids.1 The analytes showed excellent response using APPI when compared with both electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI). APPI has the advantage of requiring less heat for desolvation, resulting in less thermal degradation of the analytes and higher signal-to-noise than APCI. In terms of ultimate sensitivity, APPI is more efficient than either ESI or APCI for the analysis of corticosteroids. With some compounds, the high-resolution capability of FTICRMS was necessary to obtain an accurate mass due to contributions of the M(+.) (13)C isotope in the [M+H](+) ion peak. 相似文献
99.
A flow injection mini-column system based on short reaction times with 8-hydroxyquinoline (oxine) with ICP-AES detection is described for the isolation and preconcentration of the “fast reactive” or “toxic” aluminium fraction in water samples. Using a 3 s reaction time with oxine (5 × 10–4 mol/l) at pH 5.0, the “fast reactive” aluminium fraction is shown not to include the non-toxic AlF2+ species at low F–: Al3+ molar ratios (0.3 : 1). The complexed aluminium is isolated in a stable and recoverable form on mini-columns of Amberlite XAD-2 (0.3 cm × 5.0 cm, resin particle size range 0.08 mm–0.16 mm)). The retained aluminium is recovered by “back-flushing” the analytical column with 1 mol/l HCl for final element specific detection by ICP-AES. Detection limits (after preconcentration) of 2 μg/l, a linear range of 0–500 μg/l, and possible preconcentration factors of up to 18 times are demonstrated with the present system. Implications for the possible solution of sample stability problems encountered with labile aluminium species analysis and the development of a “field sampling” technique are discussed, where the desired Al fraction is quantitatively retained in a stable form on mini-columns. 相似文献
100.
F. Bousmina L. Zayani D. Ben Hassen-Chehimi N. Kbir-Ariguib M. Trabelsi-Ayedi 《Monatshefte für Chemie / Chemical Monthly》2003,4(10):763-768
The diagram of the ternary system Mg2+/Cl−, SO4 2−–H2O was established at 15°C by means of analytical and conductimetric measurements. Three compounds were found in this diagram, which are MgSO4·6H2O, MgSO4·7H2O, and MgCl2·6H2O. The solubility field of MgSO4·7H2O is important whereas those of MgSO4·6H2O and MgCl2·6H2O are small. The compositions (mass-%) of the two invariant points determined by the two methods are: MgSO4:MgCl2=2.73:33.80 and MgSO4: MgCl2=3.38:28.91. Both the measured and the calculated isotherm at 15°C have been used for modelling of the diagram Mg2+/Cl−, SO4 2−–H2O between 0 and 35°C. The polythermal invariant point was approximately located between 15 and 10°C. 相似文献