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51.
Fluorine has come to be recognized as a key element in materials science: in heat‐transfer agents, liquid crystals, dyes, surfactants, plastics, elastomers, membranes, and other materials. Furthermore, many fluorine‐containing biologically active agents are finding applications as pharmaceuticals and agrochemicals. Progress in synthetic fluorine chemistry has been critical to the development of these fields and has led to the invention of many novel fluorinated molecules as future drugs and materials. As a result of the electronic effects of fluorine substituents, fluorinated substrates and reagents often exhibit unusual and unique chemical properties, which often make them incompatible with established synthetic methods. Thus, the problem of how to control the unusual properties of compounds with fluorine substituents deserves much attention, so as to promote the design of facile, efficient, and environmentally benign methods for the synthesis of valuable organofluorine targets. 相似文献
52.
Paolesse R Nardis S Venanzi M Mastroianni M Russo M Fronczek FR Vicente MG 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(5):1192-1197
5,10,15-Triphenylcorrole (1) reacts with the Vilsmeier reagent (POCl(3)/DMF) to give the corresponding 3-formyl derivative 3 as the major product. The regioselectivity of the reaction was proven by X-ray crystallography and only traces of the 2-formyl isomer were observed. A more polar product is also observed and this compound becomes the major product when an excess of DMF is used for the preparation of the Vilsmeier reagent, while the formation of the 3-formyl isomer is almost completely suppressed. X-ray crystallography allowed us to identify this compound as the fully substituted N-ethane bridged derivative 4, formed from the attack of the Vilsmeier reagent at the inner core of the macrocycle. This compound is unique among porphyrinoid macrocycles, and further confirms the peculiarity of corrole chemistry. 相似文献
53.
Ya‐Ping Du Ya‐Wen Zhang Prof. Dr. Zheng‐Guang Yan Dr. Ling‐Dong Sun Prof. Dr. Song Gao Prof. Dr. Chun‐Hua Yan Prof. Dr. 《化学:亚洲杂志》2007,2(8):965-974
We report the synthesis of single‐crystalline and near‐monodispersed NaMF3 (M=Mn, Co, Ni, Mg), LiMAlF6 (M=Ca, Sr), and NaMgF3:Yb,Er nanocrystals (quasisquare nanoplates, nanorods, and nanopolygons) by the cothermolysis of multiple trifluoroacetates in hot combined organic solvents (oleic acid, oleylamine, and 1‐octadecene). The nanocrystals were characterized by XRD, TEM, superconductive quantum interference device (SQUID), and upconversion luminescence spectroscopy. By regulating the polarity of the dispersant, the NaMF3 (M=Mn, Co, Ni) nanoplates were partially aligned to form nanoarrays on copper TEM grids. The sizes of the NaMF3 nanocrystals were easily tuned by the use of proper synthetic conditions such as reaction temperature and time and solvent composition. On the basis of a series of experiments in which the reaction conditions were varied, together with GC–MS and FTIR analysis, the reaction pathways for the formation of these nanocrystals from trifluoroacetate precursors were proposed. The magnetic measurements showed that the differently sized NaMnF3 square plates displayed interesting weak ferromagnetic behavior on the nanometer scale. The strong red upconversion luminescence emitted from the NaMgF3:Yb,Er nanorods under 980‐nm near‐IR laser excitation suggests that NaMgF3 may be a good candidate host material for red upconversion luminescence. 相似文献
54.
本文按合成产物的结构类型,综述分子内 Diels-Alder 反应在有机合成方面的新进展。 相似文献
55.
7-(2-Methoxycarbonylvinyl)-3-hydroxychromones have been synthesized using Heck coupling reaction from the corresponding 7-bromo-3-hydroxychromones. Introduction of the electron acceptor (2-methoxycarbonylvinyl) group at 7-position of 3-hydroxychromone results in a 30-40 nm red shift in absorption and >50 nm red shifts of both bands in emission. This derivatization allowed us to develop dyes with absorption maxima reaching 480 nm and dual emission in the red region of the spectrum. In comparison to the parent dyes, 7-acryl-3-hydroxychromones demonstrate significantly stronger solvatochromism. This is due to the acceptor group at 7-position, which increases the transfer character of the excited state of the dyes. The new dyes are highly prospective for the development of new fluorescent probes in biological research. 相似文献
56.
Three novel perylene polyimides (PPIs) containing p‐n diblock units were designed and synthesized for use in dye‐sensitized mesoporous TiO2 solar cells. They all dissolve in m‐cresol and N‐methyl‐2‐pyrrolidone (NMP). Their visible light absorption, electrochemical and photoelectrochemical properties were systematically studied. The polyimides have band gap energies of 2.16, 2.19 and 2.25 eV deduced from ultraviolet–visible absorption spectra, and electron affinity (Ea) and ionization potential (IP) of ?3.93 and 6.10 eV for PPI1, ?3.94 and 6.13 eV for PPI2, ?3.93 and 6.59 eV for PPI3, respectively, deduced from cyclic voltammogram. Experimental data show that introduction of 4,4′‐bisaminetriphenylamine cannot only greatly enhance optic‐electro conversion efficiency, but also enhance the dissolubility which in favorable for making the devices. The relationship of structure and properties of PPI is discussed and the mechanism of photocurrent generation is explained. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
57.
Summary A reversed phase liquid chromatographic method is proposed for the analysis of basic hair dyes (raw materials and colourant formulations). The performance of the method was enhanced by introducing post-column on-line photochemical derivatisation in combination with a Diode Array Detector. On-line photoderivatisation provided an effective way of selectively transforming the analytes to compounds with different spectral properties. For each analyte two characteristic UV-Visible spectra (photoreactor on and off) were obtained with the same mobile phase and this information in combination with the chromatographic data (k' at pH 3.0 and 4.5) enabled the unambiguous identification of both commonly used, approved, and banned basic hair dyes. Additionally, this approach was found useful to improve the method sensitivity, allowing the determination of analytes present in low concentration (0.03%) in complex commercial formulations.This work constitutes part of the thesis for the Dottorato di Ricerche of Roberto Gotti. 相似文献
58.
Carolina Menna Natalia Calonghi Lanfranco Masotti Paolo Neyroz 《Journal of fluorescence》1993,3(1):33-43
This report describes a method to conjugate lucifer yellow to the external surface of liposomes. The heterobifunctional cross-linking reagentN-succinimidyl 3-(2-pyridyldithio)propionate has been used to activate DMPE molecules. The DMPE-dithiopyridine product has been mixed with DMPC to prepare liposome vesicles. These have been reduced by DTT and finally reacted with lucifer yellow-iodoacetamide to produce the fluorescence-labeled vesicles. The quenching of their fluorescence intensity by Kl is consistent with fully exposed fluorophores. The decay of the fluorescence intensity of the lipid-bound lucifer yellow is biexponential (1=7.9 ns; 2=1.1 ns), with a relative yield of 0.16. When the fluorescent liposomes are mixed with cells, the lucifer yellow-DMPE derivative is transferred. Boar spermatozoa and peripheral human blood lymphocytes have been used as cellular models. The extent of incorporation is dependent on the incubation time and temperature. At 36°C, lucifer yellow fluorescence appears in the spermatozoa cells after 10 min of incubation and reaches its maximum at about 60 min. The fluorescent phospholipid derivative seems to incorporate specifically into membrane structures. The highest labeling ratio is observed with integer, scarcely motile, spermatozoa. A poorer labeling yield (15%) is found with lymphocytes. Interestingly, photobleaching due to epiillumination of the labeled cells is apparently negligible and cells are clearly visible after irradiation times ranging from several minutes to few hours.A preliminary account of this work was presented at the Quarto Simposio su Biotecnologie Biochimiche, Capri, 28–30 June 1992. 相似文献
59.
Burton A Elomari S Chen CY Medrud RC Chan IY Bull LM Kibby C Harris TV Zones SI Vittoratos ES 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(23):5737-5748
The syntheses, structure solutions, and physicochemical and catalytic characterizations of the novel zeolites SSZ-53 and SSZ-59 are described. SSZ-53 and SSZ-59 were synthesized under hydrothermal conditions with the [1-(4-fluorophenyl)cyclopentylmethyl]trimethyl ammonium cation and 1-[1-(4-chlorophenyl)cyclopentylmethyl]-1-methyl azocanium cation, respectively, as structure-directing agents. The framework topology of SSZ-53 was solved with the FOCUS method, and the structure of SSZ-59 was determined by model building. Rietveld refinement of synchrotron X-ray powder diffraction data confirms each proposed model. SSZ-53 and SSZ-59 each possess a one-dimensional channel system delimited by 14-membered rings. Results from transmission electron microscopy, electron diffraction, catalytic experiments (spaciousness index and constraint index tests), and argon and hydrocarbon adsorption experiments are consistent with the proposed structures. 相似文献
60.
Copolymerisation of methyl methacrylate with nine novel monomer compounds, triazinyl benzanthrone dyes, triazinyl benzotriazole stabilisers and their combined structures, was investigated. Chemical bonding of the compounds in the polymers obtained was confirmed spectrophotometrically. The quantity of the chemically bonded monomer compounds was determined to be over 50%, providing a colour and a fluorescence stable to solvents. Their influence on the rate of the copolymerisation was studied. It was found that the compounds under study did not significantly affect the rate of copolymerisation. A stabilizing effect towards photo-degradation of PMMA was achieved at 0.1 wt.% initial concentration of the compounds, which made them suitable for “one-step” colouration and stabilisation of PMMA. 相似文献