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31.
Regioselectivity of nucleophilic aromatic photosubstitution has been shown experimentally to depend upon activation energies of the competing transition states. Computational means of determining relative activation energies were sought, therefore, in order to predict regioselectivity. Optimization of the three triplet transition states of 2-chloro-4-nitroanisole with hydroxide ion gave energies of insufficient accuracy to predict regioselectivity. Computed enthalpy changes from the first triplet transition state to the triplet σ-complexes correlated precisely with the experimental activation energies. This exemplifies the Bell–Evans–Polanyi Principle, and it provides an accurate means of assessing regioselectivity. 相似文献
32.
Jiang Zhao Meng Lian Yue Yu Xiaogang Yan Xianbin Xu Xiaolong Yang Guijiang Zhou Zhaoxin Wu 《Macromolecular rapid communications》2015,36(1):71-78
A series of novel red phosphorescent polymers is successfully developed through Suzuki cross‐coupling among ambipolar units, functionalized IrIII phosphorescent blocks, and fluorene‐based silane moieties. The photophysical and electrochemical investigations indicate not only highly efficient energy‐transfer from the organic segments to the phosphorescent units in the polymer backbone but also the ambipolar character of the copolymers. Benefiting from all these merits, the phosphorescent polymers can furnish organic light‐emitting diodes (OLEDs) with exceptional high electroluminescent (EL) efficiencies with a current efficiency (η L) of 8.31 cd A−1, external quantum efficiency (η ext) of 16.07%, and power efficiency (η P) of 2.95 lm W−1, representing the state‐of‐the‐art electroluminescent performances ever achieved by red phosphorescent polymers. This work here might represent a new pathway to design and synthesize highly efficient phosphorescent polymers.
33.
The synergism/inhibition level, solubilization sites and the total solubility (St) of co-solubilization systems of phenanthrene, anthracene and pyrene in Tween 80 and sodium dodecyl sulfate (SDS) are studied by 1H-NMR, 2D nuclear overhauser effect spectroscopy (NOESY) and rotating frame overhauser effect spectroscopy (ROESY). In Tween 80, inhibition for phenanthrene, anthracene and pyrene is observed in most binary and ternary systems. However, in SDS, synergism is predominant. After analysis, we find that the different synergism or inhibition situation between Tween 80 and SDS is related to the different types of surfactants used and the resulting different co-solubilization mechanisms. In addition, we also find that three polycyclic aromatic hydrocarbons (PAHs) have similar solubilization sites in both Tween 80 and SDS, which are almost unchanged in co-solubilization systems. Due to the similar solubilization sites, the chemical shift changes of surfactant and PAH protons follow the same pattern in all solubilization systems, and the order of chemical shift changes is consistent with the order of changes in the St of PAHs. In this case, it is feasible to evaluate St of PAHs by chemical shift. In both Tween 80 and SDS solutions, the ternary solubilization system has relatively high St rankings. Therefore, in practical applications, a good overall solubilization effect can be expected. 相似文献
34.
《中国化学快报》2020,31(7):1847-1850
An unexpected bistricyclic aromatic ene AF was synthesized in a tin(II) chloride-mediated reductive aromatization reaction. The obtained AF showed a highly overcrowded structural conformation as revealed by X-ray crystallography. Interestingly, AF exhibited reversible high-contrast mechanochromism and thermochromism between pale and red color. The obvious chromism is likely ascribed to the conformation transformation and trace amount of diradical species formation upon stimulus. 相似文献
35.
Anthony Jolly Dandan Miao Maxime Daigle Jean‐Franois Morin 《Angewandte Chemie (International ed. in English)》2020,59(12):4624-4633
The solution‐phase synthesis is one of the most promising strategies for the preparation of well‐defined graphene nanoribbons (GNRs) in large scale. To prepare high quality, defect‐free GNRs, cycloaromatization reactions need to be very efficient, proceed without side reaction and mild enough to accommodate the presence of various functional groups. In this Minireview, we present the latest synthetic approaches for the synthesis of GNRs and related structures, including alkyne benzannulation, photochemical cyclodehydrohalogenation, Mallory and Pd‐ and Ni‐catalyzed reactions. 相似文献
36.
Rachelle S. Jacobson Andrew R. Korte Akos Vertes J. Houston Miller 《Angewandte Chemie (International ed. in English)》2020,59(11):4484-4490
Soot (sometimes referred to as black carbon) is produced when hydrocarbon fuels are burned. Our hypothesis is that polynuclear aromatic hydrocarbon (PAH) molecules are the dominant component of soot, with individual PAH molecules forming ordered stacks that agglomerate into primary particles (PP). Here we show that the PAH composition of soot can be exactly determined and spatially resolved by low‐fluence laser desorption ionization, coupled with high‐resolution mass spectrometry imaging. This analysis revealed that PAHs of 239–838 Da, containing few oxygenated species, comprise the soot observed in an ethylene diffusion flame. As informed by chemical graph theory (CGT), the vast majority of species observed in the sampled particulate matter may be described as benzenoids, consisting of only fused 6‐membered rings. Within that limit, there is clear evidence for the presence of radical PAH in the particulate samples. Further, for benzenoid structures the observed empirical formulae limit the observed isomers to those which are nearly circular with high aromatic conjugation lengths for a given aromatic ring count. These results stand in contrast to recent reports that suggest higher aliphatic composition of primary particles. 相似文献
37.
Silica-supported mono-metal (such as Ni, Cu) complexes and mixed metal (such as Cu/Zn, Cu/Cr) complexes of chitosan have been prepared. It is found that these non-noble metal complexes could be used as efficient catalysts for the hydrogenation of aromatic nitro compounds. The effects of type of metal, reaction temperature and pressure, solvent, nitrogen/metal molar ratio in the complex catalysts on the yields from nitrobenzene to aniline have been examined. It was also found that catalysts are active for the catalytic hydrogenation of other aromatic nitro compounds such as 2-nitroanisole, 2-nitroaniline, 2-nitrotoluene and 1-chloro-4-nitrobenzene. 相似文献
38.
Anna Onopiuk Klaudia Koodziejczak Monika Marcinkowska-Lesiak Iwona Wojtasik-Kalinowska Arkadiusz Szpicer Adrian Stelmasiak Andrzej Poltorak 《Molecules (Basel, Switzerland)》2022,27(1)
Marinating is one of the most common methods of pre-processing meat. Appropriate selection of marinade ingredients can influence the physicochemical properties of the meat and can reduce the level of polycyclic aromatic hydrocarbons (PAHs) in the final product. The effects of the inclusion of natural plant extracts such as bay leaf (BL), black pepper (BP), turmeric (TU), jalapeno pepper (JP) and tamarind paste (TA) in marinades on the physicochemical properties of grilled pork neck were studied. The addition of spice extracts to marinades increased the proportion of colour components L* and b*. The use of TU, TA, JP, MX and C marinades lowered the hardness and pH of the meat. The highest phenolic compound levels were observed in the case of the mixture of all extracts (MX) and JP marinades, and the highest total antioxidant capacity was exhibited by the BL and MX marinades. The highest PAH content was recorded in the CON marinade (Σ12PAH 98.48 ± 0.81 µg/kg) and the lowest in the JP marinade (4.76 ± 0.08 µg/kg), which had the strongest, statistically significant reducing effect (95% reduction) on PAH levels. Analysis of correlation coefficients showed a relationship between the total antioxidant capacity of the marinades and the PAH content in grilled pork. 相似文献
39.
In reactions of 3-(2-amino-3-pyridyl)amino-5,5-dimethylcyclohex-2-en-1-one with aromatic aldehydes (2- and 4-hydroxy-, 2-hydroxy-3-methoxy-, 4-dimethylamino-, 4-methoxy-, 2,4- and 3,4-dimethoxy-, 3,4-methylenedioxy-, 4-bromo-, 4-fluoro-, 4-chloro-, 2-nitro- and 3-nitrobenzaldehydes, furfural, and 2-thiophenecarbaldehyde), we have obtained the corresponding 10-aryl-7,7-dimethyl-5,6,7,8,9,10-hexahydro-11H-pyrido[3,2-b][1,4]benzodiazepin-9-ones. 相似文献
40.
Production and properties of a biosurfactant applied to polycyclic aromatic hydrocarbon solubilization 总被引:1,自引:0,他引:1
Microorganisms isolated from a soil sample collected from a gasoline filling station (located in Guwahati) were tested for
their pyrene- and anthracene-degrading potential. Preliminary studies showed the ability of the organism to grow on carbon-free
mineral medium (CFMM) supplemented with pyrene as the sole source of carbon. The organisms were found to produce a bioemulsifier
when grown on CFMM with glucose or glycerol and/or pyrene as the carbon source. The organisms could also utilize anthracene
when grown on mineral salt medium along with 2% glycerol. Within 2 d, anthracene concentration dropped less than 30% of the
original concentration. Approximately 100 mg of the emulsifier was isolated from 25 mL of the 5-d-grown culture. The emulsifier
was tested to produce emulsion with both an aliphatic and an aromatic group of hydrocarbons and resulting emulsions were found
to be stable for a long period of time when keptat 10–15°C. The emulsifier was also quite stable in a pH range of 3.0–11.0.
In a concentration range of 0.5–10 mg/mL, it resulted in a linear increment of apparent pyrene and anthracene solubility in
water. 相似文献