RESUMO
π-Conjugated chiral nanorings with intriguing electronic structures and chiroptical properties have attracted considerable interests in synthetic chemistry and materials science. We present the design principles to access new chiral macrocycles (1 and 2) that are essentially built on the key components of main-group electron-donating carbazolyl moieties or the π-expanded aza[7]helicenes. Both macrocycles show the unique molecular conformations with a (quasi) figure-of-eight topology as a result of the conjugation patterns of 2,2',7,7'-spirobifluorenyl in 1 and triarylamine-coupled aza[7]helicene-based building blocks in 2. This electronic nature of redox-active, carbazole-rich backbones enabled these macrocycles to be readily oxidized chemically and electrochemically, leading to the sequential production of a series of positively charged polycationic open-shell cyclophanes. Their redox-dependent electronic states of the resulting multispin polyradicals have been characterized by VT-ESR, UV/Vis-NIR absorption and spectroelectrochemical measurements. The singlet (ΔES-T=-1.29â kcal mol-1) and a nearly degenerate singlet-triplet ground state (ΔES-T(calcd)=-0.15â kcal mol-1 and ΔES-T(exp)=0.01â kcal mol-1) were proved for diradical dications 12+2â and 22+2â , respectively. Our work provides an experimental proof for the construction of electron-donating new chiral nanorings, and more importantly for highly charged polyradicals with potential applications in chirospintronics and organic conductors.
RESUMO
As one solid waste with potential for phosphorus removal, application of slags in water treatment merits attention. But it was inhibited greatly by alkaline solution (pH>9.5) and cemented clogging generated. To give one solution, phosphorus removal was investigated by combining deep-sea bacterium Alteromonas 522-1 and basic oxygen furnace slag (BOFS). Results showed that by the combination, not only higher phosphorous removal efficiency (>90%) but also neutral solution pH of 7.8-8.0 were achieved at wide ranges of initial solution pH value of 5.0-9.0, phosphorus concentration of 5-30mg/L, salinity of 0.5-3.5%, and temperature of 15-35°C. Moreover, sedimentary property was also improved with lower amount of sludge production and alleviated BOFS cementation with increased porosity and enlarged particle size. These results provided a promising strategy for the phosphorus recovery with slags in large-scale wastewater treatment.
Assuntos
Bactérias/metabolismo , Oxigênio/química , Fósforo/isolamento & purificação , Água do Mar/microbiologia , Resíduos , Águas Residuárias/química , Poluentes Químicos da Água/isolamento & purificação , Adsorção , Biodegradação Ambiental , Concentração de Íons de Hidrogênio , Tamanho da Partícula , Salinidade , Esgotos/química , TemperaturaRESUMO
Isotopic enrichment factor (Δ, the difference between the δ value of food and a consumer tissue) is an important parameter in using stable isotope analysis (SIA) to reconstruct diets, characterize trophic relationships, elucidate patterns of resource allocation, and construct food webs. Isotopic enrichment factor has been considered as a constancy value across a broad range of animals. However, recent studies showed that the isotopic enrichment factor differed among various types of animals although the magnitude of variation was not clear. Here, we conducted a meta-analysis to synthesize and compare Δ13C and Δ15N among four types of aquatic animals (teleosts, crustaceans, reptiles and molluscs). We searched for papers published before 2014 on Web of Science and CNKI using the key words "stable isotope or isotopic fractionation or fractionation factor or isotopic enrichment or trophic enrichment". Forty-two publications that contain 140 studies on Δ13C and 159 studies on Δ15N were obtained. We conducted three parallel meta-analyses by using three types of weights (the reciprocal of variance as weights, the sample size as weights, and equal weights). The results showed that no significant difference in Δ13C among different animal types (teleosts 1.0 per thousand, crustaceans 1.3 per thousand, reptiles 0.5 per thousand, and molluscs 1.5 per thousand), while Δ15N values were significantly different (teleosts 2.4 per thousand, crustaceans 3.6 per thousand, reptiles 1.0 per thousand and molluscs 2.5 per thousand). Our results suggested that the overall mean of Δ13C could be used as a general enrichment factor, but Δ15N should be chosen according to the type of aquatic animals in using SIA to analyze trophic relationships, patterns of resource allocation and food webs.