Intensified reactive extraction of 4-hydroxypyridine with di(2-ethylhexyl) phosphoric acid in 1-octanol by using tributyl phosphate

The efficient separation of amphoteric organic compounds from dilute solutions is of great importance in the industrial field. In the present work, the reactive extractions of 4-hydroxypyridine(4-HP) with tributyl phosphate(TBP), di(2-ethylhexyl) phosphoric acid(D2EHPA) and TBP + D2EHPA dissolved in 1-octanol were investigated, respectively. The influences of the initial concentrations of TBP, D2EHPA and TBP + D2EHPA on distribution ratio(D) were discussed, as well as the reactive extraction mechanism were proposed. The obvious intensification effect was observed when the mixture of TBP and D2EHPA was used as extractant. The best extraction conditions were found to be of the molar ratio of D2EHPA and TBP at 2:1 and the equilibrium aqueous pH at 3.50-4.50. D values increased with the increase of the total concentration of TBP and D2EHPA in 1-octanol. Especially, the analysis on the extraction mechanisms clearly indicate(i) TBP in 1-octanol shows negligible reactive extraction toward 4-HP,(ii) D2EHPA in 1-octanol exhibits moderate extraction effect by forming 4-HP:D2EHPA(1:1) and 4-HP:2D2EHPA(1:2) type complexes, while(iii) D2EHPA in TBP/1-octanol demonstrates the maximum distribution ratio with the 4-HP:D2EHPA(1:1) type complex domination. The discussion provides new insights on the mechanism and opens a new way for the intensified extraction of amphoteric organic compounds by using the mixture of multiple extractants in the diluent.

Spectral Properties and Solubilization Location of 2′-Ethylhexyl 4-（N,N-Dimethylamino）benzoate in Micelles

Dual fluorescence and UV absorption of 2′-ethylhexyl 4-（N,N-dimethylamino）benzoate （EHDMAB） were investigated in cationic, non-ionic and anionic micelles. When EHDMAB was solubilized in different micelles, the UV absorption of EHDMAB was enhanced. Twisted intramolecular charge transfer （TICT） emission with longer wavelength was observed in ionic micelles, whereas TICT emission with shorter wavelength was obtained in non-ionic micelles. In particular, dual fluorescence of EHDMAB was significantly quenched by the positively charged pyridinium ions arranged in the Stern layer of cationic micelles. UV radiation absorbed mainly decays via TICT emission and radiationless deactivation. The dimethylamino group of EHDMAB experiences different polar environments in ionic and non-ionic micelles according to the polarity dependence of TICT emission of EHDMAB in organic solvents. In terms of the molecular structures and sizes of EHDMAB and surfactants, each individual EHDMAB molecule should be buried in micelles with its dimethylamino group toward the polar head groups of different micelles and with its 2′-ethylhexyl chain toward the hydrophobic micellar core. Dynamic fluorescence quenching measurements of EHDMAB provide further support for the location of EHDMAB in different micelles.

Biodegradation of 2-ethylhexyl-4-methoxycinnamate in river sediments and its impact on microbial communities

Numerous studies have evaluated the toxicity and endocrine disrupting properties of organic UV filters for aquatic organisms,but little is known about their biodegradation in river sediments and their impact on microorganisms.We have set up the sterile and microbiological systems in the laboratory,adding 2-ethylhexyl-4-methoxycinnamate(EHMC),one of organic UV filters included in the list of high yield chemicals,at concentrations of 2,20 and 200μg/L,and characterized the microbial community composition and diversity in sediments.Monitoring of EHMC degradation within 30 days revealed that the half-life in the microbial system(3.49 days)was much shorter than that in the sterile system(7.55 days).Two potential degradation products,4-mercaptobenzoic acid and 3-methoxyphenol were identified in the microbial system.Furthermore,high-throughput 16s and 18s rRNA gene sequencing showed that Proteobacteria dominated the sediment bacterial assemblages followed by Chloroflexi,Acidobacteria,Bacteroidetes and Nitrospirae;Eukaryota_uncultured fungus dominated the sediment fungal assemblages.Correlation analysis demonstrated that two bacterium genera(Anaerolineaceae_uncultured and Burkholderiaceae_uncultured)were significantly correlated with the biodegradation of EHMC.These results illustrate the biodegradability of EHMC in river sediments and its potential impact on microbial communities,which can provide useful information for eliminating the pollution of organic UV filters in natural river systems and assessing their potential ecological risks.

Solid-phase extraction and separation of indium with P_(2)O_(4)-UiO-66-MOFs (di-2-ethylhexyl phosphoric acid-UiO-66-metal-organic frameworks)

Compared with the traditional liquid–liquid extraction method,solid-phase extraction agents are of great significance for the recovery of indium metal due to their convenience,free of organic solvents,and fully exposed activity.In this study,P_(2)O_(4)(di-2-ethylhexyl phosphoric acid)was chemically modified by using UiO-66 to form the solid-phase extraction agent P_(2)O_(4)-UiO-66-MOFs(di-2-ethylhexyl phosphoric acid-UiO-66-metal-organic frameworks)to adsorb In(Ⅲ).The results show that the Zr of UiO-66 bonds with the P-OH of P_(2)O_(4) to form a composite P_(2)O_(4)-UiO-66-MOF,which was confirmed by X-ray photoelectron spectroscopy(XPS)and Fourier transform infrared spectroscopy(FT-IR).The adsorption process of indium on P_(2)O_(4)-UiO-66-MOFs followed pseudo first-order kinetics,and the adsorption isotherms fit the Langmuir adsorption isotherm model.The adsorption capabilities can reach 192.8 mg/g.After five consecutive cycles of adsorption-desorption-regeneration,the indium adsorption capacity by P_(2)O_(4)-UiO-66-MOFs remained above 99%.The adsorption mechanism analysis showed that the P=O and P-OH of P_(2)O_(4) molecules coated on the surface of P_(2)O_(4)-UiO-66-MOFs participated in the adsorption reaction of indium.In this paper,the extractant P_(2)O_(4) was modified into solid P_(2)O_(4)-UiO-66-MOFs for the first time.This work provides a new idea for the development of solid-phase extractants for the recovery of indium.