Effects of Fe3+ on Hydrothermal Humification of Agricultural Biomass.

Hydrothermal humification technology for the preparation of artificial humic matters provides a new strategy, greatly promoting the natural maturation process. Iron, as a common metal, is widely used in the conversion of waste biomass; however, the influence of Fe3+ on hydrothermal humification remains unknown. In this study, FeCl3 is used to catalyze the hydrothermal humification of corn straw, and the influence of Fe3+ on the hydrothermal humification is explored by a series of characterization techniques. Results show that Fe3+ as the catalyst can promote the decomposition of corn straw, shorten the reaction time from 24 h to 6 h, and increase the yield from 6.77 % to 14.08 %. However, artificial humic acid (A-HA) obtained from Fe3+ -catalysis hydrothermal humification contains more unstable carbon and low amount of aromatics, resulting in a significantly decreased stability of the artificial humic acid. These results provide theoretical guidance for regulating the structure and properties of artificial humic acid to meet various maintenance needs.

Roles of humic substances redox activity on environmental remediation.

Humic substances (HS) as representative natural organic matters and the most common organic compounds existing in the environment, has been applied to the treatment and remediation of environmental pollution. This review systematically introduces and summarizes the redox activity of HS for the remediation of environmental pollutants. For inorganic pollutants (such as silver, chromium, mercury, and arsenic), the redox reaction of HS can reduce their toxicity and mobilization, thereby reducing the harm of these pollutants to the environment. The concentration and chemical composition of HS, environmental pH, ionic strength, and competing components affect the degree and rate of redox reactions between inorganic pollutants and HS significantly. With regards to organic pollutants, HS has photocatalytic activity and produces a large number of reactive oxygen species (ROS) under the light which reacts with organic pollutants to accelerate the degradation of organic pollutants. Under the affection of HS, the redox of Fe(III) and Fe(II) can enhance the efficiency of Fenton-like reaction to degrade organic pollutants. Finally, the research direction of HS redox remediation of environmental pollution is prospected.

A highly water-stable dual-emission fluorescent probe based on Eu3+-loaded MOF for the simultaneous detection and quantification of Fe3+ and Al3+ in swine wastewater.

A novel dual-emissive Eu3+-loaded metal-organic framework (MOF) is designed and successfully fabricated by introducing 2-hydroxyterephthalic acid (H2BDC-OH) and Eu3+ ions into an UiO-66-type MOF material. The obtained MOF, here referred to as EuUCH, exhibits dual emission at 450 and 614 nm, and both emissions are quite stable in aqueous media in the pH range of 4-11. EuUCH is characterized by a high selectivity and sensitivity toward Fe3+ and Al3+, which yield different responsive modes. The two emissions of EuUCH are quenched by Fe3+; by contrast, only the emission at 450 nm is quenched by Al3+ showing a ratiometric fluorescence signal. More importantly, as there is no clear interference between the signals of Fe3+ and Al3+, EuUCH is successfully utilized for the simultaneous detection of Fe3+ and Al3+ in their mixtures. In addition, the simultaneous quantification of Fe3+ and Al3+ is achieved in more complicated swine wastewater with good recoveries. This work provides a water-stable dual-emissive probe and the possibility to achieve the simultaneous quantification of Fe3+ and Al3+ in complicated environment wastewater.

A luminescent Eu3+-functionalized MOF for sensitive and rapid detection of tetracycline antibiotics in swine wastewater and pig kidney.

Tetracyclines (TCs), a type of antibiotics, are widely used in human therapy and animal husbandry. Public concerns about tetracyclines residues have been raised due to their negative impact on the environment and food, causing bacterias drug resistance and human health concerns. In this work, a luminescent europium MOF (EuUCBA) is constructed via post-synthetic attachment of Eu3+ into a UiO-66 type MOF. The luminescent of EuUCBA exhibits high stability in aqueous media in the pH range of 4-11. Among 36 common veterinary drugs, the synthesized probe is highly selective and sensitive to six tetracyclines with low detection limits of 0.118 µM, 0.228 µM, 0.102 µM, 0.138 µM, 0.206 µM, and 0.078 µM for oxytetracycline (OTC), chlortetracycline (CTC), methylenetetracycline (MTC), minocycline (MOC), tetracycline (TC), and doxycycline (DOXY), respectively. Furthermore, the probe shows good anti-interference ability and fast response. Finally, EuUCBA was successfully to detect DOXY in swine wastewater and pig kidney with good recoveries. This work provides an excellent fluorescent sensor for highly selective and rapid detection of TCs residues in wastewater and complex biological samples.

Recyclable europium functionalized metal-organic fluorescent probe for detection of tryptophan in biological fluids and food products.

An europium functionalized metal-organic fluorescent probe, Eu3+@UiO-66-FDC was constructed by post-synthetic modification through coordination interactions. Eu3+@UiO-66-FDC displayed high selectivity and sensitivity toward Tryptophan (Trp) among all the 20 natural amino acids and other general compounds in food and biological samples, with a wide linear concentration range (0-1000 µM), low detection limit (0.29 µM), and a rapid response (<1 min). Besides, this probe was utilized to detect Trp in rabbit blood serum and milk samples with good recoveries, which were verified by high-performance liquid chromatography (HPLC). Notably, this fluorescent probe proved to be a recyclable material. Hence, this work provides a reliable and recyclable fluorescent probe applicable toward the detection of Trp in biological fluids and/or food products.

Highly sensitive and rapid detection of thiabendazole residues in oranges based on a luminescent Tb3+-functionalized MOF.

Thiabendazole (TBZ), has been extensively employed as a pesticide and/or a fungicide in agriculture, while its residues would threaten to public health and safety. Simple, rapid and sensitive probes for detection of TBZ in real food samples is significantly desirable. In present work, a highly selective and sensitive luminescent sensor for monitoring TBZ in oranges has been constructed based on a Tb3+-functionalized Zr-MOF (Tb3+@1). Tb3+@1 exhibited many attractive sensing properties toward TBZ, including broad linear range (0-80 µM), high selectivity, low LOD (0.271 µM) and rapid response time (less than1 min). Moreover, the probe was employed to determine TBZ in real orange samples, in which good recoveries from 98.41 to 104.48% were obtained. It only takes 35 min for the whole process of detection TBZ in real orange samples combined with QuEChERS method. Therefore, this work provided a reliable and rapid method for monitoring the TBZ in real orange samples.

Highly selective detection of Cu2+ in aqueous media based on Tb3+-functionalized metal-organic framework.

In this work, a metal-organic framework UiO-66-(COOH)2 has been synthesized and is further functionalized with Tb3+ through coordination interactions. The functionalized MOF, denoted as Tb3+@UiO-66-(COOH)2, is fully characterized and further developed as an excellent fluorescent probe to monitor Cu2+ ions in aqueous media by fluorescence quenching effect. Tb3+@UiO-66-(COOH)2 exhibits high selectivity and sensitivity, broad linear concentration range (0-200 µM), low detection limits (0.23 µM), fast response speed (within 1 min), as well as in situ naked eye observation under UV light for sensing Cu2+ ion. Furthermore, this probe was successfully employed to detect Cu2+ ion in real water with good recovery. Hence, this work developed a very excellent fluorescent sensor with high potential practical applications for detection of Cu2+ ion in environmental water samples.