Photoresponsive molecularly imprinted polymers based on 4-[(4-methacryloyloxy)phenylazo] benzenesulfonic acid for the determination of sulfamethazine.

Core-shell structured photoresponsive molecularly imprinted polymers were developed for the determination of sulfamethazine in milk samples. The photoresponsive imprinted polymers were prepared with polymethyl methacrylate containing a mass of ester groups as core, sulfamethazine as template molecules, self-synthesized water-soluble 4-[(4-methacryloyloxy)phenylazo] benzenesulfonic acid as a photoresponsive monomer, and ethylene dimethacrylate as cross-linker. Interestingly, the imprinted polymer can specifically adsorb sulfamethazine under dark and 440 nm irradiation, and release it at 365 nm. A series of adsorption experiments showed that the maximum adsorption capacity reached 12.5 mg⋅g-1 , and the adsorption equilibrium was achieved within 80 min. Moreover, the imprinted polymers display excellent reusability, with almost no performance loss after four times photo-controlled adsorption-release cycles, and the imprinted polymers have excellent selectively for sulfamethazine (imprinting factor  = 3.01). In the end, the imprinted polymers realized effective separation and enrichment of sulfamethazine in milk, with a recovery rate of over 97.5%. The material can be used as a solid-phase extractant in the process of enrichment and separation for the quantitative detection of sulfamethazine in milk samples.

Spatial distribution and eco-environmental risk assessment of heavy metals in surface sediments from a crater lake (Bosomtwe/Bosumtwi).

Thirty samples of sediments were taken from Bosumtwi Lake (also called Bosomtwe Lake) in Ghana and analyzed for the contents of Fe, As, Hg, Co, Cr, Ni, Cd, and Pb. Several pollution indices (enrichment factor (EF), contamination factor (CF), geoaccumulation (Igeo), and pollution load index (PLI)) were used to determine sedimentary pollution levels, and the risk of environmental exposure was calculated using Hakanson's potential ecological risk (PER) indices. The results from PER assessments have indicated that sediments from the Bosumtwi Lake present a moderate environmental risk. According to EF calculations, Hg in Bosumtwi lake sediments is the element of concern that is being severely enriched. Hg was the largest contributor to PER with a 97% risk contribution. Multivariate statistical analysis revealed that the main sources of Hg were agrochemicals and atmospheric deposition, whereas the sources of Fe, As, Co, Cr, and Ni to Bosumtwi Lake were natural processes and are derived from the local lithology. There was no strong significant correlation among the contents of the heavy metals, sediment grain sizes, and total organic carbon (TOC), suggesting their lack of control in the distribution of heavy metals, the source, and the transport pathway. Finally, it is strongly recommended to do a study on Hg bioavailability in Bosumtwi Lake sediments. These findings will be relevant to Bosumtwi Lake's profiling and historical development of heavy metal loads.

Cancer and non-cancer risks in humans exposed to trace elements in drinking water from a crater lake (Bosumtwi/Bosomtwe).

The total and dissolved lead, cadmium, mercury, nickel, chromium, cobalt, and arsenic in 30 water samples collected from Bosomtwe Lake were analyzed. Arsenic bioavailability was also determined using the ARSOlux test system. Except for chromium, their mean values in the study results exceeded the WHO permissible limit for potability. Cancer and non-cancer effects associated with exposure to dissolved and total metals by a child and an adult via oral and dermal routes were estimated. The hazard quotient (HQ) values obtained (except adult exposure to total arsenic of 1.71 × 1000 ) were less than unity. Between child and adult, the recorded hazard index (HI) was 0.82 and 1.75, respectively. The HI results indicate that the adult population is at risk for non-cancer health effects. Arsenic was the element of concern, and it remained biologically available for uptake by target groups. For child and adult, respectively, arsenic contributed 96.39% and 97.29% to HI values. The risk values for cancer in a child and an adult with oral and dermal exposure to dissolved and total arsenic were lower than the USEPA range. Principal component and cluster analysis identified atmospheric deposition, geogenic, and unregulated application of agrochemicals as plausible sources of water pollution in Bosomtwe Lake. PRACTITIONER POINTS: The hazard quotient (HQ) values obtained for adult exposure to total arsenic was 1.71 × 1000 . Arsenic remained biologically available for uptake by target groups. The calculated health index (HI) indicated that the adult population is at risk for non-cancer health effects. Arsenic contributed 96.39% and 97.29% to HI values for a child and an adult. Atmospheric deposition, geogenic, and unregulated application of agrochemicals were the plausible sources of water pollution in Bosomtwe Lake.

Highly sensitive electrochemical BPA sensor based on titanium nitride-reduced graphene oxide composite and core-shell molecular imprinting particles.

A sensitive electrochemical sensor was proposed via combining molecular imprinting technique with the graphene material-doped titanium nitride. The novel graphene with 3-dimensional structure displayed more binding sites and better electrochemical properties. Moreover, this study focused on coating pyrrole with electrical conductivity on the surface of silica as a monomer, and BPA as the template. The interaction made specific detection possible, between monomer and template. With a series of characterizations and electrochemical measurements, CPE (carbon paste electrode)-contained TiN-rGO composite was proved to have conductivity improved. Also, the modified polymer performed well selectivity which reflected in that it was almost impervious to distractions. Under optimized conditions, a linear dependence was observed from 0.5 to 100 nmol L-1 with a detection limit of 0.19 nmol L-1. The sensor explicated outstanding repeatability via repetitive experiment with the RSD of 0.02%, while the results of stability experiment reached the RSD of 1.90%. Eventually, it was used to analyze BPA residues in 3 kinds of daily supplies. The results indicated the potential of the sensor in environmental detection prospectively.

Selective enrichment-release of trace dibutyl phthalate via molecular-imprinting based photo-controlled switching followed by high-performance liquid chromatography analysis.

A novel intelligent photo-controlled molecularly imprinted polymers were synthesized, based on the magnetic core-shell structure, with 4-[(4-methacryloyloxy) phenylazo] benzenesulfonic acid as the functional monomer and ethylene glycol dimethyl acrylate as the cross-linking agent. Subsequently, a series of light-controlled enrichment-release performance showed that it only took about 30 and 10 min to reach the equilibrium photosensitive characteristic peak, respectively. The photo-controlled polymers could intelligently select target molecules, the maximum adsorption capacity for dibutyl phthalate was 3.88 mg/g. However, the adsorption capacity for its structural analogue dicyclohexyl phthalate was only 0.88 mg/g. The Freundlich and Langmuir isothermal equations were discussed for the specific enrichment process. Finally, the photo-controlled molecularly imprinted polymers were successfully applied to the selective detection of dibutyl phthalate, with the recovery rate of 95.4-98.4%. It could be used for the analysis of trace dibutyl phthalate in actual samples.

Ratiometric fluorescence nanosensors based on core-shell structured carbon/CdTe quantum dots and surface molecularly imprinted polymers for the detection of sulfadiazine.

Sulfadiazine is an environmental pollutant derived from abuse of antibiotics. Its content in environmental water is closely related to human health. Thus, a novel dual-emission surface molecularly imprinted nanosensor is designed for the specific adsorption and detection of sulfadiazine. In the system, blue emissive carbon quantum dots wrapped with silica served as the internal reference signal for eliminating background interference, while red emissive thioglycolic acid modified CdTe quantum dots (CdTe QDs), which are low dimensional semiconductor materials by the combination of cadmium and tellurium with excellent optical properties, were encapsulated in the imprinted layer to offer recognition signal. The fluorescence of CdTe quantum dots was quenched and the fluorescence quenching degree of carbon quantum dots was inconspicuous with the increase of concentration of sulfadiazine, thereby reflecting the color change. The detection of sulfadiazine was successfully achieved in a concentration range of 0.25-20 µmol/L with detection limit of 0.042 µmol/L and nanosensors had specific recognition for sulfadiazine over its analogues. Compared to single-emission fluorescence sensors, ratiometric fluorescence nanosensors had wider linear range and higher detection accuracy. Furthermore, the nanosensors were also successfully applied for the determination of sulfadiazine in real water and milk samples with acceptable recoveries. The study provides a feasible method for the detection of sulfadiazine and a reference for the detection of sulfonamides.

Computer-aided design and synthesis of magnetic molecularly imprinted polymers with high selectivity for the removal of phenol from water.

A molecular simulation method was introduced to compute the phenol-monomer pre-assembled system of a molecularly imprinted polymer. The interaction type and intensity between phenol and monomer were evaluated by combining binding energy and charge transfer with complex conformation. The simulation results indicate that interaction energies are simultaneously affected by the type of monomer and the ratio between phenol and monomers. At the same time, we considered that by increasing the amount of functional monomer is not always better for preparing molecularly imprinter polymers. In this study, three kinds of novel magnetic phenol-imprinted polymers with favorable specific adsorption effects were prepared by the surface imprinting technique combined with atom transfer radical polymerization. Various measures were selected to characterize the structure and morphology to obtain the optimal polymer. The characterization results show that the optimal polymer has suitable features for further adsorption process. A series of static adsorption experiments were conducted to analyze its adsorption performance, which follows the Elovich model from the kinetic analysis and the Sips equation from the isothermal analysis. To further verify the reliability and accuracy of the simulation results, the effects of different monomers on the adsorption selectivity were also determined. They display higher selectivity towards phenol than 4-nitrophenol.The results from the simulation of the pre-assembled complexes are in reasonable agreement with those from the experiment.