Removal of Cs-137 Radionuclide by Resorcinol–Formaldehyde Ion-Exchange Resins from Solutions Simulating Real Liquid Radioactive Waste

The efficiency of the removal of Cs-137 radionuclides with porous and non-porous resorcinol–formaldehyde resins from alkaline solutions simulating the composition of real liquid radioactive waste (LRW) streams has been evaluated. Resins were synthesized through the polycondensation of resorcinol and formaldehyde in an alkaline medium at a molar ratio of 1.8/2.2 and a temperature of 210 °C. The Cs-137 distribution coefficients on RFRs in alkaline solutions simulating LRW were above 103 mL/g under static sorption conditions. In a model solution with pH 11, the full dynamic sorption capacity of non-porous RFR was 0.178 mmol/g. The values of the full dynamic sorption capacities of porous RFRs were 0.274 and 1.035 mmol/g for resins obtained with calcium carbonate and toluene as templates, respectively. When the sizes of RFR beads increased two-fold, the volume until 5% cesium breakthrough decreased by 20–40%. The most pronounced beneficial effect of the RFR’s porosity was observed at flow rates from 25 to 50 BV/h. It was shown that the negative effect of metal cations on Cs-137 uptake increases in the following order: Na+ 2+ 2+ +. The number of bed volumes of LRW-simulating solution decontaminated with RFRs until 5% cesium breakthrough was above 450; that is higher than the value of known commercially available analogs. The latter shows that the developed RFRs are promising for application in technological schemes of alkaline LRW processing

FRET Pumping of Rhodamine-Based Probe in Light-Harvesting Nanoparticles for Highly Sensitive Detection of Cu2+

In this work we presented novel strategy for increasing the performance of popular fluorescent probes on the basis of rhodamine-lactam platform. This strategy is based on the incorporation of probe molecules into the light-harvesting nanoparticles to pump modulated optical signal by Förster resonant energy transfer. Using the commercially available Cu2+ probe as a reference chemical, we have developed an efficient approach to significantly improve its sensing performance. Within obtained nanoparticles coumarin-30 nanoantenna absorbs excitation light and pumps incorporated sensing molecules providing bright fluorescence to a small number of emitters, while changing the probe-analyte equilibrium from liquid-liquid to solid-liquid significantly increased the apparent association constant, which together provided a ~100-fold decrease in the detection limit. The developed nanoprobe allows highly sensitive detection of Cu2+ ions in aqueous media without organic co-solvents usually required for dissolution of the probe, and demonstrate compatibility with inexpensive fluorometers and the ability to detect low concentrations with the naked eye

Porous Resorcinol-Formaldehyde Resins

Porous ion-exchanging resorcinol-formaldehyde resins were prepared by removing an inorganic template (CaCO3) and by polymerization of a highly concentrated emulsion with toluene as a dispersing phase. As compared to original resorcinol-formaldehyde resins, the porous one is characterized with higher values of internal diffusion, providing exceptional purification coefficients. However, the amounts of the introduced CaCO3 and toluene have to be below 10 wt.% and 25 wt.%, respectively, to avoid fast degradation of the ion-exchanger. Under dynamic conditions, average purification coefficients in the model solution of Cs-137 are twice higher than those of the non-porous sample. The prepared porous ion-exchange resin can be used in cases when high Cs-137 uptake from liquid media should be realized at increased rates of solution percolation

Light Harvesting Nanoprobe for Trace Detection of Hg2+ in Water

The continuously increasing flow of toxic heavy metals to the environment due to intensive industrial activity and tightening requirements with regard to the content of metal ions in drinking and discharged waters urges the development of affordable and sensitive devices to the field control of pollutants. Here, we report a new thiated Rhodamine-lactam probe for Hg2+ detection and demonstrate how its sensitivity can be increased via the incorporation of the probe molecules into the optically transparent siloxane-acrylate coatings on polymethyl methacrylate and, alternatively, into the water-dispersible light-harvesting FRET nanoparticles (NPs), in which dye cations are separated by fluorinated tetraphenylborate anions. We have shown that the optimization of the FRET NPs composition had allowed it to reach the antenna effect of ~300 and fabricate “off/on” sensor for Hg2+ ion determination in aqueous solutions with the detection limit of ~100 pM, which is far below the maximum permissible concentration (MPC) of mercury in drinking water recommended by the World Health Organization. Although this work is more proof-of-concept than a ready-to-use analytical procedure, the suggested approaches to fabrication of the FRET NPs based on the popular rhodamine-lactam platform can be used as a background for the development of low-cost portable sensing devices for the extra-laboratory determination of hazardous metal ions

Light Harvesting Nanoprobe for Trace Detection of Hg²⁺ in Water

The continuously increasing flow of toxic heavy metals to the environment due to intensive industrial activity and tightening requirements with regard to the content of metal ions in drinking and discharged waters urges the development of affordable and sensitive devices to the field control of pollutants. Here, we report a new thiated Rhodamine-lactam probe for Hg2+ detection and demonstrate how its sensitivity can be increased via the incorporation of the probe molecules into the optically transparent siloxane-acrylate coatings on polymethyl methacrylate and, alternatively, into the water-dispersible light-harvesting FRET nanoparticles (NPs), in which dye cations are separated by fluorinated tetraphenylborate anions. We have shown that the optimization of the FRET NPs composition had allowed it to reach the antenna effect of ~300 and fabricate “off/on” sensor for Hg2+ ion determination in aqueous solutions with the detection limit of ~100 pM, which is far below the maximum permissible concentration (MPC) of mercury in drinking water recommended by the World Health Organization. Although this work is more proof-of-concept than a ready-to-use analytical procedure, the suggested approaches to fabrication of the FRET NPs based on the popular rhodamine-lactam platform can be used as a background for the development of low-cost portable sensing devices for the extra-laboratory determination of hazardous metal ions

Effect of the Resorcinol/Formaldehyde Ratio and the Temperature of the Resorcinol–Formaldehyde Gel Solidification on the Chemical Stability and Sorption Characteristics of Ion-Exchange Resins

A series of resorcinol–formaldehyde resins (RFR) samples for Cs-137 removal from liquid alkaline media have been synthesized. It has been demonstrated that the chemical stability as well as sorption characteristics are determined by the resorcinol/formaldehyde molar ratio and the solidification temperature. It has been also demonstrated that the sample synthesized at the resorcinol/formaldehyde molar ratio of 1.8/2.2 and solidified at 210 °C is characterized by the best sorption-selective characteristics and chemical stability. Under dynamic conditions, at feeding >1000 bed volumes of a model solution with pH > 13, the RFR 3-1 goes through six sorption cycles without noticeable changes in the sorption characteristics. The results are presented that demonstrate the possibility of RFR application in the decontamination of real LRW from Cs-137

Direct Femtosecond Laser Fabrication of Chemically Functionalized Ultra-Black Textures on Silicon for Sensing Applications

Here, we present the single-step laser-assisted fabrication of anti-reflective hierarchical surface textures on silicon locally functionalized with a photoluminescent (PL) molecular nanolayer. Using femtosecond-laser ablation of commercial crystalline Si wafers placed under a layer of a solution containing rhodamine 6G (R6G) a triethoxysilyl derivative, we fabricated ordered arrays of microconical protrusions with self-organized nanoscale surface morphology. At the same time, the laser-induced temperature increase facilitated surface activation and local binding of the R6G derivative to the as-fabricated nanotextured surface. The produced dual-scale surface textures showed remarkable broadband (visible to near-IR) light-absorbing properties with an averaged reflectivity of around 1%, and the capping molecular nanolayer demonstrated a strongly enhanced PL yield. By performing a pH sensing test using the produced nanotextured substrate, we confirmed the retention of sensory properties of the molecules attached to the surface and validated the potential applicability of the high-performing liquid-assisted laser processing as a key technology for the development of innovative multifunctional sensing devices in which the textured substrate (e.g., ultra-black semiconductor) plays a dual role as a support and PL signal amplifier