Shedding Light on Heavy Metal Contamination: Fluorescein-Based Chemosensor for Selective Detection of Hg2+ in Water.

This article discusses the design and analysis of a new chemical chemosensor for detecting mercury(II) ions. The chemosensor is a hydrazone made from 4-methylthiazole-5-carbaldehyde and fluorescein hydrazide. The structure of the chemosensor was confirmed using various methods, including nuclear magnetic resonance spectroscopy, infrared spectroscopy with Fourier transformation, mass spectroscopy, and quantum chemical calculations. The sensor's ability in the highly selective and sensitive discovery of Hg2+ ions in water was demonstrated. The detection limit for mercury(II) ions was determined to be 0.23 µM. The new chemosensor was also used to detect Hg2+ ions in real samples and living cells using fluorescence spectroscopy. Chemosensor 1 and its complex with Hg2+ demonstrate a significant tendency to enter and accumulate in cells even at very low concentrations.

Optical Polymorphism of Liquid-Crystalline Dispersions of DNA at High Concentrations of Crowding Polymer.

Optically active liquid-crystalline dispersions (LCD) of nucleic acids, obtained by polymer- and salt-induced (psi-) condensation, e.g., by mixing of aqueous saline solutions of low molecular weight DNA (≤106 Da) and polyethylene glycol (PEG), possess an outstanding circular dichroism (CD) signal (so-called psi-CD) and are of interest for sensor applications. Typically, such CD signals are observed in PEG content from ≈12.5% to ≈22%. However, in the literature, there are very conflicting data on the existence of psi-CD in DNA LCDs at a higher content of crowding polymer up to 30-40%. In the present work, we demonstrate that, in the range of PEG content in the system above ≈24%, optically polymorphic LCDs can be formed, characterized by both negative and positive psi-CD signals, as well as by ones rather slightly differing from the spectrum of isotropic DNA solution. Such a change in the CD signal is determined by the concentration of the stock solution of PEG used for the preparation of LCDs. We assume that various saturation of polymer chains with water molecules may affect the amount of active water, which in turn leads to a change in the hydration of DNA molecules and their transition from B-form to Z-form.

Monte-Carlo calculation of output correction factors for ionization chambers, solid-state detectors, and EBT3 film in small fields of high-energy photons.

High-energy accelerators are often used in oncological practice, but the information on the small-field dosimetry for the photon beams with nominal energy above 10 MV is limited. The goal of the present work was to determine the values of the output correction factor ( k Q clin , Q ref f clin , f ref $k_{{Q}_{{\rm{clin}}},{Q}_{{\rm{ref}}}}^{{f}_{{\rm{clin}}},{f}_{{\rm{ref}}}}$ ) for solid-state detectors (Diode E, PTW 60017; microDiamond, PTW 60019), EBT3 film, and ionization chambers (Semiflex, PTW 31010; Semiflex 3D, PTW 31021; PinPoint, PTW 31015; PinPoint 3D, PTW 31016) in the small fields formed by 10, 15, 18, and 20 MV photon beams. The output correction factors were calculated by Monte-Carlo method using EGSnrc toolkit for six field sizes (from 0.5 × 0.5 cm 2 $0.5 \times 0.5\ {\rm{cm}}^2$ to 10 × 10 cm 2 $10 \times 10\ {\rm{cm}}^2$ ) for isocentric and constant source-to-surface distance (SSD) techniques. The decrease in the field size led to an increase in k Q clin , Q ref f clin , f ref $k_{{Q}_{{\rm{clin}}},{Q}_{{\rm{ref}}}}^{{f}_{{\rm{clin}}},{f}_{{\rm{ref}}}}$ for ionization chambers, while for solid-state detectors and radiochromic film, k Q clin , Q ref f clin , f ref $k_{{Q}_{{\rm{clin}}},{Q}_{{\rm{ref}}}}^{{f}_{{\rm{clin}}},{f}_{{\rm{ref}}}}$ were less than unity at the smallest field size. A larger sensitive volume of ionization chamber corresponded to a stronger deviation of output correction factor from unity: 1.847 (125 mm3 PTW 31010) versus up to 1.183 (16 mm3 PTW 31016) at the smallest field of 10 MV beam. The calculated output correction factors were used to correct the output factors for PTW 60017, PTW 60019, and EBT3. The deviation of the corrected output factor from the results of Monte-Carlo simulation did not exceed 3% in the fields from 1.0 × 1.0 cm 2 $1.0 \times 1.0\ {\rm{cm}}^2$ to 4.0 × 4.0 cm 2 $4.0 \times 4.0\ {\rm{cm}}^2$ for 10 and 18 MV beams. Thus, Diode E, microDiamond, and EBT3 film can be recommended for small-field dosimetry of high-energy photons.

Hafnium Oxide-Based Nanoplatform for Combined Chemoradiotherapy.

Recently, the combined therapy has become one of the main approaches in cancer treatment. Combining different approaches may provide a significant outcome by triggering several death mechanisms or causing increased damage of tumor cells without hurting healthy ones. The supramolecular nanoplatform based on a high-Z metal reported here is a suitable system for the targeted delivery of chemotherapeutic compounds, imaging, and an enhanced radiotherapy outcome. HfO2 nanoparticles coated with oleic acid and a monomethoxypoly(ethylene glycol)-poly(ε-caprolactone) copolymer shell (nanoplatform) are able to accumulate inside cancer cells and release doxorubicin (DOX) under specific conditions. Neither uncoated nor coated nanoparticles show any cytotoxicity in vitro. DOX loaded onto a nanoplatform demonstrates a lower IC50 value than pure DOX. X-ray irradiation of cancer cells loaded with a nanoplatform shows a higher death rate than that for cells without nanoparticles. These results provide an important foundation for the development of complex nanoscale systems for combined cancer treatment.

Impact of the Spectral Composition of Kilovoltage X-rays on High-Z Nanoparticle-Assisted Dose Enhancement.

Nanoparticles (NPs) with a high atomic number (Z) are promising radiosensitizers for cancer therapy. However, the dependence of their efficacy on irradiation conditions is still unclear. In the present work, 11 different metal and metal oxide NPs (from Cu (ZCu = 29) to Bi2O3 (ZBi = 83)) were studied in terms of their ability to enhance the absorbed dose in combination with 237 X-ray spectra generated at a 30-300 kVp voltage using various filtration systems and anode materials. Among the studied high-Z NP materials, gold was the absolute leader by a dose enhancement factor (DEF; up to 2.51), while HfO2 and Ta2O5 were the most versatile because of the largest high-DEF region in coordinates U (voltage) and Eeff (effective energy). Several impacts of the X-ray spectral composition have been noted, as follows: (1) there are radiation sources that correspond to extremely low DEFs for all of the studied NPs, (2) NPs with a lower Z in some cases can equal or overcome by the DEF value the high-Z NPs, and (3) the change in the X-ray spectrum caused by a beam passing through the matter can significantly affect the DEF. All of these findings indicate the important role of carefully planning radiation exposure in the presence of high-Z NPs.

Radiosensitization by Gold Nanoparticles: Impact of the Size, Dose Rate, and Photon Energy.

Gold nanoparticles (GNPs) emerged as promising antitumor radiosensitizers. However, the complex dependence of GNPs radiosensitization on the irradiation conditions remains unclear. In the present study, we investigated the impacts of the dose rate and photon energy on damage of the pBR322 plasmid DNA exposed to X-rays in the presence of 12 nm, 15 nm, 21 nm, and 26 nm GNPs. The greatest radiosensitization was observed for 26 nm GNPs. The sensitizer enhancement ratio (SER) 2.74 ± 0.61 was observed at 200 kVp with 2.4 mg/mL GNPs. Reduction of X-ray tube voltage to 150 and 100 kVp led to a smaller effect. We demonstrate for the first time that the change of the dose rate differentially influences on radiosensitization by GNPs of various sizes. For 12 nm, an increase in the dose rate from 0.2 to 2.1 Gy/min led to a ~1.13-fold increase in radiosensitization. No differences in the effect of 15 nm GNPs was found within the 0.85-2.1 Gy/min range. For 21 nm and 26 nm GNPs, an enhanced radiosensitization was observed along with the decreased dose rate from 2.1 to 0.2 Gy/min. Thus, GNPs are an effective tool for increasing the efficacy of orthovoltage X-ray exposure. However, careful selection of irradiation conditions is a key prerequisite for optimal radiosensitization efficacy.

Stimulation of Cysteine-Coated CdSe/ZnS Quantum Dot Luminescence by meso-Tetrakis (p-sulfonato-phenyl) Porphyrin.

Interaction between porphyrins and quantum dots (QD) via energy and/or charge transfer is usually accompanied by reduction of the QD luminescence intensity and lifetime. However, for CdSe/ZnS-Cys QD water solutions, kept at 276 K during 3 months (aged QD), the significant increase in the luminescence intensity at the addition of meso-tetrakis (p-sulfonato-phenyl) porphyrin (TPPS4) has been observed in this study. Aggregation of QD during the storage provokes reduction in the quantum yield and lifetime of their luminescence. Using steady-state and time-resolved fluorescence techniques, we demonstrated that TPPS4 stimulated disaggregation of aged CdSe/ZnS-Cys QD in aqueous solutions, increasing the quantum yield of their luminescence, which finally reached that of the fresh-prepared QD. Disaggregation takes place due to increase in electrostatic repulsion between QD at their binding with negatively charged porphyrin molecules. Binding of just four porphyrin molecules per single QD was sufficient for total QD disaggregation. The analysis of QD luminescence decay curves demonstrated that disaggregation stronger affected the luminescence related with the electron-hole annihilation in the QD shell. The obtained results demonstrate the way to repair aged QD by adding of some molecules or ions to the solutions, stimulating QD disaggregation and restoring their luminescence characteristics, which could be important for QD biomedical applications, such as bioimaging and fluorescence diagnostics. On the other hand, the disaggregation is important for QD applications in biology and medicine since it reduces the size of the particles facilitating their internalization into living cells across the cell membrane.