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The removal of pharmaceuticals in the wastewater has been a tough problem. Herein, the Fenton-assisted electron beam radiation was employed to remove chloroquine (CQ) in aqueous solution. The results showed that electron beam removed 63% CQ at 1.5 kGy with •OH, e aq ⁻, and H• contributing to its degradation. Additionally, the presence of CO 3 2- , HCO 3 - , and humic acid decreased the degradation efficiency. Furthermore, the presence of S 3 - improved efficiency due to the generation of SO 2+ , and humic acid decreased the degradation efficiency. Furthermore, the presence of S 2 O 8 and 0.4 mM Fe(II) after 3 h. In comparison, the Fenton-assisted electron beam process effectively increased the removal efficiency of CQ up to 89%, utilizing less amounts of H 2- improved efficiency due to the generation of SO 4 and Fe •⁻ compared to the pure Fenton process. The molar ratio of the Fenton reagents influenced the efficiency of the Fenton process and the Fenton-assisted electron beam process. The low mineralization of CQ based on TOC and COD measurement was attributed to the formation of lower molecular weight organic compounds that degraded slowly. However, TOC and COD reduction in addition to dechlorination and nitrification under the Fenton-assisted electron beam process were higher, compared to the electron beam process. The degradation byproducts of CQ were identified, and the degradation mechanism was proposed. The degradation products were evaluated and determined to be less toxicity, compared to parent CQ molecule. Overall, the degradation of CQ was higher in the Fenton-assisted electron beam process with better mineralization, dechlorination, and nitrification at comparatively lower absorbed doses, compared to electron beam process and using a lower concentration of Fe 2 O 2 and 0.4 mM Fe(II) after 3 h. In comparison, the Fenton-assisted electron beam process effectively increased the removal efficiency of CQ up to 89%, utilizing less amounts of H 2 O 2 and Fe 2+ compared to the pure Fenton process. The molar ratio of the Fenton reagents influenced the efficiency of the Fenton process and the Fenton-assisted electron beam process. The low mineralization of CQ based on TOC and COD measurement was attributed to the formation of lower molecular weight organic compounds that degraded slowly. However, TOC and COD reduction in addition to dechlorination and nitrification under the Fenton-assisted electron beam process were higher, compared to the electron beam process. The degradation byproducts of CQ were identified, and the degradation mechanism was proposed. The degradation products were evaluated and determined to be less toxicity, compared to parent CQ molecule. Overall, the degradation of CQ was higher in the Fenton-assisted electron beam process with better mineralization, dechlorination, and nitrification at comparatively lower absorbed doses, compared to electron beam process and using a lower concentration of Fe 2+ compared to the Fenton process., Competing Interests: Declarations. Ethical approval and consent to participate: Not applicable. Consent for publication: Not applicable. Competing interests: The authors declare no competing interests., (© 2025. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The Raman spectra of lanthanide [Ln(H 2 O) 4 (Ala) 2 ] 2 (ClO 4 ) 6 crystals were measured with 488, 532, 633, and 1064 nm laser lines, and ROA of complexes in water were collected using 532 nm excitation. As in IR and VCD, ν(CO) stretching and β(OCO) bending vibration bands showed a tendency typical to the lanthanide contraction effect. However, in Raman, the effect is less pronounced than the IR spectrum because it is strongly perturbed by lanthanide ion luminescence, which comes from the 4f → 4f transitions. The lower the energy of the excitation line, the less the bands are perturbed by the luminescence. On the other hand, some ROA spectra taken in water revealed strong circularly polarized luminescence signals (Eu, Sm, and Er complexes). Yet, for the non-luminescing systems, it was impossible to see lanthanide ions' influence as the signals were too slight and hidden in noise., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2025 Elsevier B.V. All rights reserved.)

Telomere shortening has been linked to type 2 diabetes (T2D) and its complications. This study aims to determine whether leukocyte telomere length (LTL) could be a useful marker in predicting the onset of complications in patients suffering from T2D. Enrolled study subjects were 147 T2D patients. LTL was measured using a quantitative PCR method. Key subject's demographics and other clinical characteristics were also included. T2D patients with the shortest LTL had higher TC and non-HDL levels, compared to subjects with the longest LTL ( p = 0.013). Also, T2D patients suffering from diabetic nephropathy showed significant differences in LDL levels ( p = 0.023). While in the group of T2D patients with diabetic retinopathy, significant differences were observed for parameters, such as duration of diabetes ( p = 0.043), HbA1c ( p = 0.041), TC ( p = 0.003), LDL ( p = 0.015), Non-HDL ( p = 0.004) and TG ( p = 0.045). Logistic regression analysis confirmed a significant risk of association of TC and Non-HDL levels with LTL in the 3rd tertile LTL for the crude model adjusted for sex and age, with respective odds ratios of 0.71 (95% CI 0.56-0.91) and 0.73 (95% CI 0.58-0.91). No significant associations were found between LTL in T2D patients and the prevalence of common T2D complications. Nevertheless, a significant association was demonstrated between LTL and some markers of dyslipidemia, including in T2D patients with either diabetic nephropathy or retinopathy. Therefore, analysis of LTL in T2D patients' leukocytes demonstrates a promising potential as a marker in predicting the onset of complications in T2D. This could also help in establishing an effective treatment strategy or even prevent and delay the onset of these severe complications.

The rapid development of nanotechnology during the last two decades has created new opportunities to design and generate more advanced nanotheranostics with diversified capabilities for diagnosis, drug delivery, and treatment response monitoring in a single platform. To date, several approaches have been employed in order to develop nanotheranostics. The purpose of this review is to briefly discuss the key components of nanotheranostic systems, to present the conventional and upcoming imaging and therapeutic modalities that employ nanotheranostic systems, and to evaluate recent progress in the field of cancer nanotheranostic systems in the past five years (2020-2024). Special attention is focused on the design of cancer nanotheranostic systems, their composition, specificity, potential for multimodal imaging and therapy, and in vitro and in vivo characterization.

Apart from HER2-positive, triple-negative breast cancer (TNBC) is the second most highly invasive type of breast cancer. Although TNBC does not overexpress HER2 receptors, it has been observed that EGFR protein expression is present in this specific type of tumor, making it an attractive target for immune and radiopharmaceutical treatments. In our current study, we used 109 Pd (T 1/2 = 13.7 h) in the form of a 109 Pd/ 109m Ag in vivo generator as a source of β - particles and Auger electrons in targeted radionuclide therapy for TNBC. 109 Pd, obtained through neutron irradiation of the 108 Pd target, was deposited onto 15 nm gold nanoparticles to form Au@ 109 Pd core-shell nanoparticles, which were then conjugated to the panitumumab antibody. Au@ 109 Pd-PEG-panitumumab nanoparticles were bound, internalized, and partially routed to the nucleus in MDA-MB-231 human breast cancer cells overexpressing EGFR receptors. The Au@ 109 Pd-panitumumab radioconjugate significantly reduced the metabolic activity of MDA-MB-231 cells in a dose-dependent manner. In conclusion, we have found that Au@ 109 Pd-PEG-panitumumab nanoparticles show potential as a therapeutic agent for combined β - -Auger electron targeted radionuclide therapy of TNBC. The simultaneous emission of β - , conversion, and Auger electrons from the 109 Pd/ 109m Ag generator, similar to 161 Tb conjugates, significantly enhances the therapeutic effect. The partial localization of these nanoparticles into the cell nucleus, provided by the panitumumab vector, ensures effective therapy with Auger electrons. This is particularly important for the treatment of drug-resistant TNBC cells.

Early stages of radiolysis of solutions with 2,6-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-benzo-[1,2,4]triazin-3-yl)pyridine (CyMe4-BTP) and 6,6'-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-benzo-[1,2,4-]triazin-3-yl)-[2,2']bipyridine (CyMe4-BTBP) ligands in cyclohexanone, proposed as a solvent for selective actinide extraction, were studied by means of the pulse radiolysis technique with spectrophotometric detection. Transient UV-vis spectra of excited triplet states of ligands, formed by energy transfer from cyclohexanone excited triplet states to ligands, were recorded for the first time. The influence of typical extraction conditions (the presence of diluted acid and O 2 from air) on the mechanisms of reactions in the system studied was assessed. It was shown that an addition of benzophenone in high concentrations to the system together with its continuous saturation by O 2 could partially protect ligands from radiation damage, caused by the high-energy radiation emitted by the spent nuclear fuel.

We discussed and summarized the latest data from the global literature on the action of polyphenolic antioxidants and their metal complexes. The review also includes a summary of the outcomes of theoretical computations and our many years of experimental experience. We employed various methods, including spectroscopy (FT-IR, FT-Raman, NMR, UV/Vis), X-ray diffraction, thermal analysis, quantum calculations, and biological assays (DPPH, ABTS, FRAP, cytotoxicity, and genotoxicity tests). According to our research, the number and position of hydroxyl groups in aromatic rings, as well as the delocalization of electron charge and conjugated double bonds, have a major impact on the antioxidant effectiveness of the studied compounds. Another important factor is metal complexation, whereby high ionic potential metals (e.g., Fe(III), Cr(III), Cu(II)) enhance antioxidant properties by stabilizing electron charge, while the low ionic potential metals (e.g., Ag(I), Hg(II), Pb(II)) reduce efficacy by disrupting electron distribution. However, we observed no simple correlation between ionic potential and antioxidant capacity. This paper gives insights that will aid in identifying new, effective antioxidants, which are vital for nutrition and the prevention of neurodegenerative illnesses. Our results outline the connections between biological activity and molecular structure, offering a foundation for the methodical design of antioxidants. Our review also shows in detail how we use various complementary methods to assess the impact of metals on the electronic systems of ligands. This approach moves beyond the traditional "trial and error" method, allowing for the more efficient and rational development of future antioxidants.

This study aims to investigate the impact of the π → π* excitation localised in one monomer on the equilibrium geometry and oscillations of the AA dimer. Several low-frequency vibrations appear in pairs in the LIF spectrum because oscillations involving intermolecular hydrogen bonds are coupled, generating approximately symmetric and antisymmetric combinations (especially the COOH rocking modes, LIF: 295 and 301 cm -1 ). Furthermore, quantitative evaluation based on the TDDFT(B3LYP) results indicates that a dozen among 90 intramolecular oscillations are strongly coupled. In contrast, most vibrations are decoupled or weakly coupled, since they involve remote parts of the monomers. This makes several single vibrations active in the LIF spectrum (including the bending mode of the NH···O intramolecular hydrogen bond associated the strongest vibronic band 442 cm -1 ), while the other in each pair remains inactive. The reason for decoupling of oscillations and symmetry breaking is that the π → π* electronic excitation is entirely localised within one of the monomers, which makes them no longer equivalent in terms of geometry and dynamics. Additionally, the excitation of one monomer induces strengthening and shortening by 6 pm of only one intermolecular hydrogen bond linking the carboxylic groups of both molecules. This causes the 1.7° in-plane distortion of the dimer and lowering of its symmetry to C s group (from C 2 h state). The distortion induces the activity of two low-frequency in-plane intermolecular vibrations, i.e. the geared oscillation (LIF: 58 cm 0 ) and the shearing motion (99 cm -1 ) of the monomers.-1 ) of the monomers., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

This study investigated the role of irradiation with a high-energy electron beam in reducing mycotoxin levels of African nutmeg powder (ANP) samples. African nutmeg was procured from a local market in Accra, Ghana, cleaned, milled, packaged and irradiated using electrons of energy 9 MeV at doses of 2, 4, 6 and 8 kGy. Un-irradiated ANP served as a control. Mycotoxin levels of the treated samples were determined using appropriate standard methods. Aflatoxins B1 (AFB1) and B2 (AFB2) as well as ochratoxin A (OTA) were detected in the nutmeg samples. Irradiation significantly ( p  < 0.05) reduced mycotoxin levels of the ANP with increasing doses. Aflatoxins G1 and G2 were not detected in any of the samples. A dose of 8 kGy was effective in reducing the mycotoxin levels below the permissible limit in food. This suggests that a high-energy electron beam is effective in reducing mycotoxin levels in African nutmeg powder.

Intervertebral disc (IVD) degeneration is a leading cause of lower back pain (LBP). Current treatments primarily address symptoms without halting the degenerative process. Cell transplantation offers a promising approach for early-stage IVD degeneration, but challenges such as cell viability, retention, and harsh host environments limit its efficacy. This study aimed to compare the injectability and biocompatibility of human nucleus pulposus cells (hNPC) attached to two types of microscaffolds designed for minimally invasive delivery to IVD. Microscaffolds are developed from poly(lactic-co-glycolic acid) (PLGA) using electrospinning and femtosecond laser structuration. These microscaffolds are tested for their physical properties, injectability, and biocompatibility. This study evaluates cell adhesion, proliferation, and survival in vitro and ex vivo within a hydrogel-based nucleus pulposus model. The microscaffolds demonstrate enhanced surface architecture, facilitating cell adhesion and proliferation. Laser structuration improved porosity, supporting cell attachment and extracellular matrix deposition. Injectability tests show that microscaffolds can be delivered through small-gauge needles with minimal force, maintaining high cell viability. The findings suggest that laser-structured PLGA microscaffolds are viable for minimally invasive cell delivery. These microscaffolds enhance cell viability and retention, offering potential improvements in the therapeutic efficiency of cell-based treatments for discogenic LBP., (© 2024 Wiley‐VCH GmbH.)

Nanosilver (AgNPs) is popular nanomaterials used in food industry that makes gastrointestinal tract an essential route of its uptake. The aim of the presented study was to assess the effects of intragastric exposure to AgNPs on redox balance and steroid receptors in the testes of adult Fisher 344 rats. The animals were exposed to 20 nm AgNPs (30 mg/kg bw/day, by gavage) for 7 and 28 days compared to saline (control groups). It was demonstrated that 7-day AgNPs administration resulted in increased level of total antioxidant status (TAS), glutathione reductase (GR) activity, lower superoxide dismutase activity (SOD), decreased glutathione (GSH) level and GSH/GSSG ratio, as well as higher estrogen receptor (ESR2) and aromatase (Aro) protein expression in Leydig cells compared to the 28-day AgNPs esposure. The longer-time effects of AgNPs exposition were associated with increased lipid hydroperoxidation (LOOHs) and decreased SOD activity and androgen receptor protein level. In conclusion, the present study demonstrated the adverse gastrointestinally-mediated AgNPs effects in male gonads. In particular, the short-term AgNPs exposure impaired antioxidant defence with concurrent effects on the stimulation of estrogen signaling, while the sub-chronic AgNPs exposition revealed the increased testicle oxidative stress that attenuated androgens signaling., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Background: Convenient therapeutic protocols for hepatocellular carcinoma (HCC) are often ineffective due to late diagnosis and high tumor heterogeneity, leading to poor long-term outcomes. However, recently performed studies suggest that using nanostructures in liver cancer treatment may improve therapeutic effects. Inorganic nanoparticles represent a unique material that tend to accumulate in the liver when introduced in-vivo. Typically, this is a major drawback that prevents the therapeutic use of nanoparticles in medicine. However, in HCC tumours, this may be advantageous because nanoparticles may accumulate in the target organ, where the leaky vasculature of HCC causes their accumulation in tumour cells via the EPR effect. On the other hand, recent studies have shown that combining low- and high-LET radiation emitted from the same radionuclide, such as 161 Tb, can increase the effectiveness of radionuclide therapy. Therefore, to improve the efficacy of radionuclide therapy for hepatocellular carcinoma, we suggest utilizing radioactive palladium nanoparticles in the form of 109 Pd/ 109m Ag in-vivo generator that simultaneously emits β - particles and Auger electrons., Results: Palladium nanoparticles with a size of 5 nm were synthesized using 109 Pd produced through neutron irradiation of natural palladium or enriched 108 Pd. Unlike the 109 Pd-cyclam complex, where the daughter radionuclide diffuses away from the molecules, 109m Ag remains within the nanoparticles after the decay of 109 Pd. In vitro cell studies using radioactive 109 Pd nanoparticles revealed that the nanoparticles accumulated inside cells, reaching around 50% total uptake. The 109 Pd-PEG nanoparticles exhibited high cytotoxicity, even at low levels of radioactivity (6.25 MBq/mL), resulting in almost complete cell death at 25 MBq/mL. This cytotoxic effect was significantly greater than that of PdNPs labeled with β - ( 131 I) and Auger electron emitters ( 125 I). The metabolic viability of HCC cells was found to be correlated with cell DNA DSBs. Also, successful radioconjugate anticancer activity was observed in three-dimensional tumor spheroids, resulting in a significant treatment response., Conclusion: The results indicate that nanoparticles labeled with 109 Pd can be effectively used for combined β - - Auger electron-targeted radionuclide therapy of HCC. Due to the decay of both components (β - and Auger electrons), the 109 Pd/ 109m Ag in-vivo generator presents a unique potential in this field., (© 2024. The Author(s).)

The literature shows that both in laboratory and in industrial conditions, the photocatalytic oxidation method copes quite well with degradation of most environmental toxins and pathogenic microorganisms. However, the effective utilization of photocatalytic processes for environmental decontamination and disinfection requires significant technological advancement in both the area of semiconductor material synthesis and its application. Here, we focused on the presence and "photocatalytic capability" of photocatalysts among soil minerals and their potential contributions to the environmental decontamination in vitro and in vivo. Reactions caused by sunlight on the soil surface are involved in its normal redox activity, taking part also in the soil decontamination. However, their importance for decontamination in vivo cannot be overstated, due to the diversity of soils on the Earth, which is caused by the environmental conditions, such as climate, parent material, relief, vegetation, etc. The sunlight-induced reactions are just a part of complicated soil chemistry processes dependent on a plethora of environmental determinates. The multiplicity of affecting factors, which we tried to sketch from the perspective of chemists and environmental scientists, makes us rather skeptical about the effectiveness of the photocatalytic decontamination in vivo. On the other hand, there is a huge potential of the soils as the alternative and probably cheaper source of useful photocatalytic materials of unique properties. In our opinion, establishing collaboration between experts from different disciplines is the most crucial opportunity, as well as a challenge, for the advancement of photocatalysis.

One of the intensively developed tools for cancer therapy is drug-releasing matrices. Polyamidoamine dendrimers (PAMAM) are commonly used as nanoparticles to increase the solubility, stability and retention of drugs in the human body. Most often, drugs are encapsulated in PAMAM cavities or covalently attached to their surface. However, there are no data on the use of PAMAM dendrimers as a component of porous matrices based on polyurethane foams for the controlled release of drugs and biologically active substances. Therefore, in this work, porous materials based on polyurethane foam with incorporated third-generation poly(amidoamine) dendrimers (PAMAM G3) were synthesized and characterized. Density, water uptake and morphology of foams were examined with SEM and XPS. The PAMAM was liquefied with polyether polyol (G441) and reacted with polymeric 4,4'-diphenylmethane diisocyanate (pMDI) in the presence of silicone, water and a catalyst to obtain foam (PF1). In selected compositions, the castor oil was added (PF2). Analogs without PAMAM G3 were also synthesized (F1 and F2, respectively). An SEM analysis of foams showed that they are composed of thin ribs/walls forming an interconnected network containing hollow bubbles/pores and showing some irregularities in the structure. Foam from a G3:G441:CO (PF2) composition is characterized by a more regular structure than the foam from the composition without castor oil. The encapsulation efficiency of drugs determined by the XPS method shows that it varies depending on the matrix and the drug and ranges from several to a dozen mass percent. In vitro biological studies with direct contact and extract assays indicated that the F2 matrix was highly biocompatible. Significant toxicity of dendrimeric matrices PF1 and PF2 containing 50% of PAMAM G3 was higher against human squamous carcinoma cells than human immortalized keratinocytes. The ability of the matrices to immobilize drugs was demonstrated in the example of perspective (Nimesulide, 8-Methoxypsolarene) or approved anticancer drugs (Doxorubicin-DOX, 5-Aminolevulinic acid). Release into the culture medium and penetration of DOX into the tested SCC-15 and HaCaT cells were also proved. The results show that further modification of the obtained matrices may lead to their use as drug delivery systems, e.g., for anticancer therapy.

Cytotoxic and genotoxic effects of novel mPEG-silane coated iron(III) oxide nanoparticles doped with magnesium (Mg 0.1 -γ-Fe 2 O 3 (mPEG-silane) 0.5 ) have been investigated on human adenocarcinomic alveolar basal epithelial (A549) and human normal bronchial epithelial (BEAS-2B) cells. In the studies several molecular and cellular targets addressing to cell membrane, cytoplasm organelles and nucleus components were served as toxicological endpoints. The as-synthesized nanoparticles were found to be stable in the cell culture media and were examined for different concentration and exposure times. No cytotoxicity of the tested nanoparticles was found although these nanoparticles slightly increased reactive oxygen species in both cell types studied. Mg 0.1 -γ-Fe 2 O 3 (mPEG-silane) 0.5 nanoparticles did not produce any DNA strand breaks and oxidative DNA damages in A549 and BEAS-2B cells. Different concentration of Mg 0.1 -γ-Fe 2 O 3 (mPEG-silane) 0.5 nanoparticles and different incubation time did not affect cell migration. The lung cancer cells' uptake of the nanoparticles was more effective than in normal lung cells. Altogether, the results evidence that mPEG-silane coated iron(III) oxide nanoparticles doped with magnesium do not elucidate any deleterious effects on human normal and cancerous lung cells despite cellular uptake of these nanoparticles. Therefore, it seems reasonable to conclude that these novel biocompatible nanoparticles are promising candidates for further development towards medical applications., Competing Interests: Declaration of competing interest The authors declare that they have no conflict of interest., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Background: Positron emission tomography (PET) is now an established diagnostic method for myocardial perfusion imaging (MPI) in coronary artery disease, which is the main cause of death globally. The available tracers show several limitations, therefore, the 18 F-labelled tracer is in high demand nowadays. The preclinical studies on normal Wistar rats aimed to characterise two potential, novel radiotracers, [ 18 F]SYN1 and [ 18 F]SYN2, to evaluate which is a better candidate for PET MPI cardiotracer., Results: The dynamic microPET images showed rapid myocardial uptake for both tracers. However, the uptake was higher and also stable for [ 18 F]SYN2, with an average standardized uptake value of 3.8. The biodistribution studies confirmed that [ 18 F]SYN2 uptake in the cardiac muscle was high and stable (3.02%ID/g at 15 min and 2.79%ID/g at 6 h) compared to [ 18 F]SYN1 (1.84%ID/g at 15 min and 0.32%ID/g at 6 h). The critical organs determined in dosimetry studies were the small intestine and the kidneys. The estimated effective dose for humans was 0.00714 mSv/MBq for [ 18 F]SYN1 and 0.0109 mSv/MBq for [ 18 F]SYN2. The tested dose level of 2 mg/kg was considered to be the No Observed Adverse Effect Level (NOAEL) for both candidates. The better results were achieved for [ 18 F]SYN2, therefore, further preclinical studies were conducted only for this tracer. Radioligand binding assays showed significant responses in 3 from 68 assays: muscarinic acetylcholine M 1 and M 2 receptors and potassium channel hERG. The compound was mostly metabolised via an oxidative N-dealkylation, while the fluor substituent was not separated from the molecule., Conclusion: [ 18 F]SYN2 showed a favourable pharmacodynamic and pharmacokinetic profile, which enabled a clear visualization of the heart in microPET. The compound was well-tolerated in studies in normal rats with moderate radiation exposure. The results encourage further exploration of [ 18 F]SYN2 in clinical studies., (© 2024. The Author(s).)

New complexes of 2-(N,N-dimethylamino)pyridine with chloranilic acid (2-DMAP + CLA) and 4-(N,N-dimethylamino)pyridine with chloranilic acid (4-DMAP + CLA) were synthesized and characterized by single crystal X-ray diffraction, infrared spectroscopy, thermal analysis methods and 1 H, 13 C and 15 N NMR spectroscopy. The NMR spectroscopies were carried out in both, DMSO solution and in the solid state (CPMAS NMR). The 2-DMAP + CLA and 4-DMAP + CLA complexes crystallize in centrosymmetric P-1 and P2 1 /c space group, respectively. In both complexes, the phenomenon of proton transfer is observed, which results in the formation of strong N + -H···O - hydrogen bonds. Thermal decompositions of 2-DMAP + CLA and 4-DMAP + CLA complexes were studied by thermogravimetric analysis. Temperature dependent IR spectra revealed that methyl groups of 4-DMAP + CLA perform fast stochastic reorientational motion at room temperature which is slowed on cooling while in 2-DMAP + CLA reonrientational motion of CH 3 groups is much slower due to steric effects., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Twelve tricarbonyl rhenium(i) complexes in the '2 + 1' system with the anionic bidentate N,O-donor ligand (deprotonated 8-hydroxyquinoline (HQ) or its 2-methyl (MeHQ) or 5-chloro (ClHQ) derivative) and neutral N-donor diazoles (imidazole (Him), 2-methylimidazole (MeHim), 3,5-dimethylpyrazole (Hdmpz), and 3-phenylpyrazole (HPhpz)) were synthesized: [Re(CO) 3 (L N,O )L N ] (L N,O = Q - , MeQ - , ClQ - ; L N = Him, MeHim, Hdmpz, HPhpz). Their crystal structures were determined by the scXRD method, compared with the DFT-calculated ones, and characterized by analytical (EA) and spectroscopic techniques (FT-IR, NMR, and UV-Vis) interpreted with DFT and TD-DFT calculations. Most of the Re(i) complexes did not show relevant antibacterial activity against Gram-negative and Gram-positive bacterial strains. Only [Re(CO) 3 (MeQ)Him] demonstrated significant action 4-fold better against Gram-negative Pseudomonas aeruginosa than the free MeHQ ligand. The cytotoxicity of the compounds was estimated using human acute promyelocytic leukemia (HL-60), ovarian (SKOV-3), prostate (PC-3), and breast (MCF-7) cancer, and breast non-cancerous (MCF-10A) cell lines. Only HQ and ClHQ ligands and [Re(CO) 3 (Q)Hdmpz] complex had good selectivity toward MCF-7 cell line. HL-60 cells were sensitive to all complexes (IC 50 = 1.5-14 μM). Still, pure HQ and ClHQ ligands were slightly more active than the complexes., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Raman optical activity (ROA) spectroscopy exhibits significant potential in the study of (bio)molecules as it encodes information on their molecular structure, chirality, and conformations. Furthermore, the method reveals details on excited electronic states when applied under resonance conditions. Here, we present a combined study of the far from resonance (FFR)-ROA and resonance ROA (RROA) of a single relatively small molecular system. Notably, this study is the first to employ the density functional theory (DFT) analysis of both FFR-ROA and RROA spectra. This is illustrated for cobalamin derivatives using near-infrared and visible light excitation. Although the commonly observed monosignate RROA spectra lose additional information visible in bisignate nonresonance ROA spectra, the RROA technique acts as a complement to nonresonance ROA spectroscopy. In particular, the combination of these methods integrated with DFT calculations can reveal a complete spectral picture of the structural and conformational differences between tested compounds.

The Homa Peninsula, in southwestern Kenya, continues to yield insights into Oldowan hominin landscape behaviors. The Late Pliocene locality of Nyayanga (∼3-2.6 Ma) preserves some of the oldest Oldowan tools. At the Early Pleistocene locality of Kanjera South (∼2 Ma) toolmakers procured a diversity of raw materials from over 10 km away and strategically reduced them in a grassland-dominated ecosystem. Here, we report findings from Sare-Abururu, a younger (∼1.7 Ma) Oldowan locality approximately 12 km southeast of Kanjera South and 18 km east of Nyayanga. Sare-Abururu has yielded 1754 artifacts in relatively undisturbed low-energy silts and sands. Stable isotopic analysis of pedogenic carbonates suggests that hominin activities were carried out in a grassland-dominated setting with similar vegetation structure as documented at Kanjera South. The composition of a nearby paleo-conglomerate indicates that high-quality stone raw materials were locally abundant. Toolmakers at Sare-Abururu produced angular fragments from quartz pebbles, representing a considerable contrast to the strategies used to reduce high quality raw materials at Kanjera South. Although lithic reduction at Sare-Abururu was technologically simple, toolmakers proficiently produced cutting edges, made few mistakes and exhibited a mastery of platform management, demonstrating that expedient technical strategies do not necessarily indicate a lack of skill or suitable raw materials. Lithic procurement and reduction patterns on the Homa Peninsula appear to reflect variation in local resource contexts rather than large-scale evolutionary changes in mobility, energy budget, or toolmaker cognition., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Nanosilver is a popular nanomaterial, the potential influence of which on humans is of serious concern. Herein, we exposed male Wistar rats to two regimens: a repeated oral dose of 30 mg/kg bw silver nanoparticles (AgNPs) over 28 days and a single-dose injection of 5 mg/kg bw of AgNPs. At three different time points, we assessed antioxidant defense, oxidative stress and inflammatory parameters in the colon, as well as toxicity markers in the liver and plasma. Both experimental scenarios showed increased oxidative stress and inflammation in the colon. Oral administration seemed to be linked to increased reactive oxygen species generation and lipid peroxidation, while the effects induced by the intravenous exposure were probably mediated by silver ions released from the AgNPs. Repeated oral exposure had a more detrimental effect than the single-dose injection. In conclusion, both administration routes had a similar impact on the colon, although the underlying mechanisms are likely different.

The VCD spectra of chiral 2,3-dihydro-1H-benzo[de]isoquinolin-1-one (8-substituted naphthalene-1-carboxamide, BIQ) were studied in KBr pellets. The X-ray diffractometry revealed that the Me, Ph, and pClPh BIQs crystalize in the monoclinic P2 1 , while nBu, pMePh, and oMeOPh BIQs in the orthorhombic P2 1 2 1 2 1 space group. Only the Me-BIQ crystal exhibits the presence of cyclic amide dimers, while the others contain chains of the amid group hydrogen bonds. For all BIQs, except pMePh, the most intense IR band in the 1750-1550 cm -1 region is located at ca. 1680 cm -1 and is accompanied by two weak ones at ca. 1618 and 1590 cm -1 . For the pMePh derivative, four almost equally intense IR bands at 1662, 1639, 1614, and 1588 cm -1 are observed. This region of the IR spectra of BIQs, but pMePh, is well reproduced by calculations based on BIQ monomers. On the other hand, the complex IR pattern of pMePh is computationally reproduced when larger crystal fragments, like octamers, are considered. Registration of the VCD spectra enabled recognizing the complexity of IR contours at ca. 1680 cm -1 by the corresponding VCD motives. For (i) Me, Ph and pClPh (R)-enantiomers, two (+)(-) bands were distinguished and for (ii) nBu and pMePh ones, one VCD band with right-side asymmetry was found. For (iii) oMeOPh the VCD pattern cannot be unambiguously assigned. Thus, the VCD spectra in the ν(C=O) range diverse the studied compounds. Among the set of molecules, pMePh has exceptional crystal geometry. Therefore, its most intense ν(C=O) band position and shape can be connected with the geometry of the hydrogen bonds, interactions, and crystal packing. Interpretation of the VCD spectra is based on linear and packed BIQ octamers. This cluster model can reproduce the main features of the solid-state VCD of BIQs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Here, we present the new application of solid-state Vibrational Circular Dichroism (VCD) spectroscopy to differentiate several dutasteride (DS) solvatomorphs - the model active pharmaceutical ingredient (API). Several crystalline DS hydrochloride hydrates solvated with methanol, ethanol, acetonitrile, acetone, and acetic acid were prepared. In contrast to almost identical IR spectra, the VCD ones were very sensitive to changes in the sample composition. We marked significant differences in the shape of VCD spectra of studied DS solvatomorphs, DS hydrates, and DS polymorphic forms. Our findings, supported by DFT calculations, show that VCD spectroscopy has the pronounced ability to distinguish their crystal arrangements. We believe that this contribution will extend the use of VCD in the pharmaceutical industry for developing and designing new chiral drug products for the identification, description, and in-depth probing of several pharmaceutical solvatomorphs in the future., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Dinitrosyl iron complexes (DNICs) stabilize nitric oxide in cells and tissues and constitute an important form of its storage and transportation. DNICs may comprise low-molecular-weight ligands, e.g., thiols, imidazole groups in chemical compounds with low molecular weight (LMWDNICs), or high-molecular-weight ligands, e.g., peptides or proteins (HMWDNICs). The aim of this study was to investigate the role of low- and high-molecular-weight ligands in DNIC formation. Lysosomal and proteasomal proteolysis was inhibited by specific inhibitors. Experiments were conducted on human erythroid K562 cells and on K562 cells overexpressing a heavy chain of ferritin. Cell cultures were treated with •NO donor. DNIC formation was monitored by electron paramagnetic resonance. Pretreatment of cells with proteolysis inhibitors diminished the intensity and changed the shape of the DNIC-specific EPR signal in a treatment time-dependent manner. The level of DNIC formation was significantly influenced by the presence of protein degradation products. Interestingly, formation of HMWDNICs depended on the availability of LMWDNICs. The extent of glutathione involvement in the in vivo formation of DNICs is minor yet noticeable, aligning with our prior research findings.

This review scrutinizes current research on new methods for enhancing bituminous binder performance through radiation and radical grafting of polymer modifiers of bitumen. It investigates innovative methods, including using waste polymers as modifiers and applying radiation for polymer grafting, to overcome challenges like high costs, low aging resistance, and storage stability issues, of which separation of phases polymer/bitumen is the most significant obstacle. These advanced modification techniques promise sustainability through the decrease of the carbon footprint of transportation systems by improving the properties and durability of binders. Additionally, this review discusses the parameters and mechanistic aspects from a scientific perspective, shedding light on the underlying processes that contribute to the improved performance of modified bituminous binders.

The use of conventional methods for the treatment of cancer, such as chemotherapy or radiotherapy, and approaches such as brachytherapy in conjunction with the unique properties of nanoparticles could enable the development of novel theranostic agents. The aim of our current study was to evaluate the potential of iron oxide nanoparticles, coated with alginic acid and polyethylene glycol, functionalized with the chemotherapeutic agent doxorubicin and the monoclonal antibody bevacizumab, to serve as a nanoradiopharmaceutical agent against breast cancer. Direct radiolabeling with the therapeutic isotope Lutetium-177 ( 177 Lu) resulted in an additional therapeutic effect. Functionalization was accomplished at high percentages and radiolabeling was robust. The high cytotoxic effect of our radiolabeled and non-radiolabeled nanostructures was proven in vitro against five different breast cancer cell lines. The ex vivo biodistribution in tumor-bearing mice was investigated with three different ways of administration. The intratumoral administration of our functionalized radionanoconjugates showed high tumor accumulation and retention at the tumor site. Finally, our therapeutic efficacy study performed over a 50-day period against an aggressive triple-negative breast cancer cell line (4T1) demonstrated enhanced tumor growth retention, thus identifying the developed nanoparticles as a promising nanobrachytherapy agent against breast cancer.

Crystallographic investigations of eight homoleptic N , N '-dimethylpropyleneurea (dmpu) coordinated metal ions in the solid state, [Mg(dmpu) 5 ]I 2 (1), [Ca(dmpu) 6 ]I 2 (2), [Ca(dmpu) 6 ](ClO 4 ) 2 (3), [Ca(dmpu) 6 ](CF 3 SO 3 ) 2 (4), [Sr(dmpu) 6 ](CF 3 SO 3 ) 2 (5), [Ba(dmpu) 6 ](CF 3 SO 3 ) 2 (6), [Sc(dmpu) 6 ]I 3 (7), and [Pr(dmpu) 6 ]I(I 3 ) 2 (8), and the complex [CoBr 2 (dmpu) 2 ] (9) as well as the structures of the dmpu coordinated calcium, strontium, barium, scandium(III) and cobalt(II) ions and the cobalt(II) bromide complex in dmpu solution as determined by EXAFS are reported. The methyl groups in the dmpu molecule are close to the oxygen donor atom, causing steric restrictions, and making dmpu space-demanding at coordination to metal ions. The large volume required by the dmpu ligand at coordination contributes to crowdedness around the metal ion with often lower coordination numbers than for oxygen donor ligands without such steric restrictions. The crowdedness is seen in M⋯H distances equal to or close to the sum of the van der Waals radii. To counteract the space-demand at coordination, the dmpu molecule has an unusual ability to increase the M-O-C bond angle to facilitate as large coordination numbers as possible. M-O-C bond angles in the range of 125-170° are reported depending on the crowdedness caused by the coordination figure and the M-O bond distance. All reported structures of dmpu coordinated metal ions in both the solid state and dmpu solution are summarized to study the relationship between the M-O-C bond angle and the crowdedness around the metal ion. However, highly symmetric complexes seem to be favoured in the solid state due to favourable lattice energies. As a result, the dmpu coordinated lanthanoid(III) ions are octahedral in the solid state, while they, except lutetium, are seven-coordinate in the dmpu solution.

Purpose: Radiation-induced alterations in gene expression show great promise for dose reconstruction and for severity prediction of acute health effects. Among several genes explored as potential biomarkers, FDXR is widely used due to high upregulation in white blood cells following radiation exposure. Nonetheless, the absence of a standardized protocols for gene expression-based biodosimetry is a notable gap that warrants attention to enhance the accuracy, reproducibility and reliability. The objective of this study was to evaluate the sensitivity of transcriptional biodosimetry to differences in protocols used by different laboratories and establish guidelines for the calculation of calibration curve using FDXR expression data., Material and Methods: Two sets of irradiated blood samples generated during RENEB exercise were used. The first included samples irradiated with known doses including: 0, 0.25, 0.5, 1, 2, 3 and 4 Gy. The second set consisted of three 'blind' samples irradiated with 1.8 Gy, 0.4 Gy and a sham-irradiated sample. After irradiation, samples were incubated at 37 °C over 24 h and sent to participating laboratories, where RNA isolation and FDXR expression analysis by qPCR were performed using sets of primers/probes and reference genes specific for each laboratory. Calibration curves based on FDXR expression data were generated using non-linear and linear regression and used for dose estimation of 'blind' samples., Results: Dose estimates for sham-irradiated sample (0.020-0.024 Gy) and sample irradiated with 0.4 Gy (0.369-0.381 Gy) showed remarkable consistency across all laboratories, closely approximating the true doses regardless variation in primers/probes and reference genes used. For sample irradiated with 1.8 Gy the dose estimates were less precise (1.198-2.011 Gy) but remained within an acceptable margin for triage within the context of high dose range., Conclusion: Methodological differences in reference genes and primers/probes used for FDXR expression measurement do not have a significant impact on the dose estimates generated, provided that all reference genes performed as expected and the primers/probes target a similar set of transcript variants. The preferred method for constructing a calibration curve based on FDXR expression data involves employing linear regression to establish a function that describes the relationship between the logarithm of absorbed dose and FDXR ΔCt values. However, one should be careful with using non-irradiated sample data as these cannot be accurately represented on a logarithmic scale. A standard curve generated using this approach can give reliable dose estimations in a dose range from 50 mGy to 4 Gy at least.

Diagnostic and interventional angiograms are instrumental in the multidisciplinary approach to CAD management, enabling accurate diagnosis and effective targeted treatments that significantly enhance patient care and cardiovascular outcomes. However, cath lab staff, including interventional cardiologists, is consistently exposed to ionizing radiation, which poses inherent health risks. Radiation exposure in the cath lab primarily results from the use of fluoroscopy and cineangiography during diagnostic and interventional procedures. Understanding these risks and implementing effective radiation protection measurements are imperative to ensure the well-being of healthcare professionals while delivering high-quality cardiac care. Prolonged and repeated exposure can lead to both deterministic and stochastic effects. Deterministic effects, such as skin erythema and tissue damage, are more likely to occur at high radiation doses. Interventional cardiologists and staff may experience these effects when safety measures are not rigorously followed. In fact, while ionizing radiation is essential in the practice of radiation cardiology ward, cath lab staff faces inherent risks from radiation exposure. Stochastic effects, on the other hand, are characterized by a probabilistic relationship between radiation exposure and the likelihood of harm. These effects include the increased risk of cancer, particularly for those with long-term exposure. Interventional cardiologists, due to their frequent presence in the cath lab, face a higher lifetime cumulative radiation dose, potentially elevating their cancer risk. Protective measures, including the use of lead aprons, thyroid shields, and radiation monitoring devices, play a crucial role in reducing radiation exposure for cath lab personnel. Adherence to strict dose optimization protocols, such as minimizing fluoroscopy time and maximizing distance from the radiation source, is also essential in mitigating these risks. Ongoing research and advancements in radiation safety technology are essential in further for minimizing the adverse effects of ionizing radiation in the cath lab., (Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.net.)

Silver nanoparticles (AgNPs) are a popular engineered nanomaterial widely used in industry. Despite the benefits they bring to society, AgNPs are not neutral to human health. The aim of this study was to evaluate the effects of a single intravenous dose (5 mg/kg body weight) of 20 nm AgNPs on steroid metabolism and redox balance in the testes of adult rats. The effects were evaluated 1 day or 28 days after intervention and compared with saline-treated animals. Decreased aromatase and estrogen receptor α levels (by 21% and 27%, respectively) were observed 1 day after AgNPs administration, while increased testosterone, increased dihydrotestosterone levels, higher androgen receptors and higher aromatase expression in Leydig cells (by 43%, 50%, 20% and 32%, respectively) as well as lower (by 35%) androgen receptor protein levels were observed 28 days after exposure to AgNPs compared to control groups. The AgNPs treatment resulted in decreased superoxide dismutase activity, decreased GSH/GSSG ratio, and increased glutathione reductase activity (by 23%, 63% and 28%, respectively) compared to control animals, irrespective of the time of measurement. Increased (by 28%) intratesticular lipid hydroperoxides level was observed 1 day after AgNPs exposure, while decreased (by 70%) GSH and increased (by 43%) 7-ketocholesterol levels were observed 28 days after treatment compared to control animals. Conclusions: AgNPs exposure caused redox imbalance in the gonads shortly after AgNPs administration, while a longer perspective AgNPs exposure was associated with impaired androgen metabolism, probably due to increased oxidative stress.

The article shows that the definition of the HOMA index of geometrical aromaticity satisfies the axioms of a similarity function between the examined and benzene ring. Consequently, for purely mathematical reasons, the index works exceptionally well as an index of aromaticity: it expresses a geometric similarity to the archetypal aromatic benzene. Thus, if the molecule is geometrically similar to benzene, then it is also chemically similar, and therefore, it is aromatic. However, the similarity property legitimizes using the HOMA-like indices to express similarity to molecules other than benzene, whether cyclic or linear and existing or hypothetical. The paper demonstrates an example of HOMA-similarity to cyclohexane, which expresses a (relaxed)-saturicity property not accompanied by strong structural strains or steric hindrances. Further, it is also shown that the HOMA index can evaluate the properties of whole molecules, such as 25 unbranched catacondensed isomers of hexacene. The index exhibits a significant quadratic correlation with the total energy differences of planar isomers from which the nonplanar ones deviate. Moreover, the HOMA index of hexacene isomers significantly correlates with the Kekulé count connected to the resonance energy in the Hückel approximation. As a result, the study shows that the HOMA index can be used not only for aromaticity analyses but also as a general chemical descriptor applicable to rings, chains, composed molecular moieties, or even whole molecules.

Reaction of L-cysteine with carbonyl compounds leads to thiazolidine derivatives which undergo a stereoselective conversion to two types of chiral bicyclic products bearing two or three stereogenic centers, including the first fused oxathiane-γ-lactam system.

The interest in nanoparticles (NPs) and their effects on living organisms has been continuously growing in the last decades. A special interest is focused on the effects of NPs on the central nervous system (CNS), which seems to be the most vulnerable to their adverse effects. Non-metallic NPs seem to be less toxic than metallic ones; thus, the application of non-metallic NPs in medicine and industry is growing very fast. Hence, a closer look at the impact of non-metallic NPs on neural tissue is necessary, especially in the context of the increasing prevalence of neurodegenerative diseases. In this review, we summarize the current knowledge of the in vitro and in vivo neurotoxicity of non-metallic NPs, as well as the mechanisms associated with negative or positive effects of non-metallic NPs on the CNS., Competing Interests: The authors declare no conflict of interest.

Organophosphorus pesticides (OPs) are important factors in the etiology of many diseases, including obesity and type 2 diabetes mellitus. The aim of this study was to investigate the effect of a representative of OPs, chlorpyrifos (CPF), on viability, proliferation, differentiation, and fatty acid uptake in 3T3-L1 cells. The effect of CPF exposure on preadipocyte proliferation was examined by the MTT, NR, and BrdU assays. The impact of CPF exposure on the differentiation of preadipocytes into mature adipocytes was evaluated by Oil Red O staining and RT-qPCR. The effect of CPF on free fatty acid uptake in adipocytes was assessed with the fluorescent dye BODIPY. Our experiments demonstrated that exposure to CPF decreased the viability of 3T3-L1 cells; however, it was increased when the cells were exposed to low concentrations of the pesticide. Exposure to CPF inhibited the proliferation and differentiation of 3T3-L1 preadipocytes. CPF exposure resulted in decreased lipid accumulation, accompanied by down-regulation of the two key transcription factors in adipogenesis: C/EBPα and PPARγ. Exposure to CPF increased basal free fatty acid uptake in fully differentiated adipocytes but decreased this uptake when CPF was added during the differentiation process. Increased free fatty acid accumulation in fully differentiated adipocytes may suggest that CPF leads to adipocyte hypertrophy, one of the mechanisms leading to obesity, particularly in adults. It can therefore be concluded that CPF may disturb the activity of preadipocytes and adipocytes, although the role of this pesticide in the development of obesity requires further research.