Molecules, Volume 28, Issue 16 (August-2 2023) – 241 articles

Nitroxides are stable, low molecular-weight radicals containing a nitroxide group that has an unpaired electron. The presence of a nitroxide group determines their redox properties. The effect of the piperidine nitroxides, Tempo, Tempol, and Tempamine, on metalloproteins (hemoglobin, superoxide dismutase, catalase) and lactate dehydrogenase in red blood cells was investigated in this research. In addition, the level of lipid peroxidation and the level of protein carbonyl groups were examined as indicators of the effect of oxidative stress. Nitroxides increased superoxide dismutase activity and oxidized hemoglobin to methemoglobin, and also slightly decreased the catalase activity of red blood cells treated with nitroxides. Tempol significantly decreased lactate dehydrogenase activity. All three nitroxides had no effect on membrane lipid peroxidation and protein oxidation. Our results confirm that nitroxides have both antioxidant and prooxidative effects in human red blood cells. The piperidine nitroxides do not initiate the oxidation of proteins and lipids in the membranes of human red blood cells. Full article

In this study, graphene flakes were obtained using an electrolytic method and characterized using X-ray diffraction (XRD), Raman and FTIR spectroscopy, scanning and transmission electron microscopy (SEM/TEM). Graphene-based composites with varying concentrations of 0.5%, 1% and 3% by weight were prepared with acrylic paint, enamel and varnish matrices. The mechanical properties were evaluated using micro-hardness testing, while wettability and antimicrobial activity against three pathogens (Staphylococcus aureus 33591, Pseudomonas aeruginosa 15442, Candida albicans 10231) were also examined. The results indicate that the addition of graphene flakes significantly enhances both the mechanical and antimicrobial properties of the coatings. Full article

Due to the excellent characteristics of fluorescence-based imaging, such as non-invasive detection of biomarkers in vitro and in vivo with high sensitivity, good spatio-temporal resolution and fast response times, it has shown significant prospects in various applications. Compounds with both biological activities and fluorescent properties have the potential for integrated diagnosis and treatment application. Alectinib and Rilpivirine are two excellent drugs on sale that represent a clinically approved targeted therapy for ALK-rearranged NSCLC and have exhibited more favorable safety and tolerance profiles in Phase III clinical trials, ECHO and THRIVE, respectively. The optical properties of these two drugs, Alectinib and Rilpivirine, were deeply explored, firstly through the simulation of molecular structures, electrostatic potential, OPA/TPA and emission spectral properties and experiments on UV-vis spectra, fluorescence and cell imaging. It was found that Alectinib exhibited 7.8% of fluorescence quantum yield at the 450 nm excited wavelength, due to a larger electronic transition dipole moment (8.41 Debye), bigger charge transition quantity (0.682 e) and smaller reorganization energy (2821.6 cm⁻¹). The stronger UV-vis spectra of Rilpivirine were due to a larger electron–hole overlap index (Sr: 0.733) and were also seen in CDD plots. Furthermore, Alectinib possessed obvious active two-photon absorption properties (${\mathsf{\delta }}_{max}^{TPA}$* ϕ = 201.75 GM), which have potential TPA imaging applications in bio-systems. Lastly, Alectinib and Rilpivirine displayed green fluorescence in HeLa cells, suggesting the potential ability for biological imaging. Investigation using theoretical and experimental methods is certainly encouraged, given the particular significance of developing integrated diagnosis and treatment. Full article

Comfrey (Symphytum officinale L.) has a long tradition of use in the treatment of musculoskeletal disorders. However, due to hepatotoxic pyrrolizidine alkaloids (PAs), the EMA restricts the use of comfrey root (CR) to external use only and for short periods of time. Recent studies indicate a low permeability of PAs across the skin, calling into question the safety of topical application of products containing comfrey preparations. The aim of our work was to develop and validate an HPLC method enabling the separation of isomeric PAs from comfrey and, on this basis, to assess the potential toxicity of CR and comfrey leaf (CL) obtained from various Polish sources. The qualitative and quantitative analysis of PAs via HPLC-MS/MS was performed in MRM mode. The results obtained confirmed a lower content of PAs in CL than in CR and showed a wide variation in the composition of PAs in CR, with a much more stable profile of PAs in CL. Factor analysis confirmed that CRs and CLs differ in PA content, which is influenced by the growth conditions and geographical origin. The determined concentrations of PAs prove that in some CRs available on the Polish herbal market, the content of PAs may exceed the daily dose considered safe. Full article

Pseudostellaria heterophylla (Miq.) Pax is a popular clinical herb and nutritious health food. However, leaf spot disease caused by fungal pathogens frequently occurs and seriously influences the growth, quality, and yield of P. heterophylla. In this work, the field control roles of difenoconazole, chitosan, and their combination in the leaf spot disease in P. heterophylla and their effects on the disease resistance, photosynthetic capacity, medicinal quality, and root yield of P. heterophylla are investigated. The results manifest that 37% difenoconazole water-dispersible granule (WDG) with 5000-time + chitosan 500-time dilution liquid had a superior control capacity on leaf spot disease with the control effects of 91.17%~88.19% at 15~30 days after the last spraying, which significantly (p < 0.05) exceeded that of 37% difenoconazole WDG 3000-time dilution liquid and was significantly (p < 0.01) higher than that of 37% difenoconazole WDG 5000-time dilution liquid, chitosan 500-time dilution liquid, or chitosan 1000-time dilution liquid. Simultaneously, this combination could more effectively enhance the disease resistance, photosynthetic capacity, medicinal quality, and tuberous root yield of P. heterophylla compared to when these elements were applied alone, as well as effectively reduce difenoconazole application. This study emphasizes that chitosan combined with a low dosage of difenoconazole can be proposed as a green, efficient, and alternative formula for controlling leaf spot disease in P. heterophylla and enhancing its resistance, photosynthesis, quality, and yield. Full article

In order to examine the effect of oriented (static) electric fields (OEF) on the kinetics of some representative Suzuki–Miyaura and metal-cluster mediated reactions at ambient temperatures, density functional theory-based calculations are reported herein. Results indicate that, in general, OEF can facilitate the kinetics of the concerned reactions when applied along the suitable direction (parallel or anti-parallel with respect to the reaction axis). The reverse effect happens if the direction of the OEF is flipped. OEF (when applied along the ‘right’ direction) helps to polarize the transition states in the desired direction, thereby facilitating favorable bonding interactions. Given the growing need for finding appropriate catalysts among the scientific community, OEF can prove to be a vital route for the same. Full article

Bottle gourd (BG) oil (family Cucurbitaceae) has several pharmacological activities including a reduction of the hazard of cardiovascular and atherosclerosis conditions. This work aimed to develop and optimize self-dispersing lipid formulations (SDLFs) of BG oil by applying a full 3² factorial design. The formulation variables (oil concentration and surfactant mixture ratio) showed an obvious impact on the characters of the prepared BG-SDLFs including droplet size (DS), polydispersity index (PDI), emulsification time (ET), and transmission percentage (Tr%). The optimum BG-SDLF composed of 30% oil and Tween 80/Cremophor^® RH40 (1:1) showed good emulsification characteristics and a better drug release profile compared with BG oil. In vivo study in isoproterenol-injected rats showed that BG oil and the optimized BG-SDLF improved cardiac function, by elevating the miRNA-23a gene expression level and decreasing miRNA-21 gene expression. They also caused the inhibition of the plasma B-type natriuretic peptide (BNP), N-terminal proatrial natriuretic peptide (NT-pro-BNP), cystatin c, galectin-3, lipoprotein-associated phospholipase A2 (Lp-PLA2), matrix metallopeptidase 2 (MMP2), cardiac troponin I (cTnI), and cardiac troponin T (cTnT). Our study demonstrated that BG oil and the optimized BG-SDLF provided a cardioprotection against isoproterenol-induced cardiac toxicity with better results in groups treated with the optimized BG-SDLF. Full article

Monoamine oxidase (MAO, EC 1.4.3.4) is responsible for the oxidative breakdown of both endogenous and exogenous amines and exists in MAO-A and MAO-B isomers. Eighteen indole-based phenylallylidene derivatives were synthesized via nucleophilic addition reactions comprising three sub-series, IHC, IHMC, and IHNC, and were developed and examined for their ability to inhibit MAO. Among them, compound IHC3 showed a strong MAO-B inhibitory effect with an IC₅₀ (half-maximal inhibitory concentration) value of 1.672 μM, followed by IHC2 (IC₅₀ = 16.934 μM). Additionally, IHC3 showed the highest selectivity index (SI) value of >23.92. The effectiveness of IHC3 was lower than the reference pargyline (0.14 μM); however, the SI value was higher than pargyline (17.16). Structurally, the IHC (-H in the B-ring) sub-series exhibited relatively stronger MAO-B inhibition than the others. In the IHC series, IHC3 (-F in the A-ring) exhibited stronger MAO-B suppression than the other substituted derivatives in the order -F > -Br > -Cl > -OCH₃, -CH₃, and -H at the 2-position in the A-ring. In the reversibility and enzyme kinetics experiments, IHC3 was a reversible inhibitor with a K_i value of 0.51 ± 0.15 μM for MAO-B. Further, it was observed that IHC3 greatly decreased the cell death caused by rotenone in SH-SY5Y neuroblastoma cells. A molecular docking study of the lead molecule was also performed to determine hypothetical interactions in the enzyme-binding cavity. These findings suggest that IHC3 is a strong, specific, and reversible MAO-B inhibitor that can be used to treat neurological diseases. Full article

Hybrid organic–inorganic perovskites (HOIPs) are promising materials in several fields related to electronics, offering long carrier-diffusion lengths, high absorption coefficients, tunable band gaps, and long spin lifetimes. Recently, chiral perovskites have attracted huge interest thanks to the possibility of further widening the applications of HOIPs. Chiral materials, being intrinsically non-centrosymmetric, display several attractive physicochemical properties, including circular dichroism, circularly polarized photoluminescence, nonlinear optics, ferroelectricity, and spin-related effects. Recent studies have shown that chirality can be transferred from the chiral organic ligands into the inorganic perovskite framework, resulting in materials combining the advantages of both chirality and perovskite superior optoelectronic characteristics. As for HOIPs for photovoltaics, strong interest is currently devoted towards the development of lead-free chiral perovskites to overcome any toxicity issue. While considering the basic and general features of chiral HOIPs, this review mainly focuses on lead-free materials. It highlights the first attempts to understand the correlation between the crystal structure characteristics and the chirality-induced functional properties in lead and lead-free chiral perovskites. Full article

The dichloromethane extract of the roots of Bridelia balansae Tutcher (Phyllanthaceae) was found to show potential anticancer activity against HCT116 colorectal cancer cell. Our bioassay-guided phytochemical investigation of the roots of B. balansae led to the identification of 14 compounds including seven lignans (1–7), three phenylbenzene derivatives (8–10), two flavanone (11–12), and two triterpenoids (13–14). Among them, 4′-demethyl-4-deoxypodophyllotoxin (1) is the first aryltetralin lignan compound identified from this plant species. In addition, the stereochemistry of 1 was validated by X-ray crystallography for the first time, and its distinguished cytotoxic effect on HCT116 cells with an IC₅₀ value at 20 nM was induced via an apoptosis induction mechanism. Compound 1 could also significantly decrease the migration rate of HCT116 cells, indicating its potential application against cancer metastasis. The western blot analysis showed that 1 has the potential to inhibit cell proliferation and metastasis. Treatment of 1 resulted in the downregulation of matrix metalloproteinases 2 (MMP2) and p-Akt, while p21 was upregulated. Collectively, the present study on the phytochemical and biological profile of B. balansae has determined the plant as a useful source to produce promising anticancer lead compounds. Full article

Complexes of lanthanide ions, such as Eu(III) (red light emission) and Tb(III) (green light emission), with proper ligands can be highly luminescent and color-tunable, also attaining yellow and orange emission under UV radiation. The ligands employed in this work were poly(sodium acrylate), working as polymeric matrix, and 1,10-phenanthroline, taking advantage of its antenna effect. Possibilities of color display were further enhanced by incorporating a cationic polyfluorene with blue emission. This strategy allowed for obtaining cyan and magenta, besides the aforementioned colors. Uncoated cellulose paper was impregnated with the resulting luminescent inks, observing a strong hypsochromic shift in excitation wavelength upon drying. Hence, while a cheap UV-A lamp sufficed to reveal the polyfluorene’s blue emission, shorter wavelengths were necessary to visualize the emission due to lanthanide ions as well. The capacity to reveal, with UV-C radiation, a full-color image that remains invisible under natural light is undoubtedly useful for anti-counterfeiting applications. Furthermore, both lanthanide ion complexes and polyfluorenes were shown to have their luminescence quenched by Cu(II) ions and nitroarenes, respectively. Full article

Cancer involves a series of diseases where cellular growth is not controlled. Cancer is a leading cause of death worldwide, and the burden of cancer incidence and mortality is rapidly growing, mainly in developing countries. Many drugs are currently used, from chemotherapeutic agents to immunotherapy, among others, along with organ transplantation. Treatments can cause severe side effects, including remission and progression of the disease with serious consequences. Increased glycolytic activity is characteristic of cancer cells. Triosephosphate isomerase is essential for net ATP production in the glycolytic pathway. Notably, some post-translational events have been described that occur in human triosephosphate isomerase in which functional and structural alterations are provoked. This is considered a window of opportunity, given the differences that may exist between cancer cells and their counterpart in normal cells concerning the glycolytic enzymes. Here, we provide elements that bring out the potential of triosephosphate isomerase, under post-translational modifications, to be considered an efficacious target for treating cancer. Full article

High concentrations of graphene oxide (GO), a nanoparticle substance with rapid manufacturing development, have the ability to penetrate the soil surface down to the mineral-rich subsurface layers. The destiny and distribution of such an unusual sort of nanomaterial in the environment must therefore be fully understood. However, the way the chemistry of solutions impacts GO nanoparticle adsorption on clay minerals is still unclear. Here, the adsorption of GO on clay minerals (e.g., bentonite and kaolinite) was tested under various chemical conditions (e.g., GO concentration, soil pH, and cation valence). Non-linear Langmuir and Freundlich models have been applied to describe the adsorption isotherm by comparing the amount of adsorbed GO nanoparticle to the concentration at the equilibrium of the solution. Our results showed fondness for GO in bentonite and kaolinite under similar conditions, but the GO nanoparticle adsorption with bentonite was superior to kaolinite, mainly due to its higher surface area and surface charge. We also found that increasing the ionic strength and decreasing the pH increased the adsorption of GO nanoparticles to bentonite and kaolinite, mainly due to the interaction between these clay minerals and GO nanoparticles’ surface oxygen functional groups. Experimental data fit well to the non-linear pseudo-second-order kinetic model of Freundlich. The model of the Freundlich isotherm was more fitting at a lower pH and higher ionic strength in the bentonite soil while the lowest R² value of the Freundlich model was recorded at a higher pH and lower ionic strength in the kaolinite soil. These results improve our understanding of GO behavior in soils by revealing environmental factors influencing GO nanoparticle movement and transmission towards groundwater. Full article

Irradiation can be used for the preservation of chickpea protein as it can destroy microorganisms, bacteria, virus, or insects that might be present. However, irradiation may provoke oxidative stress, and therefore modify the functionality and nutritional value of chickpea protein. In order to study the effects of irradiation on the physicochemical properties and digestion behaviour of chickpea protein, chickpea protein concentrate (CPC) was treated with electron beam irradiation (EBI) at doses of 5, 10, 15, and 20 kGy. After irradiation, protein solubility first increased at 10 kGy and 15 kGy, and then decreased at the higher dose of 20 kGy. This was supported by SDS-PAGE, where the intensity of major protein bands first increased and then decreased. Increased doses of EBI generally led to greater oxidative modification of proteins in CPC, indicated by reduced sulfhydryls and increased carbonyls. In addition, the protein structure was modified by EBI as shown by Fourier transform infrared spectroscopy analysis, where α-helix generally decreased, and β-sheet increased. Although the protein digestibility was not significantly affected by EBI, the peptidomic analysis of the digests revealed significant differences among CPC irradiated with varying doses. A total of 337 peptides were identified from CPC irradiated with 0 kGy, 10 kGy, and 20 kGy, with 18 overlapping peptides and 60, 29, and 40 peptides specific to the groups of 0, 10, and 20 kGy respectively. Theoretical calculation showed that the distribution of peptide length, hydrophobicity, net charge, and C-terminal residues were affected by irradiation. The 2, 2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) radical scavenging activity showed a marginal decrease with an increasing dose of irradiation. In conclusion, EBI led to oxidative modification and structural changes in chickpea protein, which subsequently affected the physicochemical properties of peptides obtained from in-vitro digestion of CPC, despite similar digestibility. Full article

Here, we report a new synthetic protocol based on microwave-assisted synthesis (MAS) for the preparation of higher yields of zinc and copper in MOFs based on different bis(pyrazolyl)-tagged ligands ([M(BPZ)]_n where M = Zn(II), Cu(II), H₂BPZ = 4,4′-bipyrazole, [M(BPZ-NH₂)]_n where M = Zn(II), Cu(II); H₂BPZ-NH₂ = 3-amino-4,4′-bipyrazole, and [M_x(Me₄BPZPh)] where M = Zn(II), x = 1; Cu(II), x = 2; H₂Me₄BPZPh = bis-4′-(3′,5′-dimethyl)-pyrazolylbenzene) and, for the first time, a detailed study of their antibacterial activity, tested against Gram-negative (E. coli) and Gram-positive (S. aureus) bacteria, as representative agents of infections. The results show that all MOFs exert a broad-spectrum activity and strong efficiency in bacterial growth inhibition, with a mechanism of action based on the surface contact of MOF particles with bacterial cells through the so-called “chelation effect” and reactive oxygen species (ROS) generation, without a significant release of Zn(II) and Cu(II) ions. In addition, morphological changes were elucidated by using a scanning electron microscope (SEM) and bacterial cell damage was further confirmed by a confocal laser scanning microscopy (CLSM) test. Full article

The aim of the study was a quantitative analysis of p-chloroaniline (PCA) formation during 2% CHX activation with US and MDI methods in a root canal-like environment with the HPLC-DAD method and, thus, a safety assessment of US and MDI agitation of CHX in endodontic treatment. Two percent CHX was activated with the US method using ISO 30 and 35 K-file, and the MDI method using ISO 30.06 and 35.06 GP cones for 15, 30, 60, and 90 s. PCA concentration was assessed with the HPLC-DAD method. PCA concentration was also assessed for 2% CHX after 0, 3, 18, and 21 days of storage in ambient conditions. PCA was detected in all samples in all methods of activation. The concentration of PCA was dependent on time of activation in US ISO 30 and ISO 35 group (p < 0.05). In the MDI ISO 30.06 and ISO 35.06 groups, a similar trend was observed but without statistical significance (p > 0.05). PCA was detected in shelf-stored 2% CHX and the concentration was related to the time of storage. PCA is released after CHX activation with US and MDI, but mean concentrations are not higher than those observed from self-degradation of shelf-stored 2% CHX. Full article

Prostate-specific membrane antigen (PSMA)-based low-molecular-weight agents using beta(β)-particle-emitting radiopharmaceuticals is a new treatment paradigm for patients with metastatic castration-resistant prostate cancer. Although results have been encouraging, there is a need to improve the tumor residence time of current PSMA-based radiotherapeutics. Albumin-binding moieties have been used strategically to enhance the tumor uptake and retention of existing PSMA-based investigational agents. Previously, we developed a series of PSMA-based, β-particle-emitting, low-molecular-weight compounds. From this series, ¹⁷⁷Lu-L1 was selected as the lead agent because of its reduced off-target radiotoxicity in preclinical studies. The ligand L1 contains a PSMA-targeting Lys-Glu urea moiety with an N-bromobenzyl substituent in the ε-amino group of Lys. Here, we structurally modified ¹⁷⁷Lu-L1 to improve tumor targeting using two known albumin-binding moieties, 4-(p-iodophenyl) butyric acid moiety (IPBA) and ibuprofen (IBU), and evaluated the effects of linker length and composition. Six structurally related PSMA-targeting ligands (Alb-L1–Alb-L6) were synthesized based on the structure of ¹⁷⁷Lu-L1. The ligands were assessed for in vitro binding affinity and were radiolabeled with ¹⁷⁷Lu following standard protocols. All ¹⁷⁷Lu-labeled analogs were studied in cell uptake and selected cell efficacy studies. In vivo pharmacokinetics were investigated by conducting tissue biodistribution studies for ¹⁷⁷Lu-Alb-L2–¹⁷⁷Lu-Alb-L6 (2 h, 24 h, 72 h, and 192 h) in male NSG mice bearing human PSMA+ PC3 PIP and PSMA− PC3 flu xenografts. Preliminary therapeutic ratios of the agents were estimated from the area under the curve (AUC_0-192h) of the tumors, blood, and kidney uptake values. Compounds were obtained in >98% radiochemical yields and >99% purity. PSMA inhibition constants (K_is) of the ligands were in the ≤10 nM range. The long-linker-based agents, ¹⁷⁷Lu-Alb-L4 and ¹⁷⁷Lu-Alb-L5, displayed significantly higher tumor uptake and retention (p < 0.001) than the short-linker-bearing ¹⁷⁷Lu-Alb-L2 and ¹⁷⁷Lu-Alb-L3 and a long polyethylene glycol (PEG) linker-bearing agent, ¹⁷⁷Lu-Alb-L6. The area under the curve (AUC_0-192h) of the PSMA+ PC3 PIP tumor uptake of ¹⁷⁷Lu-Alb-L4 and ¹⁷⁷Lu-Alb-L5 were >4-fold higher than ¹⁷⁷Lu-Alb-L2, ¹⁷⁷Lu-Alb-L3, and ¹⁷⁷Lu-Alb-L6, respectively. Also, the PSMA+ PIP tumor uptake (AUC_0-192h) of ¹⁷⁷Lu-Alb-L2 and ¹⁷⁷Lu-Alb-L3 was ~1.5-fold higher than ¹⁷⁷Lu-Alb-L6. However, the lowest blood AUC_0-192h and kidney AUC_0-192h were associated with ¹⁷⁷Lu-Alb-L6 from the series. Consequently, ¹⁷⁷Lu-Alb-L6 displayed the highest ratios of AUC(tumor)-to-AUC(blood) and AUC(tumor)-to-AUC(kidney) values from the series. Among the other agents, ¹⁷⁷Lu-Alb-L4 demonstrated a nearly similar ratio of AUC(tumor)-to-AUC(blood) as ¹⁷⁷Lu-Alb-L6. The tumor-to-blood ratio was the dose-limiting therapeutic ratio for all of the compounds. Conclusions: ¹⁷⁷Lu-Alb-L4 and ¹⁷⁷Lu-Alb-L6 showed high tumor uptake in PSMA+ tumors and tumor-to-blood ratios. The data suggest that linker length and composition can be modulated to generate an optimized therapeutic agent. Full article

This study focuses on the fabrication of fiber membranes containing different concentrations of AgNO₃ via the electrospinning technique. The AgNO₃ present in the fibers is subsequently reduced to silver nanoparticles (Ag NPs) through UV irradiation. The resulting nanofiber film is characterized using scanning electron microscopy, X-ray diffraction, and evaluations of its anti-UV and anti-electromagnetic radiation properties. Experimental results demonstrate that increasing the AgNO₃ content initially decreases and then increases the fiber diameter and fiber diameter deviation. Under UV light, the nanofibers fuse and bond, leading to an increase in the fiber diameter. AgNO₃ is effectively reduced to Ag NPs after UV irradiation for more than 60 min, as confirmed by the characteristic diffraction peaks of Ag NPs in the XRD spectrum of the irradiated AgNO₃/PVB fibers. The nanofiber film containing AgNO₃ exhibits superior anti-UV performance compared to the film containing AgNO₃-derived Ag NPs. The anti-electromagnetic radiation performances of the nanofiber films containing AgNO₃ and AgNO₃-derived Ag NPs are similar, but the nanofiber film containing AgNO₃-derived Ag NPs exhibits higher performance at approximately 2.5 GHZ frequency. Additionally, at an AgNO₃ concentration of less than 0.5 wt%, the anti-electromagnetic radiation performance is poor, and the shielding effect of the nanofiber film on medium- and low-frequency electromagnetic waves surpasses that on high-frequency waves. This study provides guidance for the preparation of polyvinyl butyral nanofibers, Ag NPs, and functional materials with anti-ultraviolet and anti-electromagnetic radiation properties. Full article

Numerous studies have provided evidence that diets rich in anthocyanins show a broad spectrum of health benefits. Anthocyanins in nature are usually found in the form of glycosides. Their aglycone forms are called anthocyanidins. The chemical structure of anthocyanins is based on the flavylium cation, but they differ in the position and number of substituents. However, the bioactives and foods that contain them are frequently treated as a uniform group of compounds exhibiting the same biological activity, without paying attention to the structural differences between individual anthocyanidins. The aim of this study was to find out how structural differences impact the biological activity of the six most common dietary anthocyanidins, i.e., delphinidin (Dp), petunidin (Pt), cyanidin (Cd), malvidin (Mv), pelargonidin (Pg) and peonidin (Po). The study concentrated on redox-related phenomena and compared the following parameters: antioxidant activity (measured using various methods: spectrophotometric tests (ABTS, DPPH), ORAC assay and CAA test (cellular antioxidant activity)), the ability to inhibit growth of human colon cancer cells (HT29; determined using MTT assay), and the ability of studied compounds to protect DNA from oxidative damage (comet assay). Based on the obtained results, the relationship between the structure of studied anthocyanidins and their biological activity was assessed. The obtained results revealed that the number and position of the hydroxyl and methoxy groups in the anthocyanidin structure strongly influenced not only the color of anthocyanidins but most of all their antioxidant and biological activities. Full article

Common tansy (Tanacetum vulgare L.) is a plant with medicinal properties that has traditionally been used in folk medicine for its anthelmintic, antispasmodic, and choleretic effects, for the treatment of diarrhea and digestive problems, and externally, as an insecticide in veterinary practices. In the current study, we investigated, for the first time, the chemical profile and antioxidant activity of essential oil from a wild population of T. vulgare L. growing in Bulgaria. Common tansy essential oil (EO), which is rich in bicyclic monoterpenes, was obtained using hydrodistillation and characterized by using gas chromatography–mass spectrometry (GC-MS). Thirty-seven compounds were identified in Bulgarian tansy EO. Among the major constituents were oxygenated monoterpenes, including compounds such as camphor (25.24%), trans-chrysantenyl acetate (18.35%), cis-verbenol (10.58%), thujone (6.06%), eucaliptol (5.99%), and α-campholenal (5.98%). The analysis results identified the essential oil from T. vulgare L. grown in the western Rhodope Mountains of Bulgaria as the camphor chemotype. Furthermore, its antioxidant activity was analyzed using the oxygen radical absorbance capacity (ORAC) method and was found to be 605.4 ± 49.3 µmol TE/mL. The essential oil was also tested for single-dose acute toxicity on Wistar rats and was found to be non-toxic by oral administration. The mean lethal dose by intraperitoneal administration was LD₅₀ i.p. = 14.9 g/kg body weight. The results of the conducted study can serve as a basis for the evaluation and subsequent exploration of other pharmacotherapeutic effects of the essential oil obtained from the inflorescences of the Bulgarian species T. vulgare L. Full article

With the continuous growth of global energy demand and the late stage of conventional oilfield exploitation, the demand for developing and utilizing low-permeability heavy oil reservoirs is becoming increasingly urgent. However, the exploitation of low-permeability heavy oil reservoirs faces many challenges due to their high viscosity, low permeability, and complex geological conditions. To overcome these challenges, researchers have gradually introduced SC-CO₂ as an oil displacement agent in the exploitation of heavy oil reservoirs. However, the oil displacement mechanism of SC-CO₂ in low-permeability heavy oil reservoirs and its improvement mechanism are still not completely understood. The article provides a detailed study and understanding of the oil displacement mechanism of SC-CO₂, which involves the expansion of heavy oil volume through SC-CO₂ dissolution. This mechanism reduces the capillary resistance and flow resistance during the oil flow process. The permeation of CO₂ disrupts the internal structure and arrangement of heavy oil, reducing its viscosity. CO₂ extracts both light and heavy components from the heavy oil, reducing the residual oil saturation. In addition, the mechanism of improving the effect of oil displacement agents such as nanoparticles, polymers, and surfactants on SC-CO₂ displacement was also explored. By further exploring the mechanisms and improvement mechanisms of SC-CO₂ displacement for heavy oil, it can guide the selection and optimization of oil displacement agents. Furthermore, understanding the mechanism can also provide a theoretical basis for engineering practice and technical innovation. While the research on CO₂ flooding is analyzed and evaluated, the obstacles and challenges that still exist at this stage are indicated, and future research work on CO₂ in low-permeability heavy oil reservoirs is proposed. Full article

A natural UV-absorbing chromophore extracted from sphagnum mosses, sphagnic acid, is proposed as a new natural support to chemical UV filters for use in cosmetic applications. Sphagnic acid is structurally related to the cinnamate family of molecules, known for their strong UV absorption, efficient non-radiative decay, and antioxidant properties. In this study, transient electronic absorption spectroscopy is used, in conjunction with steady-state techniques, to model the photodynamics following photoexcitation of sphagnic acid in different solvent systems. Sphagnic acid was found in each system to relax with lifetimes of ~200 fs and ~1.5 ps before generating a cis-isomer photoproduct. This study helps to elucidate the photoprotective mechanism of a new potential natural support to sunscreens, from a unique plant source. Full article

Rakicidin B1 was isolated and purified from the culture broth of a marine Streptomyces sp. as a potent anti-cancer agent, and lately the compound and its derivatives have firstly been found to possess anti-Clostridium difficile (CD) activity but with high cytotoxicity. Herein, following our previous discovery on anti-CD activity of Rakicidin B1, structure modification was performed at the OH position of Rakicidin B1 and a new Rakicidin B1-PEG hybrids FIMP2 was facilely designed and synthesized by conjugating the PEG2000 with the scaffolds of Rakicidin B1 via the linkage of carbamate. The cytotoxicity of the FIMP2 was first evaluated against three different cancer cell lines, including HCT-8 cells, PANC-1, and Caco-2, with IC₅₀ values at 0.519 μM, 0.815 μM, and 0.586 μM, respectively. Obviously, as compared with a positive control group treated with Rakicidin B1, the IC₅₀ value of FIMP2 increased by nearly 91-fold, 50-fold, and 67-fold, suggesting that the PEGylation strategy significantly reduced the cytotoxicity of FIMP2. Thus, this preliminary result may be beneficial to increase its safety index (SI) value due to the decreased cytotoxicity of FIMP2. In addition, this decreased cytotoxicity of FIMP2 was further confirmed based on a zebrafish screening model in vivo. Thereafter, the anti-CD activity of FIMP2 was evaluated in vivo, and its efficacy to treat CDI was found to be better than that of vancomycin. The mortality and recurrence rate of FIMP2 is not as low compared with that of vancomycin; these results demonstrated that compound FIMP2 is a new, promising anti-CD agent with significant efficacy against CD recurrence with low cytotoxicity towards bodies. Full article

Black phosphorene quantum dots (BPQDs) were prepared by ultrasonic-assisted liquid-phase exfoliation and centrifugation with morphologies proved by TEM results. Furthermore, an electrochemical enzyme sensor was prepared by co-modification of BPQDs with horseradish peroxidase (HRP) on the surface of a carbon ionic liquid electrode (CILE) for the first time. The direct electrochemical behavior of HRP was studied with a pair of well-shaped voltammetric peaks that appeared, indicating that the existence of BPQDs was beneficial to accelerate the electron transfer rate between HRP and the electrode surface. This was due to the excellent properties of BPQDs, such as small particle size, high interfacial reaction activity, fast conductivity, and good biocompatibility. The presence of BPQDs on the electrode surface provided a fast channel for direct electron transfer of HRP. Therefore, the constructed electrochemical HRP biosensor was firstly used to investigate the electrocatalytic behavior of trichloroacetic acid (TCA) and potassium bromate (KBrO₃), and the wide linear detection ranges of TCA and KBrO₃ were 4.0–600.0 mmol/L and 2.0–57.0 mmol/L, respectively. The modified electrode was applied to the actual samples detection with satisfactory results. Full article

α-Aminophosphonates and related compounds are important due to their real and potential biological activity. α-Aminophosphonates may be prepared by the Kabachnik–Fields condensation of oxo compounds, amines and dialkyl phosphites, or by the aza-Pudovik addition of the same P-reagents to imines. In this review, the methods that allow for the synthesis of α-aminophosphonates with optical activity are surveyed. On the one hand, optically active catalysts or ligands may induce enantioselectivity during the Kabachnik–Fields reaction. On the other hand, asymmetric catalysis during the aza-Pudovik reaction, or hydrogenations of iminophosphonates, may prove to be a useful tool. Lastly yet importantly, it is possible to start from optically active reagents that may be associated with diastereoselectivity. The “green” aspects of the different syntheses are also considered. Full article

Dermatological diseases pose a significant burden on the quality of life of individuals and can be challenging to treat effectively. In this aspect, cannabinoids are gaining increasing importance due to their therapeutic potential in various disease entities including skin diseases. In this synthetic review, we comprehensively analyzed the existing literature in the field of potential dermatological applications of a lesser-known subgroup of cannabinoids, the so-called minor cannabinoids, such as cannabidivarin (CBDV), cannabidiforol (CBDP), cannabichromene (CBC), tetrahydrocannabivarin (THCV), cannabigerolic acid (CBGA), cannabigerol (CBG), cannabielsoin (CBE), cannabimovone (CBM) or cannabinol (CBN), while drawing attention to their unique pharmacological properties. We systematically searched the available databases for relevant studies and analyzed the data to provide an overview of current thematic knowledge. We looked through the full-text, bibliographic and factographic databases, especially Scopus, Web of Science, PubMed, Polish Scientific Journals Database, and selected the most relevant papers. Our review highlights that minor cannabinoids exhibit diverse pharmacological activities, including anti-inflammatory, analgesic, antimicrobial, and anti-itch properties. Several studies have reported their efficacy in mitigating symptoms associated with dermatological diseases such as psoriasis, eczema, acne, and pruritus. Furthermore, minor cannabinoids have shown potential in regulating sebum production, a crucial factor in acne pathogenesis. The findings of this review suggest that minor cannabinoids hold therapeutic promise in the management of dermatological diseases. Further preclinical and clinical investigations are warranted to elucidate their mechanisms of action, determine optimal dosage regimens, and assess long-term safety profiles. Incorporating minor cannabinoids into dermatological therapies could potentially offer novel treatment options of patients and improve their overall well-being. Full article

Carlina acaulis is highly valued in the traditional medicine of many European countries for its diuretic, cholagogue, anthelmintic, laxative, and emetic properties. Moreover, practitioners of natural medicine indicate that it has anti-cancer potential. However, its phytochemistry is still little known. In the present study, the polyphenolic composition of the plant was investigated using ultra-high-performance liquid chromatography coupled with a high-resolution/quadrupole time-of-flight mass spectrometer (UHPLC-HR/QTOF/MS-PDA). The fractionation of the extract was carried out using liquid-liquid extraction and preparative chromatography techniques. Cytotoxicity was assessed based on neutral red and MTT assays. The obtained data showed that the species is rich in chlorogenic acids and C-glycosides of luteolin and apigenin. The total amount of chlorogenic acids was 12.6 mg/g. Among flavonoids, kaempferol dihexosidipentose and schaftoside were the most abundant, reaching approximately 3 mg/g, followed by isoorientin, vitexin-2-O-rhamnoside, and vicenin II, each with a content of approximately 2 mg/g. Furthermore, the cytotoxic potential of the plant against human colorectal adenocarcinoma (HT29) and human cervical cancer (HeLa) cells was investigated using the normal epithelial colon cell line (CCD 841CoTr) as a reference. It has been demonstrated that the ethyl acetate fraction was the most abundant in polyphenolic compounds and had the most promising anticancer activity. Further fractionation allowed for the obtaining of some subfractions that differed in phytochemical composition. The subfractions containing polyphenolic acids and flavonoids were characterized by low cytotoxicity against cancer and normal cell lines. Meanwhile, the subfraction with fatty acids was active and decreased the viability of HeLa and HT29 with minimal negative effects on CCD 841CoTr. The effect was probably linked to traumatic acid, which was present in the fraction at a concentration of 147 mg/g of dried weight. The research demonstrated the significant potential of C. acaulis as a plant with promising attributes, thus justifying further exploration of its biological activity. Full article

3-ferrocenyl-estra-1,3,5 (10)-triene-17-one (2), [Fe(C₅H₅)(C₂₄H₂₅O₃)], crystallizes in the monoclinic space group C2. The cyclopentadienyl (Cp) rings adopt a nearly eclipsed conformation, and the Cp plane is tilted by 87.66° with respect to the substituted phenyl plane. An average Fe-C(Cp) bond length of 2.040(13) Å was determined, similar to the one reported for ferrocene. Hirshfeld surfaces and two-dimensional fingerprint plots were generated to analyze weak intermolecular C-H···π and C-H···O interactions. Density functional theory studies revealed a 1.15 kcal/mol rotational barrier for the C3-O1 single bound. Fluorescence quenching studies and in silico docking studies suggest that human serum albumin forms a complex with 2 via a static mechanism dominated by van der Waals interactions and hydrogen bonding interactions. Full article

Five new derivatives were obtained utilizing 4-chloro-7-nitrobenzofurazan (NBD-chloride) in combination with furfurylamine, adamantylamine, aminohippuric acid, phenylalanine, and dehydroabietylamine. These derivatives were then subjected to a comparative analysis of their physical, chemical, and certain biological properties alongside two analogous and known compounds derived from the glycine and 4-amino-TEMPO free radical. Full article

Two-dimensional (2D) ice I is atomic-level ice that is composed of two interlocked atomic layers saturated with hydrogen bonds. It has recently been experimentally observed, but its properties have yet to be clarified. Accordingly, we theoretically studied the hydrophobic properties of 2D ice I. On the contrary, a simulation of a hydrogen fluoride molecule on a 2D ice surface manifested that it destroyed the 2D ice structure and connected new hydrogen bonds with water molecules. Investigations of the interfacial effect between 2D and three-dimensional (3D) ice films indicated that the network structure of 2D ice was not destroyed by a 3D ice surface, as the former was saturated with hydrogen bonds. However, the surface of 3D ice reorganized to form as many hydrogen bonds as possible. Thus, the 2D ice film was hydrophobic and inhibited the growth of 3D ice. This shows that if 2D ice can be produced on an industrial scale, it can be used as an anti-3D-icing agent under low temperatures. Full article