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Valorization of Elderberry Pomace using Emerging High-Pressure Technologies: Separation of Compounds with Different Polarities using Subcritical H2O, Supercritical CO2, and CO2/H2O/EtOH Mixture
No full textThe valorization of agricultural by-products such as black elderberry pomace (BEP) is critical for advancing the circular economy and maximizing the potential of natural resources. The main objective of this study was to perform green high-pressure technologies for the comprehensive utilization of BEP, a by-product of juice processing. The study employed three processes: subcritical water extraction (SWE), supercritical CO2 extraction (SFE-CO2), and enhanced solvent extraction (ESE) to recover high-value polar and non-polar fractions. SWE was used to recover polar molecules at temperatures from 120 to 200 ℃. The unique properties of supercritical CO2 were utilized in two different ways: first, by applying pressures of 200 and 300 bar to separate non-polar fractions, and second in ESE, by using a CO2/EtOH/H2O mixture at 350 bar to extract non-polar and polar fractions. The polar fractions were analyzed by HPLC–DAD, and the lipophilic by GC–MS. HPLC analysis of the SWE extracts showed that the optimum temperature for polyphenol extraction was 200 ℃, with rutin and protocatechuic acid being the predominant compounds. The maximum recovery of rutin (5.81 μg/g dry extract, DE) was achieved at 140 ℃, while protocatechuic acid (8.79 μg/g DE) peaked at 200 ℃. The non-polar fractions were efficiently separated with SFE-CO2, rich in linoleic acid (omega-6), oleic acid (omega-9), and hexadecanoic acids. Subsequent ESE of the defatted pomace yielded high-quality polyphenolic extracts, with cyanidin 3-O-sambubioside (2.26 mg/g DE) as the major compound, together with rutin and cyanidin 3-O-glucoside. These results underline the effectiveness of high-pressure processes in the separation of bioactive compounds from BEP and highlight their potential for sustainable utilization of food waste
Supplementary material for: Ostojić, J., Savić, S. D., Manojlović, D., Metelka, R., Stanković, V.,& Stanković, D. M.. (2025). A rapid, reusable, and portable electrochemical assay for caffeine monitoring in beverage samples based on boron doped diamond and multi walled carbon nanotubes. in Diamond and Related Materials Elsevier., 156, 112450. https://doi.org/10.1016/j.diamond.2025.112450
No full textDespite potential health risks at high doses, caffeine remains the most widely consumed psychoactive drug globally, naturally occurring in more than 60 plants. Accurate determination of caffeine content is crucial to ensure the safety of consumers of caffeine-containing beverages. This work explores two different electrochemical sensors for caffeine determination: screen-printed carbon electrodes modified with multi-walled carbon nanotubes (MWCNT SPEs) and screen-printed sensors with boron-doped diamond electrodes prepared by chemical vapor deposition (BDD SPEs). These sensors offer advantages over traditional methods, potentially providing faster and more portable analysis. Two linear ranges for caffeine determination were observed at BDD SPEs in 0.5 M H2SO4. A lower linear range between 20 μM and 80 μM resulted in a limit of detection (LOD) of 3.40 μM and a limit of quantification (LOQ) of 10.30 μM, while a higher linear range between 100 μM to 500 μM provided the LOD of 9.72 μM and the LOQ of 29.45 μM of caffeine. MWCNT SPEs showed the optimal analytical parameters in the Britton-Robinson buffer at pH 2 with a broader linear range from 33 μM to 500 μM; the LOD was 8.65 μM, and the LOQ was 26.20 μM. The determination of caffeine content was successfully conducted in real dietary samples using both sensors, with validation by high-performance liquid chromatography (HPLC) and spectrophotometric analysis.Supplementary material for: [https://doi.org/10.1016/j.diamond.2025.112450]Related to published version: [https://cherry.chem.bg.ac.rs/handle/123456789/7105]Related to accepted verison: [https://cherry.chem.bg.ac.rs/handle/123456789/7106
Total Proteome and Calcium-Binding Proteins from Human Breast Milk: Exploring the Impact of Smoking and Environmental Factors
No full textThis study integrates proteome analysis of human breast milk (HBM) from a homogeneous group of mothers who are of similar age and live in the same geographical area, along with an analysis of essential and potentially toxic elements in HBM in relation to lifestyle and environmental factors. This preliminary proteomic study, which examined 11 samples of HBM from lactating women, identified a total of 1619 proteins across all samples, revealing significant differences in proteomes influenced by lactation stages, parity, and exposure to tobacco smoke. The pilot study aimed to explore the feasibility of correlating certain proteins with several elements, considered as indicators of tobacco smoke and environmental influences on HBM. Notably, a clear and significant correlation was found between altered calcium content in HBM and the proteome fraction associated with calcium-binding proteins. The findings suggest that all analyzed factors impact the HBM proteome and the activity of certain enzymes
Unlocking the power of affibody conjugated radioactive metallopharmaceuticals for targeted cancer diagnosis and therapy
No full textCancer is the second-largest death-causing disease after cardiovascular diseases. Effective research on cancer diagnosis and subsequent elimination plays a vital role in reducing the cancer-related death toll. Radiotherapy is one of the best strategies that could kill masses of solid tumour tissues; however, the efficacy is limited due to the bystander effect. This issue could be solved by the emergence of targeted delivery of radiometallic complexes, enabling clinicians to monitor the tumour regions and effectively destroy the tumour. Affibody® molecules are a class of synthetic peptides known as antibody mimics having the binding sites of an antibody. The specificity of affibodies is found to be greater than that of antibodies due to their small size. This review intends to highlight the recent developments in the field of affibody-targeted radiometallopharmaceuticals. These approaches could be essential for early cancer detection, tumour staging, and monitoring the response to therapy and could produce better therapeutic outcomes. In an attempt to provide ideas and inspiration for the researchers to design affibody-conjugated radiopharmaceuticals that are clinically applicable, we have provided an in-depth exploration of the various types of affibody-conjugated radiopharmaceuticals that are currently in clinical trials and various other pre-clinically tested conjugates in this article. Only a few review reports on affibody-conjugated radiometallopharmaceuticals, typically focusing on a specific molecular target or radionuclides reported. In this review, we provide a comprehensive overview of most radiometals, such as 111In, 68Ga, 64Cu, 55Co, 57Co, 44Sc, 99mTc, 89Zr, 90Y, 211At, 188Re, and 177Lu, choice of chelators, and potential cancer-associated molecular targets such HER2, EGFR or HER1, HER3, IGF-1R, PDGFRβ, VEGFR2, PD-L1, CAIX, PD-L1, neonatal Fc receptor (FcRn) and B7-H3. This approach highlights the advancements made over the past twenty years in affibody conjugates for radio imaging and therapy in oncology.This is the peer-reviewed version of the article: Murugan, D., Thirumalaiswamy, H. V., Murugesan, V., Venkatesan, J., Balachandran, U., Lakshminarayanan, K., Satpati, D., Nikolić, S.,& Rangasamy, L.. (2025). Unlocking the power of affibody conjugated radioactive metallopharmaceuticals for targeted cancer diagnosis and therapy. in Pharmacology & Therapeutics Elsevier., 272, 108863. [https://doi.org/10.1016/j.pharmthera.2025.108863
Why Protein Modifications Matter for Digestibility: The Case of Ara h 1 Peanut Allergen and Trypsin Cleavage
No full textTrypsin is the principal intestinal endopeptidase and proteomics digestion tool, yet the impact of protein modifications (PMs) on digestibility and allergenicity remains underexplored. We employed a proteomic approach to assess trypsin cleavage efficacy (TCE) at modified versus unmodified K/R residues in Ara h 1, a major peanut allergen. Seven of 17 PM sites showed ≥20% difference in TCE, with carbamoylation + methylation and dihydroxylation retaining significance after multiple-testing correction. The 20% threshold aligns with the 19 ± 1% baseline of porcine trypsin miscleavages. Molecular docking confirmed reduced binding affinity due to steric hindrance from methylation at R259. These findings suggest that impaired digestion at PM sites may enhance peptide sensitization potential. This study provides a basis for machine learning-driven models using public proteomic data sets to predict the influence of PMs on protease performance.Peer-reviewed manuscript: [https://cherry.chem.bg.ac.rs/handle/123456789/7149
The Content of Flavanols in Wood Waste Extracts from Serbian Cooperage
No full textThe ageing of alcoholic beverages in contact with wood has a long tradition in Serbia. Oak is most commonly used in cooperage, but other types of wood such as black locust, cherry and mulberry are also used. The cooperage industry generates large quantities of wood by- products, which can be utilised as a valuable source of phenolic compounds with high antioxidant and antimicrobial activity. Among them, flavanols are of particular interest due to their protective role in wood and their potential applications in the food industry. Cherry wood is already known as a rich source of flavanols, including catechin, epicatechin, and procyanidins [1]. However, to our knowledge, limited data is available on the content of flavanols in other wood species used in cooperage.
The aim of this study was to analyse the content of flavanols in wood waste extracts from different species used in Serbian cooperage. Identification and quantification were carried out using high-performance liquid chromatography coupled with a diode array detector (HPLC-DAD). A total of six flavanols were detected, including catechin, (-)-epicatechin, (-)-epicatechin-gallate, (-)-catechin gallate, (-)-gallocatechin and (-)-epigallocatechin-gallate.
Each species had a characteristic profile, with different dominant compounds observed. The richest sources of flavanols were black locust and Myrobalan plum, while the lowest content of flavanols was observed in oak samples. An exceptionally high content of (-)-epicatechin was found in black locust, (-)-catechin gallate in Myrobalan plum and catechin in wild cherry. White mulberry contained (-)-catechin gallate as the only compound, though in lower concentrations than Myrobalan plum. All oak samples contained (-)-epicatechin gallate as the dominant flavanol. These results highlight the species-specific flavanol profiles and suggest that wood by-products from cooperage could be further valorised as a natural source of bioactive compounds
Transient expression of PRISEs and Trichoderma-mediated elicitation promote iridoid production in Nepeta sibirica L.
No full textThe genus Nepeta is the sole representative in the plant kingdom that produces nepetalactones, a group of iridoids with a unique stereochemistry, which play key roles in plant defense and ecological interactions. This study investigates N. sibirica L., a species rich in cis,trans-nepetalactone and 1,5,9-epi-deoxyloganic acid, aiming to enhance production of these bioactive iridoids by two alternative strategies: transient expression of key iridoid biosynthesis-related genes and fungal elicitation. In vitro treatments with Trichoderma harzianum and T. viride promoted iridoid production in N. sibirica leaves. It appears that regulatory proteins COI1, MYC2, and YABBY5 provoke coordinated upregulation of the early iridoid pathway genes (NsGPPS, NsGES, NsG8H, Ns8HGO), and of NsMLPL, thus stimulating metabolic flux through the iridoid pathway and providing substrates for the downstream steps mediated by NsISY, NsNEPS1, and NsNEPS2. The N. sibirica PRISE orthologue (NsPRISE) is closely related phylogenetically to the Family 1 isoforms known as P5βRs. However, its ISY-like activity was confirmed through in vitro assays with recombinant proteins expressed heterologously in E. coli. Transient overexpression experiments, which comparatively analysed in planta function of homologous NsPRISE and previously characterized ISY and PRISE orthologues from other Nepeta species, suggested possible in vivo residual ISY-like activity of NsPRISE and its involvement in iridoid production. The current study recognized N. sibirica as a plant susceptible to agroinfiltration, with iridoid metabolism that can be induced by pathogen attack, making it an ideal candidate for developing scalable systems for bioactive compounds production
Supplementary data for: Đapović, Milica; Cvetanović, Katarina; Poštić, Vojislava; Jovanov, Vladislav; Bošković, Marko V.; Polyzoidis, Christos; Tzoganakis, Nikolaos; Rogdakis, Konstantinos; Kymakis, Emmanuel; Maslak, Veselin; Mitrović, Aleksandra. (2025). Early-stage analysis of PET – fullerene derivatives for electron transport in photovoltaics. in Phys. Chem. Chem. Phys. 27, 35, 18256-18262. https://doi.org/10.1039/D5CP02623G
No full textIn the pursuit of sustainable materials for solar cell technologies, this work presents a new class of electron transport layers (ETLs) based on PET-derived monomers and dimers hybridized with fullerene C60. These hybrids were synthesized via selective cyclopropane and furan functionalization and thoroughly characterized using electrochemical, optical, and morphological methods. Compared to the benchmark material PCBM, several PET–fullerene derivatives exhibited improved properties, including enhanced substrate coverage, stronger electron-blocking behaviour, and favourable energy level alignment. Compound 5 emerged as the most promising ETL candidate, demonstrating a smooth, pinhole-free morphology (RMS = 1.15 nm), high charge transfer resistance (Rct = 8.63 × 104 Ω), and a relatively high apparent donor density (Nd = 2.21 × 1021 cm−3). While the absolute ND values may be influenced by film morphology, the comparative analysis confirms superior performance of compound 5. These results indicate that PET–fullerene hybrids, especially compound 5, offer both environmental and functional advantages as next-generation ETL materials.Supplementary material for: [https://doi.org/10.1039/D5CP02623G]Related to published version: [https://cherry.chem.bg.ac.rs/handle/123456789/7283
Izolovanje i određivanje strukture triterpena biljne vrste Euphorbia amygdaloides
No full textEuphorbia amygdaloides L. je biljna vrsta koja pripada rodu Euphorbia L. iz porodice Euphorbicae. Biljke ovog roda već dugo su deo tradicionalne medicine širom sveta. Do sada su iz lateksa ovih biljaka izolovani mnogi specijalizovani metaboliti koji imaju široku biološku aktivnost koja se potencijalno može iskoristiti i u modernoj medicini. Ispitivanja bioloških aktivnosti ovih metabolitа dovela su do saznanja da mnogi od njih imaju antiinflamantorna, antimikrobna, antioksidativna, citotoksična i mnoga druga svojstva. Cilj sprovedenog istraživanja bio je ispitivanje specijalizovanih metabolita biljne vrste Euphorbia amygdaloides L. Kao rezultat ovog istraživanja izolovan je pentaciklični triterpen glutinol
ATR-FTIR characterization of the white willow bark extract used as a copper corrosion inhibitor
No full textAs proved inhibitor of copper corrosion in saline environment, the white willow bark (WWB) extract was characterized using the Attenuated Total Reflectance-Fourier Transform Infrared spectroscopy (ATR-FTIR) method. By identifying the bands typical for phenolic profile of WWB extract, the anti-corrodic properties of WWB were explained. The hydrogen-bonded O-H stretching vibrations present in WWB extract is attributed to the phenolic hydroxyl groups and alcoholic hydroxyl groups within glycosides. The C-H stretching vibrations typical for salicin and for glucoside part of salicin aromatic were also identified, as well as the C=C ring stretching vibrations and C-O stretching vibrations that can be attributed to phenolic and alcoholic groups. The presence of these functional groups confirms the presence of a protective film of the WWB extract on the copper surface, protecting the metal from the corrosive effect of chloride ions