The Health-Promoting Quality Attributes, Polyphenols, Iridoids and Antioxidant Activity during the Development and Ripening of Cornelian Cherry (Cornus mas L.).

This study defined the physicochemical attributes, composition, and antioxidant capacity of four Polish cultivars of cornelian cherry (CC) at six stages of development and ripening. A total of 52 metabolites were identified by UPLC-ESI-qTOF-MS/MS and quantified by HPLC-PDA. In general, phenolic acids, hydrolyzable tannins, flavonols, iridoids, antioxidant activity, organic acids, and vitamin C decreased, while anthocyanins, malic acid, sugars, and titratable acidity increased. For the first time, we determined the evolution of the CC chemical properties and the metabolic behavior and quantified the individual compounds, and groups of compounds during ripening, in particular gallotannins, ellagitannins, iridoids, and organic acids. The main novelty of our study is that CC is a valuable resource for utilization at different degrees of maturity. We showed that unripe fruits in particular deserve valorization, as they contained the highest content of total bioactive phytocompounds (5589.1-6779.6 mg/100 g dw)-primarily phenolic acids > iridoids > tannins-and the highest antioxidant capacity. The intermediate stages were the most abundant in vitamin C (341.1-495.6 mg/100 g dw), ellagic acid (5.9-31.6 mg/100 g dw), gallotannins (47.8-331.1 mg/100 g dw), and loganic acid (1393.0-2839.4 mg/100 g dw). The ripe fruits contained less bioactive phytocompounds (1403.7-1974.6 mg/100 g dw)-primarily iridoids > phenolic acids > tannins > anthocyanins-and the lowest antioxidant capacity. On the other hand, ripe fruits showed the highest content of anthocyanins (30.8-143.2 mg/100 g dw), sugars (36.4-78.9 g/100 g dw), malic acid (5.5-12.2 g/100 g dw), and, favorably for the nutritional applications, the highest sugar-to-acids ratio (3.0-6.4). Our work illustrates in detail that quality attributes and the content of health-promoting phytocompounds in CC depend on the ripening stage and on the cultivar. These results advance the scientific knowledge about CC. Our findings can be helpful to select the optimal properties of CC for the development of diverse functional foods and phytopharmaceuticals applied in the prevention of civilization diseases.

Bright photon upconversion in LiYbF4:Tm3+@LiYF4 nanoparticles and their application for singlet oxygen generation and in immunoassay for SARS-CoV-2 nucleoprotein.

Photon upconversion is an intensively investigated phenomenon in the materials sciences due to its unique applications, mainly in biomedicine for disease prevention and treatment. This study reports the synthesis and properties of tetragonal LiYbF4:Tm3+@LiYF4 core@shell nanoparticles (NPs) and their applications. The NPs had sizes ranging from 18.5 to 23.7 nm. As a result of the energy transfer between Yb3+ and Tm3+ ions, the synthesized NPs show intense emission in the ultraviolet (UV) range up to 347 nm under 975 nm excitation. The bright emission in the UV range allows for singlet oxygen generation in the presence of hematoporphyrin on the surface of NPs. Our studies show that irradiation with a 975 nm laser of the functionalized NPs allows for the production of amounts of singlet oxygen easily detectable by Singlet Oxygen Sensor Green. The high emission intensity of NPs at 800 nm allowed the application of the synthesized NPs in an upconversion-linked immunosorbent assay (ULISA) for highly sensitive detection of the nucleoprotein from SARS-CoV-2, the causative agent of Covid-19. This article proves that LiYbF4:Tm3+@LiYF4 core@shell nanoparticles can be perfect alternatives for the most commonly studied upconverting NPs based on the NaYF4 host compound and are good candidates for biomedical applications.

Ultrasensitive optical thermometry using Tb3+ doped NaSrGd(MoO4)3 based on single band ratiometric luminescence.

A lot of people are interested in optical thermometry, especially the new single-band ratiometric (SBR) technology for measuring temperature. But since SBR thermometry is still in its infancy, it is highly constrained when compared to the conventional dual-band ratiometric approach. In this paper, we propose a new SBR thermometry technique that is based on both the ground and excited state absorption processes. When these two different processes occur, the green emission of Tb3+ in the low-cost host of NaSrGd(MoO4)3 (NSGM) responds to changes in temperature in a way that is the exact opposite of what you would expect. The maximum luminescence intensity was obtained for an optimum terbium concentration of 40% mol. The resulting chromaticity coordinates (x, y) and high correlated color temperature (CCT) values of the doped phosphors give a thermally stable cold emission in the green region with a color purity of about 92%. Using this intriguing characteristic as a foundation, sensitive SBR thermometry has been successfully developed, and the optical properties of the material have also been thoroughly researched. At room temperature, the relative sensitivity reaches its maximum value of 10.9% K-1. These findings may give important information that may be used in the design of new luminescent thermometers that have excellent performance.

A Comparison of the Antiosteoporotic Effects of Cornelian Cherry (Cornus mas L.) Extracts from Red and Yellow Fruits Containing Different Constituents of Polyphenols and Iridoids in Osteoblasts and Osteoclasts.

Methods: Polyphenolic and iridoid constituents of extracts were analyzed qualitatively and quantitatively using the ultraperformance liquid chromatography system coupled with a quadrupole-time of flight mass spectrometry. Primary cultured osteoblasts isolated from mouse calvarias and osteoclast-lineage primary cultured monocytes isolated from mouse bone marrow were used for the assessment of osteoblast and osteoclast differentiation. In the osteoblast culture, cellular viability, alkaline phosphatase (ALP) activity, ALP staining, and mRNA expression of Alpl and Runx2 were examined. In the osteoclast culture, the examined parameters were cellular viability, tartrate-resistant acid phosphatase (TRAP) activity and staining, and mRNA expression of Nfatc1, Ctsk, and Acp. Results: A total of 41 main compounds of iridoids, anthocyanins, hydrolysable tannins, phenolic acids, and flavonols were identified in the three extracts. RED EXT1 contained most of the tested polyphenols and iridoids and was the only extract containing anthocyanins. YL EXT2 contained only one iridoid, loganic acid and gallic acid. YL EXT3 comprised a mixture of iridoids and polyphenols. RED EXT1, YL EXT 2, and to a lesser extent YL EXT3 promoted osteoblast differentiation increasing significantly ALP activity and the amount of ALP-positive stained cells. All extracts upregulated mRNA expression of Alpl and Runx2. RED EXT1 caused the most significant decrease in TRAP activity and the numbers of TRAP-positive multinucleated cells. RED EXT1 caused also the most significant downregulation of mRNA expression of osteoclast related genes Nfatc1, Ctsk, and Acp5. Extracts from yellow fruits, mostly YL EXT2 caused lower, but still significant inhibitory effect on TRAP and osteoclast related genes. Conclusions: The main conclusion of our study is that all three extracts, especially RED EXT1 from red cornelian cherry fruits, possess the antiosteoporotic potential and may be a promising phytomedicine candidate for the prevention and treatment of osteoporosis.

Cornelian Cherry (Cornus mas L.) Extracts Exert Cytotoxicity in Two Selected Melanoma Cell Lines-A Factorial Analysis of Time-Dependent Alterations in Values Obtained with SRB and MTT Assays.

Despite the fact that phytochemicals of Cornaceae species have long been discussed as possible auxiliary agents in contemporary treatment, the insights on their properties remain relatively scarce. This study focuses on Cornus mas L. (Cornelian cherry), the extracts of which are reported to exert a pleiotropic effect shown in both in vivo and in vitro studies. This study aimed to explore the cytotoxic effect of extracts from fruits of red (Cornus mas L. 'Podolski') and yellow (Cornus mas L. 'Yantarnyi' and 'Flava') Cornelian cherries on two melanoma cell lines (A375 and MeWo). The extracts were characterized in the context of the concentration of bioactive compounds of antioxidative properties. Cytotoxicity was investigated with the use of the following two assays: SRB and MTT. An additional, alternative protocol for the SRB assay was used in this study so as to account for possible bias. Cytotoxicity was assessed as a difference in the whole time series of cell viability, instead of analyzing differences in raw values (often found in the literature). Both extracts from Cornus mas L. induced cytotoxicity in both A375 and MeWo cell lines, although the response of these cells was different. Moreover, based on this study, there is no evidence for claiming a different magnitude of cytotoxicity between these two extracts.

Multifunctional cellulose fibers: Intense red upconversion under 1532 nm excitation and temperature-sensing properties.

The unique properties of upconverting nanoparticles are responsible for their various applications in photonic materials, medicine, analytics, or energy conversion. In this work, the NaErF4:Tm3+@NaYF4 core@shell nanoparticles were synthesized by reaction in high-boiling point solvents and incorporated into cellulose fibers. Nanoparticles showed intense upconversion under 1532 nm excitation wavelength due to Er3+ in their structure. Additional co-doping with Tm3+ ions allowed to shift of the typical green luminescence of Er3+ ions to red especially demanded in anti-counterfeiting applications. The products' composition, morphology, and structure parameters confirmed their requested properties. The article demonstrates that cellulose fibers are suitable carriers of NaErF4:Tm3+@NaYF4 NPs. We also show that the temperature-dependent emission of Er3+ ions allows for the preparation of temperature-sensing cellulose fibers.

Improvement in Luminescence Intensity of ß-NaYF4: 18%Yb3+, 2%Er3+@ß-NaYF4 Nanoparticles as a Result of Synthesis in the Presence of Stearic Acid.

The synthesis of upconverting nanoparticles (NPs) is crucial for their spectroscopic properties and further applications. Reducing the size of materials to nano-dimensions usually decreases emission intensity. Therefore, scientists around the world are trying to improve the methods of obtaining NPs to approach levels of emission intensity similar to their bulk counterparts. In this article, the effects of stearic acid on the synthesis of core@shell ß-NaYF4: 18%Yb3+, 2%Er3+@ß-NaYF4 upconverting NPs were thoroughly investigated and presented. Using a mixture of stearic acid (SA) with oleic acid and 1-octadecene as components of the reaction medium leads to the obtaining of monodispersed NPs with enhanced emission intensity when irradiated with 975 nm laser wavelength, as compared with NPs prepared analogously but without SA. This article also reports how the addition of SA influences the structural properties of core@shell NPs and reaction time. The presence of SA in the reaction medium accelerates the growth of NPs in comparison with the analogic reaction but without SA. In addition, transmission electron microscopy studies reveal an additional effect of the presence of SA on the surface of NPs, which is to cause their self-organization due to steric effects.

Influence of the synthesis route on the spectroscopic, cytotoxic, and temperature-sensing properties of oleate-capped and ligand-free core/shell nanoparticles.

The right choice of synthesis route for upconverting nanoparticles (UCNPs) is crucial for obtaining a well-defined product with a specific application capability. Thus we decided to compare the physicochemical, cytotoxic, and temperature-sensing properties of UCNPs obtained from different rare earth (RE) ions, which has been made for the first time in a single study. The core/shell NaYF4:Yb3+,Er3+/NaYF4 UCNPs were obtained by reaction in a mixture of oleic acid and octadecene, and their highly stable water colloids were prepared using the ligand-free modification method. Both oleate-capped and ligand-free UCNPs exhibited a bright upconversion emission upon 975 nm excitation. Moreover, slope values, emission quantum yields, and luminescence lifetimes confirmed an effective energy transfer between the Yb3+ and Er3+ ions. Additionally, the water colloids of the UCNPs showed temperature-sensing properties with a good thermal sensitivity level, higher than 1 % K-1 at 358 K. Evaluation of the cytotoxicity profiles of the obtained products indicated that cell viability was decreased in a dose-dependent manner in the analyzed concentration range.

Improvement of ligand-free modification strategy to obtain water-stable up-converting nanoparticles with bright emission and high reaction yield.

Water-dispersible up-converting nanoparticles (UCNPs) are known to be very effective in biomedical applications. Research groups have paid special attention to the synthesis of hydrophilic UCNPs with good physicochemical properties. Being aware of this, we decided to improve the ligand-free modification method of OA-capped NaYF4:Yb3+,Er3+/NaYF4 UCNPs prepared by precipitation in high-boiling-point solvents as the thus-far reported methods do not provide satisfactory results. Different molarities of hydrochloric acid and various mixing times were selected to remove the organic ligand from the NPs' surface and to discover the most promising modification approach. Highly water-stable colloids were obtained with a very high reaction yield of up to 96%. Moreover, the acid treatment did not affect the morphology and the size of the product. All of the crystals exhibited a bright up-conversion emission under 975-nm excitation, which confirmed the two-photon excitation and effective energy transfer between the used dopant ions. Thus, we could establish the most successful ligand-free modification procedure.

Iridoids, Flavonoids, and Antioxidant Capacity of Cornus mas, C. officinalis, and C. mas × C. officinalis Fruits.

The fruits of Cornus mas and Cornus officinalis have been known and appreciated in folk medicine for years and have a high biological value, which is mainly connected with their polyphenols and iridoids content. However, hybrids of C. mas × C. officinalis have not been investigated. The aim of this study was to evaluate the iridoids, anthocyanins, and flavonols content, and antioxidant capacity of Cornus mas, Cornus officinalis, and C. mas × C. officinalis. Iridoids and flavonoids were quantified by the High-Performance Liquid Chromatography (HPLC) method. Antioxidant capacity (AC) was measured using 2,2-diphenyl-1-picrylhydrazyl (DPPH•), 2,2'-azino-bis (3-ethyl benzothiazoline-6-sulfonic acid (ABTS•+), and ferric reducing antioxidant power (FRAP) tests. Total phenolic content (TPC) was evaluated using the Folin-Ciocalteu reagent. Among the C. mas cultivars and C. officinalis genotypes, there was considerable variation in the content of iridoids, flavonoids, and AC. Interspecific hybrids C. mas × C. officinalis contained more iridoids than C. mas and more anthocyanins than C. officinalis and additionally had higher AC and TPC than C. officinalis and most C. mas. AC, TPC, and the presence of iridoids, anthocyanins, and flavonols in hybrids C. mas × C. officinalis are reported for the first time. The Cornus species deserve special attention due to their highly biologically active substances, as well as useful medicinal properties.

Potential valorization of Cornelian cherry (Cornus mas L.) stones: Roasting and extraction of bioactive and volatile compounds.

This study aimed to characterize the antioxidant potential, bioactive and volatile compounds of the stones from fruits of Cornus mas. Both fresh and roasted stones show a high antioxidant potential (166.48-509.74 µmol TE/g dw stones), which significantly depends on the cultivars. The roasted stones preserved 43.6% (DPPH; 'Raciborski') to 97.2% (FRAP; 'Alesha') of the antioxidant activity of the non-roasted stones. In the stones, two iridoids and ellagic acid were determined. During roasting, loganic acid remained stable, whereas cornuside was completely degraded. The analyses showed a 30-fold increase in the concentration of ellagic acid and in the formation of two of its derivatives. The major aroma compound of the roasted stones was furfural, but we also identified 18 pyrazine derivatives. This study is the first attempt to valorize Cornelian cherry stones via roasting. The roasted stones can be a coffee substitute, or aromatic and bioactive additions to cereal coffees.

Manipulation of up-conversion emission in NaYF4 core@shell nanoparticles doped by Er3+, Tm3+, or Yb3+ ions by excitation wavelength-three ions-plenty of possibilities.

Nanoparticles (NPs) based on host compound NaYF4 with core@shell structures were synthesised by the precipitation reaction in high-boiling point octadecene/oleic acid solvent. Four laser wavelengths were used (808, 975, 1208, or 1532 nm) for excitation of the obtained NPs. The resulting emission and mechanisms responsible for spectroscopic properties were studied in detail. Depending on NP compositions, i.e. type of doping ion (Er3+, Tm3+, or Yb3+) or presence of dopants in the same or different phases, adjustable up-conversion (UC) could be obtained with emission peaks covering the visible to near-infrared range (475 to 1625 nm). The presented results demonstrated multifunctionality of the prepared NPs. NaYF4:2%Tm3+@NaYF4 NPs exhibited emission at 700 and 1450 nm under 808 nm laser excitation or 800 and 1625 nm emission under 1208 nm laser radiation, as a result of ground- and excited-state absorption processes (GSA and ESA, respectively). However, NaYF4:5%Er3+,2%Tm3+@NaYF4 NPs showed the most interesting properties, as they can convert all studied laser wavelengths due to the absorption of Tm3+ (808, 1208 nm) or Er3+ ions (808, 975, 1532 nm), revealing a photon avalanche process under 1208 nm laser excitation, as well as GSA and ESA at other excitation wavelengths. The NaYF4:2%Tm3+@NaYF4:5%Er3+ NPs revealed the resultant emission properties, as the dopant ions were separated within core and shell phases. The NaYF4:18%Yb3+,2%Tm3+@NaYF4 and NaYF4:18%Yb3+,2%Tm3+@NaYF4:5%Er3+ samples showed the brightest emission, around 800 nm, under 975 nm excitation, though other laser wavelengths allowed for observation of luminescence, as well, especially in NPs with Er3+ in the outer shell, capable of UC under 1532 nm. The presented results highlight the unique and universal properties of lanthanide ions for designing luminescent NPs for a variety of potential applications, such as confocal microscopy.

Cornus mas L. Stones: A Valuable By-Product as an Ellagitannin Source with High Antioxidant Potential.

The stone of Cornus mas L. remains the least known morphological part of this plant, whereas the fruit is appreciated for both consumption purposes and biological activity. The stone is considered to be a byproduct of fruit processing and very little is known about its phytochemical composition and biological properties. In this study, the complete qualitative determination of hydrolyzable tannins, their quantitative analysis, total polyphenolic content, and antioxidant properties of the stone of C. mas are presented for the first time. The 37 identified compounds included the following: various gallotannins (11), monomeric ellagitannins (7), dimeric ellagitannins (10), and trimeric ellagitannins (7). The presence of free gallic acid and ellagic acid was also reported. Our results demonstrate that C. mas stone is a source of various bioactive hydrolyzable tannins and shows high antioxidant activity which could allow potential utilization of this raw material for recovery of valuable pharmaceutical or nutraceutical substances. The principal novelty of our findings is that hydrolyzable tannins, unlike other polyphenols, have been earlier omitted in the evaluation of the biological activities of C. mas. Additionally, the potential recovery of these bioactive chemicals from the byproduct is in line with the ideas of green chemistry and sustainable production.

Author Correction: Upconverting SrF2 nanoparticles doped with Yb3+/Ho3+, Yb3+/Er3+ and Yb3+/Tm3+ ions - optimisation of synthesis method, structural, spectroscopic and cytotoxicity studies.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Upconverting SrF2 nanoparticles doped with Yb3+/Ho3+, Yb3+/Er3+ and Yb3+/Tm3+ ions - optimisation of synthesis method, structural, spectroscopic and cytotoxicity studies.

For a number of years nanomaterials have been continuously devised and comprehensively investigated because of the growing demand for them and their multifarious applications, especially in medicine. This paper reports on the properties of SrF2 nanoparticles (NPs) for applications in biomedicine, showing effective ways of their synthesis and luminescence under near infrared radiation - upconversion. NPs doped with lanthanide, Ln3+ ions (where Ln = Yb, Ho, Er, Tm) were prepared by the hydrothermal method and subjected to comprehensive studies, from determination of their structure and morphology, revealing small, 15 nm structures, through spectroscopic properties, to cytotoxicity in vitro. The effects of such factors as the reaction time, type and amount of precipitating compounds and complexing agents on the properties of products were characterized. The cytotoxicity of the synthesized and functionalized NPs was investigated, using human fibroblast cell line (MSU-1.1). The synthesized structures may decrease cells' proliferation in a dose-dependent manner in the measured concentration range (up to 100 µg/mL). However, the cells remain alive according to the fluorescent assay. Moreover, the treated cells were imaged using confocal laser scanning microscopy. Cellular uptake was confirmed by the presence of upconversion luminescence in the cells.

Formation Mechanism, Structural, and Upconversion Properties of Alkaline Rare-Earth Fluoride Nanocrystals Doped With Yb3+/Er3+ Ions.

Ultrasmall (9-30 nm) Yb3+/Er3+-doped, upconverting alkaline rare-earth fluorides that are promising for future applications were synthesized by the microwave-assisted hydrothermal method. The formation mechanism was proposed, indicating the influence of the stability of metal ions complexes with ethylenediaminetetraacetic acid on the composition of the product and tendency to form M2REF7 (M0.67RE0.33F2.33) cubic compounds in the M-RE-F systems. Their physicochemical properties (structure, morphology, and spectroscopic properties) are compared and discussed. The obtained nanoparticles exhibited emission of light in the visible spectra under excitation by 976 nm laser radiation. Excitation and emission spectra, luminescence decays, laser energy dependencies, and upconversion quantum yields were measured to determine the spectroscopic properties of prepared materials. The Yb3+/Er3+ pair of ions used as dopants was responsible for an intense yellowish-green emission. The upconversion quantum yields determined for the first time for M2REF7-based materials were 0.0192 ± 0.001% and 0.0176 ± 0.001% for Sr2LuF7:Yb3+,Er3+ and Ba2LuF7:Yb3+,Er3+ respectively, the two best emitting samples. These results indicated the prepared materials are good and promising alternatives for the most studied NaYF4:Yb3+,Er3+ nanoparticles.

Lifetime nanomanometry - high-pressure luminescence of up-converting lanthanide nanocrystals - SrF2:Yb3+,Er3.

Anti-Stokes luminescence of up-converting nanocrystals SrF2:Yb3+,Er3+ can be used as a high pressure optical sensor alternative to the ruby fluorescence-scale. In nanocrystalline SrF2:Yb3+,Er3+, high pressure reversibly shortens the emission lifetimes nearly linearly up to 5.29 GPa at least. Its advantage is the use of NIR (≈980 nm) radiation, highly penetrable for many materials. The shortening of up-conversion lifetimes has been attributed mainly to the changes in energy transfer rates, caused by decreased interatomic distances and increased overlap integrals between 4f electrons and the valence shells of ligand ions. The origin of high-pressure effects on the luminescence intensity, band ratio and their spectral position has been explained by the increased interactions and distortions of the crystal-field symmetry around the emitting ions in the compressed structure.

The immune response differentially regulates Hsp70 and glucocorticoid receptor expression in vitro and in vivo in common carp (Cyprinus carpio L.).

Heat shock or stress proteins and glucocorticoids (cortisol) regulate a sequential pro-inflammatory and anti-inflammatory cytokine expression profile to effectively kill pathogens, whilst minimizing damage to the host. Cortisol elicits its effects through the glucocorticoid receptor (GR) for which Hsp70 and Hsp90 are required as chaperones. In common carp, (Cyprinus carpio) duplicated glucocorticoid receptor genes and splice variants with different cortisol sensitivities exist. We investigated the expression profiles of heat shock proteins Hsp70, Hsc70, Hsp90alpha and Hsp90beta and the three different variants of GR in vitro in and in vivo to define their role in immune modulation. A rapid transient induction of GR1 (a and b) and Hsp70 was seen after LPS treatment in vitro in head kidney phagocytes, whereas cortisol treatment did not affect constitutive or LPS-induced expression of Hsp70 or GR1 expression. In vivo zymosan-induced peritonitis upregulated GR and Hsp70 expression which appears to increase sensitivity for cortisol-induced immune modulation. Indeed, the increased GR and Hsp70 expression correlates with inhibition of both LPS- and zymosan-induced expression of pro-inflammatory cytokines. Infection with the blood parasite T. borreli decreases GR1a expression in thymus, but increases GR2 expression in spleen. Differentially regulated expression of Hsp70 and of glucocorticoid receptor variants with different cortisol sensitivities, underlines their physiological importance in a balanced immune response.