Quality of Oil Pressed from Hemp Seed Varieties: ‘Earlina 8FC’, ‘Secuieni Jubileu’ and ‘Finola’

In the last decade, the demand for edible niche oils has increased. Therefore, the aim of this study was to characterize the seeds hemp (Cannabis sativa L.) varieties: ‘Finola’ (FIN-314)’, ‘Earlina 8FC’, and ‘Secuieni Jubileu’, and cold and hot pressed oils were prepared from each seed. The seeds were examined for moisture content, granulometric distribution, bulk density, and fat content. Seeds were pressed without and with preconditioning (60 °C), and oil yield and pressing time were recorded. The oil was filtered through cellulose membranes. Oil–water content, oil color, fatty acid profile, and sterol content were studied. From the study conducted, there are significant differences in the parameters of oil recovery and its quality compared to ‘Finola’ seed oil, which is widely reported in the literature. ‘Finola’ oil yield was the lowest, with an average of 79% compared to ‘Earlina’ (82%) and ‘S. Jubileu’ (84%). All oil samples contained a comparable amount of sterols, with campesterol (0.32 mg/g), β-sitosterol (1.3 mg/g) and Δ5-avenasterol (0.15 mg/g) predominating. From the organoleptic evaluation, it was evident that both varieties hemp oils and marc (‘Earlina’ and ‘S. Jubileu’) were not bitter like the “Finola” oil and marc. More detailed studies in this direction have to be undertaken.     

Actinide tetra-N-heterocyclic carbene ‘sandwiches’

Highly-symmetrical, thorium and uranium octakis-carbene ‘sandwich’ complexes have been prepared by ‘sandwiching’ the An(iv) cations between two anionic macrocyclic tetra-NHC ligands, one with sixteen atoms and the other with eighteen atoms. The complexes were characterized by a range of experimental methods and DFT calculations. X-ray crystallography confirms the geometry at the metal centre can be set by the size of the macrocyclic ring, leading to either square prismatic or square anti-prismatic shapes; the geometry of the latter is retained in solution, which also undergoes reversible, electrochemical one-electron oxidation or reduction for the uranium variant. DFT calculations reveal a frontier orbital picture that is similar to thorocene and uranocene, in which the NHC ligands show almost exclusively σ-donation to the metal without π-backbonding.

Highly-symmetrical, thorium and uranium octakis-carbene ‘sandwich’ complexes have been prepared by ‘sandwiching’ the An(iv) cations between two anionic macrocyclic tetra-NHC ligands, one with sixteen atoms and the other with eighteen atoms.     

Rapid Discrimination of Citrus reticulata ‘Chachi’ by Electrospray Ionization–Ion Mobility–High-Resolution Mass Spectrometry

A common idea is that some dishonest businessmen often disguise Citrus reticulata Blanco varieties as Citrus reticulata ‘Chachi’, which places consumers at risk of economic losses. In this work, we combined high-resolution ion mobility (U-shaped mobility analyzer) with high-resolution mass spectrometry to rapidly distinguish Citrus reticulata ‘Chachi’ from other Citrus species. The samples were analyzed directly through simple extraction and the analytes were separated in one second. It only took about 1 min to perform a cycle of sample analysis and data acquisition. The results showed that polymethoxylated flavones and their isomers were separated easily by the ion mobility analyzer and preliminarily identified according to the accurate mass. Moreover, the collision cross-section values of all analytes, which could be used as auxiliary parameters to characterize and identify the compounds in the samples, were measured. Twenty-four samples were grouped as two clusters by multivariate analysis, which meant that Citrus reticulata ‘Chachi’ could be effectively differentiated. It was confirmed that the developed method had the potential to rapidly separate polymethoxylated flavones and distinguish between Citrus reticulata ‘Chachi’ and other Citrus reticulata Blanco varieties.     

Toxic Metal Species and ‘Endogenous’ Metalloproteins at the Blood–Organ Interface: Analytical and Bioinorganic Aspects

Globally, human exposure to environmental pollutants causes an estimated 9 million deaths per year and it could also be implicated in the etiology of diseases that do not appear to have a genetic origin. Accordingly, there is a need to gain information about the biomolecular mechanisms that causally link exposure to inorganic environmental pollutants with distinct adverse health effects. Although the analysis of blood plasma and red blood cell (RBC) cytosol can provide important biochemical information about these mechanisms, the inherent complexity of these biological matrices can make this a difficult task. In this perspective, we will examine the use of metalloentities that are present in plasma and RBC cytosol as potential exposure biomarkers to assess human exposure to inorganic pollutants. Our primary objective is to explore the principal bioinorganic processes that contribute to increased or decreased metalloprotein concentrations in plasma and/or RBC cytosol. Furthermore, we will also identify metabolites which can form in the bloodstream and contain essential as well as toxic metals for use as exposure biomarkers. While the latter metal species represent useful biomarkers for short-term exposure, endogenous plasma metalloproteins represent indicators to assess the long-term exposure of an individual to inorganic pollutants. Based on these considerations, the quantification of metalloentities in blood plasma and/or RBC cytosol is identified as a feasible research avenue to better understand the adverse health effects that are associated with chronic exposure of various human populations to inorganic pollutants. Exposure to these pollutants will likely increase as a consequence of technological advances, including the fast-growing applications of metal-based engineering nanomaterials.     

Peptide nano ‘bead-grafting’ for SDT-facilitated immune checkpoints blocking

Combination therapies based on immune checkpoint blockade (ICB) are currently the mainstay of cancer treatment, in which the synergetic delivery of multiple drugs is the essential step. Although nanoparticle drugs (NPDs) show satisfactory anticancer effects, the promotion of active co-delivery of NPDs is premature, since the processes are usually difficult to predict and control. Targeting peptide self-assemblies have been widely used as carriers for small-molecular drugs, but remain elusive for NPDs. We describe here peptide-based nano ‘bead-grafting’ for the active delivery of quantum-dot NPDs through a co-assembly method. Based on a ‘de novo’ design, we used a ‘one-bead-one-compound (OBOC)’ combinatorial chemical screening method to select a peptide RT with high affinity for the immune checkpoint CD47, which could also form biocompatible nanofibers and efficiently trap Ag₂S quantum dots along the self-assembly path. This system can combine ICB therapy and sonodynamic therapy (SDT) to effectively inhibit tumor growth. Moreover, the tumor antigen produced by SDT can activate the adaptive immune system, which enhances the anti-tumor immune response of the ICB and shows efficient inhibition of both primary and distant tumors. This study provides a new strategy for the active control and delivery of NPDs and a new option for ICB therapy with immune checkpoints that are highly susceptible to systemic side effects.

Peptide-fibril-captured QDs form nano ‘bead-grafting’, which inhibit both the primary and distant tumors through the combination with immune checkpoint blockade (ICB) and sonodynamic therapy (SDT).     

Plasmid-DNA Delivery by Covalently Functionalized PEI-SPIONs as a Potential ‘Magnetofection’ Agent

Nanoformulations for delivering nucleotides into cells as vaccinations as well as treatment of various diseases have recently gained great attention. Applying such formulations for a local treatment strategy, e.g., for cancer therapy, is still a challenge, for which improved delivery concepts are needed. Hence, this work focuses on the synthesis of superparamagnetic iron oxide nanoparticles (SPIONs) for a prospective “magnetofection” application. By functionalizing SPIONs with an active catechol ester (CafPFP), polyethyleneimine (PEI) was covalently bound to their surface while preserving the desired nanosized particle properties with a hydrodynamic size of 86 nm. When complexed with plasmid-DNA (pDNA) up to a weight ratio of 2.5% pDNA/Fe, no significant changes in particle properties were observed, while 95% of the added pDNA was strongly bound to the SPION surface. The transfection in A375-M cells for 48 h with low amounts (10 ng) of pDNA, which carried a green fluorescent protein (GFP) sequence, resulted in a transfection efficiency of 3.5%. This value was found to be almost 3× higher compared to Lipofectamine (1.2%) for such low pDNA amounts. The pDNA-SPION system did not show cytotoxic effects on cells for the tested particle concentrations and incubation times. Through the possibility of additional covalent functionalization of the SPION surface as well as the PEI layer, Caf-PEI-SPIONs might be a promising candidate as a magnetofection agent in future.     

Hemp Seeds of the Polish ‘Bialobrzeskie’ and ‘Henola’ Varieties (Cannabis sativa L. var. sativa) as Prospective Plant Sources for Food Production

This publication characterizes the nutritional value of the Polish hemp seeds of the ‘Bialobrzeskie’ and ‘Henola’ varieties, including the profile/content of fatty acids and amino acids. Hemp seeds were found to be rich in protein, fat, and dietary fiber. Polyunsaturated fatty acids (PUFA) dominated the unsaturated fatty acids (UFA) profile. Their average share within the total fatty acids (FA) was as high as 75%. Linoleic acid belonging to this group accounted for 55% of the total FA. Lipid profile indices (Σ n − 6/Σ n − 3, Σ PUFA/Σ SFA, the thrombogenicity index, the atherogenicity index and the hypocholesterolemic/hypercholesterolemic ratio) proved the high nutritional value of hemp oil. Considering the tyrosine + phenylalanine and histidine contents, hemp protein exhibited a great degree of similarity to egg protein, which is known and valued for its high biological value.     

‘Reverse biomimetic’ synthesis of l-arogenate and its stabilized analogues from l-tyrosine

l-Arogenate (also known as l-pretyrosine) is a primary metabolite on a branch of the shikimate biosynthetic pathway to aromatic amino acids. It plays a key role in the synthesis of plant secondary metabolites including alkaloids and the phenylpropanoids that are the key to carbon fixation. Yet understanding the control of arogenate metabolism has been hampered by its extreme instability and the lack of a versatile synthetic route to arogenate and its analogues. We now report a practical synthesis of l-arogenate in seven steps from O-benzyl l-tyrosine methyl ester in an overall yield of 20%. The synthetic route also delivers the fungal metabolite spiroarogenate, as well as a range of stable saturated and substituted analogues of arogenate. The key step in the synthesis is a carboxylative dearomatization by intramolecular electrophilic capture of tyrosine''s phenolic ring using an N-chloroformylimidazolidinone moiety, generating a versatile, functionalizable spirodienone intermediate.

l-Tyrosine provides a precursor for a practical synthesis of the unstable primary metabolite l-arogenate and some stabilised arogenate analogues.     

‘Sacrificial’ supramolecular assembly and pressure-induced polymerization: toward sequence-defined functionalized nanothreads

Limited supramolecular strategies have been utilized to synthesize sequence-defined polymers, despite the prominence of noncovalent interactions in materials design. Herein, we illustrate the utility of ‘sacrificial’ aryl-perfluoroaryl supramolecular synthons to synthesize sp³-hybridized nanothreads from sp²-enriched reactants. Our strategy features A–B reactant pairs in the form of a phenol:pentafluorophenol co-crystal that is preorganized for an electronically-biased and sequence-defined polymerization. The polymerization, initiated at 12 GPa, affords an alternating copolymer featuring exogenous –OH functionalities. The external substitution is confirmed through IR spectroscopy. Importantly, the inclusion of the functional unit provides the first experimental glimpse at reaction mechanism: keto–enol tautomerization that can only occur during cycloaddition is observed through IR spectroscopy. Our approach realizes the first example of a functionalized nanothread and attains sequence definition through sacrificial supramolecular preorganization and presents a further approach for de novo design of complex nanothreads.

Supramolecular synthons are exploited to synthesize –OH functionalized sp³-rich sequence-defined nanothreads using pressure-induced polymerization of a phenol:pentafluorophenol co-crystal.      

Precise Quantification of Molybdate In Vitro by the FRET-Based Nanosensor ‘MolyProbe’

Molybdenum (Mo) is an essential trace element in all kingdoms of life. Mo is bioavailable as the oxyanion molybdate and gains biological activity in eukaryotes when bound to molybdopterin, forming the molybdenum cofactor. The imbalance of molybdate homeostasis results in growth deficiencies or toxic symptoms within plants, fungi and animals. Recently, fluorescence resonance energy transfer (FRET) methods have emerged, monitoring cellular and subcellular molybdate distribution dynamics using a genetically encoded molybdate-specific FRET nanosensor, named MolyProbe. Here, we show that the MolyProbe system is a fast and reliable in vitro assay for quantitative molybdate determination. We added a Strep-TagII affinity tag to the MolyProbe protein for quick and easy purification. This MolyProbe is highly stable, resistant to freezing and can be stored for several weeks at 4 °C. Furthermore, the molybdate sensitivity of the assay peaked at low nM levels. Additionally, The MolyProbe was applied in vitro for quantitative molybdate determination in cell extracts of the plant Arabidopsis thaliana, the fungus Neurospora crassa and the yeast Saccharomyces cerevisiae. Our results show the functionality of the Arabidopsis thaliana molybdate transporter MOT1.1 and indicate that FRET-based molybdate detection is an excellent tool for measuring bioavailable Mo.     

Lysinibacillus Isolate MK212927: A Natural Producer of Allylamine Antifungal ‘Terbinafine’

Resistance to antifungal agents represents a major clinical challenge, leading to high morbidity and mortality rates, especially in immunocompromised patients. In this study, we screened soil bacterial isolates for the capability of producing metabolites with antifungal activities via the cross-streak and agar cup-plate methods. One isolate, coded S6, showed observable antifungal activity against Candida (C.) albicans ATCC 10231 and Aspergillus (A.) niger clinical isolate. This strain was identified using a combined approach of phenotypic and molecular techniques as Lysinibacillus sp. {"type":"entrez-nucleotide","attrs":{"text":"MK212927","term_id":"1520090447"}}MK212927. The purified metabolite displayed fungicidal activity, reserved its activity in a relatively wide range of temperatures (up to 60 °C) and pH values (6–7.8) and was stable in the presence of various enzymes and detergents. As compared to fluconazole, miconazole and Lamisil, the minimum inhibitory concentration of the metabolite that showed 90% inhibition of the growth (MIC₉₀) was equivalent to that of Lamisil, half of miconazole and one fourth of fluconazole. Using different spectroscopic techniques such as FTIR, UV spectroscopy, 1D NMR and 2D NMR techniques, the purified metabolite was identified as terbinafine, an allylamine antifungal agent. It is deemed necessary to note that this is the first report of terbinafine production by Lysinibacillus sp. {"type":"entrez-nucleotide","attrs":{"text":"MK212927","term_id":"1520090447"}}MK212927, a fast-growing microbial source, with relatively high yield and that is subject to potential optimization for industrial production capabilities.     

Glass surface as strong base, ‘green’ heterogeneous catalyst and degradation reagent

Systematic screening of accelerated chemical reactions at solid/solution interfaces has been carried out in high-throughput fashion using desorption electrospray ionization mass spectrometry and it provides evidence that glass surfaces accelerate various base-catalyzed chemical reactions. The reaction types include elimination, solvolysis, condensation and oxidation, whether or not the substrates are pre-charged. In a detailed mechanistic study, we provide evidence using nanoESI showing that glass surfaces can act as strong bases and convert protic solvents into their conjugate bases which then act as bases/nucleophiles when participating in chemical reactions. In aprotic solvents such as acetonitrile, glass surfaces act as ‘green’ heterogeneous catalysts that can be recovered and reused after simple rinsing. Besides their use in organic reaction catalysis, glass surfaces are also found to act as degradation reagents for phospholipids with increasing extents of degradation occurring at low concentrations. This finding suggests that the storage of base/nucleophile-labile compounds or lipids in glass containers should be avoided.

Glass surfaces are found to be strong bases, ‘green’ heterogeneous catalysts and degradation reagents: glass microspheres act as strong bases to accelerate multiple base-catalyzed reaction types by a factor of 26–2021.     

p53‐Dependent and p53‐Independent Responses of Cells Challenged by Photosensitization

The p53 protein exerts fundamental roles in cell responses to a variety of stress stimuli. It has clear roles in controlling cell cycle, triggering apoptosis, activating autophagy and modulating DNA damage response. Little is known about the role of p53 in autophagy‐associated cell death, which can be induced by photoactivation of photosensitizers within cells. The photosensitizer 1,9‐dimethyl methylene blue (DMMB) within nanomolar concentration regimes has specific intracellular targets (mitochondria and lysosomes), photoinducing a typical scenario of cell death with autophagy. Importantly, in consequence of its subcellular localization, photoactive DMMB induces selective damage to mitochondrial DNA, saving nuclear DNA. By challenging cells having different p53 protein levels, we investigated whether p53 modulates DMMB/light‐induced phototoxicity and cell cycle dynamics. Cells lacking p53 activity were slightly more resistant to photoactivated DMMB, which was correlated with a smaller sub‐G1 population, indicative of a lower level of apoptosis. DMMB photosensitization seems to induce mostly autophagy‐associated cell death and S‐phase cell cycle arrest with replication stress. Remarkably, these responses were independent on the p53 status, indicating that p53 is not involved in either process. Despite describing some p53‐related responses in cells challenged by photosensitization, our results also provide novel information on the consequences of DMMB phototoxicity.     

Eucalyptus gunnii and Eucalyptus pulverulenta ‘Baby Blue’ Essential Oils as Potential Natural Herbicides

The phytotoxicity and eco-compatibility of essential oils (EOs) from Eucalyptus gunnii (EG) and E. pulverulenta ‘Baby Blue’ (EP), cultivated in Italy for their cut foliage, were investigated. Leaf micromorphology, EOs phytochemical characterization, and phytotoxicity were analysed. EP revealed a significantly higher oil gland density and a higher EO yield with respect to EG. In both EOs, 1,8-cineole was the major compound (~75%), followed by α-pinene in EG (13.1%) and eugenol in EP (7.5%). EO phytotoxicity was tested on both weeds (Lolium multiflorum, Portulaca oleracea) and crops (Raphanus sativus, Lactuca sativa, Lepidium sativum, Solanum lycopersicum, Pisum sativum, Cucumis sativus). EG EO inhibited germination of P. oleracea, R. sativus, and S. lycopersicum seeds (ranging from 61.5 to 94.6% for the higher dose used), while affecting only radical elongation in S. lycopersicum (ranging from 66.7 to 82.6%). EP EO inhibited germination of P. oleracea and R. sativus (ranging from 41.3 to 74.7%) and affected radical elongation of L. sativum and L. multiflorum (ranging from 57.4 to 76.0%). None of the EOs affected the germination and radical growing of L. sativa, P. sativum, and C. sativus. Moreover, EP EO was more active than EG EO in inhibiting α-amylase, a key enzyme for seed growth regulation. Brine shrimp lethality assay showed that both EOs are safe for aquatic organisms, suggesting their high eco-compatibility. The data collected provide useful information for future applications of these EOs in agriculture as safe and selective bioherbicides.     

Chemical Properties of Peanut Oil from Arachis hypogaea L. ‘Tainan 14’ and Its Oxidized Volatile Formation

Arachis hypogaea L. ‘Tainan 14’ has purple skin characteristics. This study investigated the effects of different materials (shelled or unshelled peanuts) and temperatures (120 or 140 °C) on the properties of extracted peanut oil. The results show that its antioxidant components (total flavonoid, α–tocopherol, and γ-tocopherol) and oxidative stability were mainly affected by the roasting temperature (p < 0.05). Fifty-eight volatile compounds were identified by peanut oil oxidation and divided into three main groups during the roasting process using principal component analysis. The volatile formation changes of different materials and temperatures were assessed by agglomerative hierarchical clustering analysis. These results provide useful reference information for peanut oil applications in the food industry.     

‘Aggregation-Induced Emission’ Active Mono-Cyclometalated Iridium(III) Complex Mediated Efficient Vapor-Phase Detection of Dichloromethane

Selective vapor-phase detection of dichloromethane (DCM) is a challenge, it being a well-known hazardous volatile organic solvent in trace amounts. With this in mind, we have developed an ‘Aggregation-induced Emission’ (AIE) active mono-cyclometalated iridium(III)-based (M1) probe molecule, which detects DCM sensitively and selectively in vapor phase with a response time <30 s. It reveals a turn-on emission (non-emissive to intense yellow) on exposing DCM vapor directly to the solid M1. The recorded detection limit is 4.9 ppm for DCM vapor with pristine M1. The mechanism of DCM detection was explored. Moreover, the detection of DCM vapor by M1 was extended with a low-cost filter paper as the substrate. The DCM is weakly bound with the probe and can be removed with a mild treatment, so, notably, the probe can be reused.     

Determination of the Masking Effect of the ‘Zapateria’ Defect in Flavoured Stuffed Olives Using E-Nose

Spanish-style table olives are one of the most common processed foods in the Mediterranean countries. Lack of control during fermentation can lead to one of the main defects of the olive, called ‘Zapateria’, caused by the combination of volatile fatty acids reminiscent of rotten leather. In this study, table olives altered with ‘Zapateria’ defect were stuffed with a hydrocolloid flavoured with the aroma ‘Mojo picón’ to improve consumer acceptance. Sensory analysis, determination of volatile compounds and electronic nose (E-nose) were used to evaluate the quality of the olives. The control samples had a high concentration of the defect ‘Zapateria’ and were classified in the second commercial category, while higher ‘Mojo picón’ flavour concentrations resulted in these olives being classified as ‘extra category’ (a masking effect). The main volatile compounds in olives with ‘Zapateria’ defect were cyclohexanecarboxylic acid and pentanoic acid. E-nose allowed discrimination between stuffed olives without added flavouring and olives with ‘Mojo picón’ flavouring at different concentrations. Finally, PLS regression allowed a predictive linear model to be established between E-nose and sensory analysis values. The RP2 values were 0.74 for perceived defect and 0.86 for perceived aroma. The E-nose was successfully applied for the first time to classify Spanish-style table olives with ‘Zapateria’ defect intensity and with the addition of the ‘Mojo picón’ aroma masking the defect.     

Sulfoxide hemithioindigo tweezers – visible light addressable capture and release

Introducing responsive elements into supramolecular recognition systems offers great advantages for the control of intermolecular interactions and represents an important stepping stone towards multi-purpose and reprogrammable synthetic systems. Of particular interest is implementation of light-responsiveness because of the unique ease and precision of this signal. Here we present visible light responsive hemithioindigo-based molecular tweezers that bear a highly polar sulfoxide function as an additional recognition unit inside their binding site. Sulfur oxidation allows to simultaneously enhance all crucial properties of this receptor type i.e. photoswitching capability, thermal stability of individual switching states, binding affinity, and binding modulation upon switching. With a novel titration method the thermodynamic binding parameters were determined using reduced sample amounts. Employing these strongly enhanced molecular tweezers allowed to demonstrate photocontrol of intermolecular charge transfer in a reversible manner.

Hemithioindigo based molecular tweezers with a comprehensively improved property profile are obtained by simple oxidation of the sulfur atom.     

Chemotaxonomic Identification of Key Taste and Nutritional Components in ‘Shushanggan Apricot’ Fruits by Widely Targeted Metabolomics

The chemotypic and the content variation in taste substances and nutrients in ‘Shushanggan apricot’ fruits were detected by UPLC-MS/MS. A total of 592 compounds were identified, of which sucrose contributed mainly to the sweet taste and malic acid and citric acid were important organic acids affecting sweet–sour taste. γ-linolenic acid, α-linolenic acid and linoleic acid were the dominant free fatty acids, and neochlorogenic acid and chlorogenic acid were the predominant phenolic acids. Fruit taste was positively correlated with sucrose and negatively correlated with malic acid and citric acid. The differential metabolites were significantly enriched in the biosynthesis of amino acids and 2-oxocarboxylic acid metabolism pathways, regulating the sugar and organic acid biosynthesis. Taste and nutrient differences could be revealed by variations in composition and abundance of carbohydrates, organic acids and amino acids. The purpose of this study was to provide a comprehensive chemical characterization of taste and nutrient compounds in ‘Shushanggan apricot’ fruits.