Accessing a Diverse Set of Functional Red-Light Photoswitches by Selective Copper-Catalyzed Indigo N-Arylation.

The ability to correlate the structure of a molecule with its properties is the key to the rational and accelerated design of new functional compounds and materials. Taking photoswitches as an example, the thermal stability of the metastable state is a crucial property that dictates their application in molecular systems. Indigos have recently emerged as an attractive motif for designing photoswitchable molecules due to their red-light addressability, which can be advantageous in biomedical and material applications. The lack of synthetic techniques to derivatize the abundant parent dye and a thorough understanding of the impact of structural factors on the photochemical and thermal properties hinder broad applications of this emerging photoswitch class. Herein, we report an efficient copper-catalyzed indigo N-arylation that enables the installation of a wide variety of aryl moieties carrying useful functional groups. The exclusive selectivity for monoarylation likely originates from a bimetallic cooperative mechanism through a binuclear copper-indigo intermediate. Functional N-aryl-N'-alkylindigos were prepared and shown to photoisomerize efficiently under red light. Moreover, this design allows for the modulation of thermal half-lives through N-aryl substituents, while the N'-alkyl groups enable the independent attachment of functional moieties without affecting the photochromic properties. A strong correlation between the structure of the N-aryl moiety and the thermal stability of the photogenerated Z-isomers was achieved by multivariate linear regression models obtained through a data-science workflow. This work thus builds an avenue leading to versatile red-light photoswitches and a general method for structure-property correlation that is expected to be broadly applicable to the design of photoresponsive molecules.

Small molecule inhibition of RNA binding proteins in haematologic cancer.

In recent years, advances in biomedicine have revealed an important role for post-transcriptional mechanisms of gene expression regulation in pathologic conditions. In cancer in general and leukaemia specifically, RNA binding proteins have emerged as important regulator of RNA homoeostasis that are often dysregulated in the disease state. Having established the importance of these pathogenetic mechanisms, there have been a number of efforts to target RNA binding proteins using oligonucleotide-based strategies, as well as with small organic molecules. The field is at an exciting inflection point with the convergence of biomedical knowledge, small molecule screening strategies and improved chemical methods for synthesis and construction of sophisticated small molecules. Here, we review the mechanisms of post-transcriptional gene regulation, specifically in leukaemia, current small-molecule based efforts to target RNA binding proteins, and future prospects.

Fabrication techniques of biomimetic scaffolds in three-dimensional cell culture: A review.

In the last four decades, several researchers worldwide have routinely and meticulously exercised cell culture experiments in two-dimensional (2D) platforms. Using traditionally existing 2D models, the therapeutic efficacy of drugs has been inappropriately validated due to the failure in generating the precise therapeutic response. Fortunately, a 3D model addresses the foregoing limitations by recapitulating the in vivo environment. In this context, one has to contemplate the design of an appropriate scaffold for favoring the organization of cell microenvironment. Instituting pertinent model on the platter will pave way for a precise mimicking of in vivo conditions. It is because animal cells in scaffolds oblige spontaneous formation of 3D colonies that molecularly, phenotypically, and histologically resemble the native environment. The 3D culture provides insight into the biochemical aspects of cell-cell communication, plasticity, cell division, cytoskeletal reorganization, signaling mechanisms, differentiation, and cell death. Focusing on these criteria, this paper discusses in detail, the diversification of polymeric scaffolds based on their available resources. The paper also reviews the well-founded and latest techniques of scaffold fabrication, and their applications pertaining to tissue engineering, drug screening, and tumor model development.

Evaluation of Ultrasound, Microwave, Ultrasound-Microwave, Hydrothermal and High Pressure Assisted Extraction Technologies for the Recovery of Phytochemicals and Antioxidants from Brown Macroalgae.

This study aims to explore novel extraction technologies (ultrasound-assisted extraction (UAE), microwave-assisted extraction (MAE), ultrasound-microwave-assisted extraction (UMAE), hydrothermal-assisted extraction (HAE) and high-pressure-assisted extraction (HPAE)) and extraction time post-treatment (0 and 24 h) for the recovery of phytochemicals and associated antioxidant properties from Fucus vesiculosus and Pelvetia canaliculata. When using fixed extraction conditions (solvent: 50% ethanol; extraction time: 10 min; algae/solvent ratio: 1/10) for all the novel technologies, UAE generated extracts with the highest phytochemical contents from both macroalgae. The highest yields of compounds extracted from F. vesiculosus using UAE were: total phenolic content (445.0 ± 4.6 mg gallic acid equivalents/g), total phlorotannin content (362.9 ± 3.7 mg phloroglucinol equivalents/g), total flavonoid content (286.3 ± 7.8 mg quercetin equivalents/g) and total tannin content (189.1 ± 4.4 mg catechin equivalents/g). In the case of the antioxidant activities, the highest DPPH activities were achieved by UAE and UMAE from both macroalgae, while no clear pattern was recorded in the case of FRAP activities. The highest DPPH scavenging activities (112.5 ± 0.7 mg trolox equivalents/g) and FRAP activities (284.8 ± 2.2 mg trolox equivalents/g) were achieved from F. vesiculosus. Following the extraction treatment, an additional storage post-extraction (24 h) did not improve the yields of phytochemicals or antioxidant properties of the extracts.

Frustrated Lewis-Pair-Meditated Selective Single Fluoride Substitution in Trifluoromethyl Groups.

Single fluoride substitution in trifluoromethylarenes is an ongoing synthetic challenge that often leads to "over-reaction", where multiple fluorides are replaced. Development of this reaction would allow simple access to a vast range of difluoromethyl derivatives of current interest to pharmaceutical, agrochemistry, and materials sciences. Using a catalytic frustrated Lewis pair approach, we have developed a generic protocol that allows a single substitution of one fluoride in trifluoromethyl groups with neutral phosphine and pyridine bases. The resulting phosphonium and pyridinium salts can be further functionalized via nucleophilic substitution, photoredox coupling, and electrophilic transfer reactions allowing the generation of a vast array of difluoromethyl products.

Optimisation of Ultrasound Frequency, Extraction Time and Solvent for the Recovery of Polyphenols, Phlorotannins and Associated Antioxidant Activity from Brown Seaweeds.

This study investigates ultrasound assisted extraction (UAE) process parameters (time, frequency and solvent) to obtain high yields of phlorotannins, flavonoids, total phenolics and associated antioxidant activities from 11 brown seaweed species. Optimised UAE conditions (35 kHz, 30 min and 50% ethanol) significantly improved the extraction yield from 1.5-fold to 2.2-fold in all seaweeds investigated compared to solvent extraction. Using ultrasound, the highest recovery of total phenolics (TPC: 572.3 ± 3.2 mg gallic acid equivalent/g), total phlorotannins (TPhC: 476.3 ± 2.2 mg phloroglucinol equivalent/g) and total flavonoids (TFC: 281.0 ± 1.7 mg quercetin equivalent/g) was obtained from Fucus vesiculosus seaweed. While the lowest recovery of TPC (72.6 ± 2.9 mg GAE/g), TPhC (50.3 ± 2.0 mg PGE/g) and TFC (15.2 ± 3.3 mg QE/g) was obtained from Laminaria digitata seaweed. However, extracts from Fucus serratus obtained by UAE exhibited the strongest 1,1-diphenyl-2-picryl-hydrazyl (DPPH) scavenging activity (29.1 ± 0.25 mg trolox equivalent/g) and ferric reducing antioxidant power (FRAP) value (63.9 ± 0.74 mg trolox equivalent/g). UAE under optimised conditions was an effective, low-cost and eco-friendly technique to recover biologically active polyphenols from 11 brown seaweed species.

Nucleophilic Substitution of Aliphatic Fluorides via Pseudohalide Intermediates.

A method for aliphatic fluoride functionalization with a variety of nucleophiles has been reported. Carbon-fluoride bond cleavage is thermodynamically driven by the use of silylated pseudohalides TMS-OMs or TMS-NTf2 , resulting in the formation of TMS-F and a trapped aliphatic pseudohalide intermediate. The rate of fluoride/pseudohalide exchange and the stability of this intermediate are such that little rearrangement is observed for terminal fluoride positions in linear aliphatic fluorides. The ability to convert organofluoride positions into pseudohalide groups allows facile nucleophilic attack by a wide range of nucleophiles. The late introduction of the nucleophiles also allows for a wide range of functional-group tolerance in the coupling partners. Selective alkyl fluoride mesylation is observed in the presence of other alkyl halides, allowing for orthogonal synthetic strategies.

Activating biochar by manipulating the bacterial and fungal microbiome through pre-conditioning.

Biochar can enhance plant growth and reduce diseases, but frequently the optimal doses for these two benefits do not coincide. An approach is needed that will extend the range of biochar doses resulting in a concurrence of maximum benefits for both plant productivity and disease suppression. A biochar-amended growth medium was pre-conditioned by pre-planting fertigation in order to enhance the indigenous microbial community structure and activity. Cucumber plant performance and resistance against damping-off caused by Pythium aphanidermatum were monitored. Soil microbial activity, as well as bacterial and fungal community structure, were assessed by high-throughput 16S rRNA and ITS1 gene amplicon sequencing. Pre-conditioning enhanced the efficacy of biochar for improving plant performance and suppressing soilborne disease through enriching the medium in beneficial soil microorganisms, increasing microbial and fungal diversity and activity, and eliminating biochar phytotoxic compounds. The pre-conditioning process brought dose-response curves for both growth and disease resistance into sync, resulting in maximum benefits for both. These findings suggest that pre-conditioning should be incorporated as an important stage during biochar application in soil and soilless media.

Combined Infection with Cucumber green mottle mosaic virus and Pythium Species Causes Extensive Collapse in Cucumber Plants.

In the last decade, the phenomenon of late-wilting has increased in cucumber greenhouses during Cucumber green mottle mosaic virus (CGMMV) epidemics. Because the wilting appears in defined patches accompanied by root rot, it was hypothesized that the phenomenon is caused by coinfection of soilborne pathogens and CGMMV. A field survey showed that 69% of the collapsed plants were infected with both Pythium spp. and CGMMV, whereas only 20 and 6.6% were singly infected with Pythium spp. or CGMMV, respectively. Artificial inoculations in controlled-environmental growth chambers and glasshouse experiments showed that coinfection with Pythium spinosum and CGMMV leads to a strong synergistic wilting effect and reduces growth parameters. The synergy values of the wilting effect were not influenced by the time interval between P. spinosum and CGMMV infection. However, dry mass synergy values were decreased with longer intervals between infections. The results obtained in this study support the complexity of the wilting phenomenon described in commercial cucumber grown in protected structures during infection of Pythium spp. on the background of a vast CGMMV epidemic. They encourage a wider perspective of the complexity of agricultural diseases to apply the most suitable disease management.

Hemostatic Efficacy of Nanofibrous Matrix in Rat Liver Injury Model.

This present study examined the hemostatic efficacy of nanofibrous matrix in a rat liver model. The nanofibrous matrix comprising gelatin and polycaprolactone was prepared by electrospinning method. Twelve animals underwent surgery and were followed-up for a month. Time taken to cease bleeding, activated partial thromboplastin time, prothrombin time, and fibrinogen concentration were measured. Histopathological examination of liver was also done of treated and control animals. All test animals showed very rapid hemostasis after application of electrospun sheet. Histopathological study showed quick recovery of liver wound in the test group as compared to the control group. The nanofibrous matrix has proven to be not only safe and effective as hemostat but has also shown its potential for liver regeneration.

Lipid incorporated biopolymer based edible films and coatings in food packaging: A review.

In the evolving landscape of food packaging, lipid-based edible films and coatings are emerging as a sustainable and effective solution for enhancing food quality and prolonging shelf life. This critical review aims to offer a comprehensive overview of the functional properties, roles, and fabrication techniques associated with lipid-based materials in food packaging. It explores the unique advantages of lipids, including waxes, resins, and fatty acids, in providing effective water vapor, gas, and microbial barriers. When integrated with other biopolymers, such as proteins and polysaccharides, lipid-based composite films demonstrate superior thermal, mechanical, and barrier properties. The review also covers the application of these innovative coatings in preserving a wide range of fruits and vegetables, highlighting their role in reducing moisture loss, controlling respiration rates, and maintaining firmness. Furthermore, the safety aspects of lipid-based coatings are discussed to address consumer and regulatory concerns.

The Potential of Edible Insects as a Safe, Palatable, and Sustainable Food Source in the European Union.

Entomophagy describes the practice of eating insects. Insects are considered extremely nutritious in many countries worldwide. However, there is a lethargic uptake of this practice in Europe where consuming insects and insect-based foodstuffs is often regarded with disgust. Such perceptions and concerns are often due to a lack of exposure to and availability of food-grade insects as a food source and are often driven by neophobia and cultural norms. In recent years, due to accelerating climate change, an urgency to develop alternate safe and sustainable food-sources has emerged. There are currently over 2000 species of insects approved by the World Health Organization as safe to eat and suitable for human consumption. This review article provides an updated overview of the potential of edible insects as a safe, palatable, and sustainable food source. Furthermore, legislation, food safety issues, and the nutritional composition of invertebrates including, but not limited, to crickets (Orthoptera) and mealworms (Coleoptera) are also explored within this review. This article also discusses insect farming methods and the potential upscaling of the industry with regard to future prospects for insects as a sustainable food source. Finally, the topics addressed in this article are areas of potential concern to current and future consumers of edible insects.

Carrageenan-based sustainable biomaterials for intelligent food packaging: A review.

This article explores the use of carrageenan-based biomaterials in developing sustainable and efficient intelligent food packaging solutions. The research in this field has seen a notable surge, evident from >1000 entries in databases such as Web of Science, PubMed and Science Direct between 2018 and 2023. Various film preparation techniques are explored, including solvent casting, layer-by-layer (LbL) assembly, and electrospinning. Solvent casting is commonly used to incorporate active compounds, while LbL assembly and electrospinning are favored for enhancing mechanical properties and solubility. Carrageenan's film-forming characteristics enable the production of transparent films, ideal for indicator films that facilitate visual inspection for color changes indicative of pH variations, crucial for detecting food spoilage. Surface properties can be modified using additives like plant extracts to regulate moisture interaction, affecting shelf life and food safety. These materials' antioxidant and antimicrobial attributes are highlighted, demonstrating their efficacy against pathogens such as E. coli.

Choline chloride - oxalic acid dihydrate deep eutectic solvent pretreatment of Barley straw for production of cellulose nanofibers.

This study investigates the production of cellulose nanofibers (CNF) from Barley straw using ultrasound-assisted deep eutectic solvent (US-DES) treatment for biomass fractionation and subsequent high-intensity ultrasonication (HIUS) for nano-fibrillation. Two deep eutectic solvents (DES), synthesized from choline chloride (ChCl) and oxalic acid dihydrate (OAD) at 1:1 and 2:1 M ratio, achieved solubilisation of over 80 % of lignin and hemicellulose under optimal conditions. The purification of these DES-treated materials resulted in cellulose with a purity >88 %. CNFs, characterized by a size of <100 nm, a polydispersity index under 0.5, and a zeta potential lower than -30 mV, were successfully isolated through a combination of wet grinding and HIUS treatment. SEM and XRD results showed the formation of a network of interconnected fibres with a Type I cellulose structure. This research highlights Barley straw's potential as a sustainable source of high-value CNF from agricultural waste.

Nanocellulose separation from barley straw via ultrasound-assisted choline chloride - Formic acid deep eutectic solvent pretreatment and high-intensity ultrasonication.

The present study aims at investigating the application of ultrasound assisted choline chloride (ChCl) - formic acid (FA) deep eutectic solvent (DES) pretreatment of Barley straw. In addition, the efficiency of a wet grinding followed by high intensity ultrasound (HIUS) treatment for production of cellulose nanofibers (CNF) has been evaluated. The DES (using ChCl: FA at 1:9 M ratio) treatment at 45 kHz ultrasound frequency and 3 h of treatment duration resulted in 84.68 ± 1.02 % and 82.96 ± 0.79 % of lignin and hemicellulose solubilisation, respectively. The purification of DES treated solid residue resulted in cellulose with more than 90 % purity. Further, 10 min of wet grinding followed by 40 min of HIUS treatment resulted in more than 80 % nano-fibrillation efficiency. The produced CNF had diameters less than 100 nm in number size distribution and type I cellulose structure. This study confirmed that the developed process offers a sustainable method for producing nanocellulose from agricultural waste.

Bioengineering of Cu2O structured macro-biotemplate for the ultra-efficient and selective hand-retrieval of glyphosate from agro-farms.

Glyphosate (Gly) is a massively utilized toxic herbicide exceeding its statutory restrictions, causing adverse environmental and health impacts. Engineered nanomaterials, even though are integral to remediate Gly, their practical use is limited due to time and energy driven purifications, and negative environmental impacts. Here, a 3D wide area (~1.6 ± 0.4 cm2) Cu2O nanoparticle supported biotemplate is designed using fish-scale wastes as a sustainable approach for the ultra-efficient and selective hand-remediation of Gly from real-time samples from agro-farms. While the innate metal binding and reducing ability of collagenous scales aided self-synthesis cum grafting of Cu2O, the selective binding potential of Cu2O to Gly facilitated its hand-retrieval; as assessed using optical characterizations, Fourier transform infrared spectroscopy, thermogravimetric analysis and liquid chromatography mass spectrometry. Optimization studies revealed extractions of diverse pay-loads of Gly between 0.1 µg/mL to 40 µg/mL per 80 mg biotemplate grafted with ~6.354 µg of sub-5 nm Cu2O and was exponential to the number of Cu2O@biotemplates. Even though pH and surfactant didn't have any impact on the adsorption of Gly to the Cu2O@biotemplates, increase in the ionic strength led to a drastic increase in the adsorption. Density function theory simulations unveiled the involvement of phosphonic and carboxylic groups of Gly for interaction with Cu2O with a bond length of 1.826 Å and 1.833 Å, respectively. Overall, our sustainably generated, cost-efficient, hand-retrievable Cu2O supported biotemplate can be generalized to extract diverse organophosphorus toxins from agro-farms and other sewage embodiments. SYNOPSIS: Glyphosate is an excessively applied herbicide with potent health hazards and carcinogenicity. Thus, a hand removable Cu2O-supported biotemplate to selectively and efficiently remediate glyphosate from irrigation water is developed.

Biosynthesis, classification, properties, and applications of Weissella bacteriocins.

This review aims to comprehensively chronicle the biosynthesis, classification, properties, and applications of bacteriocins produced by Weissella genus strains, particularly emphasizing their potential benefits in food preservation, human health, and animal productivity. Lactic Acid Bacteria (LAB) are a class of microorganisms well-known for their beneficial role in food fermentation, probiotics, and human health. A notable property of LAB is that they can synthesize antimicrobial peptides known as bacteriocins that exhibit antimicrobial action against both closely related and other bacteria as well. Bacteriocins produced by Weissella spp. are known to exhibit antimicrobial activity against several pathogenic bacteria including food spoilage species, making them highly invaluable for potential application in food preservation and food safety. Importantly, they provide significant health benefits to humans, including combating infections, reducing inflammation, and modulating the gut microbiota. In addition to their applications in food fermentation and probiotics, Weissella bacteriocins show promising prospects in poultry production, processing, and improving animal productivity. Future research should explore the utilization of Weissella bacteriocins in innovative food safety measures and medical applications, emphasizing their potential to combat antibiotic-resistant pathogens, enhance gut microbiota composition and function, and synergize with existing antimicrobial therapies.

Chemical modification of bacterial exopolysaccharides: Antioxidant properties and health potentials.

In recent years, there has been a burgeoning interest in the utilization of microbial exopolysaccharides (EPS) because of the added advantage of their renewable, biocompatible, and biodegradable nature in addition to intended applications. The endowed properties of bacterial EPS make them valuable candidates for a wide array of industrial applications. Modification of native EPS is known to enhance various physico-chemical and functional properties. Various modifications such as physical, chemical, biological, and enzymatic modifications were practiced improving the bioactivity of EPS. This paper comprehensively aims to review the most recent chemical modification techniques employed to modify the physico-chemical and functional changes of bacterial EPS in comparison with the unmodified forms. Chemical modification entails strategic alterations to the structure and properties of EPS through various synthetic and semi-synthetic methodologies. Emphasis is given to the antioxidant potential and functional role of these EPS derivatives in human health. Antioxidant properties reveal a significant augmentation in activity compared to their native counterparts. Such enhancement holds a strong promise for potential benefits and therapeutic applications. Chemical derivatives of EPS with overwhelming functional benefits could surely encourage EPS application, particularly as potential hydrocolloids in industrial and biomedical contexts.

Targeting IGF2BP3 enhances antileukemic effects of menin-MLL inhibition in MLL-AF4 leukemia.

ABSTRACT: RNA-binding proteins (RBPs) are emerging as a novel class of therapeutic targets in cancer, including in leukemia, given their important role in posttranscriptional gene regulation, and have the unexplored potential to be combined with existing therapies. The RBP insulin-like growth factor 2 messenger RNA-binding protein 3 (IGF2BP3) has been found to be a critical regulator of MLL-AF4 leukemogenesis and represents a promising therapeutic target. Here, we study the combined effects of targeting IGF2BP3 and menin-MLL interaction in MLL-AF4-driven leukemia in vitro and in vivo, using genetic inhibition with CRISPR-Cas9-mediated deletion of Igf2bp3 and pharmacologic inhibition of the menin-MLL interaction with multiple commercially available inhibitors. Depletion of Igf2bp3 sensitized MLL-AF4 leukemia to the effects of menin-MLL inhibition on cell growth and leukemic initiating cells in vitro. Mechanistically, we found that both Igf2bp3 depletion and menin-MLL inhibition led to increased differentiation in vitro and in vivo, seen in functional readouts and by gene expression analyses. IGF2BP3 knockdown had a greater effect on increasing survival and attenuating disease than pharmacologic menin-MLL inhibition with small molecule MI-503 alone and showed enhanced antileukemic effects in combination. Our work shows that IGF2BP3 is an oncogenic amplifier of MLL-AF4-mediated leukemogenesis and a potent therapeutic target, providing a paradigm for targeting leukemia at both the transcriptional and posttranscriptional level.

Sustainable Utilisation and Management of Food Waste for High-Value Products.

Welcome to the Special Issue on "Sustainable Utilisation and Management of Food Waste for High-Value Products" [...].