Chemical Diversity Research Articles

Phytochemical investigation and spectral characterization of isolated compounds from Pyracantha crenulata (D. Don) M. Roem (syn. Crataegus crenulata Roxb) leaves: evaluation of antioxidant activity and molecular docking analysis

Pyracantha crenulata (D. Don) M. Roem (syn. Crataegus crenulata Roxb.) is an evergreen shrub in the Rosaceae family, notable for its chemical diversity and biological potential. This study isolates and characterises six compounds (Cc-1 to Cc-6), including four new ones, using repeated column chromatography. Structural elucidation employed IR, UV-vis, 1H and 13 C NMR, and mass spectrometry. The DPPH assay was used to test the antioxidant activity in vitro. Compounds Cc-4, Cc-2, Cc-1, and Cc-5 had IC50 values of 15.734 μg/ml, 51.422 μg/ml, 62.864 μg/ml, and 71.622 μg/ml, in that order. Quantitative phytochemical analysis revealed flavonoid content (22.81 mg/g), tannin content (385.15 mg/g), and total phenolic content (128.78 mg/g). Human cyclin-dependent kinase 2 (CDK2) (PDB ID: 1hck) docked with compound Cc-4, which demonstrated strong antioxidant activity and revealed significant non-bonding interactions. The pkCSM and SwissADME analyses suggested promising drug-like properties for Cc-4, supported by BOILED-Egg diagrams highlighting its therapeutic potential.

Measuring the purity of organic chemicals: general approaches and development of an appropriate procedure for research of pure organic chemicals

Pure materials are in demand in many sectors of the national economy, including the metrological service. High purity organic material is the ultimate source of metrological traceability in organic analysis to the basic units of the International System of Units (SI). This article presents the general approaches to determining the mass fraction of the main component in pure organic chemicals, which provide a traceable connection between the certified value of substance purity and the basic SI units - mass (kilogram) and amount of substance (mole), the features of using direct and indirect measurement approaches are considered, specific analytical methods that can be used for this purpose are discussed. Determining the purity of an organic material in most cases is not a plain analytical and metrological task. Solving this issue requires the relevant instrumental methods and appropriate measurement procedure, which is able to provide a comprehensive study of organic matter and guarantee the necessary accuracy of the certified value. Taking in consideration the vast diversity of organic chemicals, the determination of the purity of organic substances will never be a standardized procedure.

Applications of ancestral sequence reconstruction for understanding the evolution of plant specialized metabolism.

Studies of enzymes in modern-day plants have documented the diversity of metabolic activities retained by species today but only provide limited insight into how those properties evolved. Ancestral sequence reconstruction (ASR) is an approach that provides statistical estimates of ancient plant enzyme sequences which can then be resurrected to test hypotheses about the evolution of catalytic activities and pathway assembly. Here, I review the insights that have been obtained using ASR to study plant metabolism and highlight important methodological aspects. Overall, studies of resurrected plant enzymes show that (i) exaptation is widespread such that even low or undetectable levels of ancestral activity with a substrate can later become the apparent primary activity of descendant enzymes, (ii) intramolecular epistasis may or may not limit evolutionary paths towards catalytic or substrate preference switches, and (iii) ancient pathway flux often differs from modern-day metabolic networks. These and other insights gained from ASR would not have been possible using only modern-day sequences. Future ASR studies characterizing entire ancestral metabolic networks as well as those that link ancient structures with enzymatic properties should continue to provide novel insights into how the chemical diversity of plants evolved. This article is part of the theme issue 'The evolution of plant metabolism'.

Evolution of plant metabolism: the state-of-the-art.

Immense chemical diversity is one of the hallmark features of plants. This chemo-diversity is mainly underpinned by a highly complex and biodiverse biochemical machinery. Plant metabolic enzymes originated and were inherited from their eukaryotic and prokaryotic ancestors and further diversified by the unprecedentedly high rates of gene duplication and functionalization experienced in land plants. Unlike prokaryotic microbes, which display frequent horizontal gene transfer events and multiple inputs of energy and organic carbon, land plants predominantly rely on organic carbon generated from CO2 and have experienced relatively few gene transfers during their recent evolutionary history. As such, plant metabolic networks have evolved in a stepwise manner using existing networks as a starting point and under various evolutionary constraints. That said, until recently, the evolution of only a handful of metabolic traits had been extensively investigated and as such, the evolution of metabolism has received a fraction of the attention of, the evolution of development, for example. Advances in metabolomics and next-generation sequencing have, however, recently led to a deeper understanding of how a wide range of plant primary and specialized (secondary) metabolic pathways have evolved both as a consequence of natural selection and of domestication and crop improvement processes. This article is part of the theme issue 'The evolution of plant metabolism'.

Phylogenomic and synteny analysis of BAHD and SCP/SCPL gene families reveal their evolutionary histories in plant specialized metabolism.

Plant chemical diversity is largely owing to a number of enzymes which catalyse reactions involved in the assembly, and in the subsequent chemical modifications, of the core structures of major classes of plant specialized metabolites. One such reaction is acylation. With this in mind, to study the deep evolutionary history of BAHD and the serine-carboxypeptidase-like (SCPL) acyltransferase genes, we assembled phylogenomic synteny networks based on a large-scale inference analysis of orthologues across whole-genome sequences of 126 species spanning Stramenopiles and Archaeplastida, including Arabidopsis thaliana, tomato (Solanum lycopersicum) and maize (Zea mays). As such, this study combined the study of genomic location with changes in gene sequences. Our analyses revealed that serine-carboxypeptidase (SCP)/serine-carboxypeptidase-like (SCPL) genes had a deeper evolutionary origin than BAHD genes, which expanded massively on the transition to land and with the development of the vascular system. The two gene families additionally display quite distinct patterns of copy number variation across phylogenies as well as differences in cross-phylogenetic syntenic network components. In unlocking the above observations, our analyses demonstrate the possibilities afforded by modern phylogenomic (syntenic) networks, but also highlight their current limitations, as demonstrated by the inability of phylogenetic methods to separate authentic SCPL acyltransferases from standard SCP peptide hydrolases.This article is part of the theme issue 'The evolution of plant metabolism'.

Understanding metabolic diversification in plants: branchpoints in the evolution of specialized metabolism.

Plants are chemical engineers par excellence. Collectively they make a vast array of structurally diverse specialized metabolites. The raw materials for building new pathways (genes encoding biosynthetic enzymes) are commonly recruited directly or indirectly from primary metabolism. Little is known about how new metabolic pathways and networks evolve in plants, or what key nodes contribute to branches that lead to the biosynthesis of diverse chemicals. Here we review the molecular mechanisms underlying the generation of biosynthetic branchpoints. We also consider examples in which new metabolites are formed through the joining of precursor molecules arising from different biosynthetic routes, a scenario that greatly increases both the diversity and complexity of specialized metabolism. Given the emerging importance of metabolic gene clustering in helping to identify new enzymes and pathways, we further cover the significance of biosynthetic gene clusters in relation to metabolic networks and dedicated biosynthetic pathways. In conclusion, an improved understanding of the branchpoints between metabolic pathways will be key in order to be able to predict and illustrate the complex structure of metabolic networks and to better understand the plasticity of plant metabolism. This article is part of the theme issue 'The evolution of plant metabolism'.

Recent Progress of Three-Dimensional Graphene-Based Composites for Photocatalysis.

Converting solar energy into fuels/chemicals through photochemical approaches holds significant promise for addressing global energy demands. Currently, semiconductor photocatalysis combined with redox techniques has been intensively researched in pollutant degradation and secondary energy generation owing to its dual advantages of oxidizability and reducibility; however, challenges remain, particularly with improving conversion efficiency. Since graphene's initial introduction in 2004, three-dimensional (3D) graphene-based photocatalysts have garnered considerable attention due to their exceptional properties, such as their large specific surface area, abundant pore structure, diverse surface chemistry, adjustable band gap, and high electrical conductivity. Herein, this review provides an in-depth analysis of the commonly used photocatalysts based on 3D graphene, outlining their construction strategies and recent applications in photocatalytic degradation of organic pollutants, H2 evolution, and CO2 reduction. Additionally, the paper explores the multifaceted roles that 3D graphene plays in enhancing photocatalytic performance. By offering a comprehensive overview, we hope to highlight the potential of 3D graphene as an environmentally beneficial material and to inspire the development of more efficient, versatile graphene-based aerogel photocatalysts for future applications.

Integrating redox-electrodialysis and electrosorption for the removal of ultra-short- to long-chain PFAS

A major challenge in per- and polyfluoroalkyl substances (PFAS) remediation has been their structural and chemical diversity, ranging from ultra-short to long-chain compounds, which amplifies the operational complexity of water treatment and purification. Here, we present an electrochemical strategy to remove PFAS from ultra-short to long-chain PFAS within a single process. A redox-polymer electrodialysis (redox-polymer ED) system leverages a water-soluble redox polymer with inexpensive nanofiltration membranes, facilitating the treatment of varied chain lengths of PFAS without membrane fouling. Our approach combines both ion migration by electrodialysis (for PFAS with chain lengths ≤C4) and electrosorption strategies (for PFAS with chain lengths ≥C6) to eliminate approximately 90% of ultra-short-, short-chain, and long-chain PFAS. At the same time, we achieve continuous desalination of the source water down to potable water level. The redox-polymer ED exhibits remarkable PFAS removal in real source water scenarios, including from matrices with 10,000 times higher salt concentrations, as well as secondary effluents from wastewaters. Additionally, the removed PFAS is mineralized with a defluorination performance between 76-100% by electrochemical oxidation, highlighting the viability of integrating the separation step with a reactive degradation process.

Chemical diversity among the essential oils of different wild growing Plantago species in Iran

Chemical diversity among the essential oils of different wild growing Plantago species in Iran

Reaping the Chemical Diversity of Morinagamyces vermicularis Using Feature-Based Molecular Networking.

Moringadepsin (6) and chaetone B (7) were isolated by us in the course of a conventional chemical screening of Morinagamyces vermicularis CBS 303.81, a fungus belonging to the relatively underexplored family Schizotheciaceae of the phylum Ascomycota. Since these metabolites did not account for the antifungal activity observed in a crude extract of this fungus, we utilized an MS/MS-based molecular networking approach to get a thorough insight into the secondary metabolites produced by this strain. Manual annotation of high-resolution fragmentation mass spectra by CANOPUS classified a major molecular family as putatively new thiodiketopiperazines. However, these results were opposite to the results of ChemWalker analysis based solely on MS/MS data, assigning these metabolites as various polyketides. Thus, targeted preparative HPLC isolation focusing on the most abundant features within this major molecular family resulted in the isolation of five secondary metabolites. Their structures were elucidated based on HRMS and NMR data as four new thiodiketopiperazine derivatives, botryosulfuranols D-G (1-4), alongside the known botryosulfuranol A (5). Compounds 1-3 and 5 exhibited moderate to weak antifungal activity against different test strains, accounting for the initial antifungal activity observed for its crude extract. Our study stressed the importance of full NMR-based structure elucidation for metabolomics research.

A versatile microbial platform as a tunable whole-cell chemical sensor.

Biosensors are used to detect and quantify chemicals produced in industrial microbiology with high specificity, sensitivity, and portability. Most biosensors, however, are limited by the need for transcription factors engineered to recognize specific molecules. In this study, we overcome the limitations typically associated with traditional biosensors by engineering Pseudomonas putida for whole-cell sensing of a variety of chemicals. Our approach integrates fluorescent reporters with synthetic auxotrophies within central metabolism that can be complemented by target analytes in growth-coupled setups. This platform enables the detection of a wide array of structurally diverse chemicals under various conditions, including co-cultures of producer cell factories and sensor strains. We also demonstrate the applicability of this versatile biosensor platform for monitoring complex biochemical processes, including plastic degradation by either purified hydrolytic enzymes or engineered bacteria. This microbial system provides a rapid, sensitive, and readily adaptable tool for monitoring cell factory performance and for environmental analyzes.

Xeniaphyllane and Xeniolide Diterpenes from the Deep-Sea Soft Coral Paragorgia arborea.

As exploration of ocean depths >1000 m is only possible by expensive remotely operated underwater vehicles, deep-sea invertebrates represent a largely untapped source of marine metabolites for potential applications in medicine. Our current study aims to investigate these deep-sea invertebrates in Ireland to discover new biological and chemical diversity. Here, we investigate the bubble gum coral, Paragorgia arborea, collected at 1500 m depth from Whittard canyon in the Northeastern Atlantic. This species was selected following chemical profiling and biological screening. The isolation and structure elucidation of the main metabolites yielded three new diterpenes, namely, miolenol (1) and epoxymiolenol (2) characterized by the rare bicyclo[7.2.0]undec-4-ene skeleton, and the xeniolide epoxycoraxeniolide A (3), together with five known diterpenes. The structures of the new compounds were identified through extensive NMR analysis with their absolute configurations assigned by comparison between experimental and TDDFT-calculated ECD. The eight compounds were screened for cytotoxicity and antimalarial activity, and none displayed noteworthy bioactivity.

Recent Advancements in Nanopharmaceuticals for Novel Drug Delivery Systems.

Nanoparticles have found applications across diverse sectors, including agriculture, food, cosmetics, chemicals, mechanical engineering, automotive, and oil and gas industries. In the medical field, nanoparticles have garnered considerable attention due to their great surface area, high solubility, rapid dissolution, and enhanced bioavailability. Nanopharmaceuticals are specifically designed to precisely deliver drug substances to targeted tissues and cells, aiming to optimize therapeutic efficacy while minimizing potential adverse effects. Furthermore, nanopharmaceuticals offer advantages, such as expedited therapeutic onset, reduced dosages, minimized variability between fed and fasted states, and enhanced patient compliance. The increasing interest in nanopharmaceuticals research among scientists and industry stakeholders highlights their potential for various medical applications from disease management to cancer treatment. This review examines the distinctive characteristics of ideal nanoparticles for efficient drug delivery, explores the current types of nanoparticles utilized in medicine, and delves into the applications of nanopharmaceuticals, including drug and gene delivery, as well as transdermal drug administration. This review provides insights into the nanopharmaceuticals field, contributing to the development of novel drug delivery systems and enhancing the potential of nanotechnology in healthcare.

Pharmacophylogenetic insights into Scutellaria strigillosa Hemsl.: chloroplast genome and untargeted metabolomics, quantitative analysis and antibacterial analysis.

Scutellaria strigillosa Hemsl., known for its traditional use in Chinese herbal medicine, is valued for heat-clearing and detoxifying, promoting diuresis, reducing swelling, alleviating pain, and preventing miscarriage. Despite its historical use, comprehensive studies on pharmacophylogenetic analysis, including genetic and chemical profiles and the antimicrobial activity of S. strigillosa are still lacking. Understanding these aspects is crucial for fully realizing its therapeutic potential and ensuring sustainable use. This study aims to elucidate these aspects through comparative genomics, metabolomics, and antimicrobial assays with Scutellaria baicalensis Georgi and Scutellaria barbata D. Don. The chloroplast genome of S. strigillosa was assembled, measuring 152,533 bp, and revealing a high degree of conservation, especially in the protein-coding regions, and identified four regions trnK(UUU)-rps16, trnN(GUU)-trnR(ACG), accD-psaI, psbE-petL) of variability that could serve as phylogenetic markers. The phylogenetic analysis revealed a closer genetic relationship of S. strigillosa with S. tuberifera and S. scordifolia than traditionally classified, suggesting a need for taxonomic reevaluation within the genus. UPLC-Q-TOF-MS analysis in negative ion mode was used to explore the chemical diversity among these species, revealing distinct variations in their chemical compositions. S. strigillosa shared a closer chemical profile with S. barbata, aligning with phylogenetic findings. Metabolomic identification through Progenesis QI software resulted in the tentative identification of 112 metabolites, including a substantial number of flavonoids, diterpenoids, iridoid glycosides, phenylethanoid glycosides, and others. HPLC analysis further detailed the concentrations of 12 actives across the species, highlighting the variation in compound content. S. strigillosa shows antibacterial activity against Staphylococcus aureus and Pseudomonas aeruginosa, similar to S. baicalensis root extracts. This research enhances the understanding of the phylogenetic and phytochemical profiles and the antibacterial activity of S. strigillosa, offering new insights into its medicinal properties. The findings suggest a need for taxonomic reevaluation within the genus and underscore the potential antibacterial activity of S. strigillosa for therapeutic applications. Further studies are encouraged to explore its full medicinal potential and contribute to the sustainable development of Scutellaria species.

PFAS: The Journey from Wonder Chemicals to Environmental Nightmares and the Search for Solutions

Per- and polyfluoroalkyl substances (PFAS) are diverse synthetic chemicals manufactured over seven decades. It is an aliphatic molecule with a basic hydrophobic structure of carbon and fluorine linked to a hydrophilic end group. Due to their physicochemical properties associated with the unique structure, PFAS has been used in a wide variety of applications including aqueous film-forming foams (AFFF), paper, carpets, non-stick cookware, etc. as they make products resistant to water, heat, and stains. These molecules have drawn great attention recently for their unique properties, high stability and low degradability, and so-called “Forever Chemicals”. PFAS has the strongest carbon-fluorine bond which makes them persistent in the environment. Hence it contaminates natural resources and endangers public health. This review discusses the discovery, development, and evolution of PFAS from the wonder chemical era to a nightmare chemical era, exposure and its impacts on human health and the environment, current remediation techniques, and future trends of PFAS molecules and related products. The primary objective of this review is to identify knowledge gaps on PFAS contamination, remediation methods, and possible PFAS alternatives.

Advancements in Pyrazine Derivatives as Anticancer Agents: A Comprehensive Review (2010-2024).

Cancer, an intricate and formidable disease, continues to challenge Medical Science with its diverse manifestations and relentless progression. In the pursuit of novel therapeutic strategies, organic heterocyclic compounds have emerged as promising candidates due to their versatile chemical structures and intricate interactions with biological systems. Among these, pyrazine derivatives are characterized by a six-membered aromatic ring containing four carbon and two nitrogen atoms situated in a 1,4-orientation. These compounds garnered significant attention for their potential as anticancer agents. This comprehensive review provides a detailed analysis of the advancements made during this timeframe, encompassing the chemical diversity of pyrazine derivatives, their mechanisms of action at the cellular level, and structure-activity relationships, spanning the years 2010 to 2024. By examining their therapeutic potential, challenges, and future prospects, this review offers valuable insights into the evolving landscape of pyrazine derivatives as potent tools in the fight against cancer.

Insights into Chemical Diversity and Potential Health-Promoting Effects of Ferns.

The scientific community is focusing on how to enhance human health and immunity through functional foods, and dietary supplements are proven to have a positive as well as a protective effect against infectious and chronic diseases. Ferns act as a taxonomical linkage between higher and lower plants and are endowed with a wide chemical diversity not subjected to sufficient scrutinization before. Even though a wealth of traditional medicinal fern uses were recorded in Chinese medicine, robust phytochemical and biological investigations of these plants are lacking. Herein, an extensive search was conducted using the keywords ferns and compounds, ferns and NMR, ferns and toxicity, and the terms ferns and chemistry, lignans, Polypodiaceae, NMR, isolation, bioactive compounds, terpenes, phenolics, phloroglucinols, monoterpenes, alkaloids, phenolics, and fatty acids were utilized with the Boolean operators AND, OR, and NOT. Databases such as PubMed, Web of Science, Science Direct, Scopus, Google Scholar, and Reaxys were utilized to reveal a wealth of information regarding fern chemistry and their health-promoting effects. Terpenes followed by phenolics represented the largest number of isolated active compounds. Regarding the neuroprotective effects, Psilotium, Polypodium, and Dryopteris species possessed as their major phenolics component unique chemical moieties including catechins, procyanidins, and bioflavonoids. In this updated chemical review, the pharmacological and chemical aspects of ferns are compiled manifesting their chemical diversity in the last seven years (2017-2024) together with a special focus on their nutritive and potential health-promoting effects.

Structural Features, Chemical Diversity, and Physical Properties of Microporous Sodalite-Type Materials: A Review

This review contains data on a wide class of microporous materials with frameworks belonging to the sodalite topological type. Various methods for the synthesis of these materials, their structural and crystal chemical features, as well as physical and chemical properties are discussed. Specific properties of sodalite-related materials make it possible to consider they as thermally stable ionic conductors, catalysts and catalyst carriers, sorbents, ion exchangers for water purification, matrices for the immobilization of radionuclides and heavy metals, hydrogen and methane storage, and stabilization of chromophores and phosphors. It has been shown that the diversity of properties of sodalite-type materials is associated with the chemical diversity of their frameworks and extra-framework components, as well as with the high elasticity of the framework.

Use of amazonian fruits in dental bleaching

Natural products stand out for their chemical diversity, thus plants are important candidates for screening new bioactive compounds. This study evaluated the effect of plant extracts combined with 16% carbamide peroxide (PC16%) on tooth whitening. Bovine teeth and composite resin blocks were randomly assigned to pigmentation and whitening protocols. For pigmentation, they were immersed in diluted coffee (14 days), and whitening was performed by mixing 1g of plant extract from each species and 0.5mL of PC16% (9 days). The extracts were prepared from fruits of species occurring in the Amazon biome: Myrciaria dubia (Myrtaceae), Bactris gasipaes (Arecaceae), Euterpe oleracea (Arecaceae), Theobroma grandiflorum (Malvaceae), and Paullinia cupana (Sapindaceae). PC16% was used alone as control, and a group without whitening was also included. Color analysis was performed using ΔE2000, ΔE1976, and WhiteIndex through an EasyShade Advanced 4.0 spectrophotometer before and after the protocols. The pH of the extracts at a concentration of 10% and micrographs after whitening were analyzed. Data were analyzed by one-dimensional ANOVA and Tukey's post-hoc test. Pigmentation showed significance only for bovine teeth (p 0.05). The pH of the pupunha and guaraná-de-maués extracts approached that of PC16%. Micrographs show that only the cupuaçu group had no surface alteration. Further research is needed to investigate variation factors, particularly given the study's limitations.

Cyclodextrin nanosponges as bioenhancers of phytochemicals

Bioavailability is the biggest obstacle to the effectiveness of biologically active compounds. Based on a set of physicochemical requirements we can determine if the compound fulfills the drug-like character and if it has the potential to become an active pharmaceutical ingredient (API) with confirmed and thoroughly examined activities. This practice is widely used in drug design of entirely new APIs, but also in search of pharmacological active substances in large compound bases such as plant-derived substances. The chemical structure diversity of plant-based compounds assures that some of them have to be well bioavailable due to good lipid membrane permeability. However, their efficiency is often limited by poor water solubility. Thus, there is a special need for bioenhancers of naturally derived compounds. In this review we present the potential of cyclodextrin nanosponges (CDNSs) as bioavailability enhancers of selected phytochemicals, namely curcumin, resveratrol, oxyresveratrol and quercetin whose very poor water solubility is the biggest obstacle to high efficiency.