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1.
Proc Natl Acad Sci U S A ; 120(25): e2303335120, 2023 06 20.
Article in English | MEDLINE | ID: mdl-37307452

ABSTRACT

Soil organic matter (SOM) is comprised of a diverse array of reactive carbon molecules, including hydrophilic and hydrophobic compounds, that impact rates of SOM formation and persistence. Despite clear importance to ecosystem science, little is known about broad-scale controls on SOM diversity and variability in soil. Here, we show that microbial decomposition drives significant variability in the molecular richness and diversity of SOM between soil horizons and across a continental-scale gradient in climate and ecosystem type (arid shrubs, coniferous, deciduous, and mixed forests, grasslands, and tundra sedges). The molecular dissimilarity of SOM was strongly influenced by ecosystem type (hydrophilic compounds: 17%, P < 0.001; hydrophobic compounds: 10% P < 0.001) and soil horizon (hydrophilic compounds: 17%, P < 0.001; hydrophobic compounds: 21%, P < 0.001), as assessed using metabolomic analysis of hydrophilic and hydrophobic metabolites. While the proportion of shared molecular features was significantly higher in the litter layer than subsoil C horizons across ecosystems (12 times and 4 times higher for hydrophilic and hydrophobic compounds, respectively), the proportion of site-specific molecular features nearly doubled from the litter layer to the subsoil horizon, suggesting greater differentiation of compounds after microbial decomposition within each ecosystem. Together, these results suggest that microbial decomposition of plant litter leads to a decrease in SOM α-molecular diversity, yet an increase in ß-molecular diversity across ecosystems. The degree of microbial degradation, determined by the position in the soil profile, exerts a greater control on SOM molecular diversity than environmental factors, such as soil texture, moisture, and ecosystem type.


Subject(s)
Ecosystem , Forests , Tundra , Carbon , Soil
2.
Chemistry ; 30(29): e202400477, 2024 May 23.
Article in English | MEDLINE | ID: mdl-38498145

ABSTRACT

We present an Ugi multicomponent approach to explore the chemical space around Aspidosperma-type monoterpene indole alkaloids. By variation of the isocyanide and carboxylic acid inputs we demonstrate the rapid generation of molecular diversity and the possibility to introduce handles for further modification. The key Ugi three-component reaction showed full diastereoselectivity towards the cis-fused ring system, which can be rationalized by DFT calculations that moreover indicate that the reaction proceeds via a Passerini-type hydrogen bonding mechanism. Several post-Ugi modifications were also performed, including Pictet-Spengler cyclization to highly complex nonacyclic natural product hybrid scaffolds.

3.
Chemistry ; 30(26): e202304166, 2024 May 08.
Article in English | MEDLINE | ID: mdl-38372433

ABSTRACT

The realms of natural products and synthetic compounds exhibit distinct chemical spaces that not only differ but also complement each other. While the convergence of these two domains has been explored through semisynthesis and conventional pharmacomodulation endeavours applied to natural frameworks, a recent and innovative approach has emerged that involves the combinatorial generation of libraries of 'natural product-like compounds' (NPLCs) through the direct synthetic derivatization of natural extracts. This has led to the production of numerous NPLCs that incorporate structural elements from both their natural (multiple saturated rings, oxygen content, chiral centres) and synthetic (aromatic rings, nitrogen and halogen content, drug-like properties) precursors. Through careful selection of extracts and reagents, specific bioactivities have been achieved, and this strategy has been deployed in various ways, showing great promise without reaching its full potential to date. This review seeks to provide an overview of reported examples involving the chemical engineering of extracts, showcasing a spectrum of natural product alterations spanning from simple substitutions to complete scaffold remodelling. It also includes an analysis of the accomplishments, perspectives and technical challenges within this field.


Subject(s)
Biological Products , Small Molecule Libraries , Biological Products/chemistry , Small Molecule Libraries/chemistry , Combinatorial Chemistry Techniques
4.
Med Mycol ; 62(4)2024 Mar 28.
Article in English | MEDLINE | ID: mdl-38499442

ABSTRACT

Microsporidia is a diverse group of obligate, intracellular, and spore-forming parasites that infect a wide range of animals. Among them, Enterocytozoon bieneusi and Encephalitozoon spp. are the most frequently reported species in humans. Limited information is available about the presence and molecular diversity of microsporidian species in the endangered Iberian lynx (Lynx pardinus). Presence of Enterocytozoon bieneusi and Encephalitozoon spp. was investigated by molecular methods in wild and captive Iberian lynxes from Spain. Overall, E. bieneusi was detected in 3.2% (8/251) of the animals examined. None of the samples tested were positive for Encephalitozoon spp. Four known (D, EbfelA, PigEBITS7, and Type IV) and a novel (named as LynxSpEb1) E. bieneusi genotypes were identified. All the genotypes found belonged to the zoonotic Group 1 of E. bieneusi. This study provides the first genotyping data of E. bieneusi in Iberian lynx in Spain. Our result indicate that the Iberian lynx does not seem to play a relevant role in the epidemiology of Encephalitozoon spp., and that this endangered felid is likely acting as spillover host rather than a true reservoir of E. bieneusi. Additional studies should be conducted to assess the impact of this parasite in the health status of the endangered Iberian lynx.


Subject(s)
Encephalitozoon , Enterocytozoon , Lynx , Microsporidia , Humans , Animals , Genotype , Lynx/parasitology , Enterocytozoon/genetics , Prevalence , Feces , Phylogeny
5.
Environ Res ; 262(Pt 1): 119799, 2024 Aug 13.
Article in English | MEDLINE | ID: mdl-39147184

ABSTRACT

Metabarcoding analysis has been demonstrated to be an effective technology for monitoring diversity and dynamics of phytoplankton including Skeletonema species. Although molecular diversity uncovered in metabarcoding projects has generally been interpreted as sum of interspecies diversity and intraspecies diversity, accumulating evidence suggests that it also harbors unprecedentedly high levels of intra-genomic variations (IGVs). As up to thousands of amplicon sequence variants (ASVs) identified in a typical metabarcoding project can be annotated to be Skeletonema species, we hypothesize that substantial portions of these ASVs are contributed by IGVs. Here, the nature of IGVs in Skeletonema species was quantitatively analyzed by carrying out single-strain metabarcoding analysis of 18S rDNA V4 in 49 strains belonging to seven Skeletonema species. Results showed that each Skeletonema strain harbored a high level of IGVs as expected. While many Skeletonema strains each contained one dominant ASV and a substantial number of ASVs displaying much lower relative abundance, other Skeletonema strains each contained multiple ASVs with comparable or nearly equally abundances. Thus the co-existence of multiple dominant ASVs in a single cell indicated a tug-of-war of these variants in evolution, which may eventually result in harmonized coexistence of multiple dominant ASVs. A total of nine dominant ASVs and 652 non-dominant ASVs were found in 49 strains of seven Skeletonema species, indicating rich interspecies and intraspecies variations, and complex evolution of IGVs in genus of Skeletonema. The results confirmed that the extensive degree of IGVs was the main contributor to the high molecular diversity revealed by metabarcoding analysis. This study highlights the importance of quantitative characterization of IGVs in Skeletonema species for accurate interpretation of species diversity in metabarcoding analysis.

6.
Mol Divers ; 28(1): 229-248, 2024 Feb.
Article in English | MEDLINE | ID: mdl-38104301

ABSTRACT

A synthetic route leading to densely functionalized 2-oxopiperazines is presented. The strategy employs a 5-center-4-component variant of Ugi multicomponent reaction followed by a deprotection/cyclization sequence. N-Boc-α-amino aldehydes were used for the first time as carbonyl components in a key Ugi 5-center-4-component reaction (U-5C-4CR). It is shown that the presented synthetic route can lead to rigid, heterocyclic scaffolds, as demonstrated by the synthesis of tetrahydro-2H-pyrazino[1,2-a]pyrazine-3,6,9(4H)-trione ß-turn mimetic and derivatives of 1,6-dioxooctahydropyrrolo[1,2-a]pyrazine and 3,8-dioxohexahydro-3H-oxazolo[3,4-a]pyrazine.


Subject(s)
Aldehydes , Pyrazines , Cyclization
7.
Proc Natl Acad Sci U S A ; 118(3)2021 01 19.
Article in English | MEDLINE | ID: mdl-33452137

ABSTRACT

Transmitter receptors constitute a key component of the molecular machinery for intercellular communication in the brain. Recent efforts have mapped the density of diverse transmitter receptors across the human cerebral cortex with an unprecedented level of detail. Here, we distill these observations into key organizational principles. We demonstrate that receptor densities form a natural axis in the human cerebral cortex, reflecting decreases in differentiation at the level of laminar organization and a sensory-to-association axis at the functional level. Along this natural axis, key organizational principles are discerned: progressive molecular diversity (increase of the diversity of receptor density); excitation/inhibition (increase of the ratio of excitatory-to-inhibitory receptor density); and mirrored, orderly changes of the density of ionotropic and metabotropic receptors. The uncovered natural axis formed by the distribution of receptors aligns with the axis that is formed by other dimensions of cortical organization, such as the myelo- and cytoarchitectonic levels. Therefore, the uncovered natural axis constitutes a unifying organizational feature linking multiple dimensions of the cerebral cortex, thus bringing order to the heterogeneity of cortical organization.


Subject(s)
Brain/metabolism , Cell Communication/genetics , Cerebral Cortex/metabolism , Receptors, Neurotransmitter/genetics , Autoradiography , Brain/diagnostic imaging , Brain/ultrastructure , Brain Mapping , Cerebral Cortex/diagnostic imaging , Cerebral Cortex/ultrastructure , Humans , Receptors, AMPA/genetics , Receptors, AMPA/isolation & purification , Receptors, GABA-A/genetics , Receptors, GABA-A/isolation & purification , Receptors, N-Methyl-D-Aspartate/genetics , Receptors, N-Methyl-D-Aspartate/isolation & purification , Receptors, Neurotransmitter/chemistry , Receptors, Neurotransmitter/classification , Receptors, Neurotransmitter/ultrastructure
8.
Int J Mol Sci ; 25(13)2024 Jun 24.
Article in English | MEDLINE | ID: mdl-39000014

ABSTRACT

Based on the nucleotide sequences of the mitochondrial genome (mitogenome) of specimens taken from two mussel species (Arcuatula senhousia and Mytilus coruscus), an investigation was performed by means of the complex approaches of the genomics, molecular phylogenetics, and evolutionary genetics. The mitogenome structure of studied mussels, like in many other invertebrates, appears to be much more variable than in vertebrates and includes changing gene order, duplications, and deletions, which were most frequent for tRNA genes; the mussel species' mitogenomes also have variable sizes. The results demonstrate some of the very important properties of protein polypeptides, such as hydrophobicity and its determination by the purine and pyrimidine nucleotide ratio. This fact might indirectly indicate the necessity of purifying natural selection for the support of polypeptide functionality. However, in accordance with the widely accepted and logical concept of natural cutoff selection for organisms living in nature, which explains its action against deleterious nucleotide substitutions in the nonsynonymous codons (mutations) and its holding of the active (effective) macromolecules of the polypeptides in a population, we were unable to get unambiguous evidence in favor of this concept in the current paper. Here, the phylogeny and systematics of mussel species from one of the largest taxons of bivalve mollusks are studied, the family known as Mytilidae. The phylogeny for Mytilidae (order Mytilida), which currently has no consensus in terms of systematics, is reconstructed using a data matrix of 26-27 mitogenomes. Initially, a set of 100 sequences from GenBank were downloaded and checked for their gender: whether they were female (F) or male (M) in origin. Our analysis of the new data confirms the known drastic differences between the F/M mitogenome lines in mussels. Phylogenetic reconstructions of the F-lines were performed using the combined set of genetic markers, reconstructing only protein-coding genes (PCGs), only rRNA + tRNA genes, and all genes. Additionally, the analysis includes the usage of nucleotide sequences composed of other data matrices, such as 20-68 mitogenome sequences. The time of divergence from MRCA, estimated via BEAST2, for Mytilidae is close to 293 Mya, suggesting that they originate in the Silurian Period. From all these data, a consensus for the phylogeny of the subfamily of Mytilinae and its systematics is suggested. In particular, the long-debated argument on mussel systematics was resolved as to whether Mytilidae, and the subfamily of Mytilinae, are monophyletic. The topology signal, which was strongly resolved in this paper and in the literature, has refuted the theory regarding the monophyly of Mytilinae.


Subject(s)
Evolution, Molecular , Genome, Mitochondrial , Phylogeny , Animals , Genome, Mitochondrial/genetics , Mytilidae/genetics , Mytilidae/classification , RNA, Transfer/genetics , Bivalvia/genetics , Bivalvia/classification , Mytilus/genetics , Mytilus/classification
9.
Molecules ; 29(11)2024 Jun 06.
Article in English | MEDLINE | ID: mdl-38893563

ABSTRACT

This study introduces a novel organosilicon-modified polysaccharide (Si-AP) synthesized via grafting and comprehensively evaluates its performance in water-based drilling fluids (WBDFs). The molecular structure of Si-AP was characterized using Fourier-transform infrared spectroscopy (FTIR) and 1H-NMR experiments. Thermalgravimetric analysis (TGA) confirmed the good thermal stability of Si-AP up to 235 °C. Si-AP significantly improves the rheological properties and fluid loss performance of WBDFs. With increasing Si-AP concentration, system viscosity increases, API filtration rate decreases, clay expansion is inhibited, and drilling cuttings hydration dispersion is suppressed, especially under high-temperature conditions. Additionally, mechanistic analysis indicates that the introduction of siloxane groups can effectively inhibit the thermal degradation of AP chains and enhance their high-temperature resistance. Si-AP can form a lubricating film by adsorbing on the surface of clay particles, improving mud cake quality, reducing the friction coefficient, and significantly enhancing the lubricating performance of WBDFs. Overall, Si-AP exhibits a higher temperature-resistance limit compared to AP and more effectively optimizes the lubrication, inhibition, and control of the filtration rate of WBDFs under high-temperature conditions. While meeting the requirements of drilling fluid systems under high temperatures, Si-AP also addresses environmental concerns and holds promise as an efficient solution for the exploitation of deep-seated oil and gas resources.

10.
J Biol Chem ; 298(1): 101457, 2022 01.
Article in English | MEDLINE | ID: mdl-34861238

ABSTRACT

Toxin-antitoxin (TA) systems are ubiquitous regulatory modules for bacterial growth and cell survival following stress. YefM-YoeB, the most prevalent type II TA system, is present in a variety of bacterial species. In Staphylococcus aureus, the YefM-YoeB system exists as two independent paralogous copies. Our previous research resolved crystal structures of the two oligomeric states (heterotetramer and heterohexamer-DNA ternary complex) of the first paralog as well as the molecular mechanism of transcriptional autoregulation of this module. However, structural details reflecting molecular diversity in both paralogs have been relatively unexplored. To understand the molecular mechanism of how Sa2YoeB and Sa2YefM regulate their own transcription and how each paralog functions independently, we solved a series of crystal structures of the Sa2YoeB-Sa2YefM. Our structural and biochemical data demonstrated that both paralogous copies adopt similar mechanisms of transcriptional autoregulation. In addition, structural analysis suggested that molecular diversity between the two paralogs might be reflected in the interaction profile of YefM and YoeB and the recognition pattern of promoter DNA by YefM. Interaction analysis revealed unique conformational and activating force effected by the interface between Sa2YoeB and Sa2YefM. In addition, the recognition pattern analysis demonstrated that residues Thr7 and Tyr14 of Sa2YefM specifically recognizes the flanking sequences (G and C) of the promoter DNA. Together, these results provide the structural insights into the molecular diversity and independent function of the paralogous copies of the YoeB-YefM TA system.


Subject(s)
Antitoxins , Bacterial Toxins , DNA, Bacterial , Staphylococcus aureus , Toxin-Antitoxin Systems , Antitoxins/chemistry , Antitoxins/metabolism , Bacterial Toxins/chemistry , Bacterial Toxins/metabolism , DNA, Bacterial/metabolism , Staphylococcus aureus/genetics , Staphylococcus aureus/metabolism
11.
Chemistry ; 29(26): e202203992, 2023 May 08.
Article in English | MEDLINE | ID: mdl-36722618

ABSTRACT

A 'top down' scaffold remodelling approach to library synthesis was applied to spirotricyclic ureas prepared by a complexity-generating oxidative dearomatisation. Eighteen structurally-distinct, sp3 -rich scaffolds were accessed from the parent tricycle through ring addition, cleavage and expansion strategies. Biological screening of a small compound library based on these scaffolds using the cell-painting assay demonstrated distinctive phenotypic responses engendered by different library members, illustrating the functional as well as structural diversity of the compounds.


Subject(s)
Small Molecule Libraries , Small Molecule Libraries/chemistry , Gene Library
12.
Med Mycol ; 61(2)2023 Feb 03.
Article in English | MEDLINE | ID: mdl-36746434

ABSTRACT

The phylum Microsporidia encompasses a diverse group of obligate, intracellular, and spore-forming organisms able to infect a wide range of animal hosts. Among them, Enterocytozoon bieneusi is the most frequently reported species in humans and animals. Little is known about the presence and epidemiology of E. bieneusi in wildlife. We investigated E. bieneusi occurrence and genetic diversity in wild and domestic mammals, through molecular-detection methods, from different regions across Portugal. A total of 756 samples were collected from 288, 242, and 226 wild carnivores, wild ungulates, and domestic animals, respectively. Overall, eight specimens were E. bieneusi-positive (1.1%, 8/756) obtained from five wild (Iberian lynx, Iberian wolf, red fox, stone marten, and wild boar) and one domestic (sheep) host. Nucleotide sequence analysis identified four genotypes of E. bieneusi, Type IV, Wildboar3, BEB6, and PtEbIX. Three of those genotypes belong to Groups 1 (Type IV and Wildboar3) and 2 (BEB6), which are known to contain genotypes capable of infecting a variety of hosts, including humans, highlighting their public health importance. PtEbIX belongs to the dog-specific Group 11. This study represents the first, largest, and most comprehensive molecular-based epidemiology survey carried out in Portugal in wild and domestic animals to date and the first worldwide identification of E. bieneusi in wolf species. Our study showed that wild carnivores and ungulates may act as reservoirs of zoonotic genotypes of E. bieneusi, establishing their role in maintaining the sylvatic cycle of this parasite while representing a potential source of infection for humans and domestic animals.


The identification of human-pathogenic genotypes of fungi-related Enterocytozoon bieneusi in wild carnivores and ungulates in Portugal suggests cross-species infection events and overlapping of the sylvatic and domestic transmission cycles, demonstrating a potential transmission risk to humans.


Subject(s)
Dog Diseases , Enterocytozoon , Microsporidiosis , Sheep Diseases , Swine Diseases , Humans , Swine , Animals , Dogs , Sheep , Animals, Domestic , Enterocytozoon/genetics , Portugal , Microsporidiosis/epidemiology , Microsporidiosis/veterinary , Phylogeny , Sus scrofa , Genotype , China/epidemiology , Prevalence , Feces , Zoonoses/epidemiology , Sheep Diseases/epidemiology
13.
Med Mycol ; 61(4)2023 Apr 03.
Article in English | MEDLINE | ID: mdl-37024274

ABSTRACT

Microsporidia are fungi-related eukaryotic intracellular parasites that opportunistically infect immunocompromised individuals such as those infected by the human immunodeficiency virus (HIV). Among them, Enterocytozoon bieneusi and Encephalitozoon spp. are the most clinically relevant species. We investigated the occurrence and genetic diversity of microsporidial and protist infections in mostly immunocompetent HIV-positive patients in Madrid, Spain. A structured questionnaire was used to retrieve data on factors potentially associated with an increased risk of infection, including sexual attitudes and sex-risk behaviour. Faecal samples (n = 96) from 81 HIV-positive patients were collected and analysed by molecular (PCR and Sanger sequencing) methods. Two microsporidial pathogens were detected: Ent. bieneusi (2.5%, 95% CI: 0.3-8.6) and Enc.intestinalis (4.9%, 95% CI: 1.4-12.2). The two Ent. bieneusi isolates were identified as zoonotic genotype A. Among protists, Entamoeba dispar was the species most prevalently found (33.3%, 95% CI: 23.2-44.7), followed by Blastocystis spp. (19.8%, 95% CI: 11.7-30.1), Giardia duodenalis (13.6%, 95% CI: 7.0-23.0), and Cryptosporidium spp. and Entamoeba histolytica (2.5%, 95% CI: 0.3-8.6 each). Cyclospora cayetanensis and Cystoisospora belli were not detected. Subtypes ST1 (70.6%, 12/17) and ST3 (29.4%, 5/17) were identified within Blastocystis sp., sub-assemblages AII and BIII (50%, 1/2 each) within G. duodenalis, and Cry. parvum and canine-adapted Cry. canis (50%, 1/2 each) within Cryptosporidium spp. Microsporidial and protist parasites were frequent in well-controlled, mostly immunocompetent HIV-positive patients and should be included in diagnostic algorithms when diarrhoea is present.


Opportunistic microsporidial and protist intestinal infections were relatively common in well-controlled HIV-positive patients in Madrid, Spain. These agents should be suspected and appropriately diagnosed in HIV-positive patients presenting with diarrhoea regardless of their immunological status.


Subject(s)
Cryptosporidiosis , Encephalitozoon , Enterocytozoon , Microsporidiosis , Protozoan Infections , Animals , Dogs , Humans , Cryptosporidiosis/complications , Cryptosporidiosis/epidemiology , Cryptosporidiosis/parasitology , Cryptosporidium/genetics , Encephalitozoon/genetics , Enterocytozoon/genetics , Feces , Genotype , HIV Infections/complications , HIV Infections/epidemiology , HIV Infections/veterinary , Microsporidia/genetics , Prevalence , Spain/epidemiology , Protozoan Infections/complications , Protozoan Infections/epidemiology , Protozoan Infections/parasitology , Microsporidiosis/complications , Microsporidiosis/epidemiology , Microsporidiosis/microbiology
14.
Environ Sci Technol ; 57(18): 7285-7297, 2023 05 09.
Article in English | MEDLINE | ID: mdl-37098046

ABSTRACT

Biochar-derived dissolved black carbon (DBC) molecules are dependent on the BC formation temperature and affect the fate of emerging contaminants in waters, such as polyvinyl chloride microplastic (MPPVC). However, the temperature-dependent evolution and MPPVC-interaction of DBC molecules remain unclear. Herein, we propose a novel DBC-MPPVC interaction mechanism by systematically interpreting heterogeneous correlations, sequential responses, and synergistic relationships of thousands of molecules and their linking functional groups. Two-dimensional correlation spectroscopy was proposed to combine Fourier transform-ion cyclotron resonance mass spectrometry and spectroscopic datasets. Increased temperature caused diverse DBC molecules and fluorophores, accompanied by molecular transformation from saturation/reduction to unsaturation/oxidation with high carbon oxidation states, especially for molecules with acidic functional groups. The temperature response of DBC molecules detected via negative-/positive-ion electrospray ionization sequentially occurred in unsaturated hydrocarbons → lignin-like → condensed aromatic → lipid-/aliphatic-/peptide-like → tannin-like → carbohydrate-like molecules. DBC molecular changes induced by temperature and MPPVC interaction were closely coordinated, with lignin-like molecules contributing the most to the interaction. Functional groups in DBC molecules with m/z < 500 showed a sequential MPPVC-interaction response of phenol/aromatic ether C-O, alkene C═C/amide C═O → polysaccharides C-O → alcohol/ether/carbohydrate C-O groups. These findings help to elucidate the critical role of DBCs in MP environmental behaviors.


Subject(s)
Microplastics , Plastics , Polyvinyl Chloride , Lignin , Temperature , Carbon , Soot , Ethers , Carbohydrates
15.
Environ Sci Technol ; 57(30): 11173-11184, 2023 08 01.
Article in English | MEDLINE | ID: mdl-37462533

ABSTRACT

Brown carbon (BrC) is one of the most mysterious aerosol components responsible for global warming and air pollution. Iron (Fe)-induced catalytic oxidation of ubiquitous phenolic compounds has been considered as a potential pathway for BrC formation in the dark. However, the reaction mechanism and product composition are still poorly understood. Herein, 13 phenolic precursors were employed to react with Fe under environmentally relevant conditions. Using Fourier transform ion cyclotron resonance mass spectrometry, a total of 764 unique molecular formulas were identified, and over 85% of them can be found in atmospheric aerosols. In particular, products derived from precursors with catechol-, guaiacol-, and syringol-like-based structures can be distinguished by their optical and molecular characteristics, indicating the structure-dependent formation of BrC from phenolic precursors. Multiple pieces of evidence indicate that under acidic conditions, the contribution of either autoxidation or oxygen-induced free radical oxidation to BrC formation is extremely limited. Ligand-to-Fe charge transfer and subsequent phenoxy radical coupling reactions were the main mechanism for the formation of polymerization products with high molecular diversity, and the efficiency of BrC generation was linearly correlated with the ionization potential of phenolic precursors. The present study uncovered how chemically diverse BrC products were formed by the Fe-phenolic compound reactions at the molecular level and also provide a new paradigm for the study of the atmospheric aerosol formation mechanism.


Subject(s)
Air Pollutants , Iron Compounds , Carbon , Aerosols/analysis , Iron Compounds/analysis , Iron , Guaiacol/analysis , Air Pollutants/analysis
16.
Angew Chem Int Ed Engl ; 62(26): e202305296, 2023 Jun 26.
Article in English | MEDLINE | ID: mdl-37102790

ABSTRACT

Selective functionalization of non-activated C(sp3 )-H bonds is a major challenge in chemistry, so functional groups are often used to enhance reactivity. Here, we present a gold(I)-catalyzed C(sp3 )-H activation of 1-bromoalkynes without any sort of electronic, or conformational bias. The reaction proceeds regiospecifically and stereospecifically to the corresponding bromocyclopentene derivatives. The latter can be readily modified, comprising an excellent library of diverse 3D scaffolds for medicinal chemistry. In addition, a mechanistic study has shown that the reaction proceeds via a so far unknown mechanism: a concerted [1,5]-H shift / C-C bond formation involving a gold-stabilized vinylcation-like transition state.


Subject(s)
Gold , Gold/chemistry , Catalysis
17.
Med Mycol ; 60(9)2022 Sep 30.
Article in English | MEDLINE | ID: mdl-36095135

ABSTRACT

Microsporidia comprises a diverse group of obligate, intracellular, and spore-forming parasites that infect a wide range of animals. Among them, Enterocytozoon bieneusi is the most frequently reported species in humans and other mammals and birds. Data on the epidemiology of E. bieneusi in wildlife are limited. Hence, E. bieneusi was investigated in eight wild ungulate species present in Spain (genera Ammotragus, Capra, Capreolus, Cervus, Dama, Ovis, Rupicapra, and Sus) by molecular methods. Faecal samples were collected from free-ranging (n = 1058) and farmed (n = 324) wild ungulates from five Spanish bioregions. The parasite was detected only in red deer (10.4%, 68/653) and wild boar (0.8%, 3/359). Enterocytozoon bieneusi infections were more common in farmed (19.4%, 63/324) than in wild (1.5%, 5/329) red deer. A total of 11 genotypes were identified in red deer, eight known (BEB6, BEB17, EbCar2, HLJD-V, MWC_d1, S5, Type IV, and Wildboar3) and three novel (DeerSpEb1, DeerSpEb2, and DeerSpEb3) genotypes. Mixed genotype infections were detected in 15.9% of farmed red deer. Two genotypes were identified in wild boar, a known (Wildboar3) and a novel (WildboarSpEb1) genotypes. All genotypes identified belonged to E. bieneusi zoonotic Groups 1 and 2. This study provides the most comprehensive epidemiological study of E. bieneusi in Spanish ungulates to date, representing the first evidence of the parasite in wild red deer populations worldwide. Spanish wild boars and red deer are reservoir of zoonotic genotypes of E. bieneusi and might play an underestimated role in the transmission of this microsporidian species to humans and other animals.


The fungal-related intracellular parasite Enterocytozoon bieneusi is a worldwide public health and veterinary problem. Here we demonstrated that it was present in wild boar, and wild and farmed red deer in Spain, with genotypes potentially capable of infecting humans, posing a public health risk.


Subject(s)
Deer , Enterocytozoon , Microsporidiosis , Sheep Diseases , Swine Diseases , Animals , Animals, Wild , China/epidemiology , Deer/parasitology , Enterocytozoon/genetics , Feces , Genotype , Humans , Microsporidiosis/epidemiology , Microsporidiosis/veterinary , Phylogeny , Prevalence , Sheep , Spain/epidemiology , Sus scrofa , Swine , Swine Diseases/epidemiology
18.
Bioorg Med Chem Lett ; 62: 128631, 2022 04 15.
Article in English | MEDLINE | ID: mdl-35181466

ABSTRACT

A "top-down" synthetic approach enabled the step-efficient synthesis of 21 diverse novel molecular scaffolds. The scaffolds were derived from four complex intermediates that had been prepared using cycloaddition chemistry. Scaffold-hopping of these intermediates was achieved through attachment of an additional ring, ring cleavage, ring expansion and/or ring fusion. It was shown that the resulting scaffolds could be decorated to yield diverse lead-like screening compounds.


Subject(s)
Molecular Structure , Cycloaddition Reaction
19.
Environ Sci Technol ; 56(18): 12793-12810, 2022 09 20.
Article in English | MEDLINE | ID: mdl-36037253

ABSTRACT

Soil organic matter (SOM) comprises a continuum of organic materials from granular organic debris to small organic molecules and contains more organic carbon than global vegetation and the atmosphere combined. It has remarkable effects on soil ecological functions and the global carbon cycle as well as the fate of pollutants in the terrestrial ecosystem. Therefore, characterization of SOM is an important topic in soil science, ecology, and environmental science. Chemical complexity and spatial heterogeneity are by far the two biggest challenges to our understanding of SOM. Recent developments in analytical techniques and methods provide the opportunity to reveal SOM composition at the molecular level and to observe its distribution in soils at micro- and nanoscales, which have greatly improved our understanding of SOM. This paper reviews the outstanding advances in SOM characterization regarding these two issues from target and nontarget analyses comprising molecular marker analysis, ultrahigh-resolution mass spectrometry analysis, and in situ microscopic imaging techniques such as synchrotron-based spectromicroscopy, nanoscale secondary ion mass spectrometry, and emerging electron and optical microscopic imaging techniques. However, current techniques and methods remain far from unlocking the unknown properties of SOM. We systematically point out the limitations of the current technologies and outline the future prospects for comprehensive characterization of SOM at the molecular level and micro- and nanoscales, paying particular attention to issues of environmental concern.


Subject(s)
Environmental Pollutants , Soil , Carbon , Carbon Cycle , Ecosystem , Soil/chemistry
20.
Mol Biol Rep ; 49(12): 11705-11714, 2022 Dec.
Article in English | MEDLINE | ID: mdl-36190613

ABSTRACT

BACKGROUND: Eggplant is an important vegetable that has long been cultivated in different parts of Iran. The major objectives of the eggplant breeding program are to improve fruit quality, increase yield performance through heterosis breeding, and introduce abilities of pest and disease resistance from wild relatives. In order to select suitable parents for breeding purposes, with respect to the genetic and morphological diversity of eggplant cultivars, it is necessary to have sufficient knowledge of genetic diversity and classification of germplasms. METHODS: This experiment was conducted in a randomized block design at the Seed and Plant Improvement Institute (SPII) in Karaj, Iran. Here, morphological diversity was assessed among a collection of eggplants which comprised four Iranian lines and 13 non-Iranian genotypes. For this purpose, 16 morphological traits were analyzed in the plants. Given the weakness of morphological analysis in providing precise characterizations of genetic divergence, a molecular study was also carried out by using five Simple Sequence Repeat (SSR) markers. In addition to the univariate analysis, the multi-descriptor variation was studied among the genotypes using two methods of multivariate analyses. RESULTS: The genotypes differed significantly in terms of the morphological traits. The multivariate analyses of morphological data indicated that eggplants from two different origins were clearly differentiated. Three main clusters were distinguished by a morphological UPGMA dendrogram in which non-Iranian genotypes, with the exception of 11,212, constituted cluster I and required the maximum number of days to flower, days to fruit set, and days to first harvest. Cluster II was identified with two Iranian lines BJ30, Y60, and one non-Iranian genotype (11,212) which showed the highest values of stem diameter, fruit diameter, fruit length, fruit length-to-width ratio, number of fruits per plant, and yield. Cluster III comprised two Iranian lines, D1 and D7, and showed the maximum plant height, number of internodes, number of nodes, number of leaves, number of stems, fruit weight, and fruits weight per plant. The highest and lowest intra-cluster genetic distances were observed in cluster I and cluster II, respectively. Based on SSR analysis, high levels of similarity were detected between several genotypes, namely, Y60 and 13,411; BJ30 and 1111; D7 and 13,521; 21,881 and 13,421. CONCLUSIONS: High levels of heterozygosity and polymorphism information content (PIC) were observed in this study. This not only indicated high levels of polymorphism and an equal distribution of the evaluated loci but also suggested that these genotypes can be considered for the development of diverse parental lines which are of interest in breeding programs.


Subject(s)
Solanum melongena , Genetic Variation/genetics , Genotype , Microsatellite Repeats/genetics , Plant Breeding , Polymorphism, Genetic , Solanum melongena/genetics
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