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Applied Microbiology and Biotechnology Mar 2024Microalgae are rich in fatty acids, proteins, and other nutrients, which have gained the general attention of researchers all over the world. For the development of...
Microalgae are rich in fatty acids, proteins, and other nutrients, which have gained the general attention of researchers all over the world. For the development of Chlorella vulgaris in food and feed industry, this study was conducted to investigate the differences in C. vulgaris' growth and nutritional components under different culture conditions (autotrophic, heterotrophic, photoheterotrophic) and the internal factors through cell counting in combination with transcriptome and nutrient analyses. The results showed that, under the photoheterotrophic condition, Chlorella's growth and the contents of lipid and protein were significantly higher than that under the heterotrophic condition, and the moisture content was lower than that under the heterotrophic condition. The saturated fatty acid content under the photoheterotrophic condition was the lowest, while the polyunsaturated fatty acid content was significantly higher than those under the other two conditions. There were 46,583 differentially expressed genes (DEGs), including 33,039 up-regulated DEGs (70.93%) and 13,544 down-regulated DEGs (29.07%), under the photoheterotrophic condition in comparison with the autotrophic condition. The fold change between the two conditions of samples of up-regulated genes was higher than that of the down-regulated genes. The KEGG enrichment showed that the up-regulated DEGs in the photoheterotrophic condition were significantly enriched in 5 pathways, including protein processing in endoplasmic reticulum pathway, photosynthesis pathway, photosynthesis-antenna protein pathway, endocytosis pathway, and phosphonate and phosphinate metabolism pathway. DEGs related to fatty acid metabolic pathways were significantly enriched in the fatty acid biosynthesis pathway and the biosynthesis of unsaturated fatty acid pathway. The qPCR analysis showed that the expression pattern of the selected genes was consistent with that of transcriptome analysis. The results of this study lay a theoretical foundation for the large-scale production of Chlorella and its application in food, feed, and biodiesel. KEY POINTS: • Nutrient levels under photoheterotrophic condition were higher than other conditions. • Six important pathways were discovered that affect changes in nutritional composition. • Explored genes encode important enzymes in the differential metabolic pathways.
Topics: Chlorella vulgaris; Fatty Acids; Photosynthesis; Metabolic Networks and Pathways; Nutrients; Biomass; Microalgae; Biofuels
PubMed: 38507095
DOI: 10.1007/s00253-024-13090-w -
Bioorganic & Medicinal Chemistry Apr 2024Reactions for drug synthesis under cell-like conditions or even inside living cells can potentially be used e.g., to minimize toxic side effects, to maximize bioactive...
Reactions for drug synthesis under cell-like conditions or even inside living cells can potentially be used e.g., to minimize toxic side effects, to maximize bioactive compound efficacy and/or to address drug delivery problems. Those reactions should be bioorthogonal to enable the generation of drug-like compounds with sufficiently good yields. In the known bioorthogonal Michael reactions, using thiols and phosphines as nucleophiles (e.g., in CS and CP bond formation reactions) is very common. No bioorthogonal Michael addition with a carbon nucleophile is known yet. Therefore, the development of such a reaction might be interesting for future drug discovery research. In this work, the metal-free Michael addition between cyclohexanone and various trans-β-nitrostyrenes (CC bond formation reaction), catalysed by a dipeptide salt H-Pro-Phe-ONa, was investigated for the first time in the presence of glutathione (GSH) and in phosphate-buffered saline (PBS). We demonstrated that with electron-withdrawing substituents on the aromatic ring and in β-position of the trans-β-nitrostyrene yields up to 64% can be obtained under physiological conditions, indicating a potential bioorthogonality of the studied Michael reaction. In addition, the selected Michael products demonstrated activity against human ovarian cancer cells A2780. This study opens up a new vista for forming bioactive compounds via CC bond formation Michael reactions under physiological (cell-like) conditions.
Topics: Humans; Female; Cell Line, Tumor; Ovarian Neoplasms; Carbon; Sulfhydryl Compounds
PubMed: 38492540
DOI: 10.1016/j.bmc.2024.117650 -
Advanced Science (Weinheim,... Jun 2024A series of new pyrazole-alkyl phosphine ligands with varying cycloalkyl ring sizes that enable additive-free regio- and chemoselective C─H arylation of heterocycles...
Regio- and Chemoselective Palladium-Catalyzed Additive-Free Direct C─H Functionalization of Heterocycles with Chloroaryl Triflates Using Pyrazole-Alkyl Phosphine Ligands.
A series of new pyrazole-alkyl phosphine ligands with varying cycloalkyl ring sizes that enable additive-free regio- and chemoselective C─H arylation of heterocycles are reported. Excellent α/β selectivity of various heterocycles such as benzo[b]thiophene, thiophene, furan, benzofuran, and thiazole can be achieved using these ligands, along with excellent chemoselectivity of C─Cl over C─OTf of chloroaryl triflates. Mechanistic studies supported by both experimental findings and density functional theory calculations indicate that the pyrazole phosphine ligands with optimal ring sizes allow the reaction to proceed with a lower energy barrier via a concerted metalation-deprotonation pathway.
PubMed: 38482750
DOI: 10.1002/advs.202309192 -
Journal of the American Chemical Society Mar 2024Methods to access chiral sulfur(VI) pharmacophores are of interest in medicinal and synthetic chemistry. We report the desymmetrization of unprotected sulfonimidamides...
Methods to access chiral sulfur(VI) pharmacophores are of interest in medicinal and synthetic chemistry. We report the desymmetrization of unprotected sulfonimidamides via asymmetric acylation with a cinchona-phosphinate catalyst. The desired products are formed in excellent yield and enantioselectivity with no observed bis-acylation. A data-science-driven approach to substrate scope evaluation was coupled to high throughput experimentation (HTE) to facilitate statistical modeling in order to inform mechanistic studies. Reaction kinetics, catalyst structural studies, and density functional theory (DFT) transition state analysis elucidated the turnover-limiting step to be the collapse of the tetrahedral intermediate and provided key insights into the catalyst-substrate structure-activity relationships responsible for the origin of the enantioselectivity. This study offers a reliable method for accessing enantioenriched sulfonimidamides to propel their application as pharmacophores and serves as an example of the mechanistic insight that can be gleaned from integrating data science and traditional physical organic techniques.
Topics: Molecular Structure; Stereoisomerism; Data Science; Cinchona Alkaloids; Catalysis; Acylation
PubMed: 38480482
DOI: 10.1021/jacs.4c00374 -
Advanced Science (Weinheim,... May 2024Despite the simplicity and abundance of ethylene, its practical application presents significant hurdles due to its nature as a highly flammable gas. Herein, a strategic...
Despite the simplicity and abundance of ethylene, its practical application presents significant hurdles due to its nature as a highly flammable gas. Herein, a strategic use of easily handled vinyl ether is reported as a latent ethylene surrogate achieved via a spin-center shift (SCS) pathway, enabling the successful three-component reaction that bridges heteroarenes and various coupling partners, including sulfinates, thiols, and phosphine oxides. Through a photoredox catalytic process, α-oxy radicals are generated by combining various radicals with phenyl vinyl ether, which are subsequently added to N-heteroarenes. Subsequently, the radical-mediated SCS pathway serves as the driving force for C─O bond cleavage, effectively engaging the phenoxy group as a leaving group. In addition, by broadening the utility of the method, a valuable synthon is provided for efficient C─H vinylation of N-heteroarenes following sulfonyl group elimination. This approach not only enriches the toolbox of synthetic methodology but also provides a more streamlined alternative, circumventing the challenges associated with direct ethylene gas usage. The versatility of the method, particularly evident in late-stage functionalizations of medicinally relevant molecules and peptides, underscores its capability to produce invaluable three-component compounds and vinylated N-heteroarene derivatives.
PubMed: 38477022
DOI: 10.1002/advs.202309800 -
Frontiers in Chemistry 2024Anhydrous hydrogen fluoride (AHF), a critical raw material for industries such as aluminum, pharmaceuticals, and petroleum, has traditionally been sourced from... (Review)
Review
Anhydrous hydrogen fluoride (AHF), a critical raw material for industries such as aluminum, pharmaceuticals, and petroleum, has traditionally been sourced from fluorite-a non-renewable mineral. The unsustainable reliance on fluorite has catalyzed the search for alternative AHF production methods. A promising substitute is fluorosilicic acid (FSA), a byproduct of the phosphate fertilizer industry previously deemed waste. Transforming fluorosilicic acid into AHF not only yields a valuable resource but also addresses the environmental and economic challenges associated with waste management. The innovative practice of producing AHF from fluorosilicic acid signals a shift towards sustainable chemical production by capitalizing on waste, potentially diminishing reliance on fluorite and reducing the industry's environmental impact. This review thoroughly dissects the AHF synthesis process from fluorosilicic acid. Despite the acknowledged importance of fluorinated compounds in numerous industrial applications, research on their synthesis from fluorosilicic acid is limited and fragmented. This review seeks to amalgamate this scattered information by closely scrutinizing diverse industrial processing methods. Additionally, it explores the current and future landscape, economic feasibility, and strategies to navigate the obstacles inherent in synthesizing AHF from fluorosilicic acid. It also assesses the environmental impact of these methods, thereby contributing to the dialogue in this emerging field. The primary aim of this manuscript is to foster further research and promote the industrial uptake of this sustainable process. Highlighting the challenges and proposing potential improvements, the review supports the responsible reuse of waste and advocates for advancements in industrial practices.
PubMed: 38476650
DOI: 10.3389/fchem.2024.1372981 -
Molecules (Basel, Switzerland) Mar 2024A convenient protocol for the synthesis of 25,26,27-tribenzoyl-28-[(()-1-diphenylphos- phanyl-propan-2-yl)oxy]-calix[4]arene via stereospecific methylation on Evans'...
A convenient protocol for the synthesis of 25,26,27-tribenzoyl-28-[(()-1-diphenylphos- phanyl-propan-2-yl)oxy]-calix[4]arene via stereospecific methylation on Evans' oxazolidinone moiety was reported. According to the C NMR analysis of this phosphine, the calix[4]arene skeleton adopted a 1,3-alternate conformation. The latter conformation of the macrocycle and the ()-chirality of the carbon atom bearing the methyl substituent were confirmed by a single-crystal X-ray diffraction study. After coordination of the phosphinated ligand to the dimeric [RuCl(-cymene)] organometallic precursor, the resulting arene-ruthenium complex was tested in the asymmetric reduction of acetophenone and alcohol was obtained with modest enantiomeric excess.
PubMed: 38474667
DOI: 10.3390/molecules29051156 -
Molecules (Basel, Switzerland) Mar 2024A wide range of platinum(0)-η-()-1,2-ditosylethene complexes bearing isocyanide, phosphine and -heterocyclic carbene ancillary ligands have been prepared with high...
Platinum(0)-η-1,2-()ditosylethene Complexes Bearing Phosphine, Isocyanide and -Heterocyclic Carbene Ligands: Synthesis and Cytotoxicity towards Ovarian and Breast Cancer Cells.
A wide range of platinum(0)-η-()-1,2-ditosylethene complexes bearing isocyanide, phosphine and -heterocyclic carbene ancillary ligands have been prepared with high yields and selectivity. All the novel products underwent thorough characterization using spectroscopic techniques, including NMR and FT-IR analyses. Additionally, for some compounds, the solid-state structures were elucidated through X-ray diffractometry. The synthesized complexes were successively evaluated for their potential as anticancer agents against two ovarian cancer cell lines (A2780 and A2780) and one breast cancer cell line (MDA-MB-231). The majority of the compounds displayed promising cytotoxicity within the micromolar range against A2780 and MDA-MB-231 cells, with IC values comparable to or even surpassing those of cisplatin. However, only a subset of compounds was cytotoxic against cisplatin-resistant cancer cells (A2780). Furthermore, the assessment of antiproliferative activity on MRC-5 normal cells revealed certain compounds to exhibit in vitro selectivity. Notably, complexes , and showed low cytotoxicity towards normal cells (IC > 100 µM) while concurrently displaying potent cytotoxicity against cancer cells.
Topics: Female; Humans; Cisplatin; Platinum; Cell Line, Tumor; Cyanides; Breast Neoplasms; Spectroscopy, Fourier Transform Infrared; Ovarian Neoplasms; Coordination Complexes; Antineoplastic Agents; Ligands; Methane; Phosphines
PubMed: 38474631
DOI: 10.3390/molecules29051119 -
Scientific Reports Mar 2024Herein, core-shell magnetic nanoparticles are modified with imidazolium-tagged phosphine and propylene glycol moieties and used for the stabilization of bimetallic AuCu...
Herein, core-shell magnetic nanoparticles are modified with imidazolium-tagged phosphine and propylene glycol moieties and used for the stabilization of bimetallic AuCu nanoparticles. The structure and morphology of the prepared material are identified with SEM, TEM, XRD, XPS, atomic absorption spectroscopy, Fourier translation infrared spectroscopy, and a vibrating sample magnetometer. This hydrophilic magnetic bimetallic catalyst is applied in the reduction of toxic nitroarenes and reductive degradation of hazardous organic dyes such as methyl orange (MO), methyl red (MR), and rhodamine B (RhB), as well as in the degradation of tetracycline (TC). This magnetic AuCu catalyst indicated superior activity in all three mentioned reactions in comparison with its single metal Au and Cu analogs. This catalyst is recycled for 17 consecutive runs in the reduction of 4-nitrophenol to 4-aminophenol without a significant decrease in catalytic activity and recycled catalyst is characterized.
PubMed: 38462664
DOI: 10.1038/s41598-024-56559-4 -
Scientific Reports Mar 2024In these studies, we designed and investigated the potential anticancer activity of five iron(II) cyclopentadienyl complexes bearing different phosphine and phosphite...
In these studies, we designed and investigated the potential anticancer activity of five iron(II) cyclopentadienyl complexes bearing different phosphine and phosphite ligands. All complexes were characterized with spectroscopic analysis viz. NMR, FT-IR, ESI-MS, UV-Vis, fluorescence, XRD (for four complexes) and elemental analyses. For biological studies, we used three types of cells-normal peripheral blood mononuclear (PBM) cells, leukemic HL-60 cells and non-small-cell lung cancer A549 cells. We evaluated cell viability and DNA damage after cell incubation with these complexes. We observed that all iron(II) complexes were more cytotoxic for HL-60 cells than for A549 cells. The complex CpFe(CO)(P(OPh))(η-N-maleimidato) 3b was the most cytotoxic with IC = 9.09 µM in HL-60 cells, IC = 19.16 µM in A549 and IC = 5.80 µM in PBM cells. The complex CpFe(CO)(P(Fu))(η-N-maleimidato) 2b was cytotoxic only for both cancer cell lines, with IC = 10.03 µM in HL-60 cells and IC = 73.54 µM in A549 cells. We also found the genotoxic potential of the complex 2b in both types of cancer cells. However, the complex CpFe(CO)(η-N-maleimidato) 1 which we studied previously, was much more genotoxic than complex 2b, especially for A549 cells. The plasmid relaxation assay showed that iron(II) complexes do not induce strand breaks in fully paired ds-DNA. The DNA titration experiment showed no intercalation of complex 2b into DNA. Molecular docking revealed however that complexes CpFe(CO)(PPh) (η-N-maleimidato) 2a, 2b, 3b and CpFe(CO)(P(OiPr))(η-N-maleimidato) 3c have the greatest potential to bind to mismatched DNA. Our studies demonstrated that the iron(II) complex 1 and 2b are the most interesting compounds in terms of selective cytotoxic action against cancer cells. However, the cellular mechanism of their anticancer activity requires further research.
Topics: Humans; Molecular Docking Simulation; Phosphites; Coordination Complexes; Iron; Carcinoma, Non-Small-Cell Lung; Leukocytes, Mononuclear; Spectroscopy, Fourier Transform Infrared; Lung Neoplasms; DNA; Maleimides; Ferrous Compounds; Antineoplastic Agents; Ligands; Cell Line, Tumor; Phosphines
PubMed: 38454122
DOI: 10.1038/s41598-024-56339-0