-
Biomolecules Mar 2021Bones are metabolically active organs. Their reconstruction is crucial for the proper functioning of the skeletal system during bone growth and remodeling, fracture... (Review)
Review
Bones are metabolically active organs. Their reconstruction is crucial for the proper functioning of the skeletal system during bone growth and remodeling, fracture healing, and maintaining calcium-phosphorus homeostasis. The bone metabolism and tissue properties are influenced by trace elements that may act either indirectly through the regulation of macromineral metabolism, or directly by affecting osteoblast and osteoclast proliferation or activity, or through becoming part of the bone mineral matrix. This study analyzes the skeletal impact of macroelements (calcium, magnesium, phosphorus), microelements (fluorine), and heavy metals (lead), and discusses the concentration of each of these elements in the various bone tissues.
Topics: Animals; Bone Density; Bone and Bones; Calcium; Fluorine; Humans; Lead; Magnesium; Phosphorus
PubMed: 33800689
DOI: 10.3390/biom11040506 -
Current Opinion in Biotechnology Apr 2022The pressing need for novel bioproduction approaches faces a limitation in the number and type of molecules accessed through synthetic biology. Halogenation is widely... (Review)
Review
The pressing need for novel bioproduction approaches faces a limitation in the number and type of molecules accessed through synthetic biology. Halogenation is widely used for tuning physicochemical properties of molecules and polymers, but traditional halogenation chemistry often lacks specificity and generates harmful by-products. Here, we pose that deploying synthetic metabolism tailored for biohalogenation represents an unique opportunity towards economically attractive and environmentally friendly organohalide production. On this background, we discuss growth-coupled selection of functional metabolic modules that harness the rich repertoire of biosynthetic and biodegradation capabilities of environmental bacteria for in vivo biohalogenation. By rationally combining these approaches, the chemical landscape of living cells can accommodate bioproduction of added-value organohalides which, as of today, are obtained by traditional chemistry.
Topics: Bacteria; Biodegradation, Environmental; Halogenation; Synthetic Biology
PubMed: 34954625
DOI: 10.1016/j.copbio.2021.11.009 -
Molecules (Basel, Switzerland) Dec 2022The development of diversity-oriented synthesis based on fluorine-containing building blocks has been one of the hot research fields in fluorine chemistry.... (Review)
Review
The development of diversity-oriented synthesis based on fluorine-containing building blocks has been one of the hot research fields in fluorine chemistry. -CF-1,3-enynes, as one type of fluorine-containing building blocks, have attracted more attention in the last few years due to their distinct reactivity. Numerous value-added trifluoromethylated or non-fluorinated compounds which have biologically relevant structural motifs, such as -, -, and -heterocycles, carboncycles, fused polycycles, and multifunctionalized allenes were synthesized from these fluorine-containing building blocks. This review summarizes the most significant developments in the area of synthesis of organofluorine compounds based on -CF-1,3-enynes, providing a detailed overview of the current state of the art.
Topics: Fluorine; Stereoisomerism
PubMed: 36558151
DOI: 10.3390/molecules27249020 -
Chembiochem : a European Journal of... Dec 2020Perfluorocarbons, saturated carbon chains in which all the hydrogen atoms are replaced with fluorine, form a separate phase from both organic and aqueous solutions.... (Review)
Review
Perfluorocarbons, saturated carbon chains in which all the hydrogen atoms are replaced with fluorine, form a separate phase from both organic and aqueous solutions. Though perfluorinated compounds are not found in living systems, they can be used to modify biomolecules to confer orthogonal behavior within natural systems, such as improved stability, engineered assembly, and cell-permeability. Perfluorinated groups also provide handles for purification, mass spectrometry, and F NMR studies in complex environments. Herein, we describe how the unique properties of perfluorocarbons have been employed to understand and manipulate biological systems.
Topics: Fluorine; Fluorocarbons; Magnetic Resonance Spectroscopy; Mass Spectrometry; Molecular Structure
PubMed: 32628804
DOI: 10.1002/cbic.202000297 -
Journal of Exposure Science &... Sep 2021Per- and polyfluoroalkyl substances (PFAS) are a class of over 4700 fluorinated compounds used in industry and consumer products. Studies have highlighted the use of...
Per- and polyfluoroalkyl substances (PFAS) are a class of over 4700 fluorinated compounds used in industry and consumer products. Studies have highlighted the use of aqueous film-forming foams (AFFFs) as an exposure source for firefighters, but little is known about PFAS occurrence inside fire stations, where firefighters spend most of their shifts. In this study, we aimed to characterize PFAS concentrations and sources inside fire stations. We measured 24 PFAS (using LC-MS/MS) and total fluorine (using particle-induced gamma ray emission) in dust from multiple rooms of 15 Massachusetts stations, many of which (60%) no longer use PFAS-containing AFFF at all and the rest of which only use it very rarely. Compared to station living rooms, turnout gear locker rooms had higher dust levels of total fluorine (p < 0.0001) and three PFAS: perfluorohexanoate (PFHxA), perfluoroheptanoate (PFHpA), and perfluorodecanoate (PFDoDA) (p < 0.05). These PFAS were also found on six wipes of station turnout gear. By contrast, the dominant PFAS in living rooms was N-ethyl perfluorooctane sulfonamidoacetic acid (N-MeFOSAA), a precursor to perfluorooctane sulfonate (PFOS) that still persists despite phase-outs almost two decades ago. The Σ PFAS accounted for less than 2% of fluorine in dust (n = 39), suggesting the potential presence of unknown PFAS. Turnout gear may be an important PFAS source in stations due to intentional additives and/or contamination from firefighting activities.
Topics: Alkanesulfonic Acids; Chromatography, Liquid; Dust; Fluorine; Fluorocarbons; Humans; Tandem Mass Spectrometry; Water Pollutants, Chemical
PubMed: 33542478
DOI: 10.1038/s41370-021-00288-7 -
Angewandte Chemie (International Ed. in... Jun 2022(Hetero)arylsulfur compounds where the S atom is in the oxidation state VI represent a large percentage of the molecular functionalities present in organic chemistry.... (Review)
Review
(Hetero)arylsulfur compounds where the S atom is in the oxidation state VI represent a large percentage of the molecular functionalities present in organic chemistry. More specifically, (hetero)aryl-S fluorides have recently received enormous attention because of their potential as chemical biology probes, as a result of their reactivity in a simple, modular, and efficient manner. Whereas the synthesis and application of the level 1 fluorination at S atoms (sulfonyl and sulfonimidoyl fluorides) have been widely studied and reviewed, the synthetic strategies towards higher levels of fluorination (levels 2 to 5) are somewhat more limited. This Minireview evaluates and summarizes the progress in the synthesis of highly fluorinated aryl-S compounds at all levels, discussing synthetic strategies, reactivity, the advantages and disadvantages of the synthetic procedures, the proposed mechanisms, and the potential upcoming opportunities.
Topics: Fluorides; Halogenation; Oxidation-Reduction
PubMed: 35303387
DOI: 10.1002/anie.202200904 -
Molecules (Basel, Switzerland) Feb 2021The synthesis of fluorine-containing small molecules has had numerous benefits of improving the quality and efficiency of many applications of these compounds. For... (Review)
Review
The synthesis of fluorine-containing small molecules has had numerous benefits of improving the quality and efficiency of many applications of these compounds. For example, fluorine adds promising functionalities in various areas of imaging (MRI, PET, and NIR); gives cell-targeting properties; and has demonstrated improvements in cell permeability, solubility, and other pharmacologic properties. For these and other numerous reasons, fluorination of molecules has grown in popularity in various fields of chemistry. Many reports show the effects observed from increasing the number of fluorine atoms on a fluorophore scaffold. This report will cover the most significant applications and improvements that fluorine has contributed to in various dye scaffolds such as BODIPY, rhodamine, phthalocyanine, and cyanine in the recent decade.
Topics: Fluorescent Dyes; Fluorine; Molecular Structure
PubMed: 33671600
DOI: 10.3390/molecules26041160 -
Chemistry (Weinheim An Der Bergstrasse,... Apr 2020Pd-mediated reactions have emerged as a powerful tool for the site-selective and bioorthogonal late-stage diversification of amino acids, peptides and related compounds.... (Review)
Review
Pd-mediated reactions have emerged as a powerful tool for the site-selective and bioorthogonal late-stage diversification of amino acids, peptides and related compounds. Indole moieties of tryptophan derivatives are susceptible to C H-activation, whereas halogenated aromatic amino acids such as halophenylalanines or halotryptophans provide a broad spectrum of different functionalisations. The compatibility of transition-metal-catalysed cross-couplings with functional groups in peptides, other biologically active compounds and even proteins has been demonstrated. This Review primarily compiles the application of different cross-coupling reactions to modify halotryptophans, halotryptophan containing peptides or halogenated, biologically active compounds derived from tryptophan. Modern approaches use regio- and stereoselective biocatalytic strategies to generate halotryptophans and derivatives on a preparative scale. The combination of bio- and chemocatalysis in cascade reactions is given by the biocompatibility and bioorthogonality of Pd-mediated reactions.
Topics: Amino Acids; Catalysis; Halogenation; Peptides; Tryptophan
PubMed: 31544296
DOI: 10.1002/chem.201903756 -
Molecules (Basel, Switzerland) Oct 2020Fluorine-containing heterocycles continue to receive considerable attention due to their unique properties. In medicinal chemistry, the incorporation of fluorine in... (Review)
Review
Fluorine-containing heterocycles continue to receive considerable attention due to their unique properties. In medicinal chemistry, the incorporation of fluorine in small molecules imparts a significant enhancement their biological activities compared to non-fluorinated molecules. In this short review, we will highlight the importance of incorporating fluorine as a basic appendage in benzothiazole and benzimidazole skeletons. The chemistry and pharmacological activities of heterocycles containing fluorine during the past years are compiled and discussed.
Topics: Agammaglobulinaemia Tyrosine Kinase; Benzimidazoles; Benzothiazoles; Chemistry, Pharmaceutical; Drug Design; Enzyme Inhibitors; Fluorine; Heterocyclic Compounds, 2-Ring; Humans; Structure-Activity Relationship
PubMed: 33066333
DOI: 10.3390/molecules25204677 -
Applied Microbiology and Biotechnology Nov 2021Fluorinated compounds are widely used in the fields of molecular imaging, pharmaceuticals, and materials. Fluorinated natural products in nature are rare, and the... (Review)
Review
Fluorinated compounds are widely used in the fields of molecular imaging, pharmaceuticals, and materials. Fluorinated natural products in nature are rare, and the introduction of fluorine atoms into organic compound molecules can give these compounds new functions and make them have better performance. Therefore, the synthesis of fluorides has attracted more and more attention from biologists and chemists. Even so, achieving selective fluorination is still a huge challenge under mild conditions. In this review, the research progress of enzymatic synthesis of fluorinated compounds is summarized since 2015, including cytochrome P450 enzymes, aldolases, fluoroacetyl coenzyme A thioesterases, lipases, transaminases, reductive aminases, purine nucleoside phosphorylases, polyketide synthases, fluoroacetate dehalogenases, tyrosine phenol-lyases, glycosidases, fluorinases, and multienzyme system. Of all enzyme-catalyzed synthesis methods, the direct formation of the C-F bond by fluorinase is the most effective and promising method. The structure and catalytic mechanism of fluorinase are introduced to understand fluorobiochemistry. Furthermore, the distribution, applications, and future development trends of fluorinated compounds are also outlined. Hopefully, this review will help researchers to understand the significance of enzymatic methods for the synthesis of fluorinated compounds and find or create excellent fluoride synthase in future research.Key points• Fluorinated compounds are distributed in plants and microorganisms, and are used in imaging, medicine, materials science.• Enzyme catalysis is essential for the synthesis of fluorinated compounds.• The loop structure of fluorinase is the key to forming the C-F bond.
Topics: Aldehyde-Lyases; Catalysis; Fluorine; Halogenation; Transaminases
PubMed: 34625820
DOI: 10.1007/s00253-021-11608-0