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Int J Mol Sci ; 25(9)2024 May 03.
Article En | MEDLINE | ID: mdl-38732218

Boronate esters are a class of compounds containing a boron atom bonded to two oxygen atoms in an ester group, often being used as precursors in the synthesis of other materials. The characterization of the structure and properties of esters is usually carried out by UV-visible, infrared, and nuclear magnetic resonance (NMR) spectroscopic techniques. With the aim to better understand our experimental data, in this article, the density functional theory (DFT) is used to analyze the UV-visible and infrared spectra, as well as the isotropic shielding and chemical shifts of the hydrogen atoms 1H, carbon 13C and boron 11B in the compound 4-(4,4,5,5-tetramethyl-1,3,2-dioxoborolan-2-yl)benzaldehyde. Furthermore, this study considers the change in its electronic and spectroscopic properties of this particular ester, when its boron atom is coordinated with a fluoride anion. The calculations were carried out using the LSDA and B3LYP functionals in Gaussian-16, and PBE in CASTEP. The results show that the B3LYP functional gives the best approximation to the experimental data. The formation of a coordinated covalent B-F bond highlights the remarkable sensitivity of the NMR chemical shifts of carbon, oxygen, and boron atoms and their surroundings. Furthermore, this bond also highlights the changes in the electron transitions bands n → π* and π → π* during the absorption and emission of a photon in the UV-vis, and in the stretching bands of the C=C bonds, and bending of BO2 in the infrared spectrum. This study not only contributes to the understanding of the properties of boronate esters but also provides important information on the interactions and responses optoelectronic of the compound when is bonded to a fluorine atom.

Benzaldehydes , Benzaldehydes/chemistry , Magnetic Resonance Spectroscopy , Density Functional Theory , Fluorine/chemistry , Boron/chemistry , Models, Molecular , Esters/chemistry , Spectrophotometry, Infrared , Molecular Structure , Ions/chemistry
Spectrochim Acta A Mol Biomol Spectrosc ; 316: 124349, 2024 Aug 05.
Article En | MEDLINE | ID: mdl-38692107

Fluorine (F) is a pivotal element in the formation of human dental and skeletal tissues, and the consumption of water and tea constitutes a significant source of fluoride intake. However, prolonged ingestion of water and tea with excessive fluoride content can lead to fluorosis, which poses a serious health hazard. In this manuscript, a novel turn-on fluorescent probe DCF synthesized by bis-coumarin and tert-butyldiphenylsilane (TBDPS) was introduced for detecting F- in potable water and tea infusions. By leveraging the unique chemical affinity between fluoride and silicon, F- triggers the silicon-oxygen bond cleavage in DCF, culminating in a conspicuous emission of yellow fluorescence. Validated through a succession of optical tests, this probe exhibits remarkable advantages in terms of superior selectivity, a low detection limit, a large Stokes shift, and robust interference resistance when detecting inorganic fluoride. Moreover, it can serve as portable test strips for on-site real-time identification and quantitative analysis of F-. Furthermore, the application of DCF for in-situ monitoring and imaging of F- in zebrafish and soybean root tissues proved its significant value for F- detection in both animal and plant systems. This probe potentially functions as an efficient instrument for delving into the toxic mechanisms of fluoride in physiological processes.

Coumarins , Fluorescent Dyes , Tea , Zebrafish , Fluorescent Dyes/chemistry , Animals , Coumarins/chemistry , Tea/chemistry , Drinking Water/analysis , Spectrometry, Fluorescence/methods , Fluorine/analysis , Fluorine/chemistry , Fluorides/analysis , Glycine max/chemistry , Limit of Detection , Optical Imaging/methods
PLoS One ; 19(5): e0302937, 2024.
Article En | MEDLINE | ID: mdl-38753637

With increasing global awareness of soil health, attention must be paid to fluorine exposure in soils, which poses a threat to human health. Therefore, this study aimed to study the fluorine adsorption characteristics of swine manure and straw biochars and their impact on fluorine adsorption-desorption in soil with batch experiments. The biochar samples originated from high-temperature anaerobic cracking of swine manure (350°C, 500°C, and 650°C) and straw (500°C). Results indicated that the adsorption of soil fluorine reached adsorption equilibrium at around 4 h after the mixing of swine manure and straw biochar. Fluorine adsorption kinetics using these biochars conformed to the quasi-two-stage kinetic model. The fluorine adsorption kinetics for biochar-treated soils conformed to the double-constant equation and the Elovich equation, and the soil treated with straw biochar showed the fastest fluorine adsorption rate. The adsorption isotherms of fluorine for biochars and biochar-treated soils could be fitted by the isothermal adsorption model of Langmuir and Freundlich. The maximal equilibrium quantity of fluorine was 73.66 mg/g for swine manure biochar. The soil, adding with 2% of swine manure biochar achieved with showed at 650°C had the smallest adsorption. This study also shows that the adsorption of fluorine by biochar gradually decreased with the increase of pH. Comparing with other factors, the mixture pH with biochars added had a significant effect on fluorine adsorption. The decreased fluorine adsorption capacities for soils treated with swine manure and straw biochars were closely related to the increased pH in soils after adding biochars. Considering the fluorine threat in soil, this study provides a theoretical basis for the application of biochars on soil fluorine adsorption.

Charcoal , Fluorine , Manure , Soil , Manure/analysis , Charcoal/chemistry , Fluorine/chemistry , Animals , Adsorption , Soil/chemistry , Swine , Kinetics , Hydrogen-Ion Concentration , Soil Pollutants/chemistry
J Am Chem Soc ; 146(19): 13641-13650, 2024 May 15.
Article En | MEDLINE | ID: mdl-38687675

The substitution of a single hydrogen atom in a protein by fluorine yields a site-specific probe for sensitive detection by 19F nuclear magnetic resonance (NMR) spectroscopy, where the absence of background signal from the protein facilitates the detection of minor conformational species. We developed genetic encoding systems for the site-selective incorporation of 4-fluorotryptophan, 5-fluorotryptophan, 6-fluorotryptophan, and 7-fluorotryptophan in response to an amber stop codon and used them to investigate conformational heterogeneity in a designed amino acid binding protein and in flaviviral NS2B-NS3 proteases. These proteases have been shown to present variable conformations in X-ray crystal structures, including flips of the indole side chains of tryptophan residues. The 19F NMR spectra of different fluorotryptophan isomers installed at the conserved site of Trp83 indicate that the indole ring flip is common in flaviviral NS2B-NS3 proteases in the apo state and suppressed by an active-site inhibitor.

Protein Conformation , Tryptophan , Tryptophan/chemistry , Tryptophan/analogs & derivatives , Models, Molecular , Nuclear Magnetic Resonance, Biomolecular , Fluorine/chemistry , Proteins/chemistry
Water Res ; 256: 121570, 2024 Jun 01.
Article En | MEDLINE | ID: mdl-38640564

Per- and polyfluoroalkyl substances (PFAS) are environmental contaminants of concern due to their long persistence in the environment, toxicity, and widespread presence in humans and wildlife. Knowledge regarding the extent of PFAS contamination in the environment is limited due to the need for analytical methods that can reliably quantify all PFAS, since traditional target methods using liquid chromatography (LC)-mass spectrometry (MS) fail to capture many. For a more comprehensive analysis, a total organic fluorine (TOF) method can be used as a screening tool. We combined TOF analysis with target LC-MS/MS analysis to create a statewide PFAS hotspot map for surface waters throughout South Carolina. Thirty-eight of 40 locations sampled contained detectable concentrations of organic fluorine (above 100 ng/L). Of the 33 target PFAS analyzed using LC-MS/MS, the most prevalent were perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluoroheptanoic acid (PFHpA), and perfluorohexanesulfonate (PFHxS). On average, LC-MS/MS only accounted for 2 % of the TOF measured. Locations with high TOF did not necessarily correlate to high total quantified PFAS concentrations and vice-versa, demonstrating the limitations of target PFAS analysis and indicating that LC-MS may miss highly contaminated sites. Results suggest that future surveys should utilize TOF to more comprehensively capture PFAS in water bodies.

Fluorocarbons , Tandem Mass Spectrometry , Water Pollutants, Chemical , South Carolina , Fluorocarbons/analysis , Water Pollutants, Chemical/analysis , Chromatography, Liquid , Environmental Monitoring/methods , Fluorine/analysis , Alkanesulfonic Acids/analysis , Liquid Chromatography-Mass Spectrometry , Caprylates
Int J Biol Macromol ; 268(Pt 2): 131724, 2024 May.
Article En | MEDLINE | ID: mdl-38653427

The emergence of novel well-defined biological macromolecular architectures containing fluorine moieties displaying superior functionalities can satisfactorily address many biomedical challenges. In this research, ABA- and AB-type glucose-based biological macromolecules were synthesized using acryl-2,3,4,6-tetra-O-acetyl-D-glucopyranoside with pentafluorophenyl (FPM), pentafluorobenzyl (FBM), phenyl (PM) and benzyl (BM) methacrylate-based macro-RAFT agents following RAFT polymerization. The macro-RAFT agents and the corresponding copolymers were characterized by 19F, 1H, and 13C NMR and FTIR spectroscopic techniques to understand the chemical structure, molecular weight by size-exclusion chromatography, thermal analysis by TGA and DSC. Thermal stability (Td5%) of the FPM and FBM fluoro-based polymers was observed in the range of 219-267 °C, while the non-fluoro PM and BM polymers exhibited in the range of 216-264 °C. Among the macro-RAFT agents, PFPM (107 °C, ΔH: 0.613 J/g) and PPM (103 °C, ΔH: 0.455 J/g) showed higher Tm values, while among the block copolymers, PFBM-b-PG (123 °C, ΔH: 0.412 J/g) and PG-b-PFPM-b-PG (126 °C, ΔH: 0.525 J/g) exhibited higher Tm values. PFBMT and PPM macro-RAFT agents, PPM-b-PG and PG-b-PPM-b-PG copolymer spin-coated films showed the highest hydrophobicity (120°) among the synthesized polymers. The block copolymers exhibited self-assembled segregation by using relatively hydrophobic segments as the core and hydrophilic moieties as the corona. Synthesized biological macromolecules exhibit maximum antibacterial activity towards S. aureus than E. coli bacteria. Fluorophenyl (PFPM) and non-fluorobenzyl-based (PBMT) macro-RAFT agents exhibit low IC50 values, suggesting high cytotoxicity. All the triblock copolymers exhibit lesser cytotoxicity than the di-block polymers.

Glucose , Macromolecular Substances , Glucose/chemistry , Macromolecular Substances/chemistry , Macromolecular Substances/chemical synthesis , Macromolecular Substances/pharmacology , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/chemical synthesis , Polymers/chemistry , Polymers/chemical synthesis , Polymers/pharmacology , Humans , Polymerization , Molecular Weight , Fluorine/chemistry , Chemistry Techniques, Synthetic
Environ Geochem Health ; 46(5): 170, 2024 Apr 09.
Article En | MEDLINE | ID: mdl-38592402

This study used a new X-ray fluorescence (XRF)-based analytical method with better precision and sensitivity to evaluate the fluorine concentrations in soil. It was hypothesized that the XRF method with a pellet-synthesizing procedure may effectively analyze the fluorine concentrations in soil with ease and reliability. The total fluorine concentrations determined using XRF were compared with those determined using three different types of analytical protocols-incineration/distillation, alkaline fusion, and aqua regia extraction procedures. Among the three procedures, the incineration/distillation procedure did not show reliable precision and reproducibility. In contrast, the total fluorine concentrations determined using the XRF analysis were linearly correlated with those determined using the alkaline fusion and aqua regia extraction procedures. Based on the results of the Korean waste leaching procedure and toxicity characteristics leaching procedure, the leachability of fluorine from soil and waste was not directly related to total fluorine concentrations in soil. Risk assessment also revealed that the fluorine-rich soils did not show non-carcinogenic toxic effects, despite exceeding the regulation level (800 mg/kg) in South Korea for total fluorine concentrations in soil. Our results suggest that XRF analysis in combination with the newly developed pretreatment method may be a promising alternative procedure for easily and rapidly determining the total fluorine concentration in soil. However, further efforts are needed to evaluate fluorine leachability and its associated risks in fluorine-contaminated soils.

Calcium Sulfate , Hydrochloric Acid , Nitric Acid , Phosphates , Fluorine , Reproducibility of Results , Soil , Waste Disposal Facilities
Chemosphere ; 358: 142164, 2024 Jun.
Article En | MEDLINE | ID: mdl-38685326

As the adverse effects of using plastics and perfluorinated alkyl substances become more apparent, there is a growing need for sustainable hydrophobic products. Cellulose and its derivatives are the most abundant and widely used polymers, and cellulose-based products have great potential in industries where plastics and other hydrophobic polymers are used, such as stain-resistant fabrics, food packaging, and oil-water separation applications. In this study, we extracted cellulose from water hyacinth (WH) biomass, known for its negative environmental impact, and converted it into hydrophobic cellulose. This addresses the issue of managing WH waste and creating an environmentally friendly hydrophobic material. Initially, aldehyde groups were introduced through oxidation with periodate, followed by direct octadecyl amine (ODA) grafting onto dialdehyde cellulose (DAC) via a Schiff base condensation. The resulting ODA modified cellulose (ODA-C) was dispersed in ethanol and used to coat various materials, including cotton fabric, cellulose filter paper, and packaging paper. The modified materials showed excellent hydrophobicity as measured by their water contact angles (WCAs), and the application of the coating was demonstrated for oil-water separation, stain-resistant hydrophobic fabric, and paper-based packaging materials. FTIR, XRD, and WCA analysis confirmed the successful modification of cellulose. A high separation efficiency of 99% was achieved for diesel/water separation using modified filter paper (MoFP), under gravity. On application of the coating, cotton fabric became hydrophobic and resisted staining from dye, and paper-based packaging materials became more robust by becoming water-resistant. Overall, the facile synthesis, low cost, high efficiency, and use of environmentally friendly sustainable materials make this a promising strategy for hydrophobically modifying surfaces for a wide range of applications while reducing the menace of water hyacinth.

Biomass , Cellulose , Hydrophobic and Hydrophilic Interactions , Silanes , Cellulose/chemistry , Cellulose/analogs & derivatives , Silanes/chemistry , Eichhornia/chemistry , Water/chemistry , Fluorine/chemistry , Oils/chemistry
Biochemistry ; 63(9): 1131-1146, 2024 May 07.
Article En | MEDLINE | ID: mdl-38598681

Despite the importance of proline conformational equilibria (trans versus cis amide and exo versus endo ring pucker) on protein structure and function, there is a lack of convenient ways to probe proline conformation. 4,4-Difluoroproline (Dfp) was identified to be a sensitive 19F NMR-based probe of proline conformational biases and cis-trans isomerism. Within model compounds and disordered peptides, the diastereotopic fluorines of Dfp exhibit similar chemical shifts (ΔδFF = 0-3 ppm) when a trans X-Dfp amide bond is present. In contrast, the diastereotopic fluorines exhibit a large (ΔδFF = 5-12 ppm) difference in chemical shift in a cis X-Dfp prolyl amide bond. DFT calculations, X-ray crystallography, and solid-state NMR spectroscopy indicated that ΔδFF directly reports on the relative preference of one proline ring pucker over the other: a fluorine which is pseudo-axial (i.e., the pro-4R-F in an exo ring pucker, or the pro-4S-F in an endo ring pucker) is downfield, while a fluorine which is pseudo-equatorial (i.e., pro-4S-F when exo, or pro-4R-F when endo) is upfield. Thus, when a proline is disordered (a mixture of exo and endo ring puckers, as at trans-Pro in peptides in water), it exhibits a small Δδ. In contrast, when the Pro is ordered (i.e., when one ring pucker is strongly preferred, as in cis-Pro amide bonds, where the endo ring pucker is strongly favored), a large Δδ is observed. Dfp can be used to identify inherent induced order in peptides and to quantify proline cis-trans isomerism. Using Dfp, we discovered that the stable polyproline II helix (PPII) formed in the denatured state (8 M urea) exhibits essentially equal populations of the exo and endo proline ring puckers. In addition, the data with Dfp suggested the specific stabilization of PPII by water over other polar solvents. These data strongly support the importance of carbonyl solvation and n → π* interactions for the stabilization of PPII. Dfp was also employed to quantify proline cis-trans isomerism as a function of phosphorylation and the R406W mutation in peptides derived from the intrinsically disordered protein tau. Dfp is minimally sterically disruptive and can be incorporated in expressed proteins, suggesting its broad application in understanding proline cis-trans isomerization, protein folding, and local order in intrinsically disordered proteins.

Fluorine , Proline , Proline/chemistry , Proline/analogs & derivatives , Fluorine/chemistry , Crystallography, X-Ray/methods , Protein Conformation , Magnetic Resonance Spectroscopy/methods , Peptides/chemistry , Nuclear Magnetic Resonance, Biomolecular/methods , Molecular Conformation
Bioorg Chem ; 147: 107388, 2024 Jun.
Article En | MEDLINE | ID: mdl-38678775

In this study, we investigated the potential of long-range fluorine-carbon J-coupling for determining the structures of deoxyfluorinated disaccharides. Three disaccharides, previously synthesized as potential galectin inhibitors, exhibited through-space fluorine-carbon J-couplings. In our independent conformational analysis of these disaccharide derivatives, we employed a combination of density functional theory (DFT) calculations and nuclear magnetic resonance (NMR) experiments. By comparing the calculated nuclear shieldings with the experimental carbon chemical shifts, we were able to identify the most probable conformers for each compound. A model comprising fluoromethane and methane molecules was used to study the relationship between molecular arrangements and intermolecular through-space J-coupling. Our study demonstrates the important effect of internuclear distance and molecular orientation on the magnitude of fluorine-carbon coupling. The experimental values for the fluorine-carbon through-space couplings (TSCs) of the disaccharides corresponded with values calculated for the most probable conformers identified by the conformational analysis. These results unlock the broader application of fluorine-carbon TSCs as powerful tools for conformational analysis of flexible molecules, offering valuable insights for future structural investigations.

Density Functional Theory , Disaccharides , Fluorine , Magnetic Resonance Spectroscopy , Fluorine/chemistry , Disaccharides/chemistry , Carbon/chemistry , Carbohydrate Conformation , Molecular Conformation
Molecules ; 29(7)2024 Mar 29.
Article En | MEDLINE | ID: mdl-38611815

A wide range of nano-objects is found in many applications of our everyday life. Recognition of their peculiar properties and ease of functionalization has prompted their engineering into multifunctional platforms that are supposed to afford efficient tools for the development of biomedical applications. However, bridging the gap between bench to bedside cannot be expected without a good knowledge of their behaviour in vivo, which can be obtained through non-invasive imaging techniques, such as positron emission tomography (PET). Their radiolabelling with [18F]-fluorine, a technique already well established and widely used routinely for PET imaging, with [18F]-FDG for example, and in preclinical investigation using [18F]-radiolabelled biological macromolecules, has, therefore, been developed. In this context, this review highlights the various nano-objects studied so far, the reasons behind their radiolabelling, and main in vitro and/or in vivo results obtained thereof. Then, the methods developed to introduce the radioelement are presented. Detailed indications on the chemical steps involved are provided, and the stability of the radiolabelling is discussed. Emphasis is then made on the techniques used to purify and analyse the radiolabelled nano-objects, a point that is rarely discussed despite its technical relevance and importance for accurate imaging. The pros and cons of the different methods developed are finally discussed from which future work can develop.

Engineering , Positron-Emission Tomography , Fluorine , Fluorodeoxyglucose F18 , Recognition, Psychology
J Chromatogr A ; 1722: 464899, 2024 May 10.
Article En | MEDLINE | ID: mdl-38626542

Perfluoroalkyl substances (PFAS) are persistent organic pollutants that pose significant risks to human health and the environment. Efficient and selective enrichment of these compounds was crucial for their accurate detection and quantification in complex matrices. Herein, we report a novel magnetic solid-phase extraction (MSPE) method using fluorine-functionalized magnetic amino-microporous organic network (Fe3O4@MONNH2@F7) adsorbent for the efficient enrichment of PFAS from aqueous samples. The core-shell Fe3O4@MONNH2@F7 nanosphere was synthesized, featuring magnetic Fe3O4 nanoparticles as the core and a porous amino-functionalized MONs coating as the shell, which was further modified by fluorination. The synthesized adsorbent material exhibited high specific surface area, hydrophobicity, and abundant fluorine groups, facilitating efficient and selective adsorption of PFAS via electrostatic attraction, hydrophobic-hydrophobic interactions, fluorine-fluorine interactions, π-CF interactions and hydrogen bonding. Furthermore, the MSPE method coupled with ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) allowed for the rapid, sensitive, and accurate determination of ultra-trace PFAS in real water samples, human serum, and human follicular fluid. Under optimal conditions, the established MSPE method demonstrated a linear range (2 to 2000 ng L-1), with a correlation coefficient exceeding 0.9977, low limits of detection ranging from 0.54 to 1.47 ng L-1, with a relative standard deviation (RSD) < 9.1%. Additionally, the method showed excellent performance in complex real samples (recovery ratio of 81.7 to 121.6 %). The adsorption mechanism was investigated through kinetic, isotherm, and molecular simulation studies, revealing that the introduction of fluorine groups enhanced the hydrophobic interaction and fluorine-fluorine attraction between the adsorbent and PFAS. This work provides a proof-of-concept strategy for designing adsorbent materials with high efficiency and selectivity by post-modification, which has great potential for the detection and analysis of PFAS in complex samples.

Fluorine , Fluorocarbons , Magnetite Nanoparticles , Solid Phase Extraction , Tandem Mass Spectrometry , Water Pollutants, Chemical , Fluorocarbons/chemistry , Fluorocarbons/analysis , Fluorocarbons/isolation & purification , Fluorine/chemistry , Solid Phase Extraction/methods , Tandem Mass Spectrometry/methods , Humans , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/isolation & purification , Adsorption , Chromatography, High Pressure Liquid/methods , Porosity , Magnetite Nanoparticles/chemistry , Hydrophobic and Hydrophilic Interactions , Limit of Detection
Water Sci Technol ; 89(8): 2177-2190, 2024 Apr.
Article En | MEDLINE | ID: mdl-38678417

The pH of Mount Ijen crater water is 0-2, resulting in water that is acidic and sulfurous. A fault near the Mount Ijen Crater causes seepage so that acidic water flows into the Banyupait River. Chemical elements and heavy metals originating from the river pollute groundwater and plants. As a result, people around the river consume heavy metals. This research aims to determine the quality of river water and groundwater, as well as determine community factors that are susceptible to dental fluorosis. The methodology used is field mapping and laboratory analysis. For water samples, the Atomic Absorption Spectrophotometer (AAS) method is used. The pH of river water at the research location exceeds the quality standard, namely pH 4-5.5. Meanwhile, groundwater fluorine and sulfate elements exceed quality standards, namely fluorine of 0.6171 mg/L and 0.6870 mg/L, and sulfate ranging from 325-683 mg/L. These two elements cause symptoms of dental fluorosis. Meanwhile, the community factors most susceptible to dental fluorosis are people in the adult age category, and the last level of education is elementary school. This is because the Banyupait River water and groundwater are exposed to fluorine and sulfate water originating from seepage from the Mount Ijen Crater.

Fluorosis, Dental , Groundwater , Rivers , Indonesia , Rivers/chemistry , Groundwater/chemistry , Humans , Water Pollutants, Chemical/analysis , Adult , Hydrogen-Ion Concentration , Child , Adolescent , Fluorine/analysis , Female , Male
BMC Oral Health ; 24(1): 444, 2024 Apr 12.
Article En | MEDLINE | ID: mdl-38609958

BACKGROUND: This study evaluated the shear bond strength (SBS) of two different polyetheretherketone (PEEK) and CAD-CAM materials after aging. METHODS: A total of 42 frameworks were designed and milled from 2 different PEEK discs (Copra Peek, P and BioHPP, B). P and B frameworks were divided into 3 subgroups (n = 7). 14 slices were prepared each from feldspathic ceramic (Vitablocs Mark II, VM), hybrid nanoceramic (Cerasmart, CS), and polymer-infiltrated ceramic (Vita Enamic, VE) blocks. After surface preparations, the slices were cemented to P and B surfaces. The samples were subjected to thermal aging (5000 cycles). SBS of all the samples was measured. Fractured surfaces were examined by SEM/EDX analysis. The Shapiro-Wilk, Two-way Robust ANOVA and Bonferroni correction tests were used to analyze the data (a = .05). RESULTS: Frameworks, ceramics, and frameworks x ceramics had significant differences (p < 0.05). The highest SBS value was seen in B-VM (p < 0.05). VM offered the highest SBS with both P and B. The differences between P-VM, P-CS, P-VE and B-CS and B-VE were insignificant (p > 0.05). According to EDX analysis, ytterbium and fluorine was seen in B content, unlike P. While VM and CS contained fluorine, barium, and aluminum; sodium and aluminum were observed in the VE structure. CONCLUSION: Bonding of P and B with VM offers higher SBS. VM, CS and VE did not make any difference in SBS for P, however VM showed a significant difference for B.

Aluminum , Benzophenones , Fluorine , Polymers , Humans , Polyethylene Glycols , Computer-Aided Design , Ketones
Methods Enzymol ; 696: 231-247, 2024.
Article En | MEDLINE | ID: mdl-38658081

Nonheme iron enzymes stand out as one of the most versatile biocatalysts for molecular functionalization. They facilitate a wide array of chemical transformations within biological processes, including hydroxylation, chlorination, epimerization, desaturation, cyclization, and more. Beyond their native biological functions, these enzymes possess substantial potential as powerful biocatalytic platforms for achieving abiological metal-catalyzed reactions, owing to their functional and structural diversity and high evolvability. To this end, our group has recently engineered a series of nonheme iron enzymes to employ non-natural radical-relay mechanisms for abiological radical transformations not previously known in biology. Notably, we have demonstrated that a nonheme iron enzyme, (S)-2-hydroxypropylphosphonate epoxidase from Streptomyces viridochromogenes (SvHppE), can be repurposed into an efficient and selective biocatalyst for radical fluorine transfer reactions. This marks the first known instance of a redox enzymatic process for C(sp3)F bond formation. This chapter outlines the detailed experimental protocol for engineering SvHPPE for fluorination reactions. Furthermore, the provided protocol could serve as a general guideline that might facilitate other engineering endeavors targeting nonheme iron enzymes for novel catalytic functions.

Biocatalysis , Fluorine , Halogenation , Protein Engineering , Streptomyces , Fluorine/chemistry , Protein Engineering/methods , Streptomyces/enzymology , Streptomyces/genetics , Oxidoreductases/metabolism , Oxidoreductases/genetics , Oxidoreductases/chemistry , Oxidation-Reduction , Nonheme Iron Proteins/chemistry , Nonheme Iron Proteins/metabolism , Nonheme Iron Proteins/genetics , Bacterial Proteins/genetics , Bacterial Proteins/metabolism , Bacterial Proteins/chemistry
Methods Enzymol ; 696: 199-229, 2024.
Article En | MEDLINE | ID: mdl-38658080

Fluorine (F) is an important element in the synthesis of molecules broadly used in medicine, agriculture, and materials. F addition to organic structures represents a unique strategy for tuning molecular properties, yet this atom is rarely found in Nature and approaches to produce fluorometabolites (such as fluorinated amino acids, key building blocks for synthesis) are relatively scarce. This chapter discusses the use of L-threonine aldolase enzymes (LTAs), a class of enzymes that catalyze reversible aldol addition to the α-carbon of glycine. The C-C bond formation ability of LTAs, together with their known substrate promiscuity, make them ideal for in vitro F biocatalysis. Here, we describe protocols to harness the activity of the low-specificity LTAs isolated from Escherichia coli and Pseudomonas putida on 2-fluoroacetaldehyde to efficiently synthesize 4-fluoro-L-threonine in vitro. This chapter also provides a comprehensive account of experimental protocols to implement these activities in vivo. These methods are illustrative and can be adapted to produce other fluorometabolites of interest.

Escherichia coli , Halogenation , Pseudomonas putida , Substrate Specificity , Escherichia coli/enzymology , Escherichia coli/genetics , Pseudomonas putida/enzymology , Biocatalysis , Amino Acids/chemistry , Glycine Hydroxymethyltransferase/metabolism , Glycine Hydroxymethyltransferase/chemistry , Glycine Hydroxymethyltransferase/genetics , Threonine/chemistry , Threonine/metabolism , Threonine/analogs & derivatives , Fluorine/chemistry , Aldehydes/chemistry , Aldehydes/metabolism
Methods Enzymol ; 696: 321-338, 2024.
Article En | MEDLINE | ID: mdl-38658086

Research on microbial defluorination is largely centred on controlled experiments using axenic or well defined microbial inocula. These approaches serve a relevant purpose in the field, offering fundamental biochemical and mechanistic insights on the intricacies of biological defluorination. However, they fail to account for the effective contribution of environmental microbial communities in the recycling of fluoroorganic pollutants, a highly relevant perspective from an environmental risk assessment standpoint, while also missing an important outlook on how community-wide dynamics can leverage the breakdown of C─F bonds in these recalcitrant compounds. With that in mind, this chapter provides experimental and methodological insights on the study of microbial defluorination in wild environmental communities, using this critical catabolic step as the de facto endpoint to evolve, select and cultivate microorganisms with improved defluorination performances.

Biodegradation, Environmental , Bacteria/metabolism , Bacteria/genetics , Environmental Pollutants/metabolism , Halogenation , Environmental Microbiology , Microbiota , Fluorine/metabolism , Fluorine/chemistry
Eur J Med Chem ; 271: 116446, 2024 May 05.
Article En | MEDLINE | ID: mdl-38678824

The strategic integration of fluorine atoms into anti-infectious agents has become a cornerstone in the field of medicinal chemistry, owing to the unique influence of fluorine on the chemical and biological properties of pharmaceuticals. This review examines the synthetic methodologies that enable the incorporation of fluorine into anti-infectious drugs, and the resultant clinical applications of these fluorine-enriched compounds. With a focus on clinically approved medications, the discussion extends to the molecular mechanisms. It further outlines the specific effects of fluorination, which contribute to the heightened efficacy of anti-infective therapies. By presenting a comprehensive analysis of current drugs and their developmental pathways, this review underscores the continuing evolution and significance of fluorine in advancing anti-infectious treatment options. The insights offered extend valuable guidance for future drug design and the development of next-generation anti-infectious agents.

Fluorine , Fluorine/chemistry , Humans , Anti-Infective Agents/pharmacology , Anti-Infective Agents/chemistry , Anti-Infective Agents/chemical synthesis , Drug Industry , Molecular Structure , Animals
Protein Expr Purif ; 219: 106461, 2024 Jul.
Article En | MEDLINE | ID: mdl-38460621

Nuclear magnetic resonance (NMR) spectroscopy NMR is a well-established technique for probing protein structure, dynamics and conformational changes. Taking advantage of the high signal sensitivity and broad chemical shift range of 19F nuclei, 19F NMR has been applied to investigate protein function at atomic resolution. In this report, we extend the unnatural amino acid site-specific incorporation into V. natriegens, an alternate protein expression system. The unnatural amino acid L-4-trifluoromethylphenylalanine (tfmF) was site-specifically introduced into the mitogen-activated protein kinase MEKK3 in V. natriegens using genetically encoded technology, which will be an extensive method for in-cell protein structure and dynamic investigation.

Nuclear Magnetic Resonance, Biomolecular , Phenylalanine/chemistry , Phenylalanine/metabolism , Phenylalanine/genetics , Fluorine/chemistry , Amino Acids/chemistry , Amino Acids/genetics , Amino Acids/metabolism
Chem Asian J ; 19(9): e202400074, 2024 May 02.
Article En | MEDLINE | ID: mdl-38545693

This work demonstrates the use of jute stick extract as a reducing and stabilizing agent for the synthesis of spherical gold nanoparticles (AuNPs). In UV-Vis spectroscopy, peak at 550 nm was used to confirm the formation of AuNPs. The spherical surface morphology of AuNPs was determined through SEM and TEM analysis. While XRD investigation revealed the crystallinity of the prepared AuNPs. To ensure the biocompatibility of synthesized AuNPs, a bacterial investigation was conducted with negative results towards bacterial strain. The, modified FTO with AuNPs were able to detect glucose in CV analysis and the constructed sensor displayed a wide linear range of 50 µM to 40 mM with a detection limit of 20 µM. Scan rate analysis was performed to determine the charge transfer coefficient (0.42) and Tafel slope (102 mV/decade). Furthermore, the interfacial surface mechanism is illustrated to understand the interaction of glucose with the electrode surface in an alkaline medium and the product formation through the dehydrogenation and hydrolysis process. The prepared sensor also showed good stability, reproducibility, and anti-interference capabilities. In the case of real sample analysis, we used a blood serum sample. A low RSD value (<10 %) suggests the practical use of AuNPs/FTO in real-life applications.

Biosensing Techniques , Electrochemical Techniques , Electrodes , Fluorine , Gold , Metal Nanoparticles , Tin Compounds , Gold/chemistry , Metal Nanoparticles/chemistry , Fluorine/chemistry , Tin Compounds/chemistry , Biocompatible Materials/chemistry , Biocompatible Materials/chemical synthesis , Glucose/analysis , Surface Properties , Humans , Blood Glucose/analysis , Particle Size