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1.
World J Microbiol Biotechnol ; 40(10): 323, 2024 Sep 18.
Artigo em Inglês | MEDLINE | ID: mdl-39292329

RESUMO

The important role of dihydroxynaphthalene-(DHN) melanin in enhancing fungal stress resistance and its importance in fungal development and pathogenicity are well-established. This melanin also aids biocontrol fungi in surviving in the environment and effectively infecting insects. However, the biosynthetic origin of melanin in the biocontrol agents, Metarhizium spp., has remained elusive due to the complexity resulting from the divergence of two DHN-like biosynthetic pathways. Through the heterologous expression of biosynthetic enzymes from these two pathways in baker's yeast Saccharomyces cerevisiae, we have confirmed the presence of DHN biosynthesis in M. roberstii, and discovered a novel naphthopyrone intermediate, 8, that can produce a different type of pigment. These two pigment biosynthetic pathways differ in terms of polyketide intermediate structures and subsequent modification steps. Stress resistance studies using recombinant yeast cells have demonstrated that both DHN and its intermediates confer resistance against UV light prior to polymerization; a similar result was observed for its naphthopyrone counterpart. This study contributes to the understanding of the intricate and diverse biosynthetic mechanisms of fungal melanin and has the potential to enhance the application efficiency of biocontrol fungi such as Metarhizium spp. in agriculture.


Assuntos
Vias Biossintéticas , Melaninas , Metarhizium , Saccharomyces cerevisiae , Metarhizium/metabolismo , Metarhizium/genética , Melaninas/metabolismo , Melaninas/biossíntese , Saccharomyces cerevisiae/metabolismo , Saccharomyces cerevisiae/genética , Naftóis/metabolismo , Proteínas Fúngicas/metabolismo , Proteínas Fúngicas/genética , Raios Ultravioleta
2.
Water Res ; 264: 122219, 2024 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-39121820

RESUMO

The presence of actinobacteria in reservoirs can lead to taste and odor issues, posing potential risks to the safety of drinking water supply. However, the response of actinobacterial communities to environmental factors in drinking water reservoirs remains largely unexplored. To address this gap, this study investigated the community structure and metabolic characteristics of odor-producing actinobacteria in water reservoirs across northern and southern China. The findings revealed differences in the actinobacterial composition across the reservoirs, with Mycobacterium sp. and Candidatus Nanopelagicus being the most prevalent genera. Notably, water temperature, nutrient levels, and metal concentrations were associated with differences in actinobacterial communities, with stochastic processes playing a major role in shaping the community assembly. In addition, three strains of odor-producing actinobacteria were cultured in raw reservoir water, namely Streptomyces antibioticus LJH21, Streptomyces sp. ZEU13, and Streptomyces sp. PQK19, with peak ATP concentrations of 51 nmol/L, 66 nmol/L, and 70 nmol/L, respectively, indicating that odor-producing actinobacteria could remain metabolically active under poor nutrient pressure. Additionally, Streptomyces antibioticus LJH21 produced the highest concentration of geosmin at 24.4 ng/L. These findings enhance our understanding of regional variances and reproductive metabolic mechanisms of actinobacteria in drinking water reservoirs, providing a solid foundation for improving drinking water quality control, especially for taste and odor.


Assuntos
Actinobacteria , Água Potável , Odorantes , Paladar , Água Potável/microbiologia , China , Abastecimento de Água , Microbiologia da Água , Naftóis
3.
J Chromatogr A ; 1732: 465231, 2024 Sep 13.
Artigo em Inglês | MEDLINE | ID: mdl-39133951

RESUMO

Macrocycles play vital roles in supramolecular chemistry and chromatography. 1,1'-Bi-2-naphthol (BINOL)-based chiral polyimine macrocycles are an emerging class of chiral macrocycles that can be constructed by one-step aldehyde-amine condensation of BINOL derivatives with other building blocks. These macrocycles exhibit good characteristics, such as facile preparation, rigid cyclic structures, multiple chiral centers, and defined molecular cavities, that make them good candidates as new chiral recognition materials for chromatographic enantioseparations. In this study, a BINOL-based [2+2] chiral polyimine macrocycle was synthesized by one-step condensation of enantiopure (S)-2,2'-dihydroxy-[1,1'-binaphthalene]-3,3'-dicarboxaldehyde with (1R,2R)-1,2-diaminocyclohexane. The product was modified with 5-bromo-1-pentene and then attached to thiolated silica using click chemistry to construct a new chiral stationary phase (CSP). The enantioselectivity of the new CSP was explored by separating various racemates under normal phase (NP) and reversed phase (RP) high performance liquid chromatography (HPLC). Thirteen racemates and eight racemates were enantioseparated under the two separation modes, respectively, including chiral alcohols, phenols, esters, ketones, amines, and organic acids. Among them, nine racemates achieved baseline separation under NP-HPLC and seven racemates achieved baseline separation under RP-HPLC. High resolution separation was observed with benzoin (Rs = 5.10), epinephrine (Rs = 4.98), 3-benzyloxy-1,2-propanediol (Rs = 4.42), and 4,4'-dimethylbenzoin (Rs = 4.52) in NP-HPLC, and with 4-methylbenzhydrol (Rs = 4.72), benzoin ethyl ether (Rs = 3.79), 1-phenyl-1-pentanol (Rs = 3.68), and 1-(3-bromophenyl)ethanol (Rs = 3.60) in RP-HPLC. Interestingly, the CSP complemented Chiralcel OD-H, Chiralpak AD-H, and CYCLOBOND I 2000 RSP columns for resolution of these test racemates, separating several racemic compounds that could not be well separated by the three commercially available columns. The influences of injected sample amount on separation were also evaluated. It was found that the column exhibited excellent stability and reproducibility after hundreds of injections, and the relative standard deviations (n = 5) of the retention time and resolution were less than 0.49% and 0.69%, respectively. This study indicates that the BINOL-based chiral macrocycle has great potential for HPLC enantioseparation.


Assuntos
Compostos Macrocíclicos , Naftóis , Dióxido de Silício , Cromatografia Líquida de Alta Pressão/métodos , Estereoisomerismo , Naftóis/química , Naftóis/isolamento & purificação , Compostos Macrocíclicos/química , Compostos Macrocíclicos/isolamento & purificação , Dióxido de Silício/química
4.
J Chromatogr A ; 1731: 465174, 2024 Aug 30.
Artigo em Inglês | MEDLINE | ID: mdl-39111195

RESUMO

The present work describes a quick, simple, and efficient method based on the use of layered double hydroxides (LDH) coupled to dispersive solid phase micro-extraction (DSPME) to remove α-naphthol (α-NAP) and ß-naphthol (ß-NAP) isomers from water samples. Three different LDHs (MgAl-LDH, NiAl-LDH, and CoAl-LDH) were used to study how the interlayer anion and molar ratio affected the removal performance. The critical factors in the DSPME procedure (pH, LDH amount, contact time) were optimized by the univariate method under the optimal conditions: pH, 4-8; LDH amount, 5 mg; and contact time, 2.5 min. The method can be successfully applied in real sample waters, removing NAP isomers even in ultra-trace concentrations. The large volume sample stacking (LVSS-CE) technique provides limits of detections (LODs) of 5.52 µg/L and 6.36 µg/L for α-naphthol and ß-naphthol, respectively. The methodology's precision was evaluated on intra- and inter-day repeatability, with %RSD less than 10% in all cases. The MgAl/Cl--LDH selectivity was tested in the presence of phenol and bisphenol A, with a removal rate of >92.80%. The elution tests suggest that the LDH MgAl/Cl--LDH could be suitable for pre-concentration of α-naphthol and ß-naphthol in future works.


Assuntos
Eletroforese Capilar , Limite de Detecção , Naftóis , Microextração em Fase Sólida , Poluentes Químicos da Água , Naftóis/química , Naftóis/análise , Naftóis/isolamento & purificação , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/isolamento & purificação , Poluentes Químicos da Água/química , Eletroforese Capilar/métodos , Microextração em Fase Sólida/métodos , Hidróxidos/química , Isomerismo , Reprodutibilidade dos Testes , Concentração de Íons de Hidrogênio
5.
Sci Rep ; 14(1): 15230, 2024 07 02.
Artigo em Inglês | MEDLINE | ID: mdl-38956405

RESUMO

Exposure of firefighting instructors to polycyclic aromatic hydrocarbons (PAHs) such as naphthalene is unavoidable during live fire training. The study aimed to investigate naphthalene uptake by measuring the urinary excretion of the naphthalene metabolite 1,2-dihydroxynaphthalene (DHN), to describe the DHN elimination kinetics and to evaluate the results by comparison to further biomarkers of PAH exposure. N = 6 male non-smoking firefighting instructors completed five training sessions each in a residential fire simulation unit under respiratory protection. All participants provided two urine samples before and another seven samples within an 18-h-interval after each session. DHN was detected by gas chromatography/tandem mass spectrometry (GC-MS/MS) in all samples (n = 237) with median concentrations ranging from 3.3 µg/g crea. (range 0.9-10.2) before exposure to 134.2 µg/g crea. (43.4-380.4) post exposure. Maximum elimination found 3.3 h (median) after onset of exposure decreased with a mean half-life of 6.6 h to 27.1 µg/g crea. (15.7-139.5) 18 h after training. DHN sensitively indicated a presumed dermal naphthalene intake during training, showing similar elimination kinetics like other naphthalene metabolites. Internal exposure of the participants transiently exceeded exposures determined for non-smokers in the general population, but was lower than at other workplaces with PAH exposure. Despite limited uptake, accumulation is possible with daily exposure.


Assuntos
Bombeiros , Naftóis , Exposição Ocupacional , Hidrocarbonetos Policíclicos Aromáticos , Humanos , Masculino , Exposição Ocupacional/análise , Adulto , Hidrocarbonetos Policíclicos Aromáticos/urina , Hidrocarbonetos Policíclicos Aromáticos/análise , Naftóis/urina , Naftalenos/urina , Naftalenos/farmacocinética , Naftalenos/análise , Eliminação Renal , Cromatografia Gasosa-Espectrometria de Massas , Biomarcadores/urina , Pessoa de Meia-Idade , Incêndios
6.
J Agric Food Chem ; 72(28): 15865-15874, 2024 Jul 17.
Artigo em Inglês | MEDLINE | ID: mdl-38955350

RESUMO

Geosmin, a ubiquitous volatile sesquiterpenoid of microbiological origin, is causative for deteriorating the quality of many foods, beverages, and drinking water, by eliciting an undesirable "earthy/musty" off-flavor. Moreover, and across species from worm to human, geosmin is a volatile, chemosensory trigger of both avoidance and attraction behaviors, suggesting its role as semiochemical. Volatiles typically are detected by chemosensory receptors of the nose, which have evolved to best detect ecologically relevant food-related odorants and semiochemicals. An insect receptor for geosmin was recently identified in flies. A human geosmin-selective receptor, however, has been elusive. Here, we report on the identification and characterization of a human odorant receptor for geosmin, with its function being conserved in orthologs across six mammalian species. Notably, the receptor from the desert-dwelling kangaroo rat showed a more than 100-fold higher sensitivity compared to its human ortholog and detected geosmin at low nmol/L concentrations in extracts from geosmin-producing actinomycetes.


Assuntos
Naftóis , Receptores Odorantes , Sesquiterpenos , Animais , Humanos , Naftóis/metabolismo , Naftóis/química , Naftóis/análise , Sesquiterpenos/metabolismo , Sesquiterpenos/análise , Sesquiterpenos/química , Receptores Odorantes/metabolismo , Receptores Odorantes/genética , Receptores Odorantes/química , Ratos , Feromônios/metabolismo , Feromônios/química , Feromônios/análise , Odorantes/análise
7.
Talanta ; 279: 126590, 2024 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-39053363

RESUMO

A fast and non-separative screening strategy is presented for the analysis of five urinary metabolites of polycyclic aromatic hydrocarbons (PAHs), namely 2-naphthol, 1-acenaphthenol, 2-hydroxyfluorene, 9-phenanthrol and 1-hydroxypyrene. These hydroxylated derivatives (OH-PAHs) were subjected to enzymatic hydrolysis and were extracted from urine using a liquid-liquid extraction (LLE). The profile signals were obtained by direct injection of the sample into a programmed temperature vaporizer coupled to a quadrupole mass spectrometer via a deactivated fused silica tubing (PTV-qMS). Semi-quantitative determination was carried out by means of partial least squares regression (PLS1) using urine samples free of the analytes and spiked at several uncorrelated concentration levels. The multivariate calibration models worked satisfactorily, with errors ranging between 30 and 33 % for all the analytes except for 1-acenaphthenol that provided an error of 39 % when external validation set was considered. The repeatability and reproducibility, expressed as relative standard deviation (RSD), were ranged between 8-16 % and 11-18 %, respectively. The proposed method could be a useful tool for semi-quantification purposes of five OH-PAHs in urine samples, identifying positive samples for subsequent further chromatographic separation (confirmation), thus saving time and costs.


Assuntos
Hidrocarbonetos Policíclicos Aromáticos , Humanos , Hidrocarbonetos Policíclicos Aromáticos/urina , Naftóis/urina , Espectrometria de Massas/métodos , Extração Líquido-Líquido , Pirenos/urina , Pirenos/química , Análise dos Mínimos Quadrados , Fenantrenos/urina , Reprodutibilidade dos Testes , Fluorenos
8.
Mikrochim Acta ; 191(7): 364, 2024 06 03.
Artigo em Inglês | MEDLINE | ID: mdl-38831034

RESUMO

CdIn2S4 and zinc tetrakis(4-carboxyphenyl)porphyrin (ZnTCPP) were synthesized by hydrothermal method, and an organic dye-sensitized inorganic semiconductor ZnTCPP/CdIn2S4 type II heterojunction was constructed on a fluorine-doped tin oxide (FTO) substrate electrode. A sandwich immunostructure for signal-attenuation photoelectrochemical (PEC) detection of cardiac troponin I (cTnI) was constructed using the ZnTCPP/CdIn2S4/FTO photoanode and a horseradish peroxidase (HRP)-ZnFe2O4-Ab2-bovine serum albumin (BSA) immunolabeling complex. The bioenzyme HRP and the HRP-like nanozyme ZnFe2O4 can co-catalyze the oxidation of 4-chloro-1-naphthol (4-CN) by H2O2 to produce an insoluble precipitate on the photoanode, thus notably reducing the anodic photocurrent for quantitative determination of cTnI. Under the optimal conditions, the photocurrent at 0 V vs. SCE in 0.1 M phosphate buffer solution (pH 7.40) containing 0.1 M ascorbic acid was linear with the logarithm of cTnI concentration from 500 fg mL-1 to 50.0 ng mL-1, and the limit of detection (LOD, S/N = 3) is 0.15 pg mL-1. Spiked recoveries were 95.1% ~ 104% for assay of cTnI in human serum samples.


Assuntos
Técnicas Eletroquímicas , Limite de Detecção , Compostos de Estanho , Troponina I , Troponina I/sangue , Humanos , Técnicas Eletroquímicas/métodos , Imunoensaio/métodos , Compostos de Estanho/química , Catálise , Peroxidase do Rábano Silvestre/química , Naftóis/química , Metaloporfirinas/química , Eletrodos , Peróxido de Hidrogênio/química , Soroalbumina Bovina/química , Processos Fotoquímicos , Animais , Técnicas Biossensoriais/métodos , Semicondutores , Bovinos , Sulfetos/química , Porfirinas/química
9.
Food Chem ; 455: 139976, 2024 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-38850978

RESUMO

Amino acids are important chiral compounds in the human body, and are important basic components that make up the human body and play an important role in the human body. Among them, different enantiomers of an amino acid may have different roles, and different types of amino acids can be interconverted. However, the content of D-amino acids is much lower than that of L-amino acids, which is difficult to be detected. At present, many of the potential roles of D-amino acids, such as the conversion of D-amino acids to each other, have not yet been fully revealed. Hence, we synthesized fluorescent probe (R)-5 by condensation of 1,1'-Bi-2-naphthol (BINOL) and 2-(Aminomethyl)pyridine with Schiff base, which can recognize both D-arginine and D-glutamic acid at low concentrations. Meanwhile, (R)-5 can be applied to paper-based sensors for the detection of arginine and glutamate in living cells and for food amino acid detection.


Assuntos
Arginina , Corantes Fluorescentes , Ácido Glutâmico , Corantes Fluorescentes/química , Ácido Glutâmico/química , Ácido Glutâmico/análise , Arginina/química , Arginina/análise , Humanos , Estereoisomerismo , Naftóis/química
10.
Photochem Photobiol Sci ; 23(7): 1425-1434, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38822993

RESUMO

Cysteine (Cys) plays an indispensable role as an antioxidant in the maintenance of bioredox homeostasis. We have constructed an efficient fluorescent probe Mito-Cys based on the binding of indole and naphthol. The acrylic ester group serves as a recognition switch for specific detection of Cys, which undergoes Michael addition and intramolecular cyclization reactions, thereby ensuring the chemical kinetics priority of Cys compared to other biothiols. The probe has good water solubility, large Stokes shift (137 nm), with a detection limit of 21.81 nM. In addition, cell imaging experiments have shown that the probe has excellent mitochondrial targeting ability (R = 0.902). The probe can distinguish between Cys, homocysteine (Hcy) and glutathione (GSH), and can detect Cys specifically and quickly (100 s) to ensure accurate quantitative analysis of Cys changes in cells. More importantly, the probe confirms that ferroptosis inducing factors trigger thiol starvation in mitochondria, which helps to gain a deeper understanding of the physiological and pathological functions related to Cys and ferroptosis.


Assuntos
Cisteína , Corantes Fluorescentes , Mitocôndrias , Peixe-Zebra , Peixe-Zebra/metabolismo , Cisteína/metabolismo , Cisteína/química , Mitocôndrias/metabolismo , Mitocôndrias/química , Corantes Fluorescentes/química , Corantes Fluorescentes/síntese química , Humanos , Animais , Indóis/química , Indóis/metabolismo , Imagem Óptica , Estrutura Molecular , Naftóis/química , Naftóis/síntese química , Naftóis/metabolismo
11.
Int J Mol Sci ; 25(11)2024 May 21.
Artigo em Inglês | MEDLINE | ID: mdl-38891794

RESUMO

The chiral H8-BINOL derivatives R-1 and R-2 were efficiently synthesized via a Suzuki coupling reaction, and they can be used as novel dialdehyde fluorescent probes for the enantioselective recognition of R/S-2-amino-1-phenylethanol. In addition, R-1 is much more effective than R-2. Scanning electron microscope images and X-ray analyses show that R-1 can form supramolecular vesicles through the self-assembly effect of the π-π force and strong hydrogen bonding. As determined via analysis, the fluorescence of the probe was significantly enhanced by mixing a small amount of S-2-amino-1-phenylethanol into R-1, with a redshift of 38 nm, whereas no significant fluorescence response was observed in R-2-amino-1-phenylethanol. The enantioselective identification of S-2-amino-1-phenylethanol by the probe R-1 was further investigated through nuclear magnetic titration and fluorescence kinetic experiments and DFT calculations. The results showed that this mechanism was not only a simple reactive probe but also realized object recognition through an ICT mechanism. As the intramolecular hydrogen bond activated the carbonyl group on the probe R-1, the carbonyl carbon atom became positively charged. As a strong nucleophile, the amino group of S-2-amino-1-phenylethanol first transferred the amino electrons to a carbonyl carbocation, resulting in a significantly enhanced fluorescence of the probe R-1 and a 38 nm redshift. Similarly, S-2-amino-1-phenylethanol alone caused severe damage to the self-assembled vesicle structure of the probe molecule itself due to its spatial structure, which made R-1 highly enantioselective towards it.


Assuntos
Amino Álcoois , Ligação de Hidrogênio , Estereoisomerismo , Amino Álcoois/química , Corantes Fluorescentes/química , Cinética , Estrutura Molecular , Modelos Moleculares , Naftóis
12.
Front Public Health ; 12: 1379252, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38903587

RESUMO

Background: Aging is one of the most important public health issues. Previous studies on the factors affecting aging focused on genetics and lifestyle, but the association between polycyclic aromatic hydrocarbons (PAHs) and aging is still unclear. Methods: This study utilized data from the National Health and Nutrition Examination Survey (NHANES) 2003-2010. A total of 8,100 participants was used to construct the biological age predictors by using recent advanced algorithms Klemera-Doubal method (KDM) and Mahalanobis distance. Two biological aging indexes, recorded as KDM-BA acceleration and PhenoAge acceleration, were used to investigate the relationship between single PAHs and biological age using a multiple linear regression analysis, and a weighted quantile sum (WQS) model was constructed to explore the mixed effects of PAHs on biological age. Finally, we constructed the restricted cubic spline (RCS) model to assess the non-linear relationship between PAHs and biological age. Results: Exposure to PAHs was associated with PhenoAge acceleration. Each unit increase in the log10-transformed level of 1-naphthol, 2-naphthol, and 2-fluorene was associated with a 0.173 (95% CI: 0.085, 0.261), 0.310 (95% CI: 0.182, 0.438), and 0.454 (95% CI: 0.309, 0.598) -year increase in PhenoAge acceleration, respectively (all corrected P < 0.05). The urinary PAH mixture was relevant to KDM-BA acceleration (ß = 0.13, 95% CI: 0, 0.26, P = 0.048) and PhenoAge acceleration (ß = 0.59, 95% CI: 0.47, 0.70, P < 0.001), and 2-naphthol had the highest weight in the weighted quantile sum (WQS) regression. The RCS analyses showed a non-linear association between 2-naphthol and 2-fluorene with KDM-BA acceleration (all P < 0.05) in addition to a non-linear association between 1-naphthol, 2-naphthol, 3-fluorene, 2-fluorene, and 1-pyrene with PhenoAge acceleration (all P < 0.05). Conclusion: Exposure to mixed PAHs is associated with increased aging, with 2-naphthol being a key component of PAHs associated with aging. This study has identified risk factors in terms of PAH components for aging.


Assuntos
Envelhecimento , Exposição Ambiental , Inquéritos Nutricionais , Hidrocarbonetos Policíclicos Aromáticos , Humanos , Masculino , Feminino , Pessoa de Meia-Idade , Adulto , Fluorenos , Idoso , Naftóis
13.
Pestic Biochem Physiol ; 202: 105906, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38879292

RESUMO

Early detection of insecticide resistance is essential to develop resistance countermeasures and depends on accurate and rapid biological and biochemical tests to monitor resistance and detect associated mechanisms. Many such studies have measured activities of esterases, enzymes associated with resistance to ester- containing insecticides, using the model substrate, α-naphthyl acetate (α-NA). However, in the field, pests are exposed to ester-containing insecticides such as malathion, that are structurally distinct from α-NA. In the current study, malathion resistance in C. quinquefasciatus (3.2- to 10.4-fold) was highly associated with esterase activity measured with either α-NA (R2 = 0.92) or malathion (R2 = 0.90). In addition, genes encoding two esterases (i.e., EST-2 and EST-3) were over-expressed in field- collected strains, but only one (EST-3) was correlated with malathion hydrolysis (R2 = 0.94) and resistance (Rs = 0.96). These results suggest that, in the strains studied, α-NA is a valid surrogate for measuring malathion hydrolysis, and that heightened expression of an esterase gene is not necessarily associated with metabolic resistance to insecticidal esters.


Assuntos
Culex , Esterases , Resistência a Inseticidas , Inseticidas , Malation , Malation/farmacologia , Animais , Esterases/metabolismo , Esterases/genética , Culex/efeitos dos fármacos , Culex/genética , Culex/enzimologia , Resistência a Inseticidas/genética , Inseticidas/farmacologia , Naftalenos/farmacologia , Hidrólise , Biomarcadores/metabolismo , Proteínas de Insetos/metabolismo , Proteínas de Insetos/genética , Naftóis
14.
Anal Methods ; 16(27): 4619-4625, 2024 Jul 11.
Artigo em Inglês | MEDLINE | ID: mdl-38920338

RESUMO

The degree of the carbohydrate antigen 125 (CA-125) level in serum is positively correlated with the severity of ovarian cancer. In this study, a facile photoelectrochemical (PEC) immunoassay was devised for sensitive detection of CA-125 employing enzyme-catalyzed precipitation to weaken the photocurrent of hollow porous In2O3 nanotubes incorporating CdS nanoparticles. Upon the addition of the target analyte, horseradish peroxidase (HRP) enriches as a result of the formation of the sandwich immunocomplex, which can catalyze the conversion of 4-chloro1-naphthol (4-CN) to benzo-4-chlorohexadienone (4-CD) employing H2O2 as a cofactor. The as-produced insoluble precipitate acts as an obstacle to hinder the absorption of visible light by photoactive materials, thereby resulting in a decrease in photocurrent. Moreover, the weakened signal can be easily read out by a digital multimeter (DMM), advancing the convenience of the detection system. The preliminary analysis data indicate that the PEC immunoassay shows an efficient response to CA-125 levels ranging from 0.1 to 100 U mL-1 with a limit of detection (LOD) as low as 0.046 U mL-1 (S/N = 3). Most importantly, the proposed portable method has shown satisfactory performance in terms of selectivity, reproducibility, stability, and analysis in complex biological matrices.


Assuntos
Antígeno Ca-125 , Técnicas Eletroquímicas , Antígeno Ca-125/sangue , Humanos , Imunoensaio/métodos , Técnicas Eletroquímicas/métodos , Limite de Detecção , Peroxidase do Rábano Silvestre/química , Compostos de Cádmio/química , Feminino , Sulfetos/química , Nanotubos/química , Peróxido de Hidrogênio/química , Naftóis/química , Neoplasias Ovarianas/sangue , Processos Fotoquímicos
15.
Org Biomol Chem ; 22(28): 5748-5758, 2024 07 17.
Artigo em Inglês | MEDLINE | ID: mdl-38920404

RESUMO

Synthetic routes to geosmin and its enantiomer are well established, but the enantioselective synthesis of stereoisomers of geosmin is unknown. Here a stereoselective synthesis of all stereoisomers of geosmin is reported, yielding all compounds in high enantiomeric purity. Furthermore, the stereoselective synthesis of a geosmin derivative isolated from a mangrove associated streptomycete was performed, establishing the absolute configuration of the natural product. Finally, a new side product of the geosmin synthase from Streptomyces ambofaciens was isolated and its structure was elucidated by NMR spectroscopy. The absolute configuration of this new compound was determined through a stereoselective synthesis.


Assuntos
Produtos Biológicos , Naftóis , Streptomyces , Estereoisomerismo , Produtos Biológicos/química , Produtos Biológicos/síntese química , Naftóis/química , Naftóis/síntese química , Streptomyces/química , Estrutura Molecular
16.
Chirality ; 36(5): e23675, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38699899

RESUMO

This study describes the interaction of human serum albumin (HSA) with the binol derivative (R)-(+)-3,3'-dibromo-1,1'-bi-2-naphthol (R-BrB), which has its optical activity based on the prohibitive energetic barrier for conversion into the enantiomer (S)-(+)-3,3'-dibromo-1,1'-bi-2-naphthol (S-BrB). The objective was to assess the ability of HSA to differentiate axial enantiomers based on their binding efficiency and their impact on the CD spectra. We discovered that both enantiomers were effective ligands, and the CD signal disappeared when equimolar amounts of R-BrB and S-BrB were simultaneously added, indicating no preference for either enantiomer. The complexation resulted in a significant signal increase at 250 nm and a bathochromic effect at 370 nm. Molecular docking simulations were performed, and the lower energy pose of R-BrB was selected for DFT calculations. The theoretical CD spectra of free and complexed R-BrB were obtained and showed alterations corroborating the experimental results. By comparing the difference spectrum (HSA:R-BrB minus HSA) with the spectrum of free RBrB in water or ethyl alcohol, we concluded that the CD signal intensification was due to the increased solubilization of R-BrB upon binding to HSA.


Assuntos
Dicroísmo Circular , Simulação de Acoplamento Molecular , Naftóis , Albumina Sérica Humana , Dicroísmo Circular/métodos , Naftóis/química , Albumina Sérica Humana/química , Estereoisomerismo , Humanos , Teoria da Densidade Funcional , Simulação por Computador , Ligação Proteica
17.
Biosens Bioelectron ; 258: 116351, 2024 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-38705074

RESUMO

Multifunctional single-atom catalysts (SACs) have been extensively investigated as outstanding signal amplifiers in bioanalysis field. Herein, a type of Fe single-atom catalysts with Fe-nitrogen coordination sites in nitrogen-doped carbon (Fe-N/C SACs) was synthesized and demonstrated to possess both catalase and peroxidase-like activity. Utilizing Fe-N/C SACs as dual signal amplifier, an efficient bipolar electrode (BPE)-based electrochemiluminescence (ECL) immunoassay was presented for determination of prostate-specific antigen (PSA). The cathode pole of the BPE-ECL platform modified with Fe-N/C SACs is served as the sensing side and luminol at the anode as signal output side. Fe-N/C SACs could catalyze decomposition of H2O2 via their high catalase-like activity and then increase the Faraday current, which can boost the ECL of luminol due to the electroneutrality in a closed BPE system. Meanwhile, in the presence of the target, glucose oxidase (GOx)-Au NPs-Ab2 was introduced through specific immunoreaction, which catalyzes the formation of H2O2. Subsequently, Fe-N/C SACs with peroxidase-like activity catalyze the reaction of H2O2 and 4-chloro-1-naphthol (4-CN) to generate insoluble precipitates, which hinders electron transfer and then inhibits the ECL at the anode. Thus, dual signal amplification of Fe-N/C SACs was achieved by increasing the initial ECL and inhibiting the ECL in the presence of target. The assay exhibits sensitive detection of PSA linearly from 1.0 pg/mL to 100 ng/mL with a detection limit of 0.62 pg/mL. The work demonstrated a new ECL enhancement strategy of SACs via BPE system and expands the application of SACs in bioanalysis field.


Assuntos
Técnicas Biossensoriais , Técnicas Eletroquímicas , Eletrodos , Peróxido de Hidrogênio , Ferro , Limite de Detecção , Medições Luminescentes , Luminol , Antígeno Prostático Específico , Catálise , Medições Luminescentes/métodos , Técnicas Eletroquímicas/métodos , Peróxido de Hidrogênio/química , Peróxido de Hidrogênio/análise , Humanos , Luminol/química , Antígeno Prostático Específico/análise , Antígeno Prostático Específico/sangue , Ferro/química , Glucose Oxidase/química , Imunoensaio/métodos , Ouro/química , Peroxidase/química , Nanopartículas Metálicas/química , Nitrogênio/química , Carbono/química , Naftóis
18.
Angew Chem Int Ed Engl ; 63(24): e202406233, 2024 06 10.
Artigo em Inglês | MEDLINE | ID: mdl-38591161

RESUMO

The precise recognition and sensing of steroids, a type of vital biomolecules, hold immense practical value across various domains. In this study, we introduced corral[4]BINOLs (C[4]BINOLs), a pair of enantiomeric conjugated deep-cavity hosts, as novel synthetic receptors for binding steroids. Due to the strong hydrophobic effect of their deep nonpolar, chiral cavities, the two enantiomers of C[4]BINOLs demonstrated exceptionally high recognition affinities (up to 1012 M-1) for 16 important steroidal compounds as well as good enantioselectiviy (up to 15.5) in aqueous solutions, establishing them as the most potent known steroid receptors. Harnessing their ultrahigh affinity, remarkable enantioselectivity, and fluorescence emission properties, the two C[4]BINOL enantiomers were employed to compose a fluorescent sensor array which achieved discrimination and sensing of 16 structurally similar steroids at low concentrations.


Assuntos
Naftóis , Esteroides , Estereoisomerismo , Esteroides/química , Esteroides/análise , Naftóis/química , Estrutura Molecular
19.
Wei Sheng Yan Jiu ; 53(2): 316-331, 2024 Mar.
Artigo em Chinês | MEDLINE | ID: mdl-38604970

RESUMO

OBJECTIVE: To establishe an analysis and identification method for 2-methylisoborneol(2-MIB) and geosmin(GSM) in water using purge and trap-gas chromatography-mass spectrometry. METHODS: The samples were enriched and analyzed using a purge and trap system, followed by the separation on a DB-624(30 m×0.25 mm, 1.4 µm) chromatographic column. Quantification was performed using gas chromatography-mass spectrometry with the selected ion monitoring and internal standard calibration. RESULTS: The calibration curves for 2-MIB and GSM showed an excellent linearity in the range of 1 to 100 ng/L with R~2 values greater than 0.999. The detection limit and quantification limit for both 2-MIB and GSM were 0.33 ng/L and 1.0 ng/L, respectively. Spike recovery experiments were further carried on the source water and drinking water at three concentration levels. It showed that the average recoveries were from 82.0% to 111.0% for 2-MIB while 84.0% to 110% for GSM. Additionally, the test precision of 2-MIB and GSM ranged from 1.9% to 7.3% and 1.9% to 5.0%(n=6), respectively. The analysis of multiple samples including the local source water, treated water and distribution network water confirmed the existence of 2-MIB and GSM. CONCLUSION: Compared to the national standard(GB/T 5750.8-2023), the proposed method enables fully automated sample introduction and analysis without the extra pre-treatment. It provides the advantages of simplicity, good repeatability and high accuracy.


Assuntos
Água Potável , Naftóis , Poluentes Químicos da Água , Água/química , Cromatografia Gasosa-Espectrometria de Massas/métodos , Água Potável/análise , Canfanos/análise , Poluentes Químicos da Água/análise , Odorantes/análise
20.
Sci Total Environ ; 927: 172227, 2024 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-38582104

RESUMO

The sensory quality of drinking water, and particularly its taste and odor (T&O) is a key determinant of consumer acceptability, as consumers evaluate water by their senses. Some of the conventional treatment processes to control compounds which impart unpleasant T&O have limitations because of their low efficiency and/or high costs. Therefore, there is a great need to develop an effective process for removing T&O compounds without secondary concerns. The primary objective of this study was to assess for the first time the effectiveness of spirulina-based carbon materials in removing geosmin (GSM) and 2-methylisoborneol (2-MIB) from water, two commonly occurring natural T&O compounds. The efficiency of the materials to remove environmentally relevant concentrations of GSM and 2-MIB (ng L-1) from ultrapure and raw water was investigated using a sensitive headspace solid-phase microextraction coupled with gas chromatography mass spectrometry (HS-SPME-GC/MS) method. Moreover, the genotoxic and cytotoxic effects of the spirulina-based materials were assessed for the first time to evaluate their safety and their potential in the treatment of water for human consumption. Based on the results, spirulina-based materials were found to be promising for drinking water treatment applications, as they did not exert geno-cytotoxic effects on human cells, while presenting high efficiency in removing GSM and 2-MIB from water.


Assuntos
Água Potável , Odorantes , Spirulina , Paladar , Poluentes Químicos da Água , Purificação da Água , Água Potável/química , Odorantes/análise , Poluentes Químicos da Água/análise , Purificação da Água/métodos , Naftóis , Humanos , Canfanos , Adsorção , Microextração em Fase Sólida/métodos , Carbono , Cromatografia Gasosa-Espectrometria de Massas
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