ABSTRACT
Foods contaminants pose a challenge for food producers and consumers. Due to its spontaneous formation during heating and storage, hydroxymethylfurfural (HMF) is a prevalent contaminant in foods rich in carbohydrates and proteins. Colorimetric assays, such as the Seliwanoff test, offer a rapid and cost-effective method for HMF quantification but require careful optimization to ensure accuracy. We addressed potential interference in the Seliwanoff assay by systematically evaluating parameters like incubation time, temperature, and resorcinol or hydrochloric acid concentration, as well as the presence of interfering carbohydrates. Samples were analyzed using a UV-Vis spectrophotometer in scan mode, and data obtained were validated using HPLC, which also enabled quantification of unreacted HMF for assessing the protocol's accuracy. Incubation time and hydrochloric acid percentage positively influenced the colorimetric assay, while the opposite effect was observed with the increase in resorcinol concentration. Interference from carbohydrates was eliminated by reducing the acid content in the working reagent. HPLC analyses corroborated the spectrophotometer data and confirmed the efficacy of the proposed method. The average HMF content in balsamic vinegar samples was 1.97 ± 0.94 mg/mL. Spectrophotometric approaches demonstrated to efficiently determine HMF in complex food matrices. The HMF levels detected in balsamic vinegars significantly exceeded the maximum limits established for honey. This finding underscores the urgent need for regulations that restrict contaminant levels in various food products.
Subject(s)
Furaldehyde , Spectrophotometry , Furaldehyde/analogs & derivatives , Furaldehyde/analysis , Spectrophotometry/methods , Chromatography, High Pressure Liquid/methods , Resorcinols/analysis , Resorcinols/chemistry , Food Contamination/analysis , Food Analysis/methods , Acetic Acid/analysis , Acetic Acid/chemistryABSTRACT
Taking advantage of the competitive binding affinity towards Ti(IV) between 4-(2-pyridylazo) resorcinol (PAR) and phthalate, a simple indicator displacement (ID)-based colorimetric assay was designed for indirect determination of a well-known phthalic acid ester, dibutyl phthalate (DBP). The indicator PAR and Ti(IV) formed a purplish-red-colored Ti(IV)-PAR complex (λmax = 540â¯nm) at a 1:1 ratio. In the presence of pre-hydrolyzed DBP, colorless complex formation of phthalate ion (emerging from alkaline hydrolysis of DBP) with Ti(IV) resulted in a hypsochromic shift in absorbance maximum, accompanying a color change from purplish-red to yellowish-orange (λmax = 390â¯nm) by the release of PAR from Ti(IV)-PAR system. Based on this mechanism, the linear response range of the system for DBP was found to lie between 0.16 and 0.37â¯mmolâ¯L-1 with an experimental detection limit of 11.6 µmol L-1. The recommended Ti(IV)-PAR system was successfully applied to DBP-containing pharmaceutical products (as real sample) after a simple clean-up process for removing possible water-soluble interferents. The analytical results obtained from the recommended method (by applying the standard addition approach) and the reference liquid chromatography-tandem mass spectrometric (LC-MS/MS) method were statistically compared using DBP-extract of the drug samples. Consequently, a simple and selective colorimetric ID strategy was proposed for the analysis of DBP in pharmaceuticals for the first time.
Subject(s)
Colorimetry , Dibutyl Phthalate , Limit of Detection , Resorcinols , Titanium , Colorimetry/methods , Resorcinols/chemistry , Resorcinols/analysis , Titanium/chemistry , Dibutyl Phthalate/analysis , Dibutyl Phthalate/chemistry , Tandem Mass Spectrometry/methods , Hydrolysis , Chromatography, High Pressure Liquid/methodsABSTRACT
A moment analysis method was developed for the study of solute permeation at the interface of spherical molecular aggregates. At first, new moment equations were developed for determining the partition equilibrium constant (Kp) and permeation rate constants (kin and kout) of solutes from the first absolute (µ1A) and second central (µ2C) moments of elution peaks measured by using high-performance liquid chromatography (HPLC). Then, the method was applied to the analysis of mass transfer phenomena of three solutes, i.e., hydroquinone, resorcinol, and catechol, at the interface of sodium dodecylsulfate (SDS) micelles. HPLC data were measured by using an ODS column and an aqueous phosphate buffer solution (pH = 7.0) as the mobile phase solvent. Pulse response experiments were conducted while changing SDS concentration (5 - 20 mmol dm-3) in the mobile phase under the conditions that the surface of ODS stationary phase was dynamically coated by SDS monomers. In order to demonstrate the effectiveness of the moment analysis method using HPLC, the values of Kp, kin, and kout were determined for the three solutes as 35 - 69, 2.4 × 10-8 - 1.4 × 10-6 m s-1, and 7.0 × 10-10 - 2.1 × 10-8 m s-1, respectively. Their values increase with an increase in the hydrophobicity of the solutes. The method has some advantages for the study of interfacial solute permeation of molecular aggregates. For example, neither immobilization nor chemical modification of both solute molecules and molecular aggregates is required when elution peaks are measured by using HPLC. Interfacial solute permeation takes place in the mobile phase without any chemical reaction or physical action on molecular aggregates. The values of Kp, kin, and kout were analytically determined from those of µ1A and µ2C by using the moment equations. The results of this study must contribute to the dissemination of an opportunity for studying the interfacial solute permeation of molecular aggregates to many researchers because of extremely high versatility of HPLC.
Subject(s)
Resorcinols , Sodium Dodecyl Sulfate , Chromatography, High Pressure Liquid/methods , Sodium Dodecyl Sulfate/chemistry , Resorcinols/chemistry , Micelles , Hydroquinones/chemistry , Catechols/chemistry , Kinetics , PermeabilityABSTRACT
Hypoxia is known as a specific signal of various diseases, such as liver fibrosis. We designed a hypoxia-sensitive fluorometric approach that cleaved the azo bond (NâN) in the presence of hypoxia-controlled agents (sodium dithionite and azoreductase). 4-(2-Pyridylazo) resorcinol (Py-NâN-RC) bears a desirable hypoxia-responsive linker (NâN), and its azo bond breakup can only occur in the presence of sodium dithionite and azoreductase and leads to the release of 2,4-dihydroxyaniline, which can react with 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane to generate yellow fluorescent silicon nanoparticles. This approach exhibited high selectivity and sensitivity toward both sodium dithionite and azoreductase over other potential interferences. The mouse liver microsome, which is known to contain azoreductase, was applied and confirmed the feasibility of the designed platform. Py-NâN-RC is expected to be a practical substrate for hypoxia-related biological analyses. Furthermore, silicon nanoparticles were successfully applied for Hela cell imaging owing to their negligible cytotoxicity and superb biocompatibility.
Subject(s)
Azo Compounds , Nanoparticles , Silicon , Silicon/chemistry , Humans , Nanoparticles/chemistry , HeLa Cells , Azo Compounds/chemistry , Animals , Mice , Resorcinols/chemistry , Hypoxia/metabolism , Cell Hypoxia , Molecular Structure , Nitroreductases/metabolismABSTRACT
This review describes novel organocatalytic methods for the enantioselective construction of spiroindans and spirochromans and the application of the methods to the total synthesis of natural products. We developed an intramolecular Friedel-Craftstype 1,4-addition in which the substrates were a resorcinol derivative and 2-cyclohexenone linked by an alkyl chain. The reaction proceeded smoothly in the presence of a cinchonidine-based primary amine (30 mol%) with water and p-bromophenol as additives. A variety of spiroindanes were obtained with high enantioselectivity under these conditions. The reaction was applied in the first total synthesis of the unusual proaporphine alkaloid (-)-misramine, which included the key steps of enantioselective spirocyclization and double reductive amination of the keto-aldehyde to form a piperidine ring toward the end of the synthesis. The total synthesis of misrametine was achieved by selective demethylation of the methoxy group from the precursor to misramine. Next, a method for highly enantioselective organocatalytic construction of spirochromans containing a tetrasubstituted stereocenter was developed. An intramolecular oxy-Michael addition was catalyzed by a bifunctional cinchona alkaloid thiourea catalyst. A variety of spirochroman compounds containing a tetrasubstituted stereocenter were obtained with excellent enantioselectivity of up to 99% enantiomeric excess. The reaction was applied to the asymmetric formal synthesis of (-)-(R)-cordiachromene.
Subject(s)
Biological Products , Catalysis , Biological Products/chemical synthesis , Biological Products/chemistry , Stereoisomerism , Spiro Compounds/chemical synthesis , Spiro Compounds/chemistry , Cinchona Alkaloids/chemistry , Cyclohexanones/chemical synthesis , Cyclohexanones/chemistry , Organic Chemistry Phenomena , Pharmaceutical Preparations/chemical synthesis , Pharmaceutical Preparations/chemistry , Amines/chemistry , Amines/chemical synthesis , Thiourea/chemistry , Thiourea/chemical synthesis , Resorcinols/chemical synthesis , Resorcinols/chemistry , Indans/chemical synthesis , Indans/chemistryABSTRACT
RATIONALE: Alkylresorcinols (AR) are cereal-specific biomarkers and have recently been found in archaeological pots. However, their low concentrations and high susceptibility to degradation make them difficult to detect using conventional gas chromatography mass spectrometry (GC/MS). Here we describe the development of a more sensitive liquid chromatography mass spectrometry (LC/MS) method to detect these compounds. METHOD: A method based on the use of ultra-high-performance liquid chromatography (UHPLC) coupled to an Orbitrap mass analyser was established and validated for the detection of low-concentration ARs in pottery. During the preliminary experiments, UHPLC-Q/Orbitrap MS (ultra-high-performance liquid chromatography-quadrupole/Orbitrap mass spectrometry) was demonstrated to be more sensitive, and a wide range of AR homologues in cereal extracts were detected, unlike UHPLC-QTOFMS (ultra-high-performance liquid chromatography-quadrupole time-of-flight mass spectrometry) and GC/MS. The developed method was utilised to profile AR homologue distribution in modern cereal samples and reanalyse AR-containing pots from the archaeological site of Must Farm. RESULTS: A highly sensitive LC/MS method with a limit of detection (LOD) of 0.02 µg/g and a limit of quantification (LOQ) of 0.06 µg/g was used to profile ARs in five modern cereal grains. The obtained LOD is 250 times lower than that obtained using the conventional GC/MS approach. AR 21:0 was the most abundant homologue in all four Triticum spp.-einkorn, emmer, Khorasan wheat and common wheat. Meanwhile, AR 25:0 was the predominant homologue in barley, potentially enabling differentiation between wheat and barley. The developed LC/MS-based method was successfully used to analyse ARs extracted from Must Farm potsherds and identified the cereal species most likely processed in the pots-emmer wheat. CONCLUSION: The described method offers an alternative and more sensitive approach for detecting and identifying ARs in ancient pottery. It has been successfully utilised to detect AR homologues in archaeological samples and discriminate which cereal species-wheat and barley-were processed in the pots.
Subject(s)
Archaeology , Edible Grain , Mass Spectrometry , Resorcinols , Chromatography, High Pressure Liquid/methods , Archaeology/methods , Resorcinols/analysis , Resorcinols/chemistry , Edible Grain/chemistry , Mass Spectrometry/methods , Reproducibility of Results , Limit of DetectionABSTRACT
Human Hsp90 chaperones are implicated in various aspects of cancer. Due to this, Hsp90 has been explored as potential target in cancer treatment. Initial attempts to use Hsp90 inhibitors in drug trials failed due to toxicity and inefficacy. The next generation of drugs were less toxic but still insufficiently effective in a clinical setting. Recently, a lot of effort is being put into understanding the consequences of Hsp90 isoform selective inhibition, expecting that this might hold the key in targeting Hsp90 for disease treatment. Here we investigate a series of compounds containing the aryl-resorcinol scaffold with a 5-membered ring as a promising class of new human Hsp90 inhibitors, reaching nanomolar affinity. We compare how the replacement of 5-membered ring, from thiadiazole to imidazole, as well as a variety of their substituents, influences the potency of these inhibitors for Hsp90 alpha and beta isoforms. To further elucidate the dissimilarity in ligand selectivity between the isoforms, a mutant protein was constructed and tested against the ligand library. In addition, we performed a series of molecular dynamics (MD) and docking simulations to further explain our experimental findings as well as evaluated key compounds in cell assays. Our results deepen the understanding of Hsp90 isoform ligand selectivity and serve as an informative base for further Hsp90 inhibitor optimization.
Subject(s)
Drug Design , HSP90 Heat-Shock Proteins , Imidazoles , Resorcinols , HSP90 Heat-Shock Proteins/antagonists & inhibitors , HSP90 Heat-Shock Proteins/metabolism , Humans , Resorcinols/chemistry , Resorcinols/pharmacology , Resorcinols/chemical synthesis , Imidazoles/chemistry , Imidazoles/pharmacology , Imidazoles/chemical synthesis , Structure-Activity Relationship , Molecular Structure , Dose-Response Relationship, Drug , Molecular Dynamics Simulation , Molecular Docking Simulation , Antineoplastic Agents/pharmacology , Antineoplastic Agents/chemistry , Antineoplastic Agents/chemical synthesisABSTRACT
Alkylresorcinols are important biomarkers for evaluating whole wheat foods. However, their structures encompass a broad spectrum of homologs, making isolating and analyzing individual alkylresorcinol notably challenging. Herein, we synthesized highly selective molecularly imprinted polymers (MIPs) utilizing a facile and cost-effective precipitation polymerization method and 5-heneicosylresorcinol (ARC21:0) as the template molecule. Various crucial preparation parameters were systematically optimized, such as different porogens, functional monomers, imprinting ratios, and polymerization time. The polymers were characterized through scanning electron microscopy and Fourier transform infrared spectroscopy, and their adsorption performances were thoroughly evaluated. MIPs exhibited a notably enhanced adsorption capacity compared with that of non-imprinted polymers, reaching an optimal adsorption amount of 71.75 mg·mL-1 and imprinting factor of 2.02. Altogether, the synthesized MIPs showed superior affinity and selectivity for ARC21:0, as confirmed by their selective extraction, suggesting their potential applications in the analysis, separation, and monitoring of ARC21:0 in whole wheat foods.
Subject(s)
Flour , Molecularly Imprinted Polymers , Resorcinols , Triticum , Triticum/chemistry , Adsorption , Resorcinols/chemistry , Flour/analysis , Molecularly Imprinted Polymers/chemistry , Solid Phase Extraction/methods , Molecular Imprinting , Polymerization , Polymers/chemistry , Polymers/chemical synthesisABSTRACT
Authenticating whole wheat foods poses a significant challenge for both the grain industry and consumers. Alkylresorcinols (ARs), serving as biomarkers of whole wheat, play a crucial role in assessing the authenticity of whole wheat foods. Herein, we introduce a novel molecularly imprinted electrochemical sensor with modifications involving a molecularly imprinted polymer (MIP) and MXene nanosheets, enabling highly sensitive and selective detection of ARs. Notably, we specifically chose 5-heneicosylresorcinol (AR21), the predominant homologue in whole wheat, as the template molecule. α-Cyclodextrin and acrylamide served as dual functional monomers, establishing a robust multiple interaction between the MIP and AR21. As a result, the sensor exhibited a wide linear range of 0.005 to 100 µg·mL-1 and a low detection limit of 2.52 ng·mL-1, demonstrating exceptional selectivity and stability. When applied to commercial whole wheat foods, the assay achieved satisfactory recoveries and accuracy, strongly validating the practicality and effectiveness of this analytical technique.
Subject(s)
Electrochemical Techniques , Food Contamination , Molecular Imprinting , Resorcinols , Triticum , alpha-Cyclodextrins , Resorcinols/chemistry , Resorcinols/analysis , Triticum/chemistry , alpha-Cyclodextrins/chemistry , Electrochemical Techniques/methods , Electrochemical Techniques/instrumentation , Food Contamination/analysis , Limit of DetectionABSTRACT
Los errores innatos del metabolismo (EIM) son más de 550 enfermedades en las que se presenta una deficiencia o ausencia de proteínas con actividad enzimática, transportadora, receptora o estructural. Cada una de estas enfermedades es rara, pero su gran variedad hace que, consideradas en conjunto, sean la principal patología neonatal. Para la detección de los metabolitos producidos en los EIM se pueden utilizar pruebas cualitativas. Su utilidad radica en que son muy rápidas y de fácil acceso, y en que sirven como pruebas presuntivas para proceder a hacer exámenes más especializados o para enfocar el diagnóstico. Teniendo en cuenta su importancia para un diagnóstico temprano de los EIM, el objetivo del presente artículo es describir el funcionamiento de las pruebas bioquímicas de resorcinol, dinitrofenilhidrazina, nitrosonaftol, nitroprusiato y Hoesch, haciendo énfasis en los metabolitos que detectan.
Inborn errors of metabolism (IEM) are more than 550 diseases in which there is a deficiency or absence of proteins with enzymatic, transporter, receptor or structural activity. Individually these diseases are rare, but because of their wide variety they are, considered together, the largest neonatal disease. To detect metabolites produced in IEM qualitative tests can be used. They are easily accessible and fast to carry out, and serve as presumptive elements before proceeding to more specialized tests or to focus diagnosis. Given their importance for the early diagnosis of IEM, this article aims to describe the functioning of the following biochemical tests: dinitrophenylhydrazine, resorcinol, nitrosonaphtol, nitroprusside and Hoesch, emphasizing in the metabolites that they detect.
Os erros inatos do metabolismo (EIM) são mais de 550 doenças nas que se apresenta uma deficiência ou ausência de proteínas com atividade enzimática, transportadora, receptora ou estrutural. Cada uma destas doenças é rara, mas sua grande variedade faz que, consideradas em conjunto, sejam a principal patologia neonatal. Para a detecção dos metabólitos produzidos nos EIM se podem utilizar provas qualitativas. Sua utilidade radica em que são muito rápidas e de fácil acesso, e em que servem como provas presuntivas para proceder a fazer exames mais especializados ou para enfocar o diagnóstico. Tendo em conta sua importância para um diagnóstico precoce dos EIM, o objetivo do presente artigo é descrever o funcionamento das provas bioquímicas de resorcinol, dinitrofenilhidrazina, nitrosonaftol, nitroprusiato e Hoesch, fazendo ênfases nos metabólitos que detectam.
Subject(s)
Humans , Infant, Newborn , Dinitrophenols , Fructose , Keto Acids , Metabolism, Inborn Errors , Nitroprusside/chemistry , Porphobilinogen , Resorcinols/chemistry , TyrosineABSTRACT
The Hypoxyloideae (Xylariaceae with Nodulisporium-like anamorphs) were evaluated by a morphological and HPLC-based chemotaxonomic survey of more than 2000 specimens and cultures. Conspecificity of recent records with ancient type specimens were established in many cases by HPLC, since their characteristic metabolites may remain stable for over 200 years. Most constitute novel natural products that were identified in the course of concurrent "mycochemical" studies. A comparison of HPLC profiles considering relationships within the Hypoxyloideae as inferred from the biogenesis of these pigments agreed fairly with concurrent molecular phylogenetic studies, based on sequences of actin, beta-tubulin, and 5.8S/ITS nrDNA genes. Anamorphic morphology and secondary metabolism of cultures agreed well at generic level and above. A combination of chemical and morphological traits is favored over PCR-based approaches for species discrimination, if only relatively few taxa of these diverse genera have been sequenced. An overview on the chemical structures and biological activities of the characteristic metabolites is provided, their ecological importance is discussed, and the utility of chemotaxonomy to support and predict phylogenetic relationships in the Hypoxyloidae is demonstrated. A polythetic approach is most useful to elucidate the phylogeny of the Xylariaceae. Chemotaxonomy to assess fungal biodiversity has considerable utility(AU)