Matrix augmentation as an efficient method for resolving interaction of bromocriptine with human serum albumin: trouble shooting and simultaneous resolution

This work reports the results of an interesting study related to the investigation of interactions of bromocriptine (BCP) with human serum albumin (HSA) by mathematicall modelling of voltammetric and spectroscopic data into an augmented data matrix and its resolution by multivariate curve resolution-alternating least squares (MCR-ALS). The quality of the results obtained by MCR-ALS was examined by MCR-BANDS and its outputs confirmed the absence of rotational ambiguities in the MCR-ALS results. BCP-HSA interactions were also modeled by molecular docking methods to verify the results obtained from experimental sections and fortunately, they were compatible. Hard modeling of the experimental data by EQUISPEC helped us to calculate the binding constant of the complex formed from BCP-HSA interactions which was in a good agreement with that of calculated from direct analysis of the experimental data. Finally, with the help of two different amperometric measurements based on BCP-HSA interactions a novel electroanalytical method was developed for biosensing of HSA in serum samples.Fil: Jalalvand, Ali R.. Kermanshah University of Medical Sciences; IránFil: Ghobadi, Sirous. Kermanshah University of Medical Sciences; IránFil: Goicoechea, Hector Casimiro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Laboratorio de Desarrollo Analítico y Quimiometría; ArgentinaFil: Faramarzi, Elahe. Kermanshah University of Medical Sciences; IránFil: Mahmoudi, Majid. Kermanshah University of Medical Sciences; Irá

Multi-level data fusion strategies for modeling three-way electrophoresis capillary and fluorescence arrays enhancing geographical and grape variety classification of wines

Capillary electrophoresis with diode array detection (CE-DAD) and multidimensional fluorescence spectroscopy (EEM) second-order data were fused and chemometrically processed for geographical and grape variety classification of wines. Multi-levels data fusion strategies on three-way data were evaluated and compared revealing their advantages/disadvantages in the classification context. Straightforward approaches based on a series of data preprocessing and feature extraction steps were developed for each studied level. Partial least square discriminant analysis (PLS-DA) and its multi-way extension (NPLS-DA) were applied to CE-DAD, EEM and fused data matrices structured as two-way and three-way arrays, respectively. Classification results achieved on each model were evaluated through global indices such as average sensitivity non-error rate and average precision. Different degrees of improvement were observed comparing the fused matrix results with those obtained using a single one, clear benefits have been demonstrated when level of data fusion increases, achieving with the high-level strategy the best classification results.Fil: Ríos Reina, Rocío. Universidad de Sevilla; EspañaFil: Azcarate, Silvana Mariela. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Ciencias de la Tierra y Ambientales de La Pampa. Universidad Nacional de La Pampa. Facultad de Ciencias Exactas y Naturales. Instituto de Ciencias de la Tierra y Ambientales de La Pampa; ArgentinaFil: Camiña, José Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Ciencias de la Tierra y Ambientales de La Pampa. Universidad Nacional de La Pampa. Facultad de Ciencias Exactas y Naturales. Instituto de Ciencias de la Tierra y Ambientales de La Pampa; ArgentinaFil: Goicoechea, Hector Casimiro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Laboratorio de Desarrollo Analítico y Quimiometría; Argentin

Parallel factor analysis of 4.2K excitation-emission matrices for the direct determination of dibenzopyrene isomers in coal-tar samples with a cryogenic fiber optic probe coupled to a commercial spectrofluorimeter

Several studies have shown high concentrations of polycyclic aromatic hydrocarbons (PAHs) in living spaces and soil adjacent to parking lots sealed with coal-tar-based products. Recent attention has been paid to the presence of seven PAHs in coal-tar samples ? namely, benz[a]anthracene, benzo[k]-fluoranthene, benzo[b]fluoranthene, benzo[a]pyrene, chrysene, dibenz[a,h]anthracene, and indeno[1,2,3-cd]pyrene ? and their association to significant increases in estimated excess lifetime cancer risk for nearby residents. Herein, we present an analytical approach to screen the presence of five highly toxic, high-molecular weight PAHs (HMW-PAHs) in coal-tar samples. These include dibenzo[a,l]pyrene, dibenzo[a,i]pyrene, dibenzo[a,e]pyrene, dibnezo[a,h]pyrene and naphtho[2,3-a]pyrene. Their direct analysis ? no without chromatographic separation ? - in a reference coal-tar sample is made possible with the combination of excitation-emission matrices (EEMs) and parallel-factor analysis (PARAFAC). EEMs are recorded at 4.2 K with the aid of a cryogenic fiber optic probe and a commercial spectrofluorimeter. The simplicity of the experimental procedure and the excellent analytical figures of merit demonstrate the screening potential of this environmentally friendly approach for the routine analysis of numerous coal-tar samples.Fil: Moore, Anthony F. T.. University of Central Florida; Estados UnidosFil: Goicoechea, Hector Casimiro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas; ArgentinaFil: Barbosa, Fernando Jr.. Universidade de Sao Paulo; BrasilFil: Campiglia, Andres D.. University of Central Florida; Estados Unido

Mathematical modeling of interactions of cabergoline with human serum albumin for biosensing of human serum albumin

In this work, we are going to study the interactions of cabergoline (CBG) with human serum albumin (HSA) by mathematical modeling of voltammetric and spectroscopic data. To achieve this goal, voltammetric and spectroscopic data will be augmented into a data matrix which will be resolved by multivariate curve resolution-alternating least squares (MCR-ALS) as a powerful chemometric tool. Then, the quality of the data fitting by MCR-ALS will be examined by MCR-BANDS to ensure about the absence of the rotational ambiguities in the results. Molecular docking will also be used to model the interactions of CBG with HSA for verifying the results obtained from experimental methods. Hard-modeling of the experimental data will be performed by EQUISPEC to compute the binding constant of the complex formed from the interactions of CBG with HSA for verifying the binding constant obtained by direct analysis of the experimental data. Finally, two chrono-amperometric measurements based on CBG-HSA interactions will be performed to develop a novel electroanalytical method for determination of electro-inactive HSA.Fil: Jalalvand, Ali R.. Kermanshah University of Medical Sciences; IránFil: Ghobadi, Sirous. Razi University; IránFil: Akbari, Vali. Razi University; Irán. Kermanshah University of Medical Sciences; IránFil: Goicoechea, Hector Casimiro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Laboratorio de Desarrollo Analítico y Quimiometría; ArgentinaFil: Faramarzi, Elahe. Kermanshah University of Medical Sciences; IránFil: Mahmoudi, Majid. Kermanshah University of Medical Sciences; Irá

Applications of liquid-phase microextraction procedures to complex samples assisted by response surface methodology for optimization

This review presents applications of liquid phase microextraction (LPME) for extracting analytes in complex samples. This process has been introduced to simplify the extraction methods, and enhance the selectivity, sample cleanup and efficiency, allowing the extraction of a wide variety of analytes. The revision was focused on those works in which the performance of the technique was optimized by the response surface methodology (RSM). Firstly, a description of the different LPME systems is presented. Then, a brief explanation of the most popular tools applied for optimization is displayed. After that, the results of a literature search of the works reported from 2009 to 2019 based on the implementation of microextraction supported by experimental design and optimization can be found summarized in a table. Finally, an illustrative example providing the necessary information to carry out this kind of work is presented. A list of the most popular software available to apply RSM is also presented.Fil: Carabajal, Maira Daniela. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Laboratorio de Desarrollo Analítico y Quimiometría; ArgentinaFil: Teglia, Carla Mariela. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Laboratorio de Desarrollo Analítico y Quimiometría; ArgentinaFil: Cerutti, Estela Soledad. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Culzoni, Maria Julia. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Laboratorio de Desarrollo Analítico y Quimiometría; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Goicoechea, Hector Casimiro. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Laboratorio de Desarrollo Analítico y Quimiometría; Argentin

The first attempt on fabrication of a nano-biosensing platform and exploiting first-order advantage from impedimetric data: application to simultaneous biosensing of doxorubicin, daunorubicin and idarubicin

In this work, for the first time, we have developed a novel and very interesting electroanalytical methodology assisted by first-order multivariate calibration (MVC) for simultaneous determination of doxorubicin (DX), daunorubicin (DN) and idarubicin (ID) as three chemotherapeutic drugs at simulated physiological conditions. A sever overlapping was observed among signals of the three drugs which hindered us for simultaneous determination of them by conventional electroanalytical techniques. Therefore, we had to assist our method by chemometric approaches to develop a novel method for simultaneous determination of DX, DN and ID. Among the existing electroanalytical methods, electrochemical impedance spectroscopy (EIS) due to its high sensitivity was chosen. After individual calibration of the three drugs with the EIS data, a set of calibration samples was designed which was used to develop several first-order MVC models by partial least squares (PLS), continuum power regression (CPR), radial basis function-partial least squares (RBF-PLS), RBF-artificial neural network (RBF-ANN) and least squares-support vector machines (LS-SVM) as linear and non-linear chemometric algorithms. Then, performance of the developed MVC models in predicting concentrations of DX, DN and ID in synthetic samples was compared to choose the best model for the analysis of real samples. Our records confirmed more superiority of RBF-PLS algorithm than the other developed models which motivated us to choose it for the analysis of real samples. Fortunately, the results of the RBF-PLS in the analysis of real samples towards simultaneous determination DX, DN and ID was acceptable.Fil: Soleimani, Shokoufeh. Kermanshah University Of Medical Sciences; IránFil: Arkan, Elham. Kermanshah University Of Medical Sciences; IránFil: Farshadnia, Tooraj. Kermanshah University Of Medical Sciences; IránFil: Mahnam, Zahra. Kermanshah University Of Medical Sciences; IránFil: Jalili, Faramarz. Kermanshah University Of Medical Sciences; IránFil: Goicoechea, Hector Casimiro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Laboratorio de Desarrollo Analítico y Quimiometría; ArgentinaFil: Jalalvand, Ali R.. Kermanshah University Of Medical Sciences; Irá

Geographical origin identification of mandarin fruits by analyzing fingerprint signatures based on multielemental composition

Given rising traders and consumers concerns, the global food industry is increasingly demanding authentic and traceable products. Consequently, there is a heightened focus on verifying geographical authenticity as food quality assurance. In this work, we assessed pattern recognition approaches based on elemental predictors to discern the provenance of mandarin juices from three distinct citrus-producing zones located in the Northeast region of Argentina. A total of 202 samples originating from two cultivars were prepared through microwave-assisted acid digestion and analyzed by microwave plasma atomic emission spectroscopy (MP-AES). Later, we applied linear discriminant analysis (LDA), k-nearest neighbor (k-NN), support vector machine (SVM), and random forest (RF) to the element data obtained. SVM accomplished the best classification performance with a 95.1% success rate, for which it was selected for citrus samples authentication. The proposed method highlights the capability of mineral profiles in accurately identifying the genuine origin of mandarin juices. By implementing this model in the food supply chain, it can prevent mislabeling fraud, thereby contributing to consumer protection.Fil: Hidalgo, Melisa Jazmin. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; ArgentinaFil: Gaiad, José Emilio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; ArgentinaFil: Goicoechea, Hector Casimiro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Laboratorio de Desarrollo Analítico y Quimiometría; ArgentinaFil: Mendoza, Alberto. Instituto Tecnologico de Monterrey.; MéxicoFil: Pérez Rodríguez, Michael. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentina. Instituto Tecnologico de Monterrey.; MéxicoFil: Pellerano, Roberto Gerardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentin

Application of Quantum Cascade Laser-Infrared Spectroscopy and Chemometrics for In-Line Discrimination of Coeluting Proteins from Preparative Size Exclusion Chromatography

An external-cavity quantum cascade laser (EC-QCL)-based flow-through mid-infrared (IR) spectrometer was placed in line with a preparative size exclusion chromatography system to demonstrate real-time analysis of protein elutions with strongly overlapping chromatographic peaks. Two different case studies involving three and four model proteins were performed under typical lab-scale purification conditions. The large optical path length (25 μm), high signal-to-noise ratios, and wide spectral coverage (1350 to 1750 cm-1) of the QCL-IR spectrometer allow for robust spectra acquisition across both the amide I and II bands. Chemometric analysis by self-modeling mixture analysis and multivariate curve resolution enabled accurate quantitation and structural fingerprinting across the protein elution transient. The acquired concentration profiles were found to be in excellent agreement with the off-line high-performance liquid chromatography reference analytics performed on the collected effluent fractions. These results demonstrate that QCL-IR detectors can be used effectively for in-line, real-time analysis of protein elutions, providing critical quality attribute data that are typically only accessible through time-consuming and resource-intensive off-line methods.Fil: Akhgar, Christopher K.. Vienna University of Technology; AustriaFil: Ebner, Julian. Vienna University of Technology; AustriaFil: Alcaraz, Mirta R.. Institute Of Chemical Technologies And Analytics; AustriaFil: Kopp, Julian. Vienna University of Technology; AustriaFil: Goicoechea, Hector Casimiro. Universidad Nacional del Litoral; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; ArgentinaFil: Spadiut, Oliver. Vienna University of Technology; AustriaFil: Schwaighofer, Andreas. Vienna University of Technology; AustriaFil: Lendl, Bernhard. Vienna University of Technology; Austri

Chemometrical-electrochemical investigation for comparing inhibitory effects of quercetin and its sulfonamide derivative on human carbonic anhydrase II: Theoretical and experimental evidence

This paper reports results of a valuable study on investigation of inhibitory effects of the sulfonamide derivative of quercetin (QD) on human carbonic anhydrase II (CA-II) by electrochemical and chemometrical approaches. To achieve this goal, a glassy carbon electrode (GCE) was chosen as the sensing platform and different electrochemical techniques such as cyclic voltammetry (CV), differential pulse voltammetry (DPV), linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) were used to investigate and comparing inhibitory effects of quercetin (Q) and QD on CA-II. By the use of EQUISPEC, SPECFIT, SQUAD and REACTLAB as efficient hard-modeling algorithms, bindings of Q and QD with CA-II were investigated and the results confirmed that the QD inhibited the CA-II stronger than Q suggesting a highly relevant role of QD's-SO2NH2 group in inhibiting activity and also was confirmed by docking studies. Finally, a novel EIS technique based on interaction of Q and CA-II was developed for sensitive electroanalytical determination of CA-II and in this section of our study, the sensitivity of the developed electroanalytical methodology was improved by the modification of the GCE was with multi-walled carbon nanotubes-ionic liquid.Fil: Khodarahmi, Reza. Kermanshah University of Medical Sciences; IránFil: Khateri, Shaya. Kermanshah University of Medical Sciences; IránFil: Adibi, Hadi. Kermanshah University of Medical Sciences; IránFil: Nasirian, Vahid. State University of Louisiana; Estados UnidosFil: Hedayati, Mehdi. Kermanshah University of Medical Sciences; IránFil: Faramarzi, Elahe. Kermanshah University of Medical Sciences; IránFil: Soleimani, Shokoufeh. Kermanshah University of Medical Sciences; IránFil: Goicoechea, Hector Casimiro. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Laboratorio de Desarrollo Analítico y Quimiometría; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste; ArgentinaFil: Jalalvand, Ali Reza. Kermanshah University Of Medical Sciences; Irá

Imágenes de fluorescencia para el monitoreo en línea de sistemas en flujo: Generación y análisis de datos multilineales

Entre las técnicas analíticas tradicionales, la espectroscopia de fluorescencia es quizás la más versátil y sensible para el análisis de una gran variedad de muestras. Las técnicas de fluorescencia en estado estacionario no convencionales, entre ellas, la espectroscopia de excitación-emisión de fluorescencia, se han convertido en poderosas herramientas de análisis para sistemas de múltiples fluoróforos, para experimentos estáticos en cubetas o en configuración en flujo, por ejemplo, acoplados a análisis de inyección en flujo (FIA) o cromatografía de líquidos (LC). En fluorescencia molecular, los espectros de excitación y emisión son particularmente anchos, lo que resulta un inconveniente para los análisis de muestras complejas, siendo la calibración multivariada una excelente alternativa para extraer la información más relevante del sistema, en términos cuantitativos o cualitativos. Para sistemas en flujo o cinéticos, un objetivo muy difícil de lograr es la independencia entre modos instrumentales, debido a que las señales cambian en el tiempo. Si bien la instrumentación moderna permite la adquisición de datos de orden superior, el principal inconveniente se basa en la velocidad de registro de los detectores, que generalmente es menor a la variación de la medida observable. La solución más obvia a este problema es realizar las mediciones de una manera más rápida, incrementando la velocidad de adquisición de las señales analíticas. En este trabajo se presenta un espectrógrafo simple, económico y de rápido registro para la adquisición de matrices de excitación-emisión (EEM) de fluorescencia en sistemas en flujo acoplado a resolución quimiométrica de datos. El espectrógrafo desarrollado se utilizó en la adquisición de datos multidimensionales y los datos generados se evaluaron de manera cuantitativa y cualitativa en términos de capacidad predictiva de un modelo de calibración de segundo orden y trilinealidad de los datos generados. Este último parámetro se evaluó para un arreglo de datos de 3-vias construidos con varias EEM registradas para diferentes muestras (modelo de calibración de segundo orden) y para un dato de tercer orden obtenido por adquisición de EEM a cada tiempo de elución de una corrida cromatográfica. Ambos modelos fueron construidos para mezclas de analitos fluorescentes. Los resultados demostraron que el espectrógrafo desarrollado permite la adquisición de EEM lo suficientemente rápida que permite lograr la obtención de datos perfectamente trilineales tanto para análisis cuantitativo mediante calibración multivariada de segundo orden, como también, en el monitoreo de sistemas en flujo, superando satisfactoriamente el inconveniente de dependencia tiempo-detección. Esta contribución representa una valiosa y poderosa herramienta para la obtención de datos de orden superior sin pérdida de multi-linealidad, significando un gran paso para la quimiometría, la química analítica y otras áreas de investigación esencialmente, en el campo de la fisicoquímica y la biología.Fil: Alcaraz, Mirta Raquel. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Morzan, Ezequiel Martin. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Sorbello, Cecilia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Goicoechea, Hector Casimiro. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; ArgentinaFil: Etchenique, Roberto Argentino. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaX Congreso Argentino de Química AnalíticaSanta RosaArgentinaUniversidad Nacional de La Pampa. Facultad de Ciencias Exactas y Naturale