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1.
ChemSusChem ; : e202301671, 2024 May 10.
Artículo en Inglés | MEDLINE | ID: mdl-38728171

RESUMEN

Carbon materials are readily available and are essential in energy storage. One of the routes used to enhance their surface area and activity is the decoration of carbons with semiconductors, such as amorphous TiO2, for application in energy storage devices.

2.
Talanta ; 268(Pt 1): 125284, 2024 Feb 01.
Artículo en Inglés | MEDLINE | ID: mdl-37866307

RESUMEN

Soybean is a legume with high technological functionality, commonly used by the food industry as an ingredient in different products. However, soybean is an allergenic food whose undeclared presence in processed foods may represent a public health risk. In this work, it was developed an efficient electrochemical immunosensor, targeting the soybean trypsin inhibitor (Gly m TI) allergen using commercial anti-Gly m TI IgG, aiming at detecting/quantifying minute amounts of soybean in different food formulations. For this purpose, model mixtures of different foods (sausages, cooked-hams, biscuits) were prepared to contain known amounts of soybean protein isolate (100,000-0.1 mg kg-1) and submitted to specific thermal treatments (autoclaving, oven-cooking, baking). The electrochemical immunosensor allowed quantifying down to 0.1 mg kg-1 of soybean in the three food matrices, raw and processed (0.0012 mg of Gly m TI/kg of matrix). Accordingly, the immunosensor is suitable for detecting traces of soybean in raw, processed, and complex foods, thus protecting 99 % of soybean-allergic patients.


Asunto(s)
Técnicas Biosensibles , Glycine max , Humanos , Alérgenos , Sistemas de Atención de Punto , Inmunoensayo
3.
ACS Omega ; 8(21): 18782-18798, 2023 May 30.
Artículo en Inglés | MEDLINE | ID: mdl-37273638

RESUMEN

Waste, in particular, biowaste, can be a valuable source of novel carbon materials. Renewable carbon materials, such as biomass-derived carbons, have gained significant attention recently as potential electrode materials for various electrochemical devices, including batteries and supercapacitors. The importance of renewable carbon materials as electrodes can be attributed to their sustainability, low cost, high purity, high surface area, and tailored properties. Fish waste recovered from the fish processing industry can be used for energy applications and prioritizing the circular economy principles. Herein, a method is proposed to prepare a high surface area biocarbon from glycogen extracted from mussel cooking wastewater. The biocarbon materials were characterized using a Brunauer-Emmett-Teller surface area analyzer to determine the specific surface area and pore size and by scanning electron microscopy coupled with energy-dispersive X-ray analysis, Raman analysis, attenuated total reflectance Fourier transform infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy. The electrochemical characterization was performed using a three-electrode system, utilizing a choline chloride-based deep eutectic solvent (DES) as an eco-friendly and sustainable electrolyte. Optimal time and temperature allowed the preparation of glycogen-based carbon materials, with a specific surface area of 1526 m2 g-1, a pore volume of 0.38 cm3 g-1, and an associated specific capacitance of 657 F g-1 at a current density of 1 A g-1, at 30 °C. The optimal material was scaled up to a two-electrode supercapacitor using a DES-based solid-state electrolyte (SSE@DES). This prototype delivered a maximum capacitance of 703 F g-1 at a 1 A g-1 of current density, showing 75% capacitance retention over 1000 cycles, delivering the highest energy density of 0.335 W h kg-1 and power density of 1341 W kg-1. Marine waste can be a sustainable source for producing nanoporous carbon materials to be incorporated as electrode materials in energy storage devices.

4.
Anal Chim Acta ; 1259: 341168, 2023 Jun 08.
Artículo en Inglés | MEDLINE | ID: mdl-37100473

RESUMEN

A plasmonic nanostructure was constructed as a biorecognition element coupled to an optical sensing platform in sandwich format, targeting the hazelnut Cor a 14 allergen-encoding gene. The analytical performance of the genosensor presented a linear dynamic range between 100 amol L-1 and 1 nmol L-1, a limit of detection (LOD) < 19.9 amol L-1, and a sensitivity of 13.4 ± 0.6 m°. The genosensor was successfully hybridized with hazelnut PCR products, tested with model foods, and further validated by real-time PCR. It reached a LOD <0.001% (10 mg kg-1) of hazelnut in wheat material (corresponding to 1.6 mg kg-1 of protein) and a sensitivity of -17.2 ± 0.5 m° for a linear range of 0.001%-1%. Herein, a new genosensing approach is proposed as a highly sensitive and specific alternative tool with potential application in monitoring hazelnut as an allergenic food, protecting the health of sensitized/allergic individuals.


Asunto(s)
Corylus , Hipersensibilidad a los Alimentos , Humanos , Alérgenos/genética , Corylus/genética , Corylus/química , Inmunoglobulina E , Proteínas de Plantas/genética , Proteínas de Plantas/análisis , Reacción en Cadena en Tiempo Real de la Polimerasa
5.
Materials (Basel) ; 16(6)2023 Mar 14.
Artículo en Inglés | MEDLINE | ID: mdl-36984217

RESUMEN

Carbon materials derived from marine waste have been drawing attention for supercapacitor applications. In this work, chitins from squid and prawn marine wastes were used as carbon precursors for further application as electrodes for energy storage devices. Chitins were obtained through a deproteinization method based on enzymatic hydrolysis as an alternative to chemical hydrolysis as commonly presented in the literature. The obtained porous carbons were characterized using a BET surface area analyzer to determine the specific surface area and pore size, as well as scanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDX), transmission electron microscopy (TEM), Raman spectroscopy, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), to characterize their morphology, composition, and structure. The electrochemical characterization was performed using a glassy carbon (GC) electrode modified with marine waste-based porous carbons as the working electrode through cyclic voltammetry and galvanostatic charge/discharge using ethaline, a choline chloride-based deep eutectic solvent (DES), as an eco-friendly and sustainable electrolyte. Squid and prawn chitin-based carbons presented a surface area of 149.3 m2 g-1 and 85.0 m2 g-1, pore volume of 0.053 cm3 g-1 and 0.029 cm3 g-1, and an associated specific capacitance of 20 and 15 F g-1 at 1 A g-1, respectively. Preliminary studies were performed to understand the effect of -OH groups on the chitin-based carbon surface with DES as an electrolyte, as well as the effect of aqueous electrolytes (1 mol L-1 sulphuric acid (H2SO4) and 1 mol L-1 potassium hydroxide (KOH)) on the capacitance and retention of the half-cell set up. It is provided, for the first time, the use of chitin-based carbon materials obtained through a one-step carbonization process combined with an eco-friendly DES electrolyte for potential application in energy storage devices.

6.
Anal Chim Acta ; 1191: 339310, 2022 Jan 25.
Artículo en Inglés | MEDLINE | ID: mdl-35033254

RESUMEN

Artificial receptors that mimic their natural biological counterparts have several advantages, such as lower production costs and increased shelf-life stability/versatility, while overcoming the ethical issues related to raising antibodies in animals. In this work, the proposed tailor-made molecularly imprinted polymer (MIP)-allergen receptors aimed at substituting or even transcending the performance of biological antibodies. For this purpose, a MIP was proposed as an artificial antibody for the recognition of hazelnut Cor a 14-allergen. The target protein was grafted onto the conducting polypyrrole receptor film using gold screen-printed electrodes (Au-SPE). The electrochemical assessment presented a linear response for the dynamic range of 100 fg mL-1-1 µg mL-1 and a LOD of 24.5 fg mL-1, as determined by square wave voltammetry from the calibration curves prepared with standards diluted in phosphate buffer. Surface plasmon resonance (SPR) was used as a secondary transducer to evaluate the performance of the Cor a 14-MIP sensor, enabling a linear dynamic range of 100 fg mL-1- 0.1 µg mL-1 and a LOD of 18.1 fg mL-1. The selectivity of the tailored-made Cor a 14-MIP was tested against potentially cross-reactive plant/animal species based on the rebinding affinity (Freundlich isotherm-KF) of homologues/similar proteins, being further compared with custom-made polyclonal anti-Cor a 14 IgG immunosensor. Results evidenced that the MIP mimics the biorecognition of biological antibodies, presenting higher selectivity (only minor cross-reactivity towards walnut and Brazil nut 2S albumins) than the Cor a 14/anti-Cor a 14 IgG immunosensor. The application of electrochemical Cor a 14-MIP sensor to model mixtures of hazelnut in pasta enabled quantifying hazelnut down to 1 mg kg-1 (corresponding to 0.16 mg kg-1 of hazelnut protein in the matrix). To the best of our knowledge, Cor a 14-MIP is the first sensor based on an artificial/synthetic biorecognition platform for the specific detection of hazelnut allergens, while presenting high-performance parameters with demonstrated application in food safety management.


Asunto(s)
Técnicas Biosensibles , Corylus , Impresión Molecular , Alérgenos , Animales , Inmunoensayo , Polímeros Impresos Molecularmente , Polímeros , Pirroles
7.
Nanomaterials (Basel) ; 11(12)2021 Nov 30.
Artículo en Inglés | MEDLINE | ID: mdl-34947610

RESUMEN

The urgent need to reduce the consumption of fossil fuels drives the demand for renewable energy and has been attracting the interest of the scientific community to develop materials with improved energy storage properties. We propose a sustainable route to produce nanoporous carbon materials with a high-surface area from commercial graphite using a dry ball-milling procedure through a systematic study of the effects of dry ball-milling conditions on the properties of the modified carbons. The microstructure and morphology of the dry ball-milled graphite/carbon composites are characterized by BET (Brunauer-Emmett-Teller) analysis, SEM (scanning electron microscopy), ATR-FTIR (attenuated total reflectance-Fourier transform infrared spectroscopy) and Raman spectroscopy. As both the electrode and electrolyte play a significant role in any electrochemical energy storage device, the gravimetric capacitance was measured for ball-milled material/glassy carbon (GC) composite electrodes in contact with a deep eutectic solvent (DES) containing choline chloride and ethylene glycol as hydrogen bond donor (HBD) in a 1:2 molar ratio. Electrochemical stability was tracked by measuring charge/discharge curves. Carbons with different specific surface areas were tested and the relationship between the calculated capacitance and the surface treatment method was established. A five-fold increase in gravimetric capacitance, 25.27 F·g-1 (G40) against 5.45 F·g-1, was found for commercial graphene in contact with DES. Optimal milling time to achieve a higher surface area was also established.

8.
Food Chem ; 361: 130122, 2021 Nov 01.
Artículo en Inglés | MEDLINE | ID: mdl-34082386

RESUMEN

Two immunosensors were advanced to target hazelnut Cor a 14 based on electrochemical and optical transduction. Both approaches were developed with two types of custom-made antibodies, namely anti-Cor a 14 IgG (rabbit) and anti-Cor a 14 IgY (hen's egg) targeting the Cor a 14 allergen. Antibody immobilisation was performed via EDC/NHS onto disposable screen-printed electrodes. The detection limit (LOD) of the electrochemical immunoassay for Cor a 14 was 5-times lower than the optical, being down to 0.05 fg mL-1 with a dynamic range of 0.1 fg mL-1 to 0.01 ng mL-1. Antibody selectivity was verified against non-target 2S albumins (potential cross-reactive plant species). Anti-Cor a 14 IgY exhibited the best specificity, presenting minor cross-reactivity with peanut/walnut. Preliminary results of the application of anti-Cor a 14 IgY electrochemical immunosensor to incurred foods established a LOD of 1 mg kg-1 of hazelnut in wheat (0.16 mg kg-1 hazelnut protein).


Asunto(s)
Alérgenos/inmunología , Corylus/inmunología , Alérgenos/química , Animales , Anticuerpos/inmunología , Antígenos de Plantas/química , Antígenos de Plantas/inmunología , Arachis/química , Arachis/inmunología , Técnicas Biosensibles , Pollos , Corylus/química , Reacciones Cruzadas , Inmunoensayo , Juglans/química , Juglans/inmunología , Nueces/inmunología , Conejos
9.
Nanomaterials (Basel) ; 12(1)2021 Dec 29.
Artículo en Inglés | MEDLINE | ID: mdl-35010051

RESUMEN

A suitable dispersion of carbon materials (e.g., carbon nanotubes (CNTs)) in an appropriate dispersant media, is a prerequisite for many technological applications (e.g., additive purposes, functionalization, mechanical reinforced materials for electrolytes and electrodes for energy storage applications, etc.). Deep eutectic solvents (DES) have been considered as a promising "green" alternative, providing a versatile replacement to volatile organic solvents due to their unique physical-chemical properties, being recognized as low-volatility fluids with great dispersant ability. The present work aims to contribute to appraise the effect of the presence of MWCNTs and Ag-functionalized MWCNTs on the physicochemical properties (viscosity, density, conductivity, surface tension and refractive index) of glyceline (choline chloride and glycerol, 1:2), a Type III DES. To benefit from possible synergetic effects, AgMWCNTs were prepared through pulse reverse electrodeposition of Ag nanoparticles into MWCNTs. Pristine MWCNTs were used as reference material and water as reference dispersant media for comparison purposes. The effect of temperature (20 to 60 °C) and concentration on the physicochemical properties of the carbon dispersions (0.2-1.0 mg cm-3) were assessed. In all assessed physicochemical properties, AgMWCNTs outperformed pristine MWCNTs dispersions. A paradoxical effect was found in the viscosity trend in glyceline media, in which a marked decrease in the viscosity was found for the MWCNTs and AgMWCNTs materials at lower temperatures. All physicochemical parameters were statistically analyzed using a two-way analysis of variance (ANOVA), at a 5% level of significance.

10.
J Phys Chem B ; 124(19): 3954-3961, 2020 May 14.
Artículo en Inglés | MEDLINE | ID: mdl-32324418

RESUMEN

The air-ionic liquid interface for a series of ionic liquids involving imidazolium cations [Cnmim] with different alkyl chain lengths (n = 2, 4, 6, 8, 10, and 12) and the same [NTf2] imide anion has been studied by polarization-resolved second harmonic generation (SHG). An increase as a function of the alkyl chain length of the orientational parameter reveals the increasing ordering of the air-pure ionic liquid interfaces although it is not possible to disentangle the change in mean tilt angle from a change in the tilt angle probability distribution width. Besides, the study of the air-mixed ([C12mim])x([C2mim])1-x[NTf2] ionic liquid interface clearly demonstrates the interfacial nonideality of the mixed ionic liquids. The long alkyl chain cation perturbs the interface as seen from the orientational parameter and displaces the short alkyl chain one for bulk mixture contents as low as 10%. At higher long alkyl chain cation bulk mixture contents, the interface behaves close to a pure long alkyl chain ionic liquid.

11.
Mikrochim Acta ; 187(5): 262, 2020 04 08.
Artículo en Inglés | MEDLINE | ID: mdl-32270383

RESUMEN

A hybrid conjugate of reduced graphene oxide/ferrous-ferric oxide nanoparticles (rGO-Fe3O4 NPs) is characterized and assembled with chitosan and laccase to form a layered functional superstructure. After its characterization by field-effect scanning electron microscopy, energy-dispersive X-ray analysis, X-ray photoelectron spectroscopy, attenuated total reflectance Fourier transform infrared, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS), the nanocomposite has been deposited on glassy carbon for the enzyme-mediated electrochemical determination of the endocrine disruptor bisphenol A (BPA). Proof-of-concept assays conducted by using CV, EIS, and square wave voltammetry reveal that the enzymatic biosensor provides linear response in a wide range of BPA concentrations (6-228 ppb), very high sensitivities, and excellent durability (over 1-month storage). Using amperometric detection, remarkable sensitivities (2080 µA µM-1 cm-2) and detection limits (18 nM) are attained. Applications to real samples of bottled water proved feasible with recoveries in the range 107-124%. Graphical abstract Reduced graphene oxide conjugated with magnetite nanoparticles (rGO-Fe3O4) was assembled with laccase (wine-colored dots) and chitosan for the electrochemical determination of bisphenol A. The enzymatic biosensor exhibited excellent linearity (6-228 ppb) and stability. Best sensitivity (2080 µA µM-1 cm-2, detection limit 18 nM) was obtained by amperometry.


Asunto(s)
Compuestos de Bencidrilo/análisis , Técnicas Biosensibles/métodos , Técnicas Electroquímicas/métodos , Grafito/química , Nanopartículas de Magnetita/química , Nanocompuestos/química , Fenoles/análisis , Compuestos de Bencidrilo/química , Quitosano/química , Agua Potable/análisis , Lacasa/química , Límite de Detección , Oxidación-Reducción , Fenoles/química , Prueba de Estudio Conceptual , Reproducibilidad de los Resultados , Contaminantes Químicos del Agua/análisis , Contaminantes Químicos del Agua/química
12.
Anal Chim Acta ; 1082: 126-135, 2019 Nov 15.
Artículo en Inglés | MEDLINE | ID: mdl-31472701

RESUMEN

Considering the high incidence level and mortality rate of ovarian cancer, particularly among the European female population, the carbohydrate antigen 125 (CA-125) was selected as the protein target for this study for the development of a MIP-based biosensor. This work presents the development of molecular imprinting polymers (MIPs) on gold electrode surface for CA-125 biomarker recognition. The preparation of the CA-125 imprinting was obtained by electropolymerization of pyrrole (Py) monomer in a gold electrode using cyclic voltammetry (CV) in order to obtain highly selective materials with great molecular recognition capability. The quantification of CA-125 biomarker was made through the comparison of two methods: electrochemical (square wave voltammetry -SWV) and optical transduction (surface plasmon resonance -SPR). SWV has been widely used in biological molecules analysis since it is a fast and sensitive technique. In turn, SPR is a non-destructive optical technique that provides high-quality analytical data of CA-125 biomarker interactions with MIP. Several analytical parameters, such as sensitivity, linear response interval, and detection limit were determined to proceed to the performance evaluation of the electrochemical and optical transduction used in the development of the CA-125 biosensor. The biosensor based in the electrochemical transduction was the one that presented the best analytical parameters, yielding a good selectivity and a detection limit (LOD) of 0.01 U/mL, providing a linear concentration range between 0.01 and 500 U/mL. This electrochemical biosensor was selected for the study and it was successfully applied in the CA-125 analysis in artificial serum samples with recovery rates ranging from 91 to 105% with an average relative error of 5.8%.


Asunto(s)
Antígeno Ca-125/sangre , Técnicas Electroquímicas/métodos , Proteínas de la Membrana/sangre , Impresión Molecular , Resonancia por Plasmón de Superficie/métodos , Antígeno Ca-125/química , Técnicas Electroquímicas/instrumentación , Electrodos , Oro/química , Humanos , Límite de Detección , Proteínas de la Membrana/química , Polímeros/química , Pirroles/química
13.
J Mol Recognit ; 31(3)2018 03.
Artículo en Inglés | MEDLINE | ID: mdl-28156029

RESUMEN

Imprinting chondroitin sulfate (CS)/silica composites with Pb(II) and Cu(II) cations was explored with CS of bovine and different fish species origin. The process was based on the assumption that particular arrangements of the linear CS chains in aqueous solution, induced so as to accommodate cross complexation with the cations, would be embodied into a tridimensional matrix created through an organoalkoxysilane sol-gel scheme. The presence of Cu(II) in the synthesis of the composites did not result in the production of significantly stronger Cu(II)-oriented binding arrangements, and therefore, the imprinting was not successful. Inversely, for Pb(II), the materials obtained exhibited a "memory" effect for the Pb(II) ions, expressed in the observation of stronger (13%-44%) binding as compared to the nonimprinted counterparts, and increased selectivity (1.5-2 folds) against Cd(II). The imprinting features observed were dependent on the CS source. However, it was not possible to identify, among a set of their properties (carboxylate and sulfate abundance, percent of disulfated units, 4S/6S ratio, and molecular weight), any that correlated directly with the observed imprinting features. The augmented selectivity provided by the cation-imprinting process may be advantageous in areas such as analytical separation, remediation, purification, sensing, and others, particularly in those cases where a certain cation is of special interest within a mixture of them.


Asunto(s)
Sulfatos de Condroitina/química , Plomo/química , Impresión Molecular , Animales , Cationes/química , Bovinos , Peces
14.
J Chromatogr A ; 1437: 107-115, 2016 Mar 11.
Artículo en Inglés | MEDLINE | ID: mdl-26875121

RESUMEN

A strategy based on water-in-oil emulsion for the dispersion of a sol-gel mixture into small droplets was employed with the view of the production of naproxen-imprinted micro- and nanospheres. The procedure, aiming at a surface imprinting process, comprised the synthesis of a naproxen-derived surfactant. The imprinting process occurred at the interface of the emulsions or microemulsions, by the migration of the NAP-surfactant head into the sol-gel drops to leave surficial imprints due mainly to ion-pair interaction with a cationic group contained within the growing sol-gel network. The surface-imprinted microspheric particles exhibited a log-normal size distribution with geometric mean diameter of 3.1µm. A mesoporous texture was found from measurements of the specific surface area (206m(2)/g) and pore diameter (Dp 2nm). Evaluation of the microspheres as packed HPLC stationary phases resulted in the determination of the selectivity factor against ibuprofen (α=2.1), demonstrating the successful imprinting. Chromatographic efficiency, evaluated by the number of theoretical plates (222platescm(-3)), emerged as an outstanding feature among the set of all relatable formats produced before, an advantage intrinsic to the location of the imprinted sites on the surface. The material presented a capacity of 3.2µmolg(-1). Additionally, exploratory work conducted on their nanoscale counterparts resulted in the production of nanospheres in the size order of 10nm providing good indications of a successful imprinting process.


Asunto(s)
Técnicas de Química Analítica/métodos , Emulsiones/química , Geles/síntesis química , Microesferas , Nanosferas , Naproxeno/química , Acilación , Geles/química , Ibuprofeno/química , Impresión Molecular/métodos , Tensoactivos/química
15.
Artículo en Inglés | MEDLINE | ID: mdl-26458249

RESUMEN

The ultraviolet-visible spectroscopy has been assessed as a technique for the evaluation of the strength of template-precursor adduct in the development of molecular imprints of the non-steroidal anti-inflammatory drug naproxen (NAP). The commonly employed approach relies on the collection of UV spectra of drug+precursor mixtures at different proportions, the spectra being recorded against blanks containing the same concentration of the precursor. The observation of either blue or red band-shifts and abatement of a major band are routinely attributed to template-precursor adduct formation. Following the described methodology, the precursors 1-(triethoxysilylpropyl)-3-(trimethoxysilylpropyl)-4,5-dihydroimidazolium iodide (AO-DHI(+)) and 4-(2-(trimethoxysilyl)ethyl)pyridine (PETMOS) provoked a blue-shift and band abatement effect on the NAP spectrum. Molecular dynamics simulations indicated a reasonable affinity between NAP and these precursors (coordination numbers 0.33 for AO-DHI(+) and 0.18 for PETMOS), hence showing that NAP-precursor complexation is in fact effective. However, time dependent density functional theory (TD-DFT) calculations of the spectra of both free and precursor-complexed NAP were identical, thus providing no theoretical basis for the complexation-induced effects observed. We realized that the intense spectral bands of AO-DHI(+) and PETMOS (at around 265 nm) superimpose partially with the NAP bands, and the apparent "blue-shifting" in the NAP spectra when mixed with AO-DHI+ and PETMOS was in this case a spurious effect of the intense background subtraction. Therefore, extreme care must be taken when interpreting other spectroscopic results obtained in a similar fashion.


Asunto(s)
Artefactos , Impresión Molecular , Naproxeno/química , Electrones , Simulación de Dinámica Molecular , Teoría Cuántica , Espectrofotometría Ultravioleta
16.
J Chromatogr A ; 1422: 43-52, 2015 Nov 27.
Artículo en Inglés | MEDLINE | ID: mdl-26601713

RESUMEN

Naproxen-imprinted xerogels in the microspherical and nanospherical forms were prepared by W/O emulsion and microemulsion, respectively. The work evolved from a sol­gel mixture previously reported for bulk synthesis. It was relatively simple to convert the original sol­gel mixture to one amenable to emulsion technique. The microspheres thus produced presented mean diameter of 3.7 µm, surface area ranging 220­340 m2/g, selectivity factor 4.3 (against ibuprofen) and imprinting factor 61. A superior capacity (9.4 µmol/g) was found, when comparing with imprints obtained from similar pre-gelification mixtures. However, slow mass transfer kinetics was deduced from column efficiency results. Concerning the nanospherical format, which constituted the first example of the production of molecularly imprinted xerogels in that format by microemulsion technique, adapting the sol­gel mixture was troublesome. In the end, nanoparticles with diameter in the order of 10 nm were finally obtained, exhibiting good indications of an efficient molecular imprinting process. Future refinements are necessary to solve serious aggregation issues, before moving to more accurate characterization of the binding characteristics or to real applications of the nanospheres.


Asunto(s)
Técnicas de Química Analítica/métodos , Microesferas , Nanosferas , Naproxeno/química , Emulsiones , Geles/química , Cinética
17.
J Chromatogr A ; 1355: 158-63, 2014 Aug 15.
Artículo en Inglés | MEDLINE | ID: mdl-24958032

RESUMEN

A different approach to the preparation of microspheric particles of molecularly imprinted xerogels (MIX) is presented here. The technique consisted of filling up the pores of spherical, mesoporous, bare silica particles with a pregelification mixture by applying pressure. Upon gelification and drying, thin layers of MIX were deposited on the mesopores. Spherical composites of S-naproxen (S-NAP) imprints were produced by following this simple strategy. The performance of the imprints was quite satisfactory in terms of recognition ability (ascertained by selectivity against ibuprofen, α=4.9, and an imprinting factor of 13) whereas an outstanding improvement on dynamic features (expressed as column efficiency), as compared to the corresponding bulk format MIX (9 vs. 1.2 theoretical plates/cm), was reached.


Asunto(s)
Microesferas , Impresión Molecular/métodos , Dióxido de Silicio/química , Geles/química , Ibuprofeno/química , Microscopía Electrónica de Rastreo , Naproxeno/química , Porosidad
18.
J Phys Chem B ; 117(51): 16565-76, 2013 Dec 27.
Artículo en Inglés | MEDLINE | ID: mdl-24308321

RESUMEN

Protein adsorption is a delicate process, which results from the balance between the properties of proteins and their solid supports. Although the relevance of some of these parameters has been already unveiled, the precise involvement of electrostatics and other weaker intermolecular forces requires further comprehension. Aiming to contribute to this task, this work explores the attachment, rearrangement, and surface aggregation of a model spheroprotein, such as bovine ß-lactoglobulin (ß-LG), onto hydrophilic substrates prefunctionalized with different alkylthiol films. Thereby, a variety of electrostatic scenarios for the adsorption of ß-LG could be recreated through the variation of the pH and the functional chemistry of the surfaces. The changes in surface mass density (plus associated water) and film flexibility were followed in situ with quartz crystal microbalance with dissipation monitoring. Film packing and aggregation were assessed by faradaic electrochemical measurements and ex situ atomic force microscopy and field effect scanning electron microscopy. In contrast to previous hypotheses arguing that electrostatic interactions between charged substrates and proteins would be the only driving force, a complex interplay between Coulombic and non-Coulombic intermolecular forces (which would depend upon the experimental conditions) has been suggested to explain the results.


Asunto(s)
Interacciones Hidrofóbicas e Hidrofílicas , Lactoglobulinas/química , Adsorción , Animales , Bovinos , Electroquímica , Concentración de Iones de Hidrógeno , Cinética , Permeabilidad , Estabilidad Proteica , Compuestos de Sulfhidrilo/química , Propiedades de Superficie
19.
J Chromatogr A ; 1314: 115-23, 2013 Nov 01.
Artículo en Inglés | MEDLINE | ID: mdl-24055223

RESUMEN

Imidazolium-based monomers were, for the first time, employed in a comprehensive investigation of the molecular imprinting process of naproxen in both acrylic and sol-gel tridimensional networks. To this end, molecularly imprinted polymer (MIP) and xerogel (MIX) were both optimized for performance, by testing different porogen, template speciation and component ratios. The developed imprints were characterized for their pore properties (nitrogen adsorption analysis), site heterogeneity, binding properties and other performance parameters such as the imprinting factor, selectivity (HPLC column tests), column efficiency and mass transfer kinetics (frontal analysis study). MIP exhibited mesoporosity (Dp 29nm), whereas MIX did not, which was reflected in both the lower number of accessible imprinted sites (4.9µmol/g versus 3.7µmol/g) and the slower binding/dissociation in MIX. The naproxen/ibuprofen selectivity ratio was estimated as 6.2 for the MIX and 2.5 for the MIP. Given the high importance of capacity and fast mass transfer in typical applications of imprinted materials, and the satisfactory selectivity of MIP, it can be concluded that the acrylic approach was globally the most advantageous. Still, the remarkably high selectivity of MIX and its reasonable capacity demonstrate that future work devoted to further optimization of both formats is worthwhile.


Asunto(s)
Acrilatos/química , Antiinflamatorios no Esteroideos/química , Geles , Imidazoles/química , Impresión Molecular , Naproxeno/química , Espectroscopía de Resonancia Magnética , Extracción en Fase Sólida , Termodinámica
20.
Carbohydr Polym ; 96(1): 163-71, 2013 Jul 01.
Artículo en Inglés | MEDLINE | ID: mdl-23688466

RESUMEN

Agars obtained by traditional hot-water (TWE) and microwave-assisted (MAE) extractions were compared in terms of their rheological and physicochemical properties and molecular self-association in solutions of low (0.05%, w/w) and high (1.5%, w/w) polymer concentrations. At low concentration, thin gelled layers were imaged by AFM. Slow or rapid cooling of the solutions influenced structure formation. In each case, TWE and MAE agar structures were different and apparently larger for MAE. At high concentration, progressive structural reinforcement was seen; while TWE agar showed a more open and irregular 3D network, MAE agar gel imaged by cryoSEM was denser and fairly uniform. The rheological (higher thermal stability and consistency) and mechanical (higher gel strength) behaviors of MAE agar seemed consistent with a positive effect of molecular mass and 3,6-anhydro-α-l-galactose content. MAE produced non-degraded agar comparable with commercial ones and if properly monitored, could be a promising alternative to TWE.


Asunto(s)
Agar/química , Gracilaria/química , Calor , Microscopía de Fuerza Atómica , Microscopía Electrónica de Rastreo , Microondas , Reología , Agua/química
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