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1.
J Hazard Mater ; 478: 135483, 2024 Oct 05.
Artículo en Inglés | MEDLINE | ID: mdl-39173372

RESUMEN

This study presents a distinctive solid-state naked-eye colorimetric sensing approach by encapsulating a chromoionophoric probe onto a hybrid macro-/meso-pore polymer scaffold for fast and selective sensing of ultra-trace Hg(II). The customized structural/surface properties of the poly(VPy-co-TM) monolith are attained by specific proportions of 2-vinylpyridine (VPy), trimethylolpropane trimethacrylate (TM), and pore-tuning solvents. The interconnected porous network of poly(VPy-co-TM), inherent superior surface area and porosity, is captivating for the homogeneous/voluminous incorporation of probe molecules, i.e., 7-((4-methoxyphenyl)diazenyl)quinoline-8-ol (MPDQ), for the target-specific colorimetric detection. The structural morphology, surface topography, and phase characteristics of the bare poly(VPy-co-TM) monolith and MPDQ@poly(VPy-co-TM) sensor are examined using HR-TEM-SAED (High-Resolution Transmission Electron Microscopy - Selected Area Electron Diffraction), FE-SEM-EDAX (Field Emission Scanning Electron Microscopy - Energy Dispersive X-ray Spectroscopy), XPS (X-ray Photoelectron Spectroscopy), p-XRD (Powder X-Ray Diffraction), FT-IR (Fourier Transform Infrared Spectroscopy), UV-Vis-DRS (Ultraviolet-Visible Diffuse Reflectance Spectroscopy), and BET/BJH (Brunauer-Emmett-Teller / Barrett-Joyner-Halenda) analysis. The distinctive properties of the sensor reveal a constrained geometrical orientation of the MPDQ probe onto the long-range continuous monolithic network of meso-/-macropore template, enabling selective interaction with Hg(II) with peculiar color transfiguration from pale yellow to deep brown. The sensor demonstrates a linear spectral-color alliance in the 0-200 ppb concentration range for Hg(II), with quantification and detection limits of 0.63 and 0.19 ppb. The sensor efficacy is verified using certified contaminated water and tobacco samples, with excellent reusability, reliability, and reproducibility of ≥ 99.23 % (RSD ≤1.89 %) and ≥ 99.19 % (RSD ≤1.94 %) of Hg(II), respectively.

2.
Anal Chim Acta ; 1307: 342625, 2024 Jun 08.
Artículo en Inglés | MEDLINE | ID: mdl-38719404

RESUMEN

BACKGROUND: Environmental contamination by heavy metal ions has caused growing ecological and public health concerns. In this line, monitoring of copper toxicity gains importance due to its application in industrial, agricultural, domestic, medical and technological sectors. Although noteworthy breakthroughs were made, critical issues, such as portability, the need for well-trained personnel, costly/complex instrumentations, long response time, and the introduction of secondary contaminants, required attention. Hence, developing a low-cost, user-friendly, real-time, portable analytical platform for rapid and on-site analysis remained imperative. Solid-state colorimetric sensors have gained widespread popularity due to their low cost, ease of use, and brilliant sensitivity/selectivity. RESULTS: We have successfully unfolded an ultra-portable azomethine-infused structurally interwoven polymer monolith as the solid-state chromatic sensor for the quantitative naked-eye detection of ultra-trace Cu2+ in industrial/environmental samples. For the sensor fabrication, non-hygroscopic conjugated Schiff-base receptors, namely N-(1E,2E)-3-(4-dimethylamino)phenyl)allylidene)-3-nitrobenzohydrazide (DPAN) and 2,3-bis(((1E,2E)-3-(4-dimethylamino)phenyl)allylidene)amino)malononitrile (DPAM) were synthesized in-house and voluminously immobilized onto a crack-free porous poly(4VP-co-EGDMA) monolith framework. The topological structure and functionalities of the porous polymer monolith and chromatic sensor materials were examined using various surface analytical and microscopic techniques. The excellent surface area and intriguing interlaced porosity features of the tailor-made polymer monolith facilitated the voluminous anchoring of the chromatic receptors for the selective/sensitive targeting of Cu2+. The DPAN and DPAM receptor-loaded poly(4VP-co-EGDMA) sensors exhibited a linear range of 0-150 µg/L, with the limit of detection of 0.11 and 0.13 µg/L for Cu2+, respectively. The sensors manifested Cu2+ specificity amidst concomitant matrix ions to highlight the relevance of the proposed solid-state sensor. SIGNIFICANCE: The sensor materials offered a reliable approach for detecting and quantifying environmentally toxic and industrially pertinent Cu2+ from aqueous samples, with the prospect of large-scale production, owing to the sensor's integrated compact design that can be reused for repeated real-time surveillance. The sensor's ability to sense/trap traces of toxic Cu2+ can provide an early warning about the growing toxicity in a particular resource, thereby providing an opportunity to initiate remediation protocols for speedy decontamination.

3.
J Hazard Mater ; 469: 133960, 2024 May 05.
Artículo en Inglés | MEDLINE | ID: mdl-38492387

RESUMEN

This study focuses on a new type of fast responsive solid-state visual colorimetric sensor, custom engineered with dual-entwined porous polymer imbued with chromoionophoric 4-(sec-butyl)- 2-((5-mercapto-1,3,4-thiadiazol-2-yl)diazenyl)phenol (SMDP) probe for selective and ultra-sensitive colorimetric sensing of Cd(II). The polymer monolith, i.e., poly(aminostyrene-co-trimethylolpropanetrimethacrylate) denoted as poly(AMST-co-TRIM), is designed through a stoichiometric blending of monomer, crosslinker, and porogens leading to superior surface area, pore and adsorption properties for the voluminous incorporation of SMDP probe for target specific ion sensing. The porosity, surface and structural characteristics of the poly(AMST-co-TRIM)monolith and poly(AMST-co-TRIM)SMDP sensor are investigated using p-XRD, XPS, TG-DTA, FT-IR, BET/BJH, FE-SEM, HR-TEM, EDAX, and SAED techniques. The poly(AMST-co-TRIM)SMDP sensor reveals a frozen geometrical orientation of SMDP molecules to bind selectively with Cd(II), forming stable charge-transfer complexes by exhibiting transitional visible color shifts from light yellow to dark green (λmax 608 nm). The sensor imposes a linear response from 0-200 ppb, with quantification and detection limits of 0.95 and 0.28 ppb. The fabricated sensor material is cost-effective and versatile in its solid-state naked-eye sensing, with excellent reusability. The sensor performance has been verified using various environmentally contaminated water and commercial cigarette samples, with a recovery of ≥ 99.12% and an RSD of ≤ 1.95%, thus reflecting exceptional data reproducibility/reliability.

4.
J Chromatogr A ; 1713: 464509, 2024 Jan 04.
Artículo en Inglés | MEDLINE | ID: mdl-37980811

RESUMEN

The current work focuses on the sequential separation of trivalent lanthanides (except Pm3+) using modified C18 silica-packed supports through the reversed-phase high-performance liquid chromatography (RP-HPLC) technique. In the current research, four indigenously synthesized amphiphilic aromatic triamide derivatives, namely N1, N1, N3, N3, N5, N5-hexa(alkyl) benzene-1,3,5-tri carboxamide (alkyl = butyl, hexyl, octyl, and decyl), were employed as column modifiers. The results show that the separation of Ln3+ can be achieved systematically (< 12 min) by tuning the modifiers' functional group and hydrophobic chain and fine-tuning the column modification procedure and separation parameters. The chromatographic studies revealed that the use of 0.168 mmol of N1, N1, N3, N3,N5, N5-hexa(hexyl)benzene-1,3,5-tricarboxamide (HHBTA) coated column and 0.419 mmol of N1, N1, N3, N3, N5, N5-hexa(octyl) benzene-1,3,5-tricarboxamide (HOBTA) modified columns offered excellent separation for the lanthanoids, using 0.1 M α-hydroxyisobutyric acid (HIBA), as mobile phase. The separated lanthanoids were quantified by post-column derivatization reaction (after the separation process) using Arsenazo (III) as the post-column reagent by integrating with a UV-Visible detector fixed at 655 nm (λmax). A systematic study on the influence of various analytical features, such as the effect of the modifier's chain length and its concentration, mobile phase composition and pH, was performed and optimized for achieving the best separation protocols.


Asunto(s)
Amidas , Elementos de la Serie de los Lantanoides , Cromatografía Líquida de Alta Presión/métodos , Dióxido de Silicio/química , Indicadores y Reactivos
5.
Environ Res ; 239(Pt 1): 117399, 2023 Dec 15.
Artículo en Inglés | MEDLINE | ID: mdl-37838196

RESUMEN

The escalating predicament of water pollution has spurred the development of new chromogenic materials for the efficient detection/screening of toxic mercuric (Hg2+) ions. In this study, we report a simple and efficient detection stratagem by infusing a chromogenic ion-receptor (BTDA), i.e., 4-(benzothiazol-2-yl)-N, N-dimethylaniline onto a structurally intertwined meso-/macro-pore polymer template for the target-specific sensing of ultra-trace Hg2+. The structural/surface features of the monolithic polymer template, prepared from glycidyl methacrylate (GMA) monomer crosslinked with ethylene glycol dimethacrylate (EGDMA), facilitate voluminous infusion and uniform decoration of ion-receptor molecules across the continuous porous poly(GMA-co-EGDMA) framework, resulting in a solid-state colorimetric sensory system. The bimodal polymer network's intriguing surface and structural morphology of the chromogenic sensor material are interpreted using scanning/transmission electron microscopy, X-ray diffraction, photoelectron spectroscopy, energy dispersive X-ray spectrometry, optical spectroscopy, surface area, porosity and thermal analysis. The proposed Hg2+ sensor offers a linear response range of 1-150 µg/L, with a detection and quantification limit of 0.29 and 0.97 µg/L, respectively. The poly(GMA-co-EGDMA)-BTDA sensor exhibits a quick ion-sensing response (40 s) with distinct color transitions from pastel yellow to olive as a function of increasing Hg2+ concentration. The matrix tolerance studies for the proposed sensory system reveal high selectivity for Hg2+, with a recovery of ≥99.2% in on-site environmental samples. The sensor material exhibits excellent data reproducibility and reliability up to seven cycles of reusability.


Asunto(s)
Mercurio , Porosidad , Reproducibilidad de los Resultados , Iones
6.
J Hazard Mater ; 459: 132248, 2023 Oct 05.
Artículo en Inglés | MEDLINE | ID: mdl-37595465

RESUMEN

This work demonstrates the fabrication of a simple, low-cost naked-eye colorimetric solid-state sensor model for selective sensing of Cd2+. The sensor was developed using a polymer monolithic architect; namely, poly(n-allylthiourea-co-ethyleneglycol dimethacrylate) (poly(ATU-co-EGD) imbued with the chromophoric probe, 3-(quinoline-8-yldiazenyl)quinoline-2,4-diol (QYQD). The concocted indigenous perforated structural assemblies were studied through various microscopic, spectroscopic, and diffraction techniques. The template possessed a uniform arrangement of interconnected macro/mesoporous networks available for the maximum hooking of the QYQD probe moieties for the rapid and enhanced Cd2+ sensing process. The developed sensor offered an enhanced solid-state color transition response from yellow to dark meron for a proportional concentration increase of Cd2+ exhibiting precise absorption spectra with λmax at 475 nm. The relative stoichiometric binding ratio of the QYQD probe with Cd2+ was observed to be 2:1. The enhanced working conditions of the developed poly(ATU-co-EGD)QYQD sensor were tuned by validating various analytical conditions. The sensor exhibited a linear response signal from 2 to 150 ppb of Cd2+, and the corresponding LOD and LOQ values were 0.31 and 1.03 ppb, respectively. The efficacious performance drive of the sensor was validated in real water and cigarette samples that showed excellent data accuracy with a recovery value of ≥ 99.72% (n = 3).

7.
J Hazard Mater ; 454: 131431, 2023 Jul 15.
Artículo en Inglés | MEDLINE | ID: mdl-37099907

RESUMEN

This study reports an efficacious solid-state optical sensor through the synergistic coalescences of an original chromoionophoric probe and a structurally engineered porous polymer monolith for the selective and sensitive colorimetric spotting of ultra-trace toxic mercury ions. The unique properties of the bimodal macro-/meso-pore structured polymer, i.e., poly(AAm-co-EGDMA) monolith, offer voluminous and uniform anchoring of probe molecules, i.e., (Z)-N-phenyl-2-(quinoline-4-yl-methylene)hydrazine-1-carbothioamide (PQMHC). The structure/surface features of the sensory system, i.e., surface area, pore dimensions, monolith framework, elemental mapping, and phase composition, were examined by p-XRD, XPS, FT-IR, HR-TEM-SAED, FE-SEM-EDAX, and BET/BJH analysis. The sensor's ion-capturing ability was established through naked eye color transition and UV-Vis-DRS response. The sensor exhibits a strong binding affinity for Hg2+, with a linear signal response in the concentration range of 0-200 µg/L (r2 >0.999), with a detection limit of 0.33 µg/L. The analytical parameters were optimized to facilitate pH-dependent visual sensing of ultra-trace Hg2+ in ≤ 30 s. The sensor exhibits high chemical/physical stability characteristics, with reliable data reproducibility (RSD ≤1.94 %), while testing with natural/synthetic water and cigarette samples. The proposed work offers a cost-effective and reusable naked-eye sensory system for the selective sensing of ultra-trace Hg2+, with potential prospects of commercialization considering their simplicity, viability, and reliability.

8.
RSC Adv ; 13(5): 3317-3328, 2023 Jan 18.
Artículo en Inglés | MEDLINE | ID: mdl-36756448

RESUMEN

Reprocessing nuclear-spent fuels is highly demanded for enhanced resource efficacy and removal of the associated radiotoxicity. The present work elucidates the rapid separation of UO2 2+ and Th4+ ions using a reversed-phase high-performance liquid chromatographic (RP-HPLC) technique by dynamically modifying the surface of a C18 silica monolith column with target-specific ionophoric ligands. For the dynamic modification, four analogous aromatic amide ligands, N 1,N 1,N 3,N 3,N 5,N 5-hexa(alkyl)benzene-1,3,5-tricarboxamide (alkyl = butyl, hexyl, octyl, and decyl) as column modifiers were synthesized. The complexation properties and retention profiles of the amide-based column modifiers for the selective and sequential separation of UO2 2+ and Th4+ ions were investigated. In addition, the selective separation of UO2 2+ and Th4+ ions among the competitive ions of similar chemical properties were also studied. The ionophore immobilized C18 silica monolith columns demonstrated a varying degree of retention behavior for UO2 2+ and Th4+ ions (UO2 2+ is retained longer than Th4+ under all analytical conditions), eventually leading to rapid separations within a period of ≤5 min. A 0.1 M solution of 2-hydroxyisobutyric acid (HIBA, 1 mL min-1) served as the mobile phase, and the qualitative and quantitative assessment of the sequentially separated 5f metal ions was achieved through post-column derivatization reaction, using arsenazo(iii) as a post-column reagent (PCR; 1.5 mL min-1) prior to analysis using a UV-vis detector, at 665 nm (λ max). The developed technique was further evaluated by standardizing various analytical parameters, including modifier concentration, mobile phase pH, mobile phase flow rate, etc., to yield the best chromatographic separation. Also, the conceptual role of alkyl chain length (in the modifier) on the retention behavior of the studied metal ions was evaluated for cutting-edge future applications.

9.
ACS Omega ; 7(45): 41461-41471, 2022 Nov 15.
Artículo en Inglés | MEDLINE | ID: mdl-36406566

RESUMEN

The current work presents a perspective to obliterate toxic Hg(II) from an aqueous environment, a strategic environmental remediation and decontamination measure. We report a simple, efficient, and reusable solid-state visual sensing strategy for the selective detection and quantitative recovery of ultratrace Hg(II). The capture of Hg(II) ions was effectuated using a macro-/mesoporous polymer monolith uniformly decorated with an azo-based chromophoric ion receptor, i.e., 7-((1H-benzo[d]imidazol-2-yl)diazenyl)quinolin-8-ol (BIDQ). The porous polymer template was synthesized through free radical polymerization of gylcidylmethacrylate and ethylene glycol dimethacrylate, leading to distinct structural and surface properties that offer exclusive solid-state colorimetric selectivity for Hg(II) upon restricted spatial dispersion of the ion receptor. The sensor provides a broad linear response range of 1-200 µg/L, with an outstanding detection limit of 0.2 µg/L for Hg(II) ions, thus effectuating reliable and reproducible sensing. Optimizing analytical parameters such as solution pH, receptor concentration, sensor quantity, kinetics, temperature, and matrix interference proved to be promising for the real-time monitoring of toxic mercury ions from aqueous/industrial systems, with maximum response in the pH range of 7.5-8.0, with a response time of ≤80 s. Density functional theory (DFT) calculations were employed to study the electronic structure of BIDQ upon chelating with Hg(II) ions, using 6-311G and LAND2Z basis sets.

10.
Photochem Photobiol Sci ; 21(7): 1273-1286, 2022 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-35384639

RESUMEN

This work reports a unique ZrO2-Ag2O heterojunction nanocomposite uniformly dispersed on a macro-/meso-porous polymer monolithic template to serve as simple and effective visible light-driven heterogeneous plasmonic photocatalysts for water decontamination. The monolithic photocatalysts' structural properties and surface morphology are characterized using various surface and structural characterization techniques. The photocatalytic performance of the proposed photocatalysts is evaluated by optimizing multiple operational parameters. The photocatalytic properties of the fabricated monolithic nanocomposite are monitored through time-dependent photocatalytic disintegration of norfloxacin drug, a widely employed antimicrobial, with considerable aquatic persistence. The analytical results conclude that a (60:40) ZrO2-Ag2O nanocomposite embedded polymer monolith exhibits superior photocatalytic activity for the complete mineralization of norfloxacin molecules under optimized conditions of solution pH (3.0), photocatalyst quantity (100 mg), pollutant concentration (15 mg/L), photosensitizers (2.0 mM KBrO3), visible light intensity (300 W/cm2 tungsten lamp) and irradiation time (≤ 1 h). The proposed new-age inorganic-organic hybrid visible light photo-catalysts with superior structural and surface properties exhibit brilliant performance and fast responsiveness for water decontamination applications, in addition to their excellent chemical stability, high durability, multi-reusability, and cost-effectiveness.


Asunto(s)
Contaminantes Ambientales , Nanocompuestos , Contaminantes Químicos del Agua , Catálisis , Luz , Nanocompuestos/química , Norfloxacino , Preparaciones Farmacéuticas , Polímeros , Porosidad , Agua , Contaminantes Químicos del Agua/química
11.
J Hazard Mater ; 421: 126828, 2022 01 05.
Artículo en Inglés | MEDLINE | ID: mdl-34396964

RESUMEN

In this work, we manifested a new approach in designing solid-state colorimetric sensors for the selective optical sensing of As3+. The sensor fabrication is modulated using, (i) a cubic mesopores of ordered silica monolith, and (ii) a bimodal macro-/meso-porous polymer monolith, as hosting templates that are immobilized with a tailor-made chromoionophoric probe (DFBEP). The surface morphology and structural dimensions of the monolith templates and the sensor materials are characterized using p-XRD, XPS, FE-SEM-EDAX, HR-TEM-SAED, FT-IR, TGA, and BET/BJH analysis. The sensing components such as pH, probe content, sensor dosage, kinetics, temperature, analyte concentration, linear response range, selectivity, and sensitivity are optimized to arrive at the best sensing conditions. The silica and polymer-based monolithic sensors show a linear spectral response in the concentration range of 2-300 and 2-200 ppb, with a detection limit of 0.87 and 0.75 ppb for As3+, respectively. The real-time ion-monitoring propensity of the sensors is tested with spiked synthetic and real water samples, with a recovery efficiency of ≥99.1% (RSD ≤1.57%). The sensors act as both naked-eye optical sensors and preconcentrators, with a response time of ≤2.5 min. The molecular and photophysical properties of the DFBEP-As3+ complex are studied by TD-DFT calculations, using the B3LYP/6-31G (d,p) method.


Asunto(s)
Arsénico , Dióxido de Silicio , Iones , Polímeros , Porosidad , Espectroscopía Infrarroja por Transformada de Fourier
12.
Environ Res ; 203: 111861, 2022 01.
Artículo en Inglés | MEDLINE | ID: mdl-34389353

RESUMEN

In this work, we report two novel solid-state opto-chemosensors that proffer exclusive selectivity and excellent sensitivity for the naked-eye detection of ultra-trace Co2+ ions. The opto-chemosensors are concocted using structurally engineered porous silica and polymer monolith templates that are uniformly arranged with a chromoionophoric probe i.e., (Z)-2-mercapto-5-(quinolin-8-yldiazenyl)pyrimidine-4,6-diol (AQTBA). The probe anchored monolithic opto-chemosensors induces sequential color transitions, from yellowish-orange to dark brown, with incremental addition of Co2+ ions. The optimized ground state structure of the AQTBA probe and its AQTBA-Co2+ complex are analyzed using a gaussian 16 program at B3LYP level, with a 6-311+ G (d, p) basis set. The structural and surface morphology of the opto-sensors are characterized using various microscopic, spectroscopic, and diffraction techniques, which discloses a uniform pattern of pore network that proffers rapid ion diffusion kinetics to the probe chelating sites. The proposed monolithic sensors exhibit a high degree of tolerance towards various foreign cations and anions, thus revealing its exclusive selectivity in targeting ultra-trace concentrations of Co2+. The silica and polymer monolithic sensors exhibit a broad linear response range of 0-200 ppb, with a detection limit of 0.35 and 0.07 ppb for Co2+ ions, respectively. The unique features of the proposed sensors are their faster response kinetics (120 s), greater reusability (nine cycles), excellent chemical and thermal durability (pH ≤ 12.0; T ≤ 200 °C), with reliable data reproducibility (recovery ≥99.3 %; RSD ≤2.3 %). The proposed solid-state opto-chemosensors paves way for maximum waste reduction strategy, along with the feasibility for real-time monitoring of environmental and industrial water samples.


Asunto(s)
Colorimetría , Agua , Cationes , Reproducibilidad de los Resultados , Dióxido de Silicio
13.
Photochem Photobiol Sci ; 20(3): 401-420, 2021 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-33721273

RESUMEN

In this work, we report on the synthesis of a new-age reusable visible-light photocatalyst using a heterojunction nanocomposite of W6+/Yb3+ on a mixed-phase mesoporous network of monolithic TiO2. The structural properties of the monolithic photocatalysts are characterized using p-XRD, SEM-EDAX, TEM-SAED, XPS, PLS, UV-Vis-DRS, FT-IR, micro-Raman, TG-DTA, and N2 isotherm analysis. The electron microscopic analysis reveals a mesoporous network of ordered worm-like monolithic design, with a polycrystalline mixed-phase (anatase/rutile) TiO2 composite, as indicated by diffraction studies. The UV-Vis-DRS analysis reveals a redshift in the light absorption characteristics of the mixed-phase TiO2 monolith as a function of W6+/Yb3+ co-doping. It is observed that the use of (8.0 mol%)W6+/0.4 (mole%)Yb3+ co-doped monolithic TiO2 photocatalyst, with an energy bandgap of 2.77 eV demonstrates superior visible-light photocatalysis, which corroborates with the PLS studies in terms of voluminous e-/h+ pair formation. The practical application of the photocatalyst has been investigated through a time-dependent dissipation of enrofloxacin, a widely employed antimicrobial drug, and its degradation pathway has been monitored by LC-MS-ESI and TOC analysis. The impact of physio-chemical parameters such as solution pH, sensitizers, drug concentration, dopant/codopant stoichiometry, catalyst quantity, and light intensity has been comprehensively studied to monitor the process efficiency.


Asunto(s)
Enrofloxacina/química , Nanocompuestos/química , Contaminantes Químicos del Agua/química , Catálisis , Cromatografía Líquida de Alta Presión , Enrofloxacina/análisis , Concentración de Iones de Hidrógeno , Luz , Espectroscopía de Fotoelectrones , Fotólisis , Espectrometría de Masa por Ionización de Electrospray , Titanio/química , Tungsteno/química , Contaminantes Químicos del Agua/análisis , Iterbio/química
14.
Anal Bioanal Chem ; 413(12): 3177-3191, 2021 May.
Artículo en Inglés | MEDLINE | ID: mdl-33677651

RESUMEN

The article demonstrates the design of two solid-state sensors for the capturing of industrially relevant ultra-trace Co(II) ions using porous monolithic silica and polymer templates. The mesoporous silica reveals high surface area and voluminous pore dimensions that ensures homogeneous anchoring of 4-((5-(allylthio)-1,3,4-thiadiazol-2-yl)diazenyl)benzene-1,3-diol, as the chromoionophore. We report a first of its kind solid-state macro-/meso-porous polymer monolithic optical sensor from a monomeric chromoionophore, i.e., 2-(4-butylphenyl)diazenyl)-2-hydroxybenzylidene)hydrazine-1-carbothioamide. The monolithic solid-state sensors are characterized using HR-TEM-SAED, FE-SEM-EDAX, p-XRD, XPS, 29Si/13C CPMAS NMR, FT-IR, TGA, and BET/BJH analysis. The electron microscopic images reveal a highly ordered hexagonal mesoporous network of honeycomb pattern for silica monolith, and a long-range macroporous framework with mesoporous channels for polymer monolith. The sensors offer exclusive ion-selectivity and sensitivity for trace cobalt ions, through a concentration proportionate visual color transition, with a response kinetics of ≤ 5 min. The optimization of ion-sensing performance reveals an excellent detection limit of 0.29 and 0.15 ppb for Co(II), using silica- and polymer-based monolithic sensors, respectively. The proposed sensors are tested with industrial wastewater and spent Li-ion batteries, which reveals a superior cobalt ion capturing efficiency of ≥ 99.2% (RSD: ≤ 2.07%).

15.
J Chromatogr Sci ; 59(1): 55-63, 2021 Jan 01.
Artículo en Inglés | MEDLINE | ID: mdl-33086378

RESUMEN

The article reports on the development of an efficient, robust and sensitive HPLC-DAD method for the simultaneous determination of five fluoroquinolone-based antimicrobial drugs, namely ciprofloxacin, moxifloxacin, norfloxacin, ofloxacin and pefloxacin in both aquatic and tablet formulations. The robustness of the high-performance liquid chromatography with diode-array detection (HPLC-DAD) method has been evaluated through the concepts of quality-by-design (QbD) and full factorial design of experiments (DoEs), using a Minitab 17 statistical tool. The proposed method offers sequential separation with well-defined peak shape and resolution, and has also been evaluated by following international council for harmonization (ICH) pharmaceutical guidelines. A linear signal response has been achieved for the target fluoroquinolones (FQ) drugs in the concentration range of 45-20,000 ng/mL, with an average correlation coefficient (r2) value of 0.9997, and a data precision and accuracy range of 99.3-100.9%, with an RSD value of ≤0.95%, for hexaplicate measurements. The methodology offers superior sensitivity for the target FQ drugs, with the limit of detection (LD) range of 10-25 ng/mL, and the limit of quantification (LQ) range of 51-86 ng/mL, respectively. Using the proposed method, the article carries the first of its kind report in studying the degradation profile monitoring and drug assay determination in tablet formulations and under various physiological buffer stress conditions, for pharmaceutical validation.


Asunto(s)
Cromatografía Líquida de Alta Presión/métodos , Fluoroquinolonas/análisis , Fluoroquinolonas/química , Antiinfecciosos/análisis , Antiinfecciosos/química , Estabilidad de Medicamentos , Límite de Detección , Modelos Lineales , Reproducibilidad de los Resultados , Comprimidos
16.
Mikrochim Acta ; 187(7): 403, 2020 06 24.
Artículo en Inglés | MEDLINE | ID: mdl-32583066

RESUMEN

The possibility of a multifunctional and reversible solid-state colorimetric sensor is described for the identification and quantification of ultra-trace Cd2+ and Hg2+ ions, using a honeycomb-structured mesoporous silica monolith conjoined with an indigenous chromoionophoric probe, i.e., 4-hexyl-6-((5-mercapto-1,3,4-thiadiazol-2-yl)diazenyl)benzene-1,3-diol (HMTAR). The amphiphilic probe is characterized using NMR, FT-IR, HR-MS, and CHNS elemental analysis. The structural and surface properties of the monolithic template have been characterized using p-XRD, XPS, TEM-SAED, SEM-EDAX, FT-IR, TG-DTA, and N2 isotherm analysis. The unique structural features and distinct analytical properties of the solid-state sensor proffer a strong response in selectively signaling the target analytes. The probe (HMTAR) exhibits a 1:1 stoichiometric binding ratio with the target ions (Cd2+ & Hg2+), with a visual color change from pale orange to dark red for Cd2+ (525 nm, λmax), and to purple for Hg2+ (530 nm, λmax), respectively, in the pH range 7.0-8.0. The influence of various analytical criteria such as pH, temperature, response kinetics, critical probe concentration, sensor quantity, matrix tolerance, linear response range, reusability, the limit of detection (LOD), and quantification (LOQ) has been investigated to validate the sensor performance. The proposed method displays a linear signal response in the concentration range 5-100 µg/L, with a LOD value of 2.67 and 2.90 µg/L, for Cd2+ and Hg2+, respectively. The real-world efficacy of the sensor material has been tested with real and synthetic water samples with a significant recovery value of ≥ 99.2%, to authenticate its data reliability and reproducibility (RSD ≤ 3.53%). Graphical abstract.

17.
Nanotechnology ; 31(41)2020 Jul 21.
Artículo en Inglés | MEDLINE | ID: mdl-32554881

RESUMEN

In this study, we report on the superior ion-capturing and sensing competence of a new breed of aqua-compatible solid-state ion-sensor using a structurally organized polymer monolith, for the ocular sensing of trace levels of divalent copper ions. The polymer monolithic template exhibits a single block framework with a uniform structural pattern and porous network that serves as an efficient host for the homogeneous probe anchoring, to constitute a renewable solid-state optical sensor. Here, a series of solid-state colorimetric Cu(II) sensors has been designed using three indigenously synthesized chelating probes (molecules) namely, 4-butyl-N-(2-(2,4-dinitrophenyl)hydrazine-1-carbonothioyl)benzamide (BNHCB), 2-(thiophen-2-ylmethylene)hydrazinen-1-carbothioamide (TMHCA), and 4-butylphenyl(diazenyl)-2-mercaptopyrimidine-4,6-diol (BDMPD). The polymer monoliths are characterized using various surface and structural analysis techniques such as HR-SEM, HR-TEM, XPS, XRD, FT-IR, EDAX, and BET surface area analysis. The fabricated solid-state sensors exhibit excellent selectivity and sensitivity for copper ions with unique color transitions that are reliable even at ultra-trace (ppb) levels. The impact of diverse sensing parameters such as solution pH, probe concentration, sensor quantity, target ion concentration, temperature, response kinetics, and matrix tolerances have been optimized. The fabricated sensor materials proffer maximum sensing efficiency in neutral pH conditions, with a limit of detection (LD) and quantification (LQ) values of 0.56 and 1.87µg l-1, 0.30 and 1.0µg l-1, and 0.12 and 0.42µg l-1, for BNHCB-, BDMPD-, and TMHCA-anchored polymer sensors, respectively. The proposed reusable solid-state colorimetric sensors are environmentally benign, cost-effective and data reproducible, with superior analytical performance.

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