Development of hybrid MIL-53(Al)@CBS for ternary adsorption of tetracyclines antibiotics in water: Physical interpretation of the adsorption mechanism.

In this study, a hybrid material, MIL-53(Al)@CBS, was synthesized via the solvothermal method, involving the growth of MIL-53(Al) crystals on cocoa bean shell residues (CBS). Physicochemical characterization techniques, including TGA, BET, FTIR, XRD, and SEM, confirmed successful hybridization. MIL-53(Al)@CBS was employed as an adsorbent for antibiotics (oxytetracycline, tetracycline, chlortetracycline) separation from aqueous solutions. Parameters like pH, adsorbent dose, concentration, time, and temperature were systematically evaluated. FTIR revealed π-π interactions and hydrogen bonds between tetracyclines and the adsorbent. MIL-53(Al)@CBS exhibited adsorption, with removal rates up to 98.92%, 99.04%, and 98.24% for OTC, TC, and CTC, respectively. Kinetics suggested adsorption depends on active site availability, with TC adsorbing fastest. Microscopic models showed adsorption on three distinct active site types with different affinities without competition or adherence to the Langmuir hypothesis. Importantly, MIL-53(Al)@CBS maintained high adsorption capacity even after ten washing cycles, highlighting its potential for water treatment.

Age of autism diagnosis in Latin American and Caribbean countries.

LAY ABSTRACT: An earlier diagnosis of autism spectrum disorder might lead to earlier intervention. However, people living in Latin American and Caribbean countries do not have much knowledge about autism spectrum disorder symptoms. It has been suggested that the older a child is when diagnosed, the fewer opportunities he or she will have to receive services. We asked 2520 caregivers of autistic children in six different Latin America and Caribbean Countries, the child's age when they noticed some developmental delays and their child's age when they received their first autism spectrum disorder diagnosis. Results indicate that, on average, caregivers were concerned about their child's development by 22 months of age; however, the diagnosis was received when the child was 46 months of age. In addition, older children with better language abilities and public health coverage (opposed to private health coverage) were diagnosed later. On the contrary, children with other medical problems and more severe behaviors received an earlier diagnosis. In our study, children were diagnosed around the time they entered formal schooling, delaying the access to early intervention programs. In summary, the characteristics of the autistic person and the type of health coverage influence the age of diagnosis in children living in Latin America and Caribbean Countries.

Application of a novel hybrid MIL-53(Al)@rice husk for the adsorption of glyphosate in water: Characteristics and mechanism of the process.

The development of new materials that have a high capacity to remove pollutants in water-based media is becoming increasingly important because of the serious contamination of water and the negative impact on biodiversity and public health. The presence of glyphosate in water, the most widely used herbicide worldwide, has triggered alerts owing to the collateral effects it may cause on human health. The main objective of the present study was to investigate the potential of the hybrid material MIL-53(Al)@RH for the adsorption of glyphosate in aqueous solution. The material was obtained following the methodology of MIL-53(Al) synthesis in the presence of hydrolyzed rice husk assisted by microwave. Batch adsorption experiments were carried out to evaluate the adsorbent dosage, pH0 solution effect, contact time, adsorbate concentration, and temperature effect. The results demonstrated that a maximum adsorption capacity of 296.95 mg g-1, at pH0 4 with a ratio of 0.04 g MIL-53(Al)@RH/50 mL of solution, was achieved in 30 min. The Avrami and pseudo-second order models appropriately described the adsorption kinetics and the equilibrium by Langmuir and Sips models. The enthalpy changes (ΔH°) determined propose an endothermic reaction governed by chemisorption, corroborating the kinetic and equilibrium settings. Hydrogen bonds, π*-π interactions, and complexation between the metal centers of MIL-53(Al) and the anionic groups of glyphosate were postulated to be involved as adsorption mechanisms. Finally, for practical application, MIL-53(Al)@RH was packed in a column for a fixed-bed test which revealed that the hybrid can remove glyphosate with an adsorption capacity of 76.304 mg L-1, utilizing 90% of the bed.

Polymeric membranes functionalized with nanomaterials (MP@NMs): A review of advances in pesticide removal.

The excessive contamination of drinking water sources by pesticides has a pernicious impact on human health and the environment since only 0.1% of pesticides is utilized effectively to control the and the rest is deposited in the environment. Filtration by polymeric membranes has become a promising technique to deal with this problem; however, the scientific community, in the need to find better pesticide retention results, has begun to meddle in the functionalization of polymeric membranes. Given the great variety of membrane, polymer, and nanomaterial synthesis methods present in the market, the possibilities of obtaining membranes that adjust to different variables and characteristics related to a certain pesticide are relatively extensive, so it is expected that this technology will represent one of the main pesticide removal strategies in the future. In this direction, this review focused on, - the main characteristics of the nanomaterials and their impact on pristine polymeric membranes; - the removal performance of functionalized membranes; and - the main mechanisms by which membranes can retain pesticides. Based on these insights, the functionalized polymeric membranes can be considered as a promising technology in the removal of pesticides since the removal performance of this technology against pesticide showed a significant increase. Obtaining membranes that adjust to different variables and characteristics related to a certain pesticide are relatively extensive, so it is expected that functionalized membrane technology will represent one of the main pesticide removal strategies in the future.

Development of an inexpensive and rapidly preparable enzymatic pencil graphite biosensor for monitoring of glyphosate in waters.

Glyphosate (GLY) is the most widely used non-selective broad-spectrum herbicide worldwide under well-reported side effects on the environment and human health. That's why it's necessary to control its presence in the environment. This work describes the development of an affordable, simple, and accurate electrochemical biosensor using a pencil graphite electrode as support, a horseradish peroxidase enzyme immobilized on a polysulfone membrane doped with multi-walled carbon nanotubes. The developed electrochemical sensor was used in the determination of GLY in river and drinking water samples. Cyclic voltammetry and amperometry were used as electrochemical detection techniques for the characterization and analytical application of the developed biosensor. The working mechanism of the biosensor is based on the inhibition of the peroxidase enzyme by GLY. Under optimal experimental conditions, the biosensor showed a linear response in the concentration range of 0.1 to 10 mg L-1. The limits of detection and quantification are 0.025 ± 0.002 and 0.084 ± 0.007 mg L-1, respectively, which covers the maximum residual limit established by the EPA for drinking water (0.7 mg L-1). The proposed biosensor demonstrated high reproducibility, excellent analytical performance, repeatability, and accuracy. The sensor proved to be selective against other pesticides, organic acids, and inorganic salts. Application on real samples showed recovery rates ranging between 98.18 ± 0.11 % and 97.32 ± 0.23 %. The analytical features of the proposed biosensor make it an effective and useful tool for the detection of GLY for environmental analysis.

HPLC-potentiometric method for determination of biogenic amines in alcoholic beverages: A reliable approach for food quality control.

Determination of ten biogenic amines in alcoholic beverages by HPLC coupled to a potentiometric detector for food quality control is herein presented. Biogenic amines were separated by ion-pair chromatography on a C18 column using a gradient mobile phase of acetic acid, acetonitrile, and butane-sulfonic acid. Detection was accomplished by a miniaturized amine-selective electrode. The method was validated following ICH and Eurachem guidelines. Linear regression models provided R2 values from 0.9870 ± 0.0019 to 0.9991 ± 0.0014 for tyramine and cadaverine, respectively. Detection and quantification limits depend on the molecular weight of BAs, ranging from 9.3 to 60.5 and from 31.1 to 202.3 µg L-1 for methylamine and spermine, respectively. Repeatability and intermediate precision showed RSD values lower than 5.8 and 8.3%, respectively. Accuracy of assays yielded recovery values from 86.4 to 109.9%. The biogenic amines content in red wine, white wine, and beer samples were 7.54, 5.24, and 4.58 mg L-1, respectively.

Challenges in the design of electrochemical sensor for glyphosate-based on new materials and biological recognition.

Glyphosate (GLY) is the main ingredient in the weed killer Roundup and the most widely used pesticide in the world. Studies of the harmful effects of GLY on human health began to become more wide-ranging after 2015. GLY is listed by the International Agency for Research on Cancer (IARC) as a carcinogenic hazard to humans. Moreover, GLY has the property to complex with transition metals and are stable for long periods, being considered a high-risk element for different matrices, such as environmental (soil and water) and food (usually genetically modified crops). Since that, it was noticed an increment in the development of new analytical methods for its determination in different matrices like food, environmental and biological fluids. Noteworthy, the application of electrochemical techniques for downstream detection sparked interest due to the ability to minimize or eliminate the use of polluting chemicals, using simple and affordable equipment. This work aims to review the contribution of the electroanalytical methods for the determination of GLY in different food and environmental matrices. Parameters such as the electrochemical transduction techniques based on the electrical measurement signals, receptor materials for electrodes preparation, and the detection mechanisms are described in this review. The literature review shows that the electrochemical sensors are powerful detection system that can be improved by their design and by their portability to fulfil the needs of the GLY determination in laboratory benches, or even in situ analysis.

Nanostructured pencil graphite electrodes for application as high power biocathodes in miniaturized biofuel cells and bio-batteries.

This work describes a simple method for the fabrication of an enzymatic electrode with high sensitivity to oxygen and good performance when applied as biocathode. Pencil graphite electrodes (PGE) were chosen as disposable transducers given their availability and good electrochemical response. After electrochemical characterization regarding hardness and surface pre-treatment suited modification with carbon-based nanostructures, namely with reduced graphene, MWCNT and carbon black for optimal performance was proceeded. The bioelectrode was finally assembled through immobilization of bilirubin oxidase (BOx) lashed on the modified surface of MWCNT via π-π stacking and amide bond functionalization. The high sensitivity towards dissolved oxygen of 648 ± 51 µA mM-1 cm-2, and a LOD of 1.7 µM, was achieved for the PGE with surface previously modified with reduced graphene (rGO), almost the double registered for direct anchorage on the bare PGE surface. Polarization curves resulted in an open circuit potential (OCP) of 1.68 V (vs Zn electrode) and generated a maximum current density of about 650 µA cm-2 in O2 saturated solution.

Biosensing based on pencil graphite electrodes.

Pencil leads have been increasingly used as electrode material in electrochemical applications. Commonly denominated as pencil graphite electrodes (PGE), they represent a viable alternative to other standard electrodes due to their comparable electrical properties but mainly for their low cost and availability, enabling disposable applications. In order to achieve the best analytical performance literature evidences the type of lead (hardness level) and electrode surface pre-treatment are critical to the envisaged application. The present review describes the use of PGE in biosensing analysis, more specifically those sensors comprising immobilized enzymes but also briefly referring nucleic acids and other biological entities. It lays an emphasis in the immobilization process of the biological entities while focusing in the analytical performance of each biosensor, mainly sensitivity, linear range and limit of detection as comparative criteria. This review also addresses the main characteristics and properties of PGEs as transducer material in the electrochemical field.

Potentiometric perchlorate determination at nanomolar concentrations in vegetables.

In this work, an expeditious method based on the multi-commutated flow-analysis concept with potentiometric detection is proposed to perform determinations of the emergent contaminant perchlorate in vegetable matrices down to nanomolar concentration. To accomplish the task, a tubular shaped potentiometric sensor selective to perchlorate ion was constructed with a PVC membrane containing 12mmol/kg of the polyamine bisnaphthalimidopropyl-4,4'-diaminodiphenylmethane and 2-nitrophenyl phenyl ether 68% (w/w) as plasticizer casted on a conductive epoxy resin. Under optimal flow conditions, the sensor responded linearly in the concentration range of 6.3×10-7-1.0×10-3mol/L perchlorate. In order to extend the determinations to lower concentrations (4.6(±1.3)×10-10mol/L perchlorate), a column packed with 70mg of sodium 2,5,8,11,14-pentaoxa-1-silacyclotetradecane-polymer was coupled to the flow-system thus enabling prior pre-concentration of the perchlorate. The proposed procedure provides a simpler alternative for the determination of perchlorate in foods, nowadays only allowed by sophisticated and expensive equipment and laborious methods.

Vortex-assisted liquid-liquid micro-extraction and high-performance liquid chromatography for a higher sensitivity methyl methacrylate determination in biological matrices.

A vortex-assisted liquid-liquid micro-extraction coupled with high-performance liquid chromatography, with UV-vis, is proposed to pre-concentrate methyl methacrylate and to improve separation in biological matrices. The use of 1-octanol as extracting phase, its volume, the need for a dispersant agent, the agitation conditions and the cooling time before phase separation were evaluated. In optimum conditions, enrichment factors of 20 (±0.5) and enrichment recovery of 99% were obtained. The straightforward association of this extraction process with the HPLC method, previously regulated by the International Organization for Standardization, afforded a detection limit of 122 ng/mL and a quantification limit of 370 ng/mL. The within-batch precision, relative standard deviation, was 3% for a sample with 1.49 µg/mL and 4% for a sample with 13.4 µg/mL. The results showed a between batch-precision of 21% for experiments performed on five different days, for a sample with a concentration of 1.10 µg/mL in methyl methacrylate.

Fully automated analytical procedure for propofol determination by sequential injection technique with spectrophotometric and fluorimetric detections.

In this work, an application of an enzymatic reaction for the determination of the highly hydrophobic drug propofol in emulsion dosage form is presented. Emulsions represent a complex and therefore challenging matrix for analysis. Ethanol was used for breakage of a lipid emulsion, which enabled optical detection. A fully automated method based on Sequential Injection Analysis was developed, allowing propofol determination without the requirement of tedious sample pre-treatment. The method was based on spectrophotometric detection after the enzymatic oxidation catalysed by horseradish peroxidase and subsequent coupling with 4-aminoantipyrine leading to a coloured product with an absorbance maximum at 485 nm. This procedure was compared with a simple fluorimetric method, which was based on the direct selective fluorescence emission of propofol in ethanol at 347 nm. Both methods provide comparable validation parameters with linear working ranges of 0.005-0.100 mg mL(-1) and 0.004-0.243 mg mL(-1) for the spectrophotometric and fluorimetric methods, respectively. The detection and quantitation limits achieved with the spectrophotometric method were 0.0016 and 0.0053 mg mL(-1), respectively. The fluorimetric method provided the detection limit of 0.0013 mg mL(-1) and limit of quantitation of 0.0043 mg mL(-1). The RSD did not exceed 5% and 2% (n=10), correspondingly. A sample throughput of approx. 14 h(-1) for the spectrophotometric and 68 h(-1) for the fluorimetric detection was achieved. Both methods proved to be suitable for the determination of propofol in pharmaceutical formulation with average recovery values of 98.1 and 98.5%.

A SO2-selective electrode based on a Zn-porphyrin for wine analysis.

This work describes the assessment of a SO2-selective electrode based on the use of the neutral carrier 5,10,15,20-tetraphenyl(porphyrinate)zinc(II) in a PVC membrane plasticized with 2-nitrophenyl phenyl ether. After being conditioned in 2 mol L(-1) diethylamine solution for 24 h, the electrode exhibited selective anionic response toward the analyte in a concentration interval of more than four decades, with an slope of -59.5 mV dec(-1), a practical detection limit of 3.7×10(-6) mol L(-1) and a low limit of linear range of 7.2×10(-6) mol L(-1). The response mechanism is based on the displacement of the diethylamine:metalloporphyrin complex equilibrium within membrane bulk, inducing a variation in the cationic-sites to ionophore ratio. In turn, free hydroxyl ions are complexed by the displaced ionophore in a ratio 1:1 and translated as single negative charge nernstian response. Finally, the selectivity of the electrode is evaluated in view of its application to wine analysis. Results had high accuracy and precision when compared with a reference method.

Physical-chemical parameters and validation of a colorimetric method for deoxycholic and ursodeoxycholic acids: kit reagent and optical sensor.

The simple and low cost ß-cyclodextrin (ß-CD)-phenolphthalein (PHP) inclusion complex was used for both the study of physical-chemical parameters and validation of analytical procedures for deoxycholic acid (DCA) and ursodeoxycholic acid (UDCA) determinations in different formulations. The usefulness of this inclusion complex is proposed either in the form of kit reagent and as an original optical sensor for DCA and UDCA. The results showed that temperature had a negative effect on the equilibrium constant resulting in high negative values of enthalpy and positive values of entropy. The half-life values for DCA and UDCA measurements were 68.71 and 294.71 days, respectively. The method was validated showing limits of detection and quantification of 4.92×10(-5) mol L(-1) and 1.64×10(-4) mol L(-1) for DCA, 1.14×10(-5) mol L(-1) and 3.79×10(-5) mol L(-1) for UDCA, respectively. The developed optical sensor also showed response linearity, ease of implementation and potential application in fast screening tasks even out of the laboratory.

A reflectance flow-through thionine sol-gel sensor for the determination of Se(IV).

In this work, a reversible sensor to assess the total Se(IV) content in samples is described. Pre-activated glass slides were spin-coated with 100 microL of a 20-h aged sol-gel mixture of 1 mL of tetramethoxysilane, 305 microL of 50 mmol L(-1) HCl and 2.0 mg of thionine. The flow-cell consisted of one of those slides as a window, and was filled with beads of a polystyrene anionic exchange resin to retain Se(IV) in the form of selenite ions. A reflectance transduction scheme at a wavelength of 596 nm was adopted. The cell was coupled to a multicommutation flow system where a programmed volume of a sample solution and 373 microL of 0.4 mmol L(-1) iodide in a 1.6 mol L(-1) HCl solution were sequentially inserted into the cell. The iodine produced from the reaction of retained Se(IV) with iodide bleached the blue color of thionine. Considering a sample volume of 2.30 mL, with which the preconcentration step was minimized, a linear dynamic working range between 1.5 to 20 microg mL(-1) and a detection limit of 0.29 microg mL(-1) were obtained. The sensor enabled us to perform approximately 200 assays, and provided results similar to those of electrothermal atomic absorption spectrometry.

Simple determination of deoxycholic and ursodeoxycholic acids by phenolphthalein-beta-cyclodextrin inclusion complex.

An expeditious colorimetric methodology for the determination of the deoxycholic acid (DCA) and of the ursodeoxycholic acid (UDCA) in pharmaceutical formulations is reported. The method is based on their competitive complexation reaction with a color indicator to form beta-cyclodextrin-inclusion complexes. Several pH color indicators were tested, but phenolphthalein (PHP) showed the best interaction with the beta-cyclodextrin (beta-CD) with an inclusion yield higher than 95%. The best concentrations of beta-cyclodextrin to form inclusion complexes were 1.24 x 10(-3) and 6.2 x 10(-4) M at pH 9.5 and 10.5. Statistical analysis of the results showed that the pH had a significant effect on the DCA determination and that high beta-CD-PHP inclusion complex concentrations had a significant negative effect on the UDCA determination (p < 0.05). The limit of detection and limit of quantification were 3.94 x 10(-5) and 1.31 x 10(-4) M for DCA (range: 6.1 x 10(-6)-3.13 x 10(-3) M), 4.08 x 10(-5) and 1.36 x 10(-4) M for UDCA (range: 6.05 x 10(-6)-3.88 x 10(-4) M). This simple and cheap method showed high stability and feasible instrumentation.

Modeling, structural, and spectroscopic studies of lanthanide-organic frameworks.

In this paper, we report the hydrothermal synthesis of three lanthanide-organic framework materials using as primary building blocks the metallic centers Eu(3+), Tb(3+), and Gd(3+) and residues of mellitic acid: [Ln(2)(MELL)(H(2)O)(6)] (where Ln(3+) = Eu(3+), Tb(3+), and Gd(3); hereafter designated as (1), (2) and (3)). Structural characterization encompasses single-crystal X-ray diffraction studies, thermal analysis, and vibrational spectroscopy, plus detailed investigations on the experimental and predicted (using the Sparkle/AM1 model) photophysical luminescent properties. Crystallographic investigations showed that the compounds are all isostructural, crystallizing in the orthorhombic space group Pnnm and structurally identical to the lanthanum 3D material reported by the group of Williams. (2) is highly photoluminescent, as confirmed by the measured quantum yield and lifetime (37% and 0.74 ms, respectively). The intensity parameters (Omega(2), Omega(4), and Omega(6)) of (1) were first calculated using the Sparkle/AM1 structures and then employed in the calculation of the rates of energy transfer (W(ET)) and back-transfer (W(BT)). Intensity parameters were used to predict the radiative decay rate. The calculated quantum yield derived from the Sparkle/AM1 structures was approximately 16%, and the experimental value was 8%. We attribute the registered differences to the fact that the theoretical model does not consider the vibronic coupling with O-H oscillators from coordinated water molecules. These results clearly attest for the efficacy of the theoretical models employed in all calculations and open a new window of interesting possibilities for the design in silico of novel and highly efficient lanthanide-organic frameworks.

On-line coupling of sequential injection extraction with restricted-access materials and post-column derivatization for sample clean-up and determination of propranolol in human plasma.

The presented paper deals with a new methodology for direct determination of propranolol in human plasma. The methodology described is based on sequential injection analysis technique (SIA) coupled with solid phase extraction (SPE) column based on restricted access materials (RAM). Special RAM column containing 30 microm polymeric material-N-vinylacetamide copolymer was integrated into the sequential injection manifold. SIA-RAM system was used for selective retention of propranolol, while the plasma matrix components were eluted with two weak organic solutions to waste. Due to the acid-basic and polarity properties of propranolol molecule and principles of reversed-phase chromatography, it was possible to retain propranolol on the N-vinylacetamide copolymer sorbent (Shodex MSpak PK-2A 30 microm (2 mm x 10 mm)). Centrifuged plasma samples were aspirated into the system and loaded onto the column using acetonitrile-water (5:95, v/v), pH 11.00, adjusted by triethylamine. The analyte was retained on the column while proteins contained in the sample were removed to waste. Interfering endogenous substances complicating detection were washed out by acetonitrile-water (15:85), pH 11.00 in the next step. The extracted analyte was eluted by means of tetrahydrofuran-water (25:75), pH 11.00 to the fluorescence detector (emission filter 385 nm). The whole procedure comprising sample pre-treatment, analyte detection and column reconditioning took about 15 min. The recoveries of propranolol from undiluted plasma were in the range 96.2-97.8% for three concentration levels of analyte. The proposed SIA-RAM method has been applied for direct determination of propranolol in human plasma.

Simple and inexpensive flow L-glutamate determination using pumpkin tissue.

This work refers to a very easy to implementate flow injection system with potentiometric detection for l-glutamate determination in food samples. The proposed procedure is based on measurement of carbon dioxide produced by decarboxylation of l-glutamate catalyzed by l-glutamate decarboxylase (E.C. 4.1.1.1.5) from Cucurbita maxima (pumpkin). The FI potentiometric system includes an enzymatic reactor with a length of 8 cm and thickness of 5 mm packed with 200 mg of a C. maxima outer layer cut in to small pieces. The proposed procedure allowed l-glutamate determinations in the concentration interval of 10-100 mmol L(-1) for an injected sample volume of 50 microL. A phosphate buffer (0.1 mol L(-1), pH 5.5) solution flowing at 1.4 mL min(-1) was used as the carrier solution in the system. The results obtained in the analysis of food samples revealed a relative error lower than 5% when compared with those provided by the spectrophometric reference procedure. The immobilized reactor retained its initial activity for 21 days. It was possible to measure 40 samples/h with the flow system proposed.