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The development of a homemade carbon black composite filament with polylactic acid (CB-PLA) is reported. Optimized filaments containing 28.5% wt. of carbon black were obtained and employed in the 3D printing of improved electrochemical sensors by fused deposition modeling (FDM) technique. The fabricated filaments were used to construct a simple electrochemical system, which was explored for detecting catechol and hydroquinone in water samples and detecting hydrogen peroxide in milk. The determination of catechol and hydroquinone was successfully performed by differential pulse voltammetry, presenting LOD values of 0.02 and 0.22 µmol L-1, respectively, and recovery values ranging from 91.1 to 112% in tap water. Furthermore, the modification of CB-PLA electrodes with Prussian blue allowed the non-enzymatic amperometric detection of hydrogen peroxide at 0.0 V (vs. carbon black reference electrode) in milk samples, with a linear range between 5.0 and 350.0 mol L-1 and low limit of detection (1.03 µmol L-1). Thus, CB-PLA can be successfully applied as additively manufactured electrochemical sensors, and the easy filament manufacturing process allows for its exploration in a diversity of applications.

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This research reports, for the first time, the immobilization of an enzyme - Rhus vernificera laccase - on cashew gum (CG) nanoparticles (NPs) and its application as a biological layer in the design and development of an electrochemical biosensor. Laccase-CG nanoparticles (LacCG-NPs) were prepared by the nanoprecipitation method and characterized by UV-Vis spectrophotometry, atomic force microscopy, scanning electron microscopy, attenuated total reflectance-Fourier-transform infrared spectroscopy, circular dichroism, cyclic voltammetry, and electrochemical impedance spectroscopy. The average size and stability of the NPs were predicted by DLS and zeta potential. The ATR-FTIR results clearly demonstrated an interaction between -NH and -OH groups to form LacCG-NPs. The average size found for LacCG-NPs was 280 ± 53 nm and a polydispersity index of 0.309 ± 0.08 indicated a good particle size distribution. The zeta potential shows a good colloidal stability. The use of a natural product to prepare the enzymatic nanoparticles, its easy synthesis and the immobilization efficiency should be highlighted. LacCG-NPs were successfully applied as a biolayer in the development of an amperometric biosensor for catechol detection. The resulting device showed a low response time (6 s), good sensitivity (7.86 µA µM-1 cm-2), wide linear range of 2.5 × 10-7-2.0 × 10-4 M, and low detection limit (50 nM).

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Carbon Black (CB) has acquired a prominent position as a carbon nanomaterial for the development of electrochemical sensors and biosensors due to its low price and extraordinary electrochemical and physical properties. These properties are highly dependent on the surface chemistry and thus, the effect of functionalization has been widely studied for different applications. Meanwhile, the influence of CB functionalization over its properties for electroanalytical applications is still being poorly explored. In this study, we describe the use of chemically functionalized CB Vulcan XC 72R for the development of sensitive electrochemical biosensors. The chemical pre-treatment increased the material wettability by raising the concentration of surface oxygenated functional groups verified from elemental analysis and FTIR measurements. In addition, it was observed an enhancement of almost 100-fold on the electron transfer rate constant (k0) related to unfunctionalized CB, confirming a remarkable improvement of the electrocatalytic properties. Finally, we constructed a Tyrosinase (Tyr) biosensor based on functionalized CB and dihexadecylphosphate (DHP) for the determination of catechol in water samples. The resulting device displayed an excellent stability with a limit of detection of 8.7 × 10-8 mol L-1 and a sensitivity of 539 mA mol-1 L. Our results demonstrate that functionalized CB provides an excellent platform for biosensors development.

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INTRODUCTION: The tree Trichilia catigua, popularly known as "catuaba", shows several biological activities and has emerged as a potential source of new drugs. Considering that more than 10 species are known under the same popular name, regulatory agencies require more rigorous quality control of this medicinal plant. OBJECTIVE: To develop and validate a methodology using capillary electrophoresis (CE) with ultraviolet (UV) detection for analysing polyphenols in the ethyl-acetate fraction (EAF) of Trichilia catigua. METHODOLOGY: Different electrophoretic conditions (such as wavelength of UV detection, voltage, buffer concentration and pH, cyclodextrin type and concentration) were investigated. After optimisation, borate buffer 80 mmol/L at pH 8.80 with 2-hydroxypropyl-ß-cyclodextrin 10 mmol/L was selected as background electrolyte. A voltage reduction was used to improve the separation of a diastereomeric pair of cinchonains. RESULTS: The method proved to be simple, sensitive, accurate, linear, precise and reproducible. For the first time in natural products analysis, a voltage reduction and hydroxypropyl-ß-cyclodextrin were used to improve the separation of diastereomeric pairs. Until now, this is the only described methodology able to separate catechin, epicatechin, cinchonains Ia, Ib, IIa, and IIb from Trichilia catigua samples on the same run in less than 12 min. When compared to the high performance liquid chromatography with photo-diode array detection (HPLC-PDA) method previously developed by our research group, the CE method was more efficient, faster, less expensive and less polluting. CONCLUSION: Our results demonstrate that this method could be employed in a quality-control laboratory for the quantification of polyphenols in EAF of Trichilia catigua. Copyright © 2016 John Wiley & Sons, Ltd.

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A glassy carbon electrode (GCE) was modified with multi-walled carbon nanotubes (MWCNT) and silver nanoparticles (AgNPs) and applied to the simultaneous determination of hydroquinone (HQ), catechol (CC), bisphenol A (BPA) and phenol by using square-wave voltammetry. The MWCNTs were deposited on the GCE and the AgNPs were then electrodeposited onto the MWCNT/GCE by the application of 10 potential sweep cycles using an AgNP colloidal suspension. The modified GCE was characterized by using SEM, which confirmed the presence of the AgNPs. The electrochemical behavior of the material was evaluated by using cyclic voltammetry, and by electrochemical impedance spectroscopy that employed hexacyanoferrate as an electrochemical probe. The results were compared to the performance of the unmodified GCE. The modified electrode has a lower charge-transfer resistance and yields an increased signal. The peaks for HQ (0.30 V), CC (0.40 V), BPA (0.74 V) and phenol (0.83 V; all versus Ag/AgCl) are well separated under optimized conditions, which facilitates their simultaneous determination. The oxidation current increases linearly with the concentrations of HQ, CC, BPA and phenol. Detection limits are in the order of 1 µM for all 4 species, and the sensor is highly stable and reproducible. The electrode was successfully employed with the simultaneous determination of HQ, CC, BPA and phenol in spiked tap water samples. Graphical abstract A glassy carbon electrode was modified with carbon nanotubes and silver nanoparticles and then successfully applied to the simultaneous determination of four phenolic compounds. The sensor showed high sensitivity in the detection of hydroquinone, catechol, bisphenol A and phenol in water samples.

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Polyphenols have attracted attention due to their antioxidant capacity and beneficial effects to health. Therefore, fast, inexpensive, and efficient methods to discriminate and to quantify polyphenols are of interest for food industry. In this paper, Layer-by-Layer films of poly(allylamine hydrochloride) and iron tetrasulfonated phthalocyanine were employed as sensor for determination of polyphenols in green tea (camellia sinensis), and green and roasted mate teas (ilex paraguariensis). The polyphenol sensor was tested in catechol standard solution by differential pulse voltammetry (DPV), reaching a limit of detection of 1.76 × 10-7 mol/L. The determination of polyphenols in the tea samples was obtained by analytical curve and catechol standard addition using electrochemical techniques. Projection techniques (information visualization) were applied to the DPV results of the tea samples and a pattern of separation following the phenolic content was obtained. The results support the application of the sensor in fast classification of beverages according to their polyphenol content.

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Volatile phenols, such as 4-ethyphenol (4-EP) and 4-ethylguaiacol (4-EG), are responsible for the "Brett character" found in wines contaminated with Brettanomyces yeast (i.e., barnyard, animal, spicy and smoky aromas). In these trials, we explore the effectiveness of polyaniline-based compounds (polyaniline emeraldin salt (PANI-ES) and polyanaline emeraldin base (PANI-EB)), for the removal of 4-EP and 4-EG from acidic model solutions and red wine. First, a screening study, performed in an acidified 12% ethanol solution, was used to optimize parameters such as contact time and the amount of polymers required to remove 4-EP and 4-EG. Then, the trapping ability of PANI agents towards 4-EP and 4-EG was evaluated in a model solution containing other wine phenolics that could potentially be trapped by PANI (i.e., gallic acid and 4-methylcatechol). The results of this trial showed that both PANI compounds were capable of removing 4-EP, 4-EG, regardless of the presence of other phenolic compounds present at a much higher concentration. Finally, the capturing ability of PANI was evaluated in a red wine sample containing 5 mg·L-1 of 4-EP, 5 mg·L-1 of 4-EG and 2.03 ± 0.02 g·L-1 of total phenolics. The results showed that PANI-EB removed significantly more 4-EP and 4-EG than PANI-ES. For instance, a treatment with 10 mg·mL-1 of PANI-EB produced a 67.8% reduction of 4-EP, 50% reduction of 4-EG and 41.38% decrease in total phenols.

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This paper reports on the use of the crude extract of avocado (CEA) fruit (Persea americana) as a source of tyrosinase enzyme. CEA was immobilized via layer by layer (LbL) technique onto indium tin oxide (ITO) substrates and applied in the detection of monophenol using a potentiometric biosensor. Poly(propylene imine) dendrimer of generation 3 (PPI-G3) was used as a counter ion in the layer by layer process due to its highly porous structure and functional groups suitable for enzyme linkage. After the immobilization of the crude CEA as multilayered films, standard samples of monophenol were detected in the 0.25-4.00 mM linear range with approximately 28 mV mM(-1) of sensitivity. This sensitivity is 14 times higher than the values found in the literature for a similar system. The results show that it is possible to obtain efficient and low-cost biosensors for monophenol detection using potentiometric transducers and alternative sources of enzymes without purification.

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An approach based on the electrochemical detection of the horseradish peroxidase enzymatic reaction by means of square wave voltammetry was developed for the determination of phenolic compounds in environmental samples. First, a systematic optimization procedure of three factors involved in the enzymatic reaction was carried out using response surface methodology through a central composite design. Second, the enzymatic electrochemical detection coupled with a multivariate calibration method based in the partial least-squares technique was optimized for the determination of a mixture of five phenolic compounds, i.e. phenol, p-aminophenol, p-chlorophenol, hydroquinone and pyrocatechol. The calibration and validation sets were built and assessed. In the calibration model, the LODs for phenolic compounds oscillated from 0.6 to 1.4 × 10(-6) mol L(-1). Recoveries for prediction samples were higher than 85%. These compounds were analyzed simultaneously in spiked samples and in water samples collected close to tanneries and landfills.

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The crude ethanolic extract from aerial parts of Pothomorphe umbellata L. (Piperaceae) and fractions obtained by partitions sequentially among water-methanol, methylene chloride, and ethyl acetate, as well as the major constituent, 4-nerolidylcatechol, were, respectively, evaluated and evidenced for antioxidant and cytotoxic effects through fluorometric microplate and microculture tetrazolium assays in HL-60 cells. The crude ethanolic extract demonstrated the preeminent antioxidant activity (IC50 = 1.2 µg/mL) against exogenous cytoplasmic reactive oxygen species, followed by the water-methanolic (IC50 = 4.5 µg/mL), methylene chloride (IC50 = 5.9 µg/mL), ethyl acetate (IC50 = 8.0 µg/mL), 4-nerolidylcatechol (IC50 = 8.6 µg/mL), and the sterol fractions (IC50 > 12.5 µg/mL). Vitamin C, the positive control used in this assay, presented IC50 value equivalent to 1.7 µg/mL. 4-Nerolidylcatechol (IC50 = 0.4 µg/mL) and methylene chloride fraction (IC50 = 2.3 µg/mL) presented considerable cytotoxicity probably because of the presence of an o-quinone, an auto-oxidation by product of the catechol. Polar compounds, present in the ethanol extract, appear to increase the solubility and stability of the major active constituent, acting synergistically with 4-nerolidylcatechol, improving its pharmacokinetic parameters and increasing significantly its antioxidant activity which, in turn, suggests that the aqueous-ethanolic extract, used in folklore medicine, is safe and effective.

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A bio-inspired complex, [(bpbpmp)Fe(III)(m-OAc)(2)Cu(II)](ClO(4)), was combined with a zwitterionic surfactant (ImS3-14) stabilizing pre-formed palladium nanoparticles and coated on a glassy carbon electrode (GCE). This bio-inspired surfactant film was capable of catalyzing redox reactions of dihydroxybenzenes, thus allowing the simultaneous electrochemical quantification of CC and HQ in cigarette residue samples by square-wave voltammetry (SWV). The best experimental conditions were obtained using phosphate buffer solution (0.1 mol L(-1), pH 7.0), with 1.3 nmol of the bio-inspired complex, 0.15 µmol of the surfactant and 1.08 nmol of Pd. The best voltammetric parameters were: frequency 100 Hz, pulse amplitude 40 mV and step potential 8 mV. The limits of detection calculated from simultaneous curves were found to be 2.2 × 10(-7) and 2.1 × 10(-7) mol L(-1) for HQ and CC respectively.

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This study describes the development of amperometric sensors based on poly(allylamine hydrochloride) (PAH) and lutetium bisphthalocyanine (LuPc(2)) films assembled using the Layer-by-Layer (LbL) technique. The films have been used as modified electrodes for catechol quantification. Electrochemical measurements have been employed to investigate the catalytic properties of the LuPc(2) immobilized in the LbL films. By chronoamperometry, the sensors present excellent sensitivity (20 nA µM(-1)) in a wide linear range (R(2)=0.994) up to 900 µM and limit of detection (s/n=3) of 37.5 × 10(-8)M for catechol. The sensors have good reproducibility and can be used at least for ten times. The work potential is +0.3 V vs. saturated calomel electrode (SCE). In voltammetry measurements, the calibration curve shows a good linearity (R(2)=0.992) in the range of catechol up to 500 µM with a sensitivity of 90 nA µM(-1) and LD of 8 µM.

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Epicuticular components were obtained using methylene chloride extraction of fresh leaves from two populations of Lithrea caustica. The methylene chloride extracts were analyzed using GC and GC-MS. The extracts from both sampled populations showed a mixture of a hydrocarbon fraction of n-alkanes from C-21 to C-33 as their main components and small amounts of monoterpene hydrocarbons. The allergen 3-(pentadec-10-enyl)-catechol was also identified in the epicuticular sample in very different proportions in both extracts. A second extract obtained after the epicuticle had been removed from the sample revealed oxygenated monoterpenes, sesquiterpene hydrocarbons and an increased amount of the allergen 3-(Pentadec-10-enyl)-catechol. These results demonstrate that the cuticle hydrocarbons of the leaves function as a lipophylic barrier that controls allergen release.

Los componentes epicuticulares se obtuvieron mediante la extracción con cloruro de metileno de hojas frescas de dos poblaciones de Lithrea caustica. Los extractos de cloruro de metileno fueron analizados mediante CG y CG-EM. Los extractos de ambas poblaciones mostraron una mezcla de una fracción de hidrocarburos n-alcanos de C-21 a C-33 como sus componentes principales y pequeñas cantidades de hidrocarburos monoterpenicos. El alérgeno 3 - (pentadec-10-enil)-catecol también fue identificado en epicuticula en proporciones muy diferentes en ambos extractos. Un segundo extracto obtenido después que la epicutícula había sido eliminada de la muestra mostró monoterpenos oxigenados, hidrocarburos sesquiterpenos y una mayor cantidad del alérgeno 3 - (Pentadec-10-enil)-catecol. Estos resultados demuestran que los hidrocarburos de la cutícula de las hojas funcionan como una barrera lipofílica que controla la liberación del alérgeno.

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The aim of the study was to develop and validate a dissolution procedure for entacapone-coated tablets. Several conditions such as medium composition, pH, surfactant concentration, and rotation speed were evaluated. The best dissolution conditions were achieved using apparatus 2, 900 mL of medium containing acetate buffer pH 5.3 at a rotation speed of 50 rpm, and a reversed-phase liquid chromatographic method for the quantification of the drug from the dissolution test, as well as to evaluate the dissolution profiles for tablets. The procedure was validated by specificity, linearity, accuracy, repeatability, intermediate precision, and robustness. The chromatographic method employed an Agilent Eclipse XDB RP-18 (150 × 4.6 mm i.d., particle size 5 µm) with a mobile phase consisting of water pH 3.0 and acetonitrile (65:35, v/v) at a flow rate of 2.0 mL/min. The dissolution procedure developed and validated was adequate for its purpose and could be applied for quality control for entacapone-coated tablets because there is no official monograph.

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The combination of metallic phthalocyanines (MPcs) and biomolecules has been explored in the literature either as mimetic systems to investigate molecular interactions or as supporting layers to immobilize biomolecules. Here, Langmuir-Blodgett (LB) films containing the phospholipid dimyristoyl phosphatidic acid (DMPA) mixed either with iron phthalocyanine (FePc) or with lutetium bisphthalocyanine (LuPc(2)) were applied as ITO modified-electrodes in the detection of catechol using cyclic voltammetry. The mixed Langmuir films of FePc + DMPA and LuPc(2) + DMPA displayed surface-pressure isotherms with no evidence of molecular-level interactions. The Fourier Transform Infrared (FTIR) spectra of the multilayer LB films confirmed the lack of interaction between the components. The DMPA and the FePc molecules were found to be oriented perpendicularly to the substrate, while LuPc(2) molecules were randomly organized. The phospholipid matrix induced a remarkable electrocatalytic effect on the phthalocyanines; as a result the mixed LB films deposited on ITO could be used to detect catechol with detection limits of 4.30 × 10(-7) and 3.34 × 10(-7) M for FePc + DMPA and LuPc(2) + DMPA, respectively. Results from kinetics experiments revealed that ion diffusion dominated the response of the modified electrodes. The sensitivity was comparable to that of other non-enzymatic sensors, which is sufficient to detect catechol in the food industry. The higher stability of the electrochemical response of the LB films and the ability to control the molecular architecture are promising for further studies with incorporation of biomolecules.

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Piper peltatum L. is used for the treatment of inflammation, malaria, and other ailments. 4-Nerolidylcatechol (4-NC) is a valuable natural product that has important anti-inflammatory, antimalarial, and antioxidant properties. 4-NC is a component of P. peltatum and P. umbellatum extracts, which are used in cosmetics. The aim of this work was to evaluate the production of plant biomass and the production of 4-NC in roots of cultivated P. peltatum over a full life cycle. Seedlings were produced in a greenhouse and then transplanted. The weight of dry plant parts (leaves, stems, roots, and inflorescences); numbers of stems, leaves, and inflorescences; and the leaf-to-stem ratio were evaluated at intervals of 60 days after transplanting (DAT). Extracts were prepared using 1:1 ethanol-chloroform and an ultrasound bath. Roots, leaves, and inflorescences contained 4-NC according to TLC photodensitometry analysis. Quantification of 4-NC in root extracts was performed using HPLC-DAD analysis. Per-hectare production of 4-NC by roots was estimated based on quantitative HPLC analysis and biomass data. Optimal per-hectare yields of 4-NC were obtained by harvesting roots between 350 and 400 DAT. In this period, the average yield was 27 kg 4-NC per hectare. Importantly, at the time of maximal overall production of root biomass (470 DAT), there was a decrease in the production of 4-NC (23.8 kg/ha), probably due to the onset of senescence.

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Entacapone is indicated for clinical use as an adjunct to levodopalcarbidopa to treat patients with idiopathic Parkinson's Disease who experience the signs and symptoms of end-of-dose wearing-off. The aim of this study was to determine the photodegradation kinetics and to elucidate the structure of the main degradation product. The stability of entacapone was studied in order to investigate the degradation kinetics of this drug using LC as a stability indicator. Entacapone was subjected to accelerated photodegradation. This study was carried out with methanolic solutions, prepared from coated tablets, in quartz cells under UV light at 254 nm. The degradation process of entacapone in solutions can be described by second-order kinetics under the experimental conditions used in this study. The LC/MS/MS determinations revealed that in the above conditions the photodegraded product formed the geometric isomer of entacapone (Z-entacapone). The obtained results show the importance of appropriate light protection during the drug development process, storage, and handling.

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Soil amendment with organic materials (crop residues animal manure, and green manure) reportedly has positive effects on soil properties, from acidity to plant-nutrient availability. To examine that hypothesis, an incubation study was conducted to assess the changes in some chemical properties of three different tropical soils (Andisol, Ultisol, and Oxisol) amended with chicken manure and green manure (Leucaena leucocephala) at the rate of 10tha(-1). The results showed that organic amendments raised soil pH and EC, regardless of the type of manure used. Manuring lowered the concentrations of Mehlich-3 extractable Ca, P, Mn and Si in all soils and decreased the concentration of Mg in the Ultisol and Oxisol. However, manure amendment led to increases in the concentrations of Mg and K in the Andisol. Organic amendments caused a decrease in KCl extractable Al. Initial soluble C levels were highest in the Oxisol (60micromolg(-1)) and lowest in the Andisol (20micromolg(-1)). The concentration of soluble C decreased exponentially with duration of incubation. Three low molecular weight organic molecules (acetic acid, catechol and oxalic acid) out of the eight tested were found in all manure-amended soils. This study quantified the release of some Al chelating organic acids, the reduction of exchangeable Al, and the changes in major plant-nutrients when organic materials were added to nutrient poor, tropical acid soils.

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Changes in the yields of the oleoresin and content of pungent bioactive principles: [6], [8], [10] gingerols and [6] shogaol of Jamaican ginger ( Zingiber officinale) were investigated during different stages of maturity (7-9 months). Ethanolic oleoresin extracts were prepared (95%, w/w) by cold maceration of dried ginger powder, and their percentage yields were calculated (w/w). The pungent bioactive principles in the ginger oleoresin were extracted with methanol and quantitatively analyzed by high performance liquid chromatography (HPLC). Ginger harvested at 8 months from Bourbon, Portland had the highest oleoresin yield (8.46 +/- 0.46%). [6] Gingerol was found to be the most abundant pungent bioactive principle in all the oleoresin samples investigated, with the 9 months sample from Bourbon, Portland containing the highest level (28.94 +/- 0.39%). The content of [6] gingerols was also found to be consistently high (7-9 months) in oleoresin samples from Johnson Mountain, St. Thomas (15.12 +/- 0.39 to 16.02 +/- 0.95%). The results suggest that Bourbon in Portland may be the most ideal location for cultivating ginger for high yields and quality, however, Johnson Mountain in St. Thomas could prove to be the least restrictive location, allowing for harvesting of good quality material throughout the maturity period (7-9 months).

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Butadiene is marketed containing p-tertbutylcatechol (p-TBC), a polymerization inhibitor that should be removed before butadiene utilization in synthetic rubber production. p-TBC can be removed from butadiene by washing with sodium hydroxide (NaOH) solution, producing a wastewater with pH 14, which contains high amounts of p-TBC, a toxic chemical compound. The aim of this work was to develop a treatment process that could reduce the content of p-TBC from the wastewater. Since p-TBC is very soluble in basic, but not in neutral and acid solutions, acidification tests were performed with phosphoric acid (H3PO4) to precipitate p-TBC. Reaction between NaOH and H3PO4 can result in crystallization of large amounts of salt without p-TBC precipitation. Under selected acidifying conditions p-TBC precipitates and the wastewater COD is highly reduced (> 90/o). Chromatographic determinations showed that the precipitated p-TBC could be recovered with 99% purity.

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