Design of experiments to optimized the determination of TDIs in agglomerated cork stoppers

Isocyanates are included into a class with an extreme commercial importance because their use in the manufacture of polyurethanes. Polyurethanes are used in several applications such as adhesives, coatings, foams, thermoplastics resins, printing inks, foundry moulds and rubbers. Agglomerated cork stoppers are currently used for still wines, semi-sparkle and gaseous wines, beer and cider. Methylene diphenyl diisocyanate (MDI) is presently the isocyanate used in the production of polyurethane based adhesive in use due to its lowest toxicity comparing with toluene diisocyanate (TDI) previously employed. However, free monomeric TDI or MDI, depending on the based polyurethane, can migrate from agglomerated cork stoppers to beverages therefore it needs to be under control. The presence of these compounds are usually investigated by HPLC with Fluorescence or UV-Vis detector depending on the derivatising agent. Ultra Performance Liquid Chromatography with Diode Array Detector (UPLC-DAD) method is replacing HPLC. The objective of this study is to determine which method is better to analyze isocyanates from agglomerated cork stoppers, essentially TDI to quantify its monomer. A Design of Experiments (DOE) with three factors, column temperature, flow and solvent, at two levels was done. Eight experiments with three replications and two repetitions were developed. Through an ANOVA the significance of the factors was evaluated and the best level’s factors were selected. As the TDI has two isomers and in this method these two isomers were not always separated an ANOVA with results of resolution between peaks was performed. The Design of Experiments reveals to be a suitable statistical tool to determine the best conditions to quantified free isocyanates from agglomerated cork stoppers to real foodstuff. The best level’s factors to maximize area was column temperature at 30ºC, flow to 0,3 mL/min and solvent 0,1% Ammonium Acetate, to maximize resolution was the same except the solvent that was 0,01% Ammonium Acetate.

Foto-oxidación de bisfenol A bajo la acción de luz visible: el monitoreo de oxígeno disuelto como evidencia de la degradación

Propósito y Método del Estudio: El semiconductor más utilizado para su uso en fotocatálisis es el TiO2 debido a sus características como bajo costo, inocuidad y eficiencia fotocatalítica; alguno de los inconvenientes del uso de este material es su capacidad de activarse con radiación UV. En el presente trabajo se modificó al catalizador TiO2 con N a través del método de síntesis coloidal con el propósito de hacerlo fotoactivo bajo radiación visible; se sintetizaron catalizadores modificados a diferentes cantidades teóricas de nitrógeno, los cuales se caracterizaron morfológica y estructuralmente; posteriormente se evaluó la actividad fotocatalítica, bajo radiación visible con una solución de Bisfenol A realizando el seguimiento de la degradación fotocatalítica mediante espectroscopia UV-Vis y cromatografía de líquidos de alta resolución acoplado a espectrometría de masas (HPLC-MS). Contribuciones y Conclusiones: los resultados confirmaron que la incorporación de Nitrógeno al TiO2 provoca cambios en la cristalinidad, morfología y área superficial, así como en su actividad con radiación visible. La evolución fotocatalitica demostró que el catalizador modificado con 5% fue el que presento mayor eficiencia en la degradación de Bisfenol A.

High-performance liquid chromatography (HPLC) and high-performance liquid chromatography mass spectrometry (HPLC/MS) for the analysis of date rape drugs

The drugs studied in this work have been reportedly used to commit drug-facilitated sexual assault (DFSA), commonly known as "date rape". Detection of the drugs was performed using high-performance liquid chromatography with ultraviolet detection (HPLC/UV) and identified with high performance-liquid chromatography mass spectrometry (HPLC/MS) using selected ion monitoring (SIM). The objective of this study was to develop a single HPLC method for the simultaneous detection, identification and quantitation of these drugs. The following drugs were simultaneously analyzed: Gamma-hydroxybutyrate (GHB), scopolamine, lysergic acid diethylamide, ketamine, flunitrazepam, and diphenhydramine. The results showed increased sensitivity with electrospray (ES) ionization versus atmospheric pressure chemical ionization (APCI) using HPLC/MS. HPLC/ES/MS was approximately six times more sensitive than HPLC/APCI/MS and about fifty times more sensitive than HPLC/UV. A limit of detection (LOD) of 100 ppb was achieved for drug analysis using this method. The average linear regression coefficient of correlation squared (r2) was 0.933 for HPLC/UV and 0.998 for HPLC/ES/MS. The detection limits achieved by this method allowed for the detection of drug dosages used in beverage tampering. This method can be used to screen beverages suspected of drug tampering. The results of this study demonstrated that solid phase microextraction (SPME) did not improve sensitivity as an extraction technique when compared to direct injections of the drug standards.

Remoção de ibuprofeno de águas por oxidação catalítica

A ocorrência e destino de fármacos no ambiente aquático tem vindo a ser reconhecido como um problema emergente em química ambiental. Alguns compostos são resistentes à degradação nas estações de tratamento de águas residuais, ETARs, enquanto que outros, ainda que sofram degradação parcial, continuam a ser lançados nos meios aquáticos em quantidades apreciáveis. O Ibuprofeno, IB, um dos anti­ inflamatórios mais consumidos por todo o mundo, é um dos fármacos mais detectados no meio hídrico. Apesar dos sistemas de tratamento convencionais utilizados nas ETARs removerem até 90% do IB das águas residuais, é frequente o efluente descarregado conter ainda quantidades significativas deste poluente. A presença destes compostos no ambiente deve ser avaliada dado que possuem actividade biológica, mesmo a baixas concentrações. Os processos avançados de oxidação com peróxido de hidrogénio, na presença de catalisadores heterogéneos, permitem melhorar significativamente a remoção deste tipo de compostos em águas. Assim, foi objectivo deste trabalho o estudo da utilização de peróxido de hidrogénio como agente oxidante na remoção de IB em soluções aquosas, na presença de complexo de acetilacetonato de Ni (II) disperso em PDMS ou encapsulado em zeólitos NaY. Para o doseamento do fármaco em solução foi necessário desenvolver um método analítico consistindo de separação cromatográfica por HPLC e detecção e quantificação por UV-Vis. Não houve necessidade de recorrer a um passo de pré­ concentração de amostras por extracção em fase sólida (SPE) devido ao facto das concentrações de IB medidas ao longo do trabalho se terem sempre encontrado acima do LOQ (811 g L-1) do método analítico por injecção directa. Deste estudo pode concluir-se que o catalisador que apresentou melhor actividade catalítica e consequentemente maior remoção do IB em solução, foi o complexo de acetilacetonato de Ni (II), disperso em PDMS. Foi avaliada a influência, na conversão do IB, de diferentes parâmetros como a concentração inicial de peróxido de hidrogénio adicionada, quantidade de catalisador utilizada na mistura reaccional e temperatura. Os resultados permitiram concluir que os aumentos destes parâmetros conduzem a um aumento da actividade catalítica da reacção. A estabilidade catalítica do acetilacetonato de Ni (II)/PDMS, foi avaliada em ensaios consecutivos com a mesma amostra e nas mesmas condições, tendo-se observado que, após 8 utilizações, o catalisador perde ligeiramente a actividade (cerca de 11% do seu valor inicial). ABSTRACT: The presence and fate of pharmaceuticals in the aquatic environment is an emergent issue in environmental chemistry. Some compounds are poorly removed in wastewater treatment plants (WWTPs) while others, in spite of being partially removed, are still present in the WWTPs effluents and discharged in the receiving water bodies. Ibuprofen, IB, a non-steroid anti-inflammatory drug, is one of the most used and also one of the most frequently detected pharmaceutical contaminants in aquifers worldwide. Its removal by conventional wastewater treatment processes used in most WWTPs is usually high (up to 90% of incoming IB may be removed), but duet the high loads present in the influents, still significant amounts of IB usually leave the WWTPs in the treated effluents. The presence of these compounds in the environment must be evaluated considering that they may have some biological activity even at low concentrations. Advanced oxidation processes using hydrogen peroxide, in the presence of heterogeneous catalysts, provide a significantly improved removal of this type of substances from waters. Therefore, it was the aim of this work to study the use of hydrogen peroxide as an oxidizing agent in the removal of IB from aqueous solutions, in the presence of the catalyst nickel (II) acetylacetonate dispersed in PDMS or encapsulated in the NaY zeolite. For the quantification of the pharmaceutical in aqueous solution it was necessary to develop an analytical methodology based in chromatographic separation by HPLC and with UV-Vis detection and quantification. There was no need for a pre­concentration step of the samples by solid phase extraction (SPE) as the IB concentrations measured were always above the limit of quantification (811 bL1 of) the analytical method. The results from this study have shown that the catalyst which presented the best catalytic activity and the highest IB removal in solution was nickel (II) acetylacetonate dispersed in PDMS.

Evaluation of the evolution of the anthocyanins profile in red wine grape varieties in Alentejo

The flavonoids (including anthocyanins) are wine compounds with important anti-oxidant activity, protecting the cells against oxidative processes, preventing cardiovascular and neurodegenerative diseases, cancer, among others (Antoniolli et al. 2015; Castañeda-Ovando et al. 2009; Hosu et al. 2014; Huang et al. 2009; Kong et al. 2003). Anthocyanins in grapes at harvest are determinant to red wine quality and their development in the grape must be characterised in order to determine the most suitable date for the harvest. Thus the aim of this research is the evaluation of anthocyanins composition in two red wine grape varieties from véraison continuing through ripening. Anthocyanins were quantified by high resolution liquid chromatography (HPLC-DAD). Additionally, the total phenols content were quantified by UV-Vis Spectrometry. The anthocyanins’ profile evolution may be dependent on the variety and ripening phase. During ripening grape samples have shown an increase of coumaryl derivatives. This information may lead us to understand the anthocyanins biosynthesis pathway in different grape varieties. The development of anthocyanins from the véraison seems to follow a pattern that coincides with the increasing accumulation of soluble sugars.

A Highly Improved Method For Sensitive Determination Of Amitriptyline In Pharmaceutical Formulations Using An Unmodified Carbon Nanotube Electrode In The Presence Of Sulfuric Acid.

The present paper describes a novel, simple and reliable differential pulse voltammetric method for determining amitriptyline (AMT) in pharmaceutical formulations. It has been described for many authors that this antidepressant is electrochemically inactive at carbon electrodes. However, the procedure proposed herein consisted in electrochemically oxidizing AMT at an unmodified carbon nanotube paste electrode in the presence of 0.1 mol L(-1) sulfuric acid used as electrolyte. At such concentration, the acid facilitated the AMT electroxidation through one-electron transfer at 1.33 V vs. Ag/AgCl, as observed by the augmentation of peak current. Concerning optimized conditions (modulation time 5 ms, scan rate 90 mV s(-1), and pulse amplitude 120 mV) a linear calibration curve was constructed in the range of 0.0-30.0 μmol L(-1), with a correlation coefficient of 0.9991 and a limit of detection of 1.61 μmol L(-1). The procedure was successfully validated for intra- and inter-day precision and accuracy. Moreover, its feasibility was assessed through analysis of commercial pharmaceutical formulations and it has been compared to the UV-vis spectrophotometric method used as standard analytical technique recommended by the Brazilian Pharmacopoeia.

Yellowing And Bleaching Of Grey Hair Caused By Photo And Thermal Degradation.

Yellowing is an undesirable phenomenon that is common in people with white and grey hair. Because white hair has no melanin, the pigment responsible for hair colour, the effects of photodegradation are more visible in this type of hair. The origin of yellowing and its relation to photodegradation processes are not properly established, and many questions remain open in this field. In this work, the photodegradation of grey hair was investigated as a function of the wavelength of incident radiation, and its ultrastructure was determined, always comparing the results obtained for the white and black fibres present in grey hair with the results of white wool. The results presented herein indicate that the photobehaviour of grey hair irradiated with a mercury lamp or with solar radiation is dependent on the wavelength range of the incident radiation and on the initial shade of yellow in the sample. Two types of grey hair were used: (1) blended grey hair (more yellow) and (2) grey hair from a single-donor (less yellow). After exposure to a full-spectrum mercury lamp for 200 h, the blended white hair turned less yellow (the yellow-blue difference, Db(*) becomes negative, Db(*)=-6), whereas the white hair from the single-donor turned slightly yellower (Db(*)=2). In contrast, VIS+IR irradiation resulted in bleaching in both types of hair, whereas a thermal treatment (at 81 °C) caused yellowing of both types of hair, resulting in a Db(*)=3 for blended white hair and Db(*)=9 for single-donor hair. The identity of the yellow chromophores was investigated by UV-Vis spectroscopy. The results obtained with this technique were contradictory, however, and it was not possible to obtain a simple correlation between the sample shade of yellow and the absorption spectra. In addition, the results are discussed in terms of the morphology differences between the pigmented and non-pigmented parts of grey hair, the yellowing and bleaching effects of grey hair, and the occurrence of dark-follow reactions.

Lawsonia Inermis-mediated Synthesis Of Silver Nanoparticles: Activity Against Human Pathogenic Fungi And Bacteria With Special Reference To Formulation Of An Antimicrobial Nanogel.

Lawsonia inermis mediated synthesis of silver nanoparticles (Ag-NPs) and its efficacy against Candida albicans, Microsporum canis, Propioniabacterium acne and Trichophyton mentagrophytes is reported. A two-step mechanism has been proposed for bioreduction and formation of an intermediate complex leading to the synthesis of capped nanoparticles was developed. In addition, antimicrobial gel for M. canis and T. mentagrophytes was also formulated. Ag-NPs were synthesized by challenging the leaft extract of L. inermis with 1 mM AgNO₃. The Ag-NPs were characterized by Ultraviolet-Visible (UV-Vis) spectrophotometer and Fourier transform infrared spectroscopy (FTIR). Transmission electron microscopy (TEM), nanoparticle tracking and analysis sytem (NTA) and zeta potential was measured to detect the size of Ag-NPs. The antimicrobial activity of Ag-NPs was evaluated by disc diffusion method against the test organisms. Thus these Ag-NPs may prove as a better candidate drug due to their biogenic nature. Moreover, Ag-NPs may be an answer to the drug-resistant microorganisms.

Esi(+)-ms And Gc-ms Study Of The Hydrolysis Of N-azobenzyl Derivatives Of Chitosan.

New N-p-chloro-, N-p-bromo-, and N-p-nitrophenylazobenzylchitosan derivatives, as well as the corresponding azophenyl and azophenyl-p-sulfonic acids, were synthesized by coupling N-benzylvchitosan with aryl diazonium salts. The synthesized molecules were analyzed by UV-Vis, FT-IR, 1H-NMR and 15N-NMR spectroscopy. The capacity of copper chelation by these materials was studied by AAS. Chitosan and the derivatives were subjected to hydrolysis and the products were analyzed by ESI(+)-MS and GC-MS, confirming the formation of N-benzyl chitosan. Furthermore, the MS results indicate that a nucleophilic aromatic substitution (SnAr) reaction occurs under hydrolysis conditions, yielding chloroaniline from N-p-bromo-, and N-p-nitrophenylazo-benzylchitosan as well as bromoaniline from N-p-chloro-, and N-p-nitrophenylazobenzyl-chitosan.

Toxicity Of Fungal-generated Silver Nanoparticles To Soil-inhabiting Pseudomonas Putida Kt2440, A Rhizospheric Bacterium Responsible For Plant Protection And Bioremediation.

Silver nanoparticles have attracted considerable attention due to their beneficial properties. But toxicity issues associated with them are also rising. The reports in the past suggested health hazards of silver nanoparticles at the cellular, molecular, or whole organismal level in eukaryotes. Whereas, there is also need to examine the exposure effects of silver nanoparticle to the microbes, which are beneficial to humans as well as environment. The available literature suggests the harmful effects of physically and chemically synthesised silver nanoparticles. The toxicity of biogenically synthesized nanoparticles has been less studied than physically and chemically synthesised nanoparticles. Hence, there is a greater need to study the toxic effects of biologically synthesised silver nanoparticles in general and mycosynthesized nanoparticles in particular. In the present study, attempts have been made to assess the risk associated with the exposure of mycosynthesized silver nanoparticles on a beneficial soil microbe Pseudomonas putida. KT2440. The study demonstrates mycosynthesis of silver nanoparticles and their characterisation by UV-vis spectrophotometry, FTIR, X-ray diffraction, nanosight LM20 - a particle size distribution analyzer and TEM. Silver nanoparticles obtained herein were found to exert the hazardous effect at the concentration of 0.4μg/ml, which warrants further detailed investigations concerning toxicity.

Preparative separation of flavonoids from the medicinal plant Davilla elliptica St. Hill. by high-speed counter-current chromatography

High-speed counter-current chromatography (HSCCC) is a major tool for the fast separation of natural products from plants. It was used for the preparative isolation of the flavonoid monoglucosides present in the aerial parts of the Davilla elliptica St. Hill. (Dilleniaceae). This species is used in Brazilian folk medicine for the treatment of gastric disorders. The optimum solvent system used was composed of a mixture of ethyl acetate-n-propanol-water (140:8:80, v/v/v) and led to a successful separation of quercetin-3-O-alpha-L-rhamnopyranoside and myricetin-3-O-alpha-L-rhamnopyranoside in approximately 3.0 hours with purity higher than 95%. Identification was performed by ¹H NMR, 13C NMR and HPLC-UV-DAD analyses.

Síntese e estudo de ortossilicatos de zinco luminescentes com aplicação da técnica sol-gel

Usually, the concepts of the Sol-Gel technique are not applied in experimental chemistry courses. This work presents a feasible experiment for chemistry instruction, which involves the synthesis of luminescent materials - Zn2SiO4, with and without Mn2+ as a dopant - by the Sol-Gel technique. The obtained materials were analyzed by scanning electron microscopy, X-Ray diffraction, IR spectroscopy and luminescence measures by UV-vis spectroscopy. The results allow the students to confirm the luminescent properties of the zinc orthosilicate luminophores as well as the structural features expected from literature data.

Desenvolvimento e validação de método espectrofotométrico para determinação de corante à base de luteína adicionado em iogurte desnatado

A simple analytical method for extraction and quantification of lutein colorant added to yogurt was developed and validated. The method allowed complete extraction of carotenoids using tetrahydrofuran in vortex, followed by centrifugation, partition to diethyl ether/petroleum ether, and drying. The carotenoids dissolved in ethanol were quantified by UV-Vis spectrophotometry. This method showed linearity in the range tested (1.41-13.42 µg g-1), limits of detection and quantification of 0.42 and 1.28 µg g-1, respectively, low relative standard deviation (3.4%) and recovery ranging from 95 to 103%. The method proved reliable for quantification of lutein added to yogurt.

Modified silicas covalently bounded to 5,10,15,20-tetrakis(2-hydroxy-5-nitrophenyl)porphyrinato iron(III): synthesis, spectroscopic and EPR characterization. Catalytic studies

In this work we have studied cyclooctene epoxidation with PhIO, using a new iron porphyrin, 5,10,15,20-tetrakis(2-hydroxy-5-nitrophenyl)porphyrinato iron(III), supported on silica matrices via eletrostatic interaction and / or covalent bonds as catalyst. These catalysts were obtained and immobilized on the solid supports propyltrimethylammonium silica (SiN+); propyltrimethylammonium and propylimidazole silica [SiN+(IPG)] and chloropropylsilica (CPS) via elestrostatic interactions and covalent binding. Characterization of the supported catalysts by UV-Vis spectroscopy and EPR (Electron paramagnetic resonance) indicated the presence of a mixture of FeII and FeIII species in all of the three obtained catalysts. In the case of (Z)-cyclooctene epoxidation by PhIO the yields observed for cis-epoxycyclooctane were satisfactory for the reactions catalyzed by the three materials (ranging from 68% to 85%). Such results indicate that immobilization of metalloporphyrins onto solid supports via groups localized on the ortho positions of their mesophenyl rings can lead to efficient catalysts for epoxidation reactions. The catalyst 1-CPS is less active than 1-SiN and 1-SiN(IPG), this argues in favour of the immobilization of this metalloporphyrin onto solids via electrostatic interactions, which is easier to achieve and results in more active oxidation catalysts. Interestingly, the activity of the supported catalysts remained the same even after three successive recyclings; therefore, they are stable under the oxidizing conditions.

Adsorção do corante azul de metileno em partículas de argilominerais: análise dos tamanhos das partículas

Interactions of cationic dye methylene blue (MB) with clay particles in aqueous suspension have been extensively studied. As already known, the number of natural negative charges on the clay modifies significantly the particle sizes dispersed in water and therefore the nature of the interaction with the dye. This work evaluated with UV-Vis spectroscopy method how the clay particle sizes weighted on the adsorption and rearrangement of the dye molecules in aqueous system. The results obtained from light-scattering measurements confirmed that larger particles are found in suspensions containing the high-charged clays as the visible absorption band related to the MB aggregates (570 nm) on these suspensions prevailed.