Optimizing potentiometric ionophore and electrode design for environmental on-site control of antibiotic drugs: Application to sulfamethoxazole

Potentiometric sensors are typically unable to carry out on-site monitoring of environmental drug contaminants because of their high limits of detection (LODs). Designing a novel ligand material for the target analyte and managing the composition of the internal reference solution have been the strategies employed here to produce for the first time a potentiometric-based direct reading method for an environmental drug contaminant. This concept has been applied to sulfamethoxazole (SMX), one of the many antibiotics used in aquaculture practices that may occur in environmental waters. The novel ligand has been produced by imprinting SMX on the surface of graphitic carbon nanostructures (CN) < 500 nm. The imprinted carbon nanostructures (ICN) were dispersed in plasticizer and entrapped in a PVC matrix that included (or not) a small amount of a lipophilic additive. The membrane composition was optimized on solid-contact electrodes, allowing near-Nernstian responses down to 5.2 μg/mL and detecting 1.6 μg/mL. The membranes offered good selectivity against most of the ionic compounds in environmental water. The best membrane cocktail was applied on the smaller end of a 1000 μL micropipette tip made of polypropylene. The tip was then filled with inner reference solution containing SMX and chlorate (as interfering compound). The corresponding concentrations were studied for 1 × 10−5 to 1 × 10−10 and 1 × 10−3 to 1 × 10−8 mol/L. The best condition allowed the detection of 5.92 ng/L (or 2.3 × 10−8 mol/L) SMX for a sub-Nernstian slope of −40.3 mV/decade from 5.0 × 10−8 to 2.4 × 10−5 mol/L.

Trimethoprim-selective electrodes with molecularly imprinted polymers acting as ionophores and potentiometric transduction on graphite solid-contact

This work proposes a new biomimetic sensor material for trimethoprim. It is prepared by means of radical polymerization, having trimethylolpropane trimethacrylate as cross-linker, benzoyl peroxide as radicalar iniciator, chloroform as porogenic solvent, and methacrylic acid and 2-vinyl pyridine as monomers. Different percentages of sensor in a range between 1 and 6% were studied. Their behavior was compared to that obtained with ion-exchanger quaternary ammonium salt (additive tetrakis(p-chlorophenyl)borate or tetraphenylborate). The effect of an anionic additive in the sensing membrane was also tested. Trimethoprim sensors with 1% of imprinted particles from methacrylic acid monomers showed the best response in terms of slope (59.7 mV/decade) and detection limit (4.01 × 10− 7 mol/L). These electrodes displayed also a good selectivity towards nickel, manganese aluminium, ammonium, lead, potassium, sodium, iron, chromium, sulfadiazine, alanine, cysteine, tryptophan, valine and glycine. The sensors were not affected by pH changes from 2 to 6. They were successfully applied to the analysis of water from aquaculture.

Elétrodo de pasta de carbono molecularmente impresso para deteção voltamétrica de Furazolidona

A furazolidona é uma substância ativa do medicamento Giarlam que contém um espetro anti-bacteriano relativamente amplo e que é frequentemente usado para tratar certas doenças bacterianas e protozoárias no homem. A maioria dos fármacos exige uma dosagem que garanta os níveis de segurança e eficácia de atuação. A necessidade de dosear os medicamentos e os seus metabólitos exige o desenvolvimento constante de métodos analíticos eficientes. Neste trabalho desenvolveu-se um novo sensor eletroquímico para a deteção da furazolidona, baseado num elétrodo de pasta de carbono modificado com um polímero molecularmente impresso. A procura de novos materiais que permitam uma melhor seletividade e sensibilidade aos sistemas de deteção é especialmente importante no desenvolvimento de métodos analíticos. Os polímeros molecularmente impressos enquadram-se nesse perfil e o seu uso tem vindo a ser cada vez mais frequente como ferramenta importante em química analítica. Assim, sintetizou-se um polímero com cavidades seletivas para a Furazolidona. Este polímero foi, misturado com grafite e perafina de modo a produzir uma pasta de carbono. Uma seringa de plástico foi usada como suporte da pasta de carbono. O comportamento eletroquímico do sensor foi avaliado e diversas condições de utilização foram estudadas e otimizadas. O sensor apresenta um comportamento linear entre a intensidade do pico e a concentração numa gama de concentrações entre 1 e 100 μM, um limite de deteção de 1 μM e uma precisão (repetibilidade) inferior a 7%. A aplicabilidade do sensor fabricado em amostras complexas foi avaliada pela deteção do fármaco em amostras de urina.

Electrochemical and quantum chemical investigations of the insecticide fipronil.

This work describes an electrochemical and quantum chemical investigation of the fipronil insecticide. Cyclic voltammetry (CV) and square wave voltammetry (SWV) experiments were performed over a graphite-polyurethane (GPU) composite electrode. The fipronil molecule presents an one?electron irreversible oxidation reaction. Profiting the SWV signal a square wave stripping voltammetry (SWSV) procedure to determine the fipronil molecule in a 0.10 mol L-1 Britton-Robinson buffer solution, pH 8.0 was developed with accumulation potential and time of 0.50 V and 120 s, respectively. The limits of detection and quantification were 0.80 and 2.67 ?g L-1, respectively. Recovery tests were performed in three natural waters samples with values ranging from 99.67 to 101.37%. Quantum chemical studies showed that the nitrogen atom of the pyrazole group is the most probable oxidation site of the fipronil molecule.

Metamorphism and Fluid Inclusion Studies of Charnockites and Associated Rocks from the Madurai Granulite Block , Southern India with Special Reference to Graphite Mineralization

The present research is aimed at studying the charnockites and associated rocks of the Madurai Granulite Block (MGB), especially in terms of their field settings, texture, mineralogy, and mineral chemistry analyzing their petrogenesis with the help of thermobarometrical studies and geochronological constraints. The mechanism of charnockitization by the influx of CO2 rich fluids and its relation to the graphite mineralization is actually a matter of discussion and study. The objectives of the present study are, to delineate petrological and structural relationship of charnockites and associated gneissic rocks, to study the field and petrogenetic aspects of graphite mineralization in the MGB, to establish and re-evaluate the P-T conditions of formation of the rocks with the aid of thermbarometric computations and to compare with the earlier studies, characterization of graphite with XRD, Raman spectroscopy and isotope studies together with a search in to its genesis and its relation to the high-grade metamorphism of the terrain, to evaluate the role of CO2 bearing fluids in the processes of charnockitization as well as in the genesis of graphite within the high-grade terrain and to delineate the metamorphic geochronology of selected rocks using ‘monazite dating’ technique with EPMA.

Optical Emission Diagnostics Of Laser Produced Plasma From Graphite And Yba2cu3o7

This thesis is entitled “OPTICAL EMISSION DIAGNOSTICS OF LASER PRODUCED PLASMA FROM GRAPHITE AND YBa2Cu3O7. The work presented in this thesis covers the experimental results on the plasma produced with moderately high power laser with irradiance range in between 10 GW cm 2 to 100 GW cm -2. The characterization of laser produced plasma from solid targets viz. graphite and high temperature superconducting material like YBa2Cu3O7 have been carried out. The fundamental frequency from a Q - switched Nd: YAG laser with 9 ns pulse duration is used for the present studies. Various optical emission emission diagnostic techniques were employed for the the characterization of the LPP which include emission spectroscopy, time resolved studies, line broadening method etc. In order to understand the physical nature of the LPP like recombination, collisional excitation and the laser interaction with plasma, the time resolved studies offer the most logical approach

Electrochemical Reduction and Voltammetric Determination of Metronidazole Benzoate at Modified Carbon Paste Electrode

A metalloporphyrin incorporated carbon paste sensor has been developed for the determination of metronidazole benzoate (MTZB). Zn(II) complex of 5,10,15,20-tetrakis (3-methoxy-4-hydroxy phenyl) porphyrin (TMHPP) was used as the active material. The MTZB gave a well-defined reduction peak at - 0.713V in 0.1 mol l -1 phosphate buffer solution of pH around 7. Compared with bare carbon paste electrode (CPE), the TMHPP Zn(II) modified electrode significantly enhanced the reduction peak current of MTZB as well as lowered its reduction potential. Under optimum conditions the reduction peak current was proportional to MTZB concentration over the range 1×10-3 mol1-1 to 1×10-5mol1-1. The detection limit was found to be 4.36×10-6mol1-1 . This sensor has been successfully applied for the determination of MTZB in pharmaceutical formulations and urine samples.

An Inter-digital Capacitive Electrode Modified as a Pressure Sensor

Inter-digital capacitive electrodes working as electric field sensors have been developed for touch panel applications. Evaluation circuits to convert variations in electric fields in such sensors into computer compatible data are commercially available. We report development of an Interdigital capacitive electrode working as a sensitive pressure sensor in the range 0-120 kPa. Essentially it is a touch/proximity sensor converted into a pressure sensor with a suitable elastomer buffer medium acting as the pressure transmitter. The performance of the sensor has been evaluated and reported. Such sensors can be made very economical in comparison to existing pressure sensors. Moreover, they are very convenient to be fabricated into sensor arrays involving a number of sensors for distributed pressure sensing applications such as in biomedical systems.

Photoemission optogalvanic studies with copper as target electrode

Photoemission optogalvanaic (POG) effect has been observed by irradiating copper target electrode, in a nitrogen discharge cell using 1.06 μm and frequency doubled 532 nm Nd:YAG laser pulse. Measurement of the nature of the variation of POG signal strength with 532 nm laser fluence confirms the two photon induced photoelectric emission from copper. However, using 1.06 μm laser pulses thermally assisted photoemission is observed.

Temporal and spatial evolution of C2 in laser induced plasma from graphite target

Laser ablation of graphite has been carried out using 1.06mm radiation from a Q-switched Nd:YAG laser and the time of flight distribution of molecular C2 present in the resultant plasma is investigated in terms of distance from the target as well as laser fluences employing time resolved spectroscopic technique. At low laser fluences the intensities of the emission lines from C2 exhibit only single peak structure while beyond a threshold laser fluence, emission from C2 shows a twin peak distribution in time. The occurrence of the faster velocity component at higher laser fluences is explained as due to species generated from recombination processes while the delayed peak is attributed to dissociation of higher carbon clusters resulting in the generation of C2 molecule. Analysis of measured data provides a fairly complete picture of the evolution and dynamics of C2 species in the laser induced plasma from graphite.

Fine structure in the time of flight distribution of C2 in laser produced plasma from graphite

Time resolved optical emission spectroscopy is employed to study the expansion dynamics of C2 species in a graphite plasma produced during the Nd : YAG ablation. At low laser fluences a single peak distribution with low kinetic energy is observed. At higher fluences a twin peak distribution is found. It has been noted that these double peak time of flight distribution splits into a triple peak structure at distances >_ 17mm from the target surface. The reason for the occurrence of multiple peak is due to different formation mechanisms of C2 species

Time resolved study of CN band emission from plasma generated by laser irradiation of graphite

Time and space resolved studies of emission from CN molecules have been carried out in the plasma produced from graphite target by 1.06 urn pulses from a Q-switched Nd:YAG laser. Depending on the laser pulse energy, time of observation and position of the sampled volume of the plasma, the features of the emission spectrum are found to change drastically. The vibrational temperature and population distribution in the different vibrational levels have been studied as functions of distance, time, laser energy and ambient gas pressure. Evidence for nonlinear effects of the plasma medium such as self focusing which exhibits threshold-like behaviour are also obtained. Temperature and electron density of the plasma have been evaluated using the relative line intensities of successive ionization stages of carbon atom. These electron density measurements are verified by using Stark broadening method.

Emission characteristics and dynamics of C2 from laser produced graphite plasma

The emission features of laser ablated graphite plume generated in a helium ambient atmosphere have been investigated with time and space resolved plasma diagnostic technique. Time resolved optical emission spectroscopy is employed to reveal the velocity distribution of different species ejected during ablation. At lower values of laser fluences only a slowly propagating component of C2 is seen. At high fluences emission from C2 shows a twin peak distribution in time. The formation of an emission peak with diminished time delay giving an energetic peak at higher laser fluences is attributed to many body recombination. It is also observed that these double peaks get modified into triple peak time of flight distribution at distances greater than 16 mm from the target. The occurrence of multiple peaks in the C2 emission is mainly due to the delays caused from the different formation mechanism of C2 species. The velocity distribution of the faster peak exhibits an oscillating character with distance from the target surface.

Time Resolved Analysis of C2 Emission from Laser Induced Graphite Plasma in Helium Atmosphere

We report time resolved study of C2 emission from laser produced carbon plasma in presence of ambient helium gas. The 1.06µm: radiation from a Nd:YAG laser was focused onto a graphite target where it·produced a transient plasma. We observed double peak structure in the time profile of C2 species. The twin peaks were observed only after a threshold laser fluence. It is proposed that the faster velocity component in the temporal profiles originates mainly due to recombination processes. The laser fluence and ambient gas dependence of the double peak intensity distribution is also reported.