An Alternative Method for the Simultaneous Determination of Copper and Lead for Quality Control of Sugar Cane Spirit using a Nanotube-Based Sensor

The development of an electroanalytical method for simultaneous determination of copper and lead ions in sugar cane spirit (cachaca) using carbon paste electrode modified with ascorbic acid and carbon nanotubes (CPE-AaCNT) is described. Squarewave voltammetry (SWV) with anodic stripping was employed, and this technique was optimized with respect to the following parameters: frequency (50 Hz), amplitude (100 mV) and scan increment (9 mV). The analytical curves were linear in the range from 0.0900 to 7.00 mg L-1 for lead and copper. The limits of detection were 48.5 and 23.9 mu g L-1 for lead and copper, respectively. The developed method was applied to the simultaneous determination of copper and lead in five commercial samples of sugar cane spirit. The results were in good agreement with those obtained by F AAS/GF AAS (flame atomic absorption spectrometry/graphite furnace atomic absorption spectrometry) and showed that CPE-AaCNT can be successfully employed in the simultaneous determination of these metals in real sugar cane spirit samples.

Use of Hg-Electroplated-Pt Ultramicroelectrode for Determining Elemental Sulphur in Naphtha Samples

This paper describes the applicability of a Hg-electroplated-Pt ultramicroelectrode in the quantification of elemental sulphur in naphtha samples by square-wave voltammetry. A reproducible deposition methodology was studied and is reported in this paper. This methodology is innovative and relies on the quality of the mercury stock solution to obtain reproducible surfaces required for the analytical methodology. All analyses were performed using a Hg-electroplated-Pt ultramicroelectrode (Hg-Pt UME) due to the low sensibility of such devices to ohmic drops in resistive solutions. The responses of the peak areas in voltammetric experiments were linear in all of the range studied. The method developed here is accurate and reproducible, with a detection limit of 0.010 mg L-1 and a good recovery range for both standard solutions of elemental sulphur (85 to 99%) and real naphtha sample (79%). These results attest to the potential for the application of this electroanalytical methodology in determining elemental sulphur in naphtha samples containing mercaptans and disulphides.

Caffeine Determination at a Carbon Fiber Ultramicroelectrodes by Fast-Scan Cyclic Voltammetry

Caffeine determination using a fast-scan voltammetric procedure at a carbon fiber ultramicroelectrode (CF-UME) is described. The CF-UME was submitted to electrochemical pretreatment. Parameters such as number of acquisition cycles, scan rate, potential window, and the electrochemical surface pretreatment were optimized. Using the optimized conditions, it was possible to achieve a LDR from 10.0 up to 200 mu mol L-1, with a LOD of 3.33 mu mol L-1. The method has been applied in the determination of caffeine in commercial samples, with errors of 1.0-3.5% in relation to the label values and recoveries of 97-114% within the linear range.

Chemical and physical factors influencing lead and copper contamination in drinking water: approach for a case study in analytical chemistry

CHEMICAL AND PHYSICAL FACTORS INFLUENCING LEAD AND COPPER CONTAMINATION IN DRINKING WATER: APPROACH FOR A CASE STUDY IN ANALYTICAL CHEMISTRY. Lead and copper concentrations in drinking water increase considerably on going from municipality reservoirs to the households sampled in Ribeirao Preto (SP-Brazil). Flushing of only 3 liters of water reduced metal concentrations by more than 50%. Relatively small changes in water pH rapidly affected corrosion processes in lead pipes, while water hardness appeared to have a long-term effect. This approach aims to encourage University teachers to use its content as a case study in disciplines of Instrumental Analytical Chemistry and consequently increase knowledge about drinking water contamination in locations where no public monitoring of trace metals is in place.

A forensic study: Lead determination in gunshot residues

Electrochemical lead analyses of gunshot residues (GSRs) were performed using an acidic solution with a bare gold microelectrode in the presence of chloride ions. GSRs from four different guns (0.38 in. revolver, 12 caliber pump-action shotgun, 0.38 repeating rifle, and a 0.22 caliber semi-automatic rifle) and six different types of ammunition (CleanRange (R), normal, semi-jacketed, especial 24g (R), 3T (R), CBC (R), and Eley (R)) were analyzed. Results obtained with the proposed methodology were compared with those from an atomic absorption spectrometry analysis, and a paired Student's t-test indicated that there was no significant difference between them at the 95% confidence level. With this methodology, a detection limit of 1.7 nmol L-1 (3 sigma/slope), a linear range between 10 and 100 nmol L-1, and a relative standard deviation of 2.5% from 10 measurements were obtained. (C) 2011 Elsevier B.V. All rights reserved.

Carbon nanotubes modified with antimony nanoparticles: A novel material for electrochemical sensing

In this study, a novel material for the electrochemical determination of bisphenol A using a nanocomposite based on multi-walled carbon nanotubes modified with antimony nanoparticles has been investigated. The morphology, structure, and electrochemical performance of the nanocomposite electrodes were characterised by field emission gun scanning electron microscopy, energy-dispersive X-ray spectroscopy, and cyclic voltammetry. A scan rate study and electrochemical impedance spectroscopy showed that the bisphenol A oxidation product is adsorbed on nanocomposite electrode surface. Differential pulse voltammetry in phosphate buffer solution at pH 6, allowed the development of a method to determine bisphenol A levels in the range of 0.5-5.0 mu mol L-1, with a detection limit of 5.24 nmol L-1 (1.19 mu g L-1). (C) 2012 Elsevier Ltd. All rights reserved.

Complete fusion enhancement and suppression of weakly bound nuclei at near barrier energies

We consider the influence of breakup channels on the complete fusion of weakly bound systems in terms of dynamic polarization potentials. It is argued that the enhancement of the cross section at sub-barrier energies may be consistent with recent experimental observations that nucleon transfer, often leading to breakup, is dominant compared to direct breakup. The main trends of the experimental complete fusion cross sections are analyzed in the framework of the DPP approach. The qualitative conclusions are supported by CDCC calculations including a sequential breakup channel, the one neutron stripping of Li-7 followed by the breakup of Li-6.

An EQCM-D study of the influence of chloride on the lead anodic oxidation

The influence of chloride on the electrodeposition of lead films and their dissolution in anodic stripping voltammetric experiments was examined. Gold substrates were plated with lead films, and mass changes were monitored by using the electrochemical quartz crystal microbalance with dissipation factor (EQCM-D). The results showed that the amount of electrodeposited lead is slightly dependent on the chloride concentration. The charge/mass ratio data indicated the presence of Pb(I) and Pb(II) as a result of film dissolution, and the precipitation and deposition of PbCl2 onto the electrode surface. Scanning electron microscopy images revealed that the morphology of the lead film was strongly influenced by chloride present in the plating solution and that much rougher films were obtained in comparison with those obtained in the absence of chloride. The rate of the anodic dissolution was higher for lead films with higher surface areas, which lead to an increase in their stripping voltammetric currents. (C) 2012 Elsevier Ltd. All rights reserved.

Use of a gold microelectrode for discrimination of gunshot residues

Gunshot residues (GSR) can be used in forensic evaluations to obtain information about the type of gun and ammunition used in a crime. In this work, we present our efforts to develop a promising new method to discriminate the type of gun [four different guns were used: two handguns (0.38 revolver and 0.380 pistol) and two long-barrelled guns (12-calibre pump-action shotgun and 0.38 repeating rifle)] and ammunition (five different types: normal, semi-jacketed, full-jacketed, green, and 3T) used by a suspect. The proposed approach is based on information obtained from cyclic voltammograms recorded in solutions containing GSR collected from the hands of the shooters, using a gold microelectrode; the information was further analysed by non-supervised pattern-recognition methods [(Principal Component Analysis (PCA) and Hierarchical Cluster Analysis (HCA)]. In all cases (gun and ammunition discrimination), good separation among different samples in the score plots and dendrograms was achieved. (C) 2012 Elsevier B.V. All rights reserved.

Fatores químicos e físicos que afetam a contaminação por chumbo e cobre em água potável: uma abordagem para o estudo de caso em química analítica

Lead and copper concentrations in drinking water increase considerably on going from municipality reservoirs to the households sampled in Ribeirão Preto (SP-Brazil). Flushing of only 3 liters of water reduced metal concentrations by more than 50%. Relatively small changes in water pH rapidly affected corrosion processes in lead pipes, while water hardness appeared to have a long-term effect. This approach aims to encourage University teachers to use its content as a case study in disciplines of Instrumental Analytical Chemistry and consequently increase knowledge about drinking water contamination in locations where no public monitoring of trace metals is in place.

Self-assembled films from chitosan and poly(vinyl sulfonic acid) on Nafion® for direct methanol fuel cell

Chitosan/poly(vinyl sulfonic acid) (PVS) films have been prepared on Nafion® membranes by the layer-by-layer (LbL) method for use in direct methanol fuel cell (DMFC). Computational methods and Fourier transform infrared (FTIR) spectra suggest that an ionic pair is formed between the sulfonic group of PVS and the protonated amine group of chitosan, thereby promoting the growth of LbL films on the Nafion® membrane as well as partial blocking of methanol. Chronopotentiometry and potential linear scanning experiments have been carried out for investigation of methanol crossover through the Nafion® and chitosan/PVS/Nafion® membranes in a diaphragm diffusion cell. On the basis of electrical impedance measurements, the values of proton resistance of the Nafion® and chitosan/PVS/Nafion® membranes are close due to the small thickness of the LbL film. Thus, it is expected an improved DMFC performance once the additional resistance of the self-assembled film is negligible compared to the result associated with the decrease in the crossover effect.

An alternative method for the simultaneous determination of copper and lead for quality control of sugar cane spirit using a nanotube-based sensor

The development of an electroanalytical method for simultaneous determination of copper and lead ions in sugar cane spirit (cachaça) using carbon paste electrode modified with ascorbic acid and carbon nanotubes (CPE-AaCNT) is described. Squarewave voltammetry (SWV) with anodic stripping was employed, and this technique was optimized with respect to the following parameters: frequency (50 Hz), amplitude (100 mV) and scan increment (9 mV). The analytical curves were linear in the range from 0.0900 to 7.00 mg L- 1 for lead and copper. The limits of detection were 48.5 and 23.9 µg L- 1 for lead and copper, respectively. The developed method was applied to the simultaneous determination of copper and lead in five commercial samples of sugar cane spirit. The results were in good agreement with those obtained by F AAS/GF AAS (flame atomic absorption spectrometry/graphite furnace atomic absorption spectrometry) and showed that CPE-AaCNT can be successfully employed in the simultaneous determination of these metals in real sugar cane spirit samples.

Metrologia dei campi di radiazioni di bassa energia

The conversion coefficients from air kerma to ICRU operational dose equivalent quantities for ENEA’s realization of the X-radiation qualities L10-L35 of the ISO “Low Air Kerma rate” series (L), N10-N40 of the ISO “Narrow spectrum” series (N) and H10-H60 of the ISO “High Air-kerma rate” (H) series and two beams at 5 kV and 7.5 kV were determined by utilising X-ray spectrum measurements. The pulse-height spectra were measured using a planar high-purity germanium spectrometer (HPGe) and unfolded to fluence spectra using a stripping procedure then validate with using Monte Carlo generated data of the spectrometer response. HPGe portable detector has a diameter of 8.5 mm and a thickness of 5 mm. The entrance window of the crystal is collimated by a 0.5 mm thick Aluminum ring to an open diameter of 6.5 mm. The crystal is mounted at a distance of 5 mm from the Berillium window (thickness 25.4 micron). The Monte Carlo method (MCNP-4C) was used to calculate the efficiency, escape and Compton curves of a planar high-purity germanium detector (HPGe) in the 5-60 keV energy. These curves were used for the determination of photon spectra produced by the X-ray machine SEIFERT ISOVOLT 160 kV in order to allow a precise characterization of photon beams in the low energy range, according to the ISO 4037. The detector was modelled with the MCNP computer code and validated with experimental data. To verify the measuring and the stripping procedure, the first and the second half-value layers and the air kerma rate were calculated from the counts spectra and compared with the values measured using an a free-air ionization chamber. For each radiation quality, the spectrum was characterized by the parameters given in ISO 4037-1. The conversion coefficients from the air kerma to the ICRU operational quantities Hp(10), Hp(0.07), H’(0.07) and H*(10) were calculated using monoenergetic conversion coefficients. The results are discussed with respect to ISO 4037-4, and compared with published results for low-energy X-ray spectra. The main motivation for this work was the lack of a treatment of the low photon energy region (from a few keV up to about 60 keV).

Untersuchungen zur Lebensweise und zur Populationskontrolle des Gemeinen Ohrwurms Forficula auricularia L. (Insecta, Dermaptera) in Rebanlagen

Der Gemeine Ohrwurm (Forficula auricularia LINNAEUS 1758) wurde bisher im Weinbau als natürlicher Gegenspieler verschiedener Rebschädlinge zu den Nützlingen gezählt. Etwa seit 2005 verursacht er aufgrund stark ansteigender Populationsdichten Schäden in pfälzischen Rebanlagen. Ohrwürmer halten sich massenhaft in den Trauben auf. Zusammen mit ihren Exkrementen geraten sie bei der Lese in großer Zahl ins Erntegut. Die Tiere werden von der weinbaulichen Praxis als sehr störend und qualitätsmindernd empfunden und ihre Einstufung als Nützling kritisch gesehen. Aufgrund dieser Problematik wurde im Mai 2007 ein durch den Forschungsring des Deutschen Weinbaus (FDW) finanziertes Forschungsprojekt am Dienstleistungszentrum Ländlicher Raum Rheinpfalz in Neustadt an der Weinstraße begonnen. Bis 2010 wurden offene Fragen zur Erfassung und Populationsbiologie des Gemeinen Ohrwurms in Rebanlagen bearbeitet, die von ihm verursachten Schäden beschrieben und Strategien zu seiner Befallsregulation entwickelt. Am Boden aktive Ohrwürmer wurden mit Bodenfallen nach BARBER (1931) aufgenommen. In der Laubwand des Rebstockes wurden die Ohrwürmer mit eigens konzipierten Bambusfallen erfasst. F. auricularia ist in pfälzischen Rebanlagen die dominierende Ohrwurm-Art. Im Projektverlauf wurde der univoltine Entwicklungszyklus des Gemeinen Ohrwurms in pfälzischen Rebanlagen vollständig aufgeklärt. In der Vegetationsperiode beeinflussten die Intensität der Bodenbewirtschaftung mit der resultierenden Flächenbegrünung, die Bodenart, die Lufttemperatur, die Luftfeuchtigkeit und die Niederschlagsmenge die Befallsdichten am Rebstock signifikant. Der Ohrwurm-Befall in den Trauben war signifikant von der Kompaktheit und vom Gewicht der Trauben sowie dem Fäulnisanteil pro Traube und von eingewachsenen Rebblättern in den Trauben abhängig. Das Überwinterungs- und Brutverhalten wurde durch die Art und Weise der Bodenbewirtschaftung beeinflusst beziehungsweise gestört.rnLabor- und Freilandversuche haben gezeigt, dass F. auricularia Pilzpathogene wie die Graufäule (Botrytis cinerea PERSOON 1794) und den Pinselschimmel (Penicillium crustosum THOM 1930) auf gesunde Trauben überträgt. Ferner haben Fraßversuche ergeben, dass der Ohrwurm nur faule und vorgeschädigte Beeren anfressen kann und keine intakten Beeren verletzt. Durch analytische und sensorische Untersuchungen wurde festgestellt, dass Ohrwurm-Kot sensorische Fehltöne im Wein verursachen kann. Diese werden durch das im Kot enthaltene 2-Methyl-1,4-benzochinon hervorgerufen, das eine Komponente des arteigenen Abwehrsekrets ist. Da sich der Ohrwurm jahreszeitlich bedingt entweder im Boden oder am Rebstock aufhält, wurden befallsregulierende Maßnahmen im Boden- und Laubwandbereich der Rebanlage durchgeführt. Durch Tiefengrubbern mit Umbruch der Begrünung im Herbst und Frühjahr wurden die überwinternden Imagines und die Gelege geschädigt, so dass in der darauf folgenden Vegetationsperiode die Befallsdichten in der Laubwand geringfügig aber nicht signifikant abnahmen. Die während der Aufwanderungsphase der Ohrwürmer Ende Juni durchgeführte mechanische Störung der Begrünung reduzierte den Ohrwurm-Befall am Rebstock bis zu drei Wochen nach der Maßnahme signifikant. In der Laubwand der Rebstöcke wurden die Befallsdichten durch die Insektizide SpinTor (Wirkstoff Spinosad: 0,01%) und Steward® (Wirkstoff Indoxacarb: 0,0125 %) sowie sekundär durch partielles Entblättern der Laubwand dauerhaft bis zur Traubenlese reduziert. rn

Surface patterning with colloidal monolayers

This thesis focuses on the controlled assembly of monodisperse polymer colloids into ordered two-dimensional arrangements. These assemblies, commonly referred to as colloidal monolayers, are subsequently used as masks for the generation of arrays of complex metal nanostructures on solid substrates.rnThe motivation of the research presented here is twofold. First, monolayer crystallization methods were developed to simplify the assembly of colloids and to produce more complex arrangements of colloids in a precise way. Second, various approaches to colloidal lithography are designed with the aim to include novel features or functions to arrays of metal nanostructures.rnThe air/water interface was exploited for the crystallization of colloidal monolayer architectures as it combines a two-dimensional confinement with a high lateral mobility of the colloids that is beneficial for the creation of high long range order. A direct assembly of colloids is presented that provides a cheap, fast and conceptually simple methodology for the preparation of ordered colloidal monolayers. The produced two-dimensional crystals can be transformed into non-close-packed architectures by a plasma-induced size reduction step, thus providing valuable masks for more sophisticated lithographic processes. Finally, the controlled co-assembly of binary colloidal crystals with defined stoichiometries on a Langmuir trough is introduced and characterized with respect to accessible configurations and size ratios. rnSeveral approaches to lithography are presented that aim at introducing different features to colloidal lithography. First, using metal-complex containing latex particles, the synthesis of which is described as well, symmetric arrays of metal nanoparticles can be created by controlled combustion of the organic material of the colloids. The process does not feature an inherent limit in nanoparticle size and is able to produce complex materials as will be demonstrated for FePt alloy particles. Precise control over both size and spacing of the particle array is presented. rnSecond, two lithographic processes are introduced to create sophisticated nanoparticle dimer units consisting of two crescent shaped nanostructures in close proximity; essentially by using a single colloid as mask to generate two structures simultaneously. Strong coupling processes of the parental plasmon resonances of the two objects are observed that are accompanied by high near-field enhancements. A plasmon hybridization model is elaborated to explain all polarization dependent shifts of the resonance positions. Last, a technique to produce laterally patterned, ultra-flat substrates without surface topographies by embedding gold nanoparticles in a silicon dioxide matrix is applied to construct robust and re-usable sensing architectures and to introduce an approach for the nanoscale patterning of solid supported lipid bilayer membranes. rn