Simultaneous determination of nonlinear optical and thermo-optic parameters of liquid samples

The authors apply the theory of photothermal lens formation and also that of pure optical nonlinearity to account for the phase modulation in a beam as it traverses a nonlinear medium. It is used to simultaneously determine the nonlinear optical refraction and the thermo-optic coefficient. They demonstrate this technique using some metal phthalocyanines dissolved in dimethyl sulfoxide, irradiated by a Q-switched Nd:YAG laser with 10 Hz repetition rate and a pulse width of 8 ns. The mechanism for reverse saturable absorption in these materials is also discussed.

Development of procedures for the triazole fungicides determination in fruits and liquid samples using microextraction techniques and chromatographic separation

Agricultural crops can be damaged by funguses, insects, worms and other organisms that cause diseases and decrease the yield of production. The effect of these damaging agents can be reduced using pesticides. Among them, triazole compounds are effective substances against fungus; for example, Oidium. Nevertheless, it has been detected that the residues of these fungicides in foods as well as in derivate products can affect the health of the consumers. Therefore, the European Union has established several regulations fixing the maximum residue of pesticide levels in a wide range of foods trying to assure the consumer safety. Hence, it is very important to develop adequate methods to determine these pesticide compounds. In most cases, gas or liquid chromatographic (GC, LC) separations are used in the analysis of the samples. But firstly, it is necessary to use proper sample treatments in order to preconcentrate and isolate the target analytes. To reach this aim, microextraction techniques are very effective tools; because allow to do both preconcentration and extraction of the analytes in one simple step that considerably reduces the source of errors. With these objectives, two remarkable techniques have been widely used during the last years: solid phase microextraction (SPME) and liquid phase microextraction (LPME) with its different options. Both techniques that avoid the use or reduce the amount of toxic solvents are convenient coupled to chromatographic equipments providing good quantitative results in a wide number of matrices and compounds. In this work simple and reliable methods have been developed using SPME and ultrasound assisted emulsification microextraction (USAEME) coupled to GC or LC for triazole fungicides determination. The proposed methods allow confidently determine triazole concentrations of μg L‐1 order in different fruit samples. Chemometric tools have been used to accomplish successful determinations. Firstly, in the selection and optimization of the variables involved in the microextraction processes; and secondly, to overcome the problems related to the overlapping peaks. Different fractional factorial designs have been used for the screening of the experimental variables; and central composite designs have been carried out to get the best experimental conditions. Trying to solve the overlapping peak problems multivariate calibration methods have been used. Parallel Factor Analysis 2 (PARAFAC2), Multivariate Curve Resolution (MCR) and Parallel Factor Analysis with Linear Dependencies (PARALIND) have been proposed, the adequate algorithms have been used according to data characteristics, and the results have been compared. Because its occurrence in Basque Country and its relevance in the production of cider and txakoli regional wines the grape and apple samples were selected. These crops are often treated with triazole compounds trying to solve the problems caused by the funguses. The peel and pulp from grape and apple, their juices and some commercial products such as musts, juice and cider have been analysed showing the adequacy of the developed methods for the triazole determination in this kind of fruit samples.

Dispersive liquid–liquid microextraction for metals enrichment: A useful strategy for improving sensitivity of laser-induced breakdown spectroscopy in liquid samples analysis

A rapid and efficient Dispersive Liquid–Liquid Microextraction (DLLME) followed by Laser-Induced Breakdown Spectroscopy detection (LIBS) was evaluated for simultaneous determination of Cr, Cu, Mn, Ni and Zn in water samples. Metals in the samples were extracted with tetrachloromethane as pyrrolidinedithiocarbamate (APDC) complexes, using vortex agitation to achieve dispersion of the extractant solvent. Several DLLME experimental factors affecting extraction efficiency were optimized with a multivariate approach. Under optimum DLLME conditions, DLLME-LIBS method was found to be of about 4.0–5.5 times more sensitive than LIBS, achieving limits of detection of about 3.7–5.6 times lower. To assess accuracy of the proposed DLLME-LIBS procedure, a certified reference material of estuarine water was analyzed.

Viscosity measurements of compressed liquid dipropyl and dibutyl adipates

The paper reports viscosity measurements of compressed liquid dipropyl (DPA) and dibutyl (DBA) adipates obtained with two vibrating wire sensors developed in our group. The vibrating wire instruments were operated in the forced oscillation, or steady-state mode. The viscosity measurements of DPA were carried out in a range of pressures up to 18. MPa and temperatures from (303 to 333). K, and DBA up to 65. MPa and temperature from (303 to 373). K, covering a total range of viscosities from (1.3 to 8.3). mPa. s. The required density data of the liquid samples were obtained in our laboratory using an Anton Paar vibrating tube densimeter and were reported in a previous paper. The viscosity results were correlated with density, using a modified hard-spheres scheme. The root mean square deviation of the data from the correlation is less than (0.21 and 0.32)% and the maximum absolute relative deviations are within (0.43 and 0.81)%, for DPA and DBA respectively. No data for the viscosity of both adipates could be found in the literature. Independent viscosity measurements were also performed, at atmospheric pressure, using an Ubbelohde capillary in order to compare with the vibrating wire results. The expanded uncertainty of these results is estimated as ±1.5% at a 95% confidence level. The two data sets agree within the uncertainty of both methods. © 2015 Published by Elsevier B.V.

Open-cell photoacoustic investigation of the thermal effusivity of liquid crystals

We report the use of an open photoacoustic cell configuration for the evaluation of thermal effusivity of liquid crystals. Initially, the method is calibrated using water and glycerol as transparent liquid samples, and the role of thermal conductivity of these liquids on the photoacoustic signal amplitude is discussed. To demonstrate the application of the present method for the evaluation of thermal effusivity of liquid crystals, we have used certain multicomponent nematic liquid crystal mixtures, namely BL001, BL002, BL032, and BL035. Each of these liquid crystal mixtures contains four to nine components and are primarily based on the cyanobiphenyl structure. The measured values of thermal effusivity of BL001 and BL002 were found to be almost the same, but differ from those of BL032 and BL035, which implies a difference in composition of the latter two from the former two mixtures.

Liquid ultraviolet matrix-assisted laser desorption/ionization - mass spectrometry for automated proteomic analysis

We have combined several key sample preparation steps for the use of a liquid matrix system to provide high analytical sensitivity in automated ultraviolet -- matrix-assisted laser desorption/ionisation -- mass spectrometry (UV-MALDI-MS). This new sample preparation protocol employs a matrix-mixture which is based on the glycerol matrix-mixture described by Sze et al. The low-femtomole sensitivity that is achievable with this new preparation protocol enables proteomic analysis of protein digests comparable to solid-state matrix systems. For automated data acquisition and analysis, the MALDI performance of this liquid matrix surpasses the conventional solid-state MALDI matrices. Besides the inherent general advantages of liquid samples for automated sample preparation and data acquisition the use of the presented liquid matrix significantly reduces the extent of unspecific ion signals in peptide mass fingerprints compared to typically used solid matrices, such as 2,5-dihydroxybenzoic acid (DHB) or alpha-cyano-hydroxycinnamic acid (CHCA). In particular, matrix and low-mass ion signals and ion signals resulting from cation adduct formation are dramatically reduced. Consequently, the confidence level of protein identification by peptide mass mapping of in-solution and in-gel digests is generally higher.

Liquid ultraviolet matrix-assisted laser desorption/ionization mass spectrometry for automated proteomic analysis

We have combined several key sample preparation steps for the use of a liquid matrix system to provide high analytical sensitivity in automated ultraviolet - matrix-assisted laser desorption/ ionisation - mass spectrometry (UV-MALDI-MS). This new sample preparation protocol employs a matrix-mixture which is based on the glycerol matrix-mixture described by Sze et al. U. Am. Soc. Mass Spectrom. 1998, 9, 166-174). The low-ferntomole sensitivity that is achievable with this new preparation protocol enables proteomic analysis of protein digests comparable to solid-state matrix systems. For automated data acquisition and analysis, the MALDI performance of this liquid matrix surpasses the conventional solid-state MALDI matrices. Besides the inherent general advantages of liquid samples for automated sample preparation and data acquisition the use of the presented liquid matrix significantly reduces the extent of unspecific ion signals in peptide mass fingerprints compared to typically used solid matrices, such as 2,5-dihydrox-ybenzoic acid (DHB) or alpha-cyano-hydroxycinnamic acid (CHCA). In particular, matrix and lowmass ion signals and ion signals resulting from cation adduct formation are dramatically reduced. Consequently, the confidence level of protein identification by peptide mass mapping of in-solution and in-gel digests is generally higher.

The potential of solid phase microextraction (SPME) for the recovery of explosives followed by gas and liquid chromatographic analysis

The potential of solid phase microextraction (SPME) in the analysis of explosives is demonstrated. A sensitive, rapid, solventless and inexpensive method for the analysis of explosives and explosive odors from solid and liquid samples has been optimized using SPME followed by HPLC and GC/ECD. SPME involves the extraction of the organic components in debris samples into sorbent-coated silica fibers, which can be transferred directly to the injector of a gas chromatograph. SPME/HPLC requires a special desorption apparatus to elute the extracted analyte onto the column at high pressure. Results for use of GC/ECD is presented and compared to the results gathered by using HPLC analysis. The relative effects of controllable variables including fiber chemistry, adsorption and desorption temperature, extraction time, and desorption time have been optimized for various high explosives. ^

The potential of solid phase microextraction (spme) for the recovery of explosives followed by gas and liquid chromatographic analysis

The potential of solid phase microextraction (SPME) in the analysis of explosives is demonstrated. A sensitive, rapid, solventless and inexpensive method for the analysis of explosives and explosive odors from solid and liquid samples has been optimized using SPME followed by HPLC and GC/ECD. SPME involves the extraction of the organic components in debris samples into sorbent-coated silica fibers, which can be transferred directly to the injector of a gas chromatograph. SPME/HPLC requires a special desorption apparatus to elute the extracted analyte onto the column at high pressure. Re suits for use of GC[ECD is presented and compared to the results gathered by using HPLC analysis. The relative effects of controllable variables including fiber chemistry, adsorption and desorption temperature, extraction time, and desorption time have been optimized for various high explosives.

A novel disposable electrochemical microcell: construction and characterization

An alternative technique for the fabrication of disposable electrochemical microcells containing working, reference and auxiliary electrodes on a single device is reported. The procedure is based on thermal-transfer of toner masks onto CD-R (recordable compact discs) gold surfaces to define the layout of the electrodes (contour). In a subsequent step, the layout is manually painted with a permanent marker pen. The unprotected gold surface is conveniently etched (chemical corrosion) and the ink is then easily removed with ethanol, generating gold surfaces without contamination. The final and reproducible area of the electrodes is defined by heat transference of a second toner mask. Silver epoxy is deposited on one of the gold bands which is the satisfactorily used as reference electrode. These microcells were electrochemically characterized by cyclic, linear, and square wave voltammetry, and several electroactive species were used as model systems. The area reproducibility of the electrodes for different microcells was studied and a relative standard deviation better than 1,0% (n = 10) was obtained. Disposable electrochemical microcells were successfully used in analysis of liquid samples with volumes lower than 200 µL and good stability and reproducibility (RSD less than 2.0%) were achieved. These microcells were also evaluated for quantification of paracetamol and dipyrone in pharmaceutical formulations.

Electrochemical immunosensor for multiplexed detection of food-borne pathogens using nanocrystal bioconjugates and MWCNT screen-printed electrode

Bacterial food poisoning is an ever-present threat that can be prevented with proper care and handling of food products. A disposable electrochemical immunosensor for the simultaneous measurements of common food pathogenic bacteria namely Escherichia coli O157:H7 (E. coli), campylobacter and salmonella were developed. The immunosensor was fabricated by immobilizing the mixture of anti-E. coli, anticampylobacter and anti-salmonella antibodies with a ratio of 1:1:1 on the surface of the multiwall carbon nanotube-polyallylamine modified screen printed electrode (MWCNT-PAH/SPE). Bacteria suspension became attached to the immobilized antibodies when the immunosensor was incubated in liquid samples. The sandwich immunoassay was performed with three antibodies conjugated with specific nanocrystal ( -E. coli-CdS, -campylobacter-PbS and -salmonella-CuS) which has releasable metal ions for electrochemical measurements. The square wave anodic stripping voltammetry (SWASV) was employed to measure released metal ions from bound antibody nanocrystal conjugates. The calibration curves for three selected bacteria were found in the range of 1 × 103 – 5 × 105 cells mL−1 with the limit of detection (LOD) 400 cells mL−1 for salmonella, 400 cells mL−1 for campylobacter and 800 cells mL−1 for E. coli. The precision and sensitivity of this method show the feasibility of multiplexed determination of bacteria in milk samples.

Dynamic and interaction of cytochrome c with Pf1 virus

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em BioOrgânica

Caracterização de materiais plásticos usados na indústria têxtil e de vestuário por FTIR

Dissertação de mestrado em Técnicas de Caracterização e Análises Químicas

New Radicals and new applications of Dynamic Nuclear Polarization of biological systems

Dynamic Nuclear Polarization (DNP) is an emerging technique that could revolutionize the NMR study of small molecules at very low concentrations by the increase in sensitivity that results from transfer of polarization between electronic and nuclear spins. Although the underlying physics has been known for a long time, in the last few years there has been a lot of excitement on the chemistry and biology NMR community caused by the demonstration that the highly polarized nuclei that are prepared in solid state at very low temperatures (1-2 K) could be rapidly transferred to liquid samples at room temperature and studied in solution by conventional NMR techniques. In favorable cases several order of magnitude increases in sensitivity have been achieved. The technique is now mature enough that a commercial instrument is available. The efficiency of DNP depends on two crucial aspects: i) the efficiency of the nuclear polarization process and ii) the efficiency of the transfer from the initial solid state to the fluid state in which NMR is measured. The preferred areas of application (iii) will be dictated by situations in which the low concentration of the sample or its intrinsic low receptivity are the limiting factors .

Noves metodologies d’anàlisi de compostos volàtils mitjançant trampes d’agulla. Aplicació a l’anàlisi d’alè, atmosfèrica i d’aigües

New methodologies for the analysis of volatile compoundsusing needle traps. Applications to breath, atmospheric andwater analysis. A new preconcentration technique has been developed for the analysis of volatile compounds based on the use of needle traps. These traps are based on stainless steel needles filled with one or more adsorbents, which allows the preconcentration of the anilities inside the trap by passing a gas flow through the needle. The parameters affecting the sorption/desorption process have been assessed (e.g. needle and liner dimensions, injector temperature, split less time, memory effects, and stability inside the needle). For liquid samples, four different sampling methodologies were studied, including passive and active sampling methods. The best results, considering the simplicity and sensitivity, are obtained by sampling the headspace volume using various cycles of a small and fix volume. Once the best conditions of analysis have been found, the method has been validated for gas and liquid samples. The results obtained show that needle traps are a good analytical methodology for the analysis of breath, environmental and liquid samples