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The recent technique of molecular beam-thermal desorption spectrometry was used here for monitoring hydrogen uptake and release from carbon nanotube networks, after electrochemical hydrogen uptake. This way, an accurate determination of the hydrogen mass absorbed in electrodes made from those assemblies can be achieved by significantly improving the signal-to-noise ratio. The hydrogen desorption mass spectra account for the enhanced surface capability for hydrogen adsorption in the electrodes and enable a comparison with the performance of a palladium electrode in similar conditions. A comparative study involving different carbon nanotube electrodes, in similar hydrogen uptake/desorption conditions, clearly confirmed the expectations about their enhanced hydrogen storage capacity and points to the great potential of carbon nanotube assemblies in replacing the heavier metal alloys as electrocatalysts. publishersversion published

Reproducibility and reliability of data is an important subject in the development of organic devices for photonics applications. This work reports the analysis of successive photoinduced birefringence creation curves in layer-by-layer films of poly(allylamine hydrochloride) (PAH) and poly{1-(4-(3-carboxy-4-hydroxyphenylazo) benzenesulfonamido)-1,2-ethanediyl, sodium salt} (PAZO) with different number of bilayers. The birefringence creation or writing curves are described by two processes: a faster one referring the contribution of trans–cis–trans photoisomerization cycles to the birefringence; and a slower one associated to the contribution of motion of the polymer chain to the birefringence. As the number of write–erase cycles increases, the characteristic times of these processes decreases, respectively, to values of 18 and 212 s independently of the number of bilayers of films while for the magnitudes the fast process prevailed relatively to the slow, by 70% against 30%. The observed behavior is explained by the thermal treatment given by the laser beam in the irradiated area with increase of free volume which contributes for the chromophore mobility. This conclusion was achieved by measuring the surface temperature during and after irradiation and analyzing by optical microscopy the film surface where an increase of holes and aggregation as a result of irradiation was observed. Infrared spectra of films after and before irradiation showed changes in the C C absorbance indicating aggregation of azobenzene groups while changes in the protonated and deprotonated carboxylic acid groups are consistent with ionization degree diminishing which is explained by the removal of water molecules by heating caused by laser. The results presented in this paper indicates that an increase in the number of write–erase cycles contributes to reliable and reproducible birefringence characteristics of PAH/PAZO films – a good new from point of view of possible applications.

This work reports a novel deltamethrin (DM) sensor able to detect nano-molar concentrations in ethanol solutions. The sensing layer consists of a thin film, obtained via a layer-by-layer technique, from alternate adsorption of poly(allylamine chloride) (PAH) and poly[1-[4-(3-carboxy-4-hydroxyphenylazo)-benzenesulfonamide)-1,2-ethanediyl]sodium salt] (PAZO) onto a solid support with interdigitaded gold electrodes. The sensor response, obtained from impedance spectroscopy measurements, was revealed to be linear with respect to the real part of impedance, taken at 100 Hz, when plotted as a function of the logarithm of deltamethrin molar concentrations in the micro- to nano-molar range. Sensor sensitivity was of 41.1 ± 0.7 kΩ per decade of concentration for an immersion time above 2 min and the reproducibility is approximately 2% in a binary solution of ethanol and deltamethrin. The main insight of this work concerns to DM detection limits as the sensor revealed to be able to detect concentrations below 0.1 nM, a value which is significantly lower than any reported in the literature and close what is appropriate for in situ environmental contaminant detection.

A recently developed thermal desorption spectrometry variant, Molecular Beam–Thermal Desorption Spectrometry (MB–TDS) is used, to monitor in real time and in-situ the dehydriding kinetics from hydrogen storage materials. It represents a real improvement in the accurate determination of hydrogen mass absorbed into a solid sample. The enhancement in the signal-to-noise ratio for trace hydrogen is reproducible, and no previous calibration with a chemical standard is required, in contrast to the conventional TDS technique. The procedure shows potential to be a means of studying dehydriding kinetics at the nanoscale in vacuum, even when the amount of hydrogen is below the detection limit of a microbalance.

In this paper, a procedure is presented that will allow (i) the power and (ii) the energy of a pulsed and tuneable TEA CO2 laser to be optimized. This type of laser represents a significant improvement in performance and portability. Combining a pulse mode with a grating tuning facility, it enables us to scan the working wavelength between 9.2 and 10.8 µm instead of the typical 1064 nm for other infrared lasers. Along the way, the study proved that there are many factors which could be improved in order to get even better results. Following an adequate procedure, the energy values could be optimized in intensity and stability, and therefore indirectly laser power. In addition, the same procedure allowed us to check the wavelengths of the laser emission lines in the absence of a spectrometer, using a previously established conversion table of the grating position versus line designation. This work is mainly intended for graduate and experimental physicists. This experimental work is being performed in our Physics Group at the New University of Lisbon, targeting physics students at the graduation level, in the aim of Bologna Master's degree.

The spectroscopic characterization of layer-by-layer (LbL) films containing liposomes is essential not only for determining the precise film architecture but also to guide the design of drug delivery systems. In this study we provide the first report of vacuum ultraviolet spectroscopy (VUV) characterization of LbL films made with liposomes from 1.2-dipalmitoyl-sn-Glycero-3-[Phospho-rac-(1- glycerol)] (Sodium Salt) (DPPG) alternated with poly(allylamine hydrochloride) (PAH). Measurements in the 6.0-9.5eV range allowed us to identify the electronic transitions responsible for the spectra, which were assigned to carboxyl, hydroxyl and phosphate groups in DPPG while the PAH spectra were governed by electronic transitions in the amino groups. The surface mass density of the LbL films could be determined, from which the formation of a DPPG bilayer was inferred. This rupture of the liposomes into bilayers was confirmed with atomic force microscopy measurements. In subsidiary experiments we ensured that the UV irradiation in vacuum had negligible damage in the DPPG liposomes during the course of the VUV measurements. In addition to demonstrating the usefulness of VUV spectroscopy, the results presented here may be exploited in biological applications of liposome-containing films.

Different types of experimental studies are performed using the hydrogen storage alloy (HSA) MlNi3.6Co0.85Al0.3Mn0.3 (Ml: La-rich mischmetal), chemically surface treated, as the anode active material for application in a proton exchange membrane fuel cell (PEMFC). The recently developed molecular beam—thermal desorption spectrometry (MB-TDS) technique is here reported for detecting the electrochemical hydrogen uptake and release by the treated HSA. The MB-TDS allows an accurate determination of the hydrogen mass absorbed into the hydrogen storage alloy (HSA), and has significant advantages in comparison with the conventional TDS method. Experimental data has revealed that the membrane electrode assembly (MEA) using such chemically treated alloy presents an enhanced surface capability for hydrogen adsorption.

Among the most efficient techniques for hydrogen desorption monitoring, thermal desorption mass spectrometry is a very sensitive one, but in certain cases can give rise to uptake misleading results due to residual hydrogen partial pressure background variations. In this work one develops a novel thermal desorption variant based on the effusive molecular beam technique that represents a significant improvement in the accurate determination of hydrogen mass absorbed on a solid sample. The enhancement in the signal-to-noise ratio for trace hydrogen is on the order of 20%, and no previous calibration with a chemical standard is required. The kinetic information obtained from the hydrogen desorption mass spectra (at a constant heating rate of 1 degrees C/min) accounts for the consistency of the technique.

Quartz Crystal Microbalance (QCM) is a widely used technique to characterize adsorption/desorption phenomena at the solid/liquid interface. However, the obtained adsorption/desorption kinetics curves are often not reproducible and present some noise and long term fluctuations. In this work, the accuracy of a commercial QCM to measure the adsorbed amount of polyelectrolytes and biological molecules was evaluated in terms of experimental QCM configurations with respect to quality, stability, and reproducibility of the measured data. Evaluation consisted in comparing the adsorption kinetics curves of the cationic polyelectrolyte poly(ethyleneimine) and the anionic 1,2-dipalmitoyl-sn-glycero-3-phospho-(1'-rac-glycerol) (sodium salt) liposomes, when setting the quartz crystal surface in stationary horizontal open, stationary horizontal closed, stationary vertical open, continuous vertical closed, and stationary vertical closed measuring configuration. For this last configuration, a new cell was designed and implemented. The analysis of the kinetics curves revealed that horizontal modes are more unstable when subjected to fostering noise due to the mechanical vibrations and lead to resonance frequency shift. This shift is caused by the measurement of non-adsorbed molecules which are deposited on the quartz crystal due to gravity force. The vertical modes proved to be more reproducible and reliable.