Alkaline sulfite/anthraquinone pretreatment followed by disk refining of Pinus radiata and Pinus caribaea wood chips for biochemical ethanol production

BACKGROUND: Alkaline sulfite/anthraquinone (ASA) cooking of Pinus radiata and Pinus caribaea wood chips followed by disk refining was used as a pretreatment for the production of low lignified and high fibrillated pulps. The pulps produced with different delignification degrees and refined at different energy inputs (250, 750 and 1600 Wh) were saccharified with cellulases and fermented to ethanol with Saccharomyces cerevisiae using separated hydrolysis and fermentation (SHF) or semi-simultaneous saccharification and fermentation (SSSF) processes. RESULTS: Delignification of ASA pulps was between 25% and 50%, with low glucans losses. Pulp yield was from 70 to 78% for pulps of P. radiata and 60% for the pulp of P. caribaea. Pulps obtained after refining were evaluated in assays of enzymatic hydrolysis. Glucans-to-glucose conversion varied from 20 to 70%, depending on the degree of delignification and fibrillation of the pulps. The best ASA pulp of P. radiata was used in SHF and SSSF experiments of ethanol production. Such experiments produced maximum ethanol concentration of 20 g L-1, which represented roughly90% of glucose conversion and an estimated amount of 260 L ethanol ton(-1) wood. P. caribaea pulp also presented good performance in the enzymatic hydrolysis and fermentation but, due to the low amount of cellulose present, only 140 L ethanol would be obtained from each ton of wood. CONCLUSION: ASA cooking followed by disk refining was shown to be an efficient pretreatment process, which generated a low lignified and high-fibrillated substrate that allowed the production of ethanol from the softwoods with high conversion yields. (C) 2012 Society of Chemical Industry

Determination of atenolol in environmental water samples and pharmaceutical formulations at a graphite-epoxy composite electrode

A bare graphite-epoxy composite was evaluated as an electrode material in the determination of atenolol in natural water samples and pharmaceutical formulations for which the analyte was spiked. Using a DPV procedure, a linear response was observed in the 4.45-84.7 mu mol L-1 range with a LOD = 2.23 mu mol L-1, without need of surface renewal between successive runs, and recoveries between 92.5 and 107.5% for pharmaceutical formulations. The results obtained from the proposed procedure agreed with HPLC results within a 95% confidence level. During the determination of atenolol in water samples, recoveries between 96.1 and 102.6% were found.

New activity in the large circumstellar disk of the Be-shell star 48 Librae

Aims. Spectroscopic, polarimetric, and high spectral resolution interferometric data covering the period 1995-2011 are analyzed to document the transition into a new phase of circumstellar disk activity in the classical Be-shell star 48 Lib. The objective is to use this broad data set to additionally test disk oscillations as the basic underlying dynamical process. Methods. The long-term disk evolution is described using the V/R ratio of the violet and red emission components of H alpha and Br gamma, radial velocities and profiles of He I and optical metal shell lines, as well as multi-band BVRI polarimetry. Single-epoch broad-band and high-resolution interferometric visibilities and phases are discussed with respect to a classical disk model and the given baseline orientations. Results. Spectroscopic signatures of disk asymmetries in 48 Lib vanished in the late nineties but recovered some time between 2004 and 2007, as shown by a new large-amplitude and long-duration V/R cycle. Variations in the radial velocity and line profile of conventional shell lines correlate with the V/R behavior. They are shared by narrow absorption cores superimposed on otherwise seemingly photospheric He I lines, which may form in high-density gas at the inner disk close to the photosphere. Large radial velocity variations continued also during the V/R-quiet years, suggesting that V/R may not always be a good indicator of global density waves in the disk. The comparison of the polarization after the recovery of the V/R activity shows a slight increase, while the polarization angle has been constant for more than 20 years, placing tight limits on any 3-D precession or warping of the disk. The broad H-band interferometry gives a disk diameter of (1.72 +/- 0.2) mas (equivalent to 15 stellar radii), position angle of the disk (50 +/- 9)degrees and a relatively low disk flattening of 1.66 +/- 0.3. Within the errors the same disk position angle is derived from polarimetric observations and from photocenter shifts across Br gamma. The high-resolution interferometric visibility and phase profiles show a double or even multiple-component structure. A preliminary estimate based on the size of the Br gamma emitting region indicates a large diameter for the disk (tens of stellar radii). Overall, no serious contradiction between the observations and the disk-oscillation model could be construed.

Determination of tetracycline in environmental water samples at a graphite-polyurethane composite electrode

A bare graphite-polyurethane composite was evaluated in the tetracycline (TC) determination in natural water samples. Using differential pulse voltammetry (DPV), a linear response was observed in the range of 4.00-40.0 µmol L-1 with limit of detection of 2.80 µmol L-1, without the need of surface renewing between successive runs. During the tetracycline determination in water samples, recoveries between 92.6 and 100% were found. The results for TC determination in water samples after a pre-concentration stage agreed with spiked value at a 95% confidence level according to student t-test.

Planetary nebulae and determination of the bulge-disk boundary

In this paper, a sample of planetary nebulae in the Galaxy's inner-disk and bulge is used to find the galactocentric distance that optimally separates these two populations in terms of their abundances. Statistical distance scales were used to investigate the distribution of abundances across the disk–bulge interface, while a Kolmogorov–Smirnov test was used to find the distance at which the chemical properties of these regions separate optimally. The statistical analysis indicates that, on average, the inner population is characterized by lower abundances than the outer component. Additionally, for the α-element abundances, the inner population does not follow the disk's radial gradient toward the Galactic Center. Based on our results, we suggest a bulge–disk interface at 1.5 kpc, marking the transition between the bulge and the inner disk of the Galaxy as defined by the intermediate-mass population.

The Gemini planet-finding campaign: the frequency of giant planets aroud debris disk stars

We have completed a high-contrast direct imaging survey for giant planets around 57 debris disk stars as part of the Gemini NICI Planet-Finding Campaign. We achieved median H-band contrasts of 12.4 mag at 0.''5 and 14.1 mag at 1'' separation. Follow-up observations of the 66 candidates with projected separation <500 AU show that all of them are background objects. To establish statistical constraints on the underlying giant planet population based on our imaging data, we have developed a new Bayesian formalism that incorporates (1) non-detections, (2) single-epoch candidates, (3) astrometric and (4) photometric information, and (5) the possibility of multiple planets per star to constrain the planet population. Our formalism allows us to include in our analysis the previously known β Pictoris and the HR 8799 planets. Our results show at 95% confidence that <13% of debris disk stars have a ≥5 M Jup planet beyond 80 AU, and <21% of debris disk stars have a ≥3 M Jup planet outside of 40 AU, based on hot-start evolutionary models. We model the population of directly imaged planets as d 2 N/dMdavpropm α a β, where m is planet mass and a is orbital semi-major axis (with a maximum value of a max). We find that β < –0.8 and/or α > 1.7. Likewise, we find that β < –0.8 and/or a max < 200 AU. For the case where the planet frequency rises sharply with mass (α > 1.7), this occurs because all the planets detected to date have masses above 5 M Jup, but planets of lower mass could easily have been detected by our search. If we ignore the β Pic and HR 8799 planets (should they belong to a rare and distinct group), we find that <20% of debris disk stars have a ≥3 M Jup planet beyond 10 AU, and β < –0.8 and/or α < –1.5. Likewise, β < –0.8 and/or a max < 125 AU. Our Bayesian constraints are not strong enough to reveal any dependence of the planet frequency on stellar host mass. Studies of transition disks have suggested that about 20% of stars are undergoing planet formation; our non-detections at large separations show that planets with orbital separation >40 AU and planet masses >3 M Jup do not carve the central holes in these disks.

Stochastic gravito-inertial modes discovered by CoRoT in the hot Be star HD51452

Context. Be stars are rapidly rotating stars with a circumstellar decretion disk. They usually undergo pressure and/or gravity pulsation modes excited by the κ-mechanism, i.e. an effect of the opacity of iron-peak elements in the envelope of the star. In the Milky Way, p-modes are observed in stars that are hotter than or equal to the B3 spectral type, while g-modes are observed at the B2 spectral type and cooler. Aims. We observed a B0IVe star, HD51452, with the high-precision, high-cadence photometric CoRoT satellite and high-resolution, ground-based HARPS and SOPHIE spectrographs to study its pulsations in great detail. We also used the lower resolution spectra available in the BeSS database. Methods. We analyzed the CoRoT and spectroscopic data with several methods: Clean-NG, FreqFind, and a sliding window method. We also analyzed spectral quantities, such as the violet over red (V/R) emission variations, to obtain information about the variation in the circumstellar environment. We calculated a stellar structure model with the ESTER code to test the various interpretation of the results. Results. We detect 189 frequencies of variations in the CoRoT light curve in the range between 0 and 4.5 c d−1. The main frequencies are also recovered in the spectroscopic data. In particular we find that HD51452 undergoes gravito-inertial modes that are not in the domain of those excited by the κ-mechanism. We propose that these are stochastic modes excited in the convective zones and that at least some of them are a multiplet of r-modes (i.e. subinertial modes mainly driven by the Coriolis acceleration). Stochastically excited gravito-inertial modes had never been observed in any star, and theory predicted that their very low amplitudes would be undetectable even with CoRoT. We suggest that the amplitudes are enhanced in HD51452 because of the very rapid stellar rotation. In addition, we find that the amplitude variations of these modes are related to the occurrence of minor outbursts. Conclusions. Thanks to CoRoT data, we have detected a new kind of pulsations in HD51452, which are stochastically excited gravito-inertial modes, probably due to its very rapid rotation. These modes are probably also present in other rapidly rotating hot Be stars.

A spectroscopic and photometric study of MSP companions in Galactic Globular Clusters

This Thesis is devoted to the study of the optical companions of Millisecond Pulsars in Galactic Globular Clusters (GCs) as a part of a large project started at the Department of Astronomy of the Bologna University, in collaboration with other institutions (Astronomical Observatory of Cagliari and Bologna, University of Virginia), specifically dedicated to the study of the environmental effects on passive stellar evolution in galactic GCs. Globular Clusters are very efficient “Kilns” for generating exotic object, such as Millisecond Pulsars (MSP), low mass X-ray binaries(LMXB) or Blue Straggler Stars (BSS). In particular MSPs are formed in binary systems containing a Neutron Star which is spun up through mass accretion from the evolving companion (e.g. Bhattacharia & van den Heuvel 1991). The final stage of this recycling process is either the core of a peeled star (generally an Helium white dwarf) or a very light almos exhausted star, orbiting a very fast rotating Neutron Star (a MSP). Despite the large difference in total mass between the disk of the Galaxy and the Galactic GC system (up a factor 103), the percentage of fast rotating pulsar in binary systems found in the latter is very higher. MSPs in GCs show spin periods in the range 1.3 ÷ 30ms, slowdown rates ˙P 1019 s/s and a lower magnetic field, respect to ”normal” radio pulsars, B 108 gauss . The high probability of disruption of a binary systems after a supernova explosion, explain why we expect only a low percentage of recycled millisecond pulsars respect to the whole pulsar population. In fact only the 10% of the known 1800 radio pulsars are radio MSPs. Is not surprising, that MSP are overabundant in GCs respect to Galactic field, since in the Galactic Disk, MSPs can only form through the evolution of primordial binaries, and only if the binary survives to the supernova explosion which lead to the neutron star formation. On the other hand, the extremely high stellar density in the core of GCs, relative to most of the rest of the Galaxy, favors the formation of several different binary systems, suitable for the recycling of NSs (Davies at al. 1998). In this thesis we will present the properties two millisecond pulsars companions discovered in two globular clusters, the Helium white dwarf orbiting the MSP PSR 1911-5958A in NGC 6752 and the second case of a tidally deformed star orbiting an eclipsing millisecond pulsar, PSR J1701-3006B in NGC6266

Fault detection in rotating machines by vibration signal processing techniques

Machines with moving parts give rise to vibrations and consequently noise. The setting up and the status of each machine yield to a peculiar vibration signature. Therefore, a change in the vibration signature, due to a change in the machine state, can be used to detect incipient defects before they become critical. This is the goal of condition monitoring, in which the informations obtained from a machine signature are used in order to detect faults at an early stage. There are a large number of signal processing techniques that can be used in order to extract interesting information from a measured vibration signal. This study seeks to detect rotating machine defects using a range of techniques including synchronous time averaging, Hilbert transform-based demodulation, continuous wavelet transform, Wigner-Ville distribution and spectral correlation density function. The detection and the diagnostic capability of these techniques are discussed and compared on the basis of experimental results concerning gear tooth faults, i.e. fatigue crack at the tooth root and tooth spalls of different sizes, as well as assembly faults in diesel engine. Moreover, the sensitivity to fault severity is assessed by the application of these signal processing techniques to gear tooth faults of different sizes.

Sviluppo di biosensori: modifiche di superfici elettrodiche e sistemi di immobilizzazione enzimatica

An amperometric glucose biosensor was developed using an anionic clay matrix (LDH) as enzyme support. The enzyme glucose oxidase (GOx) was immobilized on a layered double hydroxide Ni/Al-NO3 LDH during the electrosynthesis, which was followed by crosslinking with glutaraldehyde (GA) vapours or with GA and bovine serum albumin (GABSA) to avoid the enzyme release. The electrochemical reaction was carried out potentiostatically, at -0.9V vs. SCE, using a rotating disc Pt electrode to assure homogeneity of the electrodeposition suspension, containing GOx, Ni(NO3)2 and Al(NO3)3 in 0.3 M KNO3. The mechanism responsible of the LDH electrodeposition involves the precipitation of the LDH due to the increase of pH at the surface of the electrode, following the cathodic reduction of nitrates. The Pt surface modified with the Ni/Al-NO3 LDH shows a much reduced noise, giving rise to a better signal to noise ratio for the currents relative to H2O2 oxidation, and a linear range for H2O2 determination wider than the one observed for bare Pt electrodes. We pointed out the performances of the biosensor in terms of sensitivity to glucose, calculated from the slope of the linear part of the calibration curve for enzimatically produced H2O2; the sensitivity was dependent on parameters related to the electrodeposition in addition to working conditions. In order to optimise the glucose biosensor performances, with a reduced number of experimental runs, we applied an experimental design. A first screening was performed considering the following variables: deposition time (30 - 120 s), enzyme concentration (0.5 - 3.0 mg/mL), Ni/Al molar ratio (3:1 or 2:1) of the electrodeposition solution at a total metals concentration of 0.03 M and pH of the working buffer solution (5.5-7.0). On the basis of the results from this screening, a full factorial design was carried out, taking into account only enzyme concentration and Ni/Al molar ratio of the electrosynthesis solution. A full factorial design was performed to study linear interactions between factors and their quadratic effects and the optimal setup was evaluated by the isoresponse curves. The significant factors were: enzyme concentration (linear and quadratic terms) and the interaction between enzyme concentration and Ni/Al molar ratio. Since the major obstacle for application of amperometric glucose biosensors is the interference signal resulting from other electro-oxidizable species present in the real matrices, such as ascorbate (AA), the use of different permselective membranes on Pt-LDHGOx modified electrode was discussed with the aim of improving biosensor selectivity and stability. Conventional membranes obtained using Nafion, glutaraldehyde (GA) vapours, GA-BSA were tested together with more innovative materials like palladium hexacyanoferrate (PdHCF) and titania hydrogels. Particular attention has been devoted to hydrogels, because they possess some attractive features, which are generally considered to favour biosensor materials biocompatibility and, consequently, the functional enzyme stability. The Pt-LDH-GOx-PdHCF hydrogel biosensor presented an anti-interferant ability so that to be applied for an accurate glucose analysis in blood. To further improve the biosensor selectivity, protective membranes containing horseradish peroxidase (HRP) were also investigated with the aim of oxidising the interferants before they reach the electrode surface. In such a case glucose determination was also accomplished in real matrices with high AA content. Furthermore, the application of a LDH containing nickel in the oxidised state was performed not only as a support for the enzyme, but also as anti-interferant sistem. The result is very promising and it could be the starting point for further applications in the field of amperometric biosensors; the study could be extended to other oxidase enzymes.

Electrode Materials for Ionic Liquid Based-Supercapacitors

The development of safe, high energy and power electrochemical energy-conversion systems can be a response to the worldwide demand for a clean and low-fuel-consuming transport. This thesis work, starting from a basic studies on the ionic liquid (IL) electrolytes and carbon electrodes and concluding with tests on large-size IL-based supercapacitor prototypes demonstrated that the IL-based asymmetric configuration (AEDLCs) is a powerful strategy to develop safe, high-energy supercapacitors that might compete with lithium-ion batteries in power assist-hybrid electric vehicles (HEVs). The increase of specific energy in EDLCs was achieved following three routes: i) the use of hydrophobic ionic liquids (ILs) as electrolytes; ii) the design and preparation of carbon electrode materials of tailored morphology and surface chemistry to feature high capacitance response in IL and iii) the asymmetric double-layer carbon supercapacitor configuration (AEDLC) which consists of assembling the supercapacitor with different carbon loadings at the two electrodes in order to exploit the wide electrochemical stability window (ESW) of IL and to reach high maximum cell voltage (Vmax). Among the various ILs investigated the N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR1(2O1)TFSI) was selected because of its hydrophobicity and high thermal stability up to 350 °C together with good conductivity and wide ESW, exploitable in a wide temperature range, below 0°C. For such exceptional properties PYR1(2O1)TFSI was used for the whole study to develop large size IL-based carbon supercapacitor prototype. This work also highlights that the use of ILs determines different chemical-physical properties at the interface electrode/electrolyte with respect to that formed by conventional electrolytes. Indeed, the absence of solvent in ILs makes the properties of the interface not mediated by the solvent and, thus, the dielectric constant and double-layer thickness strictly depend on the chemistry of the IL ions. The study of carbon electrode materials evidences several factors that have to be taken into account for designing performing carbon electrodes in IL. The heat-treatment in inert atmosphere of the activated carbon AC which gave ACT carbon featuring ca. 100 F/g in IL demonstrated the importance of surface chemistry in the capacitive response of the carbons in hydrophobic ILs. The tailored mesoporosity of the xerogel carbons is a key parameter to achieve high capacitance response. The CO2-treated xerogel carbon X3a featured a high specific capacitance of 120 F/g in PYR14TFSI, however, exhibiting high pore volume, an excess of IL is required to fill the pores with respect to that necessary for the charge-discharge process. Further advances were achieved with electrodes based on the disordered template carbon DTC7 with pore size distribution centred at 2.7 nm which featured a notably high specific capacitance of 140 F/g in PYR14TFSI and a moderate pore volume, V>1.5 nm of 0.70 cm3/g. This thesis work demonstrated that by means of the asymmetric configuration (AEDLC) it was possible to reach high cell voltage up to 3.9 V. Indeed, IL-based AEDLCs with the X3a or ACT carbon electrodes exhibited specific energy and power of ca. 30 Wh/kg and 10 kW/kg, respectively. The DTC7 carbon electrodes, featuring a capacitance response higher of 20%-40% than those of X3a and ACT, respectively, enabled the development of a PYR14TFSI-based AEDLC with specific energy and power of 47 Wh/kg and 13 kW/kg at 60°C with Vmax of 3.9 V. Given the availability of the ACT carbon (obtained from a commercial material), the PYR1(2O1)TFSI-based AEDLCs assembled with ACT carbon electrodes were selected within the EU ILHYPOS project for the development of large-size prototypes. This study demonstrated that PYR1(2O1)TFSI-based AEDLC can operate between -30°C and +60°C and its cycling stability was proved at 60°C up to 27,000 cycles with high Vmax up to 3.8 V. Such AEDLC was further investigated following USABC and DOE FreedomCAR reference protocols for HEV to evaluate its dynamic pulse-power and energy features. It was demonstrated that with Vmax of 3.7 V at T> 30 °C the challenging energy and power targets stated by DOE for power-assist HEVs, and at T> 0 °C the standards for the 12V-TSS and 42V-FSS and TPA 2s-pulse applications are satisfied, if the ratio wmodule/wSC = 2 is accomplished, which, however, is a very demanding condition. Finally, suggestions for further advances in IL-based AEDLC performance were found. Particularly, given that the main contribution to the ESR is the electrode charging resistance, which in turn is affected by the ionic resistance in the pores that is also modulated by pore length, the pore geometry is a key parameter in carbon design not only because it defines the carbon surface but also because it can differentially “amplify” the effect of IL conductivity on the electrode charging-discharging process and, thus, supercapacitor time constant.

Accretion disk winds in active galactic nuclei: an X-ray view

This Thesis focuses on the X-ray study of the inner regions of Active Galactic Nuclei, in particular on the formation of high velocity winds by the accretion disk itself. Constraining AGN winds physical parameters is of paramount importance both for understanding the physics of the accretion/ejection flow onto supermassive black holes, and for quantifying the amount of feedback between the SMBH and its environment across the cosmic time. The sources selected for the present study are BAL, mini-BAL, and NAL QSOs, known to host high-velocity winds associated to the AGN nuclear regions. Observationally, a three-fold strategy has been adopted: - substantial samples of distant sources have been analyzed through spectral, photometric, and statistical techniques, to gain insights into their mean properties as a population; - a moderately sized sample of bright sources has been studied through detailed X-ray spectral analysis, to give a first flavor of the general spectral properties of these sources, also from a temporally resolved point of view; - the best nearby candidate has been thoroughly studied using the most sophisticated spectral analysis techniques applied to a large dataset with a high S/N ratio, to understand the details of the physics of its accretion/ejection flow. There are three main channels through which this Thesis has been developed: - [Archival Studies]: the XMM-Newton public archival data has been extensively used to analyze both a large sample of distant BAL QSOs, and several individual bright sources, either BAL, mini-BAL, or NAL QSOs. - [New Observational Campaign]: I proposed and was awarded with new X-ray pointings of the mini-BAL QSOs PG 1126-041 and PG 1351+640 during the XMM-Newton AO-7 and AO-8. These produced the biggest X-ray observational campaign ever made on a mini-BAL QSO (PG 1126-041), including the longest exposure so far. Thanks to the exceptional dataset, a whealth of informations have been obtained on both the intrinsic continuum and on the complex reprocessing media that happen to be in the inner regions of this AGN. Furthermore, the temporally resolved X-ray spectral analysis field has been finally opened for mini-BAL QSOs. - [Theoretical Studies]: some issues about the connection between theories and observations of AGN accretion disk winds have been investigated, through theoretical arguments and synthetic absorption line profiles studies.