Analysis and control of transient spectra using time-dependent density functional theory.

215 p.

Effect of graphene substrate on the SERS Spectra of Aromatic bifunctional molecules on metal nanoparticles

The design of molecular sensors plays a very important role within nanotechnology and especially in the development of different devices for biomedical applications. Biosensors can be classified according to various criteria such as the type of interaction established between the recognition element and the analyte or the type of signal detection from the analyte (transduction). When Raman spectroscopy is used as an optical transduction technique the variations in the Raman signal due to the physical or chemical interaction between the analyte and the recognition element has to be detected. Therefore any significant improvement in the amplification of the optical sensor signal represents a breakthrough in the design of molecular sensors. In this sense, Surface-Enhanced Raman Spectroscopy (SERS) involves an enormous enhancement of the Raman signal from a molecule in the vicinity of a metal surface. The main objective of this work is to evaluate the effect of a monolayer of graphene oxide (GO) on the distribution of metal nanoparticles (NPs) and on the global SERS enhancement of paminothiophenol (pATP) and 4-mercaptobenzoic acid (4MBA) adsorbed on this substrate. These aromatic bifunctional molecules are able to interact to metal NPs and also they offer the possibility to link with biomolecules. Additionally by decorating Au or Ag NPs on graphene sheets, a coupled EM effect caused by the aggregation of the NPs and strong electronic interactions between Au or Ag NPs and the graphene sheets are considered to be responsible for the significantly enhanced Raman signal of the analytes [1-2]. Since there are increasing needs for methods to conduct reproducible and sensitive Raman measurements, Grapheneenhanced Raman Scattering (GERS) is emerging as an important method [3].

Voltage and current spectra for matrix power converters

Matrix power converters are used for transforming one alternating-current power supply to another, with different peak voltage and frequency. There are three input lines, with sinusoidally varying voltages which are 120◦ out of phase one from another, and the output is to be delivered as a similar three-phase supply. The matrix converter switches rapidly, to connect each output line in sequence to each of the input lines in an attempt to synthesize the prescribed output voltages. The switching is carried out at high frequency and it is of practical importance to know the frequency spectra of the output voltages and of the input and output currents. We determine in this paper these spectra using a new method, which has significant advantages over the prior default method (a multiple Fourier series technique), leading to a considerably more direct calculation. In particular, the determination of the input current spectrum is feasible here, whereas it would be a significantly more daunting procedure using the prior method instead.

Transmission Spectra of Rb 87 atoms near an Optical Nanofiber.

We present measurements of the transmission spectra of 87Rb atoms at 780 nm in the vicinity of a nanofiber. A uniform distribution of fixed atoms around a nanofiber should produce a spectrum that is broadened towards the red due to shifts from the van der Waals potential. If the atoms are free, this also produces an attractive force that accelerates them until they collide with the fiber which depletes the steady-state density of near-surface atoms. It is for this reason that measurements of the van der Waals interaction are sparse. We confirm this by measuring the spectrum cold atoms from a magneto-optical trap around the fiber, revealing a symmetric line shape with nearly the natural linewidth of the transition. When we use an auxiliary 750 nm laser we are able to controllably desorb a steady flux of atoms from the fiber that reside near the surface (less than 50 nm) long enough to feel the van der Walls interaction and produce an asymmetric spectrum. We quantify the spectral asymmetry as a function of 750 nm laser power and find a maximum. Our model, which that takes into account the change in the density distribution, qualitatively explains the observations. In the future this can be used as a tool to more comprehensively study atom-surface interactions.

Truncated projective spaces, Brown–Gitler spectra and indecomposable A(1)-modules

MSC 19L41; 55S10.

Analysis of size spectra off northwest Africa: a useful indicator in tropical areas?

Changes in the size spectra of demersal fish communities off Cape Verde (1988, 1994), Guinea (1985-1995), and Mauritania (1987-2001) were studied. Intercepts and slopes showed opposite trends for Guinea and Mauritania, but were relatively stable in spite of a strong increase in landings per unit area. For Cape Verde, there were marked changes in size structure, seemingly inconsistent with the more moderate fishing pressure there. Changes in size structure do not seem to be suitable indicators of the effects of fishing in areas characterized by faster growth rates, small sizes, high species diversity, and complex interrelationships, such as the tropics. (c) 2005 International Council for the Exploration of the Sea. Published by Elsevier Ltd. All rights reserved.

Tobacco budworm resistance to pyrethroids: resistance spectra, synergists, and substitute insecticides.

1988

Retrieval of atmospheric trace gases from DOAS/MAX-DOAS ground-based spectra

The study of the atmospheric chemical composition is crucial to understand the climate changes that we are experiencing in the last decades and to monitor the air quality over industrialized areas. The Multi-AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) ground-based instruments are particularly suitable to derive the concentration of some trace gases that absorb the Visible (VIS) and Ultra-Violet (UV) solar radiation. The zenith-sky spectra acquired by the Gas Analyzer Spectrometer Correlating Optical Differences / New Generation 4 (GASCOD/NG4) instrument are exploited to retrieve the NO2 and O3 total Vertical Column Densities (VCDs) over Lecce. The results show that the NO2 total VCDs are significantly affected by the tropospheric content, consequence of the anthropogenic activity. Indeed, they present systematically lower values during Sunday, when less traffic is generally present around the measurement site, and during windy days, especially when the wind direction measured at 2 m height is not from the city of Lecce. Another MAX-DOAS instrument (SkySpec-2D) is exploited to create the first Italian MAX-DOAS site compliant to the Fiducial Reference Measurements for DOAS (FRM4DOAS) standards, in San Pietro Capofiume (SPC), located in the middle of the Po Valley. After the assessment of the SkySpec-2D’s performances through two measurement campaigns taken place in Bologna and in Rome, SkySpec-2D is installed in SPC on the 1st October 2021. Its MAX-DOAS spectra are used to retrieve the NO2 and O3 total VCDs, and aerosol extinction and NO2 tropospheric vertical profiles over the Po Valley exploiting the Bremen Optimal estimation REtrieval for Aerosol and trace gaseS (BOREAS) algorithm. Promising results are found, with high correlations against both in-situ and satellite data. In the future, these data will play an important role for air quality studies over the Po Valley and for satellite validation purposes.

Amplification mechanisms of inflationary spectra in induced gravity

Inflation is the primordial stage of accelerated expansion of the Universe which solves the issues of the initial conditions of a decelerating Universe (horizon, flatness and entropy problems). Moreover, it is supposed that quantum fluctuations originated during the first moments after the Big Bang gave rise to the formation of galaxies and other structures of the Universe when inflation ends. Among these structures also primordial black holes (PBHs) may have been generated. The interest in PBHs relies on their possible connection with dark matter: they could constitute a portion or even the whole dark matter content of our Universe.\\ In this work we consider inflation in the Induced Gravity (IR) context and study possible mechanisms of amplification of the curvature perturbations generated during the cosmic acceleration. In particular we consider the possibility of a period of Constant Roll (CR). Starting from the previous work of Starobinsky et al. Our final purpose is to analyse the power spectrum of the scalar perturbations and to find in which conditions there is an enhancement of the power spectrum possibly leading to PBHs formation.

Yellowing And Bleaching Of Grey Hair Caused By Photo And Thermal Degradation.

Yellowing is an undesirable phenomenon that is common in people with white and grey hair. Because white hair has no melanin, the pigment responsible for hair colour, the effects of photodegradation are more visible in this type of hair. The origin of yellowing and its relation to photodegradation processes are not properly established, and many questions remain open in this field. In this work, the photodegradation of grey hair was investigated as a function of the wavelength of incident radiation, and its ultrastructure was determined, always comparing the results obtained for the white and black fibres present in grey hair with the results of white wool. The results presented herein indicate that the photobehaviour of grey hair irradiated with a mercury lamp or with solar radiation is dependent on the wavelength range of the incident radiation and on the initial shade of yellow in the sample. Two types of grey hair were used: (1) blended grey hair (more yellow) and (2) grey hair from a single-donor (less yellow). After exposure to a full-spectrum mercury lamp for 200 h, the blended white hair turned less yellow (the yellow-blue difference, Db(*) becomes negative, Db(*)=-6), whereas the white hair from the single-donor turned slightly yellower (Db(*)=2). In contrast, VIS+IR irradiation resulted in bleaching in both types of hair, whereas a thermal treatment (at 81 °C) caused yellowing of both types of hair, resulting in a Db(*)=3 for blended white hair and Db(*)=9 for single-donor hair. The identity of the yellow chromophores was investigated by UV-Vis spectroscopy. The results obtained with this technique were contradictory, however, and it was not possible to obtain a simple correlation between the sample shade of yellow and the absorption spectra. In addition, the results are discussed in terms of the morphology differences between the pigmented and non-pigmented parts of grey hair, the yellowing and bleaching effects of grey hair, and the occurrence of dark-follow reactions.

Petroleomics By Electrospray Ionization Ft-icr Mass Spectrometry Coupled To Partial Least Squares With Variable Selection Methods: Prediction Of The Total Acid Number Of Crude Oils.

Negative-ion mode electrospray ionization, ESI(-), with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was coupled to a Partial Least Squares (PLS) regression and variable selection methods to estimate the total acid number (TAN) of Brazilian crude oil samples. Generally, ESI(-)-FT-ICR mass spectra present a power of resolution of ca. 500,000 and a mass accuracy less than 1 ppm, producing a data matrix containing over 5700 variables per sample. These variables correspond to heteroatom-containing species detected as deprotonated molecules, [M - H](-) ions, which are identified primarily as naphthenic acids, phenols and carbazole analog species. The TAN values for all samples ranged from 0.06 to 3.61 mg of KOH g(-1). To facilitate the spectral interpretation, three methods of variable selection were studied: variable importance in the projection (VIP), interval partial least squares (iPLS) and elimination of uninformative variables (UVE). The UVE method seems to be more appropriate for selecting important variables, reducing the dimension of the variables to 183 and producing a root mean square error of prediction of 0.32 mg of KOH g(-1). By reducing the size of the data, it was possible to relate the selected variables with their corresponding molecular formulas, thus identifying the main chemical species responsible for the TAN values.

Communication: Transient Anion States Of Phenol…(h₂o)n (n = 1, 2) Complexes: Search For Microsolvation Signatures.

We report on the shape resonance spectra of phenol-water clusters, as obtained from elastic electron scattering calculations. Our results, along with virtual orbital analysis, indicate that the well-known indirect mechanism for hydrogen elimination in the gas phase is significantly impacted on by microsolvation, due to the competition between vibronic couplings on the solute and solvent molecules. This fact suggests how relevant the solvation effects could be for the electron-driven damage of biomolecules and the biomass delignification [E. M. de Oliveira et al., Phys. Rev. A 86, 020701(R) (2012)]. We also discuss microsolvation signatures in the differential cross sections that could help to identify the solvated complexes and access the composition of gaseous admixtures of these species.

Brij Detergents Reveal New Aspects Of Membrane Microdomain In Erythrocytes.

Membrane microdomains enriched in cholesterol, sphingolipids (rafts), and specific proteins are involved in important physiological functions. However their structure, size and stability are still controversial. Given that detergent-resistant membranes (DRMs) are in the liquid-ordered state and are rich in raft-like components, they might correspond to rafts at least to some extent. Here we monitor the lateral order of biological membranes by characterizing DRMs from erythrocytes obtained with Brij-98, Brij-58, and TX-100 at 4 °C and 37 °C. All DRMs were enriched in cholesterol and contained the raft markers flotillin-2 and stomatin. However, sphingomyelin (SM) was only found to be enriched in TX-100-DRMs - a detergent that preferentially solubilizes the membrane inner leaflet - while Band 3 was present solely in Brij-DRMs. Electron paramagnetic resonance spectra showed that the acyl chain packing of Brij-DRMs was lower than TX-100-DRMs, providing evidence of their diverse lipid composition. Fatty acid analysis revealed that the SM fraction of the DRMs was enriched in lignoceric acid, which should specifically contribute to the resistance of SM to detergents. These results indicate that lipids from the outer leaflet, particularly SM, are essential for the formation of the liquid-ordered phase of DRMs. At last, the differential solubilization process induced by Brij-98 and TX-100 was monitored using giant unilamellar vesicles. This study suggests that Brij and TX-100-DRMs reflect different degrees of lateral order of the membrane microdomains. Additionally, Brij DRMs are composed by both inner and outer leaflet components, making them more physiologically relevant than TX-100-DRMs to the studies of membrane rafts.

Classification Of Frankfurters By Ft-raman Spectroscopy And Chemometric Methods.

Frankfurters are widely consumed all over the world, and the production requires a wide range of meat and non-meat ingredients. Due to these characteristics, frankfurters are products that can be easily adulterated with lower value meats, and the presence of undeclared species. Adulterations are often still difficult to detect, due the fact that the adulterant components are usually very similar to the authentic product. In this work, FT-Raman spectroscopy was employed as a rapid technique for assessing the quality of frankfurters. Based on information provided by the Raman spectra, a multivariate classification model was developed to identify the frankfurter type. The aim was to study three types of frankfurters (chicken, turkey and mixed meat) according to their Raman spectra, based on the fatty vibrational bands. Classification model was built using partial least square discriminant analysis (PLS-DA) and the performance model was evaluated in terms of sensitivity, specificity, accuracy, efficiency and Matthews's correlation coefficient. The PLS-DA models give sensitivity and specificity values on the test set in the ranges of 88%-100%, showing good performance of the classification models. The work shows the Raman spectroscopy with chemometric tools can be used as an analytical tool in quality control of frankfurters.

Biogenic Silver Nanoparticles Associated With Silver Chloride Nanoparticles (ag@agcl) Produced By Laccase From Trametes Versicolor.

In the present study, semi-purified laccase from Trametes versicolor was applied for the synthesis of silver nanoparticles, and the properties of the produced nanoparticles were characterized. All of the analyses of the spectra indicated silver nanoparticle formation. A complete characterization of the silver nanoparticles showed that a complex of silver nanoparticles and silver ions was produced, with the majority of the particles having a Ag(2+) chemical structure. A hypothetical mechanistic scheme was proposed, suggesting that the main pathway that was used was the interaction of silver ions with the T1 site of laccase, producing silver nanoparticles with the concomitant inactivation of laccase activity and posterior complexing with silver ions.