Detection of the Glass Transition of Polymers Used in Art and Art-Conservation Using Raman Spectroscopy

In this work, Raman spectroscopy was employed for the detection of the glass transition temperatures (Tg) of some thermoplastic polymers and natural terpenoid resins. In particular, our attention was focused on evaluating the Tg of polystyrene and colophony. The measurements returned Tg values in accordance with those reported in the literature obtained using the DSC technique, thus confirming the reliability of the approach proposed herein. Further studies will be focused on the evaluation of Tg temperature changes depending on materials treatments and ageing

Ligand exchange on CdSe nanoplatelets for the solar light sensitization of TiO2 and ZnO nanorod arrays

In quantum dot (QD) solar cells, the ex situ sensitization of wide band gap semiconductors (WBSCs) makes it possible to control the shape and the passivation of the nanosized sensitizer. Hence, ex situ techniques can be used to investigate how the band gap of the sensitizers affects the performance of quantum dot solar cells. The latter can be precisely controlled in 1D confined structures such as quasi-2D nanoplatelets (NPLs), the thickness of which is defined with an atomic precision. In this work, we tested and thoroughly characterized the attachment of 7, 9 and 11 monolayers thick CdSe NPLs (as well as QDs for the sake of comparison) to ZnO and to TiO2 nanorods. A crucial point of the ex situ techniques is the choice of bifunctional ligands that link the nanosized sensitizers to the WBSCs. Besides the well-known mercaptopropionic acid, we also studied two ‘atomic linkers’ (OH− and SH−) to minimize the distance between the sensitizer and the oxide. The as-prepared systems have been analyzed by UV/VIS absorption and Raman spectroscopy. Among them, SH− was found to be the most versatile linker that enabled the efficient attachment of all types of CdSe nanocrystals on ZnO and TiO2 nanorods.Fil: Szemjonov, A.. PSL Research University; Francia. Centre National de la Recherche Scientifique; FranciaFil: Tasso, Mariana Patricia. Laboratoire de Physique Et D'etude Des Materiaux; Francia. Centre National de la Recherche Scientifique; Francia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Ithurria, S.. Laboratoire de Physique Et D'etude Des Materiaux; FranciaFil: Ciofini, I.. PSL Research University; Francia. Centre National de la Recherche Scientifique; FranciaFil: Labat, F.. PSL Research University; Francia. Centre National de la Recherche Scientifique; FranciaFil: Pauporté, T.. PSL Research University; Francia. Centre National de la Recherche Scientifique; Franci

Exploring the Potential of Portable Spectroscopic Techniques for the Biochemical Characterization of Roots in Shallow Landslides

In the present work, Raman, Fourier Transform Infrared (FTIR) and elemental Laser-Induced Breakdown Spectroscopy (LIBS) spectroscopic techniques were used for the assessment of the influence of plant root composition towards shallow landslide occurrence. For this purpose, analyses were directly carried out on root samples collected from chestnut forests of the Garfagnana basin (northern Apennines, Italy) in different areas devoid and affected by shallow landslides due to frequent heavy rain events. Results have highlighted a correlation between the biochemical constituents of wooden roots and the sampling areas. In particular, different content of lignin/cellulose, as well as minerals nutrients, have been detected in roots collected where shallow landslides occurred, with respect to more stable areas. The results achieved are in line with the scientific literature which has demonstrated the link between the chemical composition of roots with their mechanical properties and, in particular, tensile strength and cohesion. Finally, portable spectroscopic instrumentations were employed without the need for either any sample preparation for Raman and LIBS spectroscopy or minimal preparation for FTIR spectroscopy. This novel and fast approach has allowed achieving information on the content of the major constituents of the root cell, such as cellulose and lignin, as well as their mineral nutrients. This approach could be reasonably included among the vegetation protection actions towards instability, as well as for the evaluation of shallow landslide susceptibility, combining geological, vegetational and biochemical parameters with sustainability

Automated characterization of varnishes photo-degradation using portable T-controlled Raman spectroscopy

In this work, a portable-Raman device (excitationwavelength 1064 nm)was employed for the first time for continuously monitoring the complex molecular dynamics of terpenoid resins (dammar, mastic, colophony, sandarac and shellac), which occur during their ageing under artificial light exposure. The instrumentation was equipped with a pyroelectric sensor allowing for temperature control of the sample's irradiated surface while the acquisition of spectra occurs by setting fixed maximum temperature and total radiant exposure. Resins were dropped into special pits over a dedicated rotating wheelmoved by a USB motor. The rotation allowed samples sliding between the positions designated for the acquisition of the Raman spectra and that for artificial ageing. Samples were exposed to artificial light for 45-days and almost 400 spectra for each resin sample were collected. The exposure to artificial light led to significant changes allowing the characterization of the alteration process. The automated acquisition of a large number of spectra overtime during light-exposure has given the possibility to distinguish fast dynamics,mainly associated to solvent evaporation, fromthose slower due to resins photo-degradation processes

Experimental study of the delayed threshold phenomenon in a semiconductor laser

An experimental study of the delayed threshold phenomenon in a Vertical Extended Cavity Semiconductor Emitting Laser is carried out. Under modulation of the pump power, the laser intensity exhibits a hysteresis behavior in the vicinity of the threshold. The temporal width of this hysteresis is measured as a function of the modulation frequency, and is proved to follow the predicted scaling law. A model based on the rate equations is derived and used to analyze the experimental observations. A frequency variation of the laser around the delayed threshold and induced by the phase-amplitude coupling is predicted and estimated

Aggregation effects on pigment coatings: Pigment red 179 as a case study

Here, we have studied, with a combined experimental and computational approach, the effect of the crystal environment and aggregation on the electronic properties of Pigment Red 179, which affect both its color and optical energy gap. Spectra acquired in the near-infrared and visible range of energies suggest that this molecule is indeed a "cool" dye, which can be employed as a red pigment that provides effective color coverage to different substrates without contributing to their heating during light irradiation. Spectra acquired on different polymer mixtures at different pigment concentrations (i.e., 2.5-10 wt %) suggest that absorption features depend on chromophoric arrangements promoted by the strong intermolecular I -\u3c0interactions. Calculations, performed at the time-dependent density functional theory level, allowed to both attribute the nature of the electronic transitions causing the observed spectra involved and understand the effect of the environment. Indeed, the visible spectra of the pigment is dominated by two localized transitions, with negligible charge transfer for both a dye monomer and dimer either in vacuum or acetonitrile solution. Instead, models including the crystal environment of the pigment show the presence of a high-wavelength S1 \ue2 S0 charge transfer transition between two adjacent molecules, in quantitative agreement with the experimental absorption energy of the crystal pigment

Evaluation of analytical performance and comparison of clinical results of the new generation method AccuTnI+3 for the measurement of cardiac troponin I using both patients and quality control plasma samples

The study aims are to evaluate the analytical performance and the clinical results of the chemiluminescent Access AccuTnI+3 immunoassay for the determination of cardiac troponin I (cTnI)with DxI 800 and Access2 platforms and to compare the clinical results obtained with this method with those of three cTnI immunoassays, recently introduced in the European market. The limits of blank (LoB), detection (LoD), and quantitation (LoQ) at 20% CV and 10% CV were 4.5 ng/L and 10.9 ng/L, 17.1 and 30.4 ng/L, respectively. The results of STAT Architect high Sensitive TnI (Abbott Diagnostics), ADVIA Centaur Troponin I Ultra (Siemens Healthcare Diagnostics), ST AIA-Pack cTnI third generation (Tosoh Bioscience), and Access AccuTnI + 3 (Beckman Coulter Diagnostics) showed very close correlations (R ranging from 0.901 to 0.994) in 122 samples of patients admitted to the emergency department. However, on average there was a difference up to 2.4-fold between the method measuring the highest (ADVIA method) and lowest cTnI values (AccuTnI + 3 method). The consensus mean values between methods ranged from 6.2% to 29.6% in 18 quality control samples distributed in an external quality control study (cTnI concentrations ranging from 29.3 ng/L to 1557.5 ng/L). In conclusion, the results of our analytical evaluation concerning the AccuTnI + 3 method, using the DxI platform, are well in agreement with those suggested by the manufacturer as well as those reported by some recent studies using the Access2 platform. Our results confirm that the AccuTnI + 3 method for the Access2 and DxI 800 platforms is a clinically usable method for cTnI measurement

Monoclonal gammopathy of renal significance (MGRS): Real-world data on outcomes and prognostic factors

Monoclonal gammopathy of renal significance (MGRS) is a recognized clinical entity. Literature regarding treatment and its outcomes in MGRS is sparse due to the rarity and misdiagnosis of MGRS. We retrospectively analyzed 280 adults with an MGRS diagnosis from 2003 to 2020 across 19 clinical centers from 12 countries. All cases required renal biopsy for the pathological diagnosis of MGRS. Amyloidosis-related to MGRS (MGRS-A) was present in 180 patients; nonamyloidosis MGRS (MGRS-NA), including a broad spectrum of renal pathologies, was diagnosed in 100 patients. The median overall survival in the studied cohort was 121.0 months (95% CI: 105.0–121.0). Patients with MGRS-A had a shorter overall survival than patients with MGRS-NA (HR = 0.41, 95%CI: 0.25–0.69; p = 0.0007). Both hematologic and renal responses were associated with longer survival. Achievement of ≥VGPR was generally predictive of a renal response (OR = 8.03 95%CI: 4.04–115.96; p < 0.0001), one-fourth of patients with ≥VGPR were renal nonresponders. In MGRS-A, factors associated with poor prognosis included elevated levels of creatinine, beta-2-microglobulin, and hemodialysis at diagnosis. In MGRS-NA, only age >65 years was associated with increased risk of death. Treatments provided similar hematologic response rates in both types of MGRS. Autologous stem cell transplantation led to better response than other treatments. This multicenter and international effort is currently the largest report on MGRS

Performance of local orbital basis sets in the self-consistent Sternheimer method for dielectric matrices of extended systems

We present a systematic study of the performance of numerical pseudo-atomic orbital basis sets in the calculation of dielectric matrices of extended systems using the self-consistent Sternheimer approach of [F. Giustino et al., Phys. Rev. B 81 (11), 115105 (2010)]. In order to cover a range of systems, from more insulating to more metallic character, we discuss results for the three semiconductors diamond, silicon, and germanium. Dielectric matrices calculated using our method fall within 1-3% of reference planewaves calculations, demonstrating that this method is promising. We find that polarization orbitals are critical for achieving good agreement with planewaves calculations, and that only a few additional \zeta 's are required for obtaining converged results, provided the split norm is properly optimized. Our present work establishes the validity of local orbital basis sets and the self-consistent Sternheimer approach for the calculation of dielectric matrices in extended systems, and prepares the ground for future studies of electronic excitations using these methods.Comment: 10 pages, 8 figure