BGO relaxation dynamics probed with heterodyne detected optical transient gratings

We used optical laser pulses to create transient gratings (TGs) with sub-10 {\mu}m spatial periodicity in a Bismuth Germanate (310) (Bi4Ge3O12) single crystal at room temperature. The TG launches phonon modes, whose dynamics were revealed via forward diffraction of a third, time-delayed, heterodyne-detected optical pulse. Acoustic oscillations have been clearly identified in a time-frequency window not covered by previous spectroscopic studies and their characteristic dynamic parameters have been measured as a function of transferred momenta magnitude and direction.Comment: 6 pages, 4 figure

Sensitivity and specificity of in vivo COVID-19 screening by detection dogs: Results of the C19-Screendog multicenter study

Trained dogs can recognize the volatile organic compounds contained in biological samples of patients with COVID-19 infection. We assessed the sensitivity and specificity of in vivo SARS-CoV- 2 screening by trained dogs. We recruited five dog-handler dyads. In the operant conditioning phase, the dogs were taught to distinguish between positive and negative sweat samples collected from volunteers’ underarms in polymeric tubes. The conditioning was validated by tests involving 16 positive and 48 negative samples held or worn in such a way that the samples were invisible to the dog and handler. In the screening phase the dogs were led by their handlers to a drive-through facility for in vivo screening of volunteers who had just received a nasopharyngeal swab from nursing staff. Each volunteer who had already swabbed was subsequently tested by two dogs, whose responses were recorded as positive, negative, or inconclusive. The dogs’ behavior was constantly monitored for attentiveness and wellbeing. All the dogs passed the conditioning phase, their responses showing a sensitivity of 83-100% and a specificity of 94-100%. The in vivo screening phase involved 1251 subjects, of whom 205 had a COVID-19 positive swab and two dogs per each subject to be screened. Screeningsensitivity and specificity were respectively 91.6-97.6% and 96.3-100% when only one dog was involved, whereas combined screening by two dogs provided a higher sensitivity. Dog wellbeing was also analysed: monitoring of stress and fatigue suggested that the screening activity did not adversely impact the dogs’ wellbeing. This work, by screening a large number of subjects, strengthen recent findings that trained dogs can discriminate between COVID-19 infected and healthy human subjects and introduce two novel research aspects: i) assessement of signs of fatigue and stress in dogs during training and testing, and ii) combining screening by two dogs to improve detection sensitivity and specificity. Using some precautions to reduce the risk of infection and spillover, in vivo COVID-19 screening by a dog-handler dyad can be suitable to quickly screen large numbers of people: it is rapid, non- invasiveand economical, since it does not involve actual sampling, lab resources or waste management, and is suitable to screen large numbers of people

Prescription appropriateness of anti-diabetes drugs in elderly patients hospitalized in a clinical setting: evidence from the REPOSI Register

Diabetes is an increasing global health burden with the highest prevalence (24.0%) observed in elderly people. Older diabetic adults have a greater risk of hospitalization and several geriatric syndromes than older nondiabetic adults. For these conditions, special care is required in prescribing therapies including anti- diabetes drugs. Aim of this study was to evaluate the appropriateness and the adherence to safety recommendations in the prescriptions of glucose-lowering drugs in hospitalized elderly patients with diabetes. Data for this cross-sectional study were obtained from the REgistro POliterapie-Società Italiana Medicina Interna (REPOSI) that collected clinical information on patients aged ≥ 65 years acutely admitted to Italian internal medicine and geriatric non-intensive care units (ICU) from 2010 up to 2019. Prescription appropriateness was assessed according to the 2019 AGS Beers Criteria and anti-diabetes drug data sheets.Among 5349 patients, 1624 (30.3%) had diagnosis of type 2 diabetes. At admission, 37.7% of diabetic patients received treatment with metformin, 37.3% insulin therapy, 16.4% sulfonylureas, and 11.4% glinides. Surprisingly, only 3.1% of diabetic patients were treated with new classes of anti- diabetes drugs. According to prescription criteria, at admission 15.4% of patients treated with metformin and 2.6% with sulfonylureas received inappropriately these treatments. At discharge, the inappropriateness of metformin therapy decreased (10.2%, P < 0.0001). According to Beers criteria, the inappropriate prescriptions of sulfonylureas raised to 29% both at admission and at discharge. This study shows a poor adherence to current guidelines on diabetes management in hospitalized elderly people with a high prevalence of inappropriate use of sulfonylureas according to the Beers criteria

Hydrogen Bonding and Solvation of a Proline-Based Peptide Model in Salt Solutions

The hydrogen bonding of water and water/salt mixtures around the proline-based tripeptide model glycyl-l-prolyl-glycinamide·HCl (GPG-NH2) is investigated here by multi-wavelength UV resonance Raman spectroscopy (UVRR) to clarify the role of ion–peptide interactions in affecting the conformational stability of this peptide. The unique sensitivity and selectivity of the UVRR technique allow us to efficiently probe the hydrogen bond interaction between water molecules and proline residues in different solvation conditions, along with its influence on trans to cis isomerism in the hydrated tripeptide. The spectroscopic data suggest a relevant role played by the cations in altering the solvation shell at the carbonyl site of proline., while the fluoride and chloride anions were found to promote the establishment of the strongest interactions on the C=O site of proline. This latter effect is reflected in the greater stabilization of the trans conformers of the tripeptide in the presence of these specific ions. The molecular view provided by UVRR experiments was complemented by the results of circular dichroism (CD) measurements that show a strong structural stabilizing effect on the β-turn motif of GPG-NH2 observed in the presence of KF as a co-solute

Water-Lipid Interface in Lipidic Mesophases with Excess Water

This study investigates the influence of excess water on the lipidic mesophase during the phase transition from diamond cubic phase (Pn3m) to reverse hexagonal phase (HII). By a combination of small angle X-ray scattering (SAXS), broadband dielectric spectroscopy (BDS), and Fourier transform infrared (FTIR) techniques, we explore the dynamics of lipids and their interaction with water during phase transition. Our BDS results reveal three relaxation processes originating from lipids, all of which exhibit a kink during the phase transition. With the excess water, these processes accelerate due to the plasticizing effect of water. Additionally, our result demonstrates that the headgroups in HII phase are more densely packed than those in Pn3m phase, which agrees with the FTIR result. Meanwhile, we investigate the influence of excess water on the lipid headgroups, the H-bonding network of water, the lipid tail, and the interface carbonyl group between the head and tail of the lipid molecule. The results indicate that excess water permeates the lipid interface and forms additional hydrogen bonds with the carbonyl groups. As a result, the headgroups are more flexible in lipidic mesophase with excess water than those in mesophases without excess water.ISSN:1359-6640ISSN:1364-549

Linear and Non-Linear Middle Infrared Spectra of Penicillin G in the CO Stretching Mode Region

In this work we report the linear and non-linear IR spectral response characterization of the CO bonds of PenicillinG sodium salt in D2O and in DMSO−d6 solutions. In order to better characterize the spectral IR features in the CO stretching region, broadband middle infrared pump-probe spectra are recorded. The role of hydrogen bonds in determining the inhomogeneous broadening and in tuning anharmonicity of the different types of oscillators is exploited. Narrow band pump experiments, at the three central frequencies of β−lactam, amide and carboxylate CO stretching modes, identify the couplings between the different types of CO oscillators opening the possibility to gather structural dynamic information. Our results show that the strongest coupling is between the β−lactam and the carboxylate CO vibrational modes

Probing Globular Protein Self-Assembling Dynamics by Heterodyne Transient Grating Experiments

In this work, we studied the propagation of ultrasonic waves of lysozyme solutions characterized by different degrees of aggregation and networking. The experimental investigation was performed by means of the transient grating (TG) spectroscopy as a function of temperature, which enabled measurement of the ultrasonic acoustic proprieties over a wide time window, ranging from nanoseconds to milliseconds. The fitting of the measured TG signal allowed the extraction of several dynamic properties, here we focused on the speed and the damping rate of sound. The temperature variation induced a series of processes in the lysozyme solutions: Protein folding-unfolding, aggregation and sol–gel transition. Our TG investigation showed how these self-assembling phenomena modulate the sound propagation, affecting both the velocity and the damping rate of the ultrasonic waves. In particular, the damping of ultrasonic acoustic waves proved to be a dynamic property very sensitive to the protein conformational rearrangements and aggregation processes

Aqueous solvation of glutathione probed by UV resonance Raman spectroscopy

The specific interactions of water molecules with the tripeptide glutathione are investigated by UV Resonance Raman spectroscopy taking advantage of its sensitivity and selectivity. The peptide-solvent interactions at different chemical sites of glutathione, i.e. the peptide backbone and the side groups of the molecule, are investigated. With the aim of gaining new insights on the mechanism regulating the hydration of glutathione, intimately related to its biological functionality, the spectra of the tripeptide solutions are examined as a function of different concentration, pH and temperature. The Amide and the OH stretching spectral regions result very sensitive to the variations of the explored experimental parameters. Our observations provide a picture of the hydrogen-bonding network around glutathione. The number and the strength of hydrogen bonds increase in the deprotonated form of tripeptide that exhibits also a more marked capacity in decreasing the intermolecular order of water in its hydration shell. According to this view, a progressive reduction in the strength of hydrogen bond interactions on amide sites is probed upon the increment of thermal motion, accompanied by conformational changes involving the trans-cis isomerization of glutathione

Hydrogen Bonding and Solvation of a Proline-Based Peptide Model in Salt Solutions

The hydrogen bonding of water and water/salt mixtures around the proline-based tripeptide model glycyl-l-prolyl-glycinamide center dot HCl (GPG-NH2) is investigated here by multi-wavelength UV resonance Raman spectroscopy (UVRR) to clarify the role of ion-peptide interactions in affecting the conformational stability of this peptide. The unique sensitivity and selectivity of the UVRR technique allow us to efficiently probe the hydrogen bond interaction between water molecules and proline residues in different solvation conditions, along with its influence on trans to cis isomerism in the hydrated tripeptide. The spectroscopic data suggest a relevant role played by the cations in altering the solvation shell at the carbonyl site of proline(.), while the fluoride and chloride anions were found to promote the establishment of the strongest interactions on the C = O site of proline. This latter effect is reflected in the greater stabilization of the trans conformers of the tripeptide in the presence of these specific ions. The molecular view provided by UVRR experiments was complemented by the results of circular dichroism (CD) measurements that show a strong structural stabilizing effect on the beta-turn motif of GPG-NH2 observed in the presence of KF as a co-solute

Operando UV Resonance Raman study of DNA-ionic liquids gels

Double-stranded DNA dissolved in aqueous solutions of imidazolium-based Ionic Liquids (ILs) exhibits a characteristic gel transition, leading to the formation of DNA ionogels. In this study, we utilize state-of-the-art operando UV Resonance Raman (UVRR) spectroscopy, along with UV and Circular Dichroism (CD) absorption experiments, to monitor the self-assembly of a class of DNA ionogels derived from low-concentration aqueous solutions of DNA in imidazolium-based ILs. Our experimental approach offers insights at the molecular level into the structural organization and interactions that stabilize the gel network. Furthermore, operando UVRR spectroscopy allows efficient monitoring of the different stages of the thermal pathway leading to the self-assembly of DNA/ILs solutions into ionogels. A key achievement of our study is demonstrating that the sol–gel transition in DNA ionogels in the presence of imidazolium-based ILs can be modulated by the length of the alkyl chain of the imidazolium cation to achieve desired premelting, melting, and gelation temperatures