Reliability and agreement testing of a new automated measurement method to determine facial vitiligo extent using standardized ultraviolet images and a dedicated algorithm.

Background: Facial repigmentation is the primary outcome measure for most vitiligo trials. The Facial Vitiligo Area Scoring Index (F-VASI) score is often chosen as the primary outcome measure to assess the efficacy of treatments for facial vitiligo. Although useful, this scoring system remains subjective and has several limitations.

Metal nanoclusters: from fundamental aspects to electronic properties and optical applications.

Monolayer-protected noble metal clusters, also called nanoclusters, can be produced with the atomic precision and in large-scale quantity and are playing an increasingly important role in the field of nanoscience. To outline the origin and the perspectives of this new field, we overview the main results obtained on free metal clusters produced in gas phase including mainly electronic properties, the giant atom concept, the optical properties, briefly the role of the metal atom (alkali, divalent, noble metal) and finally the atomic structure of clusters. We also discuss the limitations of the free clusters.

High performance {NbTaX}@PVP (X = Cl, Br) cluster-based nanocomposites coatings for solar glazing applications.

The development of highly ultraviolet (UV) and near-infrared (NIR) absorbent transparent coatings is an important enabling technology and area of research for environmental sustainability and energy conservation. Different amounts of K[{NbTaX }X ] cluster compounds (X = Cl, Br) dispersed into polyvinylpyrrolidone matrices were prepared by a simple, nontoxic and low-cost wet chemical method. The resulting solutions were used to fabricate visibly transparent, highly UV and NIR absorbent coatings by drop casting.

Controlling the Deposition Process of Nanoarchitectonic Nanocomposites Based on {NbTaX} Octahedral Cluster-Based Building Blocks (X = Cl, Br; 0 ≤ x ≤ 6, n = 2, 3, 4) for UV-NIR Blockers Coating Applications.

The antagonism between global energy needs and the obligation to slow global warming is a current challenge. In order to ensure sufficient thermal comfort, the automotive, housing and agricultural building sectors are major energy consumers. Solar control materials and more particularly, selective glazing are part of the solutions proposed to reduce global energy consumption and tackle global warming.

Nanoarchitectonics of Glass Coatings for Near-Infrared Shielding: From Solid-State Cluster-Based Niobium Chlorides to the Shaping of Nanocomposite Films.

The high potential of [{NbCl}L] cluster-based building blocks as near-infrared radiation blockers for energy saving applications is exposed in the present paper (i = inner edge-bridging ligand, a = apical ligand of the Nb; L = HO and/or Cl). To do so, a combined experimental and theoretical investigation of edge-bridged [{NbCl}Cl(HO)] cluster unit series ( = 0, 4, 6; = 2, 3, 4; = 2, 3, 4) has been carried out. By using the K[{NbCl}Cl] starting solid-state precursor, we explored the behavior of the [{NbCl}Cl] cluster unit during the different steps of its integration as a building block into a polyvinylpyrrolidone (PVP) matrix to form a glass coating composite denoted {NbCl}@PVP ( = 2 or 3).

Archaeological Mortar Characterization Using Laser-Induced Breakdown Spectroscopy (LIBS) Imaging Microscopy.

Lime mortar is a complex mixture resulting from hardening of lime, water, and aggregates. Lime mortar was used from the time of the Roman Empire until the Industrial Revolution. The recipes used differ according to the period, geographical area of preparation, craftsman, or function.

Photo-control of bimolecular reactions: reactivity of the long-lived Rhodamine 6G triplet excited state with ˙NO.

Photo-chemistry provides a non-intuitive but very powerful way to probe kinetically limited, sometimes thermodynamically non-favored reactions and, thus, access highly specific products. However, reactivity in the excited state is difficult to characterize directly, due to short lifetimes and challenges in controlling the reaction medium. Among photo-activatable reagents, rhodamine dyes find widespread uses due to a number of favorable properties including their high absorption coefficient.

Phenyl argentate aggregates [AgPh] (n = 2-8): Models for the self-assembly of atom-precise polynuclear organometallics.

Electrospray ionization of phenyl argentates formed by transmetalation reactions between phenyl lithium and silver cyanide provides access to the argentate aggregates, [AgPh], which were individually mass-selected for n = 2-8 in order to generate their gas-phase Ultraviolet Photodissociation (UVPD) "action" spectra over the range 304-399 nm. A strong bathochromic shift in optical spectra was observed with increasing size/n. Theoretical calculations allowed the assignment of the experimental UVPD spectra to specific isomer(s) and provided crucial insights into the transition from the 2D to 3D structure of the metallic component with the increasing size of the complex.

Surgical treatment of rhinophyma: Retrospective monocentric study and literature review.

Background: Treatment of rhinophyma consists primarily of destructive procedures. There is currently no consensus regarding treatment. In this study, we propose an algorithm based on a cohort of 25 patients and a literature review.

Revisiting properties of edge-bridged bromide tantalum clusters in the solid-state, in solution and vice versa: an intertwined experimental and modelling approach.

Edge-bridged halide tantalum clusters based on the {TaBr} core have been the topic of many physicostructural investigations both in solution and in the solid-state. Despite a large number of studies, the fundamental correlations between compositions, local symmetry, electronic structures of [{TaBr}L] cluster units (L = Br or HO, in solution and in the solid-state), redox states, and vibrational and absorption properties are still not well established. Using K[{TaBr}Br] as a starting precursor (i: inner and a: apical), we have investigated the behavior of the [{TaBr}Br] cluster unit in terms of oxidation properties and chemical modifications both in solution (water and organic solvent) and after recrystallization.

Functionalized Au nanoclusters as luminescent probes for protein carbonylation detection.

Atomically precise, ligand-protected gold nanoclusters (AuNCs) attract considerable attention as contrast agents in the biosensing field. However, the control of their optical properties and functionalization of surface ligands remain challenging. Here we report a strategy to tailor AuNCs for the precise detection of protein carbonylation-a causal biomarker of ageing.

Exploring Conformational Landscapes Using Trap and Release Tandem Ion Mobility Spectrometry.

The dynamics and thermodynamics of structural changes in isolated glu-fibrinopeptide B (GluFib) were investigated by tandem ion mobility spectrometry (IMS). Doubly protonated GluFib ions were first selected by IMS and then stored for a controlled duration in a thermalized ion trap. Temperature-induced conformational changes were finally monitored by IMS as a function of trapping time.

Structure and Charge Heterogeneity in Isomeric Au(MBA) Nanoclusters-Insights from Ion Mobility and Mass Spectrometry.

Atomically precise Au(MBA) nanoclusters were investigated by mass spectrometry and ion mobility spectrometry. We show that clusters sharing the same chemical composition and bearing the same net charge may display different structures and different charge repartition patterns, namely, the number of charges corresponding to deprotonation of the ligand moieties through carboxyl groups is not the same for all detected species. Part of the observed heterogeneity is a consequence of spontaneous electron loss occurring in the gas phase, which modifies the net charge of the clusters while maintaining the initial (de)protonation state.

How Spherical Are Gaseous Low Charged Dendrimer Ions: A Molecular Dynamics/Ion Mobility Study?

The globular shape of gaseous ions, resulting from the ionization of large molecules such as polymers and proteins, is a recurring subject that has undergone a renewed interest with the advent of ion mobility spectrometry (IMS), especially in conjunction with theoretical chemistry techniques such as Molecular Dynamics (MD). Globular conformations result from a fine balance between entropy and enthalpy considerations. For multiply charged ions isolated in the gas phase of a mass spectrometer, the Coulombic repulsion between the different charges tends to prevent the ions from adopting a compact, and folded 3D structure.

Kinetic study of azobenzene E/Z isomerization using ion mobility-mass spectrometry and liquid chromatography-UV detection.

Z and E azobenzene isomers are molecular switches which can interconvert both photochemically and thermally. Presently, we studied a ketal-substituted bridged azobenzene in which two stable diastereomeric conformers (Z1 and Z2) photochemically interconvert through the transient E isomer. UV-VIS absorption spectroscopy is commonly used to study the relaxation kinetics of azobenzenes, but it does not allow direct quantitation of the process in this case.

Secondary structure effects on internal proton transfer in poly-peptides.

A pump-probe approach was designed to determine the internal proton transfer (PT) rate in a series of poly-peptide radical cations containing both histidine and tryptophan. The proton transfer is driven by the gas-phase basicity difference between residues. The fragmentation scheme indicates that the gas-phase basicity of histidine is lower than that of radical tryptophan so that histidine is always pulling the proton away from tryptophan.

Second harmonic scattering from mass characterized 2D graphene oxide sheets.

In this communication, we report the second harmonic scattering from mass characterized 2D graphene oxide sheets dispersed in an aqueous suspension, in the femtosecond regime at 800 nm laser excitation. Charge-detection mass-spectrometry, performing at the single sheet level, allows for an exhaustive molar mass distribution and thus concentration for these 2D nanomaterials samples. The orientation-averaged hyperpolarizability value is (1.

In-house Implementation of Tumor Mutational Burden Testing to Predict Durable Clinical Benefit in Non-small Cell Lung Cancer and Melanoma Patients.

Tumor mutational burden (TMB) has emerged as an important potential biomarker for prediction of response to immune-checkpoint inhibitors (ICIs), notably in non-small cell lung cancer (NSCLC). However, its in-house assessment in routine clinical practice is currently challenging and validation is urgently needed. We have analyzed sixty NSCLC and thirty-six melanoma patients with ICI treatment, using the FoundationOne test (FO) in addition to in-house testing using the Oncomine TML (OTML) panel and evaluated the durable clinical benefit (DCB), defined by >6 months without progressive disease.

Isomeric Effect of Mercaptobenzoic Acids on the Synthesis, Stability, and Optical Properties of Au(MBA) Nanoclusters.

We report a simple size focusing, two-step "bottom-up" protocol to prepare water-soluble Au(MBA) nanoclusters, using the three isomers of mercaptobenzoic acids (//-MBA) as capping ligands and MeNBH as a mild reducing agent. The relative stability of the gas-phase multiply deprotonated Au(MBA) ions was investigated by collision-induced dissociation. This permitted us to evaluate the possible isomeric effect on the Au-S interfacial bond stress.

Direct Radiation Effects on the Structure and Stability of Collagen and Other Proteins.

In this review, recent progress in understanding the direct effects of radiation on the structure and stability of collagen, the most abundant protein in the human body, and other proteins is surveyed. Special emphasis is placed on the triple-helical structure of collagen, as studied by means of collagen mimetic peptides. The emerging patterns are the dose dependence of radiation processes and their abundance, the crucial role of radicals in covalent-bond formation (crosslinking) or cleavage, and the influence of the radiation energy and nature.

Sub-100 nanometer silver doped gold-cysteine supramolecular assemblies with enhanced nonlinear optical properties.

The ability of gold(i) thiolates to self-assemble into supramolecular architectures opens the route for a new class of nanomaterials with a unique structure-optical property relationship. However, for a confirmed structure-optical property relationship, a control of the supramolecular architectures is required. In this work, we report a simple synthesis of sub-100 nanometer gold-cysteine and silver doped gold-cysteine supramolecular assemblies.