The electronic structure of carbones revealed : insights from valence bond theory

In this contribution, we studied the OC-C bond in carbon suboxide and related allene compounds using the valence bond method. The nature of this bond has been the subject of debate, whether it is a regular, electron sharing bond or a dative bond. We compared the nature of this bond in carbon suboxide with the gold-CO bond in Au(CO)(2)(+), which is a typical dative bond, and we studied its charge-shift bond character. We found that the C-CO bond in carbon suboxide is unique in the sense that it cannot be assigned as either a dative or electron sharing bond, but it is an admixture of electron sharing and dative components, together with a high contribution of ionic character. These findings provide a clear basis for distinguishing the commonly found dative bonds between ligands and transition metals and the present case of what may be described as coordinative bonding to carbon

How reduced are nucleophilic gold complexes?

Nucleophilic formal gold(-i) and gold(i) complexes are investigated via Intrinsic Bond Orbital analysis and Energy Decomposition Analysis, based on density functional theory calculations. The results indicate gold(0) centres engaging in electron-sharing bonding with Al- and B- based ligands. Multiconfigurational (CASSCF) calculations corroborate the findings, highlighting the gap between the electonic structures and the oxidation state formalism

Identification and tunable optical coherent control of transition-metal spins in silicon carbide

Color centers in wide-bandgap semiconductors are attractive systems for quantum technologies since they can combine long-coherent electronic spin and bright optical properties. Several suitable centers have been identified, most famously the nitrogen-vacancy defect in diamond. However, integration in communication technology is hindered by the fact that their optical transitions lie outside telecom wavelength bands. Several transition-metal impurities in silicon carbide do emit at and near telecom wavelengths, but knowledge about their spin and optical properties is incomplete. We present all-optical identification and coherent control of molybdenum-impurity spins in silicon carbide with transitions at near-infrared wavelengths. Our results identify spin $S=1/2$ for both the electronic ground and excited state, with highly anisotropic spin properties that we apply for implementing optical control of ground-state spin coherence. Our results show optical lifetimes of $\sim$60 ns and inhomogeneous spin dephasing times of $\sim$0.3 $\mu$s, establishing relevance for quantum spin-photon interfacing.Comment: Updated version with minor correction, full Supplementary Information include

Spectroscopic Manifestations and Implications for Catalysis of Quasi-d¹⁰ Configurations in Formal Gold(III) Complexes.

Several gold +I and +III complexes are investigated computationally and spectroscopically, focusing on the d-configuration and physical oxidation state of the metal center. Density functional theory calculations reveal the non-negligible electron-sharing covalent character of the metal-to-ligand σ-bonding framework. The bonding of gold(III) is shown to be isoelectronic to the formal CuIII complex [Cu(CF3)4]1- , in which the metal center tries to populate its formally unoccupied 3dx2-y2 orbital via σ-bonding, leading to a reduced d10 CuI description. However, Au L3-edge X-ray absorption spectroscopy reveals excitation into the d-orbital of the AuIII species is still possible, showing that a genuine d10 configuration is not achieved. We also find an increased electron-sharing nature of the σ-bonds in the AuI species, relative to their AgI and CuI analogues, due to the low-lying 6s orbital. We propose that gold +I and +III complexes form similar bonds with substrates, owing primarily to participation of the 5dx2-y2 or 6s orbital, respectively, in bonding, indicating why AuI and AuIII complexes often have similar reactivity

A Predictive Model for the Pd-Catalyzed Site-Selective Oxidation of Diols

A predictive model, shaped as a set of rules, is presented that predicts site-selectivity in the mono-oxidation of diols by palladium-neocuproine catalysis. For this, the factors that govern this site-selectivity within diols and between different diols have been studied both experimentally and with computation. It is shown that an electronegative substituent antiperiplanar to the C-H bond retards hydride abstraction, resulting in a lower reactivity. This explains the selective oxidation of axial hydroxy groups in vicinal cis-diols. Furthermore, DFT calculations and competition experiments show how the reaction rate of different diols is determined by their configuration and conformational freedom. The model has been validated by the oxidation of several complex natural products, including two steroids. From a synthesis perspective, the model predicts whether a natural product comprising multiple hydroxy groups is a suitable substrate for site-selective palladium-catalyzed oxidation.</p

Human wetness perception of fabrics under dynamic skin contact

This experiment studied textile (surface texture, thickness) and non-textile (local skin temperature changes, stickiness sensation and fabric-to-skin pressure) parameters affecting skin wetness perception under dynamic interactions. Changes in fabric texture sensation between WET and DRY states and their effect on pleasantness were also studied. The surface texture of eight fabric samples, selected for their different structures, was determined from surface roughness measurements using the Kawabata Evaluation System. Sixteen participants assessed fabric wetness perception, at high pressure and low pressure conditions, stickiness, texture and pleasantness sensation on the ventral forearm. Differences in wetness perception (p < 0.05) were not determined by texture properties and/or texture sensation. Stickiness sensation and local skin temperature drop were determined as predictors of wetness perception (r2 = 0.89), and although thickness did not correlate with wetness perception directly, when combined with stickiness sensation it provided a similar predictive power (r2 = 0.86). Greater (p < 0.05) wetness perception responses at high pressure were observed compared with low pressure. Texture sensation affected pleasantness in DRY (r2 = 0.89) and WET (r2 = 0.93). In WET, pleasantness was significantly reduced (p < 0.05) compared to DRY, likely due to the concomitant increase in texture sensation (p < 0.05). In summary, under dynamic conditions, changes in stickiness sensation and wetness perception could not be attributed to fabric texture properties (i.e. surface roughness) measured by the Kawabata Evaluation System. In dynamic conditions thickness or skin temperature drop can predict fabric wetness perception only when including stickiness sensation data

Hydration and cooling in elite athletes: relationship with performance, body mass loss and body temperatures during the Doha 2019 IAAF World Athletics Championships

Purpose: To characterise hydration, cooling, body mass loss, and core (Tcore) and skin (Tsk) temperatures during World Athletics Championships in hot-humid conditions. Methods: Marathon and race-walk (20 km and 50 km) athletes (n=83, 36 women) completed a pre-race questionnaire. Pre-race and post-race body weight (n=74), Tcore (n=56) and Tsk (n=49; thermography) were measured. Results: Most athletes (93%) had a pre-planned drinking strategy (electrolytes (83%), carbohydrates (81%)) while ice slurry was less common (11%; p<0.001). More men than women relied on electrolytes and carbohydrates (91%–93% vs 67%–72%, p≤0.029). Drinking strategies were based on personal experience (91%) rather than external sources (p<0.001). Most athletes (80%) planned pre-cooling (ice vests (53%), cold towels (45%), neck collars (21%) and ice slurry (21%)) and/or midcooling (93%; head/face dousing (65%) and cold water ingestion (52%)). Menthol usage was negligible (1%–2%). Pre-race Tcore was lower in athletes using ice vests (37.5°C±0.4°C vs 37.8°C±0.3°C, p=0.024). Tcore (pre-race 37.7°C±0.3°C, post-race 39.6°C±0.6°C) was independent of event, ranking or performance (p≥0.225). Pre-race Tsk was correlated with faster race completion (r=0.32, p=0.046) and was higher in non-finishers (did not finish (DNF); 33.8°C±0.9°C vs 32.6°C±1.4°C, p=0.017). Body mass loss was higher in men than women (−2.8±1.5% vs −1.3±1.6%, p<0.001), although not associated with performance. Conclusion: Most athletes’ hydration strategies were pre-planned based on personal experience. Ice vests were the most adopted pre-cooling strategy and the only one minimising Tcore, suggesting that event organisers should be cognisant of logistics (ie, freezers). Dehydration was moderate and unrelated to performance. Pre-race Tsk was related to performance and DNF, suggesting that Tsk modulation should be incorporated into pre-race strategies

Hydration and cooling in elite athletes: relationship with performance, body mass loss and body temperatures during the Doha 2019 IAAF World Athletics Championships.

PURPOSE: To characterise hydration, cooling, body mass loss, and core (Tcore) and skin (Tsk) temperatures during World Athletics Championships in hot-humid conditions. METHODS: Marathon and race-walk (20 km and 50 km) athletes (n=83, 36 women) completed a pre-race questionnaire. Pre-race and post-race body weight (n=74), Tcore (n=56) and Tsk (n=49; thermography) were measured. RESULTS: Most athletes (93%) had a pre-planned drinking strategy (electrolytes (83%), carbohydrates (81%)) while ice slurry was less common (11%; p<0.001). More men than women relied on electrolytes and carbohydrates (91%-93% vs 67%-72%, p≤0.029). Drinking strategies were based on personal experience (91%) rather than external sources (p<0.001). Most athletes (80%) planned pre-cooling (ice vests (53%), cold towels (45%), neck collars (21%) and ice slurry (21%)) and/or mid-cooling (93%; head/face dousing (65%) and cold water ingestion (52%)). Menthol usage was negligible (1%-2%). Pre-race Tcore was lower in athletes using ice vests (37.5°C±0.4°C vs 37.8°C±0.3°C, p=0.024). Tcore (pre-race 37.7°C±0.3°C, post-race 39.6°C±0.6°C) was independent of event, ranking or performance (p≥0.225). Pre-race Tsk was correlated with faster race completion (r=0.32, p=0.046) and was higher in non-finishers (did not finish (DNF); 33.8°C±0.9°C vs 32.6°C±1.4°C, p=0.017). Body mass loss was higher in men than women (-2.8±1.5% vs -1.3±1.6%, p<0.001), although not associated with performance. CONCLUSION: Most athletes' hydration strategies were pre-planned based on personal experience. Ice vests were the most adopted pre-cooling strategy and the only one minimising Tcore, suggesting that event organisers should be cognisant of logistics (ie, freezers). Dehydration was moderate and unrelated to performance. Pre-race Tsk was related to performance and DNF, suggesting that Tsk modulation should be incorporated into pre-race strategies

Internal and external cooling methods and their effect on body temperature, thermal perception and dexterity

© 2018 The Authors. Published by PLOS. This is an open access article available under a Creative Commons licence. The published version can be accessed at the following link on the publisher’s website: https://doi.org/10.1371/journal.pone.0191416© 2018 Maley et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. Objective The present study aimed to compare a range of cooling methods possibly utilised by occupational workers, focusing on their effect on body temperature, perception and manual dexterity. Methods Ten male participants completed eight trials involving 30 min of seated rest followed by 30 min of cooling or control of no cooling (CON) (34C, 58% relative humidity). The cooling methods utilised were: ice cooling vest (CV0), phase change cooling vest melting at 14C (CV14), evaporative cooling vest (CVEV), arm immersion in 10C water (AI), portable water-perfused suit (WPS), heliox inhalation (HE) and ice slushy ingestion (SL). Immediately before and after cooling, participants were assessed for fine (Purdue pegboard task) and gross (grip and pinch strength) manual dexterity. Rectal and skin temperature, as well as thermal sensation and comfort, were monitored throughout. Results Compared with CON, SL was the only method to reduce rectal temperature (P = 0.012). All externally applied cooling methods reduced skin temperature (P0.05). Conclusion The present study observed that ice ingestion or ice applied to the skin produced the greatest effect on rectal and skin temperature, respectively. AI should not be utilised if workers require subsequent fine manual dexterity. These results will help inform future studies investigating appropriate pre-cooling methods for the occupational worker.This project is financially supported by the US Government through the Technical Support Working Group within the Combating Terrorism Technical Support Office.Published versio

Assessing heat-related health risk in Europe via the Universal Thermal Climate Index (UTCI)

In this work the potential of the Universal Thermal Climate Index (UTCI) as a heat-related health risk indicator in Europe is demonstrated. The UTCI is a bioclimate index that uses a multi-node human heat balance model to represent the heat stress induced by meteorological conditions to the human body. Using 38 years of meteorological reanalysis data, UTCI maps were computed to assess the thermal bioclimate of Europe for the summer season. Patterns of heat stress conditions and non-thermal stress regions are identified across Europe. An increase in heat stress up to 1°C is observed during recent decades. Correlation with mortality data from 17 European countries revealed that the relationship between the UTCI and death counts depends on the bioclimate of the country, and death counts increase in conditions of moderate and strong stress, i.e. when UTCI is above 26°C and 32°C. The UTCI’s ability to represent mortality patterns is demonstrated for the 2003 European heatwave. These findings confirm the importance of UTCI as a bioclimatic index that is able to both capture the thermal bioclimatic variability of Europe, and relate such variability with the effects it has on human health