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The reaction CH3C(O)O2+HO2 → CH3C(O)OOH+O2 (Reaction R5a), CH3C(O)OH + O3 (Reaction R5b), CH3 + CO2 + OH + O2 (Reaction R5c) was studied in a series of experiments conducted at 1000 mbar and (293±2) K in the HIRAC simulation chamber. For 5 the first time, products, (CH3C(O)OOH, CH3C(O)OH, O3 and OH) from all three branching pathways of the reaction have been detected directly and simultaneously. Measurements of radical precursors (CH3OH, CH3CHO), HO2 and some secondary products HCHO and HCOOH further constrained the system. Fitting a comprehensive model to the experimental data, obtained over a range of conditions, determined the 10 branching ratios α(R5a) = 0.37±0.10, α(R5b) = 0.12±0.04 and α(R5c) = 0.51±0.12 (errors at 2σ level). Improved measurement/model agreement was achieved using k(R5) = (2.4±0.4)×10-11 cm³ molecule-1 s-1, which is within the large uncertainty of the current IUPAC and JPL recommended rate coefficients for the title reaction. The rate coefficient and branching ratios are in good agreement with a recent study performed by Groß 15 et al. (2014b); taken together, these two studies show that the rate of OH regeneration through Reaction (R5) is more rapid than previously thought. GEOS-Chem has been used to assess the implications of the revised rate coefficients and branching ratios; the modelling shows an enhancement of up to 5% in OH concentrations in tropical rainforest areas and increases of up to 10% at altitudes of 6-8 km above the equator, 20 compared to calculations based on the IUPAC recommended rate coefficient and yield. The enhanced rate of acetylperoxy consumption significantly reduces PAN in remote regions (up to 30 %) with commensurate reductions in background NOx. [ABSTRACT FROM AUTHOR]

The calibration of field instruments used to measure concentrations of OH and HO2 worldwide has traditionally relied on a single method utilising the photolysis of water vapour in air in a flow tube at atmospheric pressure. Here the calibration of two FAGE (fluorescence assay by gaseous expansion) apparatuses designed for HOx (OH and HO2) measurements have been investigated as a function of external pressure using two different laser systems. The conventional method of generating known concentrations of HOx from H2O vapour photolysis in a turbulent flow tube impinging just outside the FAGE sample inlet has been used to study instrument sensitivity as a function of internal fluorescence cell pressure (1.8-3.8 mbar). An increase in the calibration constants COH and CHO2 with pressure was observed, and an empirical linear regression of the data was used to describe the trends, with ΔCOH =(17±11)% and ΔCHO2 =(31.6±4.4)% increase per millibar air (uncertainties quoted to 2σ). Presented here are the first direct measurements of the FAGE calibration constants as a function of external pressure (440–1000 mbar) in a controlled environment using the University of Leeds HIRAC chamber (Highly Instrumented Reactor for Atmospheric Chemistry). Two methods were used: the temporal decay of hydrocarbons for calibration of OH, and the kinetics of the second-order recombination of HO2 for HO2 calibrations. Over comparable conditions for the FAGE cell, the two alternative methods are in good agreement with the conventional method, with the average ratio of calibration factors (conventional : alternative) across the entire pressure range, COH(conv)/COH(alt) =1.19±0.26 and CHO2(conv)/CHO2(alt) =0.96±0.18 (2σ). These alternative calibration methods currently have comparable systematic uncertainties to the conventional method: ~28% and ~41% for the alternative OH and HO2 calibration methods respectively compared to 35% for the H2O vapour photolysis method; ways in which these can be reduced in the future are discussed. The good agreement between the very different methods of calibration leads to increased confidence in HOx field measurements and particularly in aircraft-based HOx measurements, where there are substantial variations in external pressure, and assumptions are made regarding loss rates on inlets as a function of pressure. [ABSTRACT FROM AUTHOR]

The calibration of field instruments used to measure concentrations of OH and HO2 worldwide have traditionally relied on a single method utilising the photolysis of water vapour in air in a flow tube at atmospheric pressure. Here the calibration of two FAGE (Fluorescence Assay by Gaseous Expansion) apparatuses designed for HOx (OH and HO2) measurements have been investigated as a function of external pressure and temperature, using two different laser systems. The conventional method of generating known concentrations of HOx from H2O vapour photolysis in a turbulent flowtube impinging just outside the FAGE sample inlet has been used to study instrument sensitivity as a function of internal fluorescence cell pressure (1.8-3.8mbar). An increase in the calibration constants COH and CHO2 with pressure was observed and an empirical linear regression of the data was used to describe the trends, with ΔCOH = (17±11)% and ΔCHO2 = (31.6±4.4)% increase per mbar air (uncertainties quoted to 2. Presented here are the first direct measurements of the FAGE calibration constants as a function of external pressure (440-1000mbar) in a controlled environment using the University of Leeds HIRAC chamber (Highly Instrumented Reactor for Atmospheric Chemistry). Two methods were used: the temporal decay of hydrocarbons for calibration of OH, and the kinetics of the second-order recombination of HO2 for HO2 calibrations. Over comparable conditions for the FAGE cell, the two alternative methods are in good agreement with the conventional method, with the average ratio of calibration factors (conventional : alternative) across the entire pressure range COH(conv)/COH(alt) = 1.19±0.26 and CHO2(conv) /CHO2(alt) = 0.96±0.18 (2). These alternative calibration methods currently have comparable systematic uncertainties than the conventional method: ~28% and ~41% for the alternative OH and HO2 calibration methods respectively compared to 35% for the H2O vapour photolysis method; ways in which these can be reduced in the future are discussed. The good agreement between the very different methods of calibration leads to increased confidence in HOx field measurements and particularly in aircraft based HOx measurements, where there are substantial variations in external pressure, and assumptions are made regarding loss rates on inlets as a function of pressure. [ABSTRACT FROM AUTHOR]

Abstract: A simple O3-LOPAP (Long Path Absorption Photometer) instrument for the selective detection of O3 in the atmosphere is presented, which is mainly intended to be used as an extension of a recently developed NO2-LOPAP. O3 is sampled in a stripping coil by a selective chemical reaction with the highly absorbing Indigo dye. The reduction of the optical absorption of the dye is detected in a liquid core waveguide. The instrument has a detection limit of 0.4 ppbv, an accuracy of 10%, a precision of 2% for 6 min time resolution and allows the absolute quantification of O3 according to Lambert–Beer''s law. Interferences towards nitrogen oxides (NO and NO2), N2O5, H2O2 and several VOCs were quantified in the laboratory and found to be negligible for atmospheric conditions. The new instrument was successfully validated against a commercial UV-absorption instrument during an urban field campaign and against the FTIR technique in a smog chamber under complex photosmog conditions. For the UV-absorption instrument significant positive interferences towards aromatic species were observed in the smog chamber. [Copyright &y& Elsevier]

The article presents a study which compares the efficiency of different techniques using various instruments in measuring interferences of commercial nitrogen dioxide (NO2) in the urban atmosphere and in a smog chamber. Chemiluminescence instruments with molybdenum or photolytic converters, Luminol based instrument and a proposed NO 2 Long Path Absorption Photometer (LOPAP) were compared with spectroscopic techniques. The methods and results of the study are discussed.

The article presents a study which compares the performances of different commercial nitrogen dioxide (NO2) instruments and a NO2-LOPAP in the urban atmosphere and in a smog chamber in Santiago de Chile. A field experiment was conducted wherein chemiluminescence instruments with molybdenum or photolytic converters were compared to NO2-LOPAP with spectroscopic techniques to detect interferences. Results show strong interferences and agreements in all instruments.

The article focuses on the development of a Long Path Absorption Photometer (LOPAP) instrument for the detection of NO2 in the atmosphere. The instrument is considered more sensitive than known instruments as it has an accuracy of 10 percent and a precision of 0.5 percent for three minutes time resolution. It is also deemed easier to apply than other methods. Its use is validated by intercomparison with chemiluminescence instrument with photolytic NO2 converter.

Abstract: Monoterpenes are ubiquitous in forested environments and are subject to reactions with OH radicals, NO3 radicals and O3 both within and above forest canopies. While reactions of monoterpenes with OH and O3 have received considerable attention with regard to their reaction kinetics, reaction products and secondary organic aerosol (SOA) formation those with NO3 have received relatively little consideration. To redress this imbalance and to try and assess the possible importance of NO3+monterpene reactions within forest canopies investigations have been performed on selected monterpenes. The products and aerosol formation from the NO3 radical initiated oxidation of limonene and α-pinene have been investigated in the EUPHORE photoreactor facility, and the secondary chemistry of the observed major products was then investigated in a large volume laboratory photoreactor. In addition to large yields of yet unidentified organic nitrates, pinonaldehyde and endolim have been identified as the major reaction products of the NO3 radical initiated oxidation of α-pinene and limonene, respectively. The aerosol formation has been investigated in the presence of different seed aerosols and also water vapour. The reactions lead to the formation of SOA and the results indicate the importance of the chemical character of the seed aerosol in determining the SOA yield in NO3+monoterpene reactions. The possible pathways leading to SOA formation and also their potential importance are discussed based on the laboratory results on the reaction of NO3 with the two major products. [Copyright &y& Elsevier]

Post-Coronavirus Disease 2019 (post-COVID-19) syndrome represents a cluster of persistent symptoms following Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2) infection that can severely affect quality of life. The pathogenic mechanisms and epidemiology in different regions are still under evaluation. To assess the outcomes of post-COVID-19 syndrome, we performed a questionnaire-based, cross-sectional study in previously infected individuals. Out of 549 respondents, (male:female ratio: 0.32), 29.5% had persistent symptoms at 3 months, 23.5% had persistent symptoms at 6 months, and 18.3% had persistent symptoms at 12 months after the initial infection. The most common symptoms included fatigue (8.7%), sleep disturbances (7.1%), and cognitive impairment (6.4%). The risk of developing post-COVID-19 syndrome increased for those with more symptoms in the acute phase (OR 4.24, p < 0.001) and those experiencing reinfections (OR 2.405, p < 0.001), while SARS-CoV-2 vaccination halved the risk (OR = 0.489, p = 0.004). Individuals with post-COVID-19 syndrome had a 5.7-fold higher risk of being diagnosed with a new chronic condition, with 44% reporting cardiovascular disease, and a 6.8-fold higher likelihood of needing medical care or leave. Affected individuals reported significant impairments in mobility, pain/discomfort, and anxiety/depression, with 20.7% needing to adjust their work schedules. Overall, patients with post-COVID-19 syndrome require ongoing monitoring and rehabilitation, and further socio-economic impact studies are needed.

Nowadays, infectious diseases caused by microorganisms are a major threat to human health, mostly because of drug resistance, multi-drug resistance and extensive-drug-resistance phenomena to microbial pathogens. During the last few years, obtaining hybrid azaheterocyclic drugs represents a powerful and attractive approach in modern antimicrobial therapy with very promising results including overcoming microbial drug resistance. The emphasis of this review is to notify the scientific community about the latest recent advances from the last five years in the field of hybrid azine derivatives with antimicrobial activity. The review is divided according to the main series of six-member ring azaheterocycles with one nitrogen atom and their fused analogs. In each case, the main essential data concerning synthesis and antimicrobial activity are presented.

This paper presents our approach to predicting future error-related events in a robot-mediated gamified physical training activity for stroke patients. The ability to predict future error under such conditions suggests the existence of distinguishable features and separated class characteristics between the casual gameplay state and error prune state in the data. Identifying such features provides valuable insight to creating individually tailored, adaptive games as well as possible ways to increase rehabilitation success by patients. Considering the time-series nature of sensory data created by motor actions of patients we employed a predictive analysis strategy on carefully engineered features of sequenced data. We split the data into fixed time windows and explored logistic regression models, decision trees, and recurrent neural networks to predict the likelihood of a patient making an error based on the features from the time window before the error. We achieved an 84.4% F1-score with a 0.76 ROC value in our best model for predicting motion accuracy related errors. Moreover, we computed the permutation importance of the features to explain which ones are more indicative of future errors.

In Romania, the first phase of the COVID-19 vaccination campaign prioritized medical personnel, which included healthcare students. This study aimed to assess their knowledge, attitudes towards, and perception of COVID-19 vaccination. An anonymous, single-answer, 42-item online survey was conducted from 12 January until 3 March 2021, in the country's largest University of Medicine and Pharmacy. Among the 1581 respondents (14.9% response rate), 88.5% were pro-vaccination, 7.8% were undecided, and 3.7% were vaccine resistant. The main reason for vaccine rejection was the perceived speed of vaccine development (strong agreement among the vaccine resistant, moderate agreement among the undecided, p < 0.001). Concern over long-term adverse reaction was present in only 11.5% of the respondents, significantly more frequent in the undecided and vaccine resistant. Perceived knowledge on the vaccines' safety, efficacy, and technology correlated with a pro-vaccine attitude ( p < 0.001). Most respondents had a positive stance towards vaccination in general, influencing their behaviour as future parents (99.3% of the pro-vaccination, 95.1% of the undecided, and 89.1% of the vaccine resistant will vaccinate their children, p < 0.001) and as medical professionals (99.7% of the pro-vaccination, 93.5% of those undecided, and 89.8% of the vaccine resistant would advise parents to vaccinate their children, p < 0.001). Healthcare students can thus serve as important vectors for scientifically sound information, influencing vaccine uptake in the community.

A series of aryl disilenes Tip 2 Si[double bond, length as m-dash]Si(Tip)Ar (2a-c) and para-arylene bridged tetrasiladienes, Tip 2 Si[double bond, length as m-dash]Si(Tip)-LU-Si(Tip)[double bond, length as m-dash]SiTip 2 (3a-d) are synthesized by the transfer of the Tip 2 Si[double bond, length as m-dash]SiTip unit to aryl halides and dihalides by nucleophilic disilenides Tip 2 Si[double bond, length as m-dash]SiTipLi (Tip = 2,4,6-iPr 3 C 6 H 2 , Ar = aryl substituent, LU = para-arylene linking unit). The scope of the nucleophilic Si[double bond, length as m-dash]Si transfer reaction is demonstrated to also include substrates of considerable steric bulk such as mesityl or duryl halides Ar-X (Ar = Mes = 2,4,6-Me 3 C 6 H 2 ; Ar = Dur = 2,3,5,6-Me 4 C 6 H, X = Br or I). Bridged tetrasiladienes Tip 2 Si[double bond, length as m-dash]Si(Tip)-LU-Si(Tip)[double bond, length as m-dash]SiTip 2 with more extended linking units surprisingly exhibit fluorescence at room temperature, albeit weak. DFT calculations suggest that partial charge transfer character of the excited state is a possible explanation.

A kinetic study of the gas-phase reactions of OH radicals with three unsaturated biogenic alcohols, (E)-3-hexen-1-ol, (Z)-3-hepten-1-ol, and (Z)-3-octen-1-ol, has been performed. The rate coefficients obtained are (in units of 10(-10) cm(3) molecule(-1) s(-1)) k1 (OH + (E)-CH2(OH)CH2CH═CHCH2CH3) = (1.14 ± 0.14), k2 (OH + (Z)-CH2(OH)CH2CH═CHCH2CH2CH3) = (1.28 ± 0.23), and k3 (OH + (Z)-CH2(OH)CH2CH═CHCH2CH2CH2CH3) = (1.49 ± 0.35). In addition, a product study on the reactions of OH with (E)-3-hexen-1-ol and (Z)-3-hepten-1-ol is reported. All the experiments were performed at (298 ± 2) K and 1 atm of NOx-free air in a 1080 L photoreactor with in situ FTIR detection of organics. This work constitutes the first kinetic study of the reactions of OH radicals with (Z)-3-hepten-1-ol and (Z)-3-octen-1-ol as well as the first determination of the fate of the hydroxy alkoxy radicals formed in the title reactions. An analysis of the available rates of addition of OH and Cl to the double bond of different unsaturated alcohols at 298 K has shown that they can be related by the expression log kOH = (0.29 ± 0.04) log kCl - 10.8. The atmospheric lifetimes of the alcohols studies were estimated to be around 1 h for reaction with OH radicals. The products formed in the title reactions are mainly carbonylic compounds that can contribute to the formation of ozone and PANs-type compounds in the troposphere.

Rate coefficients for the reactions of hydroxyl radicals (OH) with a series of oxygenated aromatics (two methoxybenzene and five methoxyphenol isomers) have been obtained using the relative kinetic method in 1080 and 480 L photoreactors at the University of Wuppertal, Germany. The experiments were realized at 295 ± 2 K and 1 bar total pressure of synthetic air using in situ Fourier transform infrared spectroscopy for the chemical analysis. The following rate coefficients (in units of cm(3) molecule(-1) s(-1)) were determined: methoxybenzene (anisole), (2.08 ± 0.21) × 10(-11); 1-methoxy-2-methylbenzene, (4.56 ± 0.50) × 10(-11); 2-methoxyphenol (guaiacol), (5.40 ± 0.72) × 10(-11); 3-methoxyphenol, (6.93 ± 0.67) × 10(-11); 4-methoxyphenol, (5.66 ± 0.55) × 10(-11); 2-methoxy-4-methylphenol, (7.51 ± 0.68) × 10(-11); 2,3-dimethoxyphenol, (7.49 ± 0.81) × 10(-11); and 2,6-dimethoxyphenol (syringol), (8.10 ± 0.98) × 10(-11). The rate coefficients for the reactions of OH with 2,3-dimethoxyphenol and 1-methoxy-2-methylbenzene are first time measurements. The rate coefficients determined in this work are compared with previous determinations reported in the literature and also with the values estimated using a structure-activity relationship method. A comparison is performed between the OH rate coefficients obtained for methoxylated aromatics with those of other substituted aromatics in order to understand the influence of the type, number, and position of the different substituents on the reactivity of aromatics toward OH. In addition, a comparison is made between the OH and Cl rate coefficients for the compounds. The principal atmospheric sink of these methoxylated aromatic compounds during daytime is their reaction with OH radicals. The corresponding lifetimes for reaction with OH radicals and Cl atoms are 2-8 and 11-50 h, respectively.

Anthropogenic activities are the main source of nitrophenols and chlorophenols in the atmosphere. Nitro and chlorophenols have a high potential to form ozone and secondary organic aerosol, thus investigations on the major photo oxidation pathways of these compounds are important to assess their contribution to urban air pollution and human health. Presented here are rate coefficients determined at atmospheric pressure and (298 ± 2) K using a relative kinetic method for the reactions of chlorine atoms with 2-chlorophenol (2ClP), 2-nitrophenol (2NP) and four methyl-2-nitrophenol (2-nitrocresol, nM2NP (n = 3,4,5,6)) isomers. The following rate coefficients (in units of cm(3) molecule(-1) s(-1)) have been obtained: (5.9 ± 1.5) × 10(-12) for 2ClP, (6.8 ± 2.3) × 10(-12) for 2NP, and (14.0 ± 4.9) × 10(-11), (4.3 ± 1.5) × 10(-11), (1.94 ± 0.67) × 10(-11) and (2.68 ± 0.75) × 10(-11) for the four methyl-2-nitrophenol isomers 3M2NP, 4M2NP, 5M2NP, and 6M2NP, respectively. This study represents the first kinetic investigation for the reaction of chlorine atoms with all the nitrophenols. In addition, to assist in the interpretation of the results, rate coefficients for the reactions of Cl atoms with the cresol ortho, meta, and para isomers have been determined for the first time. The rate coefficient for the reaction with 2ClP is in good agreement with previous data and the relative reactivity of 2NP, 4M2NP, 5M2NP, and 6M2NP can be rationalized based on known substituent effects. The rate coefficient for 3M2NP is anomalously large; the observation of significant NO2 production in only this reaction suggests that an ipso substitution mechanism is the cause of the enhanced reactivity.

A catalyst- and by-product-free protocol for the synthesis of σ-π conjugated organosilicon polymers is reported. The regiospecific [2+2] cycloaddition of C≡C triple bonds to Si=Si double bonds allowed the preparation of air-stable ethynyl-terminated extended monomers from 1,4-bis(ethynyl)benzene and the para-phenylene bridged tetrasiladiene, Tip2 Si=SiTip-pC6H4-SiTip=SiTip2 (Tip = 2,4,6-iPr3C6H2). The polymer obtained from the extended monomer and further tetrasiladiene exhibits pronounced σ-π conjugation, as was evident from the red-shift in the absorption spectrum compared to model systems. We show that the thermal stability of the employed bis(alkyne) co-monomer is translated into this polymer., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The reaction of a series of oxygenated aromatics (two methoxybenzene and six methoxyphenol isomers) with chlorine atoms has been studied in two simulation chambers with volumes of 1080 and 480 L at the University of Wuppertal. Experiments were performed at 295 ± 2 K and a total pressure of synthetic air of 1 bar using the relative kinetic method with in situ Fourier transform infrared spectroscopy for chemical analysis. The following rate coefficients (in units of cubic centimeter per molecule per second) were determined: (1.07 ± 0.24) × 10(-10) for methoxybenzene, (1.20 ± 0.24) × 10(-10) for 1-methoxy-2-methylbenzene, (2.97 ± 0.66) × 10(-10) for 2-methoxyphenol (guaiacol), (2.99 ± 0.62) × 10(-10) for 3-methoxyphenol, (2.86 ± 0.58) × 10(-10) for 4-methoxyphenol, (3.35 ± 0.68) × 10(-10) for 2-methoxy-4-methylphenol, (4.73 ± 1.06) × 10(-10) for 2,3-dimethoxyphenol, and (2.71 ± 0.61) × 10(-10) for 2,6-dimethoxyphenol (syringol). To the best of our knowledge, this work represents the first determination of the rate coefficients for the gas-phase reaction of the chlorine atoms with the methoxy-aromatic compounds investigated. The reactivity of the methoxylated aromatics toward Cl is compared with that of other substituted aromatic compounds, and the differences in the rate coefficients are interpreted in terms of the type, number, and position of the different substituents on the aromatic ring. The atmospheric implications of the studied reactions are also discussed.