The rates of non-adiabatic processes in large molecular systems: Toward an effective full-dimensional quantum mechanical approach.

Two computational approaches for computing the rates of internal conversions in molecular systems where a large set of nuclear degrees of freedom plays a role are discussed and compared. One approach is based on the numerical solution of the time-dependent Schrödinger equation and allows us to include almost the whole set of vibrational coordinates, thanks to the employment of effective procedures for selecting those elements of the Hilbert space which play a significant role in dynamics. The other approach, based on the time-dependent perturbation theory and limited to the use of the harmonic approximation, allows us to include the whole Hilbert space spanned by the vibrational states of the system. The two approaches are applied to the photophysics of azulene, whose anti-Kasha behavior caused by anomalous internal conversion rates is well assessed. The calculated rates for the decays of the first two excited singlet states are in very good agreement with experimental data, indicating the reliability of both methodologies.

Variability of ambient air ammonia in urban Europe (Finland, France, Italy, Spain, and the UK).

This study addressed the scarcity of NH3 measurements in urban Europe and the diverse monitoring protocols, hindering direct data comparison. Sixty-nine datasets from Finland, France, Italy, Spain, and the UK across various site types, including industrial (IND, 8), traffic (TR, 12), urban (UB, 22), suburban (SUB, 12), and regional background (RB, 15), are analyzed to this study. Among these, 26 sites provided 5, or more, years of data for time series analysis. Despite varied protocols, necessitating future harmonization, the average NH3 concentration across sites reached 8.0 ± 8.9 µg/m3. Excluding farming/agricultural hotspots (FAHs), IND and TR sites had the highest concentrations (4.7 ± 3.2 and 4.5 ± 1.0 µg/m3), followed by UB, SUB, and RB sites (3.3 ± 1.5, 2.7 ± 1.3, and 1.0 ± 0.3 µg/m3, respectively) indicating that industrial, traffic, and other urban sources were primary contributors to NH3 outside FAH regions. When referring exclusively to the FAHs, concentrations ranged from 10.0 ± 2.3 to 15.6 ± 17.2 µg/m3, with the highest concentrations being reached in RB sites close to the farming and agricultural sources, and that, on average for FAHs there is a decreasing NH3 concentration gradient towards the city. Time trends showed that over half of the sites (18/26) observed statistically significant trends. Approximately 50 % of UB and TR sites showed a decreasing trend, while 30 % an increasing one. Meta-analysis revealed a small insignificant decreasing trend for non-FAH RB sites. In FAHs, there was a significant upward trend at a rate of 3.51[0.45,6.57]%/yr. Seasonal patterns of NH3 concentrations varied, with urban areas experiencing fluctuations influenced by surrounding emissions, particularly in FAHs. Diel variation showed differing patterns at urban monitoring sites, all with higher daytime concentrations, but with variations in peak times depending on major emission sources and meteorological patterns. These results offer valuable insights into the spatio-temporal patterns of gas-phase NH3 concentrations in urban Europe, contributing to future efforts in benchmarking NH3 pollution control in urban areas.

HOW TO PREVENT HAND INJURIES - REVIEW OF EPIDEMIOLOGICAL DATA IS THE FIRST STEP IN HEALTH CARE MANAGEMENT.

BACKGROUND: Hand injuries are common affecting all ages, genders, and geographic regions. They can result in long term disability and mortality, while they place a significant financial burden in society. Although, hand injuries can be prevented. Preventive strategies can be designed, but knowledge of injuries' epidemiological characteristics is required beforehand. METHODS: We performed a review of the current literature related to hand injuries to identify their incidence, patients' demographics, type, mode, and time of the injury. RESULTS: Hand injuries constitute 6.6% to 28.6% of all injuries presenting to the Emergency Department and 28% of injuries to the musculoskeletal system. They mainly affect young male labourers. Occupational and home accidents are the commonest injury modalities, while traffic road accidents constitute a significant reason for hand injuries as well. Lacerations account for most hand injuries, followed by crush injuries, fractures and amputations. Most occupational injuries occur in the beginning of the week and especially during the morning shift, while there has been identified an increase in the number of hand injuries during the summer months. CONCLUSIONS: Hand injuries are an important health problem with impact on patient's life and on the society. Although they can be prevented. Preventive strategies need to be addressed towards many directions and people's activities, since prevention will have an important impact on people's quality of life and society's well-being.

Extended-release metformin improves cognitive impairment in frail older women with hypertension and diabetes: preliminary results from the LEOPARDESS Study.

BACKGROUND: Women have a high risk of frailty independently of age and menopause state. Diabetes and hypertension increase the risk of frailty and cognitive impairment. Metformin has been employed in post-menopausal women and some reports have shown encouraging effects in terms of attenuated frailty. However, the impact on cognitive performance of a recently introduced extended-release formulation of metformin has never been explored. METHODS: We studied consecutive frail hypertensive and diabetic older women presenting at the ASL (local health authority of the Italian Ministry of Health) Avellino, Italy, from June 2021 to August 2022, who were treated or not with extended-release metformin. We included a control group of frail older males with diabetes and hypertension treated with extended-release metformin and a control group of frail older women with diabetes and hypertension treated with regular metformin. RESULTS: A total of 145 patients successfully completed the study. At the end of the 6-month follow-up, we observed a significantly different cognitive performance compared to baseline in the group of frail women treated with extended-release metformin (p: 0.007). Then, we compared the follow-up groups and we observed significant differences between frail women treated vs. untreated (p: 0.041), between treated frail women and treated frail men (p: 0.016), and between women treated with extended-release metformin vs. women treated with regular metformin (p: 0.048). We confirmed the crucial role of extended-release metformin applying a multivariable logistic analysis to adjust for potential confounders. CONCLUSIONS: We evidenced, for the first time to the best of our knowledge, the favorable effects on cognitive impairment of extended-release metformin in frail women with diabetes and hypertension.

Electron Transfer Rates in Polar and Non-Polar Environments: a Generalization of Marcus' Theory to Include an Effective Treatment of Tunneling Effects.

A multistep kinetic model in which solvent motion is treated in the framework of Marcus theory and the rates of the elementary electron transfer step are evaluated at full quantum mechanical level is proposed and applied to the calculation of the rates of intramolecular electron transfer reactions in rigidly spaced D-Br-A (D = 1,1'-biphenyl radical anion, Br = androstane) compounds, for five acceptors (A) in three organic solvents with different polarity. The calculated rates agree well with experimental ones, and their temperature dependence is almost quantitatively reproduced.

The broad spectrum of COVID-like patients initially negative at RT-PCR testing: a cohort study.

BACKGROUND: Patients that arrive in the emergency department (ED) with COVID-19-like syndromes testing negative at the first RT-PCR represent a clinical challenge because of the lack of evidence about their management available in the literature. Our first aim was to quantify the proportion of patients testing negative at the first RT-PCR performed in our Emergency Department (ED) that were confirmed as having COVID-19 at the end of hospitalization by clinical judgment or by any subsequent microbiological testing. Secondly, we wanted to identify which variables that were available in the first assessment (ED variables) would have been useful in predicting patients, who at the end of the hospital stay were confirmed as having COVID-19 (false-negative at the first RT-PCR). METHODS: We retrospectively collected data of 115 negative patients from2020, March 1st to 2020, May 15th. Three experts revised patients' charts collecting information on the whole hospital stay and defining patients as COVID-19 or NOT-COVID-19. We compared ED variables in the two groups by univariate analysis and logistic regression. RESULTS: We classified 66 patients as COVID-19 and identified the other 49 as having a differential diagnosis (NOT-COVID), with a concordance between the three experts of 0.77 (95% confidence interval (95%CI) 0.66- 0.73). Only 15% of patients tested positive to a subsequent RT-PCR test, accounting for 25% of the clinically suspected. Having fever (odds ratio (OR) 3.32, (95%CI 0.97-12.31), p = 0.06), showing a typical pattern at the first lung ultrasound (OR 6.09, (95%CI 0.87-54.65), p = 0.08) or computed tomography scan (OR 4.18, (95%CI 1.11-17.86), p = 0.04) were associated with a higher probability of having COVID-19. CONCLUSIONS: In patients admitted to ED with COVID-19 symptoms and negative RT-PCR a comprehensive clinical evaluation integrated with lung ultrasound and computed tomography could help to detect COVID-19 patients with a false negative RT-PCR result.

Correlation of physical and cognitive impairment in diabetic and hypertensive frail older adults.

BACKGROUND: Diabetes and hypertension are common in older adults and represent established risk factors for frailty. Frailty is a multidimensional condition due to reserve loss and susceptibility to stressors with a high risk of death, hospitalizations, functional and cognitive impairment. Comorbidities such as diabetes and hypertension play a key role in increasing the risk of mortality, hospitalization, and disability. Moreover, frail patients with diabetes and hypertension are known to have an increased risk of cognitive and physical impairment. Nevertheless, no study assessed the correlation between physical and cognitive impairment in frail older adults with diabetes and hypertension. METHODS: We evaluated consecutive frail older patients with diabetes and hypertension who presented at ASL (local health unit of the Italian Ministry of Health) Avellino, Italy, from March 2021 to October 2021. The inclusion criteria were: a previous diagnosis of diabetes and hypertension with no evidence of secondary causes; age > 65 years; a frailty status; Montreal Cognitive Assessment (MoCA) score < 26. RESULTS: 179 patients successfully completed the study. We found a strong and significant correlation between MoCA score and 5-m gait speed test (r: 0.877; p < 0.001). To further verify our results, we performed a linear multivariate analysis adjusting for potential confounding factors, with MoCA score as dependent variable, which confirmed the significant association with glycemia (p < 0.001). CONCLUSIONS: This is the first study showing a significant correlation between 5-m gait speed test and MoCA score in frail diabetic and hypertensive older adults.

A global observational analysis to understand changes in air quality during exceptionally low anthropogenic emission conditions.

This global study, which has been coordinated by the World Meteorological Organization Global Atmospheric Watch (WMO/GAW) programme, aims to understand the behaviour of key air pollutant species during the COVID-19 pandemic period of exceptionally low emissions across the globe. We investigated the effects of the differences in both emissions and regional and local meteorology in 2020 compared with the period 2015-2019. By adopting a globally consistent approach, this comprehensive observational analysis focuses on changes in air quality in and around cities across the globe for the following air pollutants PM2.5, PM10, PMC (coarse fraction of PM), NO2, SO2, NOx, CO, O3 and the total gaseous oxidant (OX = NO2 + O3) during the pre-lockdown, partial lockdown, full lockdown and two relaxation periods spanning from January to September 2020. The analysis is based on in situ ground-based air quality observations at over 540 traffic, background and rural stations, from 63 cities and covering 25 countries over seven geographical regions of the world. Anomalies in the air pollutant concentrations (increases or decreases during 2020 periods compared to equivalent 2015-2019 periods) were calculated and the possible effects of meteorological conditions were analysed by computing anomalies from ERA5 reanalyses and local observations for these periods. We observed a positive correlation between the reductions in NO2 and NOx concentrations and peoples' mobility for most cities. A correlation between PMC and mobility changes was also seen for some Asian and South American cities. A clear signal was not observed for other pollutants, suggesting that sources besides vehicular emissions also substantially contributed to the change in air quality. As a global and regional overview of the changes in ambient concentrations of key air quality species, we observed decreases of up to about 70% in mean NO2 and between 30% and 40% in mean PM2.5 concentrations over 2020 full lockdown compared to the same period in 2015-2019. However, PM2.5 exhibited complex signals, even within the same region, with increases in some Spanish cities, attributed mainly to the long-range transport of African dust and/or biomass burning (corroborated with the analysis of NO2/CO ratio). Some Chinese cities showed similar increases in PM2.5 during the lockdown periods, but in this case, it was likely due to secondary PM formation. Changes in O3 concentrations were highly heterogeneous, with no overall change or small increases (as in the case of Europe), and positive anomalies of 25% and 30% in East Asia and South America, respectively, with Colombia showing the largest positive anomaly of ~70%. The SO2 anomalies were negative for 2020 compared to 2015-2019 (between ~25 to 60%) for all regions. For CO, negative anomalies were observed for all regions with the largest decrease for South America of up to ~40%. The NO2/CO ratio indicated that specific sites (such as those in Spanish cities) were affected by biomass burning plumes, which outweighed the NO2 decrease due to the general reduction in mobility (ratio of ~60%). Analysis of the total oxidant (OX = NO2 + O3) showed that primary NO2 emissions at urban locations were greater than the O3 production, whereas at background sites, OX was mostly driven by the regional contributions rather than local NO2 and O3 concentrations. The present study clearly highlights the importance of meteorology and episodic contributions (e.g., from dust, domestic, agricultural biomass burning and crop fertilizing) when analysing air quality in and around cities even during large emissions reductions. There is still the need to better understand how the chemical responses of secondary pollutants to emission change under complex meteorological conditions, along with climate change and socio-economic drivers may affect future air quality. The implications for regional and global policies are also significant, as our study clearly indicates that PM2.5 concentrations would not likely meet the World Health Organization guidelines in many parts of the world, despite the drastic reductions in mobility. Consequently, revisions of air quality regulation (e.g., the Gothenburg Protocol) with more ambitious targets that are specific to the different regions of the world may well be required.

Unexpected response to palliative radiotherapy for subcutaneous metastases of an advanced small cell pancreatic neuroendocrine carcinoma: a case report of two different radiation schedules.

BACKGROUND: Skin metastases from pancreatic neuroendocrine carcinoma (PNEC) are rare and their palliative treatment is challenging. We report our experience in the multimodal management of one of the few reported cases of metastatic PNEC with multiple visceral and subcutaneous secondary lesions, focusing on the effectiveness of palliative radiotherapy for skin metastases. CASE PRESENTATION: A 61-years old woman affected by a metastatic PNEC - with subcutaneous growing and bleeding secondary lesions (at the scalp, right scapular region and at the back of the left thoracic wall, respectively) - obtained a successful control of visceral metastases with the use of chemotherapy and an unexpected local response of her skin metastases with palliative radiotherapy. In particular, two subsequent radiation treatments were performed using different fractionation schedules (30 Gy in 10 fractions and 20 Gy in 5 fractions, respectively). Both radiation treatments were well-tolerated and patient's quality of life was improved. Local response was maintained until patient's death - that occurred due to cachexia. CONCLUSIONS: The presented case highlights the effectiveness and the good tolerance of radiotherapy in the treatment of subcutaneous metastases; nevertheless, further knowledge of the optimal local palliative approach for PNEC metastatic sites is necessary. The experience gained in this work is the occasion to encourage a routine integrated multidisciplinary team management of metastatic PNECs because of their clinical complexity. The aim is to guarantee the optimization of the care with personalized and more effective systemic and local treatments - also including supportive cares and treatment-related side effects management.

Experience of nail bed injuries at a tertiary hand trauma unit: a 12-month review and cost analysis.

The aim of this study was to analyse the management of nail bed injuries from a clinical and economic perspective. We carried out a retrospective analysis of nail bed injuries treated operatively at a tertiary Plastic Surgery Hand Trauma Unit during 2016. The National Schedule of Reference Costs (2015-2016) was used to estimate the costs of treating 630 patients. The most common mechanism was a crush injury in a door (33%). Fifty-five per cent of patients had an associated tuft fracture. The minimum cost per annum for patients treated for nail bed injuries in our unit was calculated to be £511,560 (€573,362; US$666,664). Many nail bed injuries are preventable and because they present a very high financial burden on the National Health Service, targeted prevention strategies should be considered. Level of evidence: IV.

Paraumbilical perforator flap for reconstruction of the external auditory meatus: A case report.

We herein present a technique of using the umbilical stalk for reconstruction of the external auditory meatus. A 49-year-old female presented with locally aggressive melanoma affecting her mastoid region. She underwent radical excision including the skin and soft tissues around the external ear with simultaneous lymph node clearance. The resultant defect measured 15 cm × 8 cm in diameter and was 2.5 cm deep. This was reconstructed with a similarly sized microvascular paraumbilical perforator flap that included the umbilical stalk. In the post-operative course there was complete flap survival but a prolonged wound dehiscence near the auditory meatus that required revision surgery. At 15-months follow-up, the patient was melanoma-free and the auditory meatus was patent. Hearing was also preserved. The umbilical stalk is one of the few skin covered tubed structures in the human body that may be used without major donor morbidity to "replace like with like," the auditory channel.

Incidence estimates of hand and upper extremity injuries in Italy.

OBJECTIVE: The purpose of this investigation is to estimate the incidence rates of upper extremity injuries and to give an overview of the most frequent diagnoses. MATERIALS AND METHODS: Two population databases were queried for all injuries in the upper extremities, the SINIACA-IDB (S-IDB: Emergency Department Injury Database in Italy) and the Hospital Discharge Register (HDR). The diagnoses codes of hand trauma were selected from both databases in order to estimate the national incidence rate. RESULTS: According to the S-IDB data of year 2011, total 1 479 510 ED attendances per year in Italy were estimated with an upper extremity injury (incidence rate: 2491 per 100 000 persons/year). About 880 816 Emergency Department (ED) attendances per year are due to hand injuries, while over 653 336 attendances per year concern arm injuries. The incidence rates are 1483 and 1100 per 100 000 person/year respectively. About 201 940 hospitalizations are observed in the HDR because of upper extremity injuries (incidence rate: 340 per 100 000 persons/year). Males have higher incidence rate (387 vs 280 per 100 000 persons per year). The trend in the incidence rates for the age group of inpatients shows two peaks: at age 12 (400 cases per 100 000 persons/year), and in the older age groups (700 cases per 100 000 persons/year).

From the donor's arm to blood product: a study on bacterial contamination of apheresis platelet concentrates.

BACKGROUND: Transfusion-associated bacterial infections are a quite frequent collateral effect of administration of platelet concentrates (PC). We carried out a microbiological surveillance of bacterial contamination of apheresis platelet concentrates by studying microbial flora on donors' arms before and after skin disinfection, through blood cultures with the diversion volume and with the PC. MATERIALS AND METHODS: Platelet aphereses were carried out using two Haemonetics MCS+ instruments. Cutaneous swabs were examined by the direct plate technique and blood cultures were performed using Bact/ALERT aerobic bottles. In the 5 years from January 2001 to December 2005 we tested 481 PC. RESULTS: Cutaneous swabs showed significant bacterial growth in 89% of cases before skin disinfection and in 44% after. None of the blood cultures performed on diversion blood was positive, one (0.2%) PC was positive on the fifth day after collection and the presence of a Staphylococcus epidermidis strain was demonstrated. CONCLUSIONS: Our results suggest that the skin disinfection protocol adopted in our structure is not fully satisfactory. The cultures performed on the PC showed a low prevalence of contamination, and the only positive sample was contaminated by a common skin contaminant (S. epidermidis). The culture became positive on the fifth day after collection, but on the second day the PC had been transfused to a patient, without any adverse reaction. In our experience a culture method using Bact/ALERT aerobic bottles was not able to prevent transfusion of the only contaminated PC identified in this study.