Oxygenases have been postulated to utilize d4 FeIV and d8 CuIII oxidants in proton-coupled electron transfer (PCET) hydrocarbon oxidation. In order to explore the influence the metal ion and ...d-electron count can hold over the PCET reactivity, two metastable high-valent metal–oxygen adducts, NiIII(OAc)(L) (1b) and CuIII(OAc)(L) (2b), L = N,N′-(2,6-diisopropylphenyl)-2,6-pyridinedicarboxamidate, were prepared from their low-valent precursors NiII(OAc)(L)− (1a) and CuII(OAc)(L)− (2a). The complexes 1a/b–2a/b were characterized using nuclear magnetic resonance, Fourier transform infrared, electron paramagnetic resonance, X-ray diffraction, and absorption spectroscopies and mass spectrometry. Both complexes were capable of activating substrates through a concerted PCET mechanism (hydrogen atom transfer, HAT, or concerted proton and electron transfer, CPET). The reactivity of 1b and 2b toward a series of para-substituted 2,6-di-tert-butylphenols (p-X-2,6-DTBP; X = OCH3, C(CH3)3, CH3, H, Br, CN, NO2) was studied, showing similar rates of reaction for both complexes. In the oxidation of xanthene, the d8 CuIII oxidant displayed a small increase in the rate constant compared to that of the d7 NiIII oxidant. The d8 CuIII oxidant was capable of oxidizing a large family of hydrocarbon substrates with bond dissociation enthalpy (BDEC–H) values up to 90 kcal/mol. It was previously observed that exchanging the ancillary anionic donor ligand in such complexes resulted in a 20-fold enhancement in the rate constant, an observation that is further enforced by comparison of 1b and 2b to the literature precedents. In contrast, we observed only minor differences in the rate constants upon comparing 1b to 2b. It was thus concluded that in this case the metal ion has a minor impact, while the ancillary donor ligand yields more kinetic control over HAT/CPET oxidation.
Objective
Bipolar disorder (BD) is associated with a higher risk of suicide and with worse early life stress. A serotonin (5‐hydroxytryptamine; 5‐HT) transporter‐linked polymorphic region (5‐HTTLPR) ...has been shown to influence the relationship between stress and the risk of attempting suicide in the general population, but has not been investigated in BD.
Methods
We studied 136 inpatients (93 females, 43 males) with a major depressive episode in the course of BD. Early and recent stressful life events were scored on the Social Readjustment Rating Scale (SRRS). Regional gray matter (GM) volumes were analyzed, acquiring T1‐weighted images on a 3.0 Tesla scanner.
Results
Homozygote l/l patients attempted suicide in a higher proportion than *s carriers. A separate‐slopes logistic regression showed a significant effect of 5‐HTTLPR on the relationship between stress, depression, and suicide among *s carriers, but not among l/l homozygotes, early stress associated with worse probability of attempting suicide and with earlier age at onset of BD. Exposure to early stress correlated with GM volumes in the right prefrontal cortex (Brodmann area 46) – again, in *s carriers only.
Conclusions
5‐HTTLPR modulated the relationship between early life stress and the core features of bipolar illness. 5‐HTTLPR*s carriers showed a higher sensitivity to the effects of stress; when exposed to low levels of early stress, they were protected against suicide in respect to l/l, but higher levels of stress progressively increased their risk of suicide and reduced the age at onset of illness.
In clinical scenarios, the use of biomedical sensors, devices and multi-parameter assessments is fundamental to provide a comprehensive portrait of patients’ state, in order to adapt and personalize ...rehabilitation interventions and support clinical decision-making. However, there is a huge gap between the potential of the multidomain techniques available and the limited practical use that is made in the clinical scenario. This paper reviews the current state-of-the-art and provides insights into future directions of multi-domain instrumental approaches in the clinical assessment of patients involved in neuromotor rehabilitation. We also summarize the main achievements and challenges of using multi-domain approaches in the assessment of rehabilitation for various neurological disorders affecting motor functions. Our results showed that multi-domain approaches combine information and measurements from different tools and biological signals, such as kinematics, electromyography (EMG), electroencephalography (EEG), near-infrared spectroscopy (NIRS), and clinical scales, to provide a comprehensive and objective evaluation of patients’ state and recovery. This multi-domain approach permits the progress of research in clinical and rehabilitative practice and the understanding of the pathophysiological changes occurring during and after rehabilitation. We discuss the potential benefits and limitations of multi-domain approaches for clinical decision-making, personalized therapy, and prognosis. We conclude by highlighting the need for more standardized methods, validation studies, and the integration of multi-domain approaches in clinical practice and research.
In this study we introduce a
consisting of air quality models operating at both the global and regional scale. The work is motivated by the fact that these different types of models treat specific ...portions of the atmospheric spectrum with different levels of detail, and it is hypothesized that their combination can generate an ensemble that performs better than mono-scale ensembles. A detailed analysis of the hybrid ensemble is carried out in the attempt to investigate this hypothesis and determine the real benefit it produces compared to ensembles constructed from only global-scale or only regional-scale models. The study utilizes 13 regional and 7 global models participating in the Hemispheric Transport of Air Pollutants phase 2 (HTAP2)-Air Quality Model Evaluation International Initiative phase 3 (AQMEII3) activity and focuses on surface ozone concentrations over Europe for the year 2010. Observations from 405 monitoring rural stations are used for the evaluation of the ensemble performance. The analysis first compares the modelled and measured power spectra of all models and then assesses the properties of the mono-scale ensembles, particularly their level of redundancy, in order to inform the process of constructing the hybrid ensemble. This study has been conducted in the attempt to identify that the improvements obtained by the hybrid ensemble relative to the mono-scale ensembles can be attributed to its hybrid nature. The improvements are visible in a slight increase of the diversity (4 % for the hourly time series, 10 % for the daily maximum time series) and a smaller improvement of the accuracy compared to diversity. Root mean square error (RMSE) improved by 13-16 % compared to G and by 2-3 % compared to R. Probability of detection (POD) and false-alarm rate (FAR) show a remarkable improvement, with a steep increase in the largest POD values and smallest values of FAR across the concentration ranges. The results show that the optimal set is constructed from an equal number of global and regional models at only 15 % of the stations. This implies that for the majority of the cases the regional-scale set of models governs the ensemble. However given the high degree of redundancy that characterizes the regional-scale models, no further improvement could be expected in the ensemble performance by adding yet more regional models to it. Therefore the improvement obtained with the hybrid set can confidently be attributed to the different nature of the global models. The study strongly reaffirms the importance of an in-depth inspection of any ensemble of opportunity in order to extract the maximum amount of information and to have full control over the data used in the construction of the ensemble.
Purpose
To investigate the potential of texture analysis applied on T2‐w and postcontrast T1‐w images acquired before radiotherapy for prostate cancer (PCa) and 12 months after its completion in ...quantitatively characterizing local radiation effect on the muscular component of internal obturators, as organs potentially involved in urinary toxicity.
Methods
T2‐w and postcontrast T1‐w MR images were acquired at 1.5 T before treatment (MRI1) and at 12 months of follow‐up (MRI2) in 13 patients treated with radiotherapy for PCa. Right and left internal obturator muscle contours were manually delineated upon MRI1 and then automatically propagated on MRI2 by an elastic registration method. Planning CT images were coregistered to both MRIs and dose maps were deformed accordingly. A high‐dose region receiving >55 Gy and a low‐dose region receiving <55 Gy were identified in each muscle volume. Eighteen textural features were extracted from each region of interest and differences between MRI1 and MRI2 were evaluated.
Results
A signal increase was highlighted in both T2‐w and T1‐w images in the portion of the obturators near the prostate, i.e., in the region receiving medium‐high doses. A change in the spatial organization was identified, as an increase in homogeneity and a decrease in contrast and complexity, compatible with an inflammatory status. In particular, the region receiving medium‐high doses presented more significant or, at least, stronger differences.
Conclusions
Texture analysis applied on T1‐w and T2‐w MR images has demonstrated its ability in quantitative evaluating radiation‐induced changes in obturator muscles after PCa radiotherapy.
NdxAE2-xMnO4±δ (AE: Ca, Sr) manganites with x = 0.25, 0.4, 0.5 and 0.60 are part of the Ruddlesden-Popper family of generic formula An+1BnO3n+1 with n = 1. The compositions range that can be ...successfully synthesized by the sol-gel method in air has been identified. While Sr compounds are stable in reducing atmosphere (3% H2/Ar - 850 °C/16 h), Ca ones decompose when submitted to such atmosphere. Nd0.5Sr1.5MnO4±δ was analyzed by High-Temperature X-ray diffraction (HT-XRD) showing TEC values of 12.7 × 10−6 K−1 and 14.4 × 10−6 K−1 in air and 3% H2/N2 (25–800 °C), respectively. Using standard conditions for electrode elaboration, the material reacts with YSZ electrolyte, but is chemically compatible with GDC electrolyte. A small polaron-type behavior is observed for the electrical conductivity of Nd0.5Sr1.5MnO4±δ in air and 3% H2/Ar, with respective values of 33.4 S cm−1 and 0.9 S cm−1 at 800 °C, meeting the preliminary requirements for use as symmetrical SOFC electrode.
•Ruddlesden Popper NdxSr2-xMnO4±δ are stable as S-SOFC electrode for 0.4 ≤ x ≤ 0.6.•RP NdxCa2-xMnO4±δ decompose in reducing atmosphere characteristic of SOFC anode.•Nd0.5Sr1.5MnO4±δ (NSM) is thermomechanically and chemically compatible with GDC.•NSM conductivity values in air and 3% H2/Ar are 33.4 and 0.9 S cm−1 at 800 °C.
The aim of the current study was to identify quality indicators of fat (14.50 ± 0.75%) and low‐fat (4.79 ± 0.63%) raw ground beef by monitoring changes in physicochemical and microbiological ...parameters during aerobic refrigerated storage, such as water‐holding capacity, pH, thiols, carbonyl compounds, thiobarbituric acid reactive substances (TBARS), metmyoglobin, deoxymyoglobin, oxymyoglobin color indices, pseudomonads, Brochothrix thermosphacta, and total viable counts. Meat packaged in air‐permeable polyethylene plastic film was stored under controlled isothermal conditions (0, 5, 10, and 15 °C). A population level of pseudomonads equal to 7.0 ± 0.5 log10 colony forming units (CFU)/g was considered as the potential spoilage level. Using principal component analysis, samples were distinguished on the basis of their microbial load. A significant positive correlation between microbial population and carbonyls, metmyoglobin, TBARS, water‐holding capacity, and a negative correlation with thiols and color parameters (L*, chroma) were observed. Two different approaches were followed to estimate the quality status of samples: (i) the partial least square (PLS) regression with R2 of 0.93 and root mean square error prediction of 0.44 for pseudomonads, using the above physicochemical characteristics as the dominant input variables, which allowed prediction of the microbiological status of ground beef regardless of time–temperature storage profile and fat content, and (ii) a square‐root‐type model (adjusted R2 of 0.952) that satisfactorily predicted the growth of spoilage pseudomonads under isothermal and dynamic conditions, regardless of the above physicochemical changes. The above results suggest that depending on the available input data, the two modeling approaches can accurately (and complementarily) assess quality of aerobically stored ground beef.
Practical Application
Changes in appearance and quality of fat and low‐fat raw ground beef are associated with physicochemical alteration and/or microbial growth. The study provides two different modeling approaches that can be integrated in an intelligent interface of the refrigerator having specific colorimetric and/or temperature sensors, to evaluate in a convenience way the quality of stored meat thus reducing domestic waste: the partial least square model was based on physicochemical parameters (particularly chroma, metmyoglobin, and thiobarbituric acid reactive substances), while the square root model was based on the time–temperature conditions during storage.
The present study aims to understand the influence of a reduced amount of straw litter on goats’ lying comfort and hygienic characteristics of milk and straw. Lying behaviour (frequency, lying ...posture, location and social context) of 24 Alpine goats subjected to two different straw treatments (Regular: 2 kg/straw/head + 1 kg straw/head/day, n = 12; Scarce: 1 kg straw/head + 0.5 kg straw/head/day, n = 12) was observed from video recordings using a scan sampling method at 15-min scan intervals in March 2017. Moreover, straw and milk samples were submitted to microbiological analysis for the detection of total bacteria (SPC) and Enterobacteriaceae count. No significant differences in the duration of lying were observed between treatments, except at the beginning of the experimental period (Day 1: Regular: 26.0%; Scarce: 20.3% of scans; p < .05). In both treatments lying behaviour followed the normal lying patterns for goats, with a preference for sternal lying (99.4% of scans), in contact with a pen wall (78.2% of scans) and not in contact with other goats (alone: 79.7% of scans). Milk and straw SPC and Enterobacteriaceae count were not affected by the treatment. This preliminary study suggests the possibility to reduce the amount of straw as bedding material in goat farms, without affecting animal welfare and microbiological characteristics of milk and straw litter. However, further studies are required to confirm these results under different climatic conditions.HighlightsReducing the amount of straw bedding does not affect goats’ comfortMicrobiological characteristics of milk and straw are not affected by the amount of straw beddingProvided that a daily addition is guaranteed, it seems possible to reduce management costs by reducing the amount of straw as bedding material
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