Exploring asymmetry induced entropy in tetraalkylammonium-urea DES systems: what can be learned from inelastic neutron scattering?

In this work, inelastic neutron scattering (INS) spectroscopy is used to investigate the impact of entropic factors on the behaviour of deep eutectic solvents (DES). Periodic density functional theory calculations (DFT) provide a reliable assignment of the vibrational modes of pure compounds. This assignment guides the analysis of INS spectra of binary mixtures - with particular attention to methyl torsional modes. Deviations from ideality in the mixtures of tetraalkylammonium salts with urea are readily determined through a simplified thermodynamic approach. This study reports and discusses the relationship between the cation's asymmetry, the INS spectra of the eutectic mixture and its deviation from ideality. Contrary to the majority of systems studied so far, the deep eutectic system comprised of [N2,2,2,1]Cl and urea appears to owe its deviation from ideality to entropic rather than enthalpic factors.

Meta-analysis of livestock effects on tree regeneration in oak agroforestry systems.

Livestock grazing occupies over a quarter of terrestrial land and is prevalent to agroforestry ecosystems, potentially affecting the survival, growth, and density of trees' early developmental stages, such as seeds, seedlings, and saplings. To address the effects of livestock on tree recruitment in the face of ongoing debates about their impacts, we conducted a 33-year meta-analysis in Quercus-dominated agroforestry systems. Our analysis revealed a consistently negative effect of livestock on oak acorns, seedlings, and saplings. Significantly, livestock body size influenced oak regeneration, with small-sized livestock, notably sheep and goats, having a more pronounced negative impact compared to mixed-size systems, mainly involving cattle and sheep. The effects of small-sized livestock were markedly detrimental on acorn survival and seedling/sapling density, although no studies eligible for meta-analysis examined large livestock impacts on acorns. Overall, mixed-size livestock systems, often involving cattle and sheep, lessen the negative effects. Our findings indicate that the body size and foraging behaviors of livestock should be considered for the ecological sustainability of the tree component in agroforestry systems. While protective measures have long been integral to well-managed agroforestry systems, our results underscore the importance of integrating diverse livestock sizes and applying specific protective strategies, particularly for acorns and saplings, to further refine these practices. Future research should expand to underrepresented regions and livestock types to refine global agroforestry management practices.

Intermolecular Interactions in 3-Aminopropyltrimethoxysilane, N-Methyl-3-aminopropyltrimethoxysilane and 3-Aminopropyltriethoxysilane: Insights from Computational Spectroscopy.

In this work, a computational spectroscopy approach was used to provide a complete assignment of the inelastic neutron scattering spectra of three title alkoxysilane derivatives-3-aminopropyltrimethoxysilane (APTS), N-methyl-3-aminopropyltrimethoxysilane (MAPTS), and 3-aminopropyltriethoxysilane (APTES). The simulated spectra obtained from density functional theory (DFT) calculations exhibit a remarkable match with the experimental spectra. The description of the experimental band profiles improves as the number of molecules considered in the theoretical model increases, from monomers to trimers. This highlights the significance of incorporating non-covalent interactions, encompassing classical NH···N, N-H···O, as well as C-H···N and C-H···O hydrogen bond contacts, to achieve a comprehensive understanding of the system. A distinct scenario emerges when considering optical vibrational techniques, infrared and Raman spectroscopy. In these instances, the monomer model provides a reasonable description of the experimental spectra, and no substantial alterations are observed in the simulated spectra when employing dimer and trimer models. This observation underscores the distinctive ability of neutron spectroscopy in combination with DFT calculations in assessing the structure and dynamics of molecular materials.

Neutron and Gamma-Ray Detection System Coupled to a Multirotor for Screening of Shipping Container Cargo.

In order to detect special nuclear materials and other radioactive materials in Security and Defense scenarios, normally, a combination of neutron and gamma-ray detection systems is used. In particular, to avoid illicit traffic of special nuclear materials and radioactive sources/materials, radiation portal monitors are placed at seaports to inspect shipping-container cargo. Despite their large volume (high efficiency), these detection systems are expensive, and therefore only a fraction of these containers are inspected. In this work, a novel mobile radiation detection system is presented, based on an EJ-200 plastic scintillator for the detection of gamma rays and beta particles, and a neutron detector EJ-426HD plastic scintillator (with 6Li) embedded in a compact and modular moderator. The use of silicon photomultipliers in both detectors presented advantages such as lightweight, compactness, and low power consumption. The developed detection system was integrated in a highly maneuverable multirotor. Monte Carlo simulations were validated by laboratory measurements and field tests were performed using real gamma-ray and neutron sources. The detection and localization within one meter was achieved using a maximum likelihood estimation algorithm for 137Cs sources (4 MBq), as well as the detection of 241Am-beryllium (1.45 GBq) source placed inside the shipping container.

Structural Dynamics of Chloromethanes through Computational Spectroscopy: Combining INS and DFT.

In this work, the structural dynamics of the chloromethanes CCl4, CHCl3 and CH2Cl2 were evaluated through a computational spectroscopy approach by comparing experimental inelastic neutron scattering (INS) spectra with the corresponding simulated spectra obtained from periodic DFT calculations. The overall excellent agreement between experimental and calculated spectra allows a confident assignment of the vibrational features, including not only the molecular fundamental modes but also lattice and combination modes. In particular, an impressive overtone sequence for CHCl3 is fully described by the simulated INS spectrum. In the CCl4 spectrum, the splitting of the ν3 mode at ca. 765-790 cm-1 is discussed on the basis of the Fermi resonance vs. crystal splitting controversy.

Colored Texture Analysis Fuzzy Entropy Methods with a Dermoscopic Application.

Texture analysis is a subject of intensive focus in research due to its significant role in the field of image processing. However, few studies focus on colored texture analysis and even fewer use information theory concepts. Entropy measures have been proven competent for gray scale images. However, to the best of our knowledge, there are no well-established entropy methods that deal with colored images yet. Therefore, we propose the recent colored bidimensional fuzzy entropy measure, FuzEnC2D, and introduce its new multi-channel approaches, FuzEnV2D and FuzEnM2D, for the analysis of colored images. We investigate their sensitivity to parameters and ability to identify images with different irregularity degrees, and therefore different textures. Moreover, we study their behavior with colored Brodatz images in different color spaces. After verifying the results with test images, we employ the three methods for analyzing dermoscopic images of malignant melanoma and benign melanocytic nevi. FuzEnC2D, FuzEnV2D, and FuzEnM2D illustrate a good differentiation ability between the two-similar in appearance-pigmented skin lesions. The results outperform those of a well-known texture analysis measure. Our work provides the first entropy measure studying colored images using both single and multi-channel approaches.

State-of-the-Art Mobile Radiation Detection Systems for Different Scenarios.

In the last decade, the development of more compact and lightweight radiation detection systems led to their application in handheld and small unmanned systems, particularly air-based platforms. Examples of improvements are: the use of silicon photomultiplier-based scintillators, new scintillating crystals, compact dual-mode detectors (gamma/neutron), data fusion, mobile sensor networks, cooperative detection and search. Gamma cameras and dual-particle cameras are increasingly being used for source location. This study reviews and discusses the research advancements in the field of gamma-ray and neutron measurements using mobile radiation detection systems since the Fukushima nuclear accident. Four scenarios are considered: radiological and nuclear accidents and emergencies; illicit traffic of special nuclear materials and radioactive materials; nuclear, accelerator, targets, and irradiation facilities; and naturally occurring radioactive materials monitoring-related activities. The work presented in this paper aims to: compile and review information on the radiation detection systems, contextual sensors and platforms used for each scenario; assess their advantages and limitations, looking prospectively to new research and challenges in the field; and support the decision making of national radioprotection agencies and response teams in respect to adequate detection system for each scenario. For that, an extensive literature review was conducted.

Synthesis and Biological Evaluation of 99mTc(I) Tricarbonyl Complexes Dual-Targeted at Tumoral Mitochondria.

For effective Auger therapy of cancer, the Auger-electron emitters must be delivered to the tumor cells in close proximity to a radiosensitive cellular target. Nuclear DNA is considered the most relevant target of Auger electrons to have augmented radiotoxic effects and significant cell death. However, there is a growing body of evidence that other targets, such as the mitochondria, could be relevant subcellular targets in Auger therapy. Thus, we developed dual-targeted 99mTc(I) tricarbonyl complexes containing a triphenylphosphonium (TPP) moiety to promote accumulation of 99mTc in the mitochondria, and a bombesin peptide to provide specificity towards the gastrin releasing peptide receptor (GRPr) overexpressed in prostate cancer cells. The designed dual-targeted complex, 99mTc-TPP-BBN, is efficiently internalized by human prostate cancer PC3 cells through a specific GRPr-mediated mechanism of uptake. Moreover, the radioconjugate provided an augmented accumulation of 99mTc in the mitochondria of the target tumor cells, most probably following its intracellular cleavage by cathepsin B. In addition, 99mTc-TPP-BBN showed an enhanced ability to reduce the survival of PC3 cells, in a dose-dependent manner.

Image quality of compressive single-pixel imaging using different Hadamard orderings.

Single-pixel imaging is an imaging technique that has recently attracted a lot of attention from several areas. This paper presents a study on the influence of the Hadamard basis ordering on the image reconstruction quality, using simulation and experimental methods. During this work, five different orderings, Natural, Walsh, Cake-cutting, High Frequency and Random orders, along with two different reconstruction algorithms, TVAL3 and NESTA, were tested. Also, three different noise levels and compression ratios from 0.1 to 1 were evaluated. A single-pixel camera was developed using a digital micromirror device for the experimental phase. For a compression ratio of 0.1, the Cake-cutting order achieved the best reconstruction quality, while the best contrast was achieved by Walsh order. For compression ratios of 0.5, the Walsh and Cake-cutting orders achieved similar results. Both Walsh and Cake-cutting orders reconstructed the images with good quality using compression ratios from 0.3. Finally, the TVAL3 algorithm showed better image reconstruction quality, in comparison with NESTA, when considering compression ratios from 0.1 to 0.5.

Probing the relevance of MoO2 nanoparticles' synthesis on their catalytic activity by inelastic neutron scattering.

Nanosized MoO2 can be prepared by different protocols, which yield different morphologies of the nanoparticles. Among their many properties, they can serve as catalysts for styrene oxidation (among other olefins), which is an industrially relevant transformation. In this work, we prepared MoO2 nanosized catalysts by two slightly different hydrothermal protocols using ethylenediamine and either Fe2O3 or hydroquinone. When used in catalysis, kinetic data evidenced that depending on the synthesis protocol of MoO2, induction periods occur (for the catalyst prepared with hydroquinone) with obvious different kinetic profiles and, in addition, product selectivity was also affected. To gain some insight on what is behind these results of the catalytic activity, a combined approach of studies has been conducted. DRIFT and inelastic neutron scattering (INS) techniques were used to assess the adsorbed species at the surface of both the fresh (DRIFT and INS) and recovered (INS) catalysts. Results from this study showed that when hydroquinone was used, an organic shell coated the MoO2 nanoparticles, which negatively influenced the catalytic performance.

Performance Analysis of Geiger-Müller and Cadmium Zinc Telluride Sensors Envisaging Airborne Radiological Monitoring in NORM Sites.

Radiological monitoring is fundamental for compliance with radiological protection policies in the aftermath of radiological events, such as nuclear accidents, terrorism, and out-of-commission uranium mines. An effective strategy for radiation monitoring is to use radiation detectors coupled with Unmanned Aerial Vehicles (UAVs), enabling for quicker surveillance of large areas without involving the need of human presence in the target area. The main aim of this study was to formulate the parameters for a UAV flight strategy in preparation for future field measurements using Geiger-Muller Counters (GMC) and Cadmium Zinc Telluride (CZT) spectrometers. As a proof of concept, the prepared flight strategy will be used to survey out-of-commission uranium mines in northern Portugal. Procedures to assure the calibration of the CZT and verification of the GMCs were conducted, as well as a sensitivity analysis of the sensors considering different acquisition times, distance to source, and detector response time. This article reports specific parameters, such as UAV distance to ground, time of exposition, speed, and the methodology to perform the identification and calculate the activity of possible radioactive sources. An effective flight strategy is also presented, aiming to use radiation detectors coupled with UAVs to undertake extensive monitoring of areas with enhanced levels of environmental radiation, which is of prime importance due to the lasting hazardous effects of enhanced environmental radiation in the nearby ecosystem and population.

Multifactorial Scores and Biomarkers of Prognosis of Acute Pancreatitis: Applications to Research and Practice.

Acute pancreatitis (AP) is a severe inflammation of the pancreas presented with sudden onset and severe abdominal pain with a high morbidity and mortality rate, if accompanied by severe local and systemic complications. Numerous studies have been published about the pathogenesis of AP; however, the precise mechanism behind this pathology remains unclear. Extensive research conducted over the last decades has demonstrated that the first 24 h after symptom onset are critical for the identification of patients who are at risk of developing complications or death. The identification of these subgroups of patients is crucial in order to start an aggressive approach to prevent mortality. In this sense and to avoid unnecessary overtreatment, thereby reducing the financial implications, the proper identification of mild disease is also important and necessary. A large number of multifactorial scoring systems and biochemical markers are described to predict the severity. Despite recent progress in understanding the pathophysiology of AP, more research is needed to enable a faster and more accurate prediction of severe AP. This review provides an overview of the available multifactorial scoring systems and biochemical markers for predicting severe AP with a special focus on their advantages and limitations.

Evaluation of Prognostic Factors of Severity in Acute Biliary Pancreatitis.

Acute pancreatitis (AP) is an inflammatory disorder of the pancreas that, when classified as severe, is associated with high morbidity and mortality. Promptly identifying the severity of AP is of extreme importance for improving clinical outcomes. The aim of this study was to compare the prognostic value of serological biomarkers, ratios, and multifactorial scores in patients with acute biliary pancreatitis and to identify the best predictors. In this observational and prospective study, the biomarkers, ratios and multifactorial scores were evaluated on admission and at 48 h of the symptom onset. On admission, regarding the AP severity, the white blood count (WBC) and neutrophil-lymphocyte ratio (NLR), and regarding the mortality, the WBC and the modified Marshall score (MMS) showed the best predictive values. At 48 h, regarding the AP severity, the hepcidin, NLR, systemic inflammatory response index (SIRI) and MMS and regarding the mortality, the NLR, hepcidin and the bedside index for severity in AP (BISAP) score, showed the best predictive values. The present study enabled the identification, for the first time, of SIRI as a new prognostic tool for AP severity, and validated hepcidin and the NLR as better prognostic markers than C-reactive protein (CRP) at 48 h of symptom onset.

Vibrational Dynamics of Crystalline 4-Phenylbenzaldehyde from INS Spectra and Periodic DFT Calculations.

The present work emphasizes the value of periodic density functional theory (DFT) calculations in the assessment of the vibrational spectra of molecular crystals. Periodic calculations provide a nearly one-to-one match between the calculated and observed bands in the inelastic neutron scattering (INS) spectrum of crystalline 4-phenylbenzaldehyde, thus validating their assignment and correcting previous reports based on single molecule calculations. The calculations allow the unambiguous assignment of the phenyl torsional mode at ca. 118-128 cm-1, from which a phenyl torsional barrier of ca. 4000 cm-1 is derived, and the identification of the collective mode involving the antitranslational motion of CH···O bonded pairs, a hallmark vibrational mode of systems where C-H···O contacts are an important feature.

Understanding the Structure and Dynamics of Nanocellulose-Based Composites with Neutral and ionic Poly(methacrylate) Derivatives using Inelastic Neutron Scattering and DFT Calculations.

Bacterial nanocellulose (BC)-based composites containing poly(2-hydroxyethyl methacrylate) (PHEMA), poly(methacroylcholine chloride) (PMACC) or poly(methacroylcholine hydroxide) (PMACH) were characterized by inelastic neutron scattering (INS) spectroscopy, combined with DFT (density functional theory) calculations of model systems. A reasonable match between calculated and experimental spectral lines and their intensities was used to support the vibrational assignment of the observed bands and to validate the possible structures. The differences between the spectra of the nanocomposites and the pure precursors indicate that interactions between the components are stronger for the ionic poly(methacrylate) derivatives than for the neutral counterpart. Displaced anions interact differently with cellulose chains, due to the different ability to compete with the O-H···O hydrogen bonds in cellulose. Hence, the INS is an adequate technique to delve deeper into the structure and dynamics of nanocellulose-based composites, confirming that they are true nanocomposite materials instead of simple mixtures of totally independent domains.

Dosimetric assessment of the exposure of radiotherapy patients due to cone-beam CT procedures.

Cone-beam computed tomography (CBCT) is widely used for pre-treatment verification and patient setup in image-guided radiation therapy (IGRT). CBCT imaging is employed daily and several times per patient, resulting in potentially high cumulative imaging doses to healthy tissues that surround exposed target organs. Computed tomography dose index (CTDI) is the parameter used by CBCT equipment as indication of the radiation output to patients. This study aimed to increase the knowledge on the relation between CBCT organ doses and weighted CTDI (CTDIW) for a thorax scanning protocol. A CBCT system was modelled using the Monte Carlo (MC) radiation transport program MCNPX2.7.0. Simulation results were validated against half-value layer (HVL), axial beam profile, patient skin dose (PSD) and CTDI measurements. For organ dose calculations, a male voxel phantom ("Golem") was implemented with the CBCT scanner computational model. After a successful MC model validation with measurements, a systematic comparison was performed between organ doses (and their distribution) and CTDI dosimetry concepts [CTDIW and cumulative dose quantities f100(150) and [Formula: see text]]. The results obtained show that CBCT organ doses vary between 1.2 ± 0.1 mGy and 3.3 ± 0.2 mGy for organs located within the primary beam. It was also verified that CTDIW allows prediction of absorbed doses to tissues at distances of about 5 cm from the isocentre of the CBCT system, whereas f100(150) allows prediction of organ doses at distances of about 10 cm from the isocentre, independently from its location. This study demonstrates that these dosimetric concepts are suitable methods that easily allow a good approximation of the additional CBCT imaging doses during a typical lung cancer IGRT treatment.

Murine Models of Acute Pancreatitis: A Critical Appraisal of Clinical Relevance.

Acute pancreatitis (AP) is a severe disease associated with high morbidity and mortality. Clinical studies can provide some data concerning the etiology, pathophysiology, and outcomes of this disease. However, the study of early events and new targeted therapies cannot be performed on humans due to ethical reasons. Experimental murine models can be used in the understanding of the pancreatic inflammation, because they are able to closely mimic the main features of human AP, namely their histologic glandular changes and distant organ failure. These models continue to be important research tools for the reproduction of the etiological, environmental, and genetic factors associated with the pathogenesis of this inflammatory pathology and the exploration of novel therapeutic options. This review provides an overview of several murine models of AP. Furthermore, special focus is made on the most frequently carried out models, the protocols used, and their advantages and limitations. Finally, examples are provided of the use of these models to improve knowledge of the mechanisms involved in the pathogenesis, identify new biomarkers of severity, and develop new targeted therapies.

Impact of culvert flooding on carnivore crossings.

Along many roads worldwide, drainage culverts are the only structures wildlife can safely use to cross. However, culverts inundate and can become unavailable to terrestrial fauna during rainy periods. We conducted a field study over wet and dry seasons in southern Portugal to assess the effect of culvert flooding on crossings by medium-sized carnivores. We set up track stations inside 30 culverts along intermediate-level traffic roads to evaluate complete crossings (n = 1211) and used mixed-effects models to quantify the effects. Carnivores were more likely to cross and crossed more frequently if the culvert had a natural dry pathway at the time of the crossing. Carnivores were also more likely to cross culverts with streams running through them. Moreover, culverts with flowing streams during the wet season were still more likely to be crossed during the dry season when the streams were dry. The significance of the difference in crossing rates between wet and dry seasons was species-specific. Our study reveals that flowing water and dry pathways jointly contribute to promoting crossings by this carnivore community. Culverts including streams may act as a continuation of riparian corridors, being incorporated into carnivores' movement routes. Our results lend empirical support to recommendations advising the implementation of dry pathways to provide crossing paths. Interventions to offset the transient impacts of water flooding in new or existing culverts can be a cost-effective solution promoting connectivity across roads allowing movement of individuals.

Unravelling associations between tree-seedling performance, herbivory, competition, and facilitation in high nature value farmlands.

Herbivory, plant facilitation, and competition have complex impacts on tree regeneration which are seldom investigated together. Grazing exclosure experiments have allowed quantification of the effects of large herbivores on tree regeneration dynamics but have often ignored the effect of herbivorous insects. We experimentally tested how folivory (percentage of leaf damaged by insects) and microenvironment (tree canopy cover and herbs) jointly alter performance (growth and survival) of seedlings of two dominant Mediterranean oak-species within ungulate exclosures in a 3-year field study. An agroforestry system dominated by cork oak (Quercus suber) and holm oak (Q. rotundifolia) was assessed in south-east Portugal. We aimed also to determine whether the two oak species differed in the interdependences between folivory, microenvironment, covaring factors, and seedling performance. Unexpectedly, under the low-moderate insect defoliation, growth and survival of cork and holm oak seedlings were positively associated with herbivore damage. Herb removal increased oak folivory by 1.4 times. Herb removal was also positively associated with growth, directly and indirectly through its negative effect on oak folivory. Tree canopy favored insect folivory upon cork oak seedlings directly and upon holm oak indirectly via decreasing light availability. Folivory was threefold greater upon cork than upon holm oak-seedlings. Our study shows that tree canopy, herbs, and covarying factors can affect cork and holm oak-seedling performances through complex pathways, which markedly differ for the two species. The combined effect of insect herbivory and positive and negative plant-plant interactions need to be integrated into future tree regeneration efforts toward tackling the regeneration crisis of oak agroforestry systems of the Mediterranean.

Looking inside the pores of a MCM-41 based Mo heterogeneous styrene oxidation catalyst: an inelastic neutron scattering study.

Styrene oxidation mediated by a Mo-based mesoporous catalyst can yield selectively styrene oxide or benzaldehyde. Kinetic data evidenced that styrene oxide is the initial single-product formed by the catalytic Mo-mediated process. However, after some hours of reaction benzaldehyde yield rises while that of the epoxide decreases concomitantly. The mechanistic proposal pointed to a surface assisted acid-base mechanism by which styrene oxide is interconverted into benzaldehyde through over-oxidation and cleavage of the C-C bond and releases formaldehyde as well. In an attempt to gain some insight into whether this mechanistic proposal is realistic we have conducted a combined DRIFT and inelastic neutron scattering (INS) study to assess the adsorbed species at the catalyst's surface and confirm the mechanistic proposal. INS and DRIFT provided complementary insight into surface-adsorbed species by probing donor (INS) and acceptor (DRIFT) species. INS also allowed for an estimation of product selectivity by means of a Job method stressing the power of the technique.