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Tailored light-matter interactions in the strong coupling regime enable the manipulation and control of quantum systems with up to unit efficiency 1,2 , with applications ranging from quantum information to photochemistry 3-7 . Although strong light-matter interactions are readily induced at the valence electron level using long-wavelength radiation 8 , comparable phenomena have been only recently observed with short wavelengths, accessing highly excited multi-electron and inner-shell electron states 9,10 . However, the quantum control of strong-field processes at short wavelengths has not been possible, so far, because of the lack of pulse-shaping technologies in the extreme ultraviolet (XUV) and X-ray domain. Here, exploiting pulse shaping of the seeded free-electron laser (FEL) FERMI, we demonstrate the strong-field quantum control of ultrafast Rabi dynamics in helium atoms with high fidelity. Our approach reveals a strong dressing of the ionization continuum, otherwise elusive to experimental observables. The latter is exploited to achieve control of the total ionization rate, with prospective applications in many XUV and soft X-ray experiments. Leveraging recent advances in intense few-femtosecond to attosecond XUV to soft X-ray light sources, our results open an avenue to the efficient manipulation and selective control of core electron processes and electron correlation phenomena in real time., Competing Interests: Competing interests: The authors declare no competing interests., (© 2024. The Author(s).)

Historic gardens are green spaces characterised by tree stands with several veteran specimens of high artistic and cultural value. Such valuable plant components have to cope with biotic and abiotic stress factors as well as ongoing senescence processes. Maintaining tree health is therefore crucial to preserve their ecosystem services, but also to protect the monument and visitor health. In this context, finding smart, fast and cost-effective management solutions to monitor health and detect critical conditions for both stands and individual veteran trees can promote garden conservation. For this reason, we developed a novel framework based on Sentinel2 imagery, LiDAR sources and automatic cameras to identify risk spots regarding trees in historic gardens. The pilot study area consists of two closed Italian gardens from the 16th century, which were analysed as a unique Historic Garden System (HGS). The tree health status at stand level was assessed using a criterion based on the Normalized Difference Vegetation Index weighed on tree volume (NDVI t ) and validated by a visual crown defoliation assessment. At the tree level, the health status of four veteran trees defined by the NDVI t was also evaluated using green chromatic coordinates (GCC) obtained from digital images acquired by cameras at daily intervals during one growing season. The 33% of the tree population was classified as being in poor health, i.e. "at risk". Veteran trees classified as "at risk" showed an anticipation of phenological phases and a lower GCC compared to reference trees. Despite variability determined by Sentinel medium resolution, the proposed framework showed good accuracy (0.74) for monitoring historical gardens. The semi-automatic risk point mapping system tested here proved to be effective in facilitating the management of historic gardens, which in turn could be applied in the wider context of urban greening., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

The electric dipoles of proteins in a biolayer determine their dielectric properties through the polarization density P. Hence, its reproducibility is crucial for applications, particularly in bioelectronics. Biolayers encompassing capturing antibodies covalently bound at a biosensing interface are generally preferred for their assumed higher stability. However, surface physisorption is shown to offer advantages like easily scalable fabrication processes and high stability. The present study investigates the effects of electric-field (EF)-cycling of anti-Immunoglobulin M (anti-IgM) biolayers physisorbed on Au. The impact of EF-cycling on the dielectric, optical, and mechanical properties of anti-IgM biolayer is investigated. A reduction of the dispersion (standard deviation over a set of 31 samples) of the measured P values is observed, while the set median stays almost constant. Hence, physisorption combined with EF cycling, results in a biolayer with highly reproducible bioelectronic properties. Additionally, the study provides important insights into the mechanisms of dielectric rearrangement of dipole moments in capturing biolayers after EF-cycling. Notably, EF-cycling acts as an annealing process, driving the proteins in the biolayer into a statistically more probable and stable conformational state. Understanding these phenomena enhances the knowledge of the properties of physisorbed biolayers and can inform design strategies for bioelectronic devices., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Among bacteria used as anticancer vaccines, attenuated Listeria monocytogenes (Lm at ) stands out, because it spreads from one infected cancer cell to the next, induces a strong adaptive immune response, and is suitable for repeated injection cycles. Here, we use click chemistry to functionalize the Lm at cell wall and turn the bacterium into an "intelligent carrier" of the chemotherapeutic drug doxorubicin. Doxorubicin-loaded Lm at retains most of its biological properties and, compared to the control fluorophore-functionalized bacteria, shows enhanced cytotoxicity against melanoma cells both in vitro and in a xenograft model in zebrafish. Our results show that drugs can be covalently loaded on the Lm at cell wall and pave the way to the development of new two-in-one therapeutic approaches combining immunotherapy with chemotherapy.

The light-induced ultrafast switching between molecular isomers norbornadiene and quadricyclane can reversibly store and release a substantial amount of chemical energy. Prior work observed signatures of ultrafast molecular dynamics in both isomers upon ultraviolet excitation but could not follow the electronic relaxation all the way back to the ground state experimentally. Here we study the electronic relaxation of quadricyclane after exciting in the ultraviolet (201 nanometres) using time-resolved gas-phase extreme ultraviolet photoelectron spectroscopy combined with non-adiabatic molecular dynamics simulations. We identify two competing pathways by which electronically excited quadricyclane molecules relax to the electronic ground state. The fast pathway (<100 femtoseconds) is distinguished by effective coupling to valence electronic states, while the slow pathway involves initial motions across Rydberg states and takes several hundred femtoseconds. Both pathways facilitate interconversion between the two isomers, albeit on different timescales, and we predict that the branching ratio of norbornadiene/quadricyclane products immediately after returning to the electronic ground state is approximately 3:2., (© 2024. The Author(s).)

Purpose: To prove the safety and performance of the hypothermic corneal storage medium "Corneal Chamber" and the rinsing solution "PSS-L" in support of the new Conformité Européenne (CE) certification process in accordance with the Medical Device Regulation., Methods: Fifteen (n=15) human donor corneas and 11 (n=11) porcine corneas were evaluated for the following parameters: endothelial cell density (ECD) and mortality, percentage of hexagonal cells (HEX%), coefficient of cellular area variation (CV%) and corneal transparency at Day 0 and after 14±1 days of storage in Corneal Chamber medium at 2-8°C. Then, the same parameters were assessed after rinsing of corneas in PSS-L for 1 min at room temperature. Evaluation of gentamicin sulfate carryover after corneal storage and PSS-L rinsing was performed by ultra-high performance liquid chromatography analysis on human corneas homogenates., Results: Human and porcine corneas stored in Corneal Chamber medium showed a good overall quality of the tissue according to the quality parameters evaluated. In particular, mean ECD, HEX% and CV% did not show statistically significant changes at the end of storage and endothelial mortality increased to 3.1±3.3 and 7.8±3.5% in human and porcine corneas, respectively. Tissue rinsing with PSS-L did not affect the quality parameters evaluated before and gentamicin sulfate residues were absent in human corneas., Conclusions: Corneal preservation in Corneal Chamber medium at 2-8°C for 14 days and the corneal rinse with PSS-L are safe and effective procedures allowing the preservation of the corneal quality parameters as well as the complete elimination of gentamicin sulfate from the tissues before transplantation.Cite Now., Competing Interests: Competing interests: LG, UR, CG, OR and JDT are employees of AL.CHI.MI.A. S.R.L. ER was consulted by AL.CHI.MI.A. S.R.L. for the purpose of conducting statistical analysis., (© Author(s) (or their employer(s)) 2024. Re-use permitted under CC BY-NC. No commercial re-use. See rights and permissions. Published by BMJ.)

The absolute photoabsorption cross sections of norbornadiene (NBD) and quadricyclane (QC), two isomers with chemical formula C7H8 that are attracting much interest for solar energy storage applications, have been measured from threshold up to 10.8 eV using the Fourier transform spectrometer at the SOLEIL synchrotron radiation facility. The absorption spectrum of NBD exhibits some sharp structure associated with transitions into Rydberg states, superimposed on several broad bands attributable to valence excitations. Sharp structure, although less pronounced, also appears in the absorption spectrum of QC. Assignments have been proposed for some of the absorption bands using calculated vertical transition energies and oscillator strengths for the electronically excited states of NBD and QC. Natural transition orbitals indicate that some of the electronically excited states in NBD have a mixed Rydberg/valence character, whereas the first ten excited singlet states in QC are all predominantly Rydberg in the vertical region. In NBD, a comparison between the vibrational structure observed in the experimental 11B1-11A1 (3sa1 ← 5b1) band and that predicted by Franck-Condon and Herzberg-Teller modeling has necessitated a revision of the band origin and of the vibrational assignments proposed previously. Similar comparisons have encouraged a revision of the adiabatic first ionization energy of NBD. Simulations of the vibrational structure due to excitation from the 5b2 orbital in QC into 3p and 3d Rydberg states have allowed tentative assignments to be proposed for the complex structure observed in the absorption bands between ∼5.4 and 7.0 eV., (© 2024 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).)

Hypothesis: Implementation of tissue adhesives from natural sources endowed with good mechanical properties and underwater resistance still represents a challenging research goal. Inspired by the extraordinary wet adhesion properties of mussel byssus proteins resulting from interaction of catechol and amino residues, hydrogels from soy protein isolate (SPI) and selected polyphenols i.e. caffeic acid (CA), chlorogenic acid (CGA) and gallic acid (GA) under mild aerial oxidative conditions were prepared., Experiments: The hydrogels were subjected to chemical assays, ATR FT-IR and EPR spectroscopy, rheological and morphological SEM analysis. Mechanical tests were carried out on hydrogels prepared by inclusion of agarose. Biological tests included evaluation of the antibacterial and wound healing activity, and hemocompatibility., Findings: The decrease of free NH 2 and SH groups of SPI, the EPR features, the good cohesive strength and excellent underwater resistance (15 days for SPI/GA) under conditions relevant to their use as surgical glues indicated an efficient interaction of the polyphenols with the protein in the hydrogels. The polyphenols greatly also improved the mechanical properties of the SPI/ agarose/polyphenols hydrogels. These latter proved biocompatible, hemocompatible, not harmful to skin, displayed durable adhesiveness and good water-vapour permeability. Excellent antibacterial properties and in some cases (SPI/CGA) a favourable wound healing activity on dermal fibroblasts was obtained., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Fire represents a major threat to Mediterranean terrestrial ecosystems because of the high temperatures reached during summer. While massive loads of organic, inorganic compounds and particulate matter are known to be emitted into the atmosphere from forest wildfires, less is known about the emission from vegetation surrounding fires where air temperatures higher than 100 °C can be reached. Little information exists on the emission from dead vegetation accumulated as litter over forest soils, from which fires often starts. In this study, the response of litter to heatwaves generated by nearby fires was investigated under controlled conditions. Litter samples collected in a Mediterranean maquis and a Holm oak stand during summer were placed in an enclosure flushed with a continuous flow of air, the temperature of the enclosure was progressively risen to 125 °C, until some smog developed but no flaming occurred. The gas from the enclosure was analysed for the content of CO 2 , H 2 O, and volatile organic compounds (VOC) to assess the dependence of emission from the air temperature. VOC emission was continuously determined by Proton-Transfer-Reaction mass spectrometry with time of flight (PTR-TOF-MS). Data obtained were complemented with those obtained by collecting VOC on traps that were later analysed by Gas chromatography-mass spectrometry (GC-MS). Results provided useful information to understand the emission mechanism of VOC and other gases from dead vegetation present in the litter of two Mediterranean ecosystems, both dominated by evergreen vegetation species. The study demonstrated that low molecular weight VOC and aromatic hydrocarbons (arenes) produced mostly by thermal oxidation of the wood biopolymers are emitted in addition to isoprenoids typically associated to storage organs and photosynthetic pathway. Moreover, our results support parameterization of litter VOC emission processes in air quality models., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Silvano Fares reports financial support was provided by EU commission H2020 project., (Copyright © 2023 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Spin waves represent the collective excitations of the magnetization field within a magnetic material, providing dispersion curves that can be manipulated by material design and external stimuli. Bulk and surface spin waves can be excited in a thin film with positive or negative group velocities and, by incorporating a symmetry-breaking mechanism, magnetochiral features arise. Here we study the band diagram of a chiral magnonic crystal consisting of a ferromagnetic film incorporating a periodic Dzyaloshinskii-Moriya coupling via interfacial contact with an array of heavy-metal nanowires. We provide experimental evidence for a strong asymmetry of the spin wave amplitude induced by the modulated interfacial Dzyaloshinskii-Moriya interaction, which generates a nonreciprocal propagation. Moreover, we observe the formation of flat spin-wave bands at low frequencies in the band diagram. Calculations reveal that depending on the perpendicular anisotropy, the spin-wave localization associated with the flat modes occurs in the zones with or without Dzyaloshinskii-Moriya interaction.

One of the main challenges in the deployment of visible light communication (VLC) in realistic application fields, such as intelligent transportation systems (ITSs), is represented by the presence of large background noise levels on top of the optical signal carrying the digital information. A versatile and effective digital filtering technique is, hence, crucial to face such an issue in an effective way. In this paper, we present an extensive experimental evaluation of a complete VLC system, embedding a software-defined-radio (SDR)-based digital signal processing (DSP) filter stage, which is tested either indoors, in the presence of strong artificial 100-Hz stray illumination, and outdoors, under direct sunlight. The system employs low-power automotive LED lamps, and it is tested for baud rates up to 1 Mbaud. We experimentally demonstrate that the use of the DSP technique improves 10× the performance of the VLC receiver over the original system without the filtering stage, reporting a very effective rejection of both 100-Hz and solar noise background. Indoors, the noise margin in the presence of strong 100-Hz noise is increased by up to 40 dB, whilst in the outdoor configuration, the system is capable of maintaining error-free communication in direct sunlight conditions, up to 7.5 m, improving the distance by a factor of 1.6 compared to the case without filtering. We believe that the proposed system is a very effective solution for the suppression of various types of noise effects in a large set of VLC applications.

Endothelial cells (EC) in vivo buffer and regulate the transfer of plasma fatty acid (FA) to the underlying tissues. We hypothesize that inflammation could alter the functionality of the EC, i.e., their capacity and uptake of different FA. The aim of this work is to verify the functionality of inflamed cells by analyzing their ability to uptake and accumulate exogenous saturated FA. Control and inflammatory human microvascular endothelial cells stimulated in vitro with two deuterium-labeled saturated FA (D-FA), i.e., palmitic (D 31 -PA) and myristic (D 27 -MA) acids. Cells were measured both by spontaneous and stimulated Raman imaging to extract detailed information about uptaken FA, whereas coherent anti-Stokes Raman scattering and fluorescence imaging showed the global content of FA in cells. Additionally, we employed atomic force microscopy to obtain a morphological image of the cells. The results indicate that the uptake of D-FA in inflamed cells is dependent on their concentration and type. Cells accumulated D-FA when treated with a low concentration, and the effect was more pronounced for D 27 -MA, in normal cells, but even more so, in inflamed cells. In the case of D 31 -PA, a slightly increased uptake was observed for inflamed cells when administered at higher concentration. The results provide a better understanding of the EC inflammation and indicate the impact of the pathological state of the EC on their capacity to buffer fat. All the microscopic methods used showed complementarity in the analysis of FA uptake by EC, but each method recognized this process from a different perspective., (© 2022. The Author(s).)

In this paper, we present very recent results regarding the latency characterization of a novel bidirectional visible light communication (VLC) system for vehicular applications, which could be relevant in intelligent transportation system (ITS) safety applications, such as the assisted and automated braking of cars and motorbikes in critical situations. The VLC system has been implemented using real motorbike head- and tail-lights with distances up to 27 m in a realistic outdoor scenario. We performed a detailed statistical analysis of the observed error distribution in the communication process, assessing the most probable statistical values of expected latency depending on the observed packet error rate (PER). A minimum attainable observed round-trip latency of 2.5 ms was measured. Using our dataset, we have also estimated the probability to receive correctly a message with a specific average latency for a target PER, and we compare it to the ultra-reliable low-latency (URLL) 5G communications service. In addition, a mobility model is implemented to compare the VLC and radio frequency (RF) technologies (IEEE802.11p, LTE, 5G) to support an automated braking systems for vehicles in urban platooning.

We show that magnetic skyrmions can be stabilised at room temperature in continuous [Ir/Co/Pt] 5 multilayers on SiO 2 /Si substrates without the prior application of electric current or magnetic field. While decreasing the Co thickness, a transition of the magnetic domain patterns from worm-like state to separated stripes is observed. The skyrmions are clearly imaged in both states using magnetic force microscopy. The density of skyrmions can be significantly enhanced after applying the "in-plane field procedure". Our results provide means to manipulate magnetic skyrmion density, further allowing for the optimised engineering of skyrmion-based devices.

Ti interstitials play a key role in the surface chemistry of TiO 2 . However, because of their elusive behavior, proof of their participation in catalytic processes is difficult to obtain. Here, we used DFT+U calculations to investigate the interaction between formic acid (FA) and excess Ti atoms on the rutile-TiO 2 (110) and anatase-TiO 2 (101) surfaces. The excess Ti atoms favor FA dissociation, while decreasing the relative stability of the bidentate bridging coordination over the monodentate one. FA species interact significantly with the Ti interstitials, favoring their outdiffusion. Eventually, Ti atoms can emerge at the surface forming chelate species, which are more stable than monodentate FA species in the case of rutile, and are even energetically favored in the case of anatase. The presence of Ti adatoms that can directly participate to surface processes should then be considered when formic acid and possibly carboxylate-bearing species are adsorbed onto TiO 2 particles.

Reconfigurable magnetization textures offer control of spin waves with promising properties for future low-power beyond-CMOS systems. However, materials with perpendicular magnetic anisotropy (PMA) suitable for stable magnetization-texture formation are characterized by high damping, which limits their applicability in magnonic devices. Here, we propose to overcome this limitation by using hybrid structures, i.e., a PMA layer magnetostatically coupled to a low-damping soft ferromagnetic film. We experimentally show that a periodic stripe-domain texture from a PMA layer is imprinted upon the soft layer and induces a nonreciprocal dispersion relation of the spin waves confined to the low-damping film. Moreover, an asymmetric bandgap features the spin-wave band diagram, which is a clear demonstration of collective spin-wave dynamics, a property characteristic for magnonic crystals with broken time-reversal symmetry. The composite character of the hybrid structure allows for stabilization of two magnetic states at remanence, with parallel and antiparallel orientation of net magnetization in hard and soft layers. The states can be switched using a low external magnetic field; therefore, the proposed system obtains an additional functionality of state reconfigurability. This study offers a link between reconfigurable magnetization textures and low-damping spin-wave dynamics, providing an opportunity to create miniaturized, programmable, and energy-efficient signal processing devices operating at high frequencies.

CR4056 is an imidazoline-2 receptor ligand having potent analgesic activity and synergistic effect with opioids. Very recently it has been found that CR4056 can revert the cognitive impairment in animal models of Alzheimer's disease (AD). Since several lines of evidence highlight the importance of NMDAR modulators in nociceptive signaling and in AD progression, we considered as important to investigate the effects of CR4056 on NMDAR activity. In primary culture of cortical neurons, application of NMDA and glycine elicits a current that is decreased in a dose-dependent fashion by CR4056 (IC 50 5.3 ± 0.1 µM). CR4056 antagonism is reversible, not competitive and voltage-independent and it is not blocked by pertussis toxin. CR4056 interacts with the co-agonist glycine site in a competitive way, indeed high glycine concentrations diminish its effect. Fibroblasts expressing different recombinant NMDA receptors are differently modulated by CR4056: the potency and the efficacy of the compound are higher in GluN1- GluN2B than in GluN1-GluN2A containing receptors. In lamina II neurons of spinal cord slices, single stimulation of afferent fibers evokes an NMDA-mediated current that is inhibited by 10 µM CR4056. Repetitive stimulation of the dorsal root at high frequency and high intensity produces a firing activity that is significatively depressed by CR4056. Taken together, our results broad the understanding of the molecular mechanisms of CR4056 analgesic activity, involving the modulation of NMDAR activity. Therefore, we propose that the analgesic action of CR4056 and the neuroprotective effects in AD models may be mediated also by NMDAR inhibition., Competing Interests: Part of this research has been financially supported by Rottapharm Biotech (Monza, Italy). The funder had the following involvement with the study: contributed to the design of the experiments, and to the discussion of the results. GP and RB obtained a grant from Rottapharm Biotech. LCR, GC, and ML are affiliated to Rottapharm Biotech., (© 2022 Puja, Losi, Rovati, Lanza, Caselli and Bardoni.)

The development of skyrmionic devices requires a suitable tuning of material parameters to stabilize skyrmions and control their density. It has been demonstrated recently that different skyrmion types can be simultaneously stabilized at room temperature in heterostructures involving ferromagnets, ferrimagnets, and heavy metals, offering a new platform of coding binary information in the type of skyrmion instead of the presence/absence of skyrmions. Here, we tune the energy landscape of the two skyrmion types in such heterostructures by engineering the geometrical and material parameters of the individual layers. We find that a fine adjustment of the ferromagnetic layer thickness, and thus its magnetic anisotropy, allows the trilayer system to support either one of the skyrmion types or the coexistence of both and with varying densities.

In this work we address a specific experimental and theoretical question regarding the influence of a conformational population in the modeling of photoelectron circular dichroism (PECD) spectroscopy. In the past two decades, PECD has revealed a rich and complex phenomenology in molecular processes with unprecedented insight, especially in molecular geometry sensitivity. Since the early development of this spectroscopy, theory has pointed out the importance of conformer influence on PECD; in particular, the rotation of methyl groups was surprisingly found to be responsible for strong modulation of the PECD signal. Here, to advance understanding of the effect of rotations, we have chosen to study norcamphor, a single-conformer molecule, as a benchmark for a PECD comparison between experiment and theory at the density functional theory (DFT) and time-dependent density functional theory (TDDFT) levels. The excellent agreement between experimental data and theory for norcamphor sheds light on the influence of rotations and gives a solid explanation for the reasonable qualitative agreement in the PECD of camphor, where three methyl groups are added to the same molecular structure.

The majority of excitatory neurotransmission in vertebrate CNS is mediated by glutamate binding to different types of receptors. Among them, a-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid receptor (AMPAR) and kainite receptors (KAR) are ionotropic receptors playing important pathophysiological roles. A number of small molecules acting as positive allosteric modulators (PAM) of AMPAR have been proposed as drugs for neurological disorders, however, there is no such abundance of ligands capable of modulating KARs activity. We investigated the ability of IDRA21 and of its derivative, compound 2 (c2), to modulate glutamate-evoked currents at native and recombinantly expressed AMPA and KA receptors. By using the patch clamp technique we analyzed the activity of the two compounds in primary cultures of cerebellar granule neurons and in HEK293 cells transiently transfected with KARs and AMPAR subunits. It resulted that both benzothiadiazine derivatives potentiate AMPAR and KAR mediated currents in native and recombinant receptors, c2 being always more potent and efficacious than IDRA21. The potency of both compounds was higher in native receptors than in recombinant receptors. In HEK293 cells transfected with AMPAR subunits, the efficacy of IDRA21 and c2 was much higher in GluA1 than in GluA2 homomeric receptors while their potency did not change. In recombinant KAR, both compounds had a potency in the high micromolar range, while the efficacy reached a maximum in the GluK2 expressing cells. The benzothiadiazine effect, both in native and recombinant receptors, was detected mainly on plateau current, involving a decrease in AMPAR and KAR desensitization. Our study demonstrates for the first time that two positive allosteric modulators of AMPAR, IDRA21 and its derivative, c2, potentiate KAR activity. Furthermore, we highlighted their subunit selectivity that may enable the design of potent and selective PAMs, which could be relevant for the development of new drugs and for a better understanding of KAR functions in the CNS.

In this study, extracts from non-psychoactive Cannabis sativa L. varieties were characterized by means of ultra high-performance liquid chromatography coupled with high-resolution mass spectrometry (UHPLC-HRMS) and their antiproliferative activity was assessed in vitro. The human chronic myelogenous leukaemia cell line K562 was chosen to investigate the mechanism of cell death. The effect on the cell cycle and cell death was analysed by flow cytometry. Proteins related to apoptosis were studied by western blotting. Mechanical properties of cells were assessed using the Micropipette Aspiration Technique (MAT). The results indicated that the cannabidiol (CBD)-rich extract inhibited cell proliferation of K562 cell line in a dose-dependent manner and induced apoptosis via caspase 3 and 7 activation. A significant decrease in the mitochondrial membrane potential was detected, together with the release of cytochrome c into the cytosol. The main apoptotic markers were not involved in the mechanism of cell death. The extract was also able to modify the mechanical properties of cells. Thus, this hemp extract and its pure component CBD deserve further investigation for a possible application against myeloproliferative diseases, also in association with other anticancer drugs., (© 2022 The Authors. Phytotherapy Research published by John Wiley & Sons Ltd.)

Golgi phosphoprotein 3 (GOLPH3), a highly conserved phosphatidylinositol 4-phosphate effector, is required for maintenance of Golgi architecture, vesicle trafficking, and Golgi glycosylation. GOLPH3 overexpression has been reported in several human solid cancers, including glioblastoma, breast cancer, colorectal cancer, nonsmall cell lung cancer, epithelial ovarian cancer, prostate cancer, gastric cancer, and hepatocellular carcinoma. Although the molecular mechanisms that link GOLPH3 to tumorigenesis require further investigation, it is likely that GOLPH3 may act by controlling the intracellular movement of key oncogenic molecules, between the Golgi compartments and/or between the Golgi and the endoplasmic reticulum. Indeed, numerous evidence indicates that deregulation of intracellular vesicle trafficking contributes to several aspects of cancer phenotypes. However, a direct and clear link between extracellular vesicle movements and GOLPH3 is still missing. In the past years several lines of evidence have implicated GOLPH3 in the regulation of extracellular vesicle content. Specifically, a new role for GOLPH3 has emerged in controlling the internalization of exosomes containing either oncogenic proteins or noncoding RNAs, especially micro-RNA. Although far from being elucidated, growing evidence indicates that GOLPH3 does not increase quantitatively the excretion of exosomes, but rather regulates the exosome content. In particular, recent data support a role for GOLPH3 for loading specific oncogenic molecules into the exosomes, driving both tumor malignancy and metastasis formation. Additionally, the older literature indirectly implicates GOLPH3 in cancerogenesis through its function in controlling hepatitis C virus secretion, which in turn is linked to hepatocellular carcinoma formation. Thus, GOLPH3 might promote tumorigenesis in unexpected ways, involving both direct and indirect routes. If these data are further confirmed, the spectrum of action of GOLPH3 in tumor formation will significantly expand, indicating this protein as a strong candidate for targeted cancer therapy.

We show a method to control magnetic interfacial effects in multilayers with Dzyaloshinskii-Moriya interaction (DMI) using helium (He[Formula: see text]) ion irradiation. We report results from SQUID magnetometry, ferromagnetic resonance as well as Brillouin light scattering results on multilayers with DMI as a function of irradiation fluence to study the effect of irradiation on the magnetic properties of the multilayers. Our results show clear evidence of the He[Formula: see text] irradiation effects on the magnetic properties which is consistent with interface modification due to the effects of the He[Formula: see text] irradiation. This external degree of freedom offers promising perspectives to further improve the control of magnetic skyrmions in multilayers, that could push them towards integration in future technologies., (© 2021. The Author(s).)

The role of three-dimensionality in a ferromagnetic medium in ruling the propagation properties of spin-waves (SW) has been one of the main focuses of the research activity in recent years. In this context, we investigate the evolution of the SW dispersion (frequency vs wave vector) induced by a progressive vertical undulation of a ferromagnetic film. The geometric undulation is taken along a single direction and is periodic with constant period, while the amplitude (differential maximum height with respect to the film thickness) is gradually increased from 0 to 60 nm. We study the characteristic modification of the internal effective field and link it to the resulting SW dispersions and spatial profile. These systems display at once features both of a planar film and a discretized medium, and the dispersion curves change not only when SWs propagate along the undulation direction, but also perpendicular to it. We discuss the geometric and magnetic conditions for having either the invariance of the SW group velocity with respect to even major changes in the undulation, or a large group velocity for some edge modes. We address a potential dual-band activity, namely the simultaneous propagation of two independent SW-signals, with separated frequency bands and disjoint oscillation regions., (© 2021. The Author(s).)

A new series of quinoline-based benzenesulfonamides ( QBS ) were developed as potential carbonic anhydrase inhibitors (CAIs). The target QBS CAIs is based on the 4-anilinoquinoline scaffold where the primary sulphonamide functionality was grafted at C4 of the anilino moiety as a zinc anchoring group ( QBS &nbsp; 13a - c ); thereafter, the sulphonamide group was switched to ortho - and meta -positions to afford regioisomers 9a - d and 11a - g . Moreover, a linker elongation approach was adopted where the amino linker was replaced by a hydrazide one to afford QBS &nbsp; 16 . All the described QBS have been synthesized and investigated for their CA inhibitory action against h CA I, II, IX and XII. In general, para -sulphonamide derivatives 13a - c displayed the best inhibitory activity against both cancer-related isoforms h CA IX ( K I s = 25.8, 5.5 and 18.6 nM, respectively) and h CA XII ( K I s = 9.8, 13.2 and 8.7 nM, respectively), beside the excellent h CA IX inhibitory activity exerted by meta -sulphonamide derivative 11c ( K I = 8.4 nM). The most promising QBS were further evaluated for their anticancer and pro-apoptotic activities on two cancer cell lines (MDA-MB-231 and MCF-7). In addition, molecular docking simulation studies were applied to justify the acquired CA inhibitory action of the target QBS.

We describe a new, low-cost system designed to provide multi-sensor remote condition monitoring of modern scientific laboratories and to allow users to perform actions from remote locations in the case of detection of specified events. The system is battery operated and does not require the presence of a local area network or WiFi (which are typically not available in the case of, e.g., power losses), as it exploits the growing infrastructure of Internet of Things low-power wide area networks. In particular, our system exploits the new SigFox ultra-narrow-bandwidth infrastructure and provides a bidirectional link between the instrumentation and the remote user even in the case of power line outages, which are among the most critical situations that a scientific laboratory can withstand. The system can detect the occurrence of predefined events in very short times and autonomously react with a series of predefined actions, also allowing a remote user to timely perform additional actions on the system through a user-friendly smartphone application or via a browser interface. The system also embeds a novel power loss detection architecture, which detects power line failures in less than 2 ms. We provide a full characterization of the prototype, including reaction times, connection latencies, sensor sensitivity, and power consumption.

The black coral Leiopathes glaberrima is an important habitat forming species that supports benthic biodiversity. Due to its high sensitivity to fishing activities, it has been classified as indicator of Vulnerable Marine Ecosystems (VMEs). However, the information on its habitat selection and large-scale spatial distribution in the Mediterranean Sea is poor. In this study a thorough literature review on the occurrence of L. glaberrima across the Mediterranean Sea was undertaken. Predictive modelling was carried out to produce the first continuous map of L. glaberrima suitable habitat in the central sector of the Mediterranean Sea. MaxEnt modeling was used to predict L. glaberrima probability of presence as a function of seven environmental predictors (bathymetry, slope, aspect North-South and East-West, kinetic energy due to currents at the seabed, seabed habitat types and sea bottom temperature). Our results show that bathymetry, slope and aspect are the most important factors driving L. glaberrima spatial distribution, while in less extent the other environmental variables. This study adds relevant information on the spatial distribution of vulnerable deep water corals in relation to the environmental factors in the Mediterranean Sea. It provides an important background for marine spatial planning especially for prioritizing areas for the conservation of VMEs., (© 2021. The Author(s).)

With the aim of rationalizing the experimental counterion- and solvent-dependent reactivity in the gold(i)-catalyzed Meyer-Schuster rearrangement of 1-phenyl-2-propyn-1-ol, a computational mechanistic study unraveled the unexpected formation of a gold-oxetene intermediate via commonly unfavorable 4-endo-dig cyclization triggered by the counterion in low polarity solvents.

Objective: To compare the mechanical and biological features of a polymethylmethacrylate (PMMA) disc for CAD/CAM prostheses (test samples, TG) with a traditional resin (control samples, CG)., Methods: Mechanical analysis was performed using Dynamic Mechanical Analysis (DMA) and Brillouin's micro-spectroscopy. Human keratinocyte morphology and adhesion were analyzed by scanning electronic microscopy (SEM), cytotoxicity by the MTT assay, apoptosis by flow cytometry and p53, p21 and bcl2 gene expression by real time PCR., Results: TG exhibited a higher elastic modulus than CG (range 5100-5500 ± 114.3 MPa vs 3000-3300 ± 99.97 MPa). The Brillouin frequency was found at ω B = (15.50 ± 0.05) GHz for TG and at ω B&#95;1 = (15.50 ± 0.05) GHz and ω B&#95;2 = (15.0 ± 0.1) GHz for CG where two peaks were always present independently of the sample point. SEM analysis revealed that keratinocytes on TG disks appeared to be flattened with lamellipodia. Keratinocytes on CG disks rose above the substrate with cytoplasmatic filaments. MTT viability data at 3 h and 24 h showed TG was significantly less cytotoxic than CG (p < 0.001). No significant differences emerged in apoptosis on CG and TG. Real-time PCR showed p53 expression increased after 3 h by about 9-fold in keratinocytes on TG (p < 0.001) and about 5-fold in those on CG (p < 0.001). High p53 expression persisted after 24 h on both disks. No significant variations were observed in p21 and bcl2 expression at any time-point., Significance: PMMA resins, as used in CAD/CAM technology, displayed suitable biocompatible and mechanical properties for removable prostheses., (Copyright © 2020 The Academy of Dental Materials. Published by Elsevier Inc. All rights reserved.)

The presence of islet cells double positive for insulin and glucagon (Ins + /Glu + ) has been described in the pancreas from both type 2 (T2D) and type 1 (T1D) diabetic subjects. We studied the role of pro-inflammatory cytokines on the occurrence, trajectory, and characteristics of Ins + /Glu + cells in human pancreatic islets. Pancreas samples, isolated islets, and dispersed islet cells from 3 T1D and 11 non-diabetic (ND) multi-organ donors were studied by immunofluorescence, confocal microscopy, and/or electron microscopy. ND islet cells were exposed to interleukin-1β and interferon-γ for up to 120 h. In T1D islets, we confirmed an increased prevalence of Ins + /Glu + cells. Cytokine-exposed islets showed a progressive increase of Ins + /Glu + cells that represented around 50% of endocrine cells after 120h. Concomitantly, cells expressing insulin granules only decreased significantly over time, whereas those containing only glucagon granules remained stable. Interestingly, Ins + /Glu + cells were less prone to cytokine-induced apoptosis than cells containing only insulin. Cytokine-exposed islets showed down-regulation of β-cell identity genes. In conclusion, pro-inflammatory cytokines induce Ins + /Glu + cells in human islets, possibly due to a switch from a β- to a β-/α-cell phenotype. These Ins + /Glu + cells appear to be resistant to cytokine-induced apoptosis.

The intercalation of graphite by electrochemical methods is an efficient strategy to produce massive graphene flakes. In fact, when graphite is biased inside an acidic solution, anions enter inside the stratified structure of the electrode and reduce the layer-to-layer interaction. Consequently, a gentle sonication is sufficient to disperse the graphene flakes inside the electrolyte. In view of an optimisation of the production protocol, a detailed analysis of the intercalation mechanism at the molecular length scale is mandatory. In the last 30 years, electrochemical (EC) scanning probe microscopies (e.g. EC-STM and in situ AFM) have been widely exploited in this research topic. In fact, these techniques have the possibility of combining the EC characterisation (e.g. cyclic-voltammetry, CV) with mechanical characterisation (e.g. adhesion and friction) and topography acquisition with high (molecular) lateral resolution. In this work, we investigate the tribological properties of the basal surface of graphite before and after the anion intercalation. By comparing the results acquired after the extraction of the graphite electrode from the EC cell with those collected inside the EC cell during the CV by an in situ AFM, we show how some features deriving from anisotropic friction can be exploited to unveil the very early stage of graphite exfoliation., (© 2020 Royal Microscopical Society.)

Organisms living in icy environments produce antifreeze proteins to control ice growth and recrystallization. It has been proposed that these molecules pin the surface of ice crystals, thus inducing the formation of a curved surface that arrests crystal growth. Such proteins are very appealing for many potential applications in food industry, material science and cryoconservation of organs and tissues. Unfortunately, their structural complexity has seriously hampered their practical use, while efficient and accessible synthetic analogues are highly desirable. In this paper, we used molecular dynamics based techniques to model the interaction of three short antifreeze synthetic peptides with an ice surface. The employed protocols succeeded in reproducing the ice pinning action of antifreeze peptides and the consequent ice growth arrest, as well as in distinguishing between antifreeze and control peptides, for which no such effect was observed. Principal components analysis of peptides trajectories in different simulation settings permitted to highlight the main structural features associated to antifreeze activity. Modeling results are highly correlated with experimentally measured properties, and insights on ice-peptide interactions and on conformational patterns favoring antifreeze activity will prompt the design of new and improved antifreeze peptides., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Inc. All rights reserved.)

The quantitative evaluation of the three-dimensional (3D) morphology of porous composite materials is important for understanding mass transport phenomena, which further impact their functionalities and durability. Reactive porous paint materials are composites in nature and widely used in arts and technological applications. In artistic oil paintings, ambient moisture and water and organic solvents used in conservation treatments are known to trigger multiple physical and chemical degradation processes; however, there is no complete physical model that can quantitatively describe their transport in the paint films. In the present study, model oil paints with lead white (2PbCO 3 ·Pb(OH) 2 ) and zinc white (ZnO) pigments, which are frequently found in artistic oil paintings and are associated with the widespread heavy metal soap deterioration, were studied using synchrotron X-ray nano-tomography and unilateral nuclear magnetic resonance. This study aims to establish a relationship among the paints' compositions, the 3D morphological properties and degradation. This connection is crucial for establishing reliable models that can predict transport properties of solvents used in conservation treatments and of species involved in deterioration reactions, such as soap formation.

Brillouin and Raman imaging are powerful techniques for the investigation of complex materials and they are widely used in material science and biophysics [1], [2], [3], [4], [5], [6], [7]. When dealing with microstructures, the results interpretation requires an accurate understanding of the interaction processes in presence of acoustic and chemical boundaries between different materials [8], [9], [10], [11], [12], [13], [14], [15]. The data here reported are obtained while scanning with sub-micron resolution the sharp interfaces between vitreous-SiO 2 /Water and Polyethylene (PET)/Glycerol. Molecular and acoustic vibrations were observed by means of a recently developed micro-spectrometer, which acquires simultaneously Raman and Brillouin spectra on the same point with high spatial and spectral resolution [3]. Two external optic configurations were adopted in order to evidence the dependency of the measurements on the optical scattering volume. The evolution of the detected phonon modes, propagating and not propagating, is obtained by a direct observation of the raw data for the two interfaces, which present different acoustic mismatch. These experimental records can be exploited by researchers employing Raman and Brillouin imaging to discuss the resolution limit of the techniques and to compare the effect of different experimental set-ups. Moreover, thanks to their high spectral resolution they can be useful to researchers working on acoustic phonon transport at interfaces to model the dependency of transmission of long wavelength phonons on the acoustic mismatch., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships which have or could be perceived to have influenced the work reported in this article., (© 2020 The Author(s).)

Amyotrophic Lateral Sclerosis (ALS) is a devastating neurodegenerative disease that affects both central and peripheral nervous system, leading to the degeneration of motor neurons, which eventually results in muscle atrophy, paralysis, and death. Sleep disturbances are common in patients with ALS, leading to even further deteriorated quality of life. Investigating methods to potentially assess sleep and rest disturbances in animal models of ALS is thus of crucial interest. We used an automated home cage monitoring system (DVC ® ) to capture irregular activity patterns that can potentially be associated with sleep and rest disturbances and thus to the progression of ALS in the SOD1G93A mouse model. DVC ® enables non-intrusive 24/7 long term animal activity monitoring, which we assessed together with body weight decline and neuromuscular function deterioration measured by grid hanging and grip strength tests in male and female mice from 7 until 24 weeks of age. We show that as the ALS progresses over time in SOD1G93A mice, activity patterns start becoming irregular, especially during day time, with frequent activity bouts that are neither observed in control mice nor in SOD1G93A at a younger age. The increasing irregularities of activity pattern are quantitatively captured by designing a novel digital biomarker, referred to as Regularity Disruption Index (RDI). We show that RDI is a robust measure capable of detecting home cage activity patterns that could be related to rest/sleep-related disturbances during the disease progression. Moreover, the RDI rise during the early symptomatic stage parallels grid hanging and body weight decline. The non-intrusive long-term continuous monitoring of animal activity enabled by DVC ® has been instrumental in discovering novel activity patterns potentially correlated, once validated, with sleep and rest disturbances in the SOD1G93A mouse model of the ALS disease., (Copyright © 2020 Golini, Rigamonti, Iannello, De Rosa, Scavizzi, Raspa and Mandillo.)

Over the past decades, the discovery and development of genetically encoded fluorescent proteins (FPs) has brought a revolution into our ability to study biologic phenomena directly within living matter. First, FPs enabled fluorescence-labeling of a variety of molecules of interest to study their localization, interactions and dynamic behavior at various scales-from cells to whole organisms/animals. Then, rationally engineered FP-based sensors facilitated the measurement of physicochemical parameters of living matter-especially at the intracellular level, such as ion concentration, temperature, viscosity, pressure, etc. In addition, FPs were exploited as inert tracers of the intracellular environment in which they are expressed. This oft-neglected role is made possible by two distinctive features of FPs: ( i ) the quite null, unspecific interactions of their characteristic β-barrel structure with the molecular components of the cellular environment; and ( ii ) their compatibility with the use of time-resolved fluorescence-based optical microscopy techniques. This review seeks to highlight the potential of such unique combinations of properties and report on the most significative and original applications (and related advancements of knowledge) produced to date. It is envisioned that the use of FPs as inert tracers of living matter structural organization holds a potential for several lines of further development in the next future, discussed in the last section of the review, which in turn can lead to new breakthroughs in bioimaging.

We report on the study of both perpendicular magnetic anisotropy (PMA) and Dzyaloshinskii-Moriya interaction (DMI) at an oxide/ferromagnetic metal (FM) interface, i.e., BaTiO&#95;{3} (BTO)/CoFeB. Thanks to the functional properties of the BTO film and the capability to precisely control its growth, we are able to distinguish the dominant role of the oxide termination (TiO&#95;{2} vs BaO) from the moderate effect of ferroelectric polarization in the BTO film, on the PMA and DMI at an oxide/FM interface. We find that the interfacial magnetic anisotropy energy of the BaO-BTO/CoFeB structure is 2 times larger than that of the TiO&#95;{2}-BTO/CoFeB, while the DMI of the TiO&#95;{2}-BTO/CoFeB interface is larger. We explain the observed phenomena by first principles calculations, which ascribe them to the different electronic states around the Fermi level at oxide/ferromagnetic metal interfaces and the different spin-flip process. This study paves the way for further investigation of the PMA and DMI at various oxide/FM structures and thus their applications in the promising field of energy-efficient devices.

As known, the electron density of covalently bound halogen atoms is anisotropically distributed, making them potentially able to establish many weak interactions, acting at the same time as halogen bond donors and hydrogen bond acceptors. Indeed, there are many examples in which the halogen and hydrogen bond coexist in the same structure and, if a correct bond analysis is required, their separation is mandatory. Here, the advantages and limitations of coupling the charge displacement analysis with natural orbital for chemical valence method (NOCV-CD) to separately analyze orthogonal weak interactions are shown, for both symmetric and asymmetric adducts. The methodology gives optimal results with intermolecular adducts but, in the presence of an organometallic complex, also intramolecular interactions can be correctly analyzed. Beyond the methodological aspects, it is shown that correctly separate and quantify the interactions can give interesting chemical insights about the systems., (© 2020 Wiley Periodicals, Inc.)

Integrated optically inspired wave-based processing is envisioned to outperform digital architectures in specific tasks, such as image processing and speech recognition. In this view, spin waves represent a promising route due to their nanoscale wavelength in the gigahertz frequency range and rich phenomenology. Here, a versatile, optically inspired platform using spin waves is realized, demonstrating the wavefront engineering, focusing, and robust interference of spin waves with nanoscale wavelength. In particular, magnonic nanoantennas based on tailored spin textures are used for launching spatially shaped coherent wavefronts, diffraction-limited spin-wave beams, and generating robust multi-beam interference patterns, which spatially extend for several times the spin-wave wavelength. Furthermore, it is shown that intriguing features, such as resilience to back reflection, naturally arise from the spin-wave nonreciprocity in synthetic antiferromagnets, preserving the high quality of the interference patterns from spurious counterpropagating modes. This work represents a fundamental step toward the realization of nanoscale optically inspired devices based on spin waves., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The distribution of chemical species and the mechanical modulation inside a single cell or tissue are of fundamental importance to characterize their physiological activity or their pathological conditions [1-4]. Here we analyse these properties by means of label free, non invasive, spectroscopic methods. In particular, we use a recently developed micro-spectrometer, which acquires simultaneously Raman and Brillouin spectra on the same point with subcellular resolution [5]. The techniques ability to analyse the chemical composition and the mechanical properties of single cells has been tested on NIH/3T3 murine fibroblast cells grown in adhesion on silicon substrates. Here we report the data acquired from fixed cells after their oncogenic transformation. Mechanical and chemical evolution is evident by direct inspection of raw data. Sharing our experimental records can be valuable for researchers interested in the analysis of single cells by Raman and Brillouin spectroscopy in order: i) to compare data acquired by different set-ups and ii) to correctly model the fitting functions., (© 2020 The Author(s).)

Background: GOLFIG is a chemo-immunotherapy regimen established in preclinical models that combines gemcitabine + FOLFOX (fluoropyrimidine backbone coupled to oxaliplatin) poly-chemotherapy with low-dose s. c. recombinant interleukin-2 (rIL-2) and granulocyte-macrophage colony stimulating factor (GM-CSF). Promising antitumor effects in metastatic colorectal cancer (mCRC) patients were obtained in previous phase II and III trials. Here we report the results of 15 years of follow-up. Methods: This is a multi-institutional retrospective analysis including 179 mCRC patients receiving GOLFIG regimen between June 2002 and June 2018. Sixty-two of them received the treatment as frontline (enrolled in the GOLFIG-2 phase III trial) and 117 as second/third line (49 enrolled in the GOLFIG-1 phase II trial and 68 as compassionate use). One hundred twelve patients showed a primary left side and 67 a primary right side; K/N-ras mutational status was available in 74 cases, and an activating mutation was detected in 33. Kaplan-Meier and Cox regression analyses were carried out to relate PFS and OS with different parameters. Results: Overall, we recorded a mean PFS and OS of 15.28 (95% CI: 10.36-20.20) and 24.6 (95% CI: 19.07-30.14) months, respectively, with 14 patients surviving free of progression for 10 years. This regimen, in our updated survey of the GOLFIG-2 trial, confirmed superiority over FOLFOX in terms of PFS (hazard ratio (HR) = 0.58, p = 0.006) with a trend to a longer OS (HR = 0.69, P = 0.06) in the first line. Our analysis also confirmed significant antitumor activity in pre-treated patients, reporting a mean PFS and OS of 12.55 (95% CI: 7.19-17.9) and 20.28 (95% CI: 14.4-26.13) months, respectively. Immune-related adverse events (irAEs) were recorded in 24% of the cases and were related to a longer survival (HR = 0.36; P = 0.0001). Finally, patients' outcome was not correlated to sex, sidedness, and MT-K/N-ras. Conclusions: The GOLFIG regimen is a reliable underestimated therapeutic option in pre-treated mCRC patients and offers a strong rationale to design further trials., (Copyright © 2019 Caraglia, Correale, Giannicola, Staropoli, Botta, Pastina, Nesci, Caporlingua, Francini, Ridolfi, Mini, Roviello, Ciliberto, Agostino, Strangio, Azzarello, Nardone, Falzea, Cappabianca, Bocchetti, D'Arrigo, Tripepi, Tassone, Addeo, Giordano, Pirtoli, Francini and Tagliaferri.)

We investigated the impact of singly occupied molecular orbital (SOMO) energy on the n-doping efficiency of benzimidazole derivatives. By designing and synthesizing a series of new air-stable benzimidazole-based dopants with different SOMO energy levels, we demonstrated that an increase of the dopant SOMO energy by only ∼0.3 eV enhances the electrical conductivity of a benchmark electron-transporting naphthalenediimide-bithiophene polymer by more than 1 order of magnitude. By combining electrical, X-ray diffraction, and electron paramagnetic resonance measurements with density functional theory calculations and analytical transport simulations, we quantitatively characterized the conductivity, Seebeck coefficient, spin density, and crystallinity of the doped polymer as a function of the dopant SOMO energy. Our findings strongly indicate that charge and energy transport are dominated by the (relative) position of the SOMO level, whereas morphological differences appear to play a lesser role. These results set molecular-design guidelines for next-generation n-type dopants.

Helium chemistry is notoriously very impervious. It is therefore certainly no surprise that, for example, beryllium and helium atoms, in their ground state, do not bind. Full configuration-interaction calculations show that the same turns out to be true, save for a long-range shallow attraction, for the Be + + He system. However, quite astonishingly, when one electron is re-added to Be + in an excited 2p π or 3s orbital (Be 1 P or 1 S), a bound adduct with He is formed, at an interatomic separation as short as 1.5 Å. Understanding why this happens reveals an unsuspected chemical mechanism that stabilizes helium compounds at the molecular level.

Using computational approaches, we qualitatively and quantitatively assess the bonding components of a series of experimentally characterized Au(I) diarylallenylidene complexes (N.Kim, R.A.Widenhoefer, Angew. Chem. Int. Ed. 2018, 57, 4722-4726). Our results clearly demonstrate that Au(I) engages only weakly in π-backbonding, which is, however, a tunable bonding component. Computationally identified trends in bonding are clearly correlated with the substitution patterns of the aryl substituents in the Au(I) diarylallenylidene complexes and good agreement is found with the previously reported experimental data, such as IR spectra, 13 C NMR chemical shifts and rates of decomposition together with their corresponding barrier heights, further substantiating the computational findings. The description of the bonding patterns in these complexes allow predictions of their spectroscopic features, their reactivity and stability., (©2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

The peak stress/rest ratio of left ventricular (LV) elastance, or LV force, is a load-independent index of left ventricular contractile reserve (LVCR) with stress echo (SE). To assess the accuracy of LVCR calculated during SE with approaches of different complexity. Two-hundred-forty patients were referred to SE for known or suspected coronary artery disease or heart failure and, of those, 200 patients, age 61 ± 15, 99 females, with interpretable volumetric SE were enrolled. All readers had passed the upstream quality control reading for regional wall motion abnormality (RWMA) and end-systolic volume (ESV) measurement. The employed stress was dipyridamole (0.84 mg, 6 min) in 86 (43%) and dobutamine (up to 40 mcg/kg/min) in 114 (57%) patients. All underwent SE with evaluation of RWMA and simultaneous LVCR assessment with stress/rest ratio of LV force (systolic blood pressure by cuff sphygmomanometer/ESV). ESV was calculated in each patient by two of three methods: biplane Simpson rule (S, in 100 patients), single plane area-length (AL, apical four-chamber area and length, in 100 patients), and Teichholz rule (T, from parasternal long axis and/or short axis view, in 200 patients). RMWA were observed in 54 patients. Success rate for ESV measurement was 76% (100/131) for S, 92% (100/109) for AL, and 100% (240/240) for T. There were 100 paired measurements (rest and stress) with S versus T, and 100 with AL versus T. The analysis time was the shortest for T (33 ± 8 s at rest, 34 ± 7 s at stress), intermediate for AL (70 ± 22 s at rest 67 ± 21 s at stress), and the longest for S (136 ± 24 at rest 129 ± 27 s at stress, p < 0.05 vs. T and AL). ESV absolute values were moderately correlated: T versus S (r rest = 0.746, p < 0.01, n = 100; r stress = 0.794, p < 0.01, n = 100); T vs. AL (r = 0.603 p < 0.01, n = 100, at rest and r = 0.820 p < 0.01 n = 100 at peak stress). LVCR values were tightly correlated independently of the method employed: T versus S (r = 0.899, p < 0.01, n = 100), and T versus AL (r = 0.845, p < 0.01, n = 100). LVCR can be accurately determined with all three methods used to extract the raw values of ESV necessary to generate the calculation of Force. Although S is known to be more precise in determining absolute ESV values, the relative (rest-stress) changes can be assessed, with comparable accuracy, with simpler and more feasible T and AL methods, characterized by higher success rate, shorter imaging and analysis time.

There has been a marked revival of interest in brillouin light scattering spectroscopy/microscopy over the last decade in regards to applications related to all optically studying the mechanical problems associated with systems of biological and medical interest. This revival has been driven by advancements in spectrometer design, together with mounting evidence of the critical role that mechanical properties can play in biological processes as well as the onset of diverse diseases. This feature issue contains a series of papers spanning some of the latest developments in the field of Brillouin light scattering spectroscopy and microscopy as applied to systems of biomedical interest.