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The intermetallic molecules CuSb, AgSb, and AuSb were identified in the effusive molecular beam produced at high temperature under equilibrium conditions in a double-cell-like Knudsen source. Several gaseous equilibria involving these species were studied by mass spectrometry as a function of temperature in the overall range 1349-1822 K, and the strength of the chemical bond formed between antimony and the group 11 metals was for the first time measured deriving the following thermochemical dissociation energies (D°0 , kJ/mol): 186.7 ± 5.1 (CuSb), 156.3 ± 4.9 (AgSb), 241.3 ± 5.8 (AuSb). The three species were also investigated computationally at the coupled cluster level with single, double, and noniterative quasiperturbative triple excitations (CCSD(T)). The spectroscopic parameters were calculated from the potential energy curves and the dissociation energies were evaluated at the Complete Basis Set limit, resulting in an overall good agreement with experimental values. An approximate evaluation of the spin-orbit effect was also performed. CCSD(T) calculations were further extended to the corresponding group 11 arsenide species which are here studied for the first time and the following dissociation energies (D°0 , kJ/mol): 190 ± 10 (CuAs), 151 ± 10 (AgAs), 240 ± 15 (AuAs) are proposed. Taking advantage of the new experimental and computational information here presented, the bond energy trends along group 11 and 4th and 5th periods of the periodic table were analyzed and the bond energies of the diatomic species CuBi and AuBi, yet experimentally unobserved, were predicted on an empirical basis. [ABSTRACT FROM AUTHOR]

Summary: Influenza A virus (IAV) infection in swine plays an important role in the ecology of influenza viruses. The emergence of new IAVs comes through different mechanisms, with the genetic reassortment of genes between influenza viruses, also originating from different species, being common. We performed a genetic analysis on 179 IAV isolates from humans (n. 75) and pigs (n. 104) collected in Northern Italy between 2010 and 2015, to monitor the genetic exchange between human and swine IAVs. No cases of human infection with swine strains were noticed, but direct infections of swine with H1N1pdm09 strains were detected. Moreover, we pointed out a continuous circulation of H1N1pdm09 strains in swine populations evidenced by the introduction of internal genes of this subtype. These events contribute to generating new viral variants—possibly endowed with pandemic potential—and emphasize the importance of continuous surveillance at both animal and human level. [ABSTRACT FROM AUTHOR]

Cancer care places a heavy economic burden on families and health systems, driven by high treatment costs, lengthy hospital stays, and the necessity for extensive travel to specialized facilities. To address this challenge, an integrated health care network (IHCN) was implemented for maintenance treatment in acute leukemia. The IHCN encompassed outpatient services provided by local physicians and synchronous telemedicine consultation with pediatric oncologists. This study included twenty-two pediatric patients (eleven [50.0%] females; twenty [90.9%] with B-ALL and two [9.1%] with AML). The IHCN was offered to all rural patients (n = 17) with a one-way driving distance more than 30 km, while urban patients (n = 5) received regular cancer care. Throughout the study, rural patients had a total of 510 routine clinical visits, with 367 (72%) conducted through the IHCN. Physical examinations revealed similar frequency of new abnormal findings for urban and rural patients (22.4% vs. 17.8%; p = .31). Laboratory tests indicated no significant difference in the frequency of abnormal values for various parameters between both groups. Similarly, there was no discrepancy of drug modifications or interruption in maintenance therapy between the two settings (p = .85). Moreover, patients' health-related quality of life remained within the normative range, and user satisfaction with the IHCN was notably high. The implementation of the IHCN resulted in savings of 70,158 km, 950 h of travel, and 12,277 kg CO 2 emissions. This pilot study underscores the efficacy of a telemedicine-based IHCN, ensuring safety, quality of care, cost reduction, and satisfaction for both families and health care providers in pediatric leukemia management., (© 2024 The Author(s). International Journal of Cancer published by John Wiley & Sons Ltd on behalf of UICC.)

Herpesvirus (HV) is widely distributed among cetacean populations, with the highest prevalence reported in the Mediterranean Sea. In this study, a comprehensive analysis was conducted, including epidemiological, phylogenetic, and pathological aspects, with particular emphasis on neuropathology, to better understand the impact of HV in these animals. Our results show a higher presence of HV in males compared to females, with males exhibiting a greater number of positive tissues. Additionally, adults were more frequently affected by HV infection than juveniles, with no infections detected in calves or neonates. The affected species were striped (Stenella coeruleoalba) and bottlenose dolphins (Tursiops truncatus). The highest positivity rates were observed in the genital system, cerebrum, and skin tissues. Phylogenetic analysis indicated a higher occurrence of Gammaherpesvirus (GHV) sequences but increased genetic diversity within Alphaherpesvirus (AHV). Key neuropathological features included astro-microgliosis (n = 4) and meningitis with minimal to mild perivascular cuffing (n = 2). The presence of concurrent infections with other pathogens, particularly cetacean morbillivirus (CeMV), underscores the complex nature of infectious diseases in cetaceans. However, the presence of lesions at the Central Nervous System (CNS) with molecular positivity for GHV, excluding the involvement of other potential neurotropic agents, would confirm the potential of this HV subfamily to induce neurological damage. Pathological examination identified lesions in other organs that could potentially be associated with HV, characterized by lymphoid depletion and tissue inflammation. These findings enhance our understanding of HV in odontocetes and highlight the need for ongoing research into the factors driving these infections and their broader implications., Competing Interests: The authors have declared that no competing interests exist., (Copyright: © 2024 Vargas-Castro et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

We report the first conductance measurements of [n]staffane (bicyclopentane) oligomers in single-molecule junctions. Our studies reveal two quantum transport characteristics unique to staffanes that emerge from their strained bicyclic structure. First, though staffanes are composed of weakly conjugated C-C σ-bonds, staffanes carry a shallower conductance decay value (β=0.84±0.02 n -1 ) than alkane chain analogs (β=0.96±0.03 n -1 ) when measured with the scanning tunneling microscopy break junction (STM-BJ) technique. Staffanes are thus more conductive than other σ-bonded organic backbones reported in the literature on a per atom basis. Density functional theory (DFT) calculations suggest staffane backbones are more effective conduits for charge transport because their significant bicyclic ring strain destabilizes the HOMO-2 energy, aligning it more closely with the Fermi energy of gold electrodes as oligomer order increases. Second, the monostaffane is significantly lower conducting than expected. DFT calculations suggest that short monostaffanes sterically enforce insulating gauche interelectrode orientations over syn orientations; these steric effects are alleviated in longer staffanes. Moreover, we find that [2-5]staffane wires may accommodate axial mechanical strain by "rod-bending". These findings show for the first time how bicyclic ring strain can enhance charge transmission in saturated molecular wires. These studies showcase the STM-BJ technique as a valuable tool for uncovering the stereoelectronic proclivities of molecules at material interfaces., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Cysteine is the most reactive naturally occurring amino acid due to the presence of a free thiol, presenting a tantalizing handle for covalent modification of peptides/proteins. Although many mass spectrometry experiments could benefit from site-specific modification of Cys, the utility of direct arylation has not been thoroughly explored. Recently, Spokoyny and co-workers reported a Au(III) organometallic reagent that robustly arylates Cys and tolerates a wide variety of solvents and conditions. Given the chromophoric nature of aryl groups and the known susceptibility of carbon-sulfur bonds to photodissociation, we set out to identify an aryl group that could efficiently cleave Cys carbon-sulfur bonds at 266 nm. A streamlined workflow was developed to facilitate rapid examination of a large number of aryls with minimal sample using a simple test peptide, RAAACGVLK. We were able to identify several aryl groups that yield abundant homolytic photodissociation of the adjacent Cys carbon-sulfur bonds with short activation times (<10 ms). In addition, we characterized the radical products created by photodissociation by subjecting the product ions to further collisional activation. Finally, we tested Cys arylation with human hemoglobin, identified reaction conditions that facilitate efficient modification of intact proteins, and evaluated the photochemistry and activation of these large radical ions.

Few papers focus their attention on VZV vaccination effectiveness among people living with HIV (PLWH). Flanking the live attenuated vaccine (VZL) available, a newly recombinant vaccine (RZV) was recently introduced and approved for HZ prevention among adults. PLWH represents a population on which a particular attention should be applied, in order to guarantee the vaccine efficacy and safety. We performed a literature search in USNLM, PubMed, PubMed Central, PMC and Cochrane Library. From all the publications found eligible, data were extracted and processed per population, vaccine type, immunogenicity and ADRs. The review of the 13 included studies shows that both RZV and VZL are immunogenic and have an acceptable safety profile in adults and children living with HIV. However, given the lack of research available about vaccine efficacy in preventing VZV and HZ in PLWH, additional studies need to be performed, in order to achieve a full completeness of data.

The fluorinated alcohols, (CF 3 ) 3 COH (R F9 OH) and (CF 3 ) 2 MeCOH (R F6 OH), react with W(NR) 2 Cy 2 (Cy=Cyclohexyl; R=2,6-diisopropylphenyl or 1-adamantyl) in C 6 D 6 at 55 °C to give cyclohexylidene complexes. Traditional routes to terminal alkylidene complexes (neopentylidene or neophylidene) have used either triflic acid or HCl (rarely), but relatively weak fluorinated acids are sufficient and active bisalkoxide catalysts are therefore prepared directly. An α hydrogen abstraction reaction to give a cyclohexylidene complex from a biscyclohexyl complex appears to be as facile as α hydrogen abstraction to give a neopentylidene or neophylidene ligand, but isomerization of a cyclohexene formed through β hydrogen abstraction is also a possibility. The OR F9 ligands can be replaced readily with dimethylpyrrolide (Me 2 Pyr) or other more basic alkoxides. Single crystal X-ray studies were carried out on W(NAr) 2 Cy 2 , W(NAr)(OR F9 ) 2 (C 6 H 10 )(ArNH 2 ), W(NAr)(OR F6 ) 2 (C 6 H 10 )(ArNH 2 ), W(NAd)(OR F9 ) 2 (C 6 H 10 )(AdNH 2 ), W(NAr)(O-i-Pr F6 ) 3 Cy, and W(NAd)(η 1 -Me 2 Pyr) 2 (C 6 H 10 ) (C 6 H 10 =cyclohexylidene)., (© 2024 Wiley-VCH GmbH.)

Assembling molecular machines into crystals provides a way to harness their power on large length scales, but the development of a crystal analogue to a molecular motor remains a challenge. The molecule ( Z )-5-(anthracen-9-ylmethylene)-3-butylthiazolidine-2,4-dione ( C4-ATD ) has E and Z isomers with strongly overlapping absorption spectra. This spectroscopic property allows both Z → E and E → Z photoisomerization reactions to be driven by a single light source, and simulations indicate this property can provide a route to robust oscillatory motion. Reprecipitation in an aqueous surfactant enables the growth of single crystal microwires that exhibit continuous mechanical oscillations under a wide range of illumination conditions, including ambient solar irradiation. Molecular crystal motors provide a new approach for transforming continuous light into oscillatory mechanical motion.

A 7-tungstabicyclo[4.3.0]nonane complex forms slowly upon addition of cyclohexene to the ethylene complex, W(NAr)(OSiPh 3 ) 2 (C 2 H 4 ), at 22 °C. A single-crystal X-ray study showed its structure to be closest to a square pyramid (τ = 0.23). At 22 °C, loss of cyclohexene or ring contraction of the 7-tungstabicyclo[4.3.0]nonane complex is slow. Above ∼80 °C, cyclohexene is ejected to give W(NAr)(OSiPh 3 ) 2 (C 2 H 4 ), but a sufficient amount of 7-tungstabicyclo[4.3.0]nonane complex remains in the presence of cyclohexene and the ring contracts to yield methylenecyclohexane and a methylidene complex or ethylene and a cyclohexylidene complex. Other complexes that have been observed include an 8-tungstabicyclo[4.3.0]nonane complex formed from 1,7-octadiene, a 7-tungstabicyclo[4.2.0]octane complex (formed from a methylidene complex and cyclohexene), and a methylenecyclohexane complex. 13 C-Labeling studies show that the exo-methylene group in methylenecyclohexane and the α positions in the 8-tungstabicyclo[4.3.0]nonane come from ethylene. An alternative ring contraction of a tungstacyclopentane made from two molecules of cyclohexene cannot be excluded when concentrations of ethylene are low. A cyclohexylidene complex could also form from two cyclohexenes via a newly proposed "alkyl/allyl" mechanism. The results reported here are the first experimental confirmations that a tungstacyclopentane can ring-contract thermally at a substituted WC α position to form a tungstacyclobutane and therefore metathesis-active alkylidenes.

Background: This study aimed to assess the effectiveness of 55° wide-field (WF) spectral-domain (SD) optical coherence tomography (OCT) for detecting peripheral subretinal fluid (SRF) after surgery for rhegmatogenous retinal detachment (RRD)., Methods: In this retrospective observational study, the retinal periphery was examined to evaluate the possible presence of persistent SRF after surgery. OCT scans were acquired in infrared mode to use any peripheral vessel as a landmark for better repeatability in monitoring fluid remnants., Results: A total of 80 patients (10% with high myopia) were examined using 55° WF SD OCT after successful pars plana vitrectomy (83.8%) or scleral buckling (16.3%) for RRD. A total of 18 patients (22.5%), 16 of whom underwent pars plana vitrectomy and 2 who underwent scleral buckling, showed SRF at the OCT examination during the follow-up. Potential risk factors associated with SRF persistence were analyzed, revealing a significative association with young age ( p = 0.009). After a follow-up period of 7.05 ± 2.44 months (ranging from 3 to 12 months), a complete resorption in all patients (100%) within 12 months was observed. Best-corrected visual acuity significantly improved in both groups over time., Conclusion: Using 55° WF SD-OCT successfully assessed the course of SRF reabsorption, offering a viable alternative for all those realities where technologies such as ultra-wide-field (UWF) OCT are not available.

PSonyx is a newly isolated phage that infects Corynebacterium glutamicum . This siphovirus was isolated from a French pond in the south of Paris by students from Paris-Saclay University. Its 80,277-bp singleton genome carries 136 protein-coding genes and 5 tRNAs., Competing Interests: The authors declare no conflict of interest.

Highly fluorinated [(F 6 acac)Pd(μ-HNC 6 F 5 )] 2 was prepared by the reaction of palladium bis(hexafluoroacetylacetonate), Pd(F 6 acac) 2 , with pentafluoroaniline. This compound generates a large family of crystalline polymorphs and solvates. In this paper, we present a study on the synthesis, solution phase dynamics, and crystal structures of highly fluorinated [(F 6 acac)Pd(μ-HNC 6 F 5 )] 2 . Pd 3 (μ-F 6 acac) 2 (μ-HNC 6 F 5 ) 4 is produced as a minor byproduct. We also describe the synthesis and structural characterization of trinuclear Pd 3 (μ-F 6 acac) 3 [μ-(CF 3 ) 2 C=N] 3 prepared by the reaction of Pd(F 6 acac) 2 with hexafluoroacetone imine., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

To realize an energy storage transition beyond Li-ion competitive technologies, earth-abundant elements, such as Mg, are needed. Carborane anions are particularly well-suited to realizing magnesium-ion batteries (MIBs), as their inert and weakly coordinating properties beget excellent electrolyte performance. However, utilizing these materials in actual electrochemical cells has been hampered by the reliance on the Mg 2+ salts of the commercially available [HCB 11 H 11 ] - anion, which is not soluble in more weakly binding solvents apart from the higher glymes. Herein, we demonstrate it is possible to iteratively engineer the [HCB 11 H 11 ] - anion surface synthetically to address previous solubility issues and yield a highly conductive (up to 7.33 mS cm -1 ) and electrochemically stable (up to +4.2 V vs Mg 2+/0 ) magnesium electrolyte that surpasses the state of the art. This novel non-nucleophilic electrolyte exhibits highly dissociative behavior regardless of concentration and is tolerant of prolonged periods of cycling in symmetric cells at high current densities (up to 2.0 mA cm -2 , 400 h). The hydrocarbon functionalized carborane electrolyte presented here demonstrates >96% Coulombic efficiency when paired with a Mo 6 S 8 cathode. This approach realizes a needed candidate to discover next-generation cathode materials that can enable the design of practical and commercially viable Mg batteries., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Patients' reports of their health status are increasingly used in hematopoietic stem cell transplantation (SCT) to better understand the negative impact on symptom burden and quality of life. Little is known regarding the implementation in routine clinical care, particularly how it can be used to improve supportive care. We sought to the evaluate feasibility of capturing daily patient-reported outcomes (PROs) in the acute phase of SCT to measure physical and psychosocial symptom burden. In this single-center prospective observational study, we assessed daily PRO from conditioning to neutrophil engraftment in children (age 1 to 18 year) who underwent allogeneic or autologous SCT for malignant and nonmalignant disease. The most common acute adverse effects of chemotherapy (pain, nausea, loss of appetite, sleep disturbance, and physical performance impairment) were reported daily via ePROtect, a web-based program designed to integrate health responses. From February 2021 to March 2023, 20 children undergoing allogeneic (allo-) SCT (n = 11) or autologous (auto-) SCT (n = 9) and their proxies consented to participation, all of whom were included in this analysis. A total of 359 PRO questionnaires were completed, corresponding to a median daily completion rate of 72.7% (interquartile range, 60.4% to 83.6%). After conditioning, pain perception anticipated the rise of infectious parameters and the development of mucositis, thus initiating supportive treatment. Patients reported the strongest symptom burden at a median of 8.5 days post-transplantation. At 4 weeks post-transplantation, baseline values were restored for all symptoms. There were no significant differences between auto-SCT and allo-SCT, except for nausea and loss of appetite after administration of antithymocyte globulin in allo-SCT. This study empirically documents the daily health status of children undergoing SCT and proposes an attractive modus operandi on how continuous feedback on health-related symptoms can be integrated into daily clinical practice., (Copyright © 2023 The American Society for Transplantation and Cellular Therapy. Published by Elsevier Inc. All rights reserved.)

Objective: To evaluate the safety and efficacy of a new surgical technique for the management of primary rhegmatogenous retinal detachment (RRD), consisting of localized PPV near the retinal break(s), without infusion line, associated with a drainage of subretinal fluid and cryoretinopexy., Methods: Multicentric prospective study conducted at the University Hospital of Cagliari and IRCCS Fondazione Policlinico Universitario A. Gemelli, Roma. Twenty eyes affected by RRD with the causative retinal break(s) in the superior meridians were enrolled between February 2022 and June 2022. Patients with cataract ≥3, aphakia, significant posterior capsule opacification, giant retinal tears, retinal dialysis, history of trauma and PVR ≥C2 were excluded. All eyes underwent a two-port 25-gauge PPV with localized removal of the vitreous surrounding retinal break(s), followed by 20% SF6 injection and cryopexy. The surgical time was recorded for each procedure. Best-corrected visual acuity (BCVA) was measured at baseline and postoperative 6 months., Results: Primary anatomic success at 6 months was achieved by 85% of patients. No complications occurred, except for three (15%) retinal re-detachments. The average surgical time was 8.61 ± 2.16 min. Overall, the difference between pre- and last postoperative mean BCVA was statistically significant (p = 0.02)., Conclusions: Two-port dry PPV demonstrated safety and efficacy for the treatment of RRD, reaching an 85% of anatomical success rate. Although further studies are necessary to confirm the efficacy and long-term benefit of this treatment, we believe that this surgical technique could be considered a valid and safe alternative for the management of primary RRD., (© 2023. The Author(s), under exclusive licence to The Royal College of Ophthalmologists.)

Theory of Mind (ToM) is the capacity to understand the feelings and emotional states (i.e., affective ToM) or intentions, goals, and beliefs (i.e., cognitive ToM) of others. Previous evidence on the effect of executive functions and educational attainment on affective ToM is controversial. This study was conducted to investigate: (1) the nature of the associations between affective ToM and some indexes of cognitive reserve (i.e., years of education, vocabulary) in late adulthood when age was controlled; (2) whether cognitive reserve (e.g., years of education, leisure activities, vocabulary) and age predicted affective ToM in late adulthood; (3) the associations between affective ToM and some executive functions measures in late adulthood, controlling for the effect of age; (4) whether executive functioning predicted affective ToM performance; (5) whether some executive functions (i.e., cognitive flexibility and inhibition) mediated between vocabulary score (i.e., used as an index of cognitive reserve) and affective ToM score. Fifty-six 75-93-year-old community-dwellers completed a battery of tasks to assess some executive functions and affective ToM skills (i.e., through the Reading the Mind in the Eyes Test). It was found that vocabulary, age, and participation in outdoor socio-recreational leisure activities predicted 31% of the variance in the Reading the Mind in the Eyes condition. Moreover, significant relationships were found between ToM and some executive functions, that is, cognitive flexibility and inhibition predicted 34% of the ToM score. Finally, cognitive flexibility and inhibition mediate between cognitive reserve (i.e., assessed in terms of vocabulary) and Reading the Mind in the Eyes test score.

This work demonstrates the dominance of a Ni(0/II/III) cycle for Ni-photoredox amide arylation, which contrasts with other Ni-photoredox C-heteroatom couplings that operate via Ni(I/III) self-sustained cycles. The kinetic data gathered when using different Ni precatalysts supports an initial Ni(0)-mediated oxidative addition into the aryl bromide. Using NiCl 2 as the precatalyst resulted in an observable induction period, which was found to arise from a photochemical activation event to generate Ni(0) and to be prolonged by unproductive comproportionation between the Ni(II) precatalyst and the in situ generated Ni(0) active species. Ligand exchange after oxidative addition yields a Ni(II) aryl amido complex, which was identified as the catalyst resting state for the reaction. Stoichiometric experiments showed that oxidation of this Ni(II) aryl amido intermediate was required to yield functionalized amide products. The kinetic data presented supports a rate-limiting photochemically-mediated Ni(II/III) oxidation to enable C-N reductive elimination. An alternative Ni(I/III) self-sustained manifold was discarded based on EPR and kinetic measurements. The mechanistic insights uncovered herein will inform the community on how subtle changes in Ni-photoredox reaction conditions may impact the reaction pathway, and have enabled us to include aryl chlorides as coupling partners and to reduce the Ni loading by 20-fold without any reactivity loss., (© 2023 Wiley-VCH GmbH.)

Ferrocene 1 and its dianionic Fe(bis)(dicarbollide) analogue 2 are classical compounds that display unusual stability. These compounds are not known to undergo transmetallation chemistry of the Fe-center and have been used extensively as chemical building blocks with consistent integrity. In this manuscript we describe the preparation of a charge compensated Fe(bis)(dicarbollide) species 3 Fe and its unprecedented transmetallation chemistry to Ir. Such reactions are hitherto unknown for any transition metal metallocene or metallacarborane complex. Additionally, we show that 3 Fe can be deprotonated to afford the corresponding bis(NHC) Li-carbenoid 5 that also displays unique reactivity. When 5 is reacted with [Ir(COD)Cl] 2 it also undergoes a rapid transmetallation of the ferrocene "like" core to afford 6 but with the added twist that the Li-carbenoid moiety stays intact and does not transmetalate. However, when 6 is subsequently treated with CuCl, the Li-carbenoid transmetalates to Cu, which allows the controlled formation of the corresponding heterobimetallic Ir/Cu aggregate. Lastly, when Li-carbenoid 5 is treated directly with CuCl, a double transmetallation occurs from both Fe to Cu and Li-carbenoid to Cu, resulting in the trimetallic Cu cluster 8. These novel reactions pave the way for new synthetic methods to build complicated polymetallic clusters in a controlled fashion., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

This manuscript describes skeletal isomerization strategies to install one to four quaternary germanium atoms in the sila-adamantane core, in a cluster analogy to precision germanium doping in silicon-germanium alloys. The first strategy embodies an inorganic variant of single-atom skeletal editing, where we use a sila-Wagner-Meerwein bond shift cascade to exchange a peripheral Ge atom with a core Si atom. We can install up to four Ge atoms at the quaternary diamondoid centers based on controlling the Si x Ge y stoichiometry of our precursor. We find that bridgehead Ge centers can be selectively functionalized over bridgehead Si centers in SiGe adamantanes; we use this chemistry in conjunction with scanning tunneling microscopy break-junction (STM-BJ) measurements to show that Si 8 Ge 2 adamantane wires give a 60% increase in single-molecule conductance compared with Si 10 adamantanes. These studies describe the first quantum transport measurements in sila-diamondoid structures, and demonstrate how main-chain Ge doping can be used to increase electronic transmission in sila-diamondoid-based molecular wires.

We report the synthesis and characterization of various compounds containing the 1,7,9-hydroxylated closo -dodecahydrododecaborate (B 12 H 9 (OH) 3 ) cluster motif. Specifically, we show how the parent compound can be synthesized on the multigram scale and further perhalogenated, leading to a new class of vertex-differentiated weakly coordinating anions. We show that a postmodification of the hydroxyl groups by alkylation affords further opportunities for tailoring these anions' stability, steric bulk, and solubility properties. The resulting dodecaborate-based salts were subjected to a full thermal and electrochemical stability evaluation, showing that many of these anions maintain thermal stability up to 500 °C and feature no redox activity below ∼1 V vs Fc/Fc 2- ) cluster motif. Specifically, we show how the parent compound can be synthesized on the multigram scale and further perhalogenated, leading to a new class of vertex-differentiated weakly coordinating anions. We show that a postmodification of the hydroxyl groups by alkylation affords further opportunities for tailoring these anions' stability, steric bulk, and solubility properties. The resulting dodecaborate-based salts were subjected to a full thermal and electrochemical stability evaluation, showing that many of these anions maintain thermal stability up to 500 °C and feature no redox activity below ∼1 V vs Fc/Fc + . Mixed hydroxylated/halogenated clusters show enhanced solubility compared to their purely halogenated analogs and retain weakly coordinating properties in the solid state, as demonstrated by ionic conductivity measurements of their Li + salts.

Iron sulfur clusters are critical to a plethora of biological processes; however, little is known about the elementary unit of these clusters, namely the [Fe=S] n+ fragment. Here, we report the synthesis and characterization of a terminal iron sulfido complex. Despite its high spin ( S = 5/2) ground state, structural, spectroscopic, and computational characterization provide evidence for iron sulfur multiple bond character. Intriguingly, the complex reacts with additional sulfur to afford an S = 3/2 iron(III) disulfido (S 2 2- ) complex. Preliminary studies reveal that the sulfido complex reacts with dihydroanthracene to afford an iron(II) hydrosulfido complex, akin to the reactivity of iron oxo complexes. By contrast, there is no reaction with the disulfido complex. These results provide important insight into the nature of the iron sulfide unit., Competing Interests: DECLARATION OF INTERESTS The authors declare no competing interests.

Aedes japonicus is an invasive Asian mosquito species, and to date it is widespread in many European countries. In Italy, it was first recorded in 2015 at the Austrian border and it then spread throughout the Northeast of the country. In 2019, it was also identified in Piedmont region, near the Swiss border. In the framework of the Italian program for prevention, surveillance, and response to Arboviruses, from June to November 2021, biweekly entomological surveillance was performed in the Liguria region (Northwest Italy). The collected mosquitoes were morphologically and genetically identified and molecularly analysed for the detection of West Nile and Usutu viruses. Six female mosquitoes, trapped on the 6th of July 2021 using a gravid trap in Albenga (Savona province), were morphologically identified as Ae. japonicus and the identification was genetically confirmed. The pool tested was negative for the presence of West Nile and Usutu viruses. The detection of Ae. japonicus was performed in a coastal area characterized by the presence of many floriculture activities. Considering the distance from the established Ae. japonicus mosquito populations in Italy and other European countries, this could represent an independent introduction in this country.

Patients with viral infections are at higher risk to acquire bacterial and fungal superinfections associated with a worse prognosis. We explored this critical point in the setting of patients with severe COVID-19 disease. The study included 1911 patients admitted to intensive care unit (ICU) during a 2-year study period (March 2020-March 2022). Of them, 713 (37.3%) were infected with SARS-CoV-2 and 1198 were negative (62.7%). Regression analysis was performed to determine risk factors associated with the presence of bacterial and/or fungal superinfections in SARS-CoV-2 patients and to evaluate predictors of ICU mortality. Of the 713 patients with SARS-CoV-2 infection, 473 (66.3%) had respiratory and/or bloodstream bacterial and/or fungal superinfections, while of the 1198 COVID-19-negative patients, only 369 (30%) showed respiratory and/or bloodstream bacterial and/or fungal superinfections (p < 0.0001). Baseline characteristics of COVID-19 patients included a median age of 66 (interquartile range [IQR], 58-73), a predominance of males (72.7%), and the presence of a BMI higher than 24 (median 26; IQR, 24.5-30.4). Seventy-four percent (527, 73.9%) had one or more comorbidities and 135 (18.9%) of them had received previous antibiotic therapy. Furthermore, most of them (473, 66.3%) exhibited severe radiological pictures and needed invasive mechanical ventilation. Multivariate logistic regression analysis showed that 1 unit increment in BMI rises the risk of bacterial and/or fungal superinfections acquisition by 3% and 1-day increment in ICU stays rises the risk of bacterial and/or fungal superinfections acquisition by 11%. Furthermore, 1-day increment in mechanical ventilation rises the risk of bacterial and/or fungal superinfection acquisition by 2.7 times. Furthermore, patients with both bacterial and fungal infections had a significantly higher mortality rate than patients without superinfections (45.8% vs. 26.2%, p < 0.0001). Therefore, bacterial and fungal superinfections are frequent in COVID-19 patients admitted to ICU and their presence is associated with a worse outcome. This is an important consideration for targeted therapies in critically ill SARS-CoV-2 infected patients to improve their clinical course., (© 2023 The Authors. Journal of Medical Virology published by Wiley Periodicals LLC.)

We conducted a retrospective analysis to determine the potential reduction in treatment burden through the expansion of virtual care among children with leukemia (n = 152). Patients living in urban areas traveled median distances of 1555 km compared with 7536 km for patients living in rural areas (p < .05). For the latter group, a median reduction in travel distance of 3560 km (interquartile range [IQR], 2136-5787 km), travel time of 51 h (IQR, 26-78 h), and CO 2 emissions of 623 kg (IQR, 374-1013 kg) was estimated, if every second visit was replaced by video consultations., (© 2023 The Authors. Pediatric Blood & Cancer published by Wiley Periodicals LLC.)

Purpose: Serial assessment of health condition based on self-report made by children and their proxies has consistently shown a lack of congruence. The study explored the discrepancies between mother's, father's, and children's reports on health-related quality of life (HRQOL) during the first two months of pediatric cancer treatment., Methods: In this cohort study, children and parents completed the generic and cancer-specific Pediatric Quality-of-Life Inventory (PedsQL) questionnaires at initial diagnosis and in the subsequent months. Evaluation of discrepancies included intraclass correlations between mother-child and father-child dyads at different domain levels., Results: Thirty-six children with a diagnosis of cancer between May 2020 and November 2021 and their parents were included in this study. At diagnosis, mother-child dyads showed better agreement on more domains of the PedsQL Generic Core Scale than father-child dyads; moderate agreement persisted for both parents at subsequent time points on the physical domain. The disease-specific PedsQL Cancer Module revealed moderate and better agreement for mother-child dyads during active cancer therapy. In particular, agreement of mother-child dyads was pronounced for domains such as worry (0.77 [95% CI 0.52-0.89, P < 0.001]), whereas fathers tended to overestimate the child's symptom burden for most of the remaining domains of the PedsQL Cancer Module., Conclusion: This cohort study shows that both parent proxy reports can provide valid information on child's HRQOL, but that fathers tend to overestimate, particularly for non-observable domains. Proxy reports derived from mothers more closely agreed with children's HRQOL and might be more weighted, if there is uncertainty between parents., (© 2023. The Author(s).)

Sliced cooked ham stored in modified atmosphere packaging (MAP) can be spoiled by lactic acid bacteria (LAB) which are dominating under psychrotrophic conditions. Depending on the strains, the colonization can result in a premature spoilage characterized by off-flavors, gas and slime production, discoloration, and acidification. The purpose of this study was the isolation, identification and characterization of potential food culture with protective properties, able to prevent or delay spoilage in cooked-ham. The first step was to identify by means of microbiological analysis, the microbial consortia both in unspoiled and in spoiled lots of sliced cooked ham by the use of media for the detection lactic acid bacteria and total viable count. Counts ranged from values lower than 1 Log CFU/g to 9 Log CFU/g in spoiled and unflawed samples. The interaction between consortia was then studied in order to screen for strains able to inhibit spoilage consortia. Strains showing antimicrobial activity were identified and characterized by molecular methods and tested for their physiological features. Among a total of 140 strains isolated, nine were selected for their ability to inhibit a large number of spoilage consortia, to grow and ferment at 4 °C and to produce bacteriocins. The effectiveness of the fermentation made by food culture was evaluated, through challenge tests in situ, analysing the microbial profiles of artificially inoculated cooked-ham slices during storage by high throughput 16 S rRNA gene sequencing. The native population in situ resulted competitive against the inoculated strains and only one strain was able to significantly reduce the native populations reaching about 46.7% of the relative abundance. The results obtained in this study provide information about the selection of autochthonous LAB on the base of their action against spoilage consortia, in order to select protective potential cultures able to improve the microbial quality of sliced cooked ham., 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 Ltd. All rights reserved.)

Appending functional groups to the exterior of Zn 4 L 4 self-assembled cages allows gated control of anion binding. While the unfunctionalized cages contain aryl groups in the ligand that can freely rotate, attaching inert functional groups creates a "doorstop", preventing rotation and slowing the guest exchange rate, even though the interiors of the host cavities are identically structured. The effects on anion exchange are subtle and depend on multiple factors, including anion size, the nature of the leaving anion, and the electron-withdrawing ability and steric bulk of the pendant groups. Multiple exchange mechanisms occur, and the nature of the external groups controls associative and dissociative exchange processes: these bulky groups affect both anion egress and ingress, introducing an extra layer of selectivity to the exchange. Small changes can have large effects: affinities for anions as similar as PF 6 - and SbF 6 - can vary by as much as 400-fold between identically sized cavities., (© 2022 Wiley-VCH GmbH.)

Europe has faced a massive spread of the varicella-zoster virus through the years. Since the introduction of an effective vaccine, complications and severe forms of chickenpox have been restricted. Nevertheless, among the population, some categories need specific care, such as pregnant women, who present one of the most fragile conditions facing this infection, both for the mother and the fetus. In this review, we highlight how the varicella-zoster virus can be dangerous during pregnancy, underlining the problem of treatment and vaccination, and collect information about the European epidemiology among this particular category of women.

Subcomponent self-assembly relies on cation coordination whereas the roles of anions often only emerge during the assembly process. When sites for anions are instead pre-programmed, they have the potential to be used as orthogonal elements to build up structure in a predictable and modular way. We explore this idea by combining cation (M + ) and anion (X - ) binding sites together and show the orthogonal and modular build up of structure in a multi-ion assembly. Cation binding is based on a ligand (L) made by subcomponent metal-imine chemistry (M + = Cu + , Au + ) while the site for anion binding (X - = BF 4 - , ClO 4 - ) derives from the inner cavity of cyanostar (CS) macrocycles. The two sites are connected by imine condensation between a pyridyl-aldehyde and an aniline-modified cyanostar. The target assembly [LM-CS-X-CS-ML], + generates two terminal metal complexation sites (LM and ML) with one central anion-bridging site (X) defined by cyanostar dimerization. We showcase modular assembly by isolating intermediates when the primary structure-directing ions are paired with weakly coordinating counter ions. Cation-directed (Cu + ) or anion-bridged (BF 4 - ) intermediates can be isolated along either cation-anion or anion-cation pathways. Different products can also be prepared in a modular way using Au + and ClO 4 - . This is also the first use of gold(i) in subcomponent self-assembly. Pre-programmed cation and anion binding sites combine with judicious selection of spectator ions to provide modular noncovalent syntheses of multi-component architectures., Competing Interests: The authors declare no competing financial interests., (This journal is © The Royal Society of Chemistry.)