Search

The synthesis and characterization of nine Schiff bases of pyrazolone ligands HLn(n= 1–9) and the corresponding zinc(II) complexes 1–9of composition [Zn(Ln)2] (n= 1–9) are reported. The molecular structures of complexes 2, 3, 4, 8, and 9were determined by single-crystal X-ray diffraction analysis, highlighting in all cases a distorted tetrahedral geometry around the Zn(II) ion. Density functional theory studies are performed on both the HLnligands and the derived complexes. A mechanism of dissociation and hydrolyzation of the coordinated Schiff base ligands is suggested, confirmed experimentally by powder X-ray diffraction study and photophysical studies. Complexes 1–9were investigated in vitro as anticancer agents, along with mutant p53 (mutp53) protein levels in human cancer cell lines carrying R175H and R273H mutp53 proteins. Only those complexes with the highest Zn(II) ion release via dissociation have shown a significant cytotoxic activity with reduction of mutp53 protein levels.

The irradiation of InN and InxGa1–xN samples with low-energy H ions results in exceptionally high hydrogen uptake in a crystalline semiconductor. This phenomenon is attributed to specific In–H complex formation. By exploiting spectral fingerprints of the In–H complexes observable in In L3-edge X-ray absorption spectroscopy, we provide direct evidence of complex formation. Density functional theory calculations assist in interpreting the X-ray absorption spectra and offer insights into the energetics of complex formation. We quantify the total amount of reversibly incorporated hydrogen in these semiconductors and discuss their strengths and weaknesses as innovative materials for hydrogen storage.

Curcuminoids and their complexes continue to attract attention in medicinal chemistry, but little attention has been given to their metabolic derivatives. Here, the first examples of (arene)Ru(II) complexes with curcuminoid metabolites, tetrahydrocurcumin (THcurcH), and tetrahydrobisdesmethoxycurcumin (THbdcurcH) were prepared and characterized. The neutral complexes [Ru(arene)(THcurc)Cl] and [Ru(arene)(THbdcurc)Cl] (arene = cymene, benzene, or hexamethylbenzene) were characterized by NMR spectroscopy and ESI mass spectrometry, and the crystal structures of the three complexes were determined by X-ray diffraction analysis. Compared to curcuminoids, these metabolites lose their conjugated double bond system responsible for their planarity, showing unique closed conformation structures. Both closed and open conformations have been analyzed and rationalized by using density functional theory (DFT). The cytotoxicity of the complexes was evaluated in vitro against human ovarian carcinoma cells (A2780 and A2780cisR), human breast adenocarcinoma cells (MCF-7 and MCF-7CR), as well as against non-tumorigenic human embryonic kidney cells (HEK293) and human breast (MCF-10A) cells and compared to the free ligands, cisplatin, and RAPTA-C. There is a correlation between cellular uptake and the cytotoxicity of the compounds, suggesting that cellular uptake and binding to nuclear DNA may be the major pathway for cytotoxicity. However, the levels of complex binding to DNA do not strictly correlate with the cytotoxic potency, indicating that other mechanisms are also involved. In addition, treatment of MCF-7 cells with [Ru(cym)(THcurc)Cl] showed a significant decrease in p62 protein levels, which is generally assumed as a noncisplatin-like mechanism of action involving autophagy. Hence, a cisplatin- and a noncisplatin-like concerted mechanism of action, involving both apoptosis and autophagy, is possible.

We implemented radio frequency-assisted electrostatic force microscopy (RF-EFM) to investigate the electric field response of biaxially strained molybdenum disulfide (MoS2) monolayers (MLs) in the form of mesoscopic bubbles, produced via hydrogen (H)-ion irradiation of the bulk crystal. MoS2ML, a semiconducting transition metal dichalcogenide, has recently attracted significant attention due to its promising optoelectronic properties, further tunable by strain. Here, we take advantage of the RF excitation to distinguish the intrinsic quantum capacitance of the strained ML from that due to atomic scale defects, presumably sulfur vacancies or H-passivated sulfur vacancies. In fact, at frequencies fRFlarger than the inverse defect trapping time, the defect contribution to the total capacitance and to transport is negligible. Using RF-EFM at fRF= 300 MHz, we visualize simultaneously the bubble topography and its quantum capacitance. Our finite-frequency capacitance imaging technique is noninvasive and nanoscale and can contribute to the investigation of time- and spatial-dependent phenomena, such as the electron compressibility in quantum materials, which are difficult to measure by other methods.

The development of compact fusion reactors relies on high temperature superconductors to generate the required high field. In this frame Rare-Earth Barium Copper Oxide tapes appear as the most promising solution. However, these tapes will experience a radiation harsh environment due to the high flux and fluence of energetic neutrons and of the secondary particles produced by the neutrons interaction with the materials. Realistic 3D Monte Carlo simulations represent the required tool to reliably estimate the radiation environment of the tapes, providing the starting point for experimental investigation of their radiation hardness and performance under working conditions. In this paper a comprehensive analysis of damage and energy deposition including secondary particles on a 3D model of a VIPER cable is carried out, starting from a 3D model of an ARC-class reactor.

Introduction: Patients requiring postcardiotomy veno-arterial extracorporeal membrane oxygenation (V-A-ECMO) have a high risk of early mortality. In this analysis, we evaluated whether any interinstitutional difference exists in the results of postcardiotomy V-A-ECMO.Methods: Studies on postcardiotomy V-A-ECMO were identified through a systematic review for individual patient data (IPD) meta-analysis. Analysis of interinstitutional results was performed using direct standardization, estimation of observed/expected in-hospital mortality ratio and propensity score matching.Results: Systematic review of the literature yielded 31 studies. Data from 10 studies on 1269 patients treated at 25 hospitals were available for the present analysis. In-hospital mortality was 66.7%. The relative risk of in-hospital mortality was significantly higher in six hospitals. Observed versus expected in-hospital mortality ratio showed that four hospitals were outliers with significantly increased mortality rates, and one hospital had significantly lower in-hospital mortality rate. Participating hospitals were classified as underperforming and overperforming hospitals if their observed/expected in-hospital mortality was higher or lower than 1.0, respectively. Among 395 propensity score matched pairs, the overperforming hospitals had significantly lower in-hospital mortality (60.3% vs 71.4%, p= 0.001) than underperforming hospitals. Low annual volume of postcardiotomy V-A-ECMO tended to be predictive of poor outcome only when adjusted for patients’ risk profile.Conclusions: In-hospital mortality after postcardiotomy V-A-ECMO differed significantly between participating hospitals. These findings suggest that in many centers there is room for improvement of the results of postcardiotomy V-A-ECMO.

Structural and electronic factors are crucial to rationalize the different N,Oor N,Nchelating coordination of pyrazolones containing a pyridine ring. The reactivity of proligand 3-phenyl-1-(pyridin-2-yl)-5-pyrazolone (HLpy,ph) with the (arene)Ru(II) fragment was explored. Neutral and ionic (arene)Ru(II) complexes were obtained and fully characterized, also by X-ray diffraction, revealing the ligand to coordinate in an unusual N,O-chelating fashion. Other ruthenium complexes were also synthesized with 3-methyl-1-(pyridin-2-yl)-5-pyrazolone (HLpy,me) and 3-methyl-1-(pyridin-2-yl)-4-trifluoroacetyl-5-pyrazolone (HQpy,CF3). In these complexes the ligands adopt the preferred N,N-chelating mode. Ligands and complexes were theoretically analyzed by density functional theory (DFT). The most stable tautomer of HLpy,phmatched well with the experimental behavior of this proligand and the structures of Ru-complexes were well described by calculations. The thermodynamic stability of the N,O- and N,N-coordination modes was analyzed and a proposal for the achievement of the N,O-coordination mode in complexes 1–4was proposed. Cytotoxicity tests were performed against human ovarian carcinoma (A2780 and Cisplatin-resistant A2780cis) and nontumorigenic human embryonic kidney (HEK293T) cell lines, showing the free ligands to be more cytotoxic that the ensuing (arene)Ru(II) complexes.

The tire–road friction coefficient is a critical evaluation index of the service performance of roads: it governs the stopping distance, traction control, and stability of vehicles. Moreover, friction information is also needed in many function units of modern vehicles. This paper proposes a novel data-driven approach for inference of the maximum tire–road friction coefficient using a combination of vehicle dynamics signal and machine vision data. The approach is aimed at robust road condition perception that can provide frequent measurements over large areas across all weather conditions. Two different neural network architectures were adopted to extract in-depth features behind vehicle dynamics signals and road surface images. Features from these two types of data were then fused in two different levels, namely feature level and decision level, forming a multi-feature fusion neural network. The proposed network performs better than models based only on dynamic signals or vision data. The method proposed was applied to real data obtained from an electric car in a highway driving scenario. For classification of the maximum tire–road friction coefficient, the proposed network can yield F1-score increments of 0.09 and 0.18 from dynamics-based and vision-based sub-models, respectively. For the maximum tire–road friction coefficient value regression, the proposed model also achieves the highest R-square score of 0.71. Of these two types of data collected under highway driving scenarios, the vision data contribute more to the overall performance of the proposed model. Nevertheless, the dynamics data possess excellent potential in poor lighting conditions. With these fused features, the proposed multi-feature fusion network can not only improve the accuracy of maximum tire–road friction coefficient estimation but also is deemed workable for a broader range of scenarios.

The measurement of the Cosmic Microwave Background (CMB) polarization and the spectral distortions produced on this radiation field by clusters of galaxies (Sunyaev-Zeldovich Effect, SZE) are the current frontiers in cosmology. In this paper, we report on two stratospheric balloon experiments aimed to study the research fields mentioned above. OLIMPO is a mm/submm waves telescope, with 2.6 m primary mirror coupled to four arrays of Kinetic Inductance Detectors (KID), centered at 150, 250, 350, and 460 GHz, to match the SZ spectrum, and operating at 0.3 K. The payload, flown in 2018 producing a very successful technology demonstration, includes a plug-in Differential Fourier-Transform Spectrometer. LSPE (Large Scale Polarization Explorer) is a combined balloon-borne and ground-based program dedicated to the measurement of the CMB polarization at large angular scales. LSPE/SWIPE (Short Wavelength Instrument for the Polarization Explorer), the balloon-borne instrument, includes a refractive telescope with a 50 cm optical aperture feeding three arrays of 330 multi-mode TES bolometers at 145, 210, e 240 GHz. The polarization of the incoming radiation will be modulated by a rotating Half Wave Plate (HWP), that is maintained levitating by an innovative magnetic suspension system. The detectors and the optical elements are cooled at cryogenic temperatures. The cryogenic system is designed to have a duration of 14 days with a flight performed during the polar night, to allow a coverage of a large fraction of the sky. In the paper, we describe the configuration of the two instruments, the modifications to be implemented on OLIMPO for a second scientific flight and the status of the different sub-system for LSPE/SWIPE.

Current guidelines advise using prophylactic tricuspid valve annuloplasty during mitral valve surgery, especially in the presence of annular diameter enlargement. However, several retrospective studies and a prospective randomized study from our department could not confirm that diameter enlargement is predictive of late regurgitation. We examined whether 2- and 3-dimensional echocardiographic and clinical characteristics could identify patients who will develop moderate or severe recurrent tricuspid regurgitation.

The road-transport sector has a significant impact on energy consumption. A relevant component of this energy usage is associated with rolling resistance (RR) between tires and pavement. In Denmark, CO2emissions from road transport alone have been quantified as 4.6 Mt/yr. Replacing standard stone asphalt with durable low-RR pavements is expected to reduce CO2emissions up to 1%. The Danish Road Directorate started, back in 2012, optimising a surface layer for reducing RR. The low-RR mixture was designed to provide a durable texture capable to meet all safety requirements. In 2016, two low-RR mixtures and reference asphalt concrete were paved on a test section. To evaluate the texture durability these mixtures were sampled at the construction site and tested with a circular road tester. The results show that the durability of low-RR pavements can be enhanced by using premodified binder, which reduces changes in texture properties and increases rutting resistance.

IntroductionExposure to asbestos increases the risk of lung cancer and mesothelioma. Few studies quantified the premature occurrence of these diseases in asbestos-exposed workers. Focus on premature disease onset (rate advancement or acceleration) can be useful in risk communication and for the evaluation of exposure impact. We estimated rate advancement for total mortality, lung cancer and pleural mesothelioma deaths, by classes of cumulative asbestos exposure in a pooled cohort of asbestos cement (AC) workers in Italy.MethodThe cohort study included 12 578 workers from 21 cohorts, with 6626 deaths in total, 858 deaths from lung cancer and 394 from pleural malignant neoplasm (MN). Rate advancement was estimated by fitting a competitive mortality Weibull model to the hazard of death over time since first exposure (TSFE).ResultAcceleration time (AT) was estimated at different TSFE values. The highest level of cumulative exposure compared with the lowest, for pleural MN AT was 16.9 (95% CI 14.9 to 19.2) and 33.8 (95% CI 29.8 to 38.4) years at TSFE of 20 and 40 years, respectively. For lung cancer, it was 13.3 (95% CI 12.0 to 14.7) and 26.6 (95% CI 23.9 to 29.4) years, respectively. As for total mortality, AT was 3.35 (95% CI 2.98 to 3.71) years at 20 years TSFE, and 6.70 (95% CI 5.95 to 7.41) at 40 years TSFE.ConclusionThe current study observed marked rate advancement after asbestos exposure for lung cancer and pleural mesothelioma, as well as for total mortality.

(Abstracted from Prenat Diagn2022;42:1575–1586Methods for diagnosis of genetic abnormalities have recently undergone substantial improvement. Noninvasive prenatal testing (NIPT) is performed early in pregnancy, typically at the end of the first trimester using cell-free DNA (cfDNA) to identify 3 commonly occurring trisomies (13, 18, and 21).

Two pyrazolone-based hydrazones H2L′ [in general, H2L′; in detail, H2L1= 5-methyl-2-phenyl-4-(2-phenyl-1-(2-(4-(trifluoromethyl)phenyl)hydrazineyl)ethyl)-2,4-dihydro-3H-pyrazol-3-one, H2L2= (Z)-5-methyl-2-phenyl-4-(2-phenyl-1-(2-(pyridin-2-yl)hydrazineyl)ethylidene)-2,4-dihydro-3H-pyrazol-3-one] were reacted with Zn(II) and Cu(II) acceptors affording the complexes [Zn(HL1)2(MeOH)2], [Cu(HL1)2], and [M(HL2)2] (M = Cu or Zn). X-ray and DFT studies showed the free proligands to exist in the N–H,N–H tautomeric form and that in [Zn(HL1)2(MeOH)2], zinc is six-coordinated by the N,O-chelated (HL1) ligand and other two oxygen atoms of coordinated methanol molecules, while [Cu(HL1)2] adopts a square planar geometry with the two (HL1) ligands in anti-conformation. Finally, the [M(HL2)2] complexes are octahedral with the two (HL2) ligands acting as κ-O,N,N-donors in planar conformation. Both the proligands and metal complexes were tested against the parasite Trypanosoma bruceiand Balb3T3 cells. The Zn(II) complexes were found to be very powerful, more than the starting proligands, while maintaining a good safety level. In detail, H2L1and its Zn(II) complex have high selective index (55 and >100, respectively) against T. bruceicompared to the mammalian Balb/3T3 reference cells. These results encouraged the researchers to investigate the mechanism of action of these compounds that have no structural relations with the already known drugs used against T. brucei. Interestingly, the analysis of NTP and dNTP pools in T. bruceitreated by H2L1and its Zn(II) complex showed that the drugs had a strong impact on the CTP pools, making it likely that CTP synthetase is the targeted enzyme.

A quantum-light source that delivers photons with a high brightness and a high degree of entanglement is fundamental for the development of efficient entanglement-based quantum-key distribution systems. Among all possible candidates, epitaxial quantum dots are currently emerging as one of the brightest sources of highly entangled photons. However, the optimization of both brightness and entanglement currently requires different technologies that are difficult to combine in a scalable manner. In this work, we overcome this challenge by developing a novel device consisting of a quantum dot embedded in a circular Bragg resonator, in turn, integrated onto a micromachined piezoelectric actuator. The resonator engineers the light-matter interaction to empower extraction efficiencies up to 0.69(4). Simultaneously, the actuator manipulates strain fields that tune the quantum dot for the generation of entangled photons with corrected fidelities to a maximally entangled state up to 0.96(1). This hybrid technology has the potential to overcome the limitations of the key rates that plague QD-based entangled sources for entanglement-based quantum key distribution and entanglement-based quantum networks.

Hexagonal boron nitride (hBN) is widely used as a protective layer for few-atom-thick crystals and heterostructures (HSs), and it hosts quantum emitters working up to room temperature. In both instances, strain is expected to play an important role, either as an unavoidable presence in the HS fabrication or as a tool to tune the quantum emitter electronic properties. Addressing the role of strain and exploiting its tuning potentiality require the development of efficient methods to control it and of reliable tools to quantify it. Here we present a technique based on hydrogen irradiation to induce the formation of wrinkles and bubbles in hBN, resulting in remarkably high strains of ∼2%. By combining infrared (IR) near-field scanning optical microscopy and micro-Raman measurements with numerical calculations, we characterize the response to strain for both IR-active and Raman-active modes, revealing the potential of the vibrational properties of hBN as highly sensitive strain probes.

The mobile dislocation pile-ups observed during in situ straining experiments have been used as probes to describe the short-range order (SRO) present in the γ phase of nickel-base superalloys. An experimental approach, based on the measurement of the dislocation positions, to characterise the SRO has been developed. This paper focuses on the main results we have obtained on this topic. A quantitative analysis allows to get the chemical forces associated with SRO, and also the SRO degree. For the first time, the energies associated with SRO are evaluated along a dislocation pile-up as a function of temperature. More generally, a description of the SRO is proposed: SRO is seen as a heterogeneous distribution at the micrometer scale of nanometric areas. Another characteristic has been evidenced: the reversible character of the SRO creation.

The mobile dislocation pile-ups observed during in situ straining experiments have been used as probes to describe the short-range order (SRO) present in the γ phase of nickel-base superalloys. An experimental approach, based on the measurement of the dislocation positions, to characterise the SRO has been developed. This paper focuses on the main results we have obtained on this topic. A quantitative analysis allows to get the chemical forces associated with SRO, and also the SRO degree. For the first time, the energies associated with SRO are evaluated along a dislocation pile-up as a function of temperature. More generally, a description of the SRO is proposed: SRO is seen as a heterogeneous distribution at the micrometer scale of nanometric areas. Another characteristic has been evidenced: the reversible character of the SRO creation.

The mobile dislocation pile-ups observed during in situ straining experiments have been used as probes to describe the short-range order (SRO) present in the phase of nickel-base superalloys. An experimental approach, based on the measurement of the dislocation positions, to characterise the SRO has been developed. This paper focuses on the main results we have obtained on this topic. A quantitative analysis allows to get the chemical forces associated with SRO, and also the SRO degree. For the first time, the energies associated with SRO are evaluated along a dislocation pile-up as a function of temperature. More generally, a description of the SRO is proposed: SRO is seen as a heterogeneous distribution at the micrometer scale of nanometric areas. Another characteristic has been evidenced: the reversible character of the SRO creation.

Patient's illness perception, assessed through the Brief‐Illness Perception Questionnaire (Brief‐IPQ), plays a decisive role in the treatment effectiveness of a wide range of chronic diseases; nonetheless, evidence is still lacking regarding periodontitis. The aim of the present pre‐post quasi‐experimental study was to evaluate the change in the Brief‐IPQ before and after non‐surgical periodontal treatment (NST) and to evaluate its ability to foresee the efficacy of NST. A total of 126 periodontitis participants starting NST were asked to participate in the study. The nine‐item Brief‐IPQ together with a full periodontal chart were recorded at baseline and at the 3‐month follow up (reevaluation) after NST. Pre‐post comparisons of psychometric and periodontal variables were carried out through the Wilcoxon signed‐rank test (α = 0.05). A predictive model was built to test the ability of the Brief‐IPQ items to foresee the efficacy of NST. NST led to a significant reduction in all periodontal parameters (P < 0.001); the proportion of pockets closed was 64.18%. Although the overall sum score of the Brief‐IPQ remained fairly stable (P = 0.0673), significant changes occurred for items seven (“understanding”) (P < 0.001) and 8 (“emotional response”) (P < 0.05). The best model (R2 = 0.068, F = 2.15, P = 0.033) obtained from the multivariate linear regression analysis demonstrated that item five (“identity”) (β = 2.340, P = 0.017) and item eight (“emotional response”) (β = ‐2.569, P = 0.008) significantly predict the efficacy of NST (i.e., the proportion of pockets closed at reevaluation). NST significantly ameliorates patient's understanding and emotional burden related to periodontitis. Baseline values of perceived symptoms and emotional response are predictive for the short‐term efficacy of NST.

A series of neutral ruthenium(II) arene complexes [(arene)Ru(QR)Cl] (arene = p-cymene (cym) or hexamethylbenzene (hmb)) containing 4-acyl-5-pyrazolonate QRligands with different electronic and steric substituents (R = 4-cyclohexyl, 4-stearoyl, or 4-adamantyl) and related ionic complexes [(arene)Ru(QR)(PTA)][PF6] (PTA = 1,3,5-triaza-7-phosphaadamantane) were synthesized and characterized by spectroscopy (IR, UV–vis, ESI-MS, and 1H and 13C NMR), elemental analysis, X-ray crystallography, and density functional theory studies. The cytotoxicity of the proligands and metal complexes was evaluated in vitro against human ovarian carcinoma cells (A2780 and A2780cisR), as well as against nontumorous human embryonic kidney (HEK293) cells. In general the cationic PTA-containing complexes are more cytotoxic than their neutral precursors with a chloride ligand in place of the PTA. Moreover, the complexes do not show cross-resistance and are essentially equally cytotoxic to both the A2780 and A2780cisR cell lines, although they only show limited selectivity toward the cancer cell lines.

A series of half-sandwich pentamethylcyclopentadienyl rhodium(III) and iridium(III) complexes [Cp*M(DBM/HDB/AVB)Cl] and [Cp*M(DBM/HDB/AVB)(PTA)][SO3CF3], where Cp* = pentamethylcyclopentadienyl, the proligands DBMH = dibenzoylmethane, HDBH = o-hydroxydibenzoylmethane, AVBH = avobenzone, and PTA = 1,3,5-triaza-7-phosphaadamantane, is reported. All the complexes were characterized by IR, 1H and 13C NMR spectroscopy, electrospray ionization mass spectrometry, elemental analysis, and DFT calculations. Five of the complexes have also been characterized in the solid-state by X-ray crystallography. The cytotoxicity of the complexes has been evaluated against human ovarian A2780 and A2780cisR cell lines and, with the only exception of complexes 1and 2that display a negligible cytotoxicity, exhibit moderate cytotoxicity toward both cancer cell lines. However, the complexes do not show cancer cell selectivity with respect to human embryonic kidney HEK293 cells.

Supplemental digital content is available in the text.

The outstanding mechanical performances of two-dimensional (2D) materials make them appealing for the emerging fields of flextronics and straintronics. However, their manufacturing and integration in 2D crystal-based devices rely on a thorough knowledge of their hardness, elasticity, and interface mechanics. Here, we investigate the elasticity of highly strained monolayer-thick MoS2membranes, in the shape of micrometer-sized domes, by atomic force microscopy (AFM)-based nanoindentation experiments. A dome’s crushing procedure is performed to induce a local re-adhesion of the dome’s membrane to the bulk substrate under the AFM tip’s load. It is worth noting that no breakage, damage, or variation in size and shape are recorded in 95% of the crushed domes upon unloading. Furthermore, such a procedure paves the way to address quantitatively the extent of the van der Waals interlayer interaction and adhesion of MoS2by studying pull-in instabilities and hysteresis of the loading–unloading cycles. The fundamental role and advantage of using a superimposed dome’s constraint are also discussed.

Modern cars are equipped with many sensors that measure information about the vehicle and its surroundings. These measurements are therefore related to the ride-surface conditions over which the vehicle is passing. The paper commences by outlining a four-component vision for performing road condition evaluation based on in-vehicle sensor readings and subsequent feeding of pavement management systems (PMSs) with live condition information. This is expected to enrich the functionalities of PMSs, and ultimately lead to improved maintenance and repair decisions. Next the LiRA (Live Road Assessment) project—an ongoing proof-of-concept attempt to realize the vision components—is presented. The project elements and software architecture are described in detail, listing any assumptions, compromises, and challenges. LiRA involves a fleet of 400 electric cars operating in Copenhagen, both within the city streets and nearby highways. Sensor data collection is performed with a customized Internet of Things (IoT) device installed in the cars. Data processing and structuring involve new software tools for quality control, spatio-temporal interpolation, and map matching. A hybrid approach, combining machine learning models with physical (mechanics-based) models, is currently being applied to convert data into relevant information for PMSs. Based on the experience thus far with LiRA, the vision actualization is deemed achievable, workable, and up-scalable.

Despite improvements in diagnosis and management, infective endocarditis (IE) continues to create significant morbidity and mortality due to valvular dysfunctions with congestive heart failures or embolization [1].

Guiseppe Lusignani, Luca Pettinari, and Riccardo Tedeschi introduce a top‐down parsimonious model for simulating the recoveries of both secured and unsecured non‐performing loan (NPL) portfolios and a pricing approach to estimate the fair value of NPL securitization notes issues by ABS vehicles.

Comprehensive fire surveillance will strengthen resilience and adaptation to climate change.

Three metal–organic frameworks with the general formula Co(BPZX)(BPZX2–= 3-X-4,4′-bipyrazolate, X = H, NH2, NO2) constructed with ligands having different functional groups on the same skeleton have been employed as heterogeneous catalysts for aerobic liquid-phase oxidation of cumene with O2as oxidant. O2adsorption isotherms collected at pO2= 1 atm and T= 195 and 273 K have cast light on the relative affinity of these catalysts for dioxygen. The highest gas uptake at 195 K is found for Co(BPZ)(3.2 mmol/g (10.1 wt % O2)), in line with its highest BET specific surface area (926 m2/g) in comparison with those of Co(BPZNH2)(317 m2/g) and Co(BPZNO2)(645 m2/g). The O2isosteric heat of adsorption (Qst) trend follows the order Co(BPZ)> Co(BPZNH2)> Co(BPZNO2). Interestingly, the selectivity in the cumene oxidation products was found to be dependent on the tag present in the catalyst linker: while cumene hydroperoxide (CHP) is the main product obtained with Co(BPZ)(84% selectivity to CHP after 7 h, pO2= 4 bar, and T= 363 K), further oxidation to 2-phenyl-2-propanol (PP) is observed in the presence of Co(BPZNH2)as the catalyst (69% selectivity to PP under the same experimental conditions).

Three pyrazolone-based hydrazone ligands HL′ (HL′ in general; in detail, HL1 = 2-((5-hydroxo-3-methyl-1-phenyl-1H-pyrazol-4-yl)(phenyl)methylene)-1-(2,4-nitrophenyl)hydrazine, HL2 = 2-((5-hydroxo-3-methyl-1-phenyl-1H-pyrazol-4-yl) (phenyl)methylene)-1-(4-nitrophenyl)hydrazine, and HL3 = 2-((5-hydroxo-3-methyl-1-phenyl-1H-pyrazol-4-yl)(phenyl)methylene)-1-(pyridin-2-yl)hydrazine) have been prepared starting from 4-benzoyl-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one and fully characterized in the solid state and solution, where the existing tautomeric forms were identified by taking advantage of natural abundance 1H–15N coupling in {1H–15N}-HSQC and {1H–15N}-HMBC NMR spectroscopy. Then, six half-sandwich arene-ruthenium(II) derivatives (arene = hexamethylbenzene and p-cymene) of composition [(arene)Ru(L′)Cl] have been synthesized and fully characterized by IR, 1H, and 13C NMR spectroscopy, electrospray ionization mass spectrometry, elemental analysis, and density functional theory calculations. The crystal structures of three complexes, together with the Econfigurational isomer (with respect to the C═N double bond) of the free proligand HL2 and the zwitterionic proligand HL3 were determined by X-ray analysis. The anionic ligands L1 and L2 were found bonded to ruthenium in the N,O-form, while L3 coordinates the metal in the N,N-form affording five-membered chelating rings. The cytotoxicity of the complexes was evaluated against human breast adenocarcinoma cells (MCF-7 and MCF-7CR), as well as against nontumorigenic human breast (MCF-10A) cells and compared to the free ligand and cisplatin.

In the present work, three novel halogen-appended cadmium(II) metal–organic frameworks [Cd2(L1)2(4,4′-Bipy)2]n·4n(DMF) (1), [Cd2(L2)2(4,4′-Bipy)2]n·3n(DMF) (2), and [Cd(L3)(4,4′-Bipy)]n·2n(DMF) (3) [where L1 = 5-{(4-bromobenzyl)amino}isophthalate; L2 = 5-{(4-chlorobenzyl)amino}isophthalate; L3 = 5-{(4-fluorobenzyl)amino}isophthalate; 4,4′-Bipy = 4,4′-bipyridine; and DMF = N,N′-dimethylformamide] have been synthesized under solvothermal conditions and characterized by various analytical techniques. The single-crystal X-ray diffraction analysis demonstrated that all the MOFs feature a similar type of three-dimensional structure having a binuclear [Cd2(COO)4(N)4] secondary building block unit. Moreover, MOFs 1and 2contain one-dimensional channels along the b-axis, whereas MOF 3possesses a 1D channel along the a-axis. In these MOFs, the pores are decorated with multifunctional groups, i.e., halogen and amine. The gas adsorption analysis of these MOFs demonstrate that they display high uptake of CO2(up to 5.34 mmol/g) over N2and CH4. The isosteric heat of adsorption (Qst) value for CO2at zero loadings is in the range of 18–26 kJ mol–1. In order to understand the mechanism behind the better adsorption of CO2by our MOFs, we have also performed configurational bias Monte Carlo simulation studies, which confirm that the interaction between our MOFs and CO2is stronger compared to those with N2and CH4. Various noncovalent interactions, e.g., halogen (X)···O, Cd···O, and O···O, between CO2and the halogen atom, the Cd(II) metal center, and the carboxylate group from the MOFs are observed, respectively, which may be a reason for the higher carbon dioxide adsorption. Ideal adsorbed solution theory (IAST) calculations of MOF 1demonstrate that the obtained selectivity values for CO2/CH4(50:50) and CO2/N2(15:85) are ca. 28 and 193 at 273 K, respectively. However, upon increasing the temperature to 298 K, the selectivity value (S= 34) decreases significantly for the CO2/N2mixture. We have also calculated the breakthrough analysis curves for all the MOFs using mixtures of CO2/CH4(50:50) and CO2/N2(50:50 and 15:85) at different entering gas velocities and observed larger retention times for CO2in comparison with other gases, which also signifies the stronger interaction between our MOFs and CO2. Moreover, due to the presence of Lewis acidic metal centers, these MOFs act as heterogeneous catalysts for the CO2fixation reactions with different epoxides in the presence of tetrabutyl ammonium bromide (TBAB), for conversion into industrially valuable cyclic carbonates. These MOFs exhibit a high conversion (96–99%) of epichlorohydrin (ECH) to the corresponding cyclic carbonate 4-(chloromethyl)-1,3-dioxolan-2-one after 12 h of reaction time at 1 bar of CO2pressure, at 65 °C. The MOFs can be reused up to four cycles without compromising their structural integrity as well as without losing their activity significantly.

The four zinc(II) mixed-ligand metal–organic frameworks (MIXMOFs) Zn(BPZ)x(BPZNO2)1–x, Zn(BPZ)x(BPZNH2)1–x, Zn(BPZNO2)x(BPZNH2)1–x, and Zn(BPZ)x(BPZNO2)y(BPZNH2)1–x−y(H2BPZ = 4,4′-bipyrazole; H2BPZNO2= 3-nitro-4,4′-bipyrazole; H2BPZNH2= 3-amino-4,4′-bipyrazole) were prepared through solvothermal routes and fully investigated in the solid state. Isoreticular to the end members Zn(BPZ) and Zn(BPZX) (X = NO2, NH2), they are the first examples ever reported of (pyr)azolate MIXMOFs. Their crystal structure is characterized by a three-dimensional open framework with one-dimensional square or rhombic channels decorated by the functional groups. Accurate information about ligand stoichiometric ratio was determined (for the first time on MIXMOFs) through integration of selected ligands skeleton resonances from 13C cross polarized magic angle spinning solid-state NMR spectra collected on the as-synthesized materials. Like other poly(pyrazolate) MOFs, the four MIXMOFs are thermally stable, with decomposition temperatures between 708 and 726 K. As disclosed by N2adsorption at 77 K, they are micro-mesoporous materials with Brunauer–Emmett–Teller specific surface areas in the range 400–600 m2/g. A comparative study (involving also the single-ligand analogues) of CO2adsorption capacity, CO2isosteric heat of adsorption (Qst), and CO2/N2selectivity in equimolar mixtures at p= 1 bar and T= 298 K cast light on interesting trends, depending on ligand tag nature or ligand stoichiometric ratio. In particular, the amino-decorated compounds show higher Qstvalues and CO2/N2selectivity vs the nitro-functionalized analogues; in addition, tag “dilution” [upon passing from Zn(BPZX) to Zn(BPZ)x(BPZX)1–x] increases CO2adsorption selectivity over N2. The simultaneous presence of amino and nitro groups is not beneficial for CO2uptake. Among the compounds studied, the best compromise among uptake capacity, Qst, and CO2/N2selectivity is represented by Zn(BPZ)x(BPZNH2)1–x.

This paper present a laboratory study on the influence of filler type on the rheological properties of mastics. Mastic is the main component that undergoes any deformations in asphalt structure. Low shear resistance can lead to susceptibility to permanent deformations. The type of filler used in mastic can highly influence its rheological properties. The main objective of the study was to evaluate different types of mineral fillers and their stiffening effect on unmodified and modified mastics in terms of permanent deformations. During this study performance of three mineral fillers, namely Jelsa granite, Portland cement and Aggersund limestone were investigated. The fillers used in this study were evaluated according to common filler characteristics, such as Rigden voids (RV), density, specific surface area, fineness modulus and others. Dynamic shear rheometer was used for testing mastics under repeated shear stress with multiple stress creep recovery test method. Mastics performance was tested under three different temperature conditions. Analysis of the results showed that limestone filler provide best stiffening effect. The main factors affecting that is its fine gradation, high percentage of RV and high specific surface value. This subsequently results in high amount of bitumen being as fixed one. Granite filler with low value of RV showed poor performance.

The inherent ability of plasmonic bowtie nanoapertures (NAs) to localize the electromagnetic field at a subwavelength scale was exploited to engineer the H removal process in dilute nitrides at the nanometer level. Dilute nitride semiconductor alloys (e.g. GaAsN with a small percentage of nitrogen) are characterized by peculiar optoelectronic properties and, most importantly, by an even more peculiar response to hydrogen incorporation. In this class of materials, it is indeed possible to tune post-growth the alloy bandgap energy by a controlled incorporation of hydrogen atoms. The formation of N-H complexes neutralizes all the effects N has on the host matrix, among which is the strong narrowing of bandgap energy. In the present work, bowtie NAs resonant to the N-H complex dissociation energy were numerically modeled by finite element method simulations, realized by a lithographic approach, and characterized by scanning probe microscopy and resonant scattering spectroscopies. The conditions to get the maximum field enhancement at a specific position below the metal/semiconductor interface, namely at the dilute nitride quantum well position, were identified, demonstrating the ability to achieve a plasmon-assisted spatially selective hydrogen removal in a GaAsN/GaAs quantum well sample. Hydrogen removal through bowtie NAs turns out to be way more efficient (approximately two orders of magnitude) than through the plain surface, thus indicating that bandgap engineering through plasmonic nanostructures can be optimized for future efficient realization of site-controlled single-photon emitters and for their deterministic integration in plasmonic devices.

ObjectivesModels based on the multistage theory of cancer predict that rates of malignant mesothelioma continuously increase with time since first exposure (TSFE) to asbestos, even after the end of external exposure. However, recent epidemiological studies suggest that mesothelioma rates level off many years after first exposure to asbestos. A gradual clearance of asbestos from the lungs has been suggested as a possible explanation for this phenomenon. We analysed long-term trends of pleural and peritoneal cancer mortality in subjects exposed to asbestos to evaluate whether such trends were consistent with the clearance hypothesis.MethodsWe used data from a pool of 43 Italian asbestos cohorts (51 801 subjects). The role of asbestos clearance was explored using the traditional mesothelioma multistage model, generalised to include a term representing elimination of fibres over time.ResultsRates of pleural cancer increased until 40 years of TSFE, but remained stable thereafter. On the other hand, we observed a monotonic increase of peritoneal cancer with TSFE. The model taking into account asbestos clearance fitted the data better than the traditional one for pleural (p=0.004) but not for peritoneal (p=0.09) cancer.ConclusionsRates of pleural cancer do not increase indefinitely after the exposure to asbestos, but eventually reach a plateau. This trend is well described by a model accounting for a gradual elimination of the asbestos fibres. These results are relevant for the prediction of future rates of mesothelioma and in asbestos litigations.

In recent years the pavement engineering community has shown increasing interest in shifting from a stationary falling weight deflectometer (FWD) to moving testing platforms such as the traffic speed deflectometer (TSD). This paper dealt with comparing TSD measurements against FWD measurements; it focused on the comparison methodology, utilizing experimental data for demonstration. To better account for differences in loading conditions between the two devices a new FWD deflection index was formulated first. This index served as reference/benchmark for assessing the corresponding TSD measurements. Next, a Taylor diagram was proposed for visualizing several comparison statistics. Finally, a modern agreement metric was identified and applied for ranking comparison results across different datasets. Overall, the suggested methodology is deemed generic and highly applicable to future situations, especially for assessing the worth of emerging device upgrades or improved interpretation schemes (or both).

Novel composite materials PEn(n= 1–9) have been prepared by an easily up-scalable embedding procedure of three different families of Ag(I) acylpyrazolonato complexes in polyethylene (PE) matrix. In details, PE1–PE3composites contain polynuclear [Ag(QR)]ncomplexes, PE4–PE6contain mononuclear [Ag(QR)(L)m] complexes and PE7–PE9are loaded with mononuclear [Ag(QR) (PPh3)2] complexes, respectively (where L = 1-methylimidazole or 2-ethylimidazole, m= 1 or 2, and HQR= 1-phenyl-3-methyl-4-RC(O)-5-pyrazolone, where in detail HQfb, R = −CF2CF2CF3; HQcy, R = −cyclo-C6H11; HQbe, R = −C(H)C(CH3)2). The PEncomposites, prepared by using a 1:1000 w/w silver additive/polyethylene ratio, have been characterized in bulk by IR spectroscopy and TGA analyses, which confirmed that the properties of polyethylene matrix are essentially unchanged. AFM, SEM, and EDX surface techniques show that silver additives form agglomerates with dimensions 10–100 μm on the polyethylene surface, with a slight increment of surface roughness of pristine plastic within 50 nm. However, the elastic properties of the composites are essentially the same of PE. The antibacterial activity of all composites has been tested against three bacterial strains (E. coli, P. aeruginosaand S. aureus) and results show that two classes of composites, PE1–PE3and PE4–PE6, display high and persistent bactericidal and bacteriostatic activity, comparable to PE embedded with AgNO3. By contrast, composites PE7–PE9exhibit a reduced antibacterial action. Contact and release tests in several conditions for specific migration of Ag+from plastics, indicate a very limited but time persistent release of silver ions from PE1–PE6composites, thus suggesting that they are potential antibacterial materials for future applications. Instead, PE7–PE9almost do not release silver, only trace levels of silver ions being detected, in accordance with their reduced antibacterial action. None of the composites is toxic against higher organisms, as confirmed by D. magnatest of ecotoxicity.

Novel silver(I) acylpyrazolonato coordination polymers of formula [Ag(QR)]n(1–3) have been synthesized by interaction of silver nitrate with HQRin methanol in the presence of an equivalent quantity of KOH (in general HQR= 1-phenyl-3-methyl-4-RC(O)-5-pyrazolone, in detail HQfb, R = -CF2CF2CF3; HQcy, R = -cyclo-C6H11; HQbe, R = -C(H)C(CH3)2). [Ag(QR)]nreact with 2-ethylimidazole (2EtimH), 1-methylimidazole (Meim), and triphenylphosphine (PPh3), affording the mononuclear Ag(Qfb)(EtimH) (4), Ag(Qcy)(Meim)2(5), Ag(Qbe)(Meim) (6), and Ag(QR)(PPh3)2(7–9). All complexes have been analytically and spectroscopically characterized, and for some of them the X-ray crystal structure has been resolved. In particular, the single crystal molecular structure determination of Ag(Qfb)(EtimH) and Ag(Qbe)(PPh3)2has confirmed the different coordination modes of the HQfband HQbeacylpyrazolone ligands, the former being bound to the silver(I) ion in a monodentate fashion while the latter in the O2-chelating mode. Density functional theory computations suggest new insights about metal–ligand interactions and the observed linkage isomerism. While phosphine-containing complexes Ag(QR)(PPh3)2(7–9) seem not to be able to efficiently inhibit the growth of Escherichia coliand Staphylococcus aureus, the polynuclear complexes [Ag(QR)]n(1–3) and the mononuclear Ag(Qfb)(EtimH) (4), Ag(Qcy)(Meim)2(5), and Ag(Qbe)(Meim) (6) show a high and almost steady in time antibacterial activity, comparable to that of AgNO3. This activity is likely related to the degree of saturation of the silver center and to the presence of different ancillary ligands in the diverse typologies of complexes.

Similar to the disease affecting humans, osteoarthritis (OA) is a painful musculoskeletal condition affecting 20% of the adult canine population. Several solutions have been proposed, but the results achieved to date are far from being satisfactory. New approaches, such as intra‐articular delivery of cells (including mesenchymal stromal cells), have been proposed. Among the many sources, the adipose tissue is considered very promising. We evaluated the safety, feasibility, and efficacy of a single intra‐articular injection of autologous and micro‐fragmented adipose tissue (MFAT) in 130 dogs with spontaneous OA. MFAT was obtained using a minimally invasive technique in a closed system and injected in the intra‐ and/or peri‐articular space. Clinical outcomes were determined using orthopedic examination and owners’ scores for up to 6 months. In 78% of the dogs, improvement in the orthopedic score was registered 1 month after treatment and continued gradually up to 6 months when 88% of the dogs improved, 11% did not change, and 1% worsened compared with baseline. Considering the owners’ scores at 6 months, 92% of the dogs significantly improved, 6% improved only slightly, and 2% worsened compared with baseline. No local or systemic major adverse effects were recorded. The results of this study suggest that MFAT injection in dogs with OA is safe, feasible, and beneficial. The procedure is time sparing and cost‐effective. Post injection cytological investigation, together with the clinical evidence, suggests a long‐term pain control role of this treatment. The spontaneous OA dog model has a key role in developing successful treatments for translational medicine. Stem Cells Translational Medicine2018;7:819–828 Treatment of osteoarthritis by intra‐ and/or peri‐articular injection of autologous and micro‐fragmented adipose tissue (MFAT). This minimal manipulation technique intra‐operatively provides MFAT in a short time, without expansion or enzymatic treatment providing the key elements to support a natural reparative response: scaffold (the adipose tissue structure), cells (ASCs), and growth factors (secreted cytokines and chemokines) with anti‐inflammatory and reparative properties.

We report an original case of a 17-year-old girl with osteochondral fracture following traumatic patellar dislocation of the left knee.

Oral anticoagulation is underused in patients with atrial fibrillation. We assessed the impact of a multifaceted educational intervention, versus usual care, on oral anticoagulant use in patients with atrial fibrillation.

Low-temperature polarized and time-resolved photoluminescence spectroscopy in high magnetic fields (up to 30 T) has been used to study the spin-polarization, spin-relaxation, and radiative lifetimes of excitons in wurtzite semiconductor (e.g., CdSe) colloidal nanocrystals. The applied magnetic field leads to a significant degree of circular polarization of the exciton photoluminescence, accompanied by a reduction in the photoluminescence decay time. The circular polarization arises from the Zeeman splitting of exciton levels, whereas lifetime reduction results from a polarization-preserving field-induced mixing of exciton levels. We analyze these experimental findings in terms of a simple model that combines both Zeeman effect and exciton-level mixing, as a function of the relative orientation of the nanocrystal c-axis and the magnetic field. This model is able to simultaneously describe the degree of circular polarization and lifetime reduction of the exciton photoluminescence, permitting us to quantify the exciton, electron, and hole g-factors.