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We present experimental findings and modeling insights into the expansion of bubbles within a Newtonian fluid, observed during an advanced process integrating additive manufacturing and physical foaming techniques to fabricate complex microcellular foams with orientation-graded morphologies. A physical and sustainable blowing agent (CO2) is solubilized into a biopolymer (PLA) that is 3D-printed through a cylindrical nozzle, and, at the nozzle outlet, the blowing agent foams inside the polymeric strand due to pressure drop or/and temperature rise. The experimental results show that, by engineering the temperature gradient at high printing velocities, corresponding to values of the Graetz number (i.e., the ratio of heat diffusion time and residence time inside the printer hot-end) larger than one, the microcellular foamed strands have a microstructure characterized by anisotropic bubbles oriented along two different directions. The microbubbles at the center of the strands are stretched in the extrusion direction, whereas those in the periphery are stretched radially. A foam morphology with microbubbles having two different orientations, smoothly changing within the cross section, has never been reported before. We investigate the formation mechanism of such a morphology by simplified modeling and numerical simulations. Simulation results support the experimental findings and rationalize the effects of the Graetz number on the microcellular foamed strands and on the expansion of gas bubbles in a Newtonian fluid, suggesting that the different orientations of the bubbles are due to the combined effect of high Graetz number and the radial expansion of the strand.

Since there is no current international consensus on the optimal approach for pain management in acute pancreatitis (AP), analgesic practices may vary across different healthcare settings. This study explored global disparities in analgesic use, in particular opioids, during admission and at discharge in hospitalised AP patients. This was a post hoc analysis of the prospective PAINAP database, which included all admissions for AP between April and June 2022 with a 1‐month follow‐up. Demographic details, analgesic use, and clinical outcomes were recorded during admission and at discharge. Odds ratios (ORs) for opioid use during admission and at discharge were identified using multivariable regression analyses. Amongst the 1864 patients (52% males, median age 56 (interquartile range, 41–71)) across three different continents, simple analgesics were predominantly used as the primary analgesic (70%). Opioid use during admission was lowest in European centres (67%). Admission in Asian (OR, 2.53 (95% confidence interval (CI), 1.59–4.04), p< 0.001), and Australian (OR, 5.81 (95% CI, 3.19–10.56), p< 0.001) centres was associated with opioid administration during admission compared with European centres. Increased pain severity, longer pre‐admission pain duration, organ failure, and longer length of admission increased opioid use during admission. At discharge, Asian (OR, 2.01 (95% CI, 1.40–2.88), p< 0.001) and Australian (OR, 1.91 (95% CI, 1.28–2.85), p= 0.002) centres were associated with opioid prescription compared with European centres. Increased pain severity, longer pre‐admission pain duration, acute necrotic collections, and walled‐off necrosis also increased the likelihood of opioid prescription at discharge. There are substantial intercontinental differences in opioid use for AP pain. Accordingly, there is a need for international guidelines on pain management in AP.

Single-cell sequencing has characterized cell state heterogeneity across diverse healthy and malignant tissues. However, the plasticity or heritability of these cell states remains largely unknown. To address this, we introduce PATH (phylogenetic analysis of trait heritability), a framework to quantify cell state heritability versus plasticity and infer cell state transition and proliferation dynamics from single-cell lineage tracing data. Applying PATH to a mouse model of pancreatic cancer, we observed heritability at the ends of the epithelial-to-mesenchymal transition spectrum, with higher plasticity at more intermediate states. In primary glioblastoma, we identified bidirectional transitions between stem- and mesenchymal-like cells, which use the astrocyte-like state as an intermediary. Finally, we reconstructed a phylogeny from single-cell whole-genome sequencing in B cell acute lymphoblastic leukemia and delineated the heritability of B cell differentiation states linked with genetic drivers. Altogether, PATH replaces qualitative conceptions of plasticity with quantitative measures, offering a framework to study somatic evolution.

Using contingent-claims valuation, we introduce novel hedge ratios for credit exposures using put options. Option hedge ratios are generally in line with the empirical sensitivities of credit spread changes to put option returns and, relative to stock hedge ratios, produce further reductions in volatility for a portfolio of North American firms. We show that option hedge ratios capture option-specific credit exposure related to the VIX index and the default spread, which is unaccounted for by Merton’s (1974)equity hedge ratios alone. Combining stocks and put options for credit risk hedging can be done effectively using the volatility smirk. (JELE43, E44, G10)

The zoonotic parasite Cryptosporidium parvumis a global cause of gastrointestinal disease in humans and ruminants. Sequence analysis of the highly polymorphic gp60gene enabled the classification of C. parvumisolates into multiple groups (e.g., IIa, IIc, Id) and a large number of subtypes. In Europe, subtype IIaA15G2R1 is largely predominant and has been associated with many water- and food-borne outbreaks. In this study, we generated new whole-genome sequence (WGS) data from 123 human- and ruminant-derived isolates collected in 13 European countries and included other available WGS data from Europe, Egypt, China, and the United States (n = 72) in the largest comparative genomics study to date. We applied rigorous filters to exclude mixed infections and analyzed a data set from 141 isolates from the zoonotic groups IIa (n = 119) and IId (n = 22). Based on 28,047 high-quality, biallelic genomic SNPs, we identified three distinct and strongly supported populations: Isolates from China (IId) and Egypt (IIa and IId) formed population 1; a minority of European isolates (IIa and IId) formed population 2; and the majority of European (IIa, including all IIaA15G2R1 isolates) and all isolates from the United States (IIa) clustered in population 3. Based on analyses of the population structure, population genetics, and recombination, we show that population 3 has recently emerged and expanded throughout Europe to then, possibly from the United Kingdom, reach the United States, where it also expanded. The reason(s) for the successful spread of population 3 remain elusive, although genes under selective pressure uniquely in this population were identified.

Conducting polymers are mixed ionic–electronic conductors that are emerging candidates for neuromorphic computing, bioelectronics and thermoelectrics. However, fundamental aspects of their many-body correlated electron–ion transport physics remain poorly understood. Here we show that in p-type organic electrochemical transistors it is possible to remove all of the electrons from the valence band and even access deeper bands without degradation. By adding a second, field-effect gate electrode, additional electrons or holes can be injected at set doping states. Under conditions where the counterions are unable to equilibrate in response to field-induced changes in the electronic carrier density, we observe surprising, non-equilibrium transport signatures that provide unique insights into the interaction-driven formation of a frozen, soft Coulomb gap in the density of states. Our work identifies new strategies for substantially enhancing the transport properties of conducting polymers by exploiting non-equilibrium states in the coupled system of electronic charges and counterions.

To expedite testing, time-dependent dielectric breakdown (TDDB) analyses are conducted on commercial 4H-SiC mosfets at high gate-to-source voltages ($\bm {V_{GS}}$), under Fowler–Nordheim conduction only. However, as inferred, such conditions induce impact ionization-generated holes in the dielectric layer (SiO$\bm {_{2}}$), resulting in a state transition in the effective dipolar moment. This accelerates the SiO$\bm {_{2}}$ degradation leading to an overestimation of its intrinsic lifetime at typical $V_{GS}$ values for gate driving in power converters. To address this, a physics-based approach is proposed to design TDDB tests under such conditions and to correct the intrinsic lifetime prediction at nominal $\bm {V_{GS}}$ values, shortening the testing time by up to two orders of magnitude. Thus, the proposed method is a well-suited candidate to be considered in SiC power device qualification standards, still under development.

Phthalates (PAEs), a family of organic chemicals synthesized by double esterification of 1,2-benzenecarboxylic acid, and Bisphenol-A (BPA) are molecules widely used in packaging due to their malleability and workability of plastic polymers. Their large use during these last decades causes high presence in the environment. PAEs, which are not chemically bound to the polymer, show the tendency to migrate or dissociate, especially when they are in contact with lipophilic substances and/or in case of mechanical or thermal stress. The consequence is a contamination of water surface as well as food products, e.g., food products can be contaminated during packaging and storage by migration from polymers. PAE exposure can result from direct contact or through the transfer of such compounds from one product to another, as occurs for food or bottle packaging, whereas the main exposure routes can be ingestion, inhalation, intravenous and dermal. The food contamination by PAEs and/or BPA can also occur during the production process, handling, transport, packaging and preparation, even at domestic level. This paper would like to propose a novel, rapid and easy analytical approach for determining PAEs and BPA in water samples, specifically water surface. The determination is performed by GC-FID, common equipment present in every routinely chemical laboratory. The extraction is performed by means of Dispersed Liquid Liquid MicroExtraction (DLLME) method. All the analytical parameters are investigated and discussed. The method is really sensitive showing Limit of Detection (LOD) between 2 and 19 pg and Limit of Quantification (LOQ) between 4 and 48 pg. Furthermore, the method is reproducible with a variability of less than 9.7% and an R2> 0.9718 in a linear dynamic range between 0.5 and 500 ppm.

The trace element composition of water intended for human consumption plays an important role for public health. Water is a significant source of potentially toxic and essential elements; it can provide the body by both direct recruitment and/or influencing the element concentration in agriculture, livestock products and food industry. The present study examines the concentrations of a great number of elements in the drinking waters distributed in the territory of Rome, whose water supply mainly comes from spring waters. 20 samples drawn from municipal potable facilities in Rome were analyzed by Instrumental Neutron Activation Analysis. The neutron irradiations were performed in the pneumatic channel and in the rotating rack of ENEA’s Triga Mark II reactor at 1.3 × 1013and 2.6 × 1012n cm−2s−1, respectively. In total, 38 elements were determined in each sample. The results evidence that all the studied elements for all the aqueducts resulted well below the limits posed by the regulations on water for human consumption. Besides, considering the elements not regulated, the monitored waters resulted safe from a toxicological point of view, and adequate from nutritional aims. In addition, it was also evidenced that the elemental composition resulted quite similar to that of uncontaminated natural water. Finally, a statistical approach evidences that the elemental behavior of the monitored waters is mainly determined by geochemical factors.

Small offshore centres are home to the leading booking centres of global banks and facilitate their transactions across offices worldwide. This paper investigates the factors driving booking positions in offices located in small offshore centres, with a focus on US global banks. We find that global banks tend to increase their booking positions when liquidity conditions at the global and parent levels deteriorate and when banks' risk-taking increases through leverage. Our results suggest that lower tax levels and higher secrecy explain booking centres' localisation in small offshore countries.

The energetic landscape at the interface between electron donating and accepting molecular materials favors efficient conversion of intermolecular charge-transfer (CT) states into free charge carriers (FCC) in high-performance organic solar cells. Here, we elucidate how interfacial energetics, charge generation and radiative recombination are affected by molecular arrangement. We experimentally determine the CT dissociation properties of a series of model, small molecule donor–acceptor blends, where the used acceptors (B2PYMPM, B3PYMPM and B4PYMPM) differ only in the nitrogen position of their lateral pyridine rings. We find that the formation of an ordered, face-on molecular packing in B4PYMPM is beneficial to efficient, field-independent charge separation, leading to fill factors above 70% in photovoltaic devices. This is rationalized by a comprehensive computational protocol showing that, compared to the more amorphous and isotropically oriented B2PYMPM, the higher structural order of B4PYMPM molecules leads to more delocalized CT states. Furthermore, we find no correlation between the quantum efficiency of FCC radiative recombination and the bound or unbound nature of the CT states. This work highlights the importance of structural ordering at donor–acceptor interfaces for efficient FCC generation and shows that less bound CT states do not preclude efficient radiative recombination.

2-in-1 laundry formulations have become popular among consumers as these represent a great alternative to standard detergents offering both cleaning and softening benefits in one product. Deposition aid polymers are crucial additives of a 2-in-1 formulation as they enhance the deposition of softness active ingredients. In this work, a novel class of pullulan derivatives grafted with cationic moieties (CatPs) have been synthesized and their softness and cleaning performance in a 2-in-1 laundry detergent have been assessed. Results show that the addition of cationic appendages is indispensable to observing an increase in textile softness. Compared with similar cationic polysaccharides, CatPs were also able to deliver better antiredeposition performance on both cotton-based and synthetic garments, probably on account of their higher capacity to stabilize particulate soil suspensions. The investigation of the solution behavior of CatPs with a typical laundry formulation revealed a phase separation (coacervation) occurring as a result of the association of the cationic pullulans with anionic surfactants. Results highlighted the dependence of this phenomenon on the polymer concentration and composition. This work demonstrates that CatPs represent a promising biorenewable additive for laundry detergent, providing both effective softness and cleaning performance.

A novel solution for off-chip electrothermal studies in power devices at die level and short timescales is reported. The proposed method involves acquiring a sequence of thermal images on the top of the die with an infrared (IR) camera, while the device is biased under a periodic nonharmonic modulated current. Fourier coefficients are then extracted using lock-in strategies, and the time evolution of the device thermal map is reconstructed using Fourier series. To evaluate and showcase its potential, the conventional approach of boxcar averaging is implemented and used as a reference. As a case study, a reverse-conducting insulated gate bipolar transistor (RC-IGBT) is thermally measured under both forward and reverse modes. The proposed strategy significantly improves the thermal and time resolution, overcoming the limitations of the camera’s frame rate and noise resolution. Moreover, the impact of current crowding on the power device is studied at the millisecond timescale, considering both biasing modes.

The design of multitarget drugs represents a promising strategy in medicinal chemistry and seems particularly suitable for the discovery of anti-inflammatory drugs. Here, we describe the identification of an indoline-based compound inhibiting both 5-lipoxygenase (5-LOX) and soluble epoxide hydrolase (sEH). In silicoanalysis of an in-house library identified nine compounds as potential 5-LOX inhibitors. Enzymatic and cellular assays revealed the indoline derivative 43as a notable 5-LOX inhibitor, guiding the design of new analogues. These compounds underwent extensive in vitroinvestigation revealing dual 5-LOX/sEH inhibitors, with 73showing the most promising activity (IC50s of 0.41 ± 0.01 and 0.43 ± 0.10 μM for 5-LOX and sEH, respectively). When challenged in vivo in zymosan-induced peritonitis and experimental asthma in mice, compound 73showed remarkable anti-inflammatory efficacy. These results pave the way for the rational design of 5-LOX/sEH dual inhibitors and for further investigation of their potential use as anti-inflammatory agents.

Soil-release polymers (SRPs) are essential additives of laundry detergents whose function is to enable soil release from fabric and to prevent soil redeposition during the washing cycle. The currently used SRPs are petrochemical-based; however, SRPs based on biorenewable polymers would be preferred from an environmental and regulatory perspective. To explore this possibility, we have synthesized SRPs based on hydroxyethyl cellulose (amphiphilic HEC) appended with controlled compositions of hydrophobic and cationic appendages and assessed their cleaning abilities. The results demonstrate that the introduction of hydrophobic lauryl appendages onto the HEC backbone is essential to deliver anti-redeposition and soil-release performance. Conversely, further introduction of cationic groups onto hydrophobic modified HECs had no clear impact on soil-release performance but caused significant disadvantages on anti-redeposition performance. We speculate that this poor performance arises on account of coacervation formation between the cationic HEC polymer and the anionic surfactant in the detergent, negatively impacting soil suspension and suggests that the inclusion of cationic appendages on HECs can ultimately lead to detrimental effects on performance. Interestingly, in contrast to conventional SPRs that exhibit good soil-release performance exclusively on synthetic fabrics, amphiphilic HEC displayed encouraging results on both synthetic and cotton-based textiles, possibly as a result of a good chemical affinity with natural fabrics. This work highlights that the nature and hydrophobic content of HEC ethers are key variables that govern HEC applicability as SRPs, thus paving the way for the design and synthesis of new SRPs.

In the June issue, you answered a question about SIPC protection on brokerage accounts and stated that Schwab carries excess SIPC insurance of $149.5 million per customer ("Practical Portfolio"). I was told Vanguard carries excess SIPC insurance that covers each client up to $49.5 million for securities and $1.9 million in cash, but this excess SIPC coverage is for a max of $250 million for all Vanguard clients. CLEARWATER, FLA. FDIC insurance covers principal and interest up to $250,000. [Extracted from the article]

There are currently no standardized therapies for Parkinson disease (PD). Curcumin shows anti-amyloidogenic properties in vitro and may be a promising treatment for PD. We evaluated the effects of curcumin supplementation on clinical scales and misfolded, phosphorylated α-synuclein (p-syn) accumulation in skin biopsies in 19 PD patients who received curcumin supplementation for 12 months and 14 PD patients to treated with curcumin. The patients underwent autonomic (COMPASS-31), motor (MDS-UPDRS and H&Y) and nonmotor (NMSS) questionnaires and skin biopsies to evaluate clinical involvement and p-syn load in skin nerves at the beginning and the end of study. Curcumin and curcuminoid levels were assayed in plasma and CSF. Supplemented patients showed detectable CSF curcuminoid levels that were lower than those in plasma. They showed a decrease of COMPASS-31 and NMSS scores, and a slight p-syn load decrease versus untreated patients who displayed a worsening of these parameters despite increased levodopa doses. Multiple regression models showed a significant effect of curcumin supplementation in decreasing the worsening of the clinical parameters and p-syn load at after curcumin treatment. These data suggest that curcumin can cross the blood-brain barrier, that it is effective in ameliorating clinical parameters and that it shows a tendency to decrease skin p-syn accumulation in PD patients.

Electron–hole separation in self-assembled mesomorphic nanostructures composed of donor–acceptor (DA) co-oligomers is investigated by combined microelectrostatics and kinetic Monte Carlo simulations. The relevant DA dyads are based on perylene diimide (PDI) acceptor moieties covalently bound to fluorene-thiophene-benzothiadiazole donor moieties, which form highly ordered, stacked structural motifs upon self-assembly. These are characterized by efficient electron transport along PDI stacks, whereas hole transport is almost three orders of magnitude slower. On the basis of an atomistic structure obtained by electron diffraction, the energetics of charge separation is characterized by a microelectrostatics analysis. This information is subsequently employed to compute electron–hole (e–h) separation rates and dissociation yields by kinetic Monte Carlo simulations. The latter have been calibrated against recent quantum dynamical studies for a reduced one-dimensional representation of the DA system. It is shown that charge separation of “cold” e–h pairs is characterized by dissociation rates around 109s–1, which are associated with two-dimensional transport features, where the predominant electron transport in the PDI stacking direction is assisted by a secondary mechanism that involves neighboring stacks.

Background: Indoxyl sulfate (IS) and p-cresyl sulfate (PCS) are uremic toxins associated with cardiovascular outcome in CKD patients. The present work is an analysis of the association of serum free, total IS and PCS with cardiovascular events and calcium-phosphate metabolism variables in hemodialysis patients. Methods: Serum levels of total and free IS and PCS were measured in 139 hemodialysis patients. Their relationship with calcium-phosphate metabolism variables were tested in an observational cohort study. In addition, their association with cardiovascular events was investigated during a 4-year follow-up. Results: Patients in the highest tertile (T3) of serum free IS showed lower serum 1,25(OH)2D compared to patients in the middle (T2) and lowest tertile (T1); in addition to this, T3 patients showed lower serum irisin than T1 patients and lower serum PTH than all the other subjects (T1 + T2) combined. Serum PTH was also measured during the two years after the baseline measurement and was higher in patients in the T1 than in those in the T3 of serum free IS. Cox regression analysis showed that cardiovascular risk was lower in T1 patients than in those in the T3 of serum free PCS, both using a univariate (OR 2.55, 95% CI 1.2–5.43; p = 0.015) or multivariate model (OR 2.48, 95% CI 1.12–5.51; p = 0.003). Conclusions: Serum free IS may be associated with PTH and 1,25(OH)2D secretion, whereas free PCS may predict cardiovascular risk in hemodialysis patients. Graphical abstract:

The preservation of cultural heritage, including ancient photographic materials, is of paramount importance in the field of conservation science.In this context, the microbial diversity of ‘Skull and Crossbones’, a 1983 photograph by Robert Mapplethorpe printed on silver gelatine, was assessed. We employed both culture-dependent and culture-independent methods to characterize microbial communities inhabiting this artwork. Vibrational Raman micro spectroscopy and FT-IR spectroscopy were utilized to assess the chemical degradation condition and characterize the chemical components of the silver gelatin print. The combination of molecular sequencing methods (Sanger and HTS approach) and non-invasive vibrational spectroscopy yielded valuable insights into the microbial communities thriving on photographic material and the chemical degradation of the print. Isolated fungal strains were added to the Fungal Collection at the University of Naples Federico II, and their deteriorative potential was investigated by adding substrates, commonly used in canvas photographs to the culture media. These results establish a link between microbial communities colonizing ancient photographic materials, paper decomposition, and the enzymatic patterns of the retrieved microorganisms. This information is invaluable for understanding and addressing biodeterioration progression on valuable works of art, such as historical photographs, which remain understudied.