bluuebunny/crossref_metadata_2025 huggingface dataset:
A Polymeric Extracellular Matrix Nanoremodeler for Activatable Cancer Photo‐Immunotherapy
Authors: Zhang Chi , Xu Mengke , Zeng Ziling , Wei Xin , He Shasha , Huang Jingsheng , Pu Kanyi
Published: January 2023

Cancer immunotherapy has shown tremendous potential to train the intrinsic immune system against malignancy in the clinic. However, the extracellular matrix (ECM) in tumor microenvironment is a formidable barrier that not only restricts the penetration of therapeutic drugs but also prevents the infiltration of antitumor immune cells. We herein report a semiconducting polymer‐based ECM nanoremodeler (SPNcb) to combine photodynamic antitumor activity with cancer‐specific inhibition of collagen‐crosslinking enzymes (lysyl oxidase (LOX) family) for activatable cancer photo‐immunotherapy. SPNcb is self‐assembled from an amphiphilic semiconducting polymer conjugated with a LOX inhibitor (β‐aminopropionitrile, BAPN) via a cancer biomarker (cathepsin B, CatB)‐cleavable segment. BAPN can be exclusively activated to inhibit LOX activity in the presence of the tumor‐overexpressed CatB, thus blocking collagen crosslinking and decreasing ECM stiffness. Such an ECM nanoremodeler synergizes immunogenic phototherapy and checkpoint blockade immunotherapy to improve the tumor infiltration of cytotoxic T cells, inhibiting tumor growth and metastasis.
L‐Shaped Heterobidentate Imidazo[1,5‐a]pyridin‐3‐ylidene (N,C)‐Ligands for Oxidant‐Free AuI/AuIII Catalysis
Authors: Gao Pengcheng , Xu Jihong , Zhou Tongliang , Liu Yanhong , Bisz Elwira , Dziuk Błażej , Lalancette Roger , Szostak Roman , Zhang Dongju , Szostak Michal
Published: January 2023

In the last decade, major advances have been made in homogeneous gold catalysis. However, AuI/AuIII catalytic cycle remains much less explored due to the reluctance of AuI to undergo oxidative addition and the stability of the AuIII intermediate. Herein, we report activation of aryl halides at gold(I) enabled by NHC (NHC=N‐heterocyclic carbene) ligands through the development of a new class of L‐shaped heterobidentate ImPy (ImPy=imidazo[1,5‐a]pyridin‐3‐ylidene) N,C ligands that feature hemilabile character of the amino group in combination with strong σ‐donation of the carbene center in a rigid conformation, imposed by the ligand architecture. Detailed characterization and control studies reveal key ligand features for AuI/AuIII redox cycle, wherein the hemilabile nitrogen is placed at the coordinating position of a rigid framework. Given the tremendous significance of homogeneous gold catalysis, we anticipate that this ligand platform will find widespread application.
Biomolecular Click Reactions Using a Minimal pH‐Activated Catcher/Tag Pair for Producing Native‐Sized Spider‐Silk Proteins**
Authors: Fan Ruxia , Hakanpää Johanna , Elfving Karoliina , Taberman Helena , Linder Markus B. , Aranko A. Sesilja
Published: January 2023

A type of protein/peptide pair known as Catcher/Tag pair spontaneously forms an intermolecular isopeptide bond which can be applied for biomolecular click reactions. Covalent protein conjugation using Catcher/Tag pairs has turned out to be a valuable tool in biotechnology and biomedicines, but it is essential to increase the current toolbox of orthogonal Catcher/Tag pairs to expand the range of applications further, for example, for controlled multiple‐fragment ligation. We report here the engineering of novel Catcher/Tag pairs for protein ligation, aided by a crystal structure of a minimal CnaB domain from Lactobacillus plantarum. We show that a newly engineered pair, called SilkCatcher/Tag enables efficient pH‐inducible protein ligation in addition to being compatible with the widely used SpyCatcher/Tag pair. Finally, we demonstrate the use of the SilkCatcher/Tag pair in the production of native‐sized highly repetitive spider‐silk‐like proteins with >90 % purity, which is not possible by traditional recombinant production methods.
Dynamic Lone Pair Expression as Chemical Bonding Origin of Giant Phonon Anharmonicity in Thermoelectric InTe
Authors: Zhang Jiawei , Ishikawa Daisuke , Koza Michael M. , Nishibori Eiji , Song Lirong , Baron Alfred Q. R. , Iversen Bo B.
Published: January 2023

Loosely bonded (“rattling”) atoms withs2lone pair electrons are usually associated with strong anharmonicity and unexpectedly low thermal conductivity, yet their detailed correlation remains largely unknown. Here we resolve this correlation in thermoelectric InTe by combining chemical bonding analysis, inelastic X‐ray and neutron scattering, and first principles phonon calculations. We successfully probe soft low‐lying transverse phonons dominated by large In1+z‐axis motions, and their giant anharmonicity. We show that the highly anharmonic phonons arise from the dynamic lone pair expression with unstable occupied antibonding states induced by the covalency between delocalized In1+5s2lone pair electrons and Te 5pstates. This work pinpoints the microscopic origin of strong anharmonicity driven by rattling atoms with stereochemical lone pair activity, important for designing efficient materials for thermoelectric energy conversion.
Outburst behavior of the dwarf nova CG Draconis
Authors: Usatov Maxim , Shears Jeremy
Published: January 2023

During the British Astronomical Association (BAA) 2022 campaign, 27,436 photometric observations of the dwarf nova (DN) CG Draconis were made, with 106 eclipses recorded. This work summarizes the new data available and provides updated ephemeris and commentary on the observed eclipse profiles. The orbital period found is . Two types of quasi‐periodic outbursts are identified: normal outbursts, of mag amplitude, and bright, of mag. The pattern resembles superoutbursts of SU UMa‐type DNe, however, no presence of superhumps characterizing these DNe was found. Given CG Dra is located above the period gap, it may represent a new intermediary subtype between SS Cyg and SU UMa‐type stars, or provide support to superoutburst models that do not rely on eccentric accretion disks.
A rational design of AIE‐active fluorophore for the fingerprint optical detection
Authors: Yu Le , Xu Yunjie , Kim Jungryun , Lee Jieun , Kim Jong Seung
Published: January 2023

Fingerprints are one of the distinguishing characteristics of an individual, remaining unaltered throughout one's lifetime. It should be noted that fingerprints are significant and reliable evidence in various cases, such as criminal investigations, medical diagnosis, and public security. Thus, it is necessary to develop efficient techniques for fingerprints detection. Fortunately, the fluorescence emission of aggregation‐induced emission (AIE) materials would increase instead of quenching upon excitation when they label fingerprints, which would clearly observe the structure of fingerprints. Herein, we devised a novel AIE‐active fluorophore (NI‐DB) with electron donor‐π bridge‐electron acceptor (D‐π‐A) structure based on the 1,8‐naphthalimide. To our delight, after fingerprints fixed by cyanoacrylate glue fuming, NI‐DB is capable of detecting and imaging fingerprints via its intrinsic fluorescence emission. And, with the aid of this technique, fingerprints on various object surfaces are successfully developed, suggesting the broad applicability.
Inhibition of α‐Glycosidase by Lippia dulcis Trevir. (Verbenaceae) Preparations, Quantification of Verbascoside, and Study of Its Molecular Docking
Authors: Ritter Ruas Natalia , Carvalho Pereira Aline , Lopes Silva Pereira Luciana , Mesquita Germano Carolina , Fontes Ferreira da Cunha Elaine , Alves de Carvalho Alexandre , Alves Lameira Osmar , Eduardo Brasil Pereira Pinto José , Kelly Vilela Bertolucci Suzan
Published: January 2023

This study aimed to quantify verbascoside (VEB), perform molecular docking studies of VEB with the α‐glucosidase (GL) of Bacillus stearothermophilus, and evaluate the inhibition of the enzyme by L. dulcis preparations. The substrate concentration and presence of reduced glutathione were evaluated for their effect on the in vitro inhibition of the GL enzyme. Assays were also performed in the presence and absence of simulated gastric fluid. The antidiabetic fractions 2 and 3 were the most inhibited GL, but their activity were significantly decreased in the presence of gastric fluid. Chromatographic analyses confirmed the predominant presence of VEB in the samples. The samples had VEB concentrations between 49.9 and 243.5 mg/g. Simulation of the molecular docking of VEB were consistent with its GL‐inhibitory activity. It can conclude that the crude ethanol extract and fractions show inhibitory activity against the GL enzyme.
Highly Efficient Light‐Driven CO2 to CO Reduction by an Appropriately Decorated Iron Porphyrin Molecular Catalyst
Authors: Stoumpidi Aspasia , Trapali Adelais , Poisson Marie , Barrozo Alexandre , Bertaina Sylvain , Orio Maylis , Charalambidis Georgios , Coutsolelos Athanassios G.
Published: January 2023

The photocatalytic CO2 reduction into value‐added chemicals is regarded as one promising technology to mitigate environmental issues and the energy crisis of the modern world due to the extended CO2 emissions. Recent advances have shown that iron porphyrins are considered as one of the most efficient molecular catalysts in the activation and reduction of molecules like CO2. Thus, a suitably modified FeIII porphyrin ([FeIII(TF4TMAP)](CF3SO3)5) was prepared and its catalytic activity in terms of photocatalytic reduction of CO2 was studied. This iron catalyst possesses four fluorine substituents in the ortho and the meta position of each meso‐phenyl group of the porphyrin, while trimethylammonium groups were placed in the para position. Photocatalytic studies were performed in the presence of an iridium complex as a chromophore and have shown that [FeIII(TF4TMAP)](CF3SO3)5 can effectively reduce CO2, achieving excellent turnover numbers (up to 5500 TONs) and high turnover frequencies. The main reduction product of this photocatalytic system was CO, and only a small amount of hydrogen was detected, presenting a maximum selectivity of 86 % for CO.
Role of Copper Migration in Nanoscale Ageing of Supported CuO/Al2O3 in Redox Conditions: A Combined Multiscale X‐ray and Electron Microscopy Study
Authors: Sharna Sharmin , Rouchon Virgile , Legens Christèle , Taleb Anne‐Lise , Stanescu Stefan , Bouillet Corinne , Lambert Arnold , Briois Valerie , Chiche David , Gay Anne‐Sophie , Ersen Ovidiu
Published: January 2023

Chemical Looping Combustion is a promising midterm solution to mitigate CO2 emission, by carrying out indirect fuel combustion and allowing inherent separation of CO2. During the CLC process, an oxygen carrying material is subjected to successive oxidation‐reduction reactions at high temperature which induce significant material degradation. CuO/Al2O3 based materials have been widely considered as promising oxygen carriers (OC). However, the oxygen carrier ageing mechanisms (active phase migration and interactions with the support, phase transitions) are not well understood. Herein, an in‐depth overview of the material evolution is achieved by employing a multi‐scale characterization approach. At the μm‐scale, copper migration within the alumina support has been observed using Scanning Transmission X‐ray Microscopy (STXM) and Scanning Electron Microscopy (SEM). The spatial distribution of the Cu−Al species provides information on copper mobility and the different phases interactions. A comprehensive mechanism is proposed concerning the redox behaviour of the CuO/Al2O3 system, relating the diffusion of the Cu‐species, the active phase‐support interactions, and the role of copper in the Al2O3 support phase transition to the temperature and the number of redox cycles. Understanding the ageing process of CuO/Al2O3 materials paves a way to design more stable oxygen‐carriers.
TiO2−WOxCoatings on Aluminum Open Cell Foams as Potential Packing Material for Esterification of Glycolic Acid with Ethanol
Authors: Reyes Laura , Vilcocq Léa , Zanota Marie‐Line , Meille Valérie , Nikitine Clémence , Fongarland Pascal
Published: January 2023

The application of open cell foams as catalytic supports has been developed in recent years due to their interesting features: large specific surface area (>300 m2 m−3), high void fractions (>0.9) and enhanced internal mass transport. Catalytic foams are highly appealing for the development of structured reactors, especially for multiphase systems. In this paper, catalytic packing material with potential application in structured reactors was developed. Aluminum foams with different macropore sizes were chosen as support for a TiO2−WOxcatalyst. The main features, geometric and structural, of the foams were established. At optimized conditions a maximum catalyst loading of 234 kgcatalyst m−3supportwas obtained, while maintaining significant void fraction (>0.8). The structured catalyst was successfully implemented in batch reactor for a model reaction, esterification of glycolic acid with ethanol. It was shown that the catalyst does not lose performance during the coating steps and remains active for at least 3 catalytic runs, i. e. 18 h.
Study of the bactericidal properties of ZnO/Ag0 nanoparticles in the treatment of raw sewage effluents
Authors: Moreira Micheline D. D. , Neto Nivaldo F. Andrade , Oliveira Fernanda K. F. , Paskocimas Carlos A. , Bomio Mauricio R. D. , Motta Fabiana V.
Published: January 2023

In this work, the antimicrobial treatment of raw sewage effluents (RSE) of residences was studied. For this, the RSE was collected from a treatment plant and the antimicrobial activity was evaluated using Ag0 decorated ZnO nanoparticles. ZnO/Ag0 nanoparticles were synthesized by a microwave‐assisted hydrothermal method and sonochemical method. The effect of ZnO/Ag0 nanoparticles was evaluated by varying the concentration of the catalyst to the RSE, varying the amount of silver, and varying the contact time of the catalyst with the RSE, to optimize the process. The ZnO/Ag0 nanoparticles were characterized by X‐ray diffraction, surface area using the Brunauer‐Emmett‐Teller methodology, and field emission scanning electron microscopy. The results indicate that the particles synthesized by the association of sonochemical and hydrothermal methods provide a better antimicrobial result against all tested bacteria. The results obtained in this manuscript indicate an alternative methodology in the removal of 99% of the bacteria from tailings from a real sewer, showing its applicability in the treatment for later consumption.
Undergraduate financial knowledge, attitudes, and behaviors: The impact of financial life skills course on college students
Authors: Robb Cliff A. , Chy Somalis
Published: January 2023

It is increasingly common for universities to offer financial education or life skills courses as electives. However, less is known about the potential impacts of these courses on factors beyond financial literacy, such as financial attitudes, financial stress, or financial well‐being. Our study explores these topics using a unique sample of 370 undergraduate students, half of whom opted to enroll in and complete a financial life skills course and half of whom did not. We explore various aspects of student financial life, including well‐being, stress, self‐efficacy, knowledge, behavior, and socialization. Evidence from our study did not suggest that a single‐credit financial life skills course has much impact on financial well‐being or financial stress. There were notable impacts associated with financial socialization and financial self‐efficacy that reinforce some earlier explorations of financial well‐being.
Organocatalytic Desymmetric Conjugate Addition to Cyclobutanone: An Enantio‐ and Diastereoselective Synthesis of [6,5,4]‐Fused Carbocycles
Authors: Panda Shibaram , Gayen Upasana , Ghorai Prasanta
Published: January 2023

The first organocatalytic, non‐destructive desymmetrisation of 3‐substituted cyclobutanone followed by intramolecular cyclisation is described. Owing to the slow activation of the pronucleophile by the weak Brønsted base, the α‐functionalization of ketones with tertiary‐amine‐derived Brønsted base catalysis has been chemically challenging in asymmetric transformations. Herein, we demonstrate that the cinchona‐derived squaramide catalyst works effectively for the intramolecular Michael addition of cyclobutanone to enones and affords the architecturally fascinating [6,5,4]‐fused carbocyclic skeleton in good yields and excellent diastereo‐ and enantioselectivities (up to >20 : 1drand 96 %ee). Furthermore, as a synthetic application, this method provides an alternative pathway to enantioenriched high‐value products like γ‐lactones and indan‐2‐ol derivatives.
Conversion of Ketones into Blue‐Emitting Electron‐Deficient Benzofurans
Authors: Górski Krzysztof , Ostojić Tea , Banasiewicz Marzena , Ouellette Erik T. , Grisanti Luca , Gryko Daniel T.
Published: January 2023

A novel heavy metal‐free and safe synthetic methodology enabling one‐step conversion of ketones into corresponding 4,5,6,7‐tetrafluorobenzofurans (F4BFs) has been developed. The presented approach has numerous advantageous qualities, including utilization of readily available substrates, broad scope, scalability, and good reaction yields. Importantly, some of the benzofurans prepared by this method were heretofore inaccessible by any other known transformation. Importantly, furo[2,3‐b]pyrazines and heretofore unexplored difuro[2,3‐c:3′,2′‐e]pyridazine can be prepared using this strategy. Spectroscopic studies reveal that for simple systems, absorption and fluorescence maxima fall within the UV spectral range, while π‐electron system expansion red‐shifts both spectra. Moreover, the good fluorescence quantum yields observed in solution, up to 96 %, are also maintained in the solid state. Experimental results are supported by density functional theory (DFT) calculations. The presented methodology, combined with the spectroscopic characteristics, suggest the possibility of using F4BFs in the optoelectronic industry (i. e., organic light emitting devices (OLED), organic field‐effect transistors (OFET), organic photovoltaics (OPV)) as inexpensive and readily available emissive or semiconductor materials.
Self‐Healable Elastomeric Network with Dynamic Disulfide, Imine, and Hydrogen Bonds for Flexible Strain Sensor
Authors: Zeng Wangyi , Deng Longjiang , Yang Guang
Published: January 2023

Self‐healable and stretchable elastomeric material is essential for the development of flexible electronics devices to ensure their stable performance. In this study, a strain sensor (PIH2T1‐tri/CNT‐3) composed of self‐repairable crosslinked elastomer substrate (PIH2T1‐tri, containing multiple reversible repairing sites such as disulfide, imine, and hydrogen bonds) and conductive layer (carbon nanotube, CNT) was prepared. The PIH2T1‐tri elastomer had excellent self‐healing ability (healing efficiency=91 %). It exhibited good mechanical integrity in terms of elongation at break (672 %), tensile strength (1.41 MPa). The Young's modulus (0.39 MPa) was close to that of human skin. The PIH2T1‐tri/CNT‐3 sensor also demonstrated an effective self‐healing function for electrical conduction and sensing property. Meanwhile, it had high sensitivity (gauge factor (GF)=24.1), short response time (120 ms), and long‐term durability (4000 cycles). This study offers a novel self‐healable elastomer platform with carbon based conductive components to develop flexible strain sensors towards high performance soft electronics.
In situ H2O2 Generation and Corresponding Pollutant Removal Applications: A Review
Authors: Ji Jiahui , Wang Zijie , Xu Qing , Zhu Qiaohong , Xing Mingyang
Published: January 2023

Catalytic hydrogen peroxide (H2O2) generation from oxygen and water enables a sustainable environment to operate in an effective and green energy‐to‐chemical conversion way, which has attracted increasing interest in the fields of energy production and environment treatment. In light of this, tremendous progresses and developments have been made during the past decades in catalytic H2O2 production for pollutant removal from three perspectives including photocatalysis, electrocatalysis or chemical activation. Herein, we critically review the state‐of‐the‐art developments over various procedures of H2O2 generation and its further application, with the existence of photocatalysts, electrocatalysts, and catalysts, respectively. Benefiting from extensively experimental and theoretical investigations, the performance and stability of H2O2 generation and its utilization can be maneuvered by devising catalytic platform based on numerous catalysts with predominant electronic, chemical and physical properties, which endow the catalysts with efficient electrons transportation, abundant active sites, and sufficient oxygen adsorption for H2O2 generation. Furthermore, this review also discusses the formation mechanism of H2O2 by 2e‐ORR and 2e‐WOR, as well as its functional process of activating and removing pollutants, and summarizes the design principles of various catalysts by focusing on the formation of H2O2. We finally highlight the specific challenges and prospects related to the utilization of catalysts and envision the possible future development trends in the fields of pollutant removal.
Definition of the term asymmetric synthesis—History and revision
Authors: Helmchen Günter
Published: January 2023

The widely used term asymmetric synthesis was introduced by Emil Fischer in 1894 by demonstration with examples. An early definition by Marckwald was successful in applications involving enantiomeric reaction products. The term caused difficulties in cases of diastereomeric products, because of a lack of a clear definition of the term diastereoisomers, which in turn affected the introduction of the term diastereoselectivity. Clarity was reached only after Wheland had revived a definition by Victor Meyer of 1907. Today, a definition codified by the International Union of Pure and Applied Chemistry (IUPAC) is in use, which is slightly modified here.
Analytical formulas for calculating the electrical characteristics of multiparameter arbitrary configurational homogenous ladder networks
Authors: Lakshmi Prasanna K. , Mondal Mithun
Published: January 2023

Most electrical systems are represented as ladder networks made up of resistances, inductances and capacitances. Electrical characteristics of these networks, such as voltages, currents and equivalent impedance, are difficult to compute because they require solving multiple differential‐algebraic equations. Further, circuit simulator‐based modelling is a time‐consuming and tedious process for simulating large networks with multiparameters present in various configuration. This paper presents generalised analytical formulae for computing the electrical properties of any multiparameter arbitrary section homogenous ladder network that can be reduced to series and shunt impedances. Circuit principles, chain matrix decomposition and linear transformation are used to derive the symbolic expressions. Simply plugging the values of the series and shunt impedances, as well as the number of sections, into the derived expression yields the impedance. Thereafter, the calculated impedances can be used to calculate the nodal voltages and mesh currents. Simulation results of a six‐section homogeneous ladder network are presented and compared with those of other existing techniques to validate the derived expressions. The derived expressions eliminate the need for recursive relations, complex integro‐differential equations, large state‐space matrices and simulator‐based circuit modelling, which are all clearly advantageous.
Single‐stage buck‐boost off‐grid inverter with feedforward control
Authors: Yao Zhilei , Cai Liang
Published: January 2023

Since the output voltage accuracy of the off‐grid inverter is low with the proportional‐integral (PI) control and a two‐stage inverter is often used in the low input voltage application, a single‐stage buck‐boost off‐grid inverter with feedforward control is proposed. The proposed inverter consists of a buck‐boost converter and a full‐bridge inverter. The buck‐boost converter operates at high frequency, while the full‐bridge inverter operates at line frequency. Therefore, the intermediate bus voltage is controlled as the unipolar half‐cycle sinusoidal voltage wave to reduce the voltage stress of semiconductors, and film capacitors can be used as intermediate bus capacitors for high reliability and high power density. The operating principle is illustrated. Design guidelines and example are given. The stability analysis and external characteristic analysis are given. A 500‐W proposed inverter is constructed to verify the theoretical analysis.
Elephant rewilding affects landscape openness and fauna habitat across a 92‐year period
Authors: Gordon Christopher E. , Greve Michelle , Henley Michelle , Bedetti Anka , Allin Paul , Svenning Jens‐Christian
Published: January 2023

Trophic rewilding aims to promote biodiverse self‐sustaining ecosystems through the restoration of ecologically important taxa and the trophic interactions and cascades they propagate. How rewilding effects manifest across broad temporal scales will determine ecosystem states; however, our understanding of post‐rewilding dynamics across longer time periods is limited. Here we show that the restoration of a megaherbivore, the African savannah elephant (Loxodonta africana), promotes landscape openness (i.e., various measures of vegetation composition/complexity) and modifies fauna habitat and that these effects continue to manifest up to 92 years after reintroduction. We conducted a space‐for‐time floristic survey and assessment of 17 habitat attributes (e.g., floristic diversity and cover, ground wood, tree hollows) across five comparable nature reserves in South African savannah, where elephants were reintroduced between 1927 and 2003, finding that elephant reintroduction time was positively correlated with landscape openness and some habitat attributes (e.g., large‐sized tree hollows) but negatively associated with others (e.g., large‐sized coarse woody debris). We then indexed elephant site occurrence between 2006 and 2018 using telemetry data and found positive associations between site occurrence and woody plant densities. Taken alongside the longer‐term space‐for‐time survey, this suggests that elephants are attracted to dense vegetation in the short term and that this behavior increases landscape openness in the long term. Our results suggest that trophic rewilding with elephants helps promote a semi‐open ecosystem structure of high importance for African biodiversity. More generally, our results suggest that megafauna restoration represents a promising tool to curb Earth's recent ecological losses and highlights the importance of considering long‐term ecological responses when designing and managing rewilding projects.
The ecological consequences of the timing of extreme climate events
Authors: Cinto Mejía Elizeth , Wetzel William C.
Published: January 2023

Climate change is increasing the intensity, duration, and frequency of extreme climate events (ECEs). These ECEs can have major ecological consequences, e.g., changing nutrient flows, causing extirpation, and altering organismal development. Many ECEs are discrete events that occur at distinctive times during the biological processes they impact. Because of this, ECEs are likely to have differing ecological impacts depending on when they happen, yet we lack on studies that explore how the ecological consequences of ECEs vary with when they occur. Drawing upon evidence from physiological, population, and community ecology, and previous work on ecological disturbances, we suggest that the consequences of ECEs will be sensitive to when they occur. We illustrate the importance of timing by showing how the effects of an ECE could vary depending on when it occurs through the course of (1) organismal ontogeny, (2) population dynamics, and (3) community assembly. An enhanced focus on the timing of extreme weather in climate change research will reveal how and when ECEs are altering ecosystems, possible mechanisms behind these impacts, and what ecosystems or species are most vulnerable to ECEs, helping us to make more informed predictions about the ecological consequences of climate change.
Role of plant relatedness in plant–soil feedback dynamics of sympatric Asclepias species
Authors: Duell Eric B. , Bever James D. , Wilson Gail W. T.
Published: January 2023

Plants affect associated biotic and abiotic edaphic factors, with reciprocal feedbacks from soil characteristics affecting plants. These two‐way interactions between plants and soils are collectively known as plant–soil feedbacks (PSFs). The role of phylogenetic relatedness and evolutionary histories have recently emerged as a potential driver of PSFs, although the strength and direction of feedbacks among sympatric congeners are not well‐understood. We examined plant–soil feedback responses of Asclepias syriaca, a common clonal milkweed species, with several sympatric congeners across a gradient of increasing phylogenetic distances (A. tuberosa, A. viridis, A. sullivantii, and A. verticillata, respectively). Plant–soil feedbacks were measured through productivity and colonization by arbuscular mycorrhizal (AM) fungi. Asclepias syriaca produced less biomass in soils conditioned by the most phylogenetically distant species (A. verticillata), relative to conspecific‐conditioned soils. Similarly, arbuscular mycorrhizal (AM) fungal colonization of A. syriaca roots was reduced when grown in soils conditioned by A. verticillata, compared with colonization in plants grown in soil conditioned by any of the other three Asclepias species, indicating mycorrhizal associations are a potential mechanism of observed positive PSFs. This display of differences between the most phylogenetically distant, but not close or intermediate, paring(s) suggests a potential phylogenetic threshold, although other exogenous factors cannot be ruled out. Overall, these results highlight the potential role of phylogenetic distance in influencing positive PSFs through mutualists. The role of phylogenetic relatedness and evolutionary histories have recently emerged as a potential driver of plant–soil feedbacks (PSFs), although the strength and direction of feedbacks among sympatric congeners are not well‐understood. Congeneric, sympatric milkweeds typically generated positive PSFs in terms of productivity and AM fungal colonization, suggesting the low likelihood of coexistence among tested pairs, with a strength of feedback increasing as the phylogenetic distance increases.
Color polymorphism in the Cuban endemic livebearing fish Limia vittata (Teloestei, Poeciliidae): Potential roles of sexual and natural selection
Authors: Rodriguez‐Silva Rodet , Spikes Montrai , Monsisbay Manuel Iturriaga , Schlupp Ingo
Published: January 2023

Color polymorphism can be maintained in natural populations by natural selection or sexual selection. In this study, we use two different approaches to test which of these evolutionary mechanisms may explain the presence of color polymorphism in the Cuban Limia (Limia vittata), an endemic livebearing fish from Cuba. First, we investigate the role of sexual selection using traditional binary choice tests looking at both female and male preferences relative to varying degrees of black spotting in stimulus mates. Second, we assess the role of natural selection by analyzing the frequency and geographic distribution of black‐spotted and nonspotted morphs of L. vittata in natural populations from Cuba. The frequency of black‐spotted morphs is significantly higher in brackish and saltwater environments compared with freshwater habitats, which could be related to higher predation pressure in coastal ecosystems compared with purely freshwater environments. Our results suggest that habitat variation is the most important factor in maintaining color polymorphism in L. vittata. Salinity levels could be indirectly responsible for maintaining different color morphs in this species, likely due to the regulatory effect of saline gradients on predation regimes.
Species of fast bulk‐soil nutrient cycling have lower rhizosphere effects: A nutrient spectrum of rhizosphere effects
Authors: Sun Lijuan , Tsujii Yuki , Xu Tianle , Han Mengguang , Li Rui , Han Yunfeng , Gan Dayong , Zhu Biao
Published: January 2023

Tree roots not only acquire readily‐usable soil nutrients but also affect microbial decomposition and manipulate nutrient availability in their surrounding soils, that is, rhizosphere effects (REs). Thus, REs challenge the basic understanding of how plants adapt to the environment and co‐exist with other species. Yet, how REs vary among species in response to species‐specific bulk soil nutrient cycling is not well‐known. Here, we studied how plant‐controlled microbial decomposition activities in rhizosphere soils respond to those in their corresponding bulk soils and whether these relations depend on species‐specific nutrient cycling in the bulk soils. We targeted 55 woody species of different clades and mycorrhizal types in three contrasting biomes, namely a temperate forest, a subtropical forest, and a tropical forest. We found that microbial decomposition activities in rhizosphere soils responded linearly to those in their corresponding bulk soils at the species level. Thereafter, we found that REs (parameters in rhizosphere soils minus those in corresponding bulk soils) of microbial decomposition activities had negative linear correlations with microbial decomposition activities in corresponding bulk soils. A multiple factor analysis revealed that soil organic carbon, total nitrogen, and soil water content favored bulk soil decomposition activities in all three biomes, showing that the magnitude of REs varied along a fast‐slow nutrient cycling spectrum in bulk soils. The species of fast nutrient cycling in their bulk soils tended to have smaller or even negative REs. Therefore, woody plants commonly utilize both positive and negative REs as a nutrient‐acquisition strategy. Based on the trade‐offs between REs and other nutrient‐acquisition strategies, we proposed a push and pull conceptual model which can bring plant nutrient‐acquisition cost and plant carbon economics spectrum together in the future. This model will facilitate not only the carbon and nutrient cycling but also the mechanisms of species co‐existence in forest ecosystems.
Mean corpuscular haemoglobin concentration and outcomes in heart failure with preserved ejection fraction
Authors: Choy Manting , Zhen Zhe , Dong Bin , Chen Cong , Dong Yugang , Liu Chen , Liang Weihao , Xue Ruicong
Published: January 2023

Aims

This study aims to evaluate the prognostic value of mean corpuscular haemoglobin concentration (MCHC) on clinical outcomes in patients with heart failure with preserved ejection fraction (HFpEF).

Methods and results

We analysed HFpEF participants from the Americas in the Treatment of Preserved Cardiac Function Heart Failure with an Aldosterone Antagonist (TOPCAT) trial with available baseline data (n = 1747). Patients were grouped into hypochromia or non‐hypochromia group according to a MCHC cut‐off level of 330 g/L. Cox proportional hazard model was used to explore the prognostic value of hypochromia on the long‐term clinical outcomes (the primary endpoint [composite of cardiovascular mortality, HF hospitalization and aborted cardiac arrest], any‐cause and HF hospitalization, all‐cause and cardiovascular mortality). Patients were further stratified according to baseline estimated glomerular filtration rate (eGFR) to explore the impact of renal dysfunction on the prognostic value of hypochromia. Baseline hypochromia was prevalent (n = 662, 37.9%) and strongly associated with worse clinical outcomes. In patients with worse renal function (eGFR < 60 mL/min per 1.73 m2), hypochromia was independently associated with primary endpoint (hazard ratio [HR], 1.56; 95% confidence interval [CI], 1.23–1.98; P < 0.001), any‐cause hospitalization (HR, 1.43; 95% CI, 1.20–1.71, P < 0.001) and HF hospitalization (HR, 1.40; 95% CI, 1.07–1.84; P = 0.015), whereas no significant association between hypochromia and these outcomes was found in patients with better renal function.

Conclusions

Among HFpEF patients, hypochromia (i.e. MCHC ≤ 330 g/L) is independently associated with adverse clinical outcomes, especially when in the presence of co‐morbidity renal dysfunction.
Metal Catalyzed Polymerization: From Stereoregular Poly(α‐olefins) to Tailor‐Made Biodegradable/Biorenewable Polymers and Copolymers
Authors: Capacchione Carmine , Grisi Fabia , Lamberti Marina , Mazzeo Mina , Milani Barbara , Milione Stefano , Pappalardo Daniela , Zuccaccia Cristiano , Pellecchia Claudio
Published: January 2023

Metal catalyzed polymerizations are among the most important chemical reactions, accounting for the production of about 400 million tons per year of polymeric materials, 50 % of which are polyolefins. The CIRCC research units at the University of Salerno, founded by the late Professor Adolfo Zambelli, a coworker of Giulio Natta and a pioneer in the studies of stereospecific polymerization catalysts, has a consolidated expertise in this field. Although often considered a “mature” area of research, olefin polymerization catalysis continues to drive great interest of both industrial and academic scientists. On the other hand, strong political and economic pressure toward the development of “green” and possibly biodegradable alternatives to olefin‐based polymers stimulated our group to direct increasing research efforts in the area of sustainable polymers. In this perspective, we focus on the most recent work from the CIRCC research units involved in homogeneous catalysis for polymerization of a variety of monomers, with the aim to address how the concepts and the expertise developed for olefin polymerization can be applied to the development of different metal‐catalyzed polymerizations and copolymerizations. Of course, although the results are discussed in the frame of the most important literature contributions, a comprehensive review of such a wide and diversified topic is out of the scope of the paper. References to reviews covering the different types of metal catalyzed polymerizations are provided in each chapter.
[2+2] Cycloadditions of Methylene exo‐Glycals: Synthesis of Glycopyranosylidene‐Spiro‐Azetidine‐2‐ones (β‐Lactams) and Cyclobutanones
Authors: József János , Somsák László , Tóth Marietta , Juhász László
Published: January 2023

[2+2] Cycloadditions of methylene exo‐glycal derivatives with chlorosulfonyl isocyanate and dichloroketene were studied in detail, investigating the effect of the carbohydrate moiety, protecting groups as well as reaction temperature on the yields of the transformations. These reactions gave new anomeric spiro‐β‐lactam and spiro‐cyclobutanone derivatives, whose structure was established by 1D and 2D NMR and MS experiments. The transformation of spiro‐cyclobutanone into spiro‐γ‐lactone was also demonstrated.
Model Experiments for Explaining the Processes Occurring During Conductive Battery Electrode Drying
Authors: Zihrul Christiane , Wolf Silas , Kwade Arno
Published: January 2023

During the manufacturing of lithium‐ion‐battery electrodes, the drying step has a great impact on their performance as it determines the pore microstructure and the mechanical integrity of the electrode. To derive dependencies of the electrode properties on the drying temperature, water‐based graphite anodes are dried by means of a conductive drying apparatus and analyzed during and after the drying process. Drying experiments with different temperatures from 40 to 80 °C indicate that the electrode properties strongly depend on the chosen temperature and, therefore, on the drying rate, as the investigation of the binder distribution shows. Higher drying temperatures lead to a poorly distributed binder profile with the accumulation of binder toward the surface of the coating, due to the fast receding film surface. Also, lower temperatures hinder the diffusion of the binder during the process, which also results in a less distributed binder concentration. On the contrary, the drying rate does not seem to have a major effect on the pore structure of the electrode which suggests that the binder distribution does not play a leading role in the pore structure formation process.
Frequency of and factors associated with antiseizure medication discontinuation discussions and decisions in patients with epilepsy: A multicenter retrospective chart review
Authors: Terman Samuel W. , Slinger Geertruida , Koek Adriana , Skvarce Jeremy , Springer Mellanie V. , Ziobro Julie M. , Burke James F. , Otte Willem M. , Thijs Roland D. , Braun Kees P. J.
Published: January 2023

Objective

Guidelines suggest considering antiseizure medication (ASM) discontinuation in patients with epilepsy who become seizure‐free. Little is known about how discontinuation decisions are being made in practice. We measured the frequency of, and factors associated with, discussions and decisions surrounding ASM discontinuation.

Methods

We performed a multicenter retrospective cohort study at the University of Michigan (UM) and two Dutch centers: Wilhelmina Children's Hospital (WCH) and Stichting Epilepsie Instellingen Nederland (SEIN). We screened all children and adults with outpatient epilepsy visits in January 2015 and included those with at least one visit during the subsequent 2 years where they were seizure‐free for at least one year. We recorded whether charts documented (1) a discussion with the patient about possible ASM discontinuation and (2) any planned attempt to discontinue at least one ASM. We conducted multilevel logistic regressions to determine factors associated with each outcome.

Results

We included 1058 visits from 463 patients. Of all patients who were seizure‐free at least one year, 248/463 (53%) had documentation of any discussion and 98/463 (21%) planned to discontinue at least one ASM. Corresponding frequencies for patients who were seizure‐free at least 2 years were 184/285 (65%) and 74/285 (26%). The probability of discussing or discontinuing increased with longer duration of seizure freedom. Still, even for patients who were 10 years seizure‐free, our models predicated that in only 49% of visits was a discontinuation discussion documented, and in only 16% of visits was it decided to discontinue all ASMs. Provider‐to‐provider variation explained 18% of variation in whether patients discontinued any ASM.

Significance

Only approximately half of patients with prolonged seizure freedom had a documented discussion about ASM discontinuation. Discontinuation was fairly rare even among low‐risk patients. Future work should further explore barriers to and facilitators of counseling and discontinuation attempts.
Key‐aggregate searchable encryption with multi‐user authorization and keyword untraceability for distributed IoT healthcare systems
Authors: Trivedi Hiral S. , Patel Sankita J.
Published: January 2023

Adopting Internet‐of‐Things (IoT) enables pervasive computing by integrating distributed healthcare infrastructures to enhance conventional medical services. Integrated healthcare systems store numerous encrypted electronic health records (EHR) on clouds that multiple users frequently access as per delegated access rights. Sharing any group of selected EHR within any group of users involving different encryption keys potentially heightens security and privacy concerns over inadvertent data leaks. This necessitates a searchable encryption mechanism in distributed IoT requiring secure multi‐user authorization and efficient searchable keys management with compact trapdoors. Contemporary state‐of‐the‐art protocols utilize large numbers of expensive encryption keys and keyword trapdoors while lacking secure multi‐user authorization and keyword untraceability on clouds. This motivates us to design a novel key‐aggregate searchable encryption protocol that jointly achieves multi‐user authorization and keyword untraceability for distributed IoT applications. Key‐aggregation reduces complexity in sharing documents by executing a stand‐alone trapdoor, while token‐based authorization allows keyword search only to legitimate data users. Additionally, secure dynamic indexing achieves keyword untraceability on clouds. Security analysis illustrates correctness and resilience against typical attacks. Performance and empirical analysis demonstrate a relative advantage in storage, communication, and computational costs while incorporating secure multi‐user authorization and keyword untraceability as additional security features.
Securitization of assets with payment delay risk: A financial innovation in the real estate market
Authors: Ma Chao , Zhang Hao , Zhao Hongbiao
Published: January 2023

We study a new type of securitization that deals with banks' processing time, mortgage‐receivable‐backed securities (MRBSs) issued by real estate developers. Unlike traditional mortgage‐backed securities (MBSs), the major risk of underlying assets of MRBSs is payment delay instead of default and prepayment. Using unique loan‐level data, we estimate proportional hazard models and detect factors that affect the risk of underlying assets of MRBSs, including bank characteristics, property–loan–household characteristics, local market conditions, and macroeconomic conditions. Especially, we find that the effects of house prices and loan‐to‐value ratios on MRBS risk are the opposite of those on traditional MBS risk. Based on the estimates, we simulate cash flows of an underlying‐asset pool and analyze the shortfall risk of the corresponding security tranches. We find that the securitization process imposes a natural adverse selection on the underlying assets.
A cloud‐based resource for genome coordinate‐based exploration and large‐scale analysis of chromosome aberrations and gene fusions in cancer
Authors: Wang Janet , Zheng Jeanne , Lee Elaine E. , Aguilar Boris , Phan John , Abdilleh Kawther , Taylor Ronald C. , Longabaugh William , Johansson Bertil , Mertens Fredrik , Mitelman Felix , Pot David , LaFramboise Thomas
Published: January 2023

Cytogenetic analysis provides important information on the genetic mechanisms of cancer. The Mitelman Database of Chromosome Aberrations and Gene Fusions in Cancer (Mitelman DB) is the largest catalog of acquired chromosome aberrations, presently comprising >70 000 cases across multiple cancer types. Although this resource has enabled the identification of chromosome abnormalities leading to specific cancers and cancer mechanisms, a large‐scale, systematic analysis of these aberrations and their downstream implications has been difficult due to the lack of a standard, automated mapping from aberrations to genomic coordinates. We previously introduced CytoConverter as a tool that automates such conversions. CytoConverter has now been updated with improved interpretation of karyotypes and has been integrated with the Mitelman DB, providing a comprehensive mapping of the 70 000+ cases to genomic coordinates, as well as visualization of the frequencies of chromosomal gains and losses. Importantly, all CytoConverter‐generated genomic coordinates are publicly available in Google BigQuery, a cloud‐based data warehouse, facilitating data exploration and integration with other datasets hosted by the Institute for Systems Biology Cancer Gateway in the Cloud (ISB‐CGC) Resource. We demonstrate the use of BigQuery for integrative analysis of Mitelman DB with other cancer datasets, including a comparison of the frequency of imbalances identified in Mitelman DB cases with those found in The Cancer Genome Atlas (TCGA) copy number datasets. This solution provides opportunities to leverage the power of cloud computing for low‐cost, scalable, and integrated analysis of chromosome aberrations and gene fusions in cancer.