bluuebunny/crossref_metadata_2025 huggingface dataset:
Strain‐Stabilized CsPbI3 Perovskite via Organopolysilazane for Efficient Solar Cells with Efficiency over 19%
Authors: Yu Haixuan , Li Xiongjie , Zhang Zhiguo , Ban Huaxia , Gong Xiu , Liu Zhirong , Zhang Miaomiao , Sun Qiang , Zhang Tao , Shen Yan , Zhang Xiao‐Li , Zhu Jun , Wang Mingkui
Published: October 2022

Principally, all‐inorganic perovskite crystals, such as CsPbI3, possess higher thermal stability than their organic–inorganic hybrid counterparts, like CH3NH3PbI3, due to the type of chemical bond variants. However, considering a retained strain in these stiff films, it is a challenge to stabilize CsPbI3 within the photoactive phase for photovoltaic application under ambient conditions. This article reports organopolysilazane (OPSZ) as a strain compensation layer that regulates the tense strain during the annealing process, a very attractive feature for all‐inorganic perovskite solar cells with a CsPbI3 active layer. When depositing OPSZ onto the surface of CsPbI3 film for thin‐film solar cell devices with FTO/c‐TiO2/CsPbI3/spiro‐OMeTAD/Au architecture, an efficiency of 19.12% is achieved under standard illumination test conditions. This strain compensation layer offers a viable pathway to develop efficient and stable solar cells with inorganic perovskite crystalline thin films for scale‐up and practical applications.
Strain‐Driven Thermal and Optical Instability in Silver/Amorphous‐Silicon Hyperbolic Metamaterials
Authors: Ocana‐Pujol Jose L. , Forster Lea , Spolenak Ralph , Galinski Henning
Published: October 2022

Hyperbolic metamaterials show exceptional optical properties, such as near‐perfect broadband absorption, due to their geometrically‐engineered optical anisotropy. Many of their proposed applications, such as thermophotovoltaics or radiative cooling, require high‐temperature stability. In this work, Ag/a‐Si multilayers are examined as a model system for the thermal stability of hyperbolic metamaterials. Using a combination of nanotomography, finite element simulations, and optical spectroscopy, the thermal and optical instability of the metamaterials is mapped. Although the thermal instability initiates at 300 °C, the hyperbolic dispersion persists up to 500 °C. Direct finite element simulations on tomographical data provide a route to decouple and evaluate interfacial and elastic strain energy contributions to the instability. Depending on stacking order the instability's driving force is either dominated by changes in anisotropic elastic strain energy due thermal expansion mismatch or by minimization of interfacial energy. These findings open new avenues to understand multilayer instability and pave the way to design hyperbolic metamaterials able to withstand high temperatures.
Selective Intermolecular Dual Amino‐Trifluoromethylation of Alkenes by High‐Valent Cu(III)−CF3Compounds
Authors: Chen Ning , Zhang Song‐Lin
Published: October 2022

A selective intermolecular amino‐trifluoromethylation of alkenes is developed to produce a range of biologically active β‐trifluoromethyl amines. This method exploits a crucial high‐valent Cu(III)−CF3complex as a combined source of CF3radical and Cu(II) oxidant through homolytic Cu(III)−CF3bond cleavage. This unique mode of CF3radical generation is distinct from current dominant methods that rely largely on photoredox catalysis or the use of sacrificing radical initiator. This represents a significant advantage in that it greatly simplifies the reaction conditions, brings about operational convenience, and is beneficial to suppress various side reactions under otherwise more complicated conditions. A tertiary alkyl radical generated from addition of CF3radical to alkenes is proposed to react with amines to enable C−N formation with the assistance of in‐situ Cu(II) oxidant. This reaction shows good chemo‐ and regio‐selectivity, suppressing a number of potential side reactions. The free manipulation of readily available Cu(III)−CF3compound and feedstock compounds of alkenes and anilines greatly broadens the reaction scope. The good chemo‐ and regioselectivity, and operational convenience make this reaction attractive from the synthetic viewpoint. The reactivity of high‐valent Cu(III)−CF3compounds disclosed in this study may be exploited to develop other interesting reactions, and to enrich the currently underdeveloped Cu(III) chemistry.

magnified image
Enhanced CO2 Photoreduction by Ni(OH)2‐x/WO3 Nanofibers with Efficient CO2 Activation and Charge Separation
Authors: Lin Yuan , Huang Guimei , Chen Lv , Zhang Jianhua , Liu Lijun
Published: October 2022

Electrospun WO3 nanofibers show great potential in solar‐powered CO2 reduction, but they still suffer from rapid charge recombination and difficult CO2 activation. Here, WO3 nanofibers are modified by in situ growth of freestanding oxygen‐vacancy Ni(OH)2‐x nanosheets, and explored their charge separation and CO2 reduction mechanisms by using in situ characterization techniques and density functional theory (DFT) calculations. Some electrons of Ni(OH)2‐x transferred to WO3 nanofibers upon hybridization owing to their remarkable different work function, which induces a built‐in electric field (BIEF) at interfaces with directions pointing from Ni(OH)2‐x to WO3. Driven by the electric field, the photogenerated electrons flow to Ni(OH)2‐x, while the holes remain at WO3, achieving spatial charge separation. Further, CO2 adsorbed on Ni(OH)2‐x shows apparent molecular activation, as suggested by its bent and elongated OCO bonds. The Ni(OH)2‐x/WO3 nanofibers exhibit an enhanced CO production rate with respect to WO3 (54.4 vs 8.1 µmol g−1 h−1). The 13CO2 isotope tracing experiment confirms that the CO product originated from the input CO2. This work may inspire the development of more advanced photocatalysts for CO2 activation and photoreduction by defect engineering.
Electrical Manipulation of Oxygen Ion Migrations for the Voltage‐Controlled Adjustment of Magnetic Anisotropy and Optimized Skyrmion Generations
Authors: Tran Bao Xuan , Yang Seungmo , Kim Hyun‐Joong , Ha Jae‐Hyun , Yoon Seongsoo , Kim Changsoo , Moon Kyoung‐Woong , Choi Won‐Chang , Hwang Chanyong , Hong Jung‐Il
Published: October 2022

With the prospect of energy‐efficient spintronics by voltage‐controlled magnetic anisotropy (VCMA), various mechanisms are investigated involving electron orbital state modulations for enhanced spin–orbit interactions, couplings with piezoelectric strain, and electrochemical effect at the interface within diverse magnetoelectric coupled material systems. In the present work, chemistry and spatial distributions of atoms are fine‐tuned at the interface between ferromagnetic Co and partially oxidized Gd layers via voltage‐controlled ion migrations, achieving highly sensitive and stable VCMA operations. With combined actions of chemical diffusion and electrical driving of oxygen through amorphous Gd layer, asymmetric electrical adjustments of magnetic anisotropy could be established. Accompanied changes in the domain morphologies in the magnetic thin film layers could also be confirmed at room temperature. As the fine‐adjustments of domain morphology are essential for the skyrmions generation, voltage‐controlled interfacial chemistry and magnetic anisotropy provide an effective route to stable skyrmion generations and manipulations in the low‐power spintronics technology.
Self‐Aligning Metallic Vertical Interconnect Access Formation through Microlensing Gas Phase Electrodeposition controlling Airgap and Morphology
Authors: Schlag Leslie , Isaac Nishchay A. , Hossain Mohammad M. , Hess Anna‐Lena , Wolz Benedikt C. , Reiprich Johannes , Ziegler Mario , Pezoldt Jörg , Jacobs Heiko O.
Published: October 2022

This publication reports self‐aligning metallic via microlensing gas phase electrodeposition formation. Key operational parameters to fabricate vertical ruthenium and rhodium interconnects (via) with a diameter of 100 nm are discussed. Moreover, airgaps are implemented during the deposition process, which utilizes spark discharge to generate a flux of charged nanoparticles. An inert gas flow transports the nanoparticles through a reactor chamber close to the target substrate. The substrate uses a pre‐patterned resist with openings to a silicon/silicon dioxide/metal stack to direct the deposition of the nanoparticles to form localized self‐aligning vertical interconnects. Five process parameters were identified, which impact the morphology and conductance of the resulting interconnects: spark discharge power, gas flow rate, microlens via dimensions, substrate surface potential, and in situ flash lamp power. This parameter set enables a controlled adjustment of the via interconnect morphology and its minimum feature size. Gas flow rate in combination with spark discharge power contribute significantly to the morphology of the interconnect. Spark power and microlens via dimensions have the largest influence on the surface potential of the insulating resist cover, which enables a localized microlensing gas phase electrodeposition of a via with a controlled ratio between conducting diameter and airgap.
Reduced Open‐Circuit Voltage Loss of Perovskite Solar Cells via Forming p/p+ Homojunction and Interface Electric Field on the Surfaces of Perovskite Film
Authors: Zhang Jiankai , Sun Yapeng , Huang Chengwen , Yu Bo , Yu Huangzhong
Published: October 2022

The severe nonradiative recombination losses limit the further improvement of open‐circuit voltage (Voc) and power conversion efficiency (PCE) of perovskite solar cells (PVSCs). In this work, the 4,4′‐cyclohexylidenebis [N,N‐bis(4‐methylphenyl) benzene amine] is dissolved into the antisolvent to prepare perovskite films, which reduces defects, improves the crystallinity, and induces a p/p+ homojunction on the top surface of perovskite film. Besides, the 2‐thiophenemethylammonium iodide and 2‐thiophenethylammonium iodide form interface electric field and passivate defects on the bottom surface of perovskite film. The p/p+ homojunction and interface electric field enhance the charges’ separation and transportation efficiencies in the bulk perovskite film and at the perovskite/charge transport layer interfaces, which effectively reduces nonradiative recombination losses and Voc loss of PVSCs. Consequently, low Voc loss of 0.348 V is realized, resulting in the increase in Voc from 1.082 to 1.172 V and PCE from19.15% to 23.44%. The optimized PVSCs without encapsulation maintain 88.23% of the original PCE after exposing in the air for 1500 h. This work provides a strategy to reduce the nonradiative recombination losses and Voc loss by forming p/p+ homojunction and interface electric field on the surfaces of perovskite film, which advances the development of high‐performance PVSCs.
Top‐down enrichment of oil field microbiomes to limit souring and control oil composition during extraction operations
Authors: Hillman Ethan T. , Caceres‐Martinez Louis Edwards , Kilaz Gozdem , Solomon Kevin V.
Published: October 2022

Microbial processes sour oil, corrode equipment, and degrade hydrocarbons at an annual global cost to the oil and gas industry of nearly $2 billion. However, top‐down control of these microbial processes can reduce their damage and enhance oil recovery. Here, we screened microbial communities from five oil wells in the Illinois basin and evaluated nutrient injection strategies to control metabolism and community composition. Molasses with molybdate supplementation stimulated gas and organic acid production while suppressing corrosive H2S formation in samples from two wells. These changes were accompanied with significant reshaping of the microbiome community. Simulations of field operations via a lab‐scale mini‐coreflood validated that oil well microbiomes can be engineered to inhibit deleterious H2S and shape oil hydrocarbon composition in situ. These pilot studies validate the economic potential and sustainability of top‐down approaches for microbiome engineering to control microbes in oil extraction and enhance the economic viability of oil recovery.
Endoplasmic reticulum sequestration empowers phosphorylation profiling on the yeast surface
Authors: Ezagui Jose , Russell Brittney , Mairena Yave , Stern Lawrence A.
Published: October 2022

Cells sense cues in their surrounding environment, turning extracellular stimuli into intracellular responses. Transient posttranslational modifications, such as phosphorylation, often guide these responses through tightly regulated signaling networks. There is great interest in understanding phosphorylation events that yield responses in cell signaling, but to date, methods to characterize the phosphoproteome rely on low‐throughput methods. To overcome this limitation, this study optimizes a yeast surface display system for high‐throughput screening of kinase–substrate interaction using endoplasmic reticulum (ER) sequestration. We demonstrate the ability of yeast to display phosphorylated full‐length receptor cytoplasmic domains and additionally optimized magnetic bead selections to efficiently recover yeast displaying phosphorylated domains. These lessons were applied to profiling the substrate specificity of the tyrosine kinase lymphocyte cell‐specific protein‐tyrosine kinase by mutating a phosphoacceptor motif within the CD28 cytoplasmic domain and to building multienzyme phosphorylation cascades in the yeast ER. Collectively, this study provides a facile approach for profiling kinase–substrate reactions in high throughput.
Utilization of real‐world data in assessing treatment effectiveness for diffuse large B‐cell lymphoma
Authors: Nowakowski Grzegorz , Maurer Matthew J. , Cerhan James R. , Dey Debarshi , Sehn Laurie H.
Published: October 2022

Direct comparisons of the effectiveness of the numerous novel therapies in the diffuse large B‐cell lymphoma (DLBCL) treatment landscape in a range of head‐to‐head randomized phase 3 trials would be time‐consuming and costly. Comparative effectiveness studies using real‐world data (RWD) represent a complementary approach. Recently, several studies of relapsed/refractory (R/R) DLBCL have used RWD to create observational cohorts to compare patient outcomes with cohorts derived from single‐arm phase 2 trials. Using propensity score methods to balance clinically and prognostically relevant baseline covariates, closely matched patient‐level cohorts can be generated. By incorporating appropriate measures to assess covariate balance and address potential bias in comparative effectiveness study designs, robust comparative analyses can be performed. Results from such studies have been used to supplement regulatory approval of therapies assessed in single‐arm trials. While RWD studies have a greater susceptibility to bias compared to randomized controlled trials, well‐designed and appropriately analyzed studies can provide complementary real‐world evidence on treatment effectiveness.
Residential proximity to oil and gas production sites and hematologic malignancies: A case‐control study
Authors: Forster Felix , Herrera Ronald , Hoopmann Michael , Kieschke Joachim , Deitermann Bernhilde , Radon Katja
Published: October 2022

Background

We investigated the association between residential proximity to oil and gas production sites and hematologic malignancies, due to a cancer cluster in the German state of Lower Saxony.

Methods

A registry‐based case‐control study was conducted including 3978 cases of hematologic malignancies diagnosed within 2013–2016 and 15,912 frequency‐matched controls randomly drawn by population registries. Residential proximity to 5333 oil and gas production sites at the time of diagnosis was calculated. Unconditional logistic regression models were used to estimate the association between living within 1 km of any exposure site and developing a hematologic malignancy. Models were adjusted for matching variables sex, age group, district, and year of diagnosis as well as for proximity to main streets and to agricultural land.

Results

We found no association between the development of hematologic malignancies and the proximity to all oil and gas production sites (odds ratio: 0.97; 95% confidence interval: 0.85, 1.11). Focusing on gas production sites increased the odds of developing hematologic cancer (odds ratio: 1.19; 95% confidence interval: 0.97, 1.45). In stratified analyses, associations were stronger in women and for acute myeloblastic leukemia. We also found an association in the district where the initial cluster occurred.

Conclusions

Our results suggest that residential proximity to oil and gas production is not a risk factor for all hematologic malignancies in general. Sporadic and past exposures are the most likely scenarios for mechanisms involving oil and gas production, leading to increased risk for certain subtypes of cancer in certain populations.
Contribution of phylogenetics to understanding the evolution and epidemiology of dengue virus
Authors: Yu Xi , Cheng Gong
Published: October 2022

Dengue virus (DENV) is one of the most important arboviral pathogens in the tropics and subtropics, and nearly one‐third of the world's population is at risk of infection. The transmission of DENV involves a sylvatic cycle between nonhuman primates (NHP) and Aedes genus mosquitoes, and an endemic cycle between human hosts and predominantly Aedes aegypti. DENV belongs to the genus Flavivirus of the family Flaviviridae and consists of four antigenically distinct serotypes (DENV‐1‐4). Phylogenetic analyses of DENV have revealed its origin, epidemiology, and the drivers that determine its molecular evolution in nature. This review discusses how phylogenetic research has improved our understanding of DENV evolution and how it affects viral ecology and improved our ability to analyze and predict future DENV emergence.
Nocturnal Pulse Event Frequency Is Reduced in Multiple System Atrophy
Authors: McCarter Stuart J. , Coon Elizabeth A. , Benarroch Eduardo E. , Silber Michael H. , St. Louis Erik K.
Published: October 2022

Risk of sudden death in multiple system atrophy (MSA) is greatest during sleep with unknown mechanisms. We compared nocturnal pulse event frequency in 46 MSA patients and age‐/sex‐matched controls undergoing overnight pulse oximetry. Nocturnal oxyhemoglobin desaturation indices and pulse event indices (PEIs) were recorded, and relationships between pulse oximetry variables and survival were analyzed. MSA patients had lower PEI (3.1 ± 5.3 vs. 12.8 ± 10.8, p < 0.001) despite greater hypoxic burden and similar frequency of respiratory events. Nocturnal pulse events were not associated with severity of daytime autonomic failure. Two MSA patients had suspected sudden death, both with severely reduced PEI. MSA patients have fewer nocturnal pulse events compared with controls, despite similar respiratory event frequency, suggesting abnormal cardiac responses to sleep‐disordered breathing. Whether this contributes to sudden death in MSA requires further study. ANN NEUROL 2023;93:205–212
Ocrelizumab Concentration Is a Good Predictor of SARS‐CoV‐2 Vaccination Response in Patients with Multiple Sclerosis
Authors: van Kempen Zoé L. E. , Hogenboom Laura , Toorop Alyssa A. , Steenhuis Maurice , Stalman Eileen W. , Kummer Laura Y. L. , van Dam Koos P. J. , Bloem Karien , ten Brinke Anja , van Ham S. Marieke , Kuijpers Taco W. , Wolbink Gerrit J. , Loeff Floris C. , Wieske Luuk , Eftimov Filip , Rispens Theo , Strijbis Eva M. M. , Killestein Joep ,   the T2B! immunity against SARS‐CoV‐2 study group
Published: October 2022

Ocrelizumab, an anti‐CD20 monoclonal antibody, counteracts induction of humoral immune responses after severe acute respiratory syndrome‐coronavirus 2 (SARS‐CoV‐2) vaccinations in patients with multiple sclerosis (MS). We aimed to assess if serum ocrelizumab concentration measured at the time of vaccination could predict the humoral response after SARS‐CoV‐2 vaccination. In 52 patients with MS, we found ocrelizumab concentration at the time of vaccination to be a good predictor for SARS‐CoV‐2 IgG anti‐RBD titers after vaccination (comparable to B‐cell count). As the course of ocrelizumab concentration may be predicted using pharmacokinetic models, this may be a superior biomarker to guide optimal timing for vaccinations in B‐cell depleted patients with MS. ANN NEUROL 2023;93:103–108
Lithium Enolate with a Lithium‐Alkyne Interaction in the Enantioselective Construction of Quaternary Carbon Centers: Concise Synthesis of (+)‐Goniomitine
Authors: Li Yang , Paola Elena , Wang Zongheng , Menard Gabriel , Zakarian Armen
Published: October 2022

We report a method for direct enantioselective alkylation of 3‐alkynoic and 2,3‐alkendioic acids that form quaternary stereogenic centers, and application of this method to the total enantioselective synthesis of a complex alkaloid (+)‐goniomitine. The methods were effective in the alkylation of both 3‐alkynoic acids, 2,3‐alkendioic acids substrates with a broad range of heterocyclic and functionalized alkyl group substituents. Accompanying crystallographic studies provide mechanistic insight into the structure of well‐defined chiral aggregates, highlighting cation‐π interactions between lithium and alkyne groups.
Sulfur‐Free Radical RAFT Polymerization of Methacrylates in Homogeneous Solution: Design of exo‐Olefin Chain‐Transfer Agents (R−CH2C(=CH2)Z)
Authors: Amano Maki , Uchiyama Mineto , Satoh Kotaro , Kamigaito Masami
Published: October 2022

In this work, the development of exo‐olefin compounds (R−CH2C(=CH2)Z) as chain‐transfer agents for the sulfur‐free reversible addition‐fragmentation chain transfer (RAFT) radical polymerization of methacrylates in homogeneous solution is described. A series of exo‐olefin compounds with a methyl methacrylate (MMA) dimer structure as the R group and a substituted α‐methylstyrene unit as the −CH2C(=CH2)Z (Z: Ph−Y) group were synthesized and used for the radical polymerization of MMA in toluene and PhC(CF3)2OH. These compounds underwent transfer of the CH2C(=CH2)Z group via addition‐fragmentation of the propagating methacryloyl radical. More electron‐donating (Y) substituents, such as methoxy and dimethylamino groups, produced polymers with narrower molecular weight distributions. A continuous monomer addition method further improved molecular weight control and enabled the synthesis of colorless, sulfur‐free, multiblock copolymers of methacrylates in homogeneous solutions.
Wasserstoff ermöglicht Teile des reduktiven Krebs‐Zyklus unter Katalyse von Metallen oder Meteoriten
Authors: Rauscher Sophia A. , Moran Joseph
Published: October 2022

Wasserstoff (H2) ist eine geologische Elektronenquelle, von der angenommen wird, dass sie den Stoffwechsel des letzten universellen gemeinsamen Vorfahren aller heutigen Lebewesen angetrieben hat und die immer noch im Stoffwechsel von verschiedenen modernen Organismen verwendet wird. Es wurde vermutet, dass H2unter Metallkatalyse ein geochemisches Analogon eines Teils oder des gesamten reduktiven Krebs‐Zyklus bei der Entstehung des Stoffwechsels ermöglichte, was jedoch noch nicht experimentell nachgewiesen werden konnte. Hier zeigen wir, dass drei aufeinanderfolgende Schritte des reduktiven Krebs‐Zyklus, die Umwandlung von Oxalacetat in Succinat, ohne Enzyme und in einer Eintopfreaktion mit H2als Reduktionsmittel unter milden Bedingungen, die mit der biologischen Chemie kompatibel sind, ablaufen können. Geringe katalytische Mengen an Nickel (10–20 mol %), Edelmetallen (0.1–1 mol %) oder sogar kleine Mengen an gemahlenen Meteoriten ermöglichen die Reduktionsreaktion bei Temperaturen zwischen 5 und 60 °C und über einen weiten pH‐Bereich, einschließlich pH 7. Diese Ergebnisse unterstützen die Hypothese, dass geologisch erzeugter Wasserstoff und Metallkatalysatoren frühe biochemische Netzwerke initiiert haben könnten.
Non‐Equilibrium Kinetic States of a [2]Rotaxane‐Based Molecular Shuttle Controlled by Acid Concentrations
Authors: Zhao Lei‐Min , Zheng Li‐Shuo , Wang Xiaoping , Jiang Wei
Published: October 2022

A [2]rotaxane‐based molecular shuttle with an acid‐responsive asymmetric macrocycle on a symmetric dumbbell axle is reported. Upon adding TFA, the macrocycle, namely the amine naphthotube, is protonated and translocates from the di(quaternary ammonium) station to the triazole stations because of electrostatic repulsion and weakened binding. The shuttling kinetics are slow due to the steric hindrance caused by the ethyl group on the quaternary ammonium center and can be followed by 1H NMR spectroscopy. Interestingly, it was found that the shuttling kinetics depends on the concentration of TFA. A kinetic intermediate was detected and can even be captured in the presence of a high concentration of TFA. Extensive control experiments revealed that the shuttling kinetics and the capture of the kinetic intermediate are related to the different protonation states of the rotaxanes.
Microhydrated 3‐Methyl‐3‐oxetanemethanol: Evolution of the Hydrogen‐Bonding Network from Chains to Cubes
Authors: Sun Wenhao , Schnell Melanie
Published: October 2022

Broadband rotational spectroscopy is used to investigate the geometries of 3‐methyl‐3‐oxetanemethanol and its complexes with up to six water molecules, which are produced in supersonic jets. The main low‐energy isomers of these clusters are unambiguously identified in the spectra with the support of quantum‐chemical calculations. The conformation of the 3‐methyl‐3‐oxetanemethanol geometry is found to be influenced by the microsolvation effects. The hydrogen‐bond arrangements in the hydrate complexes, which are governed by the water‐water and water‐solute interactions, exhibit characteristic configurations with increasing number of water molecules and resemble the main isomers of the corresponding pure water clusters. Evolution of the hydrogen‐bonding structures from one‐dimensional chains to two‐dimensional rings and further to multicyclic three‐dimensional networks is observed, which provides information about the build‐up process.
Deracemization through Sequential Photoredox‐Neutral and Chiral Brønsted Acid Catalysis
Authors: Gu Ziwei , Zhang Li , Li Haijun , Cao Shanshan , Yin Yanli , Zhao Xiaowei , Ban Xu , Jiang Zhiyong
Published: October 2022

Catalytic deracemization is an ideal synthetic strategy due to its formally perfect atom utilization. Asymmetric photocatalysis has been appreciated as a promising tool to accomplish this attractive reaction pattern in an economical fashion, but it remains underdeveloped. Here, we report a new platform based on photoredox‐neutral catalysis, allowing efficient and modular optical enrichment of α‐amino esters and other valuable analogues. Two single‐electron transfer processes between the photocatalyst and the substrates serve to provide the key prochiral intermediates, and the chiral Brønsted acid catalyst mediates enantioselective protonation to reconstitute a stereogenic C−H bond. The efficiency of deracemization is determined by the enantiofacial differentiation effect during the stereocentre‐forming step.
A Vitamin B2‐Photocatalysed Approach to Methionine Analogues
Authors: Knowles  Oliver J. , Johannissen Linus O. , Crisenza Giacomo E. M. , Hay Sam , Leys David , Procter David J.
Published: October 2022

Access to new non‐canonical amino acid residues is crucial for medicinal chemistry and chemical biology. Analogues of the amino acid methionine have been far less explored—despite their use in biochemistry, pharmacology and peptide bioconjugation. This is largely due to limited synthetic access. Herein, we exploit a new disconnection to access non‐natural methionines through the development of a photochemical method for the radical α‐C−H functionalization of sulfides with alkenes, in water, using inexpensive and commercially‐available riboflavin (vitamin B2) as a photocatalyst. Our photochemical conditions allow the two‐step synthesis of novel methionine analogues—by radical addition to unsaturated amino acid derivatives—and the chemoselective modification of peptide side‐chains to yield non‐natural methionine residues within small peptides. The mechanism of the bio‐inspired flavin photocatalysis has been probed by experimental, DFT and TDDFT studies.
Wide Band‐Gap Polymer Donors Functionalized with Unconventional Carbamate Side Chains for Polymer Solar Cells
Authors: Tang Jie , Liao Chentong , Duan Yuwei , Xu Xiaopeng , Deng Min , Yu Liyang , Li Ruipeng , Peng Qiang
Published: October 2022

Side‐chain engineering with heteroatoms is not only effective in tuning frontier molecular orbitals, but also possible for forming secondary bonds which can be utilized to planarize the molecular backbone, hence, improving the photon absorption as well as charge‐transport abilities of polymer solar‐cell (PSC) materials. Herein, two types of unconventional side chains, namely carboxylate and carbamate, containing various heteroatoms are introduced to the thiophene bridges in high performance benzodithiophene (BDT) based donor polymers to from the novel polymers PTzTz‐C and PTzTz‐N, respectively. In these polymers, non‐covalent O⋅⋅⋅S and N⋅⋅⋅H interactions induce a high tendency to aggregation. In a ternary‐blend PSC with PTzTz‐N added to the high‐performance D18 : BTP‐eC9 blend, complimentary absorption and improved thin‐film morphology were observed with a top power conversion efficiency of 18.76 %, which is an improvement of almost 5 % over the D18 : BTP‐eC9 binary blends.
Fabrication of anisotropic nanocomposite hydrogels by magnetic field‐induced orientation for mimicking cardiac tissue
Authors: Ma Yanzhuo , Ma Aijie , Luo Tao , Xiao Siyu , Zhou Hongwei
Published: October 2022

The ordered structure of biological tissues is a precondition for the development of high performance in these tissues. Hydrogels with anisotropic structures provide a good starting point for studying their biomimetic applications. In this work, a hydrogel that mimics the endogenous anisotropic structure of heart tissue was reported. The gel consists of acrylamide (AM) and 2‐Acrylamide‐2‐methylpro panesulfonic acid (AMPS) as gel monomers, α‐ketoglutaric acid as photoinitiator, and modified magnetic nanoparticles (Fe3O4‐RS) as crosslinking agent. Thus, AM, AMPS and Fe3O4‐Rs was called AAF for short. In the system, the orientation of Fe3O4‐Rs was arranged by an external magnetic field. Under ultraviolet (UV) irradiation, the precursor solution was polymerized in situ to form an AAF hydrogel. The structure, pore distribution, rheological properties, mechanical performance, swelling property, and biocompatibility of the prepared anisotropic AAF hydrogel were studied in this paper. Results showed that the mechanical performance of the AAF hydrogels was remarkably enhanced in comparison with the isotropic ones. The tensile strength of AAF hydrogel could reached 184 kPa in the direction of the parallel Orientation of Fe3O4‐Rs, and 80 kPa in the direction of the vertical Orientation of Fe3O4‐Rs under 25% strain (no magnetic field was applied during all test). Moreover, the anisotropic tensile ratio of AAF hydrogel also reached 2.3. The strength and modulus of anisotropic hydrogels were similar to cardiac tissue (anisotropic tensile ratio was 2.5), which has great potential for application in cardiac tissue engineering.
Cardiac innervations in diabetes mellitus—Anatomical evidence of neuropathy
Authors: Filipović Natalija , Marinović Guić Maja , Košta Vana , Vukojević Katarina
Published: October 2022

The extensive innervations of the heart include a complex network of sympathetic, parasympathetic, and sensory nerves connected in loops that serve to regulate cardiac output. Metabolic dysfunction in diabetes affects many different organ systems, including the cardiovascular system; it causes cardiac arrhythmias, silent myocardial ischemia, and sudden cardiac death, among others. These conditions are associated with damage to the nerves that innervate the heart, cardiac autonomic neuropathy (CAN), which is caused by various pathophysiological mechanisms. In this review, the main facts about the anatomy of cardiac innervations and the current knowledge of CAN, its pathophysiological mechanisms, and its diagnostic approach are discussed. In addition, anatomical evidence for CAN from human and animal studies has been summarized.
A Free‐Standing Polyaniline/Silicon Nanowire Forest as the Anode for Lithium‐ion Batteries
Authors: Eldona Calvin , Hanif Hawari Naufal , Haidar Hamid Faiq , Dempwolf Wibke , Iskandar Ferry , Peiner Erwin , Suryo Wasisto Hutomo , Sumboja Afriyanti
Published: October 2022

Despite its high theoretical capacity, silicon anode has limited intrinsic conductivity and experiences significant volume changes during charge‐discharge. To overcome these issues, facile metal‐assisted chemical etching and in‐situ polymerization of aniline are employed to produce a dense 1D polyaniline/silicon nanowire forest without noticeable agglomeration as a free‐standing anode for lithium‐ion batteries. This hybrid electrode possesses high cycling performance, delivering a stable capacity capped at 2 mAh cm−2 for 346 cycles of charge‐discharge. Maximum capacity of 2 mAh cm−2 is also achievable at high‐rate cell testing of 2 mA cm−2, which cannot be obtained by the anode with plain silicon wafer and silicon nanowire only. The introduction of polyaniline on the silicon nanowire is shown to reduce the solid electrolyte interface (SEI) resistance, stabilize the SEI layer, further alleviate the effect of volume changes, and boost the conductivity of the hybrid anode, resulting in the high electrochemical performance of the anode.
Application of improved neighbor propagation algorithm in international communication and cooperation to promote internationalization of higher education
Authors: Liang Weitao , Jia Caiying
Published: October 2022

Most educational institutions use web 3.0 and blended learning technologies to improve student learning. Because not all students are intrinsically motivated to learn, the instructor in an e‐learning environment has significant challenges, lowering student performance. As a result, by merging the global dimension, intercultural, and international education functions, the Internationalization Standard for Higher Education (ISHE) is introduced. The Internationalization standard higher education (IoHE) process minimizes the difficulties in education resources because of the effective utilization of Information and Communication Technology (ICT). The ICT process improves innovative learning and boosts the e‐learning platform. To achieve the effectiveness of web 3.0 with a blended learning process, an Improved Neighbor Propagation Algorithm (INPA) with a concept‐mind mapping tool is introduced in this study. Student data are classified based on machine learning in an online environment. Classification is the process of predicting the class of given student data points. The relationship between each data point is examined here, and a tree structure is formed according to the concept. Mind Mapping is a suitable method that helps learn, increases information recording, shows how diverse facts and ideas are related, and improves problem‐solving. The concept and mind map are linked with different ideas, and the respective Collaborative Online International Learning (COIL) program is conducted to enhance the student's performance. The discussed blended learning‐based internationalization higher education process is evaluated with the case studies. The numerical results of the proposed INPA algorithm improve the student performance by 98.9%, satisfaction ratio by 97.5%, engagement level by 95.6%, accuracy ratio by 98.1%, the precision ratio by 96.2%, and recall ratio by 95.4% compared with other existing methods.
Prognostic value of circulating proteins in patients undergoing surgery for pancreatic cancer
Authors: Lindgaard Sidsel C. , Sztupinszki Zsófia , Maag Emil , Hansen Carsten P. , Chen Inna M. , Johansen Astrid Z. , Hasselby Jane P. , Bojesen Stig E. , Nielsen Dorte , Johansen Julia S.
Published: October 2022

Background

Pancreatic ductal adenocarcinoma (PDAC) is the fourth leading cause of cancer death. Less than 20% of patients are diagnosed with resectable disease. Identifying truly resectable disease is challenging because 20%–40% of the patients subjected to resection are found to have advanced disease during surgery. The aim of our study was to identify panels of circulating proteins that could be used to distinguish patients with unresectable PDAC from patients with resectable PDAC and to identify prognostic signatures for both groups.

Methods

We measured 92 circulating immuno‐oncology‐related proteins using the proximity extension assay from Olink Proteomics in 273 patients eligible for surgery for PDAC. Two bioinformaticians worked independently of one another on the same data. LASSO and Ridge regression were used in the statistical analyses.

Results

One protein index for determining resectability had an AUC value of 0.66. Several indices for prognosis had AUC values between 0.50 and 0.75 and were therefore not better than existing prognostic markers.

Discussion

Our study did not reveal any new high‐performing protein panels that could be used to identify patients with inoperable PDAC before surgery. The panel of 92 proteins investigated has previously been found to be applicable for diagnostic use in patients with PDAC, but it does not seem to warrant further investigation regarding resectability in the subgroup of patients with PDAC referred to surgery.
Lay representations of diversity: Questioning assumptions about categorical differences and social inequality
Authors: Diamanti Stavroula , Iatridis Tilemachos , Kadianaki Irini
Published: October 2022

Despite social psychology's emphasis on “diversity,” social psychological research on lay representations of diversity is pending. Capitalising on a string of critical diversity studies in other disciplines and based on social representations theory, this article presents a qualitative study on how lay Greek people interviewed about the meaning of diversity understand and use this term in talk. Our reflexive thematic analysis identified certain semantic tensions regarding the forms and value of diversity, which directly speak to findings in other cultural contexts and question the assumingly palliative effect of diversity on intergroup relations and social inequality. We suggest that the ideological input of this powerful concept be addressed rather than considering diversity a descriptive term or a self‐evident end in itself.
Ferulic acid relieved ulcerative colitis by inhibiting the TXNIP/NLRP3 pathway in rats
Authors: Yu Sheng , Qian Haihua , Zhang Dan , Jiang Zhenzhen
Published: October 2022

Ulcerative colitis (UC) is a disorder of the bowel that is characterized by a chronic inflammatory response. The traditional Chinese herbal medicine ferulic acid (FA) is known for its antioxidant, antiapoptotic, and antiinflammatory properties. However, its role in UC is still unclear. Thus, the current study was conducted to investigate the role of FA in UC. Rats were treated with 2,4,6‐triabrobenzene sulfonic acid to induce UC and subjected to FA. Human intestinal microvascular endothelial cells (HIMECs) were treated with tumor necrosis factor‐α (TNF‐α) and pretreated with FA. Pathological changes in colonic tissues were visualized via hematoxylin‐eosin staining. Enzyme linked immunosorbent assay was conducted to detect interleukin (IL)‐6, IL‐12, and IL‐1β levels. Cell morphology was visualized by using a microscope, and viability was detected by using MTT. The percentage of apoptosis was detected via flow cytometry. Western blot analysis was performed to detect the expression of the apoptosis‐related proteins thioredoxin‐interacting protein (TXNIP) and NOD‐like receptor pyrin domain‐containing 3 (NLRP3). In vivo FA administration alleviated intestinal injury in UC rats and inhibited inflammatory factor levels (IL‐6, IL‐12, and IL‐1β), apoptosis‐related protein expression (caspase‐1 and caspase‐3) and the TXNIP/NLRP3 signaling pathway. In vitro, TNF‐α treatment reduced HIMEC viability, increased cell apoptosis and inflammatory factor levels and activated the TXNIP/NLRP3 signaling pathway. However, FA treatment restored the viability of HIMECs, reduced TNF‐α‐induced cell apoptosis and inflammation and inhibited the TXNIP/NLRP3 signaling pathway. Furthermore, with increasing FA concentration, the effects were stronger. In summary, FA inhibits the inflammatory injury of endothelial cells in ulcerative colitis or alleviates TNF‐α‐induced HIMEC injury by inhibiting the TXNIP/NLRP3 signaling pathway.
Save more with less: The impact of employer defaults and match rates on retirement saving
Authors: Blanchett David , Finke Michael , Liu Zhikun
Published: October 2022

Employers control two primary levers that can motivate retirement savings among defined contribution plan participants—default savings rates and match rates. Setting a higher default savings rate can increase plan contributions among passive savers who accept the default. A higher match rate incentivizes active savers to increase contributions. This study uses a large sample of defined contribution participants to estimate the interaction between employer match and default rates on savings outcomes among new participants. Selecting a higher default rate has the largest impact on employee savings rates. Plans with low default savings rates that match a high percentage of employee earnings induce higher‐income participants to actively move away from the low default savings rate, resulting in a wider savings gap between higher‐ and lower‐income employees. When employees are defaulted in at a higher rate, fewer move away from the default savings rate and the default investment choice (e.g., a target‐date fund). A higher default savings rate results in higher and more equal savings rates among employees, and higher acceptance of professionally managed defaults investments.
Dynamic Interactions Between Brilliant Green and MscL Investigated by Solid‐State NMR Spectroscopy and Molecular Dynamics Simulations
Authors: Ma Shaojie , Zhang Yan , Zhang Xuning , Xie Huayong , Tong Qiong , Yu Kunqian , Yang Jun
Published: October 2022

The mechanosensitive ion channel of large conductance (MscL) is a promising template for the development of new antibiotics due to its high conservation and uniqueness to microbes. Brilliant green (BG), a triarylmethane dye, has been identified as a new antibiotic targeted MscL. However, the detailed binding sites to MscL and the dynamic pathway of BG through the MscL channel remain unknown. Here, the dynamic interactions between BG and MscL were investigated using solid‐state NMR spectroscopy and molecule dynamics (MD) simulations. Residue site‐specific binding sites of BG to the MscL channel were identified by solid‐state NMR. In addition, MD simulations revealed that BG conducts through the MscL channel via residues along the inner surface of the pore sequentially, in which the strong hydrophobic interactions between BG and hydrophobic residues F23 and I27 in the hydrophobic gate region of the MscL channel are major restrictions. Particularly, it was demonstrated that BG activates the MscL channel by reducing the hydrophobicity of the F23 in the gate region by water molecules that are bound to BG. Taken together, these simulations and experimental data provide novel insights into the dynamic interactions between BG and MscL, based on which new hydrophobic antibiotics and adjuvants targeting MscL can be developed.
Orthogonal Crosslinking: A Strategy to Generate Novel Protein Topology and Function
Authors: Wang Zheng , Rabb Johnathan D. , Lin Qing
Published: October 2022

Compared to the disulfide bond, other naturally occurring intramolecular crosslinks have received little attention, presumably due to their rarity in the vast protein space. Here we presented examples of natural non‐disulfide crosslinks, which we refer to as orthogonal crosslinks, emphasizing their effect on protein topology and function. We summarize recent efforts on expanding orthogonal crosslinks by using either the enzymes that catalyze protein circularization or the genetic code expansion strategy to add electrophilic amino acids site‐specifically in proteins. The advantages and disadvantages of each method are discussed, along with their applications to generate novel protein topology and function. In particular, we highlight our recent work on spontaneous orthogonal crosslinking, in which a carbamate‐based crosslink was generated in situ, and its applications in designing orthogonally crosslinked domain antibodies with their topology‐mimicking bacterial adhesins.
Photoresponsive Type III Porous Liquids
Authors: Brand Michael C. , Rankin Nicola , Cooper Andrew I. , Greenaway Rebecca L.
Published: October 2022

Porous materials are the subject of extensive research because of potential applications in areas such as gas adsorption and molecular separations. Until recently, most porous materials were solids, but there is now an emerging class of materials known as porous liquids. The incorporation of intrinsic porosity or cavities in a liquid can result in free‐flowing materials that are capable of gas uptakes that are significantly higher than conventional non‐porous liquids. A handful of porous liquids have also been investigated for gas separations. Until now, the release of gas from porous liquids has relied on molecular displacement (e.g., by adding small solvent molecules), pressure or temperature swings, or sonication. Here, we explore a new method of gas release which involves photoisomerisable porous liquids comprising a photoresponsive MOF dispersed in an ionic liquid. This results in the selective uptake of CO2over CH4and allows gas release to be controlled by using UV light.
A novel fault classification method using reconstructed distance‐based discriminant locality preserving projection for industrial processes
Authors: Zhang Cuicui , Dong Jie , Peng Kaixiang
Published: October 2022

Fault detection and classification is a crucial issue in modern industrial processes for ensuring steady operation and high product quality. The process data collected and stored fully reflect the equipment running state and the production process. Moreover, the extracted nonlinear features can directly affect the effectiveness of the data‐driven fault classification model. In this paper, a novel fault classification method based on nonlinear feature extraction using reconstructed distance‐based discriminant locality preserving projection (RD‐DLPP) is proposed. First, a hypersphere model for each class of data is developed according to the spatial structures and classes information in high‐dimensional space. The hyperspheres are used as indicators to evaluate the discriminatory difficulty of samples. Second, the constraints of the correlations between the k‐nearest neighbour points of the sample and the hypersphere are introduced, which can efficiently reconstruct new measure metrics between the sample and its k‐nearest neighbour points. Finally, an improved fault classification model based on RD‐DLPP is established for the construction of the highly discriminant subspace. The Bayesian decision is then used to classify the samples. The feasibility and efficiency of the proposed method are verified by the Tennessee Eastman process as a case study.