bluuebunny/crossref_metadata_2025 huggingface dataset:
Cell‐Reprogramming‐Inspired Dynamically Responsive Hydrogel Boosts the Induction of Pluripotency via Phase‐Separated Biomolecular Condensates
Authors: Zhu Fei , Yan Na , Lu Xukun , Xu Junchao , Gu Haiyan , Liang Jie , Cheng Keman , Wang Xiaona , Ma Xiaotu , Ma Nana , Zhao Xiao , Chen Chunying , Nie Guangjun
Published: March 2023

Induced pluripotent stem cells (iPSCs) have wide applications in disease modeling, personalized medicine, and tissue engineering. The generation of iPSCs from somatic cells via transcriptional‐factor‐ or chemical molecule‐based approaches are time‐consuming and inefficient. Here, a cell‐reprogramming‐inspired dynamically responsive hydrogel is fabricated via a synthetic‐biology‐based strategy. Human and mouse somatic cells (including senescent cells) are efficiently reprogrammed into iPSCs that exhibit key features of embryonic stem cells. The cell‐reprogramming‐responsive hydrogel possesses dynamic bioresponsiveness, and it faithfully senses metabolic remodeling and extracellular acidification during cell reprogramming, responding by changing its mechanical properties accordingly. Mechanistic study demonstrates that the autonomous change of the mechanical properties of the cell‐reprogramming‐responsive hydrogel elicits the formation of Yes‐associated protein (YAP) biomolecular condensates with the appropriate timing during cell reprogramming, ensuring a faster and more efficient generation of iPSCs than conventional cell reprogramming approach. Taken together, this study reveals the robust induction of pluripotency by coordination of cell‐reprogramming‐inspired dynamically responsive hydrogel and phase‐separated biomolecular condensates.
Skeletal Network Enabling New‐Generation Thermoplastic Vulcanizates
Authors: Yu Shuangjian , Wu Siwu , Fang Shifeng , Tang Zhenghai , Zhang Liqun , Guo Baochun
Published: March 2023

Upcycling of cross‐linked rubbers is pressing. The introduction of dynamic covalent bonds into the networks is a popular tactic for recycling thermosetting polymers, but it is very challenging to integrate engineering performance and continuous yet stable reprocessability. Based on traditional rubber formulations, herein, a straightforward strategy is presented for constructing a skeletal network (SN) through interfacial crosslinking and percolation of rubbery granules in a rubber matrix. Rapid exchange reactions involving dynamic interfacial sulfides realize repeated “fragmentation and healing” in the solid‐state and consequent reconfiguration of the SN topology of the elastomer, thus endowing the resultant SN elastomer with continuous yet stable re‐extrudability. These SN elastomers with hierarchical structures exhibit high gel contents, high resilience, low creep, and reinforcibility competitive to traditional vulcanizates. Specifically, SN elastomers exhibit better overall performance than commercial thermoplastic vulcanizates (TPVs) materials. Overall, a new concept of thermoplastic vulcanizates is proposed, which will promote the sustainable development of rubbers.
g‐C3N4 Monolayer/2D Mica Nanohybrids with Highly Effective UV–HEV‐Screening Function
Authors: Piao Huiyan , Choi Goeun , Rejinold N. Sanoj , Vinu Ajayan , Choy Jin‐Ho
Published: March 2023

Excessive exposure to ultraviolet (UV) and high‐energy visible (HEV) light can cause sunburns, wrinkles, and even skin cancer. Therefore, the development of effective UV–HEV‐shielding agents is of great importance to human health. In this study, semiconducting graphitic carbon nitride (g‐C3N4) is incorporated into the interlayer space of mica through the intercalation of cyanamide and subsequent pyrolysis reactions to form a semiconductor–insulator nanohybrid, namely g‐C3N4–mica, with a 1:1 heterostructure. The g‐C3N4–mica nanohybrid exhibits excellent UV–HEV absorption properties below 450 nm, and its photocatalytic activity is quenched owing to the effective screening of photocatalytic active sites by the insulating mica. It is strongly believed that the proposed g‐C3N4–mica nanohybrid can be applied as a UV–HEV blocking agent owing to its excellent UV–HEV (200–450 nm)‐screening property without any photocatalytic effect or phototoxicity.
Trilayered Block Copolymer Nanostructures Formed by an Iterative Layering Strategy
Authors: Argudo Pablo G. , Demazy Nils , Fleury Guillaume
Published: March 2023

Nanostructured block copolymer (BCP) thin films enable the formation on‐demand of a variety of periodic patterns at the nanometer scale by tuning the macromolecular BCP characteristics and annealing processes. Significant progress in the control of the self‐assembly has been witnessed over the past decade with the implementation of robust directed self‐assembly methods. However, the self‐assembled structural patterns obtained at equilibrium are limited and methods to expand the range of structural configurations are required to harness additional functionalities. Here, this work demonstrates how polystyrene‐b‐poly(methyl methacrylate) BCP thin layers can be stacked to produce a library of complex 3D hierarchical heterostructures. In this iterative assembly process based on simple building bricks (i.e., immobilized BCP patterns forming Holes, Lines and Dots), the stacking configuration (i.e., self‐assembly and registration) of a BCP thin film is directed with respect to the previous layer using confinement effects and interfacial energy tuning. This responsive layering can lead to intricate 3D Al2O3 structures and opens the way to a broad variety of structural designs toward functional applications.
InP Low‐Dimensional Nanomaterials for Electronic and Optoelectronic Device Applications: A Review
Authors: Yue Lin‐Qing , Shi Yan‐Lei , Sun Nie‐Feng , Qiang Sheng , Qin Jing‐Kai , Zhen Liang , Xu Cheng‐Yan
Published: March 2023

The suitable direct bandgap, high carrier mobility, biologically nontoxicity, and size‐dependent physical properties of low‐dimensional indium phosphide InP (0D, 1D, and 2D) have attracted great interest from scientists. The appealing optical and electronic properties make them promising for the fabrication of state‐of‐the‐art nanoscale electronic and optoelectronic devices including photodiode, photodetector, and solar cells. This Review focuses on the recent development of low‐dimensional InP materials. The synthesis methods and growth mechanisms of high quality low‐dimensional InP are comprehensively recapped. The multifunctional applications in electronic and optoelectronic devices of low‐dimensional InP are discussed, and typical strategies to resolve the main challenges limiting the performance of low‐dimensional InP‐based application are then reviewed. Finally, a brief perspective on the challenges and opportunities of low‐dimensional InP in synthesis, electronics, and optoelectronics applications is also provided.
Frequency Reconfigurable and Multifunctional Metastructure Regulated by Nematic Liquid Crystal: Broadband Circular to Linear Polarization Converter
Authors: Qiao Zhen , Zhang Wei , Li Yu‐Peng , Li Bing‐Xiang , Zhang Hai‐Feng
Published: March 2023

With the tunability of the nematic liquid crystal (NLC), a broadband frequency reconfigurable and versatile metastructure (MS) is proposed and theoretically investigated in this paper, combining circular‐to‐linear (CTL) polarization conversion (PC) and circular‐to‐circular (CTC) PC simultaneously. The MS is composed of two via‐coupled modules, which can respond differently to the incident waves. Each module is connected utilizing a metal via a column, thus exceedingly enhancing the energy transmission and reducing the loss when transmitting. When the applied bias voltage (Vbias) is 0 V, the NCL molecules follow the initial orientation. The MS converts the incident right circular polarized (RCP) waves into linear polarized (LP) waves within 8.11–9.95 gigahertz (GHz) with a relative bandwidth of 20.38% and achieves the PC of left circular polarized (LCP) into RCP waves. As the Vbias reaches 20 V, the original operating interval reconfigures and shifts overall toward a lower frequency. The bandwidth of CTL is 7.66–9.02 GHz, and the CTC PC is broadened to 20.20%. Meanwhile, the structure justification is verified, and the inducing mechanism of PC is expounded. Possessing the merits of versatile collaborative processing and wide operating bands, such an MS is promising to be a polarization‐controlled application candidate and enrich multifunctional designs.
Photo‐Response with Radical Afterglow by Regulation of Spin Populations and Hole‐Electron Distributions
Authors: Yang Yujie , Wang Jiaqiang , Yang Jie , Tong Lihuan , Li Dan , Yang Yuqi , Fang Manman , Li Zhen
Published: March 2023

No matter photoinduced organic radicals have been reported frequently, they are usually non‐luminescent at ambient conditions. The internal mechanism on stability and electronic transitions of photoinduced radicals, is thus crucial for the development of relevant materials. Herein, a series of photoinduced radical emission systems were developed conveniently through doping benzoic acids into the hydrogen donor polyvinyl alcohol (PVA) matrix. Visual photoinduced radical emission and photochromism could be observed on Ph‐3COOH@PVA film with the formation of cyclohexadienyl‐type structure. For the first time, radical afterglow appeared with energy transfer from triplet state. The appropriate introduction of carboxylic groups to three nonadjacent carbon atoms on the benzene ring was the best for decreasing spin population and promoting electronic transitions of the radical. This study largely expands the radical emission property from both internal mechanism and practical application.
Non‐planar Nest‐like [Fe2S2] Cluster Sites for Efficient Oxygen Reduction Catalysis
Authors: Wang Ming , Zhang Zhong , Zhang Songlin , Liu Wei , Shang Wenzhe , Su Xiaofang , Liang Yan , Wang Furi , Ma Xujiao , Li Yadong , Liu Yiwei
Published: March 2023

Metal‐nitrogen‐carbon catalysts, as promising alternative to platinum‐based catalysts for oxygen reduction reaction (ORR), are still highly expected to achieve better performance by modulating the composition and spatial structure of active site. Herein, we constructed the non‐planar nest‐like [Fe2S2] cluster sites in N‐doped carbon plane. Adjacent double Fe atoms effectively weaken the O−O bond by forming a peroxide bridge‐like adsorption configuration, and the introduction of S atoms breaks the planar coordination of Fe resulting in greater structural deformation tension, lower spin state, and downward shifted Fe d‐band center, which together facilitate the release of OH* intermediate. Hence, the non‐planar [Fe2S2] cluster catalyst, with a half‐wave potential of 0.92 V, displays superior ORR activity than that of planar [FeN4] or [Fe2N6]. This work provides insights into the co‐regulation of atomic composition and spatial configuration for efficient oxygen reduction catalysis.
A Modular Tubular Flow System with Replaceable Photocatalyst Membranes for Scalable Coupling and Hydrogenation
Authors: Li Yajiao , Zhang Dongsheng , Ye Jiani , Mai Yuanqiang , Wang Chao , Yang Yong , Li Yongwang , Besenbacher Flemming , Niemantsverdriet Hans , Rosei Federico , Pan Feng , Su Ren
Published: March 2023

Heterogeneous photocatalysis is effective for the selective synthesis of value‐added chemicals at lab‐scale, yet falls short of requirements for mass production (low cost and user friendliness). Here we report the design and fabrication of a modular tubular flow system embedded with replaceable photocatalyst membranes for scalable photocatalytic C−C, C−N homocoupling and hydrogenation reactions, which can be operated in either circular and continuous flow mode with high performance. The photocatalyst membranes almost fully occupy the volume of the reactor, thus enabling optimal absorption of the incident light. Additionally, the porous structured photocatalyst membranes facilitate the mass transfer of the reactants to efficiently use the active sites, resulting in 0th‐order reaction kinetics and a high space‐time yield compared to the batch reaction system at practical application levels and prolonged reaction times.
Preparation and properties of cellulose acetate graft copolymer‐coated adsorbent resin for hemoperfusion device
Authors: Gao Xingtong , Liu Kai , Liu Peng , Bai Xiaoyu , Li Aixiang , Lyu Zijian , Li Qiuhong
Published: March 2023

In this paper, acrylic acid (AA) and sodium styrene sulfonate (SSS) were grafted onto the surface of cellulose acetate (CA) by free radical polymerization to obtain a heparin unit‐containing graft copolymer CA‐g‐P(AA/SSS). It was used to coat the adsorbent resin for disposable hemoperfusion devices to improve blood compatibility. The adsorption capacity of the modified CA‐coated adsorbent resin to creatinine, Vitamin B12, bilirubin, and imidacloprid was tested. The results showed that the modified CA‐coated adsorbent resin had a good adsorption effect on small and medium‐sized molecules. The hemolysis and coagulation tests showed that the CA‐g‐P(AA/SSS) coating could greatly improve the blood compatibility of the adsorbent resin. The hemolysis rate was 1.6%, which met the requirement of international standards for the hemolysis rate of blood contact equipment less than 5%. The coagulation index was higher than 1.55, which was comparable to the heparin‐preflashed HA130 currently in use. In addition, the CA‐g‐P(AA/SSS)‐coated adsorbent resin has good biocompatibility, no pyrogenic reaction, low vitro cytotoxicity, and no acute systemic toxicity. The resin has a good application prospect in uremia, hyperbilirubinemia, and rapid treatment of pesticide poisoning.
Separation, recovery and upgrading of 2,3‐butanediol from fermentation broth
Authors: Rajale Trideep , Yang Xiaokun , Judge Elizabeth J. , Moore Cameron M. , Martinez Abraham , Guo Mond F. , Ramasamy Karthikeyan K. , Elander Richard , Sutton Andrew D.
Published: March 2023

2,3‐Butanediol (BDO) is a bio‐derived building block available from biomass through biochemical methods in high titers (>120 g L−1) making it an attractive target for production and further upgrading to chemical products and fuels such as sustainable aviation fuel. A key challenge to enable the adoption of BDO as a precursor is the effective separation and isolation of this molecule from the fermentation broth. 2,3‐Butanediol has a boiling point higher than that of water (177°C), and as a consequence, separation via distillation methods is an energy‐intensive and therefore costly approach. We have improved the BDO separation through conversion to a 1,3‐dioxolane directly in fermentation broth via reaction with bio‐derived aldehydes catalyzed by a solid acid catalyst. The resulting dioxolane phase separates from the fermentation broth, allowing for easy decantation and isolation in >90% isolated yield. Isolated dioxolane can be used directly as a compression iginition fuel, trans‐acetalized to recover high‐purity BDO or used directly in a catalytic process as a BDO synthon to produce methyl ethyl ketone with aldehyde recovery in near quantitative yield.
Tuning the Surface Wettability of Pd/COFs for Selective Hydrogenation
Authors: Li Xiang , Li He , Li Chunzhi , Wang Maodi , Yang Qihua
Published: March 2023

Covalent organic frameworks (COFs) with imine linkage are promising solid supports to disperse ultra‐fine metal nanoparticles (NPs), but the modulation of their surface wettability, an important parameter affecting the catalytic performance of metal NPs, is still very challenging. Here, we report the preparation of two imine‐linked COFs with moderate and strong surface hydrophobicity by changing the carbon chain length of side oxyalkyl groups. Ultra‐small Pd NPs with an average size of ∼2.0 nm was successfully loaded on the two COFs, attributed to the strong interactions of Pd NPs and imine linkage as evidenced by the electron donating from imine linkage to Pd NPs by XPS characterizations. The TOF of Pd/COF is much higher than commercial Pd/C (714 h−1 vs 489 h−1) in the hydrogenation of nitrobenzene, which is attributed to the electron rich Pd, the hydrophobic surface and crystalline structure of COFs. Pd NPs on COFs with strong hydrophobicity are more active than those on COFs with moderate hydrophilicity in the hydrogenation of moderate lipophilic nitro compounds such as nitrobenzene, methyl nitrobenzene and nitronaphthalene. Reversed tendency was observed for the hydrogenation of moderate hydrophilic p‐amino‐nitrobenzene. The modulation of the surface wettability of COFs provides an efficient strategy to improve the catalytic performance of supported metal NPs.
Role of Titanium in Ti/SiO2‐Supported Metallocene‐based Olefin Polymerization Catalysts. Part 1: Genesis of Active Sites and Catalytic Performance
Authors: Zanoni Silvia , Welle Alexandre , Cirriez Virginie , Weckhuysen Bert M.
Published: March 2023

Performance enhancement of metallocene‐based olefin polymerization catalysts can be obtained, among others, by the chemical modification of their support. We investigated a titanated SiO2 (Ti/SiO2) as an improved support material for zirconocene catalysts, which lead to ∼35 % higher ethylene polymerization yields when compared to the unmodified SiO2‐supported metallocene. The improved catalytic performance of the modified catalyst was found to be related to the presence of a Ti‐based active site, second to the Zirconocene centers, as well as to a higher Lewis acidity in the titanated supported‐MAO, which improved the activation of the Zr‐based centers. The Ti active species were generated by reduction of the Ti/SiO2 support with the methylaluminoxane (MAO) co‐catalysts, which introduced oxygen vacancies (VO) and Ti3+ species, as confirmed by probe molecule Fourier Transform Infrared (FT‐IR) spectroscopy and UV‐Vis Diffuse Reflectance Spectroscopy (DRS). The higher Lewis acidity was linked to 5‐coordinated Ti4+, as detected by probe molecules FT‐IR spectroscopy.
N‐Doped Porous Carbon with Outstanding Pb2+ Adsorption Capacity in Wastewater
Authors: Hu Le , Chen Wenjie , Niu Yuxin , Wang Na , Liu Bin , Song Fuxiang
Published: March 2023

An N‐doped porous carbon (NPC) with porous structure was successfully prepared by a one‐step calcination method. The NPC with its abundant modified active functional groups was used in adsorption experiments, showing that the adsorption capacity of NPC for Pb2+ was up to 179.86 mg g−1 at pH 5. It displayed a fast kinetic adsorption rate and high selective adsorption and cyclic adsorption capacities. The Pb2+ adsorption mechanism consisted in cationic‐π interactions and electrostatic attraction. Thus, the developed NPC has a high potential for application in the removal of Pb2+ from wastewater, due to its excellent adsorption behavior and porous structure.
Assembling Artificial Photosynthetic Models in Water Using β‐Cyclodextrin‐Conjugated Phthalocyanines as Building Blocks
Authors: Chen Xiao‐Fei , Gobeze Habtom B. , D'Souza Francis , P. Ng Dennis K.
Published: March 2023

Two water‐soluble zinc(II) phthalocyanines substituted with two or four permethylated β‐cyclodextrin (β‐CD) moieties at the α positions have been utilized as building blocks for the construction of artificial photosynthetic models in water. The hydrophilic and bulky β‐CD moieties not only can increase the water solubility of the phthalocyanine core and prevent its stacking in water but can also bind with a tetrasulfonated zinc(II) porphyrin (ZnTPPS) and/or sodium 2‐anthraquinonesulfonate (AQ) in water through host–guest interactions. The binding interactions of these species have been studied spectroscopically, while the photoinduced processes of the resulting complexes have been investigated using steady‐state and time‐resolved spectroscopic methods. In the ternary complexes, the ZnTPPS units serve as light‐harvesting antennas to capture the light energy and transfer it to the phthalocyanine core via efficient excitation energy transfer. The excited phthalocyanine is subsequently quenched by the electron‐deficient AQ units through electron transfer. Femtosecond transient absorption spectroscopy provides clear evidence for the singlet‐singlet energy transfer from the photo‐excited ZnTPPS to the phthalocyanine core with a rate constant (kENT) in the order of 109 s−1. The population of phthalocyanine radical cations indicates the occurrence of electron transfer from the excited phthalocyanine to the AQ moieties, forming a charge‐separated state.
Circular dichroism of molecular aggregates: A tutorial
Authors: Bertocchi Francesco , Sissa Cristina , Painelli Anna
Published: March 2023

In this tutorial, we guide the reader through two alternative approaches to the calculation of circular dichroism (CD) spectra of chiral supramolecular assemblies of non‐chiral chromophores. The two seemingly different approaches rely on the same basic approximations and are therefore expected to lead to similar results. For a dimer, we obtain explicit analytic expressions for the CD responses in the two approaches and demonstrate the perfect equivalence of the two methods. Numerical results for larger systems further validate this result. We hope that this tutorial will help young students and scientists entering the field to approach the fascinating topic of supramolecular chirality.
Wassermanagement als Schlüsselparameter für die Skalierung eines CO2‐Elektrolyseurs
Authors: Hoof Lucas , Pellumbi Kevinjeorjios , Heuser Stephan , Siegmund Daniel , junge Puring Kai , Apfel Ulf-Peter
Published: March 2023

Eine der größten Herausforderungen der elektrochemischen Umwandlung von CO2 zu CO in Zero‐Gap‐Elektrolyseuren ist die Skalierung dieser Systeme in den industriellen Maßstab. Trotz der bemerkenswerten Ergebnisse der letzten Jahre, sind bisher nur wenige Fortschritte bei der Skalierung dieser Technologie erzielt worden. In diesem Beitrag wird gezeigt, wie die Steuerung des Wassergehalts an der Kathode es ermöglicht Flutungsprozesse zu minimieren und aussichtsreiche experimentelle Ergebnisse auf größere CO2 Elektrolysesysteme zu übertragen.
Oligomeric, phosphorylated, and truncated tau and spliceosome pathology within the entorhinal–hippocampal connectome across stages of Alzheimer's disease
Authors: Mahady Laura J. , Perez Sylvia E. , Malek‐Ahmadi Michael , Mufson Elliott J.
Published: March 2023

Neurofibrillary tangles (NFTs) contain abnormally phosphorylated tau proteins, which spread within components of the medial temporal lobe (MTL) memory circuit in Alzheimer's disease (AD). Here, we used quantitative immunohistochemistry to determine the density of posttranslational oligomeric (TOC1 and TNT1), phosphorylated (AT8), and late truncated (TauC3) tau epitopes within the MTL subfields including entorhinal cortex (EC) layer II, subiculum, Cornu Ammonis (CA) subfields, and dentate gyrus (DG) in subjects who died with a clinical diagnosis of no cognitive impairment (NCI), mild cognitive impairment (MCI), and AD. We also examined whether alterations of the nuclear alternative splicing protein, SRSF2, are associated with tau pathology. Although a significant increase in TOC1, TNT1, and AT8 neuron density occurred in the EC in MCI and AD, subicular, DG granule cell, and CA1 and CA3 densities were only significantly higher in AD. TauC3 counts were not different between connectome regions and clinical groups. SRSF2 intensity in AT8‐positive cells decreased significantly in all regions independent of the clinical groups examined. CA1 and subicular AT8, TauC3, and oligomeric densities correlated across clinical groups. EC AT8 counts correlated with CA subfields and subicular and DG values across clinical groups. Oligomeric and AT8 CA1, EC, and subicular density correlated with Braak stage. Decreased nuclear SRSF2 in the presence of cytoplasmic phosphorylated tau suggests a dual‐hit process in NFT formation within the entorhinal hippocampal connectome during the onset of AD. Although oligomeric and phosphorylated tau follow a stereotypical pattern, clinical disease stage determined density of tau deposition and not anatomic location within the entorhinal–hippocampal connectome.
Utilization of a cell‐penetrating peptide‐adaptor for delivery of human papillomavirus proteinE2into cervical cancer cells to arrest cell growth and promote cell death
Authors: LeCher Julia C. , Didier Hope L. , Dickson Robert L. , Slaughter Lauren R. , Bejarano Juana C. , Ho Steven , Nowak Scott J. , Chrestensen Carol A. , McMurry Jonathan L.
Published: March 2023

Background

Human papillomavirus (HPV) is the causative agent of nearly all forms of cervical cancer, which can arise upon viral integration into the host genome and concurrent loss of viral regulatory gene E2. Gene‐based delivery approaches show that E2 reintroduction reduces proliferative capacity and promotes apoptosis in vitro.

Aims

This work explored if our calcium‐dependent protein‐based delivery system, TAT‐CaM, could deliver functional E2 protein directly into cervical cancer cells to limit proliferative capacity and induce cell death.

Materials and Results

TAT‐CaM and the HPV16 E2 protein containing a CaM‐binding sequence (CBS‐E2) were expressed and purified fromEscherichia coli. Calcium‐dependent binding kinetics were verified by biolayer interferometry. Equimolar TAT‐CaM:CBS‐E2 constructs were delivered into the HPV16+SiHa cell line and uptake verified by confocal microscopy. Proliferative capacity was measured by MTS assay and cell death was measured by release of lactate dehydrogenase. As a control, human microvascular cells (HMECs) were used. As expected, TAT‐CaM bound CBS‐E2 with high affinity in the presence of calcium and rapidly disassociated upon its removal. After introduction by TAT‐CaM, fluorescently labeled CBS‐E2 was detected in cellular interiors by orthogonal projections taken at the depth of the nucleus. In dividing cells, E2 relocalized to regions associated with the mitotic spindle. Cells receiving a daily dose of CBS‐E2 for 4 days showed a significant reduction in metabolic activity at low doses and increased cell death at high doses compared to controls. This phenotype was retained for 7 days with no further treatments. When subcultured on day 12, treated cells regained their proliferative capacity.

Conclusions

Using the TAT‐CaM platform, bioactive E2 protein was delivered into living cervical cancer cells, inducing senescence and cell death in a time‐ and dose‐dependent manner. These results suggest that this nucleic acid and virus‐free delivery method could be harnessed to develop novel, effective protein therapeutics.
Can Li Atoms Anchored on Boron‐ and Nitrogen‐Doped Graphene Catalyze Dinitrogen Molecules to Ammonia? A DFT Study
Authors: Singh Verma Tushar , Paramita Samal Pragnya , Selvaraj Kaliaperumal , Krishnamurty Sailaja
Published: March 2023

The most successful electrochemical conversion of ammonia from dinitrogen molecule reported to date is through a Li mediated mechanism. In the framework of the above fact and that Li anchored graphene is an experimentally feasible system, the present work is a computational experiment to identify the potential of Li anchored graphene as a catalyst for N2 to NH3 conversion as a function of (a) minimum number of Li atoms needed for anchoring on graphene sheets and (b) the role of chemical modification of graphene surfaces. The studies bring forth an understanding that Li anchored graphene sheets are potential catalysts for ammonia conversion with preferential adsorption of N2 through end‐on configuration on Li atoms anchored on doped and pristine graphene surfaces. This mode of adsorption being characteristic of Nitrogen Reduction Reaction (NRR) through enzymatic pathway, examination of the same followed by analysis of electronic properties demonstrates that tri‐Li atoms (Tri Atom Catalysts, TACs) are more efficient as catalysts for NRR as compared to two Li atoms (Di Atom Catalysts, DACs). Either way, the rate determining step was found to be *NH2→*NH3 step (mixed pathway) with ΔGmax=1.02 eV and *NH2−*NH3→*NH2 step (enzymatic pathway) with ΔGmax=1.11 eV for 1B doped TAC and DAC on graphene sheet, respectively. Consequently, this work identifies the viability of Li anchored graphene based 2‐D sheets as hetero‐atom catalyst for NRR.
The fear that remains: Associations between trauma, related psychopathology, and fear‐potentiated startle in youth resettled as refugees
Authors: Grasser Lana Ruvolo , Saad Bassem , Bazzi Celine , Suhaiban Hiba Abu , Mammo Dalia F. , Izar Ragda , Rass Noor Abou , Winters Sterling J. , Nashef Raya , Ali Ayat Abed , Javanbakht Arash , Jovanovic Tanja
Published: March 2023

Fear‐potentiated startle (FPS) can be used to measure fear and safety learning—behaviors affected by trauma that may map onto posttraumatic stress disorder (PTSD). Therefore, FPS could be a candidate biomarker of trauma‐related psychopathology and a potential identifier of trauma‐exposed youth in need of focused treatment. We enrolled n = 71 (35 females, Mage = 12.7 years) Syrian youth exposed to civilian war trauma. Eyeblink electromyogram (EMG) data from a differential conditioning FPS paradigm were obtained 2.5 years after resettlement. Youth provided self‐report of trauma exposure (Harvard Trauma Questionnaire) and PTSD symptoms (UCLA PTSD Reaction Index). While FPS during conditioning was not associated with symptoms, associations with psychopathology emerged in fear extinction. Probable PTSD was associated with FPS in the last block of extinction, such that FPS to threat cue was significantly greater in the PTSD+ group compared to the PTSD– group at the end of extinction (F = 6.25, p = .015). As with adults, we observed a deficit in extinction learning but not fear conditioning in youth with PTSD. These results support the use of trauma‐informed cognitive behavioral therapy based on the learning principles of extinction in youth with PTSD.
Density of predating Asian hornets at hives disturbs the 3D flight performance of honey bees and decreases predation success
Authors: Poidatz Juliette , Chiron Guillaume , Kennedy Peter , Osborne Juliet , Requier Fabrice
Published: March 2023

Automated 3D image‐based tracking systems are new and promising devices to investigate the foraging behavior of flying animals with great accuracy and precision. 3D analyses can provide accurate assessments of flight performance in regard to speed, curvature, and hovering. However, there have been few applications of this technology in ecology, particularly for insects. We used this technology to analyze the behavioral interactions between the Western honey bee Apis mellifera and its invasive predator the Asian hornet, Vespa velutina nigrithorax. We investigated whether predation success could be affected by flight speed, flight curvature, and hovering of the Asian hornet and honey bees in front of one beehive. We recorded a total of 603,259 flight trajectories and 5175 predator–prey flight interactions leading to 126 successful predation events, representing 2.4% predation success. Flight speeds of hornets in front of hive entrances were much lower than that of their bee prey; in contrast to hovering capacity, while curvature range overlapped between the two species. There were large differences in speed, curvature, and hovering between the exit and entrance flights of honey bees. Interestingly, we found hornet density affected flight performance of both honey bees and hornets. Higher hornet density led to a decrease in the speed of honey bees leaving the hive, and an increase in the speed of honey bees entering the hive, together with more curved flight trajectories. These effects suggest some predator avoidance behavior by the bees. Higher honey bee flight curvature resulted in lower hornet predation success. Results showed an increase in predation success when hornet number increased up to 8 individuals, above which predation success decreased, likely due to competition among predators. Although based on a single colony, this study reveals interesting outcomes derived from the use of automated 3D tracking to derive accurate measures of individual behavior and behavioral interactions among flying species.
Emigration patterns of motile cryptofauna and their implications for trophic functioning in coral reefs
Authors: Wolfe Kennedy , Desbiens Amelia A. , Mumby Peter J.
Published: March 2023

Patterns of movement of marine species can reflect strategies of reproduction and dispersal, species' interactions, trophodynamics, and susceptibility to change, and thus critically inform how we manage populations and ecosystems. On coral reefs, the density and diversity of metazoan taxa are greatest in dead coral and rubble, which are suggested to fuel food webs from the bottom up. Yet, biomass and secondary productivity in rubble is predominantly available in some of the smallest individuals, limiting how accessible this energy is to higher trophic levels. We address the bioavailability of motile coral reef cryptofauna based on small‐scale patterns of emigration in rubble. We deployed modified RUbble Biodiversity Samplers (RUBS) and emergence traps in a shallow rubble patch at Heron Island, Great Barrier Reef, to detect community‐level differences in the directional influx of motile cryptofauna under five habitat accessibility regimes. The mean density (0.13–4.5 ind cm−3) and biomass (0.14–5.2 mg cm−3) of cryptofauna were high and varied depending on microhabitat accessibility. Emergent zooplankton represented a distinct community (dominated by the Appendicularia and Calanoida) with the lowest density and biomass, indicating constraints on nocturnal resource availability. Mean cryptofauna density and biomass were greatest when interstitial access within rubble was blocked, driven by the rapid proliferation of small harpacticoid copepods from the rubble surface, leading to trophic simplification. Individuals with high biomass (e.g., decapods, gobies, and echinoderms) were greatest when interstitial access within rubble was unrestricted. Treatments with a closed rubble surface did not differ from those completely open, suggesting that top‐down predation does not diminish rubble‐derived resources. Our results show that conspecific cues and species' interactions (e.g., competition and predation) within rubble are most critical in shaping ecological outcomes within the cryptobiome. These findings have implications for prey accessibility through trophic and community size structuring in rubble, which may become increasingly relevant as benthic reef complexity shifts in the Anthropocene.
Inflammatory biomarkers in assessing severity and prognosis of immune checkpoint inhibitor‐associated cardiotoxicity
Authors: Liang Lin , Cui Chanjuan , Lv Dan , Li Yiqun , Huang Liyan , Feng Jiayu , An Tao , Tian Pengchao , Yang Ke , Hu Linjun , Gao Lizhen , Zhang Jian , Zhang Yuhui , Ma Fei , Wang Yanfeng
Published: March 2023

Aims

Inflammatory biomarkers, including CRP, the neutrophil‐to‐lymphocyte ratio (NLR), and the neutrophil‐to‐eosinophil ratio (NER), may predict outcomes in cancer. However, their value in immune checkpoint inhibitor (ICI) therapy‐associated cardiotoxicity remains elusive. We aimed to characterize the relationship of inflammatory markers with severity of ICI‐related cardiotoxicities (iRCs) and prognosis among patients with iRCs.

Methods

Patients who were diagnosed with iRCs between January 2019 and December 2021 were retrospectively enrolled and were dichotomized based on iRC severity into low‐grade (grade 1–2) vs. high‐grade (grade 3–4) groups.

Results

Forty‐seven patients were included. The median time‐to‐event from first ICI infusion to onset of iRCs was 35 days (IQR: 19.0–65.5 days). When compared with respective baseline values, cardiac biomarkers and inflammatory markers were significantly elevated at onset of iRCs. Compared with low‐grade iRCs, NER at iRC onset was significantly increased among patients with high‐grade iRCs (Group × Time, P < 0.01). When grouped by the median NER (184.33) at iRC onset, NER ≥ 184.33 was associated with high‐grade iRCs (OR: 10.77, P < 0.05) and had a 36.3% increased mortality compared to the lower NER group (HR: 2.67, P < 0.05).

Conclusions

In patients who develop iRCs, NER is significantly elevated at iRC onset, and higher NER correlates with greater iRC severity and higher mortality. Larger datasets are needed to validate these findings.
Association between lactate/albumin ratio and mortality in patients with heart failure after myocardial infarction
Authors: Chen Yang , Yang Ke , Wu Bingyuan , Lin Wanwen , Chen Simin , Xu Xiaochun , Peng Chaoquan , Xie Dongmei
Published: March 2023

Aims

Lactate/albumin ratio (L/A) is a recognized prognostic index of patients with heart failure (HF) after myocardial infarction (MI). We aim to evaluate the prognostic value of L/A ratio in predicting in‐hospital mortality for those patients.

Methods and results

We enrolled qualified patients from Medical Information Mart for Intensive Care IV database for retrospective study. A receiver operating characteristic (ROC) curve of the subjects was applied to determine the predicted value and the best cut‐off value of L/A on admission. Univariate/multivariate Cox regression analysis and restricted cubic splines (RCS) were performed to identify the association between hospital admission and hospital mortality. The Kaplan–Meier (KM) method was used to draw the survival curve of the two groups with different L/A levels at admission. L/A values at admission were significantly higher in the death groups than the survival groups [1.36 (1.20) vs. 0.62 (0.36), P < 0.05], and area under the ROC curve [0.780 (95% confidence interval, 0.772–0.827)] was better than other indicators, and the best the cut‐off value was 0.671. Data of Cox regression analysis showed that higher L/A value supposed to be an independent risk factor for in‐hospital mortality. RCS analysis showed evidence of an increasing trend and a non‐linear relationship between L/A and in‐hospital mortality (P value was non‐linear <0.05). KM survival curves were significantly lower in the high L/A group than the low L/A group (P < 0.001), and the former group had an increased risk of in‐hospital mortality compared with the latter one (log rank P < 0.001).

Conclusions

Elevated L/A ratio on admission is an independent predictor of high in‐hospital mortality in post‐MI heart failure patients, which proved to be better than lactate, Sequential Organ Failure Assessment score and other related indicators.
Design and Synthesis of Linearly Fused Triquinanes through Tandem‐Metathesis: Access to Basic Core of Cucumin, Capnellene, Chondrosterin, and Xeromphalinone
Authors: Kotha Sambasivarao , Reddy Keesari Ramakrishna
Published: March 2023

Herein, a short synthetic approach to linearly fused tricyclic enone 1 and cis‐anti‐cis type hydroxy‐triquinane 2 has been described in an efficient manner by employing tandem‐metathesis as a key step. The triquinane‐based enone 1 is prepared by a Babler–Dauben oxidation of hydroxy‐triquinane 2, which is assembled by following a three‐step sequence involving a regio‐ and stereoselective allylation, vinyl Grignard addition, and tandem‐metathesis. Our strategy relies on exo‐tricyclic ketone, which is derived from readily available exo‐dicyclopentadiene‐1‐one. The newly synthesized molecules were identified and characterized by nuclear magnetic resonance spectroscopy (NMR), and high‐resolution mass spectrometry (HRMS) data. It is worth mentioning that tricyclic enone 1 is present as a core unit of many naturally occurring polyquinanes, particularly xeromphalinone family members. Hence, our approach may be useful in the synthesis of such bioactive molecules.
Effects of pre‐treated sludge on sludge stabilization and electricity generation in microbial fuel cell
Authors: Demir Özlem , Gümüş Elif
Published: March 2023

In this study, based on the advantage of having high organic content of sludge both sludge treatment and electricity generation in the microbial fuel cell were investigated. The hydrolysis step of anaerobic digestion which is known as rate‐limiting step was tried to accelerate with the pre‐treatment methods such as Fenton and thermal/alkaline for sludge stabilization in the microbial fuel cell. The chemical oxygen demand and organic matter removal were 53% and 64% in the anaerobic chamber of the microbial fuel cell fed with raw sludge, respectively. In the microbial fuel cell fed with pre‐treated sludge using Fenton Process, these removal efficiencies were found to be 59% and 60%, respectively, while in thermal/alkaline microbial fuel cells were 83.3% and 85%, respectively. The current densities in microbial fuel cells fed with raw sludge, Fenton process sludge and thermal/alkaline sludge were 0.002, 0.221 and 38 mA/cm2, respectively. As a result, it can be concluded that, the microbial fuel cell fed with pre‐treated sludge can be used for both the sludge treatment and the electricity generation by improving the decomposition of organic matter and accelerating the rate‐limiting step in the anaerobic chamber.
Highly efficient removal of methylene blue from aqueous solution by magnetic biochar prepared from hawthorn seeds
Authors: Özer Asiye , Toprak Mahmut
Published: March 2023

Magnetic biochar was prepared in one step with simultaneous activation and magnetization processes under CO2 atmosphere in the presence of a mixture of FeCl3·6H2O and hawthorn seeds as precursor. The magnetic biochar used as a potential adsorbent for the removal of methylene blue (MB) from aqueous solution was characterized by BET, FTIR, SEM and vibrating sample magnetometer. The produced magnetic biochar showed a high surface area of 489.166 m2/g, a pore size of 2.16 nm, a pore volume of 0.26 cm3 /g and a saturation magnetization of 29.84 emu/g. Batch adsorption studies were performed at different initial dye concentration, pH and temperature. The adsorption capacity of the magnetic biochar showed a good result for the adsorption of MB (147 mg/g). Of the two models used, the Langmuir isotherm fitted the equilibrium data better than the Freundlich isotherm. The kinetics study showed that the adsorption of MB was fitted better with pseudo‐second‐order kinetics model and the intra‐particle diffusion process was one of the main mechanisms controlling the adsorption rate. Moreover, thermodynamic parameters showed that the process of adsorption was endothermic and spontaneous. The experimental results showed that the magnetic biochar would be promising for practical wastewater treatment.
Gender‐ethnicity intersectional variation in work–family dynamics: Family interference with work, guilt, and job satisfaction
Authors: Hwang Seonyoung , Hoque Kim
Published: March 2023

Although guilt is often considered the most prevalent emotional outcome of work–family conflict (WFC), most work–family research focuses on family‐related guilt stemming from work interference with family, rather than job‐related guilt stemming from family interference with work (FIW). In addition, there is little understanding of how different employee social groups experience the implications of FIW in their daily lives. To address these research gaps, this study explores the relationship between daily FIW and job‐related guilt, and its subsequent impact on job satisfaction. It also investigates variation in these relationships by (1) gender and (2) the intersection of gender and ethnicity. Bayesian multilevel structural equation modeling using data from 5‐day diary surveys from 210 solicitors in Britain shows daily FIW is associated with higher job‐related guilt and subsequently lower job satisfaction. The relationship is stronger for women than men in general, but is also stronger for South Asian women than white British women (and men), and for South Asian men than white British men. This suggests that studies focusing on single social group characteristics (e.g., gender) are likely to obscure intersectional effects that might produce significant within‐group variation. The findings also highlight the importance of integrating workplace inequality arguments into theorization of WFC.
Characterizing engineering outreach educators' talk moves: An exploratory framework
Authors: Miel Karen , Swanson Rebecca D. , Portsmore Merredith , Paul Kelli M. , Moison Elizabeth A. , Kim Jungsun , Maltese Adam V.
Published: March 2023

Background

Despite the prevalence and potential of K–12 engineering outreach programs, the moment‐to‐moment dynamics of outreach educators' facilitation of engineering learning experiences are understudied. There is a need to identify outreach educators' teaching moves and to explore the implications of these moves.

Purpose/Hypothesis

We offer a preliminary framework for characterizing engineering outreach educators' teaching moves in relation to principles of ambitious instruction. This study describes outreach educators' teaching moves and identifies learning opportunities afforded by these moves.

Design/Method

Through discourse analysis of video recordings of a university‐led engineering outreach program, we identified teaching moves of novice engineering outreach educators in interaction with elementary student design teams. We considered 18 outreach educators' teaching moves through a lens of ambitious instruction.

Results

In small group interactions, outreach educators used ambitious, conservative, and inclusive teaching moves. These novice educators utilized talk moves that centered students' ideas and agency. Ambitious moves included two novel teaching moves: design check‐ins and revoicing tangible manifestations of students' ideas. Ambitious moves offered students opportunities to engage in engineering design. Conservative moves provided opportunities for students to make technical and affective progress, and to experience engineering norms.

Conclusions

Our work is formative in describing engineering outreach educators' teaching moves and points to outreach educators' capability in using ambitious moves. Ambitious engineering instruction may be a useful framework for designing engineering outreach to support students' participation and progress in engineering design. Additionally, conservative teaching moves, typically considered constraining, may support productive student affect and engagement in engineering design.
Synthesis of 5‐spirocycle camptothecin using ring‐closing metathesis strategy
Authors: Ke Xi , Wang Xianheng , Liu Yuan , Zuo Linming , Wang Yuhe , Zhao Changkuo
Published: March 2023

Camptothecin (CPT) is an important natural product targeting to Topoisomerase I (Topo I). Despite the high antitumor activity, this compound cannot enter clinical trial owing to its high toxicity and low bio‐availability. In this project, the ring‐closing metathesis (RCM) synthesis strategy was employed to introduce spirocycle functional group in the 5‐position of CPT. Thus, in the catalysis of Grubbs II catalyst, 5,5‐diallylcamptothecin underwent RCM reaction to give 5‐spirocycle CPT compound in 73% yield.