bluuebunny/crossref_metadata_2025 huggingface dataset:
Hydroponics and Synergetic Technologies: A Deep Dive into Small and Medium-Scale Applications
Authors: Singh Bal Veer , Ashutosh  , Janbandhu Mohit Shalikram , Satapathy Satya Narayan , Das Hiren , Yadav Babita , Pratiksha Km , Singh Shakti
Published: October 2023

Hydroponics, the practice of soilless plant cultivation, has undergone significant transformation over the years, evolving from its roots in ancient civilizations to its modern, high-tech systems. This paper explores this journey, focusing on technological advancements that have not only refined the principles of hydroponics but have also democratized its accessibility. Early accounts of hydroponic-like practices can be traced back to the Hanging Gardens of Babylon, the Floating Gardens of the Aztecs, and historical records in China and Egypt. The formalization of hydroponics, however, took place in the 20th century, although the concept had been introduced much earlier by Sir Francis Bacon in 1627. Technological leaps in nutrient solutions have been pivotal; German botanists Julius von Sachs and Wilhelm Knop's work in 1860 set the scientific basis for soilless culture. Modern hydroponic systems such as Nutrient Film Technique (NFT), Aeroponics, and Deep Water Culture (DWC) employ pumps, timers, and nutrient reservoirs for efficient cultivation. These systems have scaled hydroponics from a lab-scale practice to a commercial-scale operation, making it accessible to both hobbyist gardeners and large-scale agriculturalists. Another transformative development is in the area of hydroponic lighting. High-Pressure Sodium (HPS) and Light Emitting Diode (LED) lights offer sustainable and efficient alternatives to natural light, thus enabling year-round, indoor hydroponic farming. The automation of hydroponic systems via computer-controlled environments has drastically reduced the manual labor required, making it accessible to individuals without specialized horticultural skills. Lastly, the paper delves into synergistic technologies like smart monitoring systems, Internet of Things (IoT), and renewable energy sources that are setting new paradigms for hydroponics. Smart sensors and analytics provide real-time data for nutrient and environmental control, while IoT devices offer remote management capabilities. Renewable energy sources like solar and wind power bring sustainability to hydroponic setups, thereby reducing the carbon footprint. These technologies collectively create an environment that is conducive not just for optimal plant growth, but also for operational sustainability and efficiency.
Facile Preparation of Hierarchical Micro‐/Nanostructure Superhydrophobic Surface with Excellent Corrosion Resistance on Ti6Al4V‐Based Composite for Nuclear Fuel Reprocessing
Authors: Tang Mingkai , Zhang Lichao
Published: October 2023

To address the poor corrosion resistance of titanium matrix composites treatment vessels for nuclear fuel reprocessing in HF solution at room temperature and high concentration of HCl/HNO3 solutions at high temperature, hierarchical micro‐/nanostructure surfaces with adjustable superhydrophobicity are prepared on Ti6Al4V‐based composites by laser microengraving followed by fluorosilane modification. The effect of topography and composition of the surface on wettability is investigated. More importantly, the anticorrosion mechanism of the as‐prepared surface in the earlier corrosive solutions that can destroy the anticorrosion inert oxide film of the composite easily is investigated and elucidated for the first time. The results indicate that the surface is composed of regular parallel linear peak‐like microscale structures and radiating flocculent nanostructures. It shows excellent and stable superhydrophobicity (contact angle of 158.4°, sliding angle of 4.7°). Due to the unique solid–air–liquid interface induced by the micro‐/nanostructures and high charge transfer resistance induced by the fluorosilane film, the impedance modulus of the superhydrophobic surface can be one order of magnitude higher than that of the bare surface. The composite can be corroded hardly when immersed in 5% HCl/HNO3 solutions at 80 °C for more than 10 days and 4% HF solution at room temperature for 3 days.
A Variational Beam Model for Failure of Cellular and Truss‐Based Architected Materials
Authors: Karapiperis Konstantinos , Radi Kaoutar , Wang Zifan , Kochmann Dennis M.
Published: October 2023

A variational formulation of a beam model is presented for predicting the inelastic and geometrically nonlinear mechanical behavior of cellular and truss‐based architected materials. Emphasis is placed on the constitutive description of base materials commonly used in additive manufacturing, including polymers and metals, and the derivation of effective incremental potentials incorporating the effects of damage and viscoplasticity. The model is demonstrated in a variety of problems including the fracture of polymeric honeycombs, the tightening of woven architected materials, as well as the compression of metallic foams. The model's easy calibration–on the basis of single‐strut tests–and its successful validation—through experiments of additively manufactured specimens–indicate its promise as an efficient design tool for architected materials within a wide range of engineering applications.
Modeling the Progression of Placental Transport from Early‐ to Late‐Stage Pregnancy by Tuning Trophoblast Differentiation and Vascularization
Authors: Kouthouridis Sonya , Sotra Alexander , Khan Zaim , Alvarado Justin , Raha Sandeep , Zhang Boyang
Published: October 2023

The early‐stage placental barrier is characterized by a lack of fetal circulation and by a thick trophoblastic barrier, whereas the later‐stage placenta consists of vascularized chorionic villi encased in a thin, differentiated trophoblast layer, ideal for nutrient transport. In this work, predictive models of early‐ and late‐stage placental transport are created using blastocyst‐derived placental stem cells (PSCs) by modulating PSC differentiation and model vascularization. PSC differentiation results in a thinner, fused trophoblast layer, as well as an increase in human chorionic gonadotropin secretion, barrier permeability, and secretion of certain inflammatory cytokines, which are consistent with in vivo findings. Further, gene expression confirms this shift toward a differentiated trophoblast subtype. Vascularization results in a molecule type‐ and size‐dependent change in dextran and insulin permeability. These results demonstrate that trophoblast differentiation and vascularization have critical effects on placental barrier permeability and that this model can be used as a predictive measure to assess fetal toxicity of xenobiotic substances at different stages of pregnancy.
Current State and Future Perspectives of Printable Organic and Perovskite Solar Cells
Authors: Li Fengzhu , Lin Francis R. , Jen Alex K.‐Y.
Published: October 2023

Photovoltaic technology presents a sustainable solution to address the escalating global energy consumption and a reliable strategy for achieving net‐zero carbon emissions by 2050. Emerging photovoltaic technologies, especially the printable organic and perovskite solar cells, have attracted extensive attention due to their rapidly transcending power conversion efficiencies and facile processability, providing great potential to revolutionize the global photovoltaic market. To accelerate these technologies to translate from the laboratory scale to the industrial level, it is critical to develop well‐defined and scalable protocols to deposit high‐quality thin films of photoactive and charge‐transporting materials. Herein, the current state of printable organic and perovskite solar cells is summarized and the view regarding the challenges and prospects toward their commercialization is shared. Different printing techniques are first introduced to provide a correlation between material properties and printing mechanisms, and the optimization of ink formulation and film‐formation during large‐area deposition of different functional layers in devices are then discussed. Engineering perspectives are also discussed to analyze the criteria for module design. Finally, perspectives are provided regarding the future development of these solar cells toward practical commercialization. It is believed that this perspective will provide insight into the development of printable solar cells and other electronic devices.
Lotus Effect Inspired Hydrophobic Strategy for Stable Zn Metal Anodes
Authors: Han Lishun , Guo Yiming , Ning Fanghua , Liu Xiaoyu , Yi Jin , Luo Qun , Qu Baihua , Yue Jili , Lu Yangfan , Li Qian
Published: October 2023

Zn‐ion batteries (ZIBs) have long suffered from the unstable Zn metal anode, which faces numerous challenges concerning dendrite growth, corrosion, and hydrogen evolution reaction. The absence of H2O adsorption control techniques has become a bottleneck for the further development of ZIBs. Using the stearic acid (SA)‐modified Cu@Zn (SA‐Cu@Zn) anode as an example, this work illustrates how the lotus effect controls the H2O adsorption energy on the Zn metal anode. In situ integrated Cu nanorods arrays and hydrophobic long‐chain alkyl groups are constructed, which provide zincophilic ordered channels and hydrophobic property. Consequently, the SA‐Cu@Zn anode exhibits long‐term cycling stability over 2000 h and high average Coulombic efficiency (CE) of 99.83% at 1 mA cm−2 for 1 mAh cm−2, which improves the electrochemical performance of the Zn||V2O5 full cell. Density functional theory (DFT) calculations combined with water contact angle (CA) measurements demonstrate that the SA‐Cu@Zn exhibits larger water CA and weaker H2O adsorption than Zn. Moreover, the presence of Cu ensures the selective adsorption of Zn on the SA‐Cu@Zn anode, well explaining how the excellent reversibility is achieved. This work demonstrates the effectiveness of the lotus effect on controllable H2O adsorption and Zn deposition mechanism, offering a universal strategy for achieving stable ZIB anodes.
Achieving Desired Pseudo‐Planar Heterojunction Organic Solar Cells via Binary‐Dilution Strategy
Authors: Wen Lin , Mao Houdong , Zhang Lifu , Zhang Jiayou , Qin Zhao , Tan Licheng , Chen Yiwang
Published: October 2023

The sequential deposition process has demonstrated the great possibility to achieve a photolayer architecture with an ideal gradient phase separation morphology, which has a vital influence on the physical processes that determine the performance of organic solar cells (OSCs). However, the controllable preparation of pseudo‐planar heterojunction (P‐PHJ) with gradient distribution has not been effectively elucidated. Herein, a binary‐dilution strategy is proposed, the PM6 solution with micro acceptor BO‐4Cl and the L8‐BO solution with micro donor PM6 respectively, to form P‐PHJ film. This architecture exists good donor (D) and acceptor (A) vertical gradient distribution and larger D/A interpenetrating regions, which promotes exciton generation and dissociation, shortens charge transport distance and optimizes carrier dynamics. Moreover, the dilution of PM6 by BO‐4Cl promotes the regulation of active layer aggregation size and phase purity, thus alleviating energy disorder and voltage loss. As a result, the P‐PHJ device exhibits an outstanding power conversion efficiency of 19.32% with an excellent short‐circuit current density of 26.92 mA cm−2, much higher than planar binary heterojunction (17.67%) and ternary bulk heterojunction (18.49%) devices. This research proves a simple but effective method to provide an avenue for constructing desirable active layer morphology and high‐performance OSCs.
Organic Source‐Gated Phototransistors with > 104 Photo‐To‐Dark Current Ratio in the Visible Range at Zero Gate‐Source Bias
Authors: Bestelink Eva , Zschieschang Ute , Askew Leslie , Klauk Hagen , Sporea Radu A.
Published: October 2023

With growing interest in organic phototransistors, as not only sensors but also neuromorphic computing elements, the vast majority of research investigates structures comprising Ohmic source/drain contacts. Here, it is shown how source‐gated transistors (SGTs), in which a source contact barrier dominates electrical characteristics, can be implemented as phototransistors. Organic photo‐SGTs (OPSGTs) based on vacuum‐processed small‐molecule dinaphtho[2,3‐b:2′,3′‐f]thieno[3,2‐]thiophene (DNTT) demonstrate low saturation voltage, exceptional tolerance to channel length variation, and photo‐to‐dark current ratio (PDCR) peaks over 106 for 819 µW broad spectrum incident light power. At zero gate‐source voltage, the PDCR reaches 104, showing promise for simple sensor circuit implementation in medical and wellbeing applications.
Strain Effects on Flexible Perovskite Solar Cells
Authors: Liang Hongbo , Yang Wenhan , Xia Junmin , Gu Hao , Meng Xiangchuan , Yang Gege , Fu Ying , Wang Bin , Cai Hairui , Chen Yiwang , Yang Shengchun , Liang Chao
Published: October 2023

Flexible perovskite solar cells (f‐PSCs) as a promising power source have grabbed surging attention from academia and industry specialists by integrating with different wearable and portable electronics. With the development of low‐temperature solution preparation technology and the application of different engineering strategies, the power conversion efficiency of f‐PSCs has approached 24%. Due to the inherent properties and application scenarios of f‐PSCs, the study of strain in these devices is recognized as one of the key factors in obtaining ideal devices and promoting commercialization. The strains mainly from the change of bond and lattice volume can promote phase transformation, induce decomposition of perovskite film, decrease mechanical stability, etc. However, the effect of strain on the performance of f‐PSCs has not been systematically summarized yet. Herein, the sources of strain, evaluation methods, impacts on f‐PSCs, and the engineering strategies to modulate strain are summarized. Furthermore, the problems and future challenges in this regard are raised, and solutions and outlooks are offered. This review is dedicated to summarizing and enhancing the research into the strain of f‐PSCs to provide some new insights that can further improve the optoelectronic performance and stability of flexible devices.
Yield response of maize hybrids with different ear flex to nitrogen rate and plant density
Authors: DeBruin Jason , Hensley Rebecca , Underwood Haley , Munaro Eugenia
Published: October 2023

Maize (Zea mays L.) hybrids are frequently labeled as fixed or flex hybrid ear types by seed companies based on pre‐commercial trials or field observations during commercialization. However, the underlying physiological cause and the associated management with each hybrid ear type remains a question for growers. Experiments were conducted at multiple locations across 3 years to determine the yield and yield component response to combinations of plant density (4, 6, 8, 10, and 12 plant m−2) and nitrogen (N) rate (0, 78, 159, 235, and 314 kg N ha−1) for three fixed and four flex hybrid ear types. Optimal plant density (OPD) to reach maximum yield was 1.7 plant m−2 greater for fixed hybrid ear type compared to the flex hybrid ear type for N rates greater than 78 kg N ha−1. Flex hybrid ear type achieved similar yield at lower OPD through increased kernel weight (KW) without reduced kernels per square meter. Potential kernel number at silk appearance and established kernels 15 days after silk appearance were similar between hybrid ear types, indicating that the flex component was driven by KW. Fixed hybrid ear type displayed a lower threshold value of total aboveground biomass per plant at physiological maturity to set kernels compared to a flex hybrid ear type. Selection of a flex hybrid ear type provides opportunity for reduced planting density with similar yield potential and N management practices.
Revisiting biodiesel hedging
Authors: Franken Jason R. V. , Irwin Scott H.
Published: October 2023

Previous research found that both soybean oil and heating oil futures should be used to hedge biodiesel price risk. This was sensible because blending mandates caused biodiesel prices to be driven by that of its primary input—soybean oil. Much has changed in recent years, with plummeting demand during the coronavirus disease (COVID) pandemic, biodiesel plants struggling to break‐even in 2020, and then incurring losses in 2021 as soybean oil prices skyrocketed with the rise of renewable diesel—a relatively new biomass‐based diesel fuel in high demand largely due to green policies in California. This study revisits the appropriate strategies for hedging biodiesel production risk and finds that soybean oil has become a less important hedging vehicle. [EconLit Citations: Q420, Q410, Q480, Q160, Q110, Q130].
What we know and don't know about great ape cultural communication in the wild
Authors: Kalan Ammie K. , Nakano Robyn , Warshawski Lindsey
Published: October 2023

Following the first descriptions of culture in primates, widespread agreement has developed that the term can be applied to nonhumans as group‐specific, socially learned behaviors. While behaviors such as those involving extractive tool use have been researched intensively, we propose that behaviors that are more subtle, less likely to be ecologically constrained, and more likely to be socially shaped, such as cultural forms of communication, provide compelling evidence of culture in nonhuman primates. Additionally, cultural forms of communication can provide novel insights into animal cognition such as the capacity for conformity, conventionalized meanings, arbitrariness in signal forms, and even symbolism. In this paper we focus on evidence from studies conducted on wild great apes. First, we provide a thorough review of what exactly we do know, and by extension don't know, about great ape cultural communication. We argue that detailed research on both vocal and gestural communication in wild great apes shows a more nuanced and variable repertoire than once assumed, with increasing support for group‐specific variation. Second, we discuss the relevance of great ape cultural communication and its potential for illustrating evolutionary continuity for human‐like cultural attributes, namely cumulative culture and symbolism. In sum, a concerted effort to examine cultural forms of communication in great apes could reveal novel evidence for cultural capacities that have thus far been heavily debated in the literature and can simultaneously contribute to an improved understanding of the complex minds of our closest living relatives.
“Heal the sick”: Health status and caregiving during the 17th–18th century in Northern Italy (St. Biagio cemetery, Ravenna)
Authors: De Luca Federica , Pasini Alba , Scianò Filippo , Zedda Nicoletta , Guarnieri Chiara , Masotti Sabrina , Bramanti Barbara , Gualdi‐Russo Emanuela , Rinaldo Natascia
Published: October 2023

Objective

The study of health‐related care provision in archeology gives important indications on the culture and community organization of past populations. This study aims to assess the health status of the skeletal assemblage recovered from the burial site of St. Biagio (Ravenna, 17th–18th Centuries); next, we identified likely instances of need for and receipt of caregiving in response to the condition, to examine evidence of community attitudes toward disease and disability.

Materials and Methods

The skeletal assemblage is composed of 133 individuals in a generally good state of preservation. Sex and age‐at‐death were estimated through classical anthropological methods. Health status was inferred through the biological index of frailty (BIF) and paleopathological analysis was performed through macroscopic and radiographic investigations. The “bioarcheology of care” approach was applied to individuals who showed evidence of impairment and disability.

Results

The skeletal assemblage of St. Biagio was equally represented by males and females (50% males), with a higher percentage of adults (83.4%) than subadults (10.5%), and this is reflected in the high life expectancy at birth (40.3 years). No significant differences in health status emerged between age groups and sexes, with a generally high percentage of joint diseases, antemortem trauma, and infectious diseases. Evidence of care and compassion was found in some individuals with a high degree of impairment or disability, as in the case of probable Angelman syndrome.

Discussion

This study provided important insights into the biological and social aspects of an Early Modern population in Northern Italy, showing that people with functional and/or visible abnormalities were probably cared for in life and were presumably considered full members of the society.
Consumer participation in homelessness service delivery in Australia: What is it for?
Authors: Constantine Skye
Published: October 2023

The involvement of people with lived experience is broadly recognised as beneficial, and possibly essential, to effective service and policy planning. However, in the field of homelessness service delivery, this has not been thoroughly researched. To build a greater understanding of participation activities and identify opportunities for lived experience contributions in addressing homelessness, this study investigates the representations of consumer participation by a homelessness service network in Victoria over 10 years (2011–2020). This study found that the homelessness services appear to have actively aspired to meaningful service user participation however tensions for policy and practice remain. These include whether lived experience contributions are valued as “experience” or “expertise”; whether participation is available for those with “living” (current) or “lived” (past) experience; and whether feedback can translate into influence, affecting services and policy change.
Unhealthy white matter connectivity, cognition, and racialization in older adults
Authors: Royse Sarah K. , Snitz Beth E. , Hengenius James B. , Huppert Theodore J. , Roush Rebecca E. , Ehrenkranz Rebecca E. , Wilson James D. , Bertolet Marnie , Reese Alexandria C. , Cisneros Geraldine , Potopenko Katey , Becker James T. , Cohen Ann D. , Shaaban C. Elizabeth
Published: October 2023

INTRODUCTION

White matter hyperintensities (WMH) may promote clinical Alzheimer's disease (AD) disparities between Black American (BA) and non‐Hispanic White (nHW) populations. Using a novel measurement, unhealthy white matter connectivity (UWMC), we interrogated racialized group differences in associations between WMH in AD pathology‐affected regions and cognition.

METHODS

UWMC is the proportion of white matter fibers that pass through WMH for every pair of brain regions. Individual regression models tested associations of UWMC in beta‐amyloid (Aβ) or tau pathology‐affected regions with cognition overall, stratified by racialized group, and with a racialized group interaction.

RESULTS

In 201 older adults ranging from cognitively unimpaired to AD, BA participants exhibited greater UWMC and worse cognition than nHW participants. UWMC was negatively associated with cognition in 17 and 5 Aβ‐ and tau‐affected regions, respectively. Racialization did not modify these relationships.

DISCUSSION

Differential UWMC burden, not differential UWMC‐and‐cognition associations, may drive clinical AD disparities between racialized groups.

Highlights

Unhealthy white matter connectivity (UWMC) in Alzheimer's disease (AD) pathology–affected brain regions is associated with cognition.

Relationships between UWMC and cognition are similar between Black American (BA) and non‐Hispanic White (nHW) individuals.

More UWMC may partially drive higher clinical AD burden in BA versus nHW populations.

UWMC risk factors, particularly social and environmental, should be identified.
An Ultra‐Wideband Janus Metastructure with Graphene for Detector Based on Anapole Mode in the Terahertz Region
Authors: Li Si‐ying , Tang Zhao , Cheng Yang , Zhang Hai‐feng
Published: October 2023

In this paper, an ultra‐wideband Janus metastructure (MS) utilizing anapole mode for detector in the terahertz (THz) range by graphene is proposed. Specifically, when Fermi level (Ef) is set to 0.9 eV, the MS demonstrates ultra‐broadband absorption exceeding 0.9 from 0.754 to 5 THz in the −z‐direction with a relative bandwidth of 147.6 %, in which perfect absorption of over 98% develops from 3.24 to 5 THz. In the case of the +z‐direction, the absorptivity maintains around 0.6 within the 0.745 ∼ 5 THz range. As Ef equals 0 eV, the difference in absorption between the −z‐direction and +z‐direction exceeds 0.9 from 4.49 to 4.76 THz. The study also explores the MS for refractive index sensing near 3.71 THz by a unique difference detection, measuring two refractive index ranges: 1.2 ∼ 2.6 and 4.5 ∼ 4.7, with corresponding sensitivities of 0.0450 and 0.0304, respectively. Owing to its highly symmetrical structure, the MS is insensitive to the polarization state of the electromagnetic (EM) waves, performing remarkable angular stability as the incident angle varies from 0 to 60 degrees in the −z‐direction. These splendid properties make the design a good candidate for biomedical sensing, EM cloaking, and full‐space EM wave control.
Evoking Ferroptosis by Synergistic Enhancement of a Cyclopentadienyl Iridium‐Betulin Immune Agonist
Authors: Lv Mengdi , Zheng Yue , Wu Jian , Shen Zhengqi , Guo Binglian , Hu Guojing , Huang Yuanlei , Zhao Jingyue , Qian Yong , Su Zhi , Wu Chao , Xue Xuling , Liu Hong‐Ke , Mao Zong‐Wan
Published: October 2023

Ferroptosis is a form of programmed cell death driven by iron‐dependent lipid peroxidation (LPO) with the potential for antitumor immunity activation. In this study, a nonferrous cyclopentadienyl metal‐based ferroptosis inducer [Ir(Cp*)(Bet)Cl]Cl (Ir‐Bet) was developed by a metal‐ligand synergistic enhancement (MLSE) strategy involving the reaction of [Ir(Cp*)Cl]2Cl2 with the natural product Betulin. The fusion of Betulin with iridium cyclopentadienyl (Ir‐Cp*) species as Ir‐Bet not only tremendously enhanced the antiproliferative activity toward cancer cells, but also activated ferritinophagy for iron homeostasis regulation by PI3K/Akt/mTOR cascade inhibition with a lower dosage of Betulin, and then evoked an immune response by nuclear factor kappa‐B (NF‐κB) activation of Ir‐Cp* species. Further immunogenic cell death (ICD) occurred by remarkable ferroptosis through glutathione (GSH) depletion, glutathione peroxidase 4 (GPX4) deactivation and ferritinophagy. An in vivo vaccination experiment demonstrated desirable antitumor and immunogenic effects of Ir‐Bet by increasing the ratio of cytotoxic T cells (CTLs)/regulatory T cells (Tregs).
Homolytic C−H Bond Activation by Phosphine−Quinone‐Based Radical Ion Pairs
Authors: Helling Christoph , van der Zee Lars J. C. , Hofman Jelle , de Zwart Felix J. , Mathew Simon , Nieger Martin , Slootweg J. Chris
Published: October 2023

Herein, we present the formation of transient radical ion pairs (RIPs) by single‐electron transfer (SET) in phosphine−quinone systems and explore their potential for the activation of C−H bonds. PMes3 (Mes=2,4,6‐Me3C6H2) reacts with DDQ (2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone) with formation of the P−O bonded zwitterionic adduct Mes3P−DDQ (1), while the reaction with the sterically more crowded PTip3 (Tip=2,4,6‐iPr3C6H2) afforded C−H bond activation product Tip2P(H)(2‐[CMe2(DDQ)]‐4,6‐iPr2‐C6H2) (2). UV/Vis and EPR spectroscopic studies showed that the latter reaction proceeds via initial SET, forming RIP [PTip3]⋅+[DDQ]⋅−, and subsequent homolytic C−H bond activation, which was supported by DFT calculations. The isolation of analogous products, Tip2P(H)(2‐[CMe2{TCQ−B(C6F5)3}]‐4,6‐iPr2‐C6H2) (4, TCQ=tetrachloro‐1,4‐benzoquinone) and Tip2P(H)(2‐[CMe2{oQtBu−B(C6F5)3}]‐4,6‐iPr2‐C6H2) (8, oQtBu=3,5‐di‐tert‐butyl‐1,2‐benzoquinone), from reactions of PTip3 with Lewis‐acid activated quinones, TCQ−B(C6F5)3 and oQtBu−B(C6F5)3, respectively, further supports the proposed radical mechanism. As such, this study presents key mechanistic insights into the homolytic C−H bond activation by the synergistic action of radical ion pairs.
Assessment of ammonium fluoride as a mobile phase additive for sensitivity gains in electrospray ionization
Authors: McFadden Jeremy Ryan , Ames David Michael
Published: October 2023

Ammonium fluoride has been shown to improve sensitivity when using electrospray ionization (ESI) coupled with mass spectrometry (MS). Recent internal investigation furthered that claim, through the observation of improved sensitivity when analyzing steroid molecules. This work focuses on extending those observations to other small molecules to understand the impact ammonium fluoride has on detection sensitivity with optimized instrument conditions. Using conventional liquid chromatography ESI‐MS we investigated sensitivity differences between ammonium fluoride, formic acid, or ammonium hydroxide as mobile phase additives. Full source optimization was performed for nine compounds at three different organic concentrations (30%, 60%, or 90%) with formic acid, ammonium fluoride, and ammonium hydroxide adjustment. Optimization results were compiled to generate individual methods by compound, polarity, mobile phase, and organic concentration. Flow injection analysis was performed with fully optimized methods to compare compounds across different solvent systems under optimal conditions. Negative ESI data showed 2–22‐fold sensitivity improvements for all compounds with ammonium fluoride. Positive ESI data showed > 1–11‐fold improvement in sensitivity for four of seven compounds and no change for three of seven compounds with ammonium fluoride. Ammonium fluoride improved ESI− sensitivity for all compounds studied when using optimized source conditions. Investigation with ESI+ analyses showed mixed results, with four of seven compounds showing improvement and others showing equivalency or slight loss in sensitivity, suggesting potential sensitivity gains for some analogs with ESI+.
Evaluation of Pickering emulsions stabilized with nano‐cellulose and nano‐chitin treated with deep eutectic solvent
Authors: Wu Xinyu , Lian Hailan , Yuan Yang , Hong Shu , Deng Junqian
Published: October 2023

Developing bio‐friendly and degradable Pickering emulsifiers as surfactants to replace traditional surfactants with bio‐toxicity is imperative in the food, coating, cosmetics, and pharmaceutical industries. Nanocellulose and chitin can be used directly as an emulsifier to prepare Pickering o/w emulsions. As the concentration of nanoparticles increases, the stability of the emulsion also increases, and an overly large nanoparticle aspect ratio is not conducive to the stabilization of the emulsion. In comparison, nanocellulose‐prepared Pickering emulsion has improved stability. Of these, nanocellulose prepared by DES with a molar ratio of 3:1 to LA:CC has been shown to have the best stability when used to equilibrate the oil/water mass ratio of 2/8. The Zeta potential is −38.4 mV, and the size of the droplets is the most uniform. With a mean droplet diameter of 770 nm. This study had certain research significance and reference value for the development of bio‐friendly surfactants.
Umpolung Reactivity of Diazo Arylidene Succinimides: Distal C−H Functionalization of α‐Thiocarbonyls from the Reactive Carbenoid Center
Authors: Bankar Onkar S. , Laha Debasish , Meher Kajal B. , Bhat Ramakrishna G.
Published: October 2023

Herein, for the first time we have explored the umpolung reactivity of the vinylogous carbon center of diazo arylidene succinimide (DAS) through rhodium catalysis to achieve [2,3]‐Stevens rearrangement of α‐thioether esters. The protocol has successfully demonstrated the distal C−H bond functionalization of the α‐thioether esters. Alongside, the carbenoid reactivity of DAS has also been achieved with Doyle‐Kirmse reaction of allyl/propargyl phenyl sulfides. The protocol proved to be practical to synthesize a wide variety of [2,3]‐Stevens rearrangement products exclusively and the possible side products emanating from Pummerer rearrangement and [1,2]‐Stevens rearrangement were not observed. This catalytic protocol works smoothly in environmentally benign solvent under open air to afford the corresponding desired products with excellent diastereo‐, regio‐ and chemo‐selectivities in good to excellent yields. The protocol also proved to be scalable on gram quantity.
Increased incidence of renal and urinary tract anomalies among individuals with fetal alcohol spectrum disorders (FASD)
Authors: Dyląg Katarzyna Anna , Dumnicka Paulina , Kowalska Katarzyna , Migas‐Majoch Agata , Przybyszewska Katarzyna , Drożdż Dorota
Published: October 2023

Background

Fetal alcohol spectrum disorders (FASD) in a spectrum of neurodevelopmental conditions resulting from prenatal alcohol exposure (PAE). Animal models have confirmed the toxic effects of PAE on the kidneys and urinary tract, yet the evidence from human studies is contradictory. The purpose of this study was to establish the incidence of renal and urinary tract anomalies (RUTA), impaired kidney function, and hypertension among patients with FASD.

Methods

Children from the FASD Diagnostic Center with FASD diagnosis (FAS, pFAS, or ARND) were offered participation in the study. The control group consisted of patients from the Gastroenterology Department of the same hospital. The patients underwent renal and urinary tract ultrasound examination. The serum creatinine level was also evaluated and the blood pressure was taken twice. Polish OLAF charts were used to determine the percentiles of blood pressure.

Results

The incidence of kidney and urinary tract defects in the study group was significantly higher than in the control group (OR: 2.64 [1.60–4.34]). The kidney size among FASD patients was significantly lower (73 mm [60–83] vs. 83 mm [70–96]; p < .001) when compared to the control group. No differences were observed in the estimated glomerular filtration rate. In the study group, significantly lower systolic blood, diastolic blood pressure, percentile of systolic pressure, and diastolic pressure were observed.

Conclusions

RUTA occurred more frequently among patients with FASD compared to the control group, and decreased kidney size was also demonstrated among patients with FASD. However, impaired kidney function and the risk of hypertension were not observed.
Dendrobium huoshanense Polysaccharide Improves High‐Fat Diet Induced Liver Injury by Regulating the Gut‐Liver Axis
Authors: Ma Meng‐Hua , Gao Lei‐Lei , Chen Chuang‐Bo , Gu Fang‐li , Wu Si‐Qi , Li Fang , Han Bang‐Xing
Published: October 2023

Dendrobium huoshanense is an important Traditional Chinese medicine that thickens the stomach and intestines. Its active ingredient Dendrobium huoshanense polysaccharide (DHP), was revealed to relieve the symptoms of liver injury. However, its mechanism of action remains poorly understood. This study aimed to investigate the mechanism of DHP in protecting the liver. The effects of DHP on lipid levels, liver function, and intestinal barrier function were investigated in mice with high‐fat diet‐induced liver damage. Changes in the gut flora and their metabolites were analyzed using 16S rRNA sequencing and metabolomics. The results showed that DHP reduced lipid levels, liver injury, and intestinal permeability. DHP altered the intestinal flora structure and increased the relative abundance of Bifidobacterium animalis and Clostridium disporicum. Furthermore, fecal metabolomics revealed that DHP altered fecal metabolites and significantly increased levels of gut‐derived metabolites, spermidine, and indole, which have been reported to inhibit liver injury and improve lipid metabolism and the intestinal barrier. Correlation analysis showed that spermidine and indole levels were significantly negatively correlated with liver injury‐related parameters and positively correlated with the intestinal species B. animalis enriched by DHP. Overall, this study confirmed that DHP prevented liver injury by regulating intestinal microbiota dysbiosis and fecal metabolites.
Harnessing a Biocatalyst to Bioremediate the Purification of Alkylglycosides
Authors: Wahart Alice J. C. , Dolan Jonathan P. , Anderson Simon D. , Cheallaigh Aisling Ní , Staniland Jessica , Lima Marcelo A. , Skidmore Mark A. , Miller Gavin J. , Cosgrove Sebastian C.
Published: October 2023

As the world moves towards net‐zero carbon emissions, the development of sustainable chemical manufacturing processes is essential. Within manufacturing, purification by distillation is often used, however this process is energy intensive and methods that could obviate or reduce its use are desirable. Developed herein is an alternative, oxidative biocatalytic approach that enables purification of alkyl monoglucosides (essential bio‐based surfactant components). Implementing an immobilised engineered alcohol oxidase, a long‐chain alcohol by‐product derived from alkyl monoglucoside synthesis (normally removed by distillation) is selectively oxidised to an aldehyde, conjugated to an amine resin and then removed by simple filtration. This affords recovery of the purified alkyl monoglucoside. The approach lays a blueprint for further development of sustainable alkylglycoside purification using biocatalysis and, importantly, for refining other important chemical feedstocks that currently rely on distillation.
In‐Situ Growth of Cu2S‐MoS2 Bimetallic Electrocatalyst on Carbon Cloth for Hydrogen Evolution Reaction
Authors: Jin Zhongxin , Pang Haijun , Li Kunqi , Yang Mengle , Xin Jianjiao , Ma Huiyuan , Wu Qiong , Wang Xinming , Yang Guixin
Published: October 2023

Hydrogen evolution reaction (HER) is one of prospective methods to produce hydrogen energy, and the key technology of which lies in the preparation of electrocatalysts. Preparations of catalysts with high efficiency, low price and good stability are expected. In this work, a new polyoxometalate‐based copper‐organic framework, [{CuII(C10N6H7)4(H2O)2}H6(PMo12O40)2] ⋅ 12H2O (1) [C10N6H7: 3‐(1H‐pyrazol‐4‐yl)‐5‐(pyridin‐4‐yl)‐1,2,4‐triazole], was synthesized as an electrocatalyst precursor, and confirmed by infrared spectroscopy (IR), single‐crystal X‐ray diffraction (SXRD) and X‐ray powder diffraction (PXRD). A new electrocatalyst (Cu2S‐MoS2@CC‐1) was synthesized from 1, thiourea (TU) and carbon cloth (CC) by a one‐pot hydrothermal method. Due to the synergistic effects between Cu2S and MoS2, the Cu2S‐MoS2@CC‐1 catalyst exhibits high electrocatalytic HER activity and good stability in 0.5 M H2SO4. Namely, Cu2S‐MoS2@CC‐1 shows low overpotential of 150 mV@10 mA cm−2 vs reversible hydrogen electrode (RHE) and small Tafel slope of 61 mV dec−1, and remains good stability at least 94 h and over 1000 catalytic cycles. This method provides a promising strategy for development of non‐noble metal catalysts.
Machine Learning‐Based Quantification of Patient Factors Impacting Remission in Patients With Ulcerative Colitis: Insights from Etrolizumab Phase III Clinical Trials
Authors: Harun Rashed , Lu James , Kassir Nastya , Zhang Wenhui
Published: October 2023

Etrolizumab, an investigational anti‐β7 integrin monoclonal antibody, has undergone evaluation for safety and efficacy in phase III clinical trials on patients with moderate to severe ulcerative colitis (UC). Etrolizumab was terminated because mixed efficacy results were shown in the induction and maintenance phase in patients with UC. In this post hoc analysis, we characterized the impact of explanatory variables on the probability of remission using XGBoost machine learning (ML) models alongside with the SHapley Additive exPlanations framework for explainability. We used patient‐level data encompassing demographics, physiology, disease history, clinical questionnaires, histology, serum biomarkers, and etrolizumab drug exposure to develop ML models aimed at predicting remission. Baseline covariates and early etrolizumab exposure at week 4 in the induction phase were utilized to develop an induction ML model, whereas covariates from the end of the induction phase and early etrolizumab exposure at week 4 in the maintenance phase were used to develop a maintenance ML model. Both the induction and maintenance ML models exhibited good predictive performance, achieving an area under the receiver operating characteristic curve (AUROC) of 0.74 ± 0.03 and 0.75 ± 0.06 (mean ± SD), respectively. Compared with placebo, the highest tertile of etrolizumab exposure contributed to 15.0% (95% confidence interval (CI): 9.7–19.9) and 17.0% (95% CI: 8.1–26.4) increases in remission probability in the induction and maintenance phases, respectively. Additionally, the key covariates that predicted remission were CRP, MAdCAM‐1, and stool frequency for the induction phase and white blood cells, fecal calprotectin and age for the maintenance phase. These findings hold significant implications for establishing stratification factors in the design of future clinical trials.
A Dynamic Water Channel Affects O2 Stability in [FeFe]‐Hydrogenases
Authors: Brocks Claudia , Das Chandan K. , Duan Jifu , Yadav Shanika , Apfel Ulf‐Peter , Ghosh Subhasri , Hofmann Eckhard , Winkler Martin , Engelbrecht Vera , Schäfer Lars V. , Happe Thomas
Published: October 2023

[FeFe]‐hydrogenases are capable of reducing protons at a high rate. However, molecular oxygen (O2) induces the degradation of their catalytic cofactor, the H‐cluster, which consists of a cubane [4Fe4S] subcluster (4FeH) and a unique diiron moiety (2FeH). Previous attempts to prevent O2‐induced damage have focused on enhancing the protein's sieving effect for O2 by blocking the hydrophobic gas channels that connect the protein surface and the 2FeH. In this study, we aimed to block an O2 diffusion pathway and shield 4FeH instead. Molecular dynamics (MD) simulations identified a novel water channel (WH) surrounding the H‐cluster. As this hydrophilic path may be accessible for O2 molecules we applied site‐directed mutagenesis targeting amino acids along WH in proximity to 4FeH to block O2 diffusion. Protein film electrochemistry experiments demonstrate increased O2 stabilities for variants G302S and S357T, and MD simulations based on high‐resolution crystal structures confirmed an enhanced local sieving effect for O2 in the environment of the 4FeH in both cases. The results strongly suggest that, in wild type proteins, O2 diffuses from the 4FeH to the 2FeH. These results reveal new strategies for improving the O2 stability of [FeFe]‐hydrogenases by focusing on the O2 diffusion network near the active site.
Structural analysis of an lysergic acid diethylamide (LSD) analogue N‐methyl‐N‐isopropyllysergamide (MiPLA): Insights from Rotamers in NMR spectra
Authors: Shoda Takuji , Tsuji Genichiro , Kawamura Maiko , Kurohara Takashi , Misawa Takashi , Kikura‐Hanajiri Ruri , Demizu Yosuke
Published: October 2023

Lysergic acid diethylamide (LSD) is a hallucinogenic compound that binds to and activates the serotonin 2A receptor and is classified as a controlled narcotic in Japan. Recently, MiPLA, an N‐methyl‐N‐isopropyl derivative of LSD, has been detected in paper‐sheet products in several countries. This study focuses on the synthesis of MiPLA and includes a comprehensive analysis involving structural and liquid chromatography–mass spectrometry (LC‐MS). Particularly, MiPLA was synthesized in three‐steps starting from ergometrine maleate, which resulted in the formation of (8S)‐isomer, iso‐MiPLA, as a by‐product. The LC‐MS results showed that LSD, MiPLA, and iso‐MiPLA exhibited different retention times. Their chemical structures were determined using nuclear magnetic resonance spectroscopy, which revealed the presence of rotamers involving the N‐methyl‐N‐isopropyl groups of tertiary amides in MiPLA and iso‐MiPLA.
Enhanced Long‐Term Stability of a Photosensitizer with a Hydroxamic Acid Anchor in Dye‐Sensitized Photocatalytic Hydrogen Generation
Authors: Salerno Giorgia , Cecconi Bianca , Bettucci Ottavia , Monai Matteo , Zani Lorenzo , Franchi Daniele , Calamante Massimo , Mordini Alessandro , Montini Tiziano , Fornasiero Paolo , Manfredi Norberto , Abbotto Alessandro
Published: October 2023

Climate change mitigation on a global scale will only be possible through the achievement of ambitious decarbonisation goals, requiring an energy transition that involves switching from fossil fuels to clean fuels such as hydrogen. The photocatalytic approach is one of the most studied methods for directly converting sunlight into hydrogen. In this work, we present the synthesis, characterization, and application of the PTZ1‐HA dye, which was obtained by replacing the terminal conventional carboxylic anchoring moieties of a previously studied phenothiazine‐based dye (PTZ1) with hydroxamic acid functionalities. The photoinduced performance of the two dyes as photosensitizers was compared in both dye‐sensitized solar cells and dye‐sensitized photocatalytic systems. PTZ1‐HA‐sensitized photocatalysts showed improved stability in hydrogen generation due to the introduction of the hydroxamic acid as an alternative anchor group, which was shown to slow down hydrolysis in aqueous media. Even though the light harvesting ability of PTZ1‐HA was lower than that of PTZ1, the higher stability of PTZ1‐HA‐sensitized devices allowed for improved photocatalytic generation of H2 over prolonged periods. The superior long‐term efficiency of the hydroxamic acid based dye is important in view of potential practical applications.
Hyperspectral imaging of foodborne pathogens at colony and cellular levels for rapid identification in dairy products
Authors: Sekhon Amninder Singh , Unger Phoebe , Sharma Sonali , Singh Bhupinderjeet , Chen Xiongzhi , Ganjyal Girish M. , Michael Minto
Published: October 2023

This study evaluated the efficacy of hyperspectral imaging (HSI) for the rapid identification of pathogens in dairy products at the colony and cellular levels. The colony and cellular levels studies were designed as completely randomized with six replications. Three strains of Listeria monocytogenes, four strains of Escherichia coli O157: H7, Big Six Shiga toxin‐producing E. coli, three strains of Staphylococcus aureus, and ten serovars of Salmonella were used in this study. Pure cultures were streaked for isolation on respective selective media, and hyperspectral data (400–1100 nm wavelength) at the colony and cellular levels were collected and stored as reference libraries. Whole milk and whole milk powder were artificially inoculated (<10 CFU/g or mL) with individual pathogenic strains/serovars. All milk and milk powder samples were enriched using brain heart infusion (BHI) broth at 37°C for 24 h, streaked for isolation on the respective selective media, and hyperspectral data for individual pathogenic strains/serovars at the colony and cellular levels were acquired and treated as test samples data. The acquired colony or cellular images were imported into ENVI software and three regions of interest were selected for each image to obtain hyperspectral data for reference libraries and test samples. Using the kNN classifier and cross‐validation technique, overall classification accuracies of 90.38% and 34% were obtained for the colony‐ and cellular‐level identification, respectively. The individual classification accuracies of pathogens in dairy products at the colony level varied between 77.5% to 100%, whereas the accuracy varied between 2.78% and 49.17% for the cellular level.