bluuebunny/crossref_metadata_2025 huggingface dataset:
Microfluidic Precision Manufacture of High Performance Liquid Chromatographic Microspheres
Authors: Sun Kaiyue , Zeng Juxing , Liu Ya , Zhou Zhuoheng , Chen Jikai , Chen Jiawei , Huang Xiangyu , Gao Fan , Wang Xin , Zhang Xin , Wang Xiaofei , Eeltink Sebastiaan , Zhang Bo
Published: October 2024

A key bottleneck in developing chromatographic material is the chemically entangled control of morphology, pore structure, and material chemistry, which holds back precision material manufacture in order to pursue advanced separation performance. In this work, a precision manufacture strategy based on droplet microfluidics was developed, for production of highly efficient chromatographic microspheres with independent control over particle morphology, pore structure and material chemistry. The droplet‐synthesized microspheres display extremely narrow particle size distribution (CV<3 %), enabling a 100 % production yield due to complete elimination of sieving steps. More importantly, the size of the droplet‐synthesized microspheres is freely adjustable without the need for re‐optimizing chemical recipes or reaction conditions. The resulting materials exhibit excellent separation efficiencies, achieving a reduced plate height of hmin=1.67. This precision manufacture strategy also allows for flexible pore design and continuous pore size adjustment across three orders of magnitudes, providing a novel vehicle for resolution fine‐tuning targeting protein separation. Besides traditional silica, organic–inorganic hybrid silica, zirconia, and titania microspheres can also be precisely synthesized on the same platform, supporting various separation applications and operating conditions. Powered by precision manufacture, super‐throughput production, and versatile chemistry, the high‐performance droplet‐synthesized separation material will pave the way towards green and precision chromatographic industry.
Strengthen Water O−H Bond in Electrolytes for Enhanced Reversibility and Safety in Aqueous Aluminum Ion Batteries
Authors: Zhao Z. , Zhang Z. , Wang W. , Xu T. , Yu X.
Published: October 2024

Aqueous aluminum‐ion batteries present a promising prospect for large‐scale energy storage applications, owing to the abundance, inherent safety, and the high theoretical capacity of aluminum. However, their voltage output and energy density are significantly hindered by challenges such as complex hydrogen evolution and uncontrollable solvation reactions. In this work, we demonstrate that water decomposition is restrain by increasing the electron density of water protons and increasing the dissociation energy of H2O through robust dipole interactions with highly polar dimethylformamide (DMF) molecules. Moreover, the incorporation of dimethyl methylphosphonate (DMMP) flame retardant effectively addresses the flammability risk arising from a substantial presence of organic additives The in‐depth study with experimental and theoretical simulations reveals that the water‐poor solvation structure with reduced water activity is achieved, which can (i) effectively mitigate undesired solvated H2O‐mediated side reactions on the Al anode; (ii) boost the de‐solvation kinetics of Al3+ while preventing cathode structural distortion; (iii) reduce the flammability of hybrid electrolytes. As a proof of concept, the Al//AlxMnO2 full cell employing a hybrid electrolyte demonstrate enhanced stability (deliver 335 mAh g−1 while retaining 71 % capacity for 400 cycles) compared to those with pure electrolyte.
Electrolyte Reconfiguration by Cation/Anion Cross‐coordination for Highly Reversible and Facile Sodium Storage
Authors: Hou Xin , Wang Shuo , Wang Bo , Qiu Yanling , Jiang Mingqin , Tang Yongfu , Zheng Qiong , Li Xianfeng
Published: October 2024

Hard carbon (HC) materials are promising anodes for sodium‐ion batteries (SIBs) owing to low cost, high specific capacity and low working potential. However, the poor compatibility of the electrolyte with HC leads to low initial coulombic efficiency (ICE) and sluggish Na+ transport kinetics. Here, we propose an electrolyte reconfiguration strategy based on the hard and soft acid and base (HSAB) theory by introducing methyltriphenylphosphonium bromide (MTPPB). MTPPB can realize a spontaneous cross‐coordination solvation structure with NaPF6 by selective affinity, synchronously optimizing the interfacial chemistry and sodium storage process. The advantages of the chemical π–π bridging of MTPP+‐HC and interaction of MTPP+‐PF6− contribute to preferential and oriented reduction of PF6−, forming a low‐resistance supramolecular SEI. Additionally, Na+‐Br− coordination weakens the Na+‐solvent interactions, facilitating Na+ de‐solvation kinetics. Consequently, the HC||Na cell achieves a superior ICE of 96.6 %, desirable rate capability under 25 °C and invisible capacity decay after 500 cycles at 1 C under −20 °C. The Na4Fe3(PO4)2P2O7||HC pouch battery displays a high ICE of 90.3 % and a 15 % increment of energy density under 25 °C. This work provides a guidance through electrolyte reconfiguration engineering for designing practical HC‐based SIBs with high energy/power density and long‐life span in the extended operating‐temperature range.
Oxenoid Reactivity Enabled by Targeted Photoactivation of Periodate
Authors: Bossonnet Andre , Garner Ruth A. , O'Brien James , Trujillo Cristina , Trowbridge Aaron D.
Published: October 2024

The chemistry of low‐valent intermediates continues to inspire new modes of reactivity across synthetic chemistry. But while the generation and reactivity of both carbenes and nitrenes are well‐established, difficulties in accessing oxene, their oxygen‐based congener, has severely hampered its application in synthesis. Here, we report a conceptually novel approach towards oxenoid reactivity through the violet‐light photolysis of tetrabutylammonium periodate. Computational studies reveal an unexpected geometric change upon periodate photoexcitation that facilitates intersystem crossing and near‐barrierless dissociation of triplet periodate into oxene. Under these operationally simple conditions, we have demonstrated the epoxidation of a wide range of substituted olefins, revealing unprecedented functional group compatibility. By overcoming the historic challenges associated with employing oxene as an intermediate in organic chemistry, we believe that this platform will inspire the development of new reactive oxygen‐based methodologies across industry and academia.
Site‐Specific Quadruple‐Functionalised Antibodies
Authors: Journeaux Toby , Geeson Michael B. , Murray Thomas V. , Papworth Monika A. , Gothard Matt , Kettle Jason G. , Vasco Aldrin V. , Bernardes Gonçalo J. L.
Published: October 2024

Antibody–drug conjugates (ADCs) are a growing class of chemotherapeutic agents that have yielded striking clinical successes. However, the efficacy of ADCs often suffers from issues associated with tumor heterogeneity and resistance. To overcome these problems, a new generation of ADCs comprising a single monoclonal antibody with multiple different payloads attached, termed multi‐payload ADCs, have been developed. Here we deploy multiple orthogonal site‐specific protein modification strategies to generate highly homogeneous multi‐functionalised antibody conjugates comprising up to four different functionalities installed at four unique sites on the antibody. This work, which includes the use of a site‐specific cyclopropenone (CPO)‐based reagent, represents the first example of a homogeneous multi‐payload ADC with a payload count greater than two, and thereby facilitates the development of the next generation of ADCs.
Multifunctional Nanocomposite Polymer‐integrated Ca‐doped CeO2 Electrolyte for Robust and High‐rate All‐solid‐state Sodium‐ion Batteries
Authors: Yang Pan , Wu Zhenzhen , Li Mingli , Zhang Cheng , Wang Yiqing , Zhu Yutong , Li Meng , Wang Yun , Li Dong‐sheng , Chen Hao , Zhang Shanqing
Published: October 2024

Due to the seamless interfaces between solid polymer electrolytes (SPEs) and electrode materials, SPEs‐based all‐solid‐state sodium‐ion batteries (ASSSIBs) are considered promising energy storage systems. However, the sluggish Na+ transport and uncontrollable Na dendrite propagation still hinder the practical application of SPEs‐based ASSSIBs. Herein, Ca‐doped CeO2 (Ca−CeO2) nanotube framework is synthesized and integrated with poly (ethylene oxide) methyl ether acrylate‐perfluoropolyether copolymer (PEOA‐PFPE), resulting in multifunctional solid nanocomposite electrolytes (namely SNEs, i.e., PEOA‐PFPE/Ca−CeO2). Our investigations demonstrate that the fluorous effect incurred by the fluorine‐containing PEOA‐PFPE and the oxygen vacancy effect induced by the Ca−CeO2 framework could synergistically promote the dissociation of sodium salt, ultimately enhancing the Na+ mobility in SNEs. Besides, the resultant SNEs construct rapid Na+ transport channels and homogenize the Na deposition in SNEs/Na interface, which effectively prevents the Na dendrite growth. Furthermore, the assembled carbon‐coated sodium vanadium phosphate (NVP@C)||PEOA‐PFPE/Ca−CeO2||Na coin cell delivers impressive rate capability of 97.9 mAh g−1 at 2 C and outstanding cycling stability with capacity retention of 84.3 % after 300 cycles at 1 C. This work illustrates that constructing multifunctional SNEs via incorporating functional inorganic frameworks into fluorine‐containing SPEs could be a promising strategy for the commercialization of robust and high‐performance ASSSIBs.
Facile Access to Phosphorus Ylide‐fused Heteroarenes Possessing Tunable Optoelectronic Properties and High Nonlinear Optical Performances
Authors: Zhang Kaihua , Wang Xiaofeng , Zhou Zhiruo , Guo Jing , Liu Hao , Zhai Yaxin , Yao Yifan , Yang Kun , Zeng Zebing
Published: October 2024

We report here a novel family of ylidic P‐heteroarenes (P1–P6), structurally featuring unique phosphonium cyclopentadienylide (P−Cp)‐fused π‐skeletons and synthetically prepared via an unexpected one‐pot [2+3]/[3+3] phospha‐annulation reaction. While the facile and modular synthesis allows the fine‐tuning of their optical absorptions and redox properties, single‐crystallographic and theoretical analysis of these P‐heteroarenes further reveal that the fusion of P−Cp moiety leads to substantial intramolecular charge‐separated features with high ylidic character values of up to 84 %. Benefitted from such dipolar structures, these P‐heteroarenes not only allows stepwise electrophilic substitution reaction for further structural π‐expansions, but also exhibit excellent nonlinear optical (NLO) responses and optical limiting (OL) performances comparable to or exceed those of C60. As a model compound, the persistent radical‐anion salt of P5a was also prepared through chemical reduction, thus offering valuable insights into the electronic structures of reduced P‐ylidic species. Our work not only established a highly efficient synthetic method toward new P‐heteroarenes, but also provide fundamental understanding of those fused‐ring ylidic P‐heterocycles with promising NLO/OL applications.
Carbon Nanotubes and Their Composites for Flexible Electrochemical Biosensors
Authors: Gazzato Luana , Frasconi Marco
Published: October 2024

Flexible biosensors play a crucial role for healthcare management and disease diagnosis. Electrochemical biosensors have attracted significant attention for wearable sensing applications owing to their numerous advantages, including high sensitivity and selectivity, inherent miniaturization and rapid response times. Challenges lie in the development of highly conductive and flexible electrodes that can be integrated with biorecognition components to engineer selective biosensor interfaces. Carbon nanotubes (CNTs) hold significant promise as materials for wearable flexible sensor fabrication. This review highlights recent strategies for fabricating conductive and flexible electrodes, whether in the form of films or fibers, based on CNTs and their composites. Additionally, the review explores emerging biosensing applications, including flexible sensors for the direct electrochemical detection of biomarkers, sensors functionalized with enzymes, antibodies, or DNA, and sensors interfaced with cells to monitor transient biochemical signals.
Role of supplier engagement to reduce Scope 3 emissions in circular supply chains
Authors: Butt Atif Saleem , Alghababsheh Mohmmad , Sindhwani Rahul , Gwalani Hema
Published: October 2024

Purchasing firms/buyers committed to driving environmental change in their supply chains must address emissions from all three scopes, particularly Scope 3 emissions. Hence, supplier engagement has emerged as a critical strategy for achieving net‐zero emissions. However, studies about how purchasing firms engage with suppliers and how such engagement mitigates Scope 3 emissions are relatively scant. This study fills this important gap in supply chain management literature. The study employs a multiple‐case study approach. Overall, 42 semi‐structured interviews with senior managers from four purchasing and four supplying firms are undertaken. The results unveil six of the best strategies that purchasing firms have deployed to effectively engage suppliers and bring them on track to reduce Scope 3 emissions. These include effective communication, building trust, providing support and guidance, using suppliers' data effectively, refining engagement programs through consistent feedback, and developing supplier incentive programs. The study offers both theoretical insights and practical implications. For instance, it suggests that effective engagement with suppliers will help suppliers mitigate Scope 3 emissions, and buyers can also overcome conflicting targets to reduce Scope 3 emission targets in procurement. The paper concludes with a discussion of limitations and suggestions for future research.
Amide Synthesis from Decarboxylative Coupling of Isocyanates and Carboxylic Acids
Authors: Wang R. , Liu W. H.
Published: October 2024

Isocyanates are versatile electrophiles that can react with a wide range of nucleophiles to afford important organic structures. Although the reactions between isocyanates and alcohols, amines and organometallic reagents have been well established, the synthesis of amides through the decarboxylative condensation of carboxylic acids and isocyanates is less appreciated. In this review, the synthesis of isocyanates and its application on amide synthesis through the condensation with carboxylic acids are summarized and discussed. It is our hope that this review will attract more attention to this less mentioned transformation and inspire new developments in the fields of organic synthesis, polymer synthesis and chemical biology.
Different treatment modalities for underexpanded stents—Effectiveness and outcomes: A practical guide
Authors: Lupu Lior , Hashim Hayder D. , Haberman Dan , Chitturi Kalyan R. , Abusnina Waiel , Chaturvedi Abhishek , Satler Lowell F. , Waksman Ron , Ben‐Dor Itsik
Published: October 2024

Underexpanded stents are a dreaded complication of percutaneous coronary intervention (PCI) and are a major predictor of stent thrombosis and in‐stent restenosis. Lesion preparation and plaque modification before stent implantation are essential to prevent stent underexpansion and optimize the technical outcomes of PCI. Once stent underexpansion occurs, the treatment options are limited. New devices for the treatment of complex calcified lesions have emerged in the past few years, and experience has accumulated with their use in the treatment of underexpanded stents. This review aims to provide an evidence‐based, practical summary of the approach to stent underexpansion, with particular attention to the expected luminal gain, complication rates, and technical nuances of various treatment options. These modalities include the ultrahigh pressure OPN noncompliant balloon, excimer laser coronary angioplasty, rotational and orbital atherectomy, and intravascular lithotripsy. The data gathered for each of these modalities and our experience in treating this complex condition were used to formulate a treatment algorithm for such cases.
Gallbladder sludge and microlithiasis disappearance in a cystic fibrosis patient 1 year after triple combination therapy initiation
Authors: Tagliati Corrado , Veri Daniele , Pietra Andrea , Lanni Giuseppe , Battista Davide , Fogante Marco , Argalia Giulio , Lanza Cecilia , Pantano Stefano , Collini Francesca , Di Sabatino Maria , Ripani Pietro
Published: October 2024

Key Clinical Message

Gallstones, microlithiasis, gallbladder sludge, and micro‐gallbladder are frequently reported in cystic fibrosis patients, and modulators could modify gallbladder disease, probably reducing biliary secretions viscosity.
Designing Sustainable Copper‐Based Hybrid Framework Catalysts for One‐Pot Multicomponent Organic Reactions
Authors: Poojita  , Sharma Vishal , Singh Virender , Mandal Tapas Kumar , Paul Avijit Kumar
Published: October 2024

The recent breakthroughs in heterogeneous catalysis emphasize the need for novel materials capable of driving organic transformations. The present study explores two copper phosphonate hybrid framework materials, 2D Cu3[(Hhedp)2(C4H4N2)].2H2O (Cu(II)Pyz‐P) and 3D Cu3[(H3hedp)2(C4H4N2)4(SO4)].2H2O (Cu(I/II)Pyz‐P), as single crystals isolated via hydrothermal synthetic strategy using H4hedp (1‐hydroxyethane 1,1‐diphosphonic acid) and N‐donor secondary ligand (Pyrazine; C4H4N2). Cu(II)Pyz‐P contains exclusively +2 oxidation state of copper, while Cu(I/II)Pyz‐P is characterized by a mixed oxidation state, where copper +2 phosphonate is embedded within the network formed by copper +1 state. Moreover, magnetic study elucidates the distinct oxidation states of both compounds by showing deviations from each other. The aforementioned compounds are exceedingly effective for catalyzing multicomponent reactions, that is, A3 coupling reaction and click reaction. Cu(I/II)Pyz‐P ensures the regioselective synthesis of triazole with high purity, while A3 coupling reaction is facilitated by both the compounds. Solvent‐ and additive‐free efficient multicomponent reactions are explored for the first time in the copper phosphonate hybrid framework structures. The present study reveals the promise of copper‐based hybrid phosphonate frameworks as durable and efficient catalysts for organic synthesis, providing cost‐effective and sustainable ways for advanced catalytic transformations.
Tuning Sb Atoms on Cu‐Based Catalysts for Electrochemical Conversion of CO2 to Syngas
Authors: Li Ke , Sun Jifei , Liu Shuang , Xu Jingwen , Shen Chunyue , Jiang Taoli , Yuan Yuan , Chuai Mingyan , Xu Yan , Liu Zaichun , Chen Wei
Published: October 2024

The electrochemical CO2RR into syngas provides an attractive way to produce raw materials for synthesizing various value‐added chemicals. However, a wide range of tunable syngas ratio of CO/H2 is hard to achieve during the electrochemical CO2 conversion process. Herein, we propose a facile electrodeposition method for the preparation of Sb modified Cu‐based catalysts with a high activity for the ratio‐tunable production of syngas. The Cu10Sb1 catalyst reaches a high FE of 71% for CO at a potential of −1.09 V versus RHE with the tunable CO/H2 ratio of syngas from ∼0.6 to ∼7.8 at the applied potentials from −0.78 V to −1.09 V. Theoretical calculations reveal the tuning effect of Sb atoms on Cu‐based catalyst for the electrochemical conversion of CO2 to syngas, in which the formation of CO on Sb modified Cu‐based catalyst possesses lower energy barrier in potential‐limiting steps during CO2RR. Meanwhile, the robust charge interaction between COOH* species and the surface of Sb modified Cu‐based catalyst enhances the activity of COOH* species, thus improving FE and current density for conversion into syngas products. This work brings a new strategy for the synthesis of low‐cost syngas catalyst and the tuning effect of metal atom on Cu‐based catalyst for CO2RR.
Micro Heat Exchanger: Design, Operation and Economics
Authors: Sohrabi Somayeh , Hajshahvaladi Leila , Ahmadzadeh Hamidreza , Ojagh Seyed Mohammad Amin , Heidarpoor Farnaz , Dana Farnaz , Sohrabi Ehsan , Moraveji Mostafa Keshavarz
Published: October 2024

Where precision is paramount in managing temperature and fluid dynamics, micro heat exchangers (MHXs) emerge as indispensable tools. This review investigates the significance of MHX technology, offering readers a comprehensive roapmap from conceptualization to market application. We dissect the nuances of material selection, shedding light on cutting‐edge advancements poised to revolutionize MHX efficiency. Furthermore, we explore how the geometry of MHX influences heat transfer dynamics and pressure drop, providing insights into enhancing the overall effectiveness. We delve into the various types of control instrumentation, offering a detailed analysis of their applicability. Beyond the technical prowess, the economic landscape plays a pivotal role in the adoption of MHX technology.
Challenges in implementation of molecular classification in early stage endometrial cancer—An NRG Oncology cooperative group mixed‐methods study
Authors: Wilson Elise M. , Huang Ruizhi , Jones Kristen D. , Hagemann Ian S. , Temkin Sarah M. , McAlpine Jessica N. , Powell Matthew A. , Kepper Maura M. , Hagemann Andrea R.
Published: October 2024

Background

Professional guidelines recommend molecular profiling for mismatch repair (MMR), p53, and polymerase epsilon (POLE) status in endometrial cancer (EC). However, adoption in the United States has not been documented, and barriers to the implementation of testing have not been described.

Methods

In this mixed‐methods study, implementation science frameworks were used to develop a quantitative survey. Gynecologic oncologists, medical oncologists, radiation oncologists, and pathologists affiliated with NRG Oncology programs were contacted through snowball sampling and were surveyed during 2022–2023. A subset of respondents was interviewed. Statistical and thematic analyses were performed.

Results

At least 403 NRG Oncology‐affiliated providers were contacted for the survey, and 107 (26.6%) responded. Greater than 90% of respondents perceived POLE, MMR, and p53 status as important for clinical care. MMR and p53 tests were perceived as easy to obtain, but only 24.2% of respondents reported that POLE testing was moderately or very easy to obtain. Respondents from academic sites reported better access to molecular classification and perceived greater importance of molecular classification compared with respondents from community sites. In thematic analysis of 13 qualitative interviews, cost concerns were reported as large barriers to testing. Interviewees reported a desire for prospective data to guide treatment selection based on classification results.

Conclusions

Although integrating molecular classification into standard pathologic reporting is recommended, and clinicians perceive molecular profiling in early stage EC as important, survey respondents noted significant implementation barriers. Implementation challenges that differ between community oncology and academic practice settings were identified. Strategies to improve equitable access to molecular classification of early stage EC are needed.
Reproductive autonomy and breastfeeding in young breast cancer survivors
Authors: Peccatori Fedro A. , Prosperi Porta Romana , Azim Hatem A.
Published: October 2024

Breastfeeding is an essential part of the maternity experience also for breast cancer survivors and time has come to include reproductive autonomy in the research agenda of health care professionals dedicated to the care of young women with breast cancer.
Converting Second‐Order Saddle Points to Transition States: New Principles for the Design of 4π Photoswitches
Authors: Mirzanejad Amir , Muechler Lukas
Published: October 2024

Molecular photoswitches have demonstrated potential for storing solar energy at the molecular level, with power densities comparable to commercial batteries and hydroelectric energy storage. However, development of efficient photoswitches is hindered by limitations in cyclability and optical properties of existing materials. We here demonstrate that certain limitations in photoswitches based on electrocyclizations stem from the issue of controlling competition between Woodward‐Hoffmann allowed and forbidden pathways. Our approach moves beyond the traditional view of activation barriers and reveals that second‐order saddle points are crucial in dictating the competition between disrotatory and conrotatory pathways. These insights suggest new opportunities to manipulate the competition between these pathways through geometric constraints, fundamentally altering the connectivity of the potential energy surface. Our study also emphasizes the necessity of multi‐reference methods and the need to conduct higher‐dimensional explorations for competing pathways beyond photoswitch design.
Alkylcyanation of Unactivated Alkenes with Protic C(sp3)−H Feedstocks via Radical‐Initiated Intramolecular Cyano Group Migration Enabled by Photoredox/Brønsted Base Dual Catalysis
Authors: Hong Yang , Deng Hong‐Ping
Published: October 2024

Cyanofunctionalization of alkenes via radical‐initiated cyano migration was a straightforward pathway to access alkyl nitriles. Herein, By the synergistic merger of photoredox catalysis and Brønsted base catalysis, a mild protocol of alkylcyanation of unactivated alkenes with protic C(sp3)−H feedstocks via intramolecular 1,4‐cyano group migration was reported. This method was enabled in an atom‐, and step‐economy manner, delivering a series of γ‐cyanoester derivatives in moderate to excellent yields.
Evolution of aberrant brain‐wide spatiotemporal dynamics of resting‐state networks in a Huntington's disease mouse model
Authors: Vasilkovska Tamara , Verschuuren Marlies , Pustina Dorian , van den Berg Monica , Van Audekerke Johan , Pintelon Isabel , Cachope Roger , De Vos Winnok H. , Van der Linden Annemie , Adhikari Mohit H. , Verhoye Marleen
Published: October 2024

Background

Huntington's disease (HD) is marked by irreversible loss of neuronal function for which currently no availability for disease‐modifying treatment exists. Advances in the understanding of disease progression can aid biomarker development, which in turn can accelerate therapeutic discovery.

Methods

We characterised the progression of altered dynamics of whole‐brain network states in the zQ175DN mouse model of HD using a dynamic functional connectivity (FC) approach to resting‐state fMRI and identified quasi‐periodic patterns (QPPs) of brain activity constituting the most prominent resting‐state networks.

Results

The occurrence of the normative QPPs, as observed in healthy controls, was reduced in the HD model as the phenotype progressed. This uncovered progressive cessation of synchronous brain activity with phenotypic progression, which is not observed with the conventional static FC approaches. To better understand the potential underlying cause of the observed changes in these brain states, we further assessed how mutant huntingtin (mHTT) protein deposition affects astrocytes and pericytes – one of the most important effectors of neurovascular coupling, along phenotypic progression. Increased cell‐type dependent mHTT deposition was observed at the age of onset of motor anomalies, in the caudate putamen, somatosensory and motor cortex, regions that are prominently involved in HD pathology as seen in humans.

Conclusion

Our findings provide meaningful insights into the development and progression of altered functional brain dynamics in this HD model and open new avenues in assessing the dynamics of whole brain states, through QPPs, in clinical HD research.

Highlights

Hyperactivity in the LCN‐linked regions within short QPPs observed before motor impairment onset.

DMLN QPP presents a progressive decrease in DMLN activity and occurrence along HD‐like phenotype development.

Breakdown of the LCN DMLN state flux at motor onset leads to a subsequent absence of the LCN DMLN QPP at an advanced HD‐like stage.
Fight, retreat, repeat: The male–male agonistic behavior in the wood‐feeding cockroach, Panesthia angustipennis spadica (Dictyoptera: Blattodea: Blaberidae)
Authors: Osaki Haruka , Nakazono Tomohiro , Yabe Kiyotaka , Takata Mamoru , Mikaelyan Aram
Published: October 2024

Competition is one of the most critical factors affecting animal behaviors. Aggressive interactions are central to acquiring resources or mating partners. Agonistic behavior is more common among males than females. Although laboratory observations of these behaviors give detailed descriptions under controlled conditions, field observations without human intervention are required because those supply information that provides insights into their function. In this paper, we report on the field observation and auxiliary laboratory experiments of male–male agonistic behavior of a wood‐feeding cockroach, Panesthia angustipennis, and discuss its strategy. In the field, a male pushed the opponent with the horn on the pronotum out of a gap between two logs, under which a female was. After pushing, the male repeatedly returned to a place close to the female, even if it did not subdue the opponent entirely. It suggests that the male–male agonistic behavior in P. angustipennis has both attack and avoidance. The bout was repeated as the ejected male reapproached the male. In contrast, the inferior male often escaped in the laboratory recording after field observation. Keeping the fighting experience for several days may contribute to the males avoiding a “losing battle.” This study significantly enhances our understanding of the mating strategy of P. angustipennis through male–male agonistic behavior and provides possibilities for its cognitive aspects from the fighting experience.
Association between clinician team segregation, receipt of cardiovascular care and outcomes in valvular heart diseases
Authors: Bolakale‐Rufai Ikeoluwapo Kendra , Knapp Shannon M. , Bisono Janina Quintero , Johnson Adedoyin , Moore Wanda , Yankah Ekow , Yee Ryan , Trabue Dalancee , Nallamothu Brahmajee , Hollingsworth John M. , Watty Stephen , Williamson Francesca , Pool Natalie , Hebdon Megan , Ezema Nneamaka , Capers Quinn , Blount Courtland , Kimbrough Nia , Johnson Denee , Evans Jalynn , Foree Brandi , Holman Anastacia , Lightbourne Karen , Brown David , Edmonds Brownsyne Tucker , Breathett Khadijah
Published: October 2024

Aims

Racial disparities exist in clinical outcomes for valvular heart disease (VHD). It is unknown whether clinician segregation contributes to these disparities. Among an adequately insured population, we evaluated the relationship between clinician segregation in a hospital and receipt of care by a cardiologist according to patient race. We also evaluated the association between clinician segregation, race and care by a cardiologist on 30‐day readmission and 1‐year survival.

Methods and results

Using Optum's Clinformatics® Data Mart Database (CDM, US commercial and Medicare beneficiaries) from 2010 to 2018, we identified patients with a primary diagnosis of VHD. Hospitals were categorized into low, medium and high segregation groups (SG), according to clinician segregation index (SI). SI can range from 0–1 (0: the ratio of Black to White patients is the same for all clinicians; 1: each clinician treats only Black or only White patients). Outcomes were analysed using generalized linear mixed effect models. Among 8649 patients [median age 75 (67–82), 45.4% female, 16.1% Black, 83.9% White], odds of care from a cardiologist did not vary across race for all SGs [Low SG adjusted odds ratio (aOR): 0.79 (95% CI: 0.58–1.08), P = 0.14; Medium SG aOR: 0.86 (95% CI: 0.60–1.25), P = 0.43; High SG aOR: 1.07 (95% CI: 0.68–1.69), P = 0.76]. Among those that received care from a cardiologist, there was no difference in the 30‐day readmission between Black and White patients across SGs [Low SG aOR: 1.05 (95% CI: 0.83–1.31), P = 0.70; Medium SG aOR: 1.22 (95% CI: 0.92–1.61), P = 0.17; High SG aOR: 0.81 (95% CI: 0.57–1.17), P = 0.27]. Among patients that did not receive care from a cardiologist, Black patients in low SG had higher odds of 30‐day readmission compared to White patients [aOR: 2.74 (95%CI:1.38–5.43), P < 0.01]. Odds of 1‐year survival were similar across race for all SG irrespective of receipt of care from a cardiologist [seen by a cardiologist: Low SG aOR: 1.13 (95% CI: 0.86–1.48), P = 0.38; Medium SG aOR: 0.83 (95% CI: 0.59–1.17), P = 0.29; High SG aOR: 1.01 (95% CI: 0.66–1.52), P = 0.98; not seen by a cardiologist: Low SG aOR: 0.56 (95% CI: 0.23–1.34), P = 0.19; Medium SG aOR: 0.81 (95% CI: 0.28–2.37), P = 0.70; High SG aOR: 0.63 (95% CI: 0.23–1.74), P = 0.37].

Conclusions

Among an insured population, race was not associated with care by a cardiologist for VHD or survival. Black patients not seen by cardiologists had higher odds of 30‐day readmission in low clinician SG.
Assembly of Thiazino[3,4‐a]Isoquinoline and Thiazepino[5,4‐a]Isoquinoline Frameworks from Isoquinolinium 1,4‐Zwitterionic Thiolates Through [5+1] and [5+2] Cycloaddition Reactions
Authors: Wang Ji‐Yun , Wang Yu‐Ting , Zou Xiao , Chen Xi , Yan Sheng‐Hu , Zhang Yue , Shen Jie‐Fa , Zuo Hang‐Dong
Published: October 2024

Two cycloaddition modes of isoquinolinium 1,4‐zwitterionic thiolates have been established. Upon choosing α‐bromo ketones as the counterpart, a range of isoquinoline‐fused thiazines can be attained with yields ranging from moderate to excellent through a formal [5+1] reaction pathway, exhibiting remarkable substrate adaptability and resilience to diverse functional groups. Additionally, a library of unprecedented thiazepino[5,4‐a]isoquinolines, a novel category of seven‐membered heterocycles, has been synthesized via a [5+2] pathway utilizing acetylenedicarboxylate as the reactive component. Notably, this reaction process stands out for its exceptional 100 % atomic utilization efficiency.
Gilding the Lily: Studies on the Effects of Successive Loading of Light Energy‐Storing Molecules with Norbornadiene Units
Authors: Schulte Robin , Schade Dustin , Paululat Thomas , Ihmels Heiko
Published: October 2024

The photochromic norbornadiene‐quadricyclane cycle has emerged as a promising basis for molecular solar thermal (MOST) energy storage. In this context, it has been established that multifunctional photoswitches with several norbornadiene units at one central aromatic core have favorable photochemical properties and storage capacities. Nevertheless, a maximum number of three norbornadiene units has been combined in one molecule, so far. In this work, scope and limits of this approach should be further assessed. Thus, exemplary polyfunctionalized derivatives have been synthesized by Suzuki‐Miyaura reactions, and their suitability for MOST applications was investigated. These compounds were converted into the corresponding quadricyclanes by direct UV irradiation (λex=315 nm) with moderate quantum yields, whereas the reaction is more efficient upon irradiation with λex=520 nm in the presence of photosensitizers. But these molecules showed low stabilities and short half‐lives of 1 to 2 days. Moreover, the photochemical reaction is hampered by the close vicinity of photoactive units. Therefore, it appears that in such assemblies, a maximum number of three norbornadiene units is the limit to keep the optimal balance of photochemical properties required for MOST applications.
Advancements in Graphite Anodes for Lithium‐Ion and Sodium‐Ion Batteries: A Review
Authors: Xiong Kai , Qi Tianshuang , Zhang Xiong
Published: October 2024

Amidst the escalating global energy demand and the rapid advancement of renewable energy technologies, battery technology plays an indispensable role in energy storage. As a crucial anode material, Graphite enhances performance with significant economic and environmental benefits. This review provides an overview of recent advancements in the modification techniques for graphite materials utilized in lithium‐ion and sodium‐ion batteries. This review initially presents various modification approaches for graphite materials in lithium‐ion batteries, such as electrolyte modification, interfacial engineering, purification and morphological modification, composite modification, surface modification, and structural modification, while also addressing the applications and challenges of graphite anode materials in this context. Subsequently, it focuses on the modification methods for graphite anode materials in sodium‐ion batteries, including composite material modification, electrolyte optimization, surface modification, and structural modification, along with their respective applications and challenges. It then compares the modification strategies across different battery systems and proposes innovative modification methods and alternative materials for future graphite anode materials to further enhance their performance in batteries. Finally, the review concludes with a summary of the significance of researching graphite anode material modifications and offers perspectives on future developments.
Patient and carer feedback and engagement with ECHOMANTRA, a digital guided intervention for anorexia nervosa
Authors: Cardi Valentina , Rowlands Katie , Ambwani Suman , Macdonald Pamela , Arcelus Jon , Schmidt Ulrike , Treasure Janet
Published: October 2024

Objective

We developed ECHOMANTRA, a digital guided intervention for patients with anorexia nervosa and their carers to provide support during transition from inpatient care to community settings. This study reports on participants' engagement with, and feedback of, ECHOMANTRA.

Method

Patients and carers (N = 184 dyads) were given access to ECHOMANTRA for 12 months. The intervention included online groups, a workbook and recovery‐oriented videoclips. Satisfactory engagement was defined as attendance of a minimum of four online groups by each dyad. Participants received an Intervention Feedback Form to measure frequency of use and provide feedback of the intervention. Those who did not meet the engagement criterion were asked to complete an Obstacles to Engagement Form.

Results

19% of the sample reached the engagement criterion. Seventy‐six patients and 60 carers completed the Intervention Feedback Form. Of those, approximately 60% reported using at least a quarter of the workbook and videoclips. Overall, participants found the materials useful and easy to access (median = 3 on a scale 1–5). Obstacles to engagement (35 patients and 14 carers) included lack of time due to caring responsibilities, treatment, work/school commitments.

Conclusion

A more personalised form of support may be needed to enhance motivation and ability to change following inpatient care.
Evaluating Models of the Ageing BOLD Response
Authors: Henson R. N. , Olszowy W. , Tsvetanov K. A. , Yadav P. S. ,   Cam‐CAN, Zeidman P.
Published: October 2024

Neural activity cannot be directly observed using fMRI; rather it must be inferred from the hemodynamic responses that neural activity causes. Solving this inverse problem is made possible through the use of forward models, which generate predicted hemodynamic responses given hypothesised underlying neural activity. Commonly‐used hemodynamic models were developed to explain data from healthy young participants; however, studies of ageing and dementia are increasingly shifting the focus toward elderly populations. We evaluated the validity of a range of hemodynamic models across the healthy adult lifespan: from basis sets for the linear convolution models commonly used to analyse fMRI studies, to more advanced models including nonlinear fitting of a parameterised hemodynamic response function (HRF) and nonlinear fitting of a biophysical generative model (hemodynamic modelling, HDM). Using an exceptionally large sample of participants, and a sensorimotor task optimized for detecting the shape of the BOLD response to brief stimulation, we first characterised the effects of age on descriptive features of the response (e.g., peak amplitude and latency). We then compared these to features from more complex nonlinear models, fit to four regions of interest engaged by the task, namely left auditory cortex, bilateral visual cortex, left (contralateral) motor cortex and right (ipsilateral) motor cortex. Finally, we validated the extent to which parameter estimates from these models have predictive validity, in terms of how well they predict age in cross‐validated multiple regression. We conclude that age‐related differences in the BOLD response can be captured effectively by models with three free parameters. Furthermore, we show that biophysical models like the HDM have predictive validity comparable to more common models, while additionally providing insights into underlying mechanisms, which go beyond descriptive features like peak amplitude or latency, and include estimation of nonlinear effects. Here, the HDM revealed that most of the effects of age on the BOLD response could be explained by an increased rate of vasoactive signal decay and decreased transit rate of blood, rather than changes in neural activity per se. However, in the absence of other types of neural/hemodynamic data, unique interpretation of HDM parameters is difficult from fMRI data alone, and some brain regions in some tasks (e.g., ipsilateral motor cortex) can show responses that are more difficult to capture using current models.
Potential of constructing all‐encompassing soil–plant‐atmosphere‐continuum stations and datasets from meteorological, flux, soil moisture station networks and plant‐relevant observations
Authors: Shi Haiyang
Published: October 2024

The establishment of SPAC (soil–plant‐atmosphere continuum) stations is essential for comprehensive monitoring of land‐atmosphere interactions and ecological and hydrological processes. This paper addresses the critical limitations of existing observation networks, which often rely on single‐aspect observations, resulting in insufficient data for a holistic understanding of SPAC dynamics. Specifically, SPAC stations provide critical multi‐variable observations that enhance process‐based model calibration and physical constraints and improve the empirical basis of data‐driven models. Advanced technologies such as machine learning and remote sensing are proposed to transform current weather and soil moisture stations into quasi‐SPAC sites capable of estimating carbon and water flux data. Additionally, the strategic placement of new SPAC sites in regions projected to be sensitive to future climate change and climate risks, as indicated by models such as CMIP6, is recommended. Furthermore, promoting comprehensive observational systems like Europe's Integrated Carbon Observation System (ICOS) in other regions, establishing a unified management framework and coordinating the upgrading of existing global observation networks are essential steps. Ultimately, the proposed enhancements will advance global ecological and hydrological studies, providing a more integrated and accurate understanding of the SPAC system and its responses to climate variability.
Drivers and Buffers of Stream Flashiness in the Mid‐Atlantic United States
Authors: Hurley Rachel , Brandes David , Kelleher Christa
Published: October 2024

Flashiness is a hydrologic signature used to describe the responsiveness of streamflow to precipitation. In practise, flashiness has most often been correlated with rainfall intensity and the presence of urban land cover or imperviousness. However, a number of watershed characteristics can influence flashiness, necessitating further investigation of how this particular watershed behaviour and its associated drivers vary at regional scales. We investigated how ten measurable watershed characteristics are empirically related to flashiness of 195 gauged streams in the Mid‐Atlantic region using linear regression analysis. The selected gauges had drainage areas ranging in size from 15 to 250 km2. To explore multiple quantifications of flashiness, we determined both the Richards‐Baker flashiness index, calculated from the continuous hydrograph, and number of peaks‐over‐threshold, for all watersheds for a 10‐year period. As found in other studies, the percentage of watershed development was strongly correlated with stream flashiness, though significant inverse relationships also existed for forest cover, water and wetlands and carbonate geology. Differences in flashiness values between rural and suburban watersheds were not significant, with a significant increase in flashiness (p < 0.01) occurring at 80% development or ~ 25% imperviousness. In addition, we found significant differences in relationships between watershed characteristics and flashiness when differentiated by physiographic regions. For the study area and each of its five physiographic sub‐regions, we identified the four most important predictors through multiple regression. The overall mid‐Atlantic model suggested that development, wetlands and compactness ratio as the most important predictors (adj R2 = 0.57). Significant predictors of stream flashiness varied among regions; however, wetlands served as a significant buffer of flashiness in four of five sub‐regions demonstrating the importance of wetlands in modulating flash‐flooding. In all physiographic regions, empirical models of flashiness values outperformed the Mid‐Atlantic regional model, underscoring the value of local landscape characteristics in augmenting or modulating flashy watershed responses. Our findings suggest the potential for improvements to operational flash‐flood forecasting using hydrologic characteristics of the landscape.
Idea of macro‐scale and micro‐scale prestressed ceramics
Authors: Gu Junfeng , Fu Shuai , Ping Hang , Ji Wei , Zou Ji , Wang Hao , Wang Weimin , Zhang Fan , Liu Hanxing , Fu Zhengyi
Published: October 2024

The brittleness of ceramics restricts their engineering application. Prestressing is promising to solve the problem, yet still lacks enough attention and extensive investigation. This work proposes the idea of macro‐scale and micro‐scale prestressed ceramics: to form compressive prestress in macro‐ or micro‐scale range in the ceramics by designed additional force, which offsets the fracture stress at the crack tips, then enhances the strength of ceramics. The macro‐scale prestressed ceramic has a designed long‐range ordering stress distribution in a large scale, similar to the reinforced concrete and tempered glass. The micro‐scale ceramic has a designed short‐range ordered stress distribution, similar to that in the natural biomaterials. Strategies constructing the macro‐scale and micro‐scale prestressed ceramics are planned. Future research interests and challenges are prospected for developing the mechanical properties of ceramics.