bluuebunny/crossref_metadata_2025 huggingface dataset:
Intelligent Stress‐Adaptive Binder Enabled by Shear‐Thickening Property for Silicon Electrodes of Lithium‐Ion Batteries
Authors: Kwon Ohhyun , Kim Tae Yong , Kim Taewon , Kang Jihyeon , Jang Seohyeon , Eom Hojong , Choi Seyoung , Shin Junhyeop , Park Jongkwon , Seol Myeong‐Lok , Han Jeong Woo , Park Soomin , Lee Hyun‐Wook , Nam Inho
Published: April 2024

Elastic binders with supramolecular interactions are widely explored to mitigate the stress caused by the volume expansion of electrode materials, such as Si, S, or Li metals, in next‐generation secondary batteries. Herein, a new class of elastic binders is proposed with an automatic stress‐control mechanism capable of responding in real time to dynamic local stress variations. Specifically, this study focuses on the shear‐thickening behavior, wherein polymers automatically amplify their viscoelasticity in response to local shear‐stress changes. To realize an intelligent stress‐adaptive binder, starch analogs exhibiting shear‐thickening properties and unique crystallinity are employed as binders for highly expandable Si anodes. The shear‐thickening mechanism is comprehensively investigated using deep‐learning‐based molecular dynamics (MD) simulations and in situ transmission electron microscopy (TEM) analysis, which determines the optimal conditions for effectively limiting dynamic local surface expansion. Among the starch analogs, the amylose and long‐chain amylopectin (AMLAP) binder demonstrates improved high‐rate capability (1710 mAh g−1 at 5 C) and superior reversible capacity (2025 and 1493 mAh g−1 after 100 and 500 cycles, respectively, at 1 C) with optimal shear‐thickening properties. Furthermore, AMLAP exhibits favorable characteristics for affordable large‐scale production. Hence, this study clearly demonstrates that the shear‐thickening properties of binders can be considered a new factor in fabricating stable electrodes with extremely expandable materials.
Translocation and Confinement of Tetraamines in Adaptable Microporous Cavities
Authors: Rubio‐Gaspar Ana , Misturini Alechania , Millan Reisel , Almora‐Barrios Neyvis , Tatay Sergio , Bon Volodymyr , Bonneau Mickaele , Guillerm Vincent , Eddaoudi Mohamed , Navalón Sergio , Kaskel Stefan , Armentano Donatella , Martí‐Gastaldo Carlos
Published: April 2024

Metal‐Organic Frameworks can be grafted with amines by coordination to metal vacancies to create amine‐appended solid adsorbents, which are being considered as an alternative to using aqueous amine solutions for CO2 capture. In this study, we propose an alternative mechanism that does not rely on the use of neutral metal vacancies as binding sites but is enabled by the structural adaptability of heterobimetallic Ti2Ca2 clusters. The combination of hard (Ti4+) and soft (Ca2+) metal centers in the inorganic nodes of the framework enables MUV‐10 to adapt its pore windows to the presence of triethylenetetramine molecules. This dynamic cluster response facilitates the translocation and binding of tetraamine inside the microporous cavities to enable the formation of bis‐coordinate adducts that are stable in water. The extension of this grafting concept from MUV‐10 to larger cavities not restrictive to CO2 diffusion will complement other strategies available for the design of molecular sorbents for decarbonization applications.
Dehydration‐Induced Cluster Consolidation in a Metal‐Organic Framework for Sieving Hexane Isomers
Authors: Jiang Zhi‐Jie , Wang Ying , Luo Dong , Wei Rong‐Jia , Lu Weigang , Li Dan
Published: April 2024

Metal‐organic frameworks (MOFs) that exhibit dynamic phase‐transition behavior under external stimuli could have great potential in adsorptive separations. Here we report on a zinc‐based microporous MOF (JNU‐80) and its reversible transformation between two crystalline phases: large pore (JNU‐80‐LP) and narrow pore (JNU‐80‐NP). Specifically, JNU‐80‐LP can undergo a dehydration‐induced cluster consolidation under heat treatment, resulting in JNU‐80‐NP with a reduced channel that allows exclusion of di‐branched hexane isomers while high adsorption of linear and mono‐branched hexane isomers. We further demonstrate the fabrication of MOF‐polymer composite (JNU‐80‐NP‐block) and its application in the purification of di‐branched isomers from liquid‐phase hexane mixtures (98 % di‐branched) at room temperature, affording the di‐branched hexane isomers with 99.5 % purity and close to 90 % recovery rate over ten cycles. This work illustrates an interesting dehydration‐induced cluster consolidation in MOF structure and the ensuing channel shrinkage for sieving di‐branched hexane isomers, which may have important implications for the development of MOFs with dynamic behavior and their potential applications in non‐thermal driven separation technologies.
Lithium Pre‐Storage Enables High Initial Coulombic Efficiency and Stable Lithium‐Enriched Silicon/Graphite Anode
Authors: Gao Ying‐Jie , Cui Cheng‐Hao , Huang Zhi‐Kun , Pan Guo‐Yu , Gu Yuan‐Fan , Yang Ya‐Nan , Bai Fan , Sun Zhuang , Zhang Tao
Published: April 2024

Application of silicon‐based anodes is significantly challenged by low initial Coulombic efficiency (ICE) and poor cyclability. Traditional pre‐lithiation reagents often pose safety concerns due to their unstable chemical nature. Achieving a balance between water‐stability and high ICE in prelithiated silicon is a critical issue. Here, we present a lithium‐enriched silicon/graphite material with an ultra‐high ICE of ≥110 % through a high‐stable lithium pre‐storage methodology. Lithium pre‐storage prepared a nano‐drilled graphite material with surficial lithium functional groups, which can form chemical bonds with adjacent silicon during high‐temperature sintering. This results in an unexpected O−Li−Si interaction, leading to in situ pre‐lithiation of silicon nanoparticles and providing high stability in air and water. Additionally, the lithium‐enriched silicon/graphite materials impart a combination of high ICE, high specific capacity (620 mAh g−1), and long cycling stability (>400 cycles). This study opens up a promising avenue for highly air‐ and water‐stable silicon anode prelithiation methods.
Boron‐Catalyzed C1 Copolymerization of Arsonium and Sulfoxonium Ylides toward Unrepresented Structures and Fluorescence Properties
Authors: Zhou Mingtao , Hadjichristidis Nikos
Published: April 2024

The first synthesis of well‐defined poly(methylene‐co‐1,1‐diphenylpropenenylene) (C1‐co‐C1’), equivalent to poly(ethylene‐co‐diphenylbutadiene) copolymers was accomplished by C1 copolymerization of novel diphenylpropenyl triphenyl arsonium ylides (Ph2AY) and dimethylsulfoxonium methylide (Me2SY) using B‐thexylborepane as initiator. All polymerization conditions, including feed ratio, temperature, and reaction time, were optimized. A series of photoluminescent poly(ethylene‐co‐diphenylbutadiene)s were synthesized at different feed ratios, opening a new synthetic horizon for poly(ethylene‐co‐disubstitutedbutadiene) copolymers. Notably, a new C1 segment, arising from a double bond rearrangement, was confirmed by NMR, resulting in an unprecedented two‐monomer three‐structure random terpolymer. An unexpected red‐shift phenomenon in the fluorescence spectra was observed with increasing the ratio of Ph2AY in the copolymer. This shift is attributed to the aggregation of diphenylbutadiene segment, similar to through‐space conjugation (TSC), likely induced by a decrease in the crystallinity of copolymers. Furthermore, another disubstituted allylic triphenyl arsonium ylides, (E)‐2‐phenylbutenyl triphenyl arsonium ylide (MePhAY) was also synthesized and investigated. These additional compounds expand the knowledge and the potential applications of such copolymerization techniques in advanced materials.
Enhancing Ion Adsorption Capability through the Strong Interaction in Co9S8‐Carbon Hybrids Achieves Superior Sodium Ion Storage
Authors: Ma Xinyi , He Xiaoyue , Yu Lai , Ahmad Nazir , Tao Zongzhi , Jiang Zi Xuan , Liang Jia Cheng , Zeng Suyuan , Shi Liang , Zhang Genqiang
Published: April 2024

Metal sulfides materials are promising anode candidates for Na+ storage due to their low cost and high theoretical capacity, while the complex phase transition and inevitable volume expansion during cycling restrain their practical applications. Herein, a simple one‐pot manipulation strategy was designed to construct Co9S8 nanoparticles strongly encapsulated in carbon nanotubes (Co9S8@C/NTs) composite structure with enhanced structural stability and reaction kinetics, resulting in greatly improved Na+ storage performance. Specifically, the obtained Co9S8@C/NTs could exhibit a remarkable capacity of 500 mAh g−1 at 0.5 A g−1 after 100 cycles and exceptional cycling stability over 600 cycles with 88 % capacity retention at 1 A g−1. Furthermore, the theoretical calculations combined with systematic characterizations confirm that the strong interaction between Co9S8 and the carbon matrix could greatly enhance the Na+ adsorption ability and facilitate the electron transfer dynamics for superior Na+ storage capability. More importantly, the full cell device can deliver an outstanding energy density of 144.32 Wh kg−1 and a decent cycling life with 82 % capacity retention of almost 100 cycles at 0.1 A g−1. This work could provide more valuable insights for designing advanced metal sulfide nanocomposites and demonstrate fascinating prospects for commercial application.
The normative values of pain thresholds in healthy Taiwanese
Authors: Pan Li‐Ling Hope , Ling Yu‐Hsiang , Lai Kuan‐Lin , Wang Yen‐Feng , Hsiao Fu‐Jung , Chen Shih‐Pin , Liu Hung‐Yu , Chen Wei‐Ta , Wang Shuu‐Jiun
Published: April 2024

Objective

Quantitative sensory testing is widely used in clinical and research settings to assess the sensory functions of healthy subjects and patients. It is of importance to establish normative values in a healthy population to provide reference for studies involving patients. Given the absence of normative values for pain thresholds in Taiwan, the aim of this study was to report the normative values for future reference in the Taiwanese population and compare the differences between male and female participants.

Methods

Healthy adults without any chronic or acute pain condition were recruited. The pain thresholds were assessed over the cephalic (supraorbital area and masseter muscle) and extracephalic (medio‐volar forearm and thenar eminence) areas. The heat, cold, mechanical punctate, and pressure pain thresholds were measured with a standardized protocol. Comparisons between male and female participants were performed.

Results

One hundred and thirty healthy participants (55 males: 30.4 ± 7.4 years; 75 females: 30.5 ± 8.1 years) finished the assessments. Male participants were less sensitive to mechanical stimuli, including pressure over masseter muscle (male vs. female: 178.5 ± 56.7 vs. 156.6 ± 58.4 kPa, p = .034) and punctate over medio‐volar forearm (male vs. female: 116.4 ± 45.2 vs. 98.7 ± 65.4 g, p = .011), compared to female participants. However, female participants were less sensitive to cold stimuli, indicated by lower cold pain thresholds over the supraorbital area (male vs. female: 18.6 ± 8.4 vs. 13.6 ± 9.3°C, p = .004), compared to male participants. No significant differences were found between sexes in other pain threshold parameters.

Conclusions

We provided the normative values of healthy male and female adults in Taiwan. This information is crucial for comparison in future pain‐related studies to identify potential hypoalgesia or hyperalgesia of tested subjects.
5Z‐7‐Oxozaenol attenuates cuprizone‐induced demyelination in mice through microglia polarization regulation
Authors: Chen Shiyu , Liu Siyao , Huang Yalun , Huang Shiwen , Zhang Wanzhou , Xie Huifang , Lu Lingli
Published: April 2024

Introduction

Demyelination is a key factor in axonal degeneration and neural loss, leading to disability in multiple sclerosis (MS) patients. Transforming growth factor beta activated kinase 1 (TAK1) is a critical molecule involved in immune and inflammatory signaling pathways. Knockout of microglia TAK1 can inhibit autoimmune inflammation of the brain and spinal cord and improve the outcome of MS. However, it is unclear whether inhibiting TAK1 can alleviate demyelination.

Methods

Eight‐week‐old male c57bl/6j mice were randomly divided into five groups: (a) the control group, (b) the group treated with cuprizone (CPZ) only, (c) the group treated with 5Z‐7‐Oxozaenol (OZ) only, and (d) the group treated with both cuprizone and 15 μg/30 μg OZ. Demyelination in the mice of this study was induced by administration of CPZ (ig) at a daily dose of 400 mg/kg for consecutive 5 weeks. OZ was intraperitoneally administered at mentioned doses twice a week, starting from week 3 after beginning cuprizone treatment. Histology, rotarod test, grasping test, pole test, Western blot, RT‐PCR, and ELISA were used to evaluate corpus callosum demyelination, behavioral impairment, oligodendrocyte differentiation, TAK1 signaling pathway expression, microglia, and related cytokines.

Results

Our results demonstrated that OZ protected against myelin loss and behavior impairment caused by CPZ. Additionally, OZ rescued the loss of oligodendrocytes in CPZ‐induced mice. OZ inhibited the activation of JNK, p65, and p38 pathways, transformed M1 polarized microglia into M2 phenotype, and increased brain‐derived neurotrophic factor (BDNF) expression to attenuate demyelination in CPZ‐treated mice. Furthermore, OZ reduced the expression of proinflammatory cytokines and increases anti‐inflammatory cytokines in CPZ‐treated mice.

Conclusion

These findings suggest that inhibiting TAK1 may be an effective approach for treating demyelinating diseases.
Pharmaceutical proteins at the interfaces and the role of albumin
Authors: Velankar Ketki Y. , Gawalt Ellen S. , Wen Yi , Meng Wilson S.
Published: April 2024

A critical measure of the quality of pharmaceutical proteins is the preservation of native conformations of the active pharmaceutical ingredients. Denaturation of the active proteins in any step before administration into patients could lead to loss of potency and/or aggregation, which is associated with an increased risk of immunogenicity of the products. Interfacial stress enhances protein instability as their adsorption to the air‐liquid and liquid–solid interfaces are implicated in the formation of denatured proteins and aggregates. While excipients in protein formulations have been employed to reduce the risk of aggregation, the roles of albumin as a stabilizer have not been reviewed from practical and theoretical standpoints. The amphiphilic nature of albumin makes it accumulate at the interfaces. In this review, we aim to bridge the knowledge gap between interfacial instability and the influence of albumin as a surface‐active excipient in the context of reducing the immunogenicity risk of protein formulations.
Review of patient‐reported outcomes (PROs) and non‐PROs in randomized controlled trials addressing head/neck cancers
Authors: Gode Michelle , Faggion Clovis Mariano
Published: April 2024

Background

To assess the frequency of patient‐reported outcomes (PROs) and non‐PROs in randomized controlled trials (RCTs) addressing head/neck cancers.

Methods

We included RCTs about interventions to treat head/neck cancers. PubMed was searched on September 16, 2022 and included studies published during three periods (2000–2002, 2010–2012, and 2020–2022). Data on types of outcomes and instruments to measure them were extracted and organized into PROs and non‐PROs, and temporal trends for reporting outcomes were determined.

Results

There was a reduction in the frequency of non‐PROs (40% to 22%) and an increase in PROs (5% to 19%) over 20 years. The frequency of reporting both non‐PROs and PROs seemed to be stable over the same period (55% to 58%). A great variety of instruments to measure PROs and non‐PROs was identified.

Conclusions

There has been a growth in the types of PROs in more recent years, and they were more frequently reported in RCTs. However, head/neck cancer trials with a combination of PROs and non‐PROs were the most prevalent.
Soft and hard tissue evaluation of guided socket shield implant cases
Authors: Trejo Pedro M. , Rivas Raysa , Trejo Corletta C. , Min Seiko , Nishikawa Arisa
Published: April 2024

Background

The socket‐shield (SS) technique results in long‐term functional osseo‐ and dento‐integration, preserving the dimensional stability of hard and soft tissues over time. This study aimed to describe the successful implementation of a surgical technique to facilitate “SS” cases.

Methods

The cases included males and females aged 32–81 years consecutively treated between 2020 and 2023 (longest follow‐up, 3.5 years). For each case, pre‐ and post‐operative cone‐beam computed tomography (Digital Imaging and Communications in Medicine files) and intraoral optical scans (IOS; STL files) were performed. Digital immediate implant placement and simultaneous tooth extraction and SS production were planned using an implant planning software. Implants were planned considering sagittal‐ridge and tooth‐root angular‐configuration. Surgical guides were used to perform the digitally‐supported SS technique. All cases were planned and surgically performed by one operator (Pedro M. Trejo). Preoperative digital IOS‐models were superimposed to post‐operative models to assess soft‐tissue changes. Pre and post sagittal views were used to assess the radiographic buccal‐plate thickness at various healing times. An investigator not involved with case planning or treatment performed measurements.

Results

Results reflected soft‐tissue stability with minimal mean thickness change at 0‐, 1‐, 2‐, and 3‐mm measurement levels of 0.03, ‐0.2, 0.14, ‐0.07, and 0.04 mm, respectively, with a mean gingival‐margin change of 0.04 mm. The free gingival‐margin change ranged from a 0.58‐mm gain in height to a ‐0.57‐mm loss. The mean radiographic buccal‐plate thickness post‐operatively was 2.04 mm (range, 0.7–2.9 mm).

Conclusion

The digitally‐supported guided SS technique enables predictable immediate implant‐placement positions and stable buccal peri‐implant soft and hard tissues over time.

Key Points

Why are these cases new information?

The uniqueness of the surgical technique described herein is that it results in favorable positions of immediate, socket‐shielded (SSed), implant placements, with soft‐ and hard‐tissue stability as the byproduct.

What are the keys to successful management of these cases?

Digitally, plan for the best possible implant position within the alveolar housing to satisfy prosthetic requirements, and then adjust this position to accommodate the socket shield dimensions.

Digitally, provide a space/gap between the future dentinal shield and the implant.

Clinically, allow for time to carve the final position and dimensions of the shield. Plan ahead the extent of the apical third of the SS, and the removal of the apex, if dealing with a long root.

What are the primary limitations to success in these cases?

Inadequate use of digital technology; case‐sensitive technique requires proper execution of each digital and technical clinical step.
Enterolyin S, a Polythiazole‐containing Hemolytic Peptide from Enterococcus caccae
Authors: Shi Chengyou , Patel Varshal A. , Mitchell Douglas A. , Zhao Huimin
Published: April 2024

The β‐hemolytic factor streptolysin S (SLS) is an important linear azol(in)e‐containing peptide (LAP) that contributes significantly to the virulence of Streptococcus pyogenes. Despite its discovery 85 years ago, SLS has evaded structural characterizing owing to its notoriously problematic physicochemical properties. Here, we report the discovery and characterization of a structurally analogous hemolytic peptide from Enterococcus caccae, termed enterolysin S (ELS). Through heterologous expression, site‐directed mutagenesis, chemoselective modification, and high‐resolution mass spectrometry, we found that ELS contains an intriguing contiguous octathiazole moiety. The discovery of ELS expands our knowledge of hemolytic LAPs by adding a new member to this virulence‐promoting family of modified peptides.
In Situ Formation of Suspended Graphene Windows for Lab‐Based XPS in Liquid and Gas Environments
Authors: Jones Elizabeth S. , Drivas Charalampos , Gibson Joshua S. , Swallow Jack E. N. , Jones Leanne A. H. , Bricknell Thomas D. J. , van Spronsen Matthijs A. , Held Georg , Isaacs Mark A. , Parlett Christopher M. A. , Weatherup Robert S.
Published: April 2024

Environmental cells sealed with photoelectron‐transparent graphene windows are promising for extending X‐ray photoelectron spectroscopy (XPS) to liquid and high‐pressure gas environments for in situ and operando studies. However, the reliable production of graphene windows that are sufficiently leak‐tight for extended measurements remains a challenge. Here we demonstrate a PDMS/Au(100 nm)‐supported transfer method that reliably produces suspended graphene on perforated silicon nitride membranes without significant contamination. A yield of ~95 % is achieved based on single‐layer graphene covering >98 % of the holes in the silicon nitride membrane. Even higher coverages are achieved for stacked bilayer graphene, allowing wet etching (aqueous KI/I2) of the Au support to be observed in a conventional lab‐based XPS system, thereby demonstrating the in situ formation of leak‐tight, suspended graphene windows. Furthermore, these windows allow gas‐phase measurements at close to atmospheric pressure, showing future promise for XPS under higher‐pressure gas environments in conventional lab‐based systems.
Efficient Alkaline Water Oxidation Electrocatalysis Enabled via the Modulation of Sn‐Containing Anions towards NiFe Oxyhydroxide
Authors: Xu Jiaxin , Yang Ruotao , Hou Tianjue , Chen Jinxin , Yang Hongyuan , Menezes Prashanth W. , Chen Ziliang
Published: April 2024

Despite being considered as efficient non‐noble metal‐based electrocatalysts for alkaline oxygen evolution reaction (OER), NiFe (oxy)hydroxides (NiFeOxHy) typically fall short of meeting practical requirements. To address this challenge, herein, we introduce a facile in situ electrochemical incorporation technique to form Sn‐doped NiFe‐layered double hydroxide (NiFeSn‐LDH) precatalysts. Subsequently, under the alkaline OER process, the precatalyst evolves into stannate ion‐adsorbed NiFe oxyhydroxides (NiFeOOH). The presence of these stable stannate oxyanions plays a key role in mitigating Fe leaching, optimizing the electronic structure of NiFeOOH, and improving its reaction kinetics, thereby significantly enhancing alkaline OER performance. Notably, the nickel foam‐supported NiFeSn‐LDH demonstrates impressive results delivering a large current density of 100 mA cm−2 at an overpotential as low as ~260 mV and maintaining the industrial‐relevant ~500 mA cm−2 current density over 5 days with negligible activity decay, surpassing the performances of most of the transition metal‐based electrocatalysts. Comprehensive advanced characterizations of the precatalysts, before and after the OER reactions, have been performed to uncover stable residual stannate ions at the surface of NiFeOxHy and to determine their pivotal role in promoting alkaline OER.
Application of time‐space neighborhood standardization technology to complex multi‐stage process fault detection
Authors: Feng Liwei , Guo Shaofeng , Wu Yifei , Xing Yu , Li Yuan
Published: April 2024

To solve the problem that the multi‐stage process with dynamicity and nonlinear is hard to monitor effectively, the time‐space neighborhood standardization (TSNS) method is proposed, which is further applied to partial least squares (PLS) to propose TSNS and PLS (TSNS‐PLS) method for process fault detection. TSNS can transform multi‐stage data into single‐stage data that approximately obeys a standard normal distribution, remove temporal correlation between samples at previous and subsequent moments in the process data, and separate online fault samples. TSNS makes the transformed process data satisfy the requirements of the PLS method for process data and can significantly improve the fault detection rate of the PLS method. Finally, the performance of TSNS‐PLS was examined by a numerical simulation process and the penicillin fermentation process design fault detection experiment.
A Case‐Study on the Photophysics of Chalcogen‐Substituted Zinc(II) Phthalocyanines
Authors: Ezquerra Riega Sergio D. , Gutierrez Suburu Matías E. , Rodríguez Hernán B. , Lantaño Beatriz , Kleinschmidt Martin , Marian Christel M. , Strassert Cristian A.
Published: April 2024

Singlet dioxygen has been widely applied in different disciplines such as medicine (photodynamic therapy or blood sterilization), remediation (wastewater treatment) or industrial processes (fine chemicals synthesis). Particularly, it can be conveniently generated by energy transfer between a photosensitizer's triplet state and triplet dioxygen upon irradiation with visible light. Among the best photosensitizers, substituted zinc(II) phthalocyanines are prominent due to their excellent photophysical properties, which can be tuned by structural modifications, such as halogen‐ and chalcogen‐atom substitution. These patterns allow for the enhancement of spin‐orbit coupling, commonly attributed to the heavy atom effect, which correlates with the atomic number (
) and the spin‐orbit coupling constant (
) of the introduced heteroatom. Herein, a fully systematic analysis of the effect exerted by chalcogen atoms on the photophysical characteristics (absorption and fluorescence properties, lifetimes and singlet dioxygen photogeneration), involving 30 custom‐made β‐tetrasubstituted chalcogen‐bearing zinc(II) phthalocyanines is described and evaluated regarding the heavy atom effect. Besides, the intersystem crossing rate constants are estimated by several independent methods and a quantitative profile of the heavy atom is provided by using linear correlations between relative intersystem crossing rates and relative atomic numbers. Good linear trends for both intersystem crossing rates (S1‐T1 and T1‐S0) were obtained, with a dependency on the atomic number and the spin‐orbit coupling constant scaling as
and
, respectively The trend shows to be independent of the solvent and temperature.
TEMPO/O2 Synergistically Mediated BiBrO‐Photocatalyzed Decarboxylative Phosphorylation of N‐Arylglycines
Authors: Ouyang Wen‐Tao , Ji Hong‐Tao , Liu Yuan‐Yuan , Li Ting , Jiang Yan‐Fang , Lu Yu‐Han , Jiang Jun , He Wei‐Min
Published: April 2024

With both TEMPO and O2 (in air) as the homogeneous redox mediators, BiBrO as the heterogeneous semiconductor photocatalyst, the first example of semi‐heterogeneous photocatalytic decarboxylative phosphorylation of N‐arylglycines with diarylphosphine oxides was established. A series of α‐amino phosphinoxides were efficiently synthesized.
How Inert is Single‐Stranded DNA Towards DNA‐Stabilized Silver Nanoclusters? A Case Study
Authors: Rück Vanessa , Cerretani Cecilia , Vosch Tom
Published: April 2024

A case study, detailing the effect of different DNA oligomers on a NIR‐emitting DNA‐stabilized silver nanocluster (DNA‐AgNC), is reported. The presence of single‐stranded DNA oligomers was found to adversely affect the chemical stability of (DNA)2[Ag16Cl2]8+ with distinct degrees of destruction depending on the DNA sequence. To increase the chemical stability of the DNA‐AgNC, we implemented two protection strategies. First, hybridization of the bare DNA strands with the corresponding complementary sequences dramatically reduced the destruction of (DNA)2[Ag16Cl2]8+, as demonstrated by the decreased drops in both the absorption and emission spectra. Secondly, saturation of the free DNA oligomers with silver cations left (DNA)2[Ag16Cl2]8+ intact. Our investigation can thus provide an easy‐to‐implement approach to discover DNA sequences that are intrinsically less reactive towards preformed DNA‐AgNCs, and give an idea on how to protect DNA‐AgNCs from bare DNA strands.
Distinct patterns of voxel‐ and connection‐based white matter hyperintensity distribution and associated factors in early‐onset and late‐onset Alzheimer's disease
Authors: Hong Hui , Chen Yutong , Liu Weiran , Luo Xiao , Zhang Minming ,   for the Alzheimer's Disease Neuroimaging Initiative (ADNI)
Published: April 2024

Introduction

The distribution of voxel‐ and connection‐based white matter hyperintensity (WMH) patterns in early‐onset Alzheimer's disease (EOAD) and late‐onset Alzheimer's disease (LOAD), as well as factors associated with these patterns, remain unclear.

Method

We analyzed the WMH distribution patterns in EOAD and LOAD at the voxel and connection levels, each compared with their age‐matched cognitively unimpaired participants. Linear regression assessed the independent effects of amyloid and vascular risk factors on WMH distribution patterns in both groups.

Results

Patients with EOAD showed increased WMH burden in the posterior region at the voxel level, and in occipital region tracts and visual network at the connection level, compared to controls. LOAD exhibited extensive involvement across various brain areas in both levels. Amyloid accumulation was associated WMH distribution in the early‐onset group, whereas the late‐onset group demonstrated associations with both amyloid and vascular risk factors.

Discussion

EOAD showed posterior‐focused WMH distribution pattern, whereas LOAD was with a wider distribution. Amyloid accumulation was associated with connection‐based WMH patterns in both early‐onset and late‐onset groups, with additional independent effects of vascular risk factors in late‐onset group.

Highlights

Both early‐onset Alzheimer's disease (EOAD) and late‐onset AD (LOAD) showed increased white matter hyperintensity (WMH) volume compared with their age‐matched cognitively unimpaired participants.

EOAD and LOAD exhibited distinct patterns of WMH distribution, with EOAD showing a posterior‐focused pattern and LOAD displaying a wider distribution across both voxel‐ and connection‐based levels.

In both EOAD and LOAD, amyloid accumulation was associated with connection‐based WMH patterns, with additional independent effects of vascular risk factors observed in LOAD.
Asymmetrical disassortative pollination mediated by long‐/short‐tongued pollinators in a distylous Limonium myrianthum (Plumbaginaceae) with a short corolla tubular small flower
Authors: Jiao Fangfang , Wang Xiaowei , Zhang Aiqin
Published: April 2024

In heterostylous plants, short‐tongued pollinators are often ineffective/inefficient owing to the limitations imposed by a long corolla tube. However, it is unclear how disassortative pollen transfer is achieved in small flowers. We investigated the pollination pattern and floral morph variation by analyzing heterostylous syndrome, pollinator groups, and pollen deposition after a single visitation in two Limonium myrianthum populations with short‐corolla‐tubular small flowers. The predominant pollinators in the Hutubi population were pollen‐seeking short‐tongued syrphids, which can only transfer pollen between high‐level sexual organs. In the Xishan population, nectar‐seeking short‐tongued insects were efficient pollinators with symmetrical disassortative pollen transfer between high‐ and low‐level sexual organs, whereas long‐tongued pollinators had a low efficiency between high‐level sexual organs due to the low contact probability with the stigma of long‐styled flowers (L‐morph), which no longer offered the same advantage observed in tubular flowers. Asymmetrical disassortative pollination may cause the female fitness of short‐styled (S‐morph) individuals in the Hutubi and L‐morph individuals in the Xishan population to suffer greater selection pressure and exhibit a higher degree of floral morph variation. Limonium myrianthum exhibits an unusual pollination pattern in which the small flowers with short corolla tubes make it possible for short‐tongued insects to become effective pollinators. However, factors such as the position of stigma–anther within the flower, pollinator species and their preference further caused asymmetrical disassortative pollen transfer. Therefore, more factors should be considered when evaluating the effectiveness of short‐ and long‐tongued insects in pollination service.
Breeding records and the detection of nesting predators of wild‐release red‐crowned cranes into non‐breeding areas of the Yancheng National Nature Reserve, China
Authors: Dawei Wu , Xinyi Hu , Hao Chen , Guoyuang Chen , Weihua Chen , Changhu Lu
Published: April 2024

The western population of the red‐crowned crane Grus japonensis in mainland China has been decreasing in the past few decades and wild population enhancement programmes have been launched in this country. First, 14 captive‐bred red‐crowned cranes were released into the core area of Yancheng National Nature Reserve for Rare Birds (YNNR), one of the most important wintering areas of this species, in 2013 (seven individuals) and 2015 (seven individuals) and then 8 more captive‐bred cranes were released into YNNR from February 2022 to February 2023. We used satellite positioning and drone monitoring to study the status of released cranes. The results showed that two individuals (No. BJZ001 and BJZ008) from the first group of released cranes were found breeding in 6 of 7 years in the YNNR from 2017 to 2023. Three individuals (No. WNNR022, WNNR025 and WNNR026) from the second group of released cranes were recorded breeding in YNNR in 2023. All released cranes lived in the YNNR year round and did not migrate with wild cranes. Raccoon dogs, Nyctereutes procyonoides, were first recorded as red‐crowned crane nest predators in the YNNR. Although these released cranes breed successfully in the YNNR, nestlings might face the threat of predators in non‐traditional breeding areas. Further research is needed to determine whether offsprings of released individuals migrate with wild cranes and if breeding in their original wintering grounds is truly beneficial for population growth.
Comparison of Electrical Conductivity and Schottky Behavior of 4‐[2‐(9‐anthryl)vinyl]pyridine Based Two 1D Coordination Polymers of Zn(II) and Cd(II)
Authors: Hossain Ersad , Sk Ramjan , Das Mainak , Goura Joydeb , Roy Sourav , Ray Partha Pratim , Mir Mohammad Hedayetullah , Frontera Antonio , Mukhopadhyay Subrata
Published: April 2024

With the increase in demand of electronic devices in the modern civilization, research in material science is being projected to grow in faster rate. In this facet, coordination polymer (CP) based electronic device is one of the promising candidates to the material researchers. Herein, two new Zn(II) and Cd(II) based one‐dimensional (1D) CPs, denoted as [Zn(4‐avp)2(5‐nip)] ⋅ (solvent)x (1) and [Cd(4‐avp)(5‐nip)(CH3OH)] (2) have been synthesized using relatively less explored highly conjugated polycyclic aromatic hydrocarbon (PAH) based monodentate ligand, 4‐[2‐(9‐anthryl)vinyl]pyridine (4‐avp) and bidentate linker 5‐nitroisophthalic acid (H25‐nip). In this instance, the CP 1 creates 1D chain polymer, while CP 2 is made up with 1D ladder polymer. It is interesting to note that both the CPs exhibit semiconducting nature and generate metal‐semiconductor (MS) junction Schottky barrier diodes (SBDs). However, Cd‐based CP 2 shows higher charge transport as compared to Zn‐CP 1, which could be due to stronger π⋅⋅⋅π contacts as well as larger size of Cd metal in CP 2. The experimental results are well corroborated with theoretical density of states (DOS) calculations.
Comparative validation of automated presurgical tractography based on constrained spherical deconvolution and diffusion tensor imaging with direct electrical stimulation
Authors: Radwan Ahmed Mohamed , Emsell Louise , Vansteelandt Kristof , Cleeren Evy , Peeters Ronald , De Vleeschouwer Steven , Theys Tom , Dupont Patrick , Sunaert Stefan
Published: April 2024

Objectives

Accurate presurgical brain mapping enables preoperative risk assessment and intraoperative guidance. This cross‐sectional study investigated whether constrained spherical deconvolution (CSD) methods were more accurate than diffusion tensor imaging (DTI)‐based methods for presurgical white matter mapping using intraoperative direct electrical stimulation (DES) as the ground truth.

Methods

Five different tractography methods were compared (three DTI‐based and two CSD‐based) in 22 preoperative neurosurgical patients undergoing surgery with DES mapping. The corticospinal tract (CST, N = 20) and arcuate fasciculus (AF, N = 7) bundles were reconstructed, then minimum distances between tractograms and DES coordinates were compared between tractography methods. Receiver‐operating characteristic (ROC) curves were used for both bundles. For the CST, binary agreement, linear modeling, and posthoc testing were used to compare tractography methods while correcting for relative lesion and bundle volumes.

Results

Distance measures between 154 positive (functional response, pDES) and negative (no response, nDES) coordinates, and 134 tractograms resulted in 860 data points. Higher agreement was found between pDES coordinates and CSD‐based compared to DTI‐based tractograms. ROC curves showed overall higher sensitivity at shorter distance cutoffs for CSD (8.5 mm) compared to DTI (14.5 mm). CSD‐based CST tractograms showed significantly higher agreement with pDES, which was confirmed by linear modeling and posthoc tests (PFWE < .05).

Conclusions

CSD‐based CST tractograms were more accurate than DTI‐based ones when validated using DES‐based assessment of motor and sensory function. This demonstrates the potential benefits of structural mapping using CSD in clinical practice.
Functional gradients reveal cortical hierarchy changes in multiple sclerosis
Authors: De Rosa Alessandro Pasquale , d'Ambrosio Alessandro , Bisecco Alvino , Altieri Manuela , Cirillo Mario , Gallo Antonio , Esposito Fabrizio
Published: April 2024

Functional gradient (FG) analysis represents an increasingly popular methodological perspective for investigating brain hierarchical organization but whether and how network hierarchy changes concomitant with functional connectivity alterations in multiple sclerosis (MS) has remained elusive. Here, we analyzed FG components to uncover possible alterations in cortical hierarchy using resting‐state functional MRI (rs‐fMRI) data acquired in 122 MS patients and 97 healthy control (HC) subjects. Cortical hierarchy was assessed by deriving regional FG scores from rs‐fMRI connectivity matrices using a functional parcellation of the cerebral cortex. The FG analysis identified a primary (visual‐to‐sensorimotor) and a secondary (sensory‐to‐transmodal) component. Results showed a significant alteration in cortical hierarchy as indexed by regional changes in FG scores in MS patients within the sensorimotor network and a compression (i.e., a reduced standard deviation across all cortical parcels) of the sensory‐transmodal gradient axis, suggesting disrupted segregation between sensory and cognitive processing. Moreover, FG scores within limbic and default mode networks were significantly correlated (, p < .005 after Bonferroni correction for both) with the symbol digit modality test (SDMT) score, a measure of information processing speed commonly used in MS neuropsychological assessments. Finally, leveraging supervised machine learning, we tested the predictive value of network‐level FG features, highlighting the prominent role of the FG scores within the default mode network in the accurate prediction of SDMT scores in MS patients (average mean absolute error of 1.22 ± 0.07 points on a hold‐out set of 24 patients). Our work provides a comprehensive evaluation of FG alterations in MS, shedding light on the hierarchical organization of the MS brain and suggesting that FG connectivity analysis can be regarded as a valuable approach in rs‐fMRI studies across different MS populations.
Evoked oscillatory cortical activity during acute pain: Probing brain in pain by transcranial magnetic stimulation combined with electroencephalogram
Authors: De Martino Enrico , Casali Adenauer , Casarotto Silvia , Hassan Gabriel , Couto Bruno Andry , Rosanova Mario , Graven‐Nielsen Thomas , de Andrade Daniel Ciampi
Published: April 2024

Temporal dynamics of local cortical rhythms during acute pain remain largely unknown. The current study used a novel approach based on transcranial magnetic stimulation combined with electroencephalogram (TMS‐EEG) to investigate evoked‐oscillatory cortical activity during acute pain. Motor (M1) and dorsolateral prefrontal cortex (DLPFC) were probed by TMS, respectively, to record oscillatory power (event‐related spectral perturbation and relative spectral power) and phase synchronization (inter‐trial coherence) by 63 EEG channels during experimentally induced acute heat pain in 24 healthy participants. TMS‐EEG was recorded before, during, and after noxious heat (acute pain condition) and non‐noxious warm (Control condition), delivered in a randomized sequence. The main frequency bands (α, β1, and β2) of TMS‐evoked potentials after M1 and DLPFC stimulation were recorded close to the TMS coil and remotely. Cold and heat pain thresholds were measured before TMS‐EEG. Over M1, acute pain decreased α‐band oscillatory power locally and α‐band phase synchronization remotely in parietal–occipital clusters compared with non‐noxious warm (all p < .05). The remote (parietal–occipital) decrease in α‐band phase synchronization during acute pain correlated with the cold (p = .001) and heat pain thresholds (p = .023) and to local (M1) α‐band oscillatory power decrease (p = .024). Over DLPFC, acute pain only decreased β1‐band power locally compared with non‐noxious warm (p = .015). Thus, evoked‐oscillatory cortical activity to M1 stimulation is reduced by acute pain in central and parietal–occipital regions and correlated with pain sensitivity, in contrast to DLPFC, which had only local effects. This finding expands the significance of α and β band oscillations and may have relevance for pain therapies.
Predicting anxiety, depression, and insomnia among Bangladeshi university students using tree‐based machine learning models
Authors: Chowdhury Arman Hossain , Rad Dana , Rahman Md. Siddikur
Published: April 2024

Background and Aims

Mental health problem is a rising public health concern. People of all ages, specially Bangladeshi university students, are more affected by this burden. Thus, the objective of the study was to use tree‐based machine learning (ML) models to identify major risk factors and predict anxiety, depression, and insomnia in university students.

Methods

A social media‐based cross‐sectional survey was employed for data collection. We used Generalized Anxiety Disorder (GAD‐7), Patient Health Questionnaire (PHQ‐9) and Insomnia Severity Index (ISI‐7) scale for measuring students' anxiety, depression and insomnia problems. The tree‐based supervised decision tree (DT), random forest (RF) and robust eXtreme Gradient Boosting (XGBoost) ML algorithms were used to build the prediction models and their predictive performance was evaluated using confusion matrix and receiver operating characteristic (ROC) curves.

Results

Of the 1250 students surveyed, 64.7% were male and 35.3% were female. The students' ages ranged from 18 to 26 years old, with an average age of 22.24 years (SD = 1.30). Majority of the students (72.6%) were from rural areas and social media addicted (56.6%). Almost 83.3% of the students had moderate to severe anxiety, 84.7% had moderate to severe depression and 76.5% had moderate to severe insomnia problems. Students' social media addiction, age, academic performance, smoking status, monthly family income and morningness‐eveningness are the main risk factors of anxiety, depression and insomnia. The highest predictive performance was observed from the XGBoost model for anxiety, depression and insomnia.

Conclusion

The study findings offer valuable insights for stakeholders, families and policymakers enabling a more profound comprehension of the pressing mental health disorders. This understanding can guide the formulation of improved policy strategies, initiatives for mental health promotion, and the development of effective counseling services within university campus. Additionally, our proposed model might play a critical role in diagnosing and predicting mental health problems among Bangladeshi university students and similar settings.
Anthropometry of the nose pre‐ and post‐photogrammetric adjustments in a sample of Syrian medical students. A cross‐sectional study
Authors: Torbey André , Mdawr Elian , Kahal Fares , Rmman Mohammad , Omar Abdullah , Alzabibi Mhd Amin , Kadri Saeed A. , Tawahri Enaam , Nahas Louei Darjazini
Published: April 2024

Background and Aims

The individual's perceived beauty, sense of identity, and general well‐being are all influenced by the social implications of the esthetics of their facial appearance. One of the major indicators of one's facial beauty is anthropometric proportions. This study was conducted to measure and evaluate the anthropometric proportions in a Syrian population, and to determine their desired nasal shape.

Methods

A cross‐sectional study was conducted on Syrian university students. Lateral and frontal pictures of the participants were taken using Canon EOS 250D from a standard distance of 100 cm. These pictures were analyzed, then nasal measurements were adjusted according to the participants' desire using Adobe Photoshop 2020. All anthropometric measurements were conducted on AutoCAD® 2019 software before and after the adjustments. Data was analyzed using the SPSS‐25 using paired samplesTtest to compare the means.

Results

The study included 53 females and 47 males. The mean age was 22.25. The mean unadjusted nasofrontal angle, nasolabial angle, nasomental angle, nasofacial angle, nasal index, Byrd and Hobar ratio, and Powell‐modified Baum ratio were 141.80, 102.18, 129.21, 34.60, 71.71, 0.62, and 3.08 in the rhinoplasty‐negative participants, and 145.89, 102.03, 130.20, 32.44, 67.96, 0.64, and 3.06 in the rhinoplasty‐positive participants, respectively. While the mean of the adjusted previously mentioned angles were 144.59, 106.32, 131.19, 31.15, 62.91, 0.60, and 3.19 in the rhinoplasty‐negative participants, and 146.31, 102, 130.20, 31, 62.55, 0.62, and 3.08 in the rhinoplasty‐positive participants, respectively.

Conclusion

In contrast to other populations, our study concluded that Syrians had unique anthropometric measurements and facial esthetics preferences. Moreover, the local plastic surgeons were able to identify most of the preferred nasal measurements for rhinoplasty in this ethnic group. It is advisable to use photogrammetry before rhinoplasty to identify the preferred nasal measurements of each individual to ensure the patient's satisfaction with the outcome of the surgery.

Level of Evidence

Level IV, cross‐sectional study.