bluuebunny/crossref_metadata_2025 huggingface dataset:
Burden and social distribution of occupational psychosocial exposures in the United States workforce, 2022
Authors: Stephan‐Recaido Shelley C. , Peckham Trevor K. , Hawkins Devan , Baker Marissa G.
Published: August 2024

Objective

To characterize the burden and social distribution of occupational psychosocial exposures in the United States (US).

Methods

We merged 2022 US employment and demographic data from the Current Population Survey (CPS) with occupational characteristic data from the Occupational Information Network (O*NET), wage data from the Occupational Employment and Wage Statistics Survey, and hours worked from the CPS, to estimate the number and proportion of US workers at risk of exposure to 19 psychosocial hazards. We additionally estimated the number and proportion of US workers over‐ or underrepresented in exposure burden.

Results

Of the exposures examined, US workers were most commonly employed in occupations with high time pressure (67.5 million US workers exposed; 43.2% US workers exposed), high emotional labor (57.1 million; 36.6%), and low wages (47.8 million; 30.6%). The burden of exposures was uneven across sociodemographic strata, attributable to occupational segregation. The full data set is available online at https://deohs.washington.edu/us-exposure-burden.

Conclusions

Work‐related psychosocial exposures are ubiquitous and should be considered in occupational and public health research, policy, and interventions to reduce the burden of disease and health inequities in the United States.
Considering challenges for the new Alzheimer's drugs: Clinical, population, and health system perspectives
Authors: Walsh Sebastian , Merrick Richard , Milne Richard , Nurock Shirley , Richard Edo , Brayne Carol
Published: August 2024

Recent approvals of amyloid immunotherapy drugs for early Alzheimer's disease (AD) have been highly controversial. In this piece, we consider challenges from the clinical, population health, and health systems perspectives to the role that the new AD drugs might be expected to play, now and in the future, in alleviating the morbidity caused by AD in the population. Clinically, short‐term effects are small, adverse events are frequent, treatment regimens are burdensome, and, crucially, long‐term effects are unknown. At a population level, there is always likely to be a trade‐off between breadth of access and magnitude of benefit for any given individual. At a health system level, roll out of treatment even for only narrowly‐defined patient groups will involve considerable resources to identify and treat eligible patients, with profound opportunity costs. Our considered view on current evidence is that there are challenges from each perspective to imagining a foreseeable future in which amyloid immunotherapy significantly alleviates AD morbidity at scale.

Highlights

Recent approvals of Alzheimer's drugs have met with excitement but also controversy.

Trial effects are small, adverse effects concerning, and long‐term effects unknown.

Results from trial cohorts may not generalize to broader, more complex patients.

Significant resource requirements of eligibility assessment and drug administration.

Use in “presymptomatic” populations is not supported by current evidence.
Regulating the Scaling Relations in Ammonia Synthesis through a Light‐Driven Bendable Seesaw Effect on Tailored Iron Catalyst
Authors: Yang Yi , Wang Pei , Zhang Xiaohu , Wang Shengyao , Ding Xing , Ma Hongshan , Wang He , Li Yuanzhi , Jiang Bo , Song Hui , Hai Xiao , Lu Yue , Chen Hao , Ye Jinhua
Published: August 2024

Advancing the energy‐intensive Haber–Bosch process faces significant challenges due to the intrinsic constraints of scaling relations in heterogeneous catalysis. Herein, we reported an approach of bending the “seesaw effect” to regulate the scaling relations over a tailored α‐Fe metallic material (α‐Fe‐110s), realizing highly efficient light‐driven thermal catalytic ammonia synthesis with a rate of 1260 μmol gcatalyst−1 h−1 without additional heating. Specifically, the thermal catalytic activity of α‐Fe‐110s was significantly enhanced by the novel stepped {110} surface, exhibiting a 3.8‐fold increase compared to the commercial fused‐iron catalyst with promoters at 350 °C. The photo‐induced hot electron transfer further accelerates the dinitrogen dissociation and hydrogenation simultaneously, effectively overcoming the limitation of scaling relation over identical sites. Consequently, the ammonia production rate of α‐Fe‐110s was further enhanced by 30 times at the same temperature with irradiation. This work designs an efficient and sustainable system for ammonia synthesis and provides a novel approach for regulating the scaling relations in heterogeneous catalysis.
Fused Hexabenzocoronene‐Porphyrin Conjugates with Tailorable Excited‐State Lifetimes
Authors: Oleszak Christoph , Schol Peter R. , Ritterhoff Christian L. , Krug Marcel , Martin Max M. , Bo Yifan , Meyer Bernd , Clark Timothy , Guldi Dirk M. , Jux Norbert
Published: August 2024

A new clear‐cut strategy for fusing N‐heterocyclic and carbon‐pure systems is introduced en route to a versatile platform of multi‐purpose tetrapyrrolic chromophores. In particular, three novel C−C bond‐fused porphyrin‐hexabenzocoronene (HBC) conjugates were synthesized under oxidative cyclodehydrogenation conditions, starting from tailor‐made nickel porphyrin precursors. The fusion of the individual aromatic systems via 5‐membered rings led to highly soluble π‐extended porphyrins in excellent yields. The resulting porphyrin‐HBC conjugates exhibit absorption cross‐sections that are of interdisciplinary interest in the ever‐growing field of organic photovoltaics and near‐infrared (NIR) dyes. Quantum chemical calculations show that the newly formed 5‐membered rings induce biradicaloid character in the porphyrin core, which has a strong impact on excited state lifetimes. This is confirmed by a thorough optoelectronic and time‐resolved characterization in order to understand these unique features better. Broadened absorption characteristics go hand‐in‐hand with short‐lived excited states with up to six orders of magnitude faster decay rates.
An Integrated Module Performs Selective ‘Online’ Epoxidation in the Biosynthesis of the Antibiotic Mupirocin
Authors: Winter Ashley J. , de Courcy‐Ireland Felix , Phillips Annabel P. , Barker Joseph M. , Bakar Nurfarhanim A. , Akter Nahida , Wang Luoyi , Song Zhongshu , Crosby John , Williams Christopher , Willis Christine L. , Crump Matthew P.
Published: August 2024

The delineation of the complex biosynthesis of the potent antibiotic mupirocin, which consists of a mixture of pseudomonic acids (PAs) isolated from Pseudomonas fluorescens NCIMB 10586, presents significant challenges, and the timing and mechanisms of several key transformations remain elusive. Particularly intriguing are the steps that process the linear backbone from the initial polyketide assembly phase to generate the first cyclic intermediate PA‐B. These include epoxidation as well as incorporation of the tetrahydropyran (THP) ring and fatty acid side chain required for biological activity. Herein, we show that the mini‐module MmpE performs a rare online (ACP‐substrate) epoxidation and is integrated (‘in‐cis’) into the polyketide synthase via a docking domain. A linear polyketide fragment with six asymmetric centres was synthesised using a convergent approach and used to demonstrate substrate flux via an atypical KS0 and a previously unannotated ACP (MmpE_ACP). MmpE_ACP‐bound synthetic substrates were critical in demonstrating successful epoxidation in vitro by the purified MmpE oxidoreductase domain. Alongside feeding studies, these results confirm the timing as well as chain length dependence of this selective epoxidation. These mechanistic studies pinpoint the location and nature of the polyketide substrate prior to the key formation of the THP ring and esterification that generate PA‐B.
Uncovering a Latent Bioactive Interleukin‐6 Glycoform
Authors: Liu Yanbo , Maki Yuta , Okamoto Ryo , Satoh Ayano , Todokoro Yasuto , Kanemitsu Yurie , Otani Keito , Kajihara Yasuhiro
Published: August 2024

A bioinspired semisynthesis of human‐interleukin‐6 bearing N‐glycan at Asn143 (143glycosyl‐IL‐6) was performed by intentional glycosylation effects and protein folding chemistry for regioselective peptide‐backbone activation. 143Glycosyl‐IL‐6 is a genetically coded cytokine, but isolation was difficult owing to a tiny amount. IL6‐polypeptide (1–141‐position) with an intentionally inserted cysteine at 142‐position was expressed in E. coli. The expressed polypeptide was treated with a chemical folding process to make a specific helices bundle conformation through native two‐disulfide bonds (43–49 and 72–82). Utilizing the successfully formed free‐142‐cysteine, sequential conversions using cyanylation of 142‐cysteine, hydrazinolysis, and thioesterification created a long polypeptide (1–141)‐thioester. However, the resultant polypeptide‐thioester caused considerable aggregation owing to a highly hydrophobic peptide sequence. After the reduction of two‐disulfide bonds of polypeptide (1–141)‐thioester, an unprecedented hydrophilic N‐glycan tag was inserted at the resultant cysteine thiols. The N‐glycan tags greatly stabilized polypeptide‐thioester. The subsequent native chemical ligation and desulfurization successfully gave a whole 143glycosyl‐IL‐6 polypeptide (183‐amino acids). Removal of four N‐glycan tags and immediate one‐pot in vitro folding protocol efficiently produced the folded 143glycosyl‐IL‐6. The folded 143glycosyl‐IL‐6 exhibited potent cell proliferation activity. The combined studies with molecular dynamics simulation, semisynthesis, and bioassays predict the bioactive conformation of latent 143glycosyl‐IL‐6.
Quasi‐Planar Core Based Spiro‐Type Hole‐Transporting Material for Dopant‐Free Perovskite Solar Cells
Authors: Shao Guang , Wang Dian , Zhou Zu‐Kun , Yu Hui‐Juan , Kang Tao , Zhu Wei‐Hua , Xiao Jing , Yu Zhi‐Lan , Peng Lifen , Chen Jian , Ul Ain Qurat , Chen Yu , Yang Hua , Qiu Zeliang , Hu Ruiyuan , Khan Ammar Ahmed , A Alamry Khalid , Zhang Yi , Xia Jianxing , Nazeeruddin Mohammad Khaja
Published: August 2024

Hole‐transporting material (HTMs) are crucial for obtaining the stability and high efficiency of perovskite solar cells (PSCs). However, the current state‐of‐the‐art n‐i‐p PSCs relied on the use of 2,2′,7,7′‐tetrakis(N,N‐di‐p‐methoxyphenylamine)‐9,9′‐spirobifluorene (spiro‐OMeTAD) exhibit inferior intrinsic and ambient stability due to the p‐dopant and hydrophilic Li‐TFSI additive. In this study, a new spiro‐type HTM with a critical quasi‐planar core (Z‐W‐03) is developed to improve both the thermal and ambient stability of PSCs. The results suggest that the planar carbazole structure effectively passivates the trap states compared to the triphenylamine with a propeller‐like conformation in spiro‐OMeTAD. This passivation effect leads to the shallower trap states when the quasi‐planar HTMs interact with the Pb‐dimer. Consequently, the device using Z‐W‐03 achieves a higher Voc of 1.178 V compared to the spiro‐OMeTAD's 1.155 V, resulting in an enhanced efficiency of 24.02 %. In addition, the double‐column π–π stacking of Z‐W‐03 results in high hole mobility (~10−4 cm2 V−1 s−1) even without p‐dopant. Moreover, when the surface interface is modified, the undoped Z‐W‐03 device can achieve an efficiency of nearly 23 %. Compared to the PSCs using spiro‐OMeTAD, those with Z‐W‐03 exhibit enhanced stability under N2 and ambient conditions. This superior performance is attributed to the quasi‐planar core structure and the presence of multiple CH/π and π–π intermolecular stacking in Z‐W‐03. The multiple CH/π and π–π intermolecular contacts of HTMs can improve the hole hopping transport. Therefore, it is imperative to focus on further molecular structure design and optimization of spiro‐type HTMs incorporating quasi‐planar cores and carbazole moieties for the commercialization of PSCs.
Deoxygenative Geminal Silylboration of Amides Using Silylboronates: Synthesis and Use of α‐Boryl‐α‐Silylalkylamines
Authors: Watanabe Koh , Nagao Kazunori , Ohmiya Hirohisa
Published: August 2024

α‐Silylalkylamines and α‐borylalkylamines are versatile synthetic intermediates and attractive scaffolds found in pharmaceutical drugs and agrochemicals. Despite great progress on synthetic methods for preparation of α‐silylalkylamines or α‐borylalkylamines, there are no general strategies for preparation of α‐boryl‐α‐silylalkylamines and the reactivity has not been explored. Here we report deoxygenative geminal silylboration of amides using silylboronates in the presence of alkoxide base catalyst, producing α‐boryl‐α‐silylalkylamines. The silicon and boron groups in α‐boryl‐α‐silylalkylamines are found to be utilized to chemoselective transformations, such as protonation and alkylation. This protocol serves various α‐silylalkylamines and α‐borylalkylamines from readily available amides.
Expansion of Structure Property in Cascade Nazarov Cyclization and Cycloexpansion Reaction to Diverse Angular Tricycles and Total Synthesis of Nominal Madreporanone
Authors: Fang Kun , Dou Bao‐Heng , Zhang Fu‐Min , Wang Yun‐Peng , Shan Zi‐Rui , Wang Xiao‐Yu , Hou Si‐Hua , Tu Yong‐Qiang , Ding Tong‐Mei
Published: August 2024

A cascade Nazarov cyclization/dicycloexpansions reaction was developed for the precise synthesis of the angularly fused M/5/N (M=5, 6; N=4–9, 13) tricyclic skeletons. The prioritized expansion of the first ring played a critical role in the transformations, due to the release of ring strain, and the nature of the substituents present on the substrate is another influencing factor. This pioneering cascade reaction features broad substrates scope (33 examples), short reaction time, exceptional yields (up to 95 %), and remarkable regioselectivities (>20 : 1). Exploiting the synthetic application of this cascade reaction, we successfully executed a succinct total synthesis of nominal madreporanone for the first time.
Reconstruction of Ferromagnetic/Paramagnetic Cobalt‐Based Electrocatalysts under Gradient Magnetic Fields for Enhanced Oxygen Evolution
Authors: Ma Shengyu , Wang Kaixi , Rafique Moniba , Han Jiecai , Fu Qiang , Jiang Sida , Wang Xianjie , Yao Tai , Xu Ping , Song Bo
Published: August 2024

The rational manipulation of the surface reconstruction of catalysts is a key factor in achieving highly efficient water oxidation, but it is a challenge due to the complex reaction conditions. Herein, we introduce a novel in situ reconstruction strategy under a gradient magnetic field to form highly catalytically active species on the surface of ferromagnetic/paramagnetic CoFe2O4@CoBDC core–shell structure for electrochemical oxygen evolution reaction (OER). We demonstrate that the Kelvin force from the cores’ local gradient magnetic field modulates the shells’ surface reconstruction, leading to a higher proportion of Co2+ as active sites. These Co sites with optimized electronic configuration exhibit more favorable adsorption energy for oxygen‐containing intermediates and lower the activation energy of the overall catalytic reaction. As a result, a significant enhancement in OER performance is achieved with a large current density increment about 128 % at 1.63 V and an overpotential reduction by 28 mV at 10 mA cm−2 after reconstruction. Interestingly, after removing the external magnetic field, the activity could persist for over 100 h. This work showcases the directional surface reconstruction of catalysts under a gradient magnetic field for enhanced water oxidation.
Organocatalytic Atroposelective Synthesis of Axially Chiral Indolyl Ketosulfoxonium Ylides
Authors: Zhang Ji‐Wei , Zhang Yichi , Huang Yong
Published: August 2024

Despite recent advancements in the catalytic generation of axial chirality, reports on non‐biaryl atropisomers remain limited because of the stringent steric requirements necessary to establish effective rotational brakes. Herein, we present a novel class of monoaryl atropisomers, indolyl ketosulfoxonium ylides, and describe an organocatalytic protocol for their synthesis. We discovered that a chiral phosphoric acid (CPA) serves as an effective catalyst for the highly enantioselective iodination of ortho‐aminophenylethynyl sulfoxonium ylides. Under the optimized reaction conditions, a strong preference for the intended iodination process over the competing protonation was observed. Subsequently, intramolecular amide cyclization enabled the formation of sterically congested indole fragments. Furthermore, the synthetic utility of the products was demonstrated by showcasing versatile transformations into other chiral scaffolds with complete retention of optical purity.
Palladium(0) and Brønsted Acid Co‐Catalyzed Enantioselective Hydro‐Cyclization of 2,4‐Dienyl Hydrazones and Oximes
Authors: Li Yu‐Fan , Gui Wu‐Tao , Pi Fu , Chen Zhi , Zhu Lei , Ouyang Qin , Du Wei , Chen Ying‐Chun
Published: August 2024

The transition metal‐catalyzed asymmetric hydro‐functionalization of 1,3‐dienes has been well explored, but most reactions focus on electron‐neutral substrates in an intermolecular manner. Here we first demonstrate that readily available 2,4‐dienyl hydrazones and oximes can be efficiently utilized in the hydro‐cyclization reaction under co‐catalysis of a Brønsted acid and a chiral palladium complex, furnishing multifunctional dihydropyrazones and dihydroisoxazoles, respectively. Diverse substitution patterns for both types of electron‐deficient diene compounds are tolerated, and corresponding heterocycles were generally constructed with moderate to excellent enantioselectivity, which can be elaborated to access products with higher molecular complexity and diversity. Control experiments and density functional theory calculations support that α‐regioselective protonation of dienyl substrates by acid and concurrent π‐Lewis base activation of Pd0 complex is energetically favoured in the formation of active π‐allylpalladium intermediates, and an outer‐sphere allylic amination or etherification mode is adopted to deliver the observed cyclized products enantioselectively.
Programmable Reconfiguration of Supramolecular Bottlebrush Block Copolymers: From Solution Self‐Assembly to Co‐Crystallization‐Assistant Self‐Assembly
Authors: Zhang Kaixing , Wu Yanggui , Chen Senbin , Zhu Jintao
Published: August 2024

Achieving structural reconfiguration of supramolecular bottlebrush block copolymers toward topological engineering is of particular interest but challenging. Here, we address the creation of supramolecular architectures to discover how assembled topology influences the structured aggregates, combining hydrogen‐bonded (H‐bonded) bottlebrush block copolymers and electrostatic interaction induced polymer/inorganic eutectics. We first design H‐bonding linear‐brush block copolymer P(NBDAP‐co‐NBC)‐b‐P(NBPEO), bearing linear block P(NBDAP‐co‐NBC) (poly(norbornene‐terminated diaminopyridine‐co‐norbornene‐terminated hexane)) with pendant H‐bonding DAP (diaminopyridine) motifs, and PEO (poly(ethylene oxide)) densely grafted P(NBPEO) brush block. Thanks to H‐bonding association between DAP and thymine (Thy), incorporation of Thy‐functionalized polystyrene (Thy‐PS65) enables solution self‐assembly and formation of H‐bonded bottlebrush block copolymers, generating augmented nanospheres with increasing Thy‐PS65 amount. Noteworthy that integration of inorganic cluster silicotungstic acid (STA) to P(NBC‐co‐NBDAP)‐b‐P(NBPEO), endows the formation of PEO/STA eutectic core. Therefore, co‐crystallization‐assistant self‐assembly at the interfaces of polymeric, inorganic and supramolecular chemistry is realized, reflecting multi‐stage morphology transformation from hexagonal platelets, needle‐like, curved rod‐like micelles, finally to end‐to‐end closed rings, by gradually increasing Thy‐PS65 while fixing STA content. Interestingly, such solution self‐assembly to co‐crystallization‐assistant self‐assembly strategy not only endows unique nanostructure transition, also induce in‐to‐out reconfiguration of PS domains. These findings clearly provide unique methodology towards programmable fabrication of geometrical objects promising in smart materials.
Cell Surface Engineering by Phase‐Separated Coacervates for Antibody Display and Targeted Cancer Cell Therapy
Authors: Chen Hongfei , Bao Yishu , Li Xiaojing , Chen Fangke , Sugimura Ryohichi , Zeng Xiangze , Xia Jiang
Published: August 2024

Cell therapies such as CAR−T have demonstrated significant clinical successes, driving the investigation of immune cell surface engineering using natural and synthetic materials to enhance their therapeutic performance. However, many of these materials do not fully replicate the dynamic nature of the extracellular matrix (ECM). This study presents a cell surface engineering strategy that utilizes phase‐separated peptide coacervates to decorate the surface of immune cells. We meticulously designed a tripeptide, Fmoc−Lys−Gly−Dopa−OH (KGdelta; Fmoc=fluorenylmethyloxycarbonyl; delta=Dopa, dihydroxyphenylalanine), that forms coacervates in aqueous solution via phase separation. These coacervates, mirroring the phase separation properties of ECM proteins, coat the natural killer (NK) cell surface with the assistance of Fe3+ ions and create an outer layer capable of encapsulating monoclonal antibodies (mAb), such as Trastuzumab. The antibody‐embedded coacervate layer equips the NK cells with the ability to recognize cancer cells and eliminate them through enhanced antibody‐dependent cellular cytotoxicity (ADCC). This work thus presents a unique strategy of cell surface functionalization and demonstrates its use in displaying cancer‐targeting mAb for cancer therapies, highlighting its potential application in the field of cancer therapy.
Cobalt‐Catalyzed Intramolecular Markovnikov Hydrocarbonylation of Unactivated Alkenes via Hydrogen Atom Transfer
Authors: Jiang Donghao , Li Xinzhu , Xiao Mengdie , Cheng Li‐Jie
Published: August 2024

A cobalt‐catalyzed intramolecular Markovnikov hydroalkoxycarbonylation and hydroaminocarbonylation of unactivated alkenes has been developed, enabling highly chemo‐ and regioselective synthesis of α‐alkylated γ‐lactones and α‐alkylated γ‐lactams in good yields. The mild reaction conditions allow use of mono‐, di‐ and trisubstituted alkenes bearing a variety of functional groups. Preliminary mechanistic studies suggest the reaction proceeds through a CO‐mediated hydrogen atom transfer (HAT) and radical‐polar crossover (RPC) process, in which a cationic acylcobalt(IV) complex is proposed as the key intermediate.
Thermotropic “Plumber's Nightmare”—A Tight Liquid Organic Double Framework
Authors: Li Ya‐Xin , Jia Ruo‐Yin , Ungar Goran , Ma Tao , Zhao Kai , Zeng Xiang‐Bing , Cheng Xiao‐Hong
Published: August 2024

Gyroid, double diamond and the body‐centred “Plumber's nightmare” are the three most common bicontinuous cubic phases in lyotropic liquid crystals and block copolymers. While the first two are also present in solvent‐free thermotropics, the latter had never been found. Containing six‐fold junctions, it was unlikely to form in the more common phases with rod‐like cores normal to the network columns, where a maximum of four branches can join at a junction. The solution has therefore been sought in side‐branched mesogens that lie in axial bundles joined at their ends by flexible “hinges”. But for the tightly packed double framework, geometric models predicted that the side‐chains should be very short. The true Plumber's nightmare reported here, using fluorescent dithienofluorenone rod‐like mesogen, has been achieved with, indeed, no side chains at all, but with 6 flexible end‐chains. Such molecules normally form columnar phases, but the key to converting a complex helical column–forming mesogen into a framework‐forming one was the addition of just one methyl group to each pendant chain. A geometry‐based explanation is given.
Modified nanomagnetite silica core shell with new Cu (II) N,N‐ chelating complex as an efficient and reusable catalyst in the C‐N bond formation
Authors: Rahmatzadeh Setareh , Sardarian Ali Reza , Rafipour Danial
Published: August 2024

In this article, initially, the TCTCl (DiPrAEA)2 ligand was synthesized and characterized by Fourier transform infrared (FT‐IR), X‐ray crystallography, 1H‐ and 13C‐NMR spectroscopy, and elemental analysis. The crystallographic structure data for the ligand has been deposited at the Cambridge Crystallographic Data Centre (CCDC No. 2282732). Then, using of this novel multidentate ligand, a novel and stable copper (II) nanocatalyst complex was synthesized by anchoring copper (II) acetate onto the core‐shell surface (Fe3O4@SiO2) via the novel multidentate ligand TCTCl (DiPrAEA)2. The successful synthesis of the Fe3O4@SiO2‐NH‐TCT (DiPrAEA)2‐Cu (II) nanocatalyst was confirmed by employing physicochemical techniques such as FT‐IR, X‐ray diffraction, ultraviolet‐visible, thermogravimetric analysis, X‐ray photoelectron spectroscopy, Brunauer–Emmett–Teller, energy‐dispersive X‐ray, dynamic light scattering, inductively coupled plasma, transmission electron microscopy, field emission scanning electron microscopy, and vibrating sample magnetometer. Subsequently, this novel copper (II) nanomagnetic complex was evaluated as an efficient, reusable, and novel catalyst for the formation of C‐N bonds via the Ullmann coupling reaction of aryl halides and nitrogen‐containing compounds. The influence of this novel TCTCl (DiPrAEA)2 ligand on the reactivity and stability of the nanomagnetic copper complex was visible in the Ullmann reaction, which resulted in rapid reaction times and excellent yields, and seven times reusability.
Self‐healing, low oil leakage and recyclable thermally conductive Al2O3/boron nitride@siloxane composites based on reversible dynamic network
Authors: Tu Zhiting , Wu Weijian , Hao Zhifeng , Chen Xiang , Chen Qiuling , Huang Xiaonan , Selim Mohamed S. , Yu Jian
Published: August 2024

In order to overcome the commercialized silicone‐based thermal interface materials' issues such as oil leakage and mechanical damage, we developed a thermoset silicone rubber matrix (SR) achieved through the condensation reaction of hydroxyl silicone oil and tetraethyl silicate. Additionally, we constructed a self‐healing and recyclable silicone rubber matrix (SCNR) by incorporating heat reversible ionic and hydrogen bonds between carboxyl and amino functionalized polydimethylsiloxane. Finally, the flexible, low oil leakage, self‐healing, and recyclable composites Al2O3/BN@SR/SCNR was prepared by adjusting the ratio of SR/SCNR and the spherical alumina and boron nitride (BN) fillers. The results indicated that with SR/SCNR mass ratio of 1/0.075 and filler content of 70 wt%, the thermal conductivity of the composite reaches 1.866 W m−1 K−1, 646% increasing over the SR/SCNR matrix. The self‐healing efficiency reaches 97% and the thermal conductivity remains essentially unchanged after being recycled for three times. The composites can be bent and twisted multiple times and still return to their original shape. Notably, the oil leakage of the Al2O3/BN@SR/SCNR composites is significantly lower than that of additive silicone composites. Therefore, the recyclable thermal conductivity composite developed in this study provides a promising solution for improving the durability of heat dissipation materials in electronic devices.
Excited‐State Dynamics and Optical Properties of Silica Under Ultrafast Laser Irradiation
Authors: Tsaturyan Arshak A. , Kachan Elena , Stoian Razvan , Colombier Jean‐Philippe
Published: August 2024

Excited by intense infrared ultrafast light pulses, a wide bandgap material undergoes nonlinear ionization, generating a high density of free electrons in conduction states. As a result, the electronic band structure is critically modified and the bandgap shrinks. This induces rapid changes in optical properties, dramatically affecting the absorption spectrum during light coupling to the dielectric surface or during nonlinear propagation inside the bulk. This study analyzes the structural behavior and the modification of the optical properties of laser‐excited silica glass at the molecular cluster level through first‐principles simulations. Employing density functional theory and the GW approximations for band structure under nonequilibrium conditions, alongside the Bethe–Salpeter equation, the dynamics of the optical properties of fused silica are comprehensively explored. The behavior of excited fused silica in a wide photon energy range (from a few to 20 eV) is thus predicted. Laser‐induced electron excitation triggers a redistribution of charges between oxygen and silicon atoms, accompanied by a significant increase in electronic pressure, local atomic structure rearrangement, and material expansion. Molecular dynamics simulations offer a temporal perspective on the excited state dynamics, unveiling the intricate interplay between electronic and atomic effects on bandgap evolution. The analysis sheds light on excitonic resonances, intraband and interband transitions in fused silica under ultrafast laser irradiation, providing valuable insights into its excited state behavior and optical properties.
Honeybee (Apis mellifera L.) pollination enhances the yield and flavor quality of kiwifruit
Authors: Ji Quanzhi , Wang Xue , Huang Ting , Wang Xinyu , Zhao Yazhou
Published: August 2024

Pollination is essential for achieving high yields and enhancing the quality of kiwifruit cultivation, both of which significantly influence growers' interests and consumers' preferences. However, compared to studies on yield, there are fewer studies exploring the impact of pollination methods on the flavor of kiwifruit Actinidia chinensis Planchon. This study examined the effects of bee (Apis mellifera L.) pollination and artificial pollination on the yield and flavor of kiwifruit in the main producing areas of China. Compared with those pollinated artificially, bee‐pollinated kiwifruit exhibited a greater fruit set rate, heavier fruit weight, and greater number of seeds. Notably, the number of seeds was positively correlated with fruit weight in bee‐pollinated kiwifruit, whereas no such correlation was detected in artificially pollinated fruit. Bee pollination not only enhanced the yield but also improved the flavor of kiwifruit. Specifically, bee‐pollinated kiwifruit contained higher levels of sucrose and lower concentrations of glucose and fructose, while the acid content was less affected by pollination methods. Furthermore, significant differences were observed in the volatile organic compound (VOC) levels in kiwifruit subjected to different pollination treatments, with bee‐pollinated fruit exhibiting a superior flavor. Our findings provide new insights into the beneficial role of bee pollination in enhancing kiwifruit yield and quality, underscoring the crucial importance of bees in kiwifruit pollination.
The relationship between distress tolerance and behavioral activation on anxiety and depression symptomatology in autistic youth: Leveraging self and caregiver perspectives
Authors: Schwartzman Jessica M. , Antezana Ligia , Conner Caitlin M.
Published: August 2024

Anxiety and depression are prevalent among autistic adolescents and may be difficult to accurately diagnose and treat given various factors (e.g., diagnostic overshadowing, heterogeneity). Therefore, efforts to examine transdiagnostic factors (i.e., distress tolerance, behavioral activation) may afford more parsimonious means for assessment and treatment. To our knowledge, there has been little research on distress tolerance, behavioral activation, and depressive and anxiety symptoms in autistic adolescents to guide diagnostic practices and treatment planning. In the current study, we examined the interrelationships between these transdiagnostic factors and depressive and anxiety symptoms using ratings from 100 verbally fluent autistic adolescents without intellectual disability (Mage = 13.70, SDage = 2.23, Range: 11:00–17:11 years) and 100 of their caregivers. Many adolescents reported male sex assigned at birth (61%), cisgender (87%), not Hispanic/Latinx (90%), and White (80%) identities. A series of correlational analyses were employed to examine associations between these constructs from youth and caregiver perspectives, and multiple linear regression analyses were conducted to explore the mediating roles of distress tolerance and behavioral activation. Preliminary results show that low distress tolerance and behavioral activation were associated with more severe internalizing symptoms per self‐ and caregiver‐report. Some differences by rater emerged, which highlight the importance of multi‐informant ratings in autism. Results from mediation analyses may show that behavioral activation may be more salient to assessments and treatment planning for depression than distress tolerance, while distress tolerance may be important for both anxiety and depression; however, findings are preliminary given the cross‐sectional nature of the data. Findings suggest that these transdiagnostic concepts may be important to individualizing treatment approaches, including the timing of certain approaches, for anxiety and/or depression in autistic adolescents.
Stahlbetonbalken unter reiner Querkraftbeanspruchung
Authors: Schmidt Thilo , Feldick Lion , Dridiger Andreas , Albert Andrej
Published: August 2024

Die Querkrafttragfähigkeit von Stahlbetonbauteilen wird üblicherweise experimentell untersucht, indem die Versuchskörper durch vertikale Lasten beansprucht werden. Infolge dieser Beanspruchung entstehen in den Versuchskörpern Schnittgrößen in Form von Biegemomenten und Querkräften. Diese Schnittgrößen lassen sich unter solch einer Belastungssituation jedoch nicht unabhängig voneinander steuern. Dieser Beitrag stellt einen Versuchsaufbau vor, der es ermöglichen soll, ein konstantes Biegemoment und eine konstante Querkraft beliebiger Größe in einem Stahlbetonbalken zu erzeugen. Die Belastungssituation zur Erzeugung einer konstanten Querkraft in einem Balken mit Rechteckquerschnitt wurde in drei Bauteilversuchen umgesetzt. Zusätzlich wurde ein FEM‐Modell für Vergleichsberechnungen entwickelt. In den Bauteilversuchen zeigten alle Probekörper ein schlagartiges Versagen ohne erkennbare Vorankündigung. Bezüglich des Kraft‐Verformungs‐Verhaltens und der berechneten Tragfähigkeiten zeigten sich gute Übereinstimmungen zwischen den Bauteilversuchen und den begleitenden FEM‐Simulationen. Zur Erzeugung eines Zustands reiner Querkraftbeanspruchung in Stahlbetonbalken wird der vorgestellte Versuchsaufbau als grundsätzlich geeignet angesehen.
Chemically defined production of engineered cardiac tissue microspheres from hydrogel‐encapsulated pluripotent stem cells
Authors: Finklea Ferdous B. , Hashemi Mohammadjafar , Tian Yuan , Hammons Hanna , Halloin Caroline , Triebert Wiebke , Zweigerdt Robert , Lipke Elizabeth A.
Published: August 2024

Chemically defined, suspension culture conditions are a key requirement in realizing clinical translation of engineered cardiac tissues (ECTs). Building on our previous work producing functional ECT microspheres through differentiation of biomaterial encapsulated human induced pluripotent stem cells (hiPSCs), here we establish the ability to use chemically defined culture conditions, including stem cell media (E8) and cardiac differentiation media (chemically defined differentiation media with three components, CDM3). A custom microfluidic cell encapsulation system was used to encapsulate hiPSCs at a range of initial cell concentrations and diameters in the hybrid biomaterial, poly(ethylene glycol)‐fibrinogen (PF), for the formation of highly spherical and uniform ECT microspheres for subsequent cardiac differentiation. Initial microsphere diameter could be tightly controlled, and microspheres could be produced with an initial diameter between 400 and 800 µm. Three days after encapsulation, cardiac differentiation was initiated through small molecule modulation of Wnt signaling in CDM3. Cardiac differentiation occurred resulting in in situ ECT formation; results showed that this differentiation protocol could be used to achieve cardiomyocyte (CM) contents greater than 90%, although there was relatively high variability in CM content and yield between differentiation batches. Spontaneous contraction of ECT microspheres initiated between Days 7 and 10 of differentiation and ECT microspheres responded to electrical pacing up to 1.5 Hz. Resulting CMs had well‐defined sarcomeres and the gap junction protein, connexin 43, and had appropriate temporal changes in gene expression. In summary, this study demonstrated the proof‐of‐concept to produce functional ECT microspheres with chemically defined media in suspension culture in combination with biomaterial support of microsphere encapsulated hiPSCs.
Locked‐in syndrome: A qualitative study of a life story
Authors: Hordila Mona Lisa , García‐Bravo Cristina , Palacios‐Ceña Domingo , Pérez‐Corrales Jorge
Published: August 2024

Introduction

Locked‐in syndrome (LIS) is characterized by tetraplegia, anarthria, paralysis of cranial nerves, and facial musculature, with the preservation of consciousness and cognitive abilities, as well as vertical eye movements and eyelid movements, hearing, and breathing. Three types of LIS are distinguished: classic, incomplete, and total. The aim of the present study was to describe the life history of a person with LIS, as well as the wife's experience and perspective of this life history.

Methods

A qualitative life history study was conducted with two participants: a 54‐year‐old man diagnosed with LIS and his 50‐year‐old wife. Data were collected through interviews and autobiographical documents submitted by the participants and analyzed following Braun and Clarke's method of inductive thematic analysis.

Results

Five main themes were identified: (1) how to understand and overcome the new situation; (2) the process of care and rehabilitation; (3) communication; (4) writing as a way of helping oneself and others; and (5) personal autonomy and social participation.

Conclusion

The participants valued the support of their friends and family in the acceptance stage of the new situation, giving special importance to the communication skills and medical attention received after diagnosis.
Exploring the drivers of modern slavery reporting quality in Indonesia
Authors: Muawanah Afifah , Adhariani Desi
Published: August 2024

Vulnerability to modern slavery in Indonesia, particularly driven by poverty and discrimination against minority groups, has become a primary concern in the context of information transparency. This study aims to investigate the factors that can support the reporting quality of modern slavery in Indonesia, namely the industry sector, profitability, social responsibility commitment, and gender diversity as the moderating variable. The research utilized a sample of 225 companies listed on the Indonesia stock exchange (IDX) from 2020 to 2022. Data were collected from financial reports and sustainability reports as well as the Refinitiv Eikon database. Panel data regression analysis was conducted to analyze the determinants of the disclosure quality. The research findings indicate that high‐risk industry sectors tend to disclose less information regarding modern slavery, with this outcome having a partially negative impact. However, profitability is not associated with the quality of voluntary modern slavery disclosure. In contrast, corporate responsibility commitment is positively associated. Additionally, this study reveals that gender diversity does not moderate the association between the industry sector, profitability, and corporate responsibility commitment with the disclosure quality of modern slavery. This research contributes to the growing literature on the accountability of modern slavery in an emerging country context through institutional theory and gender socialization theory lenses by identifying the firm‐level factors to enhance corporate disclosure in this area. This study also contributes to corporate understanding of modern slavery issues within supply chains. With growing attention to this problem, the awareness of labor exploitation within corporate supply chains is also increasing. The findings of this research can assist companies in recognizing the importance of transparency and voluntary disclosure regarding modern slavery in their supply chains.
Drivers of green brand loyalty: Stakeholder engagement through corporate social responsibility and brand experience
Authors: Hue Truong Thi
Published: August 2024

This study aims to determine the drivers related to corporate social responsibility (CSR) and green brand experience that drive green brand loyalty (GBL), ranking the relative importance of these drivers while providing additional explanations for the ranking results. Data were collected from individuals with at least 5 years of experience consuming green agricultural products in Vietnam. The Delphi method and analytic hierarchy process (AHP) were employed in combination to address the research objectives. The research results indicated that both CSR and green brand experience can promote stakeholder engagement and enhance GBL, with components of green brand experience being evaluated as more crucial. The drivers within green brand experience and CSR were ranked in importance. The study makes significant scientific and practical contributions by combining qualitative and quantitative methods in this field, integrating components of CSR and green brand experience within an analytical framework to compare their importance in fostering GBL.
Methoxy Chalcone Derivatives: Promising Antimicrobial Agents Against Phytopathogens
Authors: Santos Tamiris A. C. , Sousa Ferreira Cassia , Barreto Alves Péricles , Scher Ricardo , Assis Pinheiro Liciane , Vilaça Costa Emmanoel , Roberto Gagliardi Paulo , Fernandes Roberta P. M.
Published: August 2024

Chalcone (E)‐1,3‐diphenyl‐prop‐2‐en‐1‐one and a series of 14 methoxylated derivatives have been synthesized via Claisen–Schmidt aldol condensation and characterized by FTIR, CG/MS/DIC, 1D (1H and 13C), 2D (COSY, HSQC, and HMBC) NMR, and EMAR techniques. All molecules were tested at 1 mM concentration for antifungal (Sclerotium sp., Macrophomina phaesolina and Colletotrichum gloeosporioides), antibacterial (Acidovorax citrulli two strains), and antiprotozoal (Phytomonas serpens) activities. Unmodified chalcone (CH0) and derivatives CH1, CH2, CH8 stood out in terms of antifungal activity. CH0 presented IC50 values of 47.3 μM (9.8 μg/mL) for the fungus C. gloeosporioides. In addition, fluorescence microscopy indicated that CH0 promoted loss of hyphal cell membrane integrity. The CH1 and CH2 derivatives promoted the inhibition of Sclerotium sp. with IC50 of 127.5 μM (32.9 μg/mL) and 110.4 μM (29.6 μg/mL), respectively. All molecules showed high activity against the phytoparasite P. serpens with IC50 values of 0.98, 2.40, 10.25, and 3.11 μM for the derivatives CH2, CH3, CH5 and CH14 respectively. The results demonstrated that derivatives methoxylated in both rings (CH2) as well as derivatives with a furan ring associated with the methoxy group in ring A, as well as unmodified chalcone can be promising agricultural fungicides for controlling the fungi studied.
Unveiling the hidden culprit: Parathyroid adenoma induced recurrent renal calculus and pancreatitis—A case report
Authors: Pandit Aakash Kumar , Pokharel Prajjwal , Sapkota Kabin , Dhakal Sanket , Kurmi Ram Narayan , Ranjan Mukesh Kumar
Published: August 2024

Key Clinical Message

This case report describes a 52‐year‐old patient presenting with recurrent episodes of pancreatitis and renal stones. Further investigation revealed hypocalcemia and elevated parathyroid hormone (PTH) levels, leading to diagnosis of a parathyroid adenoma. This case highlights the importance of considering primary hyperparathyroidism in patients with recurrent pancreatitis and renal stones, as early diagnosis and surgical intervention can prevent recurrence and reduce morbidity.

Primary Hyperparathyroidism secondary to Parathyroid adenoma, rarely presents as acute pancreatitis. A 38‐year‐young male with a history of recurrent renal stones referred from a local center, presented to the emergency services, with a diagnosis of acute pancreatitis and bilateral renal stones. Laboratory evaluation showed an elevated calcium level, elevated PTH levels, low vitamin D, and low phosphorus levels. CT scan done outside was suggestive of acute pancreatitis along with bilateral renal calculi. USG neck and MIBI scan done as a part of hypercalcemia evaluation showed presence of a right parathyroid adenoma. Parathyroid adenoma was later removed, and calcium and parathyroid levels were normal on subsequent follow ups.
Abdominal cocoon syndrome, a rare and interesting cause of intestinal obstruction: A case report
Authors: Menberu Endeshaw , Guteta Solomon , Bekele Tesfaye , Mengistu Simeon Mulugeta , Aliye Yonathan , Daba Merga , Mustefa Abdulhamid
Published: August 2024

Key Clinical Message

Abdominal cocoon syndrome is a rare cause of bowel obstruction, with variable presentation. It needs a high index of suspicion for diagnosis. Surgical management with the release of adhesions is the preferred option for a healthy bowel. Iatrogenic bowel perforation is a possibility during bowel manipulation and the release of thick fibrous adhesions resulting in bowel resection.

Abdominal cocoon syndrome, also known as encapsulating peritoneal sclerosis, is a rare cause of intestinal obstruction in which the small intestine may be entirely or partially wrapped in a thick sac of fibrous tissue that resembles a cocoon. We present a male Ethiopian patient, 60 years of age, who had a 6‐day history of symptoms of intermittent intestinal obstruction. Before his current presentation, he had a 6‐month history of sporadic vomiting and periodic abdominal pain. These symptoms would go away on their own. An exploratory laparotomy was performed for the preoperative diagnosis of small intestine obstruction secondary to primary small bowel volvulus after a plain abdomen x‐ray confirmed the small bowel obstruction diagnosis. But during surgery, we discovered something unexpected: a mass formed by the encasing membrane over the small bowel. En bloc resection of the mass and distal ileum with ileo‐transverse anastomosis was performed. The patient was discharged after 5 days of an uneventful post‐operative stay. The morbidity and mortality of this rare instance can be decreased by awareness, prompt diagnosis, and appropriate intervention. We discuss diagnostic and therapeutic challenges encountered during the management of this patient.
Gold Microflower Modified Screen‐Printed Carbon Electrode for the Electrochemical Detection of Lactic Acid in Blood and Sweat
Authors: Krishna Murali , Neena P. K. , Pradeep Aarathi , Vasu Suneesh Punathil , Satheesh Babu T. G.
Published: August 2024

A nonenzymatic electrochemical lactic acid sensor was fabricated by electrodepositing gold microflowers on a screen‐printed carbon electrode and used to determine lactic acid in human serum and sweat quantitatively. Extensive voltammetric studies with lactic acid in phosphate‐buffer saline (PBS) and the analysis of the reduction product proved beyond doubt that lactic acid undergoes two‐electron reduction to form lactaldehyde. The reduction current increased quantitively with lactic acid concentration from 0.5–8.5 mM in 0.1 M PBS. The sensor showed excellent sensitivities of 1243 μA mM−1 cm−2 and 2752 μA mM−1 cm−2 in two linear ranges, 0.5–2.5 mM and 2.5–8.5 mM, respectively with a detection limit of 0.012±0.0014 mM. The performance of the sensor was validated by estimating lactic acid in human serum and the sweat generated through physical exercise. The estimated lactic acid concentrations are in good agreement with clinical analysis data. This indicates the potential applicability of the sensor in the point‐of‐care detection of lactic acid.