bluuebunny/crossref_metadata_2025 huggingface dataset:
Infant Temperament Is Associated With Milk Cortisol but Not With Maternal Childhood Trauma
Authors: Apanasewicz Anna , Matyas Maja , Piosek Magdalena , Jamrozik Natalia , Winczowska Patrycja , Krzystek‐Korpacka Małgorzata , Ziomkiewicz Anna
Published: September 2024

Previous studies have suggested that maternal childhood trauma (MCT) may influence infant temperament, but the underlying physiological mechanisms remain unclear. This study sought to confirm the involvement of breast milk cortisol in the link between MCT and infant temperament. The study sample included 90 mother–infant dyads recruited from the urban Polish population. MCT was assessed based on the Early Life Stress Questionnaire (ELSQ) and infant temperamental factors (surgency/extraversion, negative affectivity, and orienting/regulation) using the Infant Behavior Questionnaire‐Revised at 12 months of life. Cortisol was assayed in milk samples collected at 5 months of life using the ELISA method. Based on the ELSQ median, the sample was divided into low and high MCT groups. The ANCOVA models with milk cortisol as a covariant were run to check the effect of low versus high MCT on infant temperament. We found a positive association between milk cortisol and orienting/regulation. Surprisingly, the low and high MCT groups did not significantly differ in milk cortisol. Furthermore, we found that MCT was unrelated to any infant temperamental factor. While recent literature on the association between milk cortisol and infant temperament is inconsistent, our results suggest that high orienting/regulation might be an adaptation to adverse environments such as stress. Moreover, the infant's temperament appears to be more responsive to the current exposition to maternal stress than her experience of traumatic stress.
Integrating amyloid imaging and genetics for early risk stratification of Alzheimer's disease
Authors: He Bing , Wu Ruiming , Sangani Neel , Pugalenthi Pradeep Varathan , Patania Alice , Risacher Shannon L. , Nho Kwangsik , Apostolova Liana G. , Shen Li , Saykin Andrew J. , Yan Jingwen ,   for the Alzheimer's Disease Neuroimaging Initiative
Published: September 2024

INTRODUCTION

Alzheimer's disease (AD) initiates years prior to symptoms, underscoring the importance of early detection. While amyloid accumulation starts early, individuals with substantial amyloid burden may remain cognitively normal, implying that amyloid alone is not sufficient for early risk assessment.

METHODS

Given the genetic susceptibility of AD, a multi‐factorial pseudotime approach was proposed to integrate amyloid imaging and genotype data for estimating a risk score. Validation involved association with cognitive decline and survival analysis across risk‐stratified groups, focusing on patients with mild cognitive impairment (MCI).

RESULTS

Our risk score outperformed amyloid composite standardized uptake value ratio in correlation with cognitive scores. MCI subjects with lower pseudotime risk score showed substantial delayed onset of AD and slower cognitive decline. Moreover, pseudotime risk score demonstrated strong capability in risk stratification within traditionally defined subgroups such as early MCI, apolipoprotein E (APOE) ε4+ MCI, APOE ε4– MCI, and amyloid+ MCI.

DISCUSSION

Our risk score holds great potential to improve the precision of early risk assessment.

Highlights

Accurate early risk assessment is critical for the success of clinical trials.

A new risk score was built from integrating amyloid imaging and genetic data.

Our risk score demonstrated improved capability in early risk stratification.
Polyphenol Oxidase Activity on Guaiacyl and Syringyl Lignin Units
Authors: de O. G. Silva Caio , Sun Peicheng , Barrett Kristian , Sanders Mark G. , van Berkel Willem J. H. , Kabel Mirjam A. , Meyer Anne S. , Agger Jane W.
Published: September 2024

The natural heterogeneity of guaiacyl (G) and syringyl (S) compounds resulting from lignin processing hampers their direct use as plant‐based chemicals and materials. Herein, we explore six short polyphenol oxidases (PPOs) from lignocellulose‐degrading ascomycetes for their capacity to react with G‐type and S‐type phenolic compounds. All six PPOs catalyze the ortho‐hydroxylation of G‐type compounds (guaiacol, vanillic acid, and ferulic acid), forming the corresponding methoxy‐ortho‐diphenols. Remarkably, a subset of these PPOs is also active towards S‐compounds (syringol, syringic acid, and sinapic acid) resulting in identical methoxy‐ortho‐diphenols. Assays with 18O2 demonstrate that these PPOs in particular catalyze ortho‐hydroxylation and ortho‐demethoxylation of S‐compounds and generate methanol as a co‐product. Oxidative (ortho−) demethoxylation of S‐compounds is a novel reaction for PPOs, which we propose occurs by a distinct reaction mechanism as compared to aryl‐O‐demethylases. We further show that addition of a reducing agent can steer the PPO reaction to form methoxy‐ortho‐diphenols from both G‐ and S‐type substrates rather than reactive quinones that lead to unfavorable polymerization. Application of PPOs opens for new routes to reduce the heterogeneity and methoxylation degree of mixtures of G and S lignin‐derived compounds.
Employing Singlet‐Singlet Energy Transfer for Boosting the Reactivity of Type I Photoinitiators in Radical Photopolymerization
Authors: Niederst Léo , Allonas Xavier , Morone Marika , van den Branden Stefan
Published: September 2024

A remarkable and unexpected increase in the photopolymerization efficiency of an acrylic resin by a bisacylphosphine oxide photoinitiator was observed when an optical brightener was present in the medium. High values for the maximal rates of photopolymerization were obtained by RT‐FTIR at 365 nm under a very low irradiance of 1 mW/cm2. Fluorescence studies revealed that the quenching process occurs through singlet‐singlet energy transfer between the first singlet excited state of the optical brightener and the ground state photoinitiator. This mechanism acts as an additional pathway for the excitation of the photoinitiator, thereby increasing the total amount of initiating radicals. Using the Förster resonance energy transfer model, we calculated the relative efficiency of the photosensitization process with respect to the direct excitation efficiency of the photoinitiator. The results demonstrate that the photosensitization process can be predicted, paving the way for further improvements in photoinitiating systems.
Elektrochemische Identifizierung und Quantifizierung von Durchgangs‐Protonenkanälen in Graphenoxid‐Membranen
Authors: Wang Yiqing , Eigler Siegfried
Published: September 2024

Membranen aus Graphenoxid (GO) sind aufgrund ihrer Protonenleitfähigkeit vielversprechende Kandidaten für Energieanwendungen. Kanäle in diesen Membranen sind für die Funktion verantwortlich. Deren Identifizierung ist aber aufgrund ihrer anisotropen Natur herausfordernd. Hier wird eine elektrochemische Reduktionsmethode zur Identifizierung und Quantifizierung von durchgehenden Protonenkanälen in GO‐Membranen vorgestellt. Der Schlüssel hierzu liegt in der optischen Beobachtung der Membranen und der auftretenden Kontrastveränderung, wenn GO elektrochemisch reduziert wird. Es wurden drei protonendominierte Dreiphasengrenzflächen gefunden, die für die Reduktionsreaktionen von GO‐Membranen entscheidend sind. Basierend auf diesen Ergebnissen wird eine Methode zur Identifizierung und Quantifizierung von Durchgangskanälen in gestapelten GO‐Protonenmembranen vorgeschlagen, die eine einfache Drei‐Elektroden‐Apparatur in Kombination mit Echtzeit‐Bildgebung der Membranoberfläche verwendet.
A Helicene‐Based Single‐Molecule Inductor and Capacitor with Frequency‐Dependent Charge‐Transport Pathways
Authors: He Pengxing , Ye Jingyao , Zhang Junrui , Lu Taige , Cui Wenying , Liu Junyang , Shen Chengshuo , Hong Wenjing , Liu Xunshan
Published: September 2024

Despite extensive studies has been explored on single‐molecule switches and rectifiers, the design of single‐molecule inductors has not been explored due to the experimental challenges in the investigation of frequency‐dependent charge transport at the single‐molecule scale. In this study, we synthesized a helicene‐based helical molecular wire and carried out meticulous single‐molecule conductance measurements, combined with current–voltage (IV) studies with varying frequencies using the scanning tunneling microscope break junction (STM‐BJ) technique. Our results reveal the formation of a single‐molecule junction and highlight the unique behavior of the molecular wire in response to different alternating current (AC) varying frequencies. The transport of charges occurs selectively either through the coiled backbone of the conjugated helical structure or vertically via π–π stacking, depending on the frequency of the applied AC. Notably, our investigation demonstrates the functionality of the wire as an inductor at low frequencies, and a capacitor at high frequencies. This work lays the foundation for a systematic approach to designing, fabricating, and implementing single‐molecule logic devices such as inductors and wave filters.
Control of Dynamic Chirality in Donor‐Acceptor Fluorophores
Authors: Coehlo Max , Frédéric Lucas , Poulard Laurélie , Ferdi Nawal , Estaque Lilian , Desmarchelier Alaric , Clavier Gilles , Dognon Jean‐Pierre , Favereau Ludovic , Giorgi Michel , Naubron Jean‐Valère , Pieters Gregory
Published: September 2024

Recently, the control of dynamic chirality has emerged as a powerful strategy to design chiral functional materials. In this context, we describe herein a molecular design in which a tethered configurationally stable binaphthyl chiral unit efficiently controls the dynamic chirality of donor‐acceptor fluorophores, involving diverse indolocarbazoles as electron donors and terephthalonitrile as an electron acceptor. The high conformational discrimination in such a molecular system suggested by density functional theory calculations is experimentally probed using electronic and vibrational circular dichroism and confirmed by the crystallization of these chiral molecules in gel and their single crystal X‐ray diffraction analysis. This work also highlights the positive effect of the configurationally stable chiral unit on the magnitude of the dissymmetry factors of the active dynamically chiral fluorophores, both in ground and excited states, through chiral perturbation.
Triple Regulations via Fe Redox Boosting Nitrate Reduction to Ammonia at Industrial Current Densities
Authors: Yang Wenhao , Chang Ziwei , Yu Xu , Shen Ruxiang , Wang Lianzhou , Cui Xiangzhi , Shi Jianlin
Published: September 2024

Electrochemical nitrate reduction reaction (NO3−RR) has promising prospects for green synthesis of ammonia and environmental remediation. However, the performance of catalysts at high current density usually suffers from the high energy barrier for the nitrate (NO3−) to nitrite (NO2−) and the competitive hydrogen evolution. Herein, we proposed a two‐step relay mechanism through spontaneous redox reaction followed electrochemical reaction by introducing low‐valence Fe species into Ni2P nanosheets to significantly enhance the NO3−RR performance at industrial current density. The existence of low‐valence Fe species bypasses the NO3− to NO2− step through the spontaneous redox with NO3− to produce NO2− and Fe2O3, regulates the electronic structure of Ni2P to reduce the barrier of NO2− to NH3, thirdly prohibits the hydrogen evolution by consuming the excess active hydrogen through reduction of Fe2O3 to recover low‐valence Fe species. The triple regulations via Fe redox during the two‐step relay reactions guarantee the Fe‐Ni2P@NF high ammonia yield of 120.1 mg h−1 cm−2 with Faraday efficiency of more than 90% over a wide potential window and a long‐term stability of more than 130 h at ~1000 mA cm−2. This work provides a new strategy to realize the design and synthesis of nitrate reduction electrocatalysts at high current densities.
Enabling Visible Light Sensitization of YbIII, NdIII and ErIII in Dimeric LnIII/GaIII Metallacrowns through Functionalization with RuII Complexes for NIR‐II Multiplex Imaging
Authors: Bădescu‐Singureanu Codruţa C. , Nizovtsev Anton S. , Pecoraro Vincent L. , Petoud Stéphane , Eliseeva Svetlana V.
Published: September 2024

Multiplex imaging in the second near‐infrared window (NIR‐II, 1000–1700 nm) provides exciting opportunities for more precise understanding of biological processes and more accurate diagnosis of diseases by enabling real‐time acquisition of images with improved contrast and spatial resolution in deeper tissues. Today, the number of imaging agents suitable for this modality remains very scarce. In this work, we have synthesized and fully characterized, including theoretical calculations, a series of dimeric LnIII/GaIII metallacrowns bearing RuII polypyridyl complexes, LnRu‐3 (Ln=YIII, YbIII, NdIII, ErIII). Relaxed structures of YRu‐3 in the ground and the excited electronic states have been calculated using dispersion‐corrected density functional theory methods. Detailed photophysical studies of LnRu‐3 have demonstrated that characteristic emission signals of YbIII, NdIII and ErIII in the NIR‐II range can be sensitized upon excitation in the visible range through RuII‐centered metal‐to‐ligand charge transfer (MLCT) states. We have also showed that these NIR‐II signals are unambiguously detected in an imaging experiment using capillaries and biological tissue‐mimicking phantoms. This work opens unprecedented perspectives for NIR‐II multiplex imaging using LnIII‐based molecular compounds.
Novel Cu(II) and Zn(II) Nanocomplexes Based on 5,6‐Diphenyl‐1,2,4‐Triazine: Preparation, Spectroscopic, TD‐DFT Calculations, Molecular Docking and Solvatochromic Studies
Authors: Boshra Mona , Adly Omima M. I. , Abdelrhman Ebtesam M. , Eid Mohamed F. , Samy Fatma
Published: September 2024

The reaction between 2‐hydroxy‐1‐naphthaldehyde and 3‐hydrazino‐5,6‐diphenyl‐1,2,4‐triazine produced a novel hydrazone ligand (DTHMN), which reacted with Cu(II) and Zn(II) metal ion in molar ratio 1:1, giving octahedral Cu(II)‐DTHMN and tetrahedral Zn(II)‐DTHMN nanosized complexes. The structural geometries have been elucidated on the basis of elemental analysis, nuclear magnetic resonance, infrared, electronic, and electron spin resonance spectra, and magnetic and molar conductance measurements as well as x‐ray diffraction and thermal analysis. TEM analysis showed that Zn(II)‐DTHMN complex has nano‐rode morphology shape. On the other hand, Cu(II)‐DTHMN has sphere shape within nanodomain. The DTHMN ligand exhibits ONN chelating sites through N‐triazine ring, azomethine nitrogen, and deprotonated OH group, forming the mononuclear metal complexes. The synthesized compounds showed a distinct solvatochromic behavior in different polar solvents. A bathochromic alteration is observed when moving from less to high polar solvents, indicating strong solute–solvent interactions accompanied by intramolecular charge transfer (ICT). The ground and excited state dipole moments of these compounds were determined experimentally by solvatochromic shift method using Bilot–Kawski, Lippert–Mataga, Bakhshiev, and Kawski–Chamma–Viallet functions and a microscopic Reichardt's solvent polarity parameter (ETN). The dipole moment is increased significantly upon excitation referring to stabilizing the excited species includes n–π* transition by polarity of solvent. The experimental results are generally consistent with those values obtained by B3LYP/GENECP method at 6‐311G(d,p) basis set for C, H, N, and O atoms and SDD (Stuttgart/Dresden) basis set for the metal atoms. The compounds were tested for antimicrobial efficiency against Gram‐positive bacteria, Gram‐negative bacteria, and fungus strain. Finally, molecular docking was used to study the interactions between donors (the current compounds) and receptors FabH–CoA complex (PDB code: 1HNJ).
Preparation of magnetic scaffolds via supercritical carbon dioxide foaming process using iron oxide nanoparticles coated with CO2‐philic materials as nucleating agents
Authors: Jiao Zhen , Zhang Shuo , Wang Jinjing , Zhang Yi
Published: September 2024

The iron oxide nanoparticles (IONs), coated with different materials, are synthesized and utilized as nucleating agents to prepare magnetic multi‐modal porous scaffolds of poly (lactic‐co‐glycolic acid)/IONs using the supercritical carbon dioxide (ScCO2) foaming process. The effects of the modification materials, including citric acid, polycaprolactone, and polyvinyl acetate, on the foaming process and properties of the magnetic scaffolds are systematically investigated. The results indicate that the solubility and diffusion ability of CO2 in the foaming materials played a vital role in the foaming process. The use of CO2‐philic materials and high pressure proves beneficial in generating micropores. The scaffolds with multi‐modal porous structures can be obtained at relatively low pressure for the ScCO2 foaming systems evaluated in this study. Furthermore, the prepared scaffolds exhibit high porosity and a good compressive modulus (higher than 0.4 MPa), satisfying the requirements of tissue engineering for soft tissue scaffolds.
Anatomical description of a pygmy sperm whale, Kogia breviceps (Cetacea: Kogiidae), pre‐term calf using CT scan and 3D reconstructions
Authors: Bennati‐Madureira Lara , Gomes Gabriel Leandro , Daros Kellen Adriana Curci , Casas André Luis da Silva
Published: September 2024

Little is known about the biology of pygmy sperm whales, Kogia breviceps (De Blainville, 1838), being that most anatomical descriptions for the species derive from necropsy after stranding or from osteological material preserved in museums. This species is rarely seen despite its wide distribution, and its reproductive behaviour is still being investigated. The eventual occurrence of pregnant female strandings and the collection and description of foetuses can give clues about the organisms' mostly unknown early development. However, this type of biological material is extremely rare, limiting anatomical analysis due to the risk of damage or loss. Here, we describe the external and internal anatomy of an 84 cm long K. breviceps foetus. The methods utilised were non‐intrusive, meaning that no incisions were made on the specimen. The foetus was analysed using computed tomography images and a three‐dimensional reconstruction of the skeleton. A great number of features were observed, such as axial and appendicular skeletal structures, internal organs, echolocation apparatus and umbilical cord, as well as diagnostic characters of the species, such as the asymmetrical skull, spermaceti chamber and false gill pigmentation. We suggest that more specimens on different stages of development should be analysed by the same technique, as well as further comparison with specimens from other taxa, in order to facilitate more comparative studies on embryonic and foetal development of cetaceans.
EGB761 ameliorates mild cognitive impairment by inhibiting the pyroptosis and apoptosis in both in vivo and in vitro experiments
Authors: Zhang Xiaolu , Sun Yingxin , Zheng Yujia , Zhang Ruifeng , Yan Xu , Wei Huayuan , Yang Lin , Jiang Xijuan
Published: September 2024

Mild cognitive impairment (MCI) is a neurodegenerative condition that is clinically prevalent among the elderly. EGB761 is widely recognized for its promising therapeutic properties in both the prevention and treatment of neurodegenerative disorders. The aim of this study was to investigate the effects of EGB761 in MCI and the underlying molecular mechanism. Four‐month‐old SAMP8 mice were used as an in vivo MCI model, and BV2 microglial cells were treated with β‐amyloid (Aβ) 1–42 to establish an in vitro model. First, the cognitive function was evaluated by the Morris water maze. Then, Aβ levels were measured by enzyme‐linked immunosorbent assay. Finally, the underlying molecular mechanism was investigated both in vivo and in vitro. It was found that EGB761 treatment improved the cognitive impairment of SAMP8 mice. In addition, EGB761 inhibited NOD‐like receptor protein 3 inflammasome‐mediated pyroptosis‐related mRNAs and proteins and reduced pyroptosis markers, including gasdermin D fluorescence intensity, propidium iodide‐positive cell count, and the lactate dehydrogenase content. Furthermore, EGB761 inhibited extrinsic and intrinsic apoptosis. Thus, EGB761 had protective effects against pyroptosis and apoptosis in BV2 microglial cells induced by Aβ1‐42 and SAMP8 mice.
Unraveling the Genetics of Shared Clinical and Serological Manifestations in Patients With Systemic Inflammatory Autoimmune Diseases
Authors: Bianchi Matteo , Kozyrev Sergey V. , Notarnicola Antonella , Sandling Johanna K. , Pettersson Mats , Leonard Dag , Sjöwall Christopher , Gunnarsson Iva , Rantapää‐Dahlqvist Solbritt , Bengtsson Anders A. , Jönsen Andreas , Svenungsson Elisabet , Enocsson Helena , Kvarnström Marika , Forsblad‐d'Elia Helena , Bucher Sara Magnusson , Norheim Katrine B. , Baecklund Eva , Jonsson Roland , Hammenfors Daniel , Eriksson Per , Mandl Thomas , Omdal Roald , Padyukov Leonid , Andersson Helena , Molberg Øyvind , Diederichsen Louise Pyndt , Syvänen Ann‐Christine , Wahren‐Herlenius Marie , Nordmark Gunnel , Lundberg Ingrid E. , Rönnblom Lars , Lindblad‐Toh Kerstin ,   with the DISSECT consortium and the ImmunoArray consortium
Published: September 2024

Objective

Systemic inflammatory autoimmune diseases (SIADs) such as systemic lupus erythematosus (SLE), primary Sjögren disease (pSS), and idiopathic inflammatory myopathies (myositis) are complex conditions characterized by shared circulating autoantibodies and clinical manifestations, including skin rashes, among others. This study was aimed at elucidating the genetics underlying these common features.

Methods

We performed targeted DNA sequencing of coding and regulatory regions from approximately 1,900 immune‐related genes in a large cohort of 2,292 well‐characterized Scandinavian patients with SIADs with SLE, pSS, and myositis as well as 1,252 controls. A gene‐based functionally weighted genetic score for aggregate testing of all genetic variants, including rare variants, was complemented by in silico functional analyses and in vitro reporter experiments.

Results

Case–control association analysis detected known and potentially novel genetic loci in agreement with previous genetic and transcriptomics findings linked to the SIAD autoimmune background. Intriguingly, case–case comparisons between patient subgroups with and without specific autoantibodies revealed that the subgroups defined by antinuclear antibodies and anti–double‐stranded DNA antibodies have unique genetic profiles reflecting their heterogeneity. When focusing on clinical features, we overall showed that dual‐specificity phosphatase 1 (DUSP1) protective genetic variants lead to increased gene expression and potentially to anti‐inflammatory effects on the SIAD‐associated skin phenotype. This is consistent with recent genetic findings on eczema and with the previously reported down‐regulation of the MAPK signaling‐related gene DUSP1 in other skin disorders.

Conclusion

Together, this suggests common molecular mechanisms potentially underlying overlapping clinical manifestations shared among different disorders and informs clinical heterogeneity, which could be translated to improve disease diagnostic and treatment, also in more generalized disease frameworks.
Sanierung des Gottfried‐Böhm‐Parkhauses
Authors: Walz Marcus , Sauer Marc , Scherzer Jan , Muratovic Edin
Published: September 2024

Das von Gottfried Böhm entworfene und 1986 fertiggestellte Parkhaus Stadtmitte in Landau ist ein markantes Beispiel expressionistischer Betonarchitektur. Es steht unter Denkmalschutz und ist bekannt für die ästhetische Verwendung von rötlich pigmentiertem Beton, der an den roten Pfälzer Sandstein erinnert. Das fünfgeschossige Gebäude mit einer Nutzfläche von 9000 m2 bietet Platz für 300 Fahrzeuge. Es hat eine offene Fassade mit unregelmäßigen Brüstungselementen, die an Felsen erinnern, und einen verglasten Aufzugsturm an der Ostfassade, der den Blick auf die Stadt freigibt. Die Konstruktion besteht überwiegend aus Stahl‐ und Spannbetonfertigteilen, das Dachtragwerk ist in Stahl ausgeführt. Die Geschosse sind halbgeschossig versetzt, um die Anpassung an das Gelände zu erleichtern. Die Eigentümerin, die VR Bank Südpfalz eG, initiierte im Jahr 2021 die Sanierung des Parkhauses aufgrund von Schäden durch Chlorideintrag und schadhaften Vergussfugen. Besondere Maßnahmen waren die nahezu vollständige Erneuerung der untersten Parkebene, der Einbau von Spannbetonfertigteilträgern und das Aufbringen eines hochfesten Oberflächenschutzes.
Deep‐eutectic‐solvent‐assisted hydrothermal carbonization of sewage sludge for green wood bioadhesive production
Authors: Xu Zhi‐Xiang , Dou Rui , Tan Yi , Xiong Huan‐Ran , Chen Yong‐Xing , Leng Li‐Jian , Vlaskin Mikhail , Osman Sameh M. , Luque Rafael
Published: September 2024

This study reports the use of deep‐eutectic‐solvent‐ (DES‐) assisted hydrothermal carbonization (HTC) to disrupt the floc structure of sewage sludge (SS) for deep carbonization, with the resulting hydrochars employed in the preparation of formaldehyde‐free plywood bioadhesives. Sewage‐sludge‐based bioadhesive exhibits an excellent wet shear strength, complying with the requirements of Chinese national standard GB/T 9846–2015 (≥0.7 MPa). The molecular weight of proteins and the formation of covalent bonds via dehydration have a notable role in improving adhesive performance (wet shear strength). The Maillard reaction is a key reaction during HTC to destroy the secondary structure of proteins, resulting in the release of more OH and NH2. The main reaction during hot‐press treatment is dehydration. High ash content in bioadhesives improves flame resistance potential, particularly on addition of DES. A plausible mechanism is proposed for this. This work provides a new method for the valorization of SS‐derived hydrochars and contributes to the development of greener formaldehyde‐free wood bioadhesives.
Sandwiched naphthyl carbazole: Inversion Circularly Polarized Luminescence based on a pull‐push electron valve strategy
Authors: Qi Qi , Junfeng Li , Yueming Sun
Published: September 2024

Inspired by circularly polarized luminescence (CPL), artificial CPL assembly has attracted intense attention. However, precise manipulation of chiral transfer from achiral and luminescent materials remains a formidable challenge. Two sandwiched carbazole and binaphthol derivatives composed of pyridine or trifluoride methyl benzene have been synthesized. Among R‐1 and R‐2, their spectra were found in the violet region, both in the solution and the film state. They exhibit the photoluminescence dissymmetry factors up to 1.4 × 10−3 for R‐2 and an opposite value of −5.6 × 10−4 for R‐1. Theoretical CPL and circular dichroism (CD) studies were in good agreement with the experimental data and deciphered their opposite signals by the transition electric and magnetic moment. Our study offers a strategy for studying the charge and chiral transfer.
A label‐free and signal‐amplifiable fluorescent biosensor based on aptamer‐conjugated gold nanoparticles and hybridization chain reaction for determination of carcinoembryonic antigen
Authors: Liu Siyao , Yang Xingjie , Xiao Peng , Wang Wei , Zhu Shaoqing , Chu Jingzhi , Zhou Chenguang
Published: September 2024

The sensitive detection of cancer biomarkers is crucial for early accurate diagnostics and therapy of cancer patients. Carcinoembryonic antigen (CEA) is a tumor‐associated antigen derived from colon cancer and embryonic tissues. In this study, we have developed a label‐free fluorescence biosensing platform for the quantification of CEA with the “turn‐on” signal output. This platform employs a label‐free strategy that incorporates an aptamer‐modified gold nanoparticle (Apt@AuNP) probe for the recognition of CEA, in combination with hybridization chain reaction (HCR) amplification. In the presence of target CEA, Apt@AuNPs selectively capture CEA, resulting in a reduction of subsequent complementary chains (CP) binding on Apt@AuNPs. The remaining CP, acting as the initiator sequence for HCR, triggers the HCR, leading to the formation of abundant G‐quadruplex structures. By employing Thioflavin T (ThT) for the formation of G‐quadruplex/ThT complexes, the biosensor exhibits a significant enhancement of the fluorescence signal. Under optimized conditions, the biosensor platform demonstrates a limit of detection of 0.03 nM and a linear range from 0.1 to 2.5 nM. Additionally, the specificity investigation reveals the high selectivity of this fluorescent biosensor. Finally, the performance of this method has been validated by successfully detecting CEA in real‐life samples, highlighting its potential for clinical applications.
Fostering resilience and post‐traumatic growth in overseas Chinese left‐behind children: The role of autonomy, competence, and relatedness
Authors: Zhao Shengyu , Zhang Ke , Lin Yingying , Han Li , Liao Chuanjing , Ye Rufang , Na Meng , Alam Syed Shah
Published: September 2024

Objective

This study examines the impact of parental migration on the psychological well‐being and development of left‐behind children (LBCs) in Zhejiang, China, within the broader context of the country's rural transformations and urban migration. It investigates how intellectual and relational engagement (RE), autonomy (AUT), competence (COM), and relatedness (RES) contribute to resilience (REL) and post‐traumatic growth (PTG) in these children, reflecting on the shift from viewing parental separation merely as a source of trauma to recognizing its potential to foster significant personal growth.

Methods

Utilizing a cross‐sectional design, the research was conducted in April and May 2023 with 1348 LBCs from a total sample of 4049 students inZhejiang. A two‐step random, stratified, cluster‐based sampling strategy was employed, and structural equation modeling was used to examine the hypothesized relationships among the constructs.

Results

The statistical analysis demonstrated significant positive effects of intellectual engagement (IE), AUT, COM, and RE on both REL and PTG (p < .05 for all). IE strongly correlated with AUT (r = .68, p < .001) and COM (r = .71, p < .001), enhancing REL and facilitating PTG. Additionally, the presence of secure and consistent relationships was identified as crucial for maintaining psychological well‐being, with high correlation coefficients (r > .60) underscoring their importance. Notably, REL was found to moderate the relationships among RES, COM, and PTG, highlighting its critical role in the psychological adaptation of left‐behind children.

Conclusion

The study underscores the importance of nurturing intellectual and REs, AUT, and COM to enhance psychological REL and well‐being among LBAs. These elements are crucial for supporting the mental health and developmental needs of children facing the challenges of parental migration. The findings advocate for targeted interventions that can address the unique needs of this vulnerable population, emphasizing the potential for growth and adaptation despite adversities.
A systematic review on investigating major depressive disorder and bipolar disorder using MRI and genetic data from 2018 to 2024
Authors: Sun Kai , Wang Xin , Zhou Guifei , Lv Wenchao , Song Rujia , Wei Wei , Liu Zhenyu , Yu Changbin
Published: September 2024

The incidence of affective disorders, of which major depression disorder (MDD) and bipolar disorder (BD) are two main types, has increased rapidly in recent years. They significantly impact patients, their families, and society. However, while affective disorders have become a major issue worldwide, their pathogenesis remains unclear. In the last 6 years, research using magnetic resonance imaging (MRI) and genetic data has gained prominence in understanding their pathophysiology and etiology. This systematic review collected the studies of MDD and BD research published between January 1, 2018, and February 1, 2024, focusing on studies using MRI and genetic data and indexed in the Web of Science and PubMed database. It aims to investigate the similarities and differences in their imaging phenotypes and underlying molecular bases. After exclusions, a total of 80 articles were included in this review. Research on MDD and BD reveals the critical role of epigenetic modifications, such as DNA methylation, in brain structure and function changes. The genes and pathways implicated in MDD are directly associated with depressive symptoms. In contrast, those implicated in BD are associated with mood regulation and cognitive functions. In addition, functional imaging studies have revealed that abnormalities in MDD are frequently concentrated in regions involved in emotion regulation and stress response. In contrast, those in BD are frequently concentrated in the neural circuits related to reward processing and emotional stability. Further multimodal and multiscale studies are needed to advance the field of mood disorder research.
Local TSH/TSHR signaling promotes CD8+ T cell exhaustion and immune evasion in colorectal carcinoma
Authors: Zeng Sisi , Hu Huiling , Li Zhiyang , Hu Qi , Shen Rong , Li Mingzhou , Liang Yunshi , Mao Zuokang , Zhang Yandong , Zhan Wanqi , Zhu Qin , Wang Feifei , Xiao Jianbiao , Xu Bohan , Liu Guanglong , Wang Yanan , Li Bingsong , Xu Shaowan , Zhang Zhaowen , Zhang Ceng , Wang Zhizhang , Liang Li
Published: September 2024

Background

Dysfunction of CD8+ T cells in the tumor microenvironment (TME) contributes to tumor immune escape and immunotherapy tolerance. The effects of hormones such as leptin, steroid hormones, and glucocorticoids on T cell function have been reported previously. However, the mechanism underlying thyroid‐stimulating hormone (TSH)/thyroid‐stimulating hormone receptor (TSHR) signaling in CD8+ T cell exhaustion and tumor immune evasion remain poorly understood. This study was aimed at investigating the effects of TSH/TSHR signaling on the function of CD8+ T cells and immune evasion in colorectal cancer (CRC).

Methods

TSHR expression levels in CD8+ T cells were assessed with immunofluorescence and flow cytometry. Functional investigations involved manipulation of TSHR expression in cellular and mouse models to study its role in CD8+ T cells. Mechanistic insights were mainly gained through RNA‐sequencing, Western blotting, chromatin immunoprecipitation and luciferase activity assay. Immunofluorescence, flow cytometry and Western blotting were used to investigate the source of TSH and TSHR in CRC tissues.

Results

TSHR was highly expressed in cancer cells and CD8+ T cells in CRC tissues. TSH/TSHR signaling was identified as the intrinsic pathway promoting CD8+ T cell exhaustion. Conditional deletion of TSHR in CD8+ tumor‐infiltrating lymphocytes (TILs) improved effector differentiation and suppressed the expression of immune checkpoint receptors such as programmed cell death 1 (PD‐1) and hepatitis A virus cellular receptor 2 (HAVCR2 or TIM3) through the protein kinase A (PKA)/cAMP‐response element binding protein (CREB) signaling pathway. CRC cells secreted TSHR via exosomes to increase the TSHR level in CD8+ T cells, resulting in immunosuppression in the TME. Myeloid‐derived suppressor cells (MDSCs) was the main source of TSH within the TME. Low expression of TSHR in CRC was a predictor of immunotherapy response.

Conclusions

The present findings highlighted the role of endogenous TSH/TSHR signaling in CD8+ T cell exhaustion and immune evasion in CRC. TSHR may be suitable as a predictive and therapeutic biomarker in CRC immunotherapy.
Expression of MxA in esophageal cancer cell lines can influence sensitivity to chemotherapeutic agents but this does not require apoptosis
Authors: Hayes R. M. , O'Donovan T. R. , McKenna S. L.
Published: September 2024

Esophageal cancer is a poor prognosis cancer characterized by intrinsic or acquired resistance to chemotherapeutic agents. The primary determinants of treatment failure are unknown. Expression of an anti‐viral protein, myxovirus resistance protein A (MxA) is de‐regulated in many cancers, including esophageal cancer, and its activity has been linked to apoptosis. This study has assessed whether MxA expression can influence the response of esophageal cancer cells to the chemotherapeutic agents 5‐fluorouracil (5‐FU) or oxaliplatin. MxA protein was differentially expressed in a panel of five esophageal cancer cell lines. KYSE450 and KYSE140 cells did not express MxA and were apoptosis incompetent. FLO‐1, KYSE270, and OE21 cells expressed MxA, were more drug‐sensitive and were apoptosis competent. MxA was artificially overexpressed in cell lines with no endogenous expression (KYSE450 and KYSE140). This increased the resistance of KYSE450 but not KYSE140 cells. Both cell lines remained apoptosis incompetent. We then evaluated siRNA knockdown of MxA in FLO‐1 cells and CRISPR knockout in OE21 cells. Knockdown of MxA significantly increased drug sensitivity and caspase‐3 activation in FLO‐1 cells. OE21‐MX1KO cells were also more drug‐sensitive, but in contrast to FLO‐1 cells, caspase‐3 activation was reduced. Collectively these data indicate that MxA can promote resistance to chemotherapy, but this does not always correspond with effects on apoptosis. Effects on apoptosis are cell line specific, suggesting that other co‐operating pathways determine the overall impact of MxA. Importantly, in cancer cells that overexpress the protein, drug sensitivity can be improved by interfering with MxA.
Preparation, Characterization, In Vitro Biological Evaluation, DFT Calculations, and Molecular Docking Investigations of 1H‐Imidazole‐2‐Carboxylic acid and Histidine‐Based Mixed‐Ligand Complexes
Authors: Abd El‐Lateef Hany M. , Khalaf Mai M. , Abdou Aly
Published: September 2024

Mixed‐ligand complexes incorporating 1H‐Imidazole‐2‐Carboxylic acid (IMCA) and Histidine (LHIS) show promise for biomedical and biotechnological applications. This study synthesizes and characterizes FeIMCALHIS, CoIMCALHIS, and NiIMCALHIS coordination compounds using metal chloride salts (FeCl3.6H2O, CoCl2.6H2O, NiCl2.6H2O) in ethanolic solutions. The complexes are characterized by spectroscopic methods (IR, UV‐vis, and mass spectra), elemental analysis, conductivity, magnetic, and thermal analysis. Molar conductivity indicates their non‐electrolytic nature. UV‐vis spectra reveal absorption bands with pathochromic shifts, and electronic spectra show characteristic metal‐ligand transitions, indicating their structural configuration and coordination geometry. 3D geometry optimization shows six‐coordination around Fe(III) and Co(II) in FeIMCALHIS and CoIMCALHIS, and four‐coordination around Ni(II) in NiIMCALHIS. Analysis of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) suggests decreased electron donation ability upon coordination. Electronic structure parameters (HOMO, LUMO, ionization potential, energy gap, electron affinity, chemical potentials, and electronegativity) provide further insights into stability and reactivity. The metal complexes exhibit enhanced antimicrobial, antioxidant, and anti‐inflammatory activity compared to individual ligands, with FeIMCALHIS showing notable antimicrobial activity. Molecular docking analysis reveals strong binding interactions with target proteins, highlighting their potential therapeutic applications.
Cyclometalated Iridium(III) Complex with Substituted Benzimidazole: pH Directed Organelle‐Specific Localization Within Lysosome
Authors: Sil Subhra , Hussain Afaq , Das Sarma Jayasri , Gupta Parna
Published: September 2024

We report the synthesis and pH dependent emission spectral behaviour of four emissive iridium(III) complexes (Ir1–Ir4) with two isomeric pairs of bis‐trifluoromethyl appended benzimidazole ligands. The imidazolyl hydrogen(N−H) has been replaced by phenyl groups (N−Ph) in two ligands to understand the impact of hydrogen bonding on the photophysical properties of the complexes and it indeed plays interesting role in the charge‐transfer dynamics. The pH dependent electronic spectral change is observed for two of the complexes. The enhancement of emission intensity is observed at different wavelength for pH<7 and pH>7 for Ir1 and Ir3. The emission sensing of biogenic amines with pka values ranging from 5.80–9.74 is reported along with cellular imaging. The complex Ir1 specifically localizes within lysosome (pH=4.5–5) and thus image this organelle with great precision. The detail electronic spectra and electrochemical behaviour were reported here along with TDDFT results.
Breast cancer cell derived exosomes reduces glycolysis of activated CD8 + T cells in a AKT‐mTOR dependent manner
Authors: Choudhury Abhishek , Chatterjee Soumya , Dalui Shauryabrota , Ghosh Pronabesh , Daptary Altamas Hossain , Mollah Golam Kibria , Bhattacharyya Arindam
Published: September 2024

Cytotoxic CD8+ T cells plays a pivotal role in the adaptive immune system to protect the organism against infections and cancer. During activation and response, T cells undergo a metabolic reprogramming that involves various metabolic pathways, with a predominant reliance on glycolysis to meet their increased energy demands and enhanced effector response. Recently, extracellular vesicles (EVs) known as exosomes have been recognized as crucial signaling mediators in regulating the tumor microenvironment (TME). Recent reports indicates that exosomes may transfer biologically functional molecules to the recipient cells, thereby facilitate cancer progression, angiogenesis, metastasis, drug resistance, and immunosuppression by reprogramming the metabolism of cancer cells. This study sought to enlighten possible involvement of cancer‐derived exosomes in CD8 + T cell glucose metabolism and discover a regulated signalome as a mechanism of action. We observed reduction in glucose metabolism due to downregulation of AKT/mTOR signalome in activated CD8 + T cells after cancer derived exosome exposure. In‐vivo murine breast tumor studies showed better tumor control and antitumor CD8 + T cell glycolysis and effector response after abrogation of exosome release from breast cancer cells. Summarizing, the present study establishes an immune evasion mechanism of breast cancer cell secreted exosomes that will act as a foundation for future precision cancer therapeutics.
Do autism and psychopathy co‐occur? A systematic review and clinical discussion
Authors: Murphy David , Walker Freya , Broyd Josephine
Published: September 2024

Background

Although the prevalence is unknown, psychopathy can be a possible co‐occurring condition associated with autism especially among forensic populations. However, the relationship between these two conditions remains poorly understood.

Aims

To carry out a systematic review of the available literature exploring the relationship between autism and psychopathy.

Methods

A systematic literature review following Preferred Reporting Items for Systematic Reviews and Meta‐Analyses guidelines using terms for autism and psychopathy to search the literature databases Scopus, Pubmed, Web of Science, ASSIA, APA Psych Info, Medline and EMBASE from 1980 to March 2024. For inclusion, we required that a recognised measure of autism and psychopathy or associated features of the latter had been used.

Results

Of the 4230 potential articles identified, 37 met the selection criteria. Insufficient and inconsistent methodologies for data pooling meant that a narrative analysis was used. Although there is some overlap, four broad themes emerged relating to (1) assessment and frequency of co‐occurrence, (2) behavioural and neurophysiological expressions of empathy, (3) behavioural contagion effects, mirroring, mimicry and other linking mechanisms and (4) emotional face perception and theory of mind characteristics. Within these areas there are some specific differences between the two conditions. However, the research to date examining the relationship between autism and psychopathy has mostly been with children and males, carried out with non‐clinical non‐forensic populations, as well as using self‐report measures and parental ratings. Prior research has also largely focused on looking for differences between these conditions rather than co‐occurrence.

Conclusion

This review outlines a case for considering autism and psychopathy as distinct, but potentially co‐occurring conditions and highlights the need for more research into how the two conditions interact with clinical populations. There also appears to be a need for guidelines on when and how to assess psychopathy with autistic individuals and a better understanding of the therapeutic needs and factors influencing the long‐term outcomes of autistic individuals who may also present with co‐occurring psychopathy.
PLS‐Guided Mutant Recombination to Improve the Stability of Bovine Enterokinases Obtained by Directed Evolution
Authors: Li Weina , Shen Weinfeng , Venanzi Niccolo A. E. , Zhang Cheng , Li Yiwen , Fan Daidi , Dalby Paul A.
Published: September 2024

Activity and thermostability are critical yet challenging to improve simultaneously in enzymes. Using directed evolution, we previously identified bovine enterokinase (EKL) variants with enhanced soluble expression and thermal stability. Partial least‐squares (PLS) analysis of 321 EKL variants revealed the impact of individual mutations and identified neutral or detrimental mutations in top‐performing variants. Leveraging PLS rankings, we created new variants with fewer mutations and enhanced stability. Most original and PLS‐guided variants exhibited an activity‐stability trade‐off. However, two new triple‐ and quadruple‐mutants improved both activity and stability, surpassing the trade‐off limit. Recombining PLS‐guided mutations likely eliminated neutral or harmful mutations, enhancing stability. MD simulations linked residue‐specific dynamics with stability, pinpointing critical structural regions near aggregation‐prone areas. Our findings validate PLS as a potent strategy to enhance enzyme properties, complementing directed evolution.
Catalytic Reductive Addition of Imine for Chiral Amine Synthesis: Recent Advances and Future Perspectives
Authors: Xia Tingting , Yu Zhiying , Wu Xianqing , Qu Jingping , Chen Yifeng
Published: September 2024

Optically active amine represents the most important structure motif in natural products and biologically active compounds. Stereoselective reductive addition of imine with the utilization of electrophilic component offers a concise and operationally simple method for the synthesis of chiral amines. This review mainly highlights recent significant synthetic methodology developments in reductive addition of imine for chiral amine synthesis including chiral auxiliary‐mediated diastereoselective transformation, asymmetric transition metal catalysis, organocatalysis, and enzymatic catalysis. In addition, the electrophilic reagents scopes and mechanistic aspects have also been introduced in this review.
Electrochemical Deconstructive Methoxylation of Arylalcohols–A Synthetic and Mechanistic Investigation
Authors: Maashi Hussain A. , Lewis‐Atwell Toby , Harnedy James , Grayson Matthew N. , Morrill Louis C.
Published: September 2024

Herein, we report a mechanistic investigation of a recently developed electrochemical method for the deconstructive methoxylation of arylalcohols. A combination of synthetic, electroanalytical, and computational experiments have been performed to gain a deeper understanding of the reaction mechanism and the structural requirements for fragmentation to occur. It was found that 2‐arylalcohols undergo anodic oxidation to form the corresponding aromatic radical cations, which fragment to form oxocarbenium ions and benzylic radical intermediates via mesolytic cleavage, with further anodic oxidation and trapping of the benzylic carbocation with methanol to generate the observed methyl ether products. It was also found that the electrochemical fragmentation of 2‐arylalkanols is promoted by structural features that stabilize the oxocarbenium ions and/or benzylic radical intermediates formed upon mesolytic cleavage of the aromatic radical cations. With an enhanced understanding of the reaction mechanism and the structural features that promote fragmentation, it is anticipated that alternative electrosynthetic transformations will be developed that utilize this powerful, yet underdeveloped, mode of substrate activation.