bluuebunny/crossref_metadata_2025_split huggingface dataset:
Catalytic Synthesis of Atropoisomers via Non‐Canonical Friedel‐Crafts Reactions
Authors: Ye Xutong , Yu Xixiang , Deng Rui , Zhong Fangrui , Wu Guojiao 
Published: February 2024

AbstractThe Friedel‐Crafts reaction stands as a powerful synthetic tool for C−H functionalization of aromatic feedstocks, which is conventionally realized through electrophilic alkylation and acylation. The burgeoning interests in axially chiral compounds across diverse fields have spurred extensive exploration of this classic transformation for catalytic atroposelective synthesis. Consequently, the past decade has witnessed the rapid expansion of various non‐canonical Friedel‐Crafts reactions, including electrophilic arylation, alkenylation, halogenation, sulfenylation, and amination of aryl C−H bonds, thereby delving into new chemical spaces. A range of catalytic atroposelective synthetic methods have been devised for these significant arene C−H functionalization. This review provides a comprehensive overview of the cutting‐edge catalytic synthesis of atropoisomers through non‐canonical Friedel‐Crafts reactions, categorized into three parts based on the type of bond formation on the aromatics: C(sp2)−C(sp3) bond formations, C(sp2)−C(sp2) bond formations and C(sp2)−heteroatom bond formations. The richness of electrophiles and the modulation of atroposelectivity by diverse chiral organocatalysts, particularly chiral Brønsted acids, are elucidated. We anticipate that the repertoire of asymmetric Friedel‐Crafts reaction will continue to flourish and to be demonstrated in not only scientific researches but also industrial organic synthesis.
Ligand Relay Catalysis Enables Asymmetric Migratory Hydroarylation for the Concise Synthesis of Chiral α‐(Hetero)Aryl‐Substituted Amines
Authors: Zhou Junqian , He Yuli , Liu Zihao , Wang You , Zhu Shaolin 
Published: February 2024

AbstractComplementary to the design of a single structurally complex chiral ligand to promote each step in transition‐metal catalysis, multiligand relay catalysis through dynamic ligand exchange with each step in the catalytic cycle promoted by its best ligand provides an attractive approach to enhance the whole reaction reactivity and selectivity. Herein, a regio‐ and enantioselective NiH‐catalyzed migratory hydroarylation process with a simple combination of a chain‐walking ligand and an asymmetric arylation ligand, producing high‐value chiral α‐(hetero)aryl‐substituted amines and their derivatives under mild conditions, is reported. The potential synthetic applications of this transformation are demonstrated by the concise synthesis of (S)‐nicotine and a CDK8 inhibitor.
CD38‐Specific Gallium‐68 Labeled Peptide Radiotracer Enables Pharmacodynamic Monitoring in Multiple Myeloma with PET
Authors: Sharma Ajay Kumar , Gupta Kuldeep , Mishra Akhilesh , Lofland Gabriela , Marsh Ian , Kumar Dhiraj , Ghiaur Gabriel , Imus Philip , Rowe Steven P. , Hobbs Robert F. , Gocke Christian B. , Nimmagadda Sridhar 
Published: February 2024

AbstractThe limited availability of molecularly targeted low‐molecular‐weight imaging agents for monitoring multiple myeloma (MM)‐targeted therapies has been a significant challenge in the field. In response, a first‐in‐class peptide‐based radiotracer, [68Ga]Ga‐AJ206, is developed that can be seamlessly integrated into the standard clinical workflow and is specifically designed to noninvasively quantify CD38 levels and pharmacodynamics by positron emission tomography (PET). A bicyclic peptide, AJ206, is synthesized and exhibits high affinity to CD38 (KD: 19.1 ± 0.99 × 10−9 m) by surface plasmon resonance. Further, [68Ga]Ga‐AJ206‐PET shows high contrast within 60 min and suitable absorbed dose estimates for clinical use. Additionally, [68Ga]Ga‐AJ206 detects CD38 expression in cell line‐derived xenografts, patient‐derived xenografts (PDXs), and disseminated disease models in a manner consistent with flow cytometry and immunohistochemistry findings. Moreover, [68Ga]Ga‐AJ206‐PET successfully quantifies CD38 pharmacodynamics in PDXs, revealing increased CD38 expression in the tumor following all‐trans retinoic acid (ATRA) therapy. In conclusion, [68Ga]Ga‐AJ206 exhibits the salient features required for clinical translation, providing CD38‐specific high‐contrast images in multiple models of MM. [68Ga]Ga‐AJ206‐PET could be useful for quantifying total CD38 levels and pharmacodynamics during therapy to evaluate approved and new therapies in MM and other diseases with CD38 involvement.
Arrays of Hierarchical Zincophilic Nanorods with Trapping‐and‐Leveling Deposition for Ultrastable Zn Metal Anodes
Authors: Tian Cong , Wang Hongfei , Xie Liyan , Zhong Yijun , Hu Yong 
Published: February 2024

AbstractRechargeable aqueous zinc‐ion batteries (ZIBs) are highly promising for large‐scale sustainable energy storage applications, but there remain serious problems such as Zn dendrites and side reactions that limit the cycling performance. Herein, arrays of core–shell nanorods on Cu foam are developed to stabilize zinc anodes, which have a hierarchical topological structure consisting of N‐doped carbon layers embedded with a zincophilic component of Cu5Zn8 alloy (Cu5Zn8@NC). It is found that the inner Cu5Zn8 alloys have minimized nucleation barriers and act as preferred nucleation sites, and the hierarchical arrays provide the protective layers to further accommodate the high‐capacity plating Zn, leading to a trapping‐and‐leveling process of Zn deposition. The as‐obtained Zn layers play an important role in homogenizing the interfacial ionic fluxes and reducing the local current densities. As a result, the optimized Cu5Zn8@NC host yields a superb Coulombic efficiency of 99.7% over 5000 plating/stripping cycles, and the corresponding symmetric cell delivers an ultralong dendrite‐free cycle life of 7000 h with a low overpotential of 16.5 mV at 1 mA cm−2 and 1 mAh cm−2. The ZIB assembled with the zinc anode and a V2O5 cathode exhibits long‐term charging/discharging cycles as well, up to 89.2% capacity retention after 10 000 cycles.
Breast size in lactating women and the content of macronutrients in human milk
Authors: Babiszewska‐Aksamit Magdalena , Żelaźniewicz Agnieszka , Apanasewicz Anna , Piosek Magdalena , Winczowska Patrycja , Barbarska Olga , Ziomkiewicz Anna 
Published: February 2024

AbstractIntroductionAlthough the primary function of a woman's breast is milk synthesis, only a few studies have evaluated the relationship between breast size and human milk composition, showing equivocal results. This study aims to test if breast size during fully established lactation is related to energy density and content of macronutrients in human milk.Materials and MethodsMothers of healthy, born‐on‐term infants at stage III of lactogenesis (N = 137) provided breast milk samples. Milk composition was analyzed using midinfrared transmission spectroscopy. The breast size index was calculated by dividing the breast by the circumference below the breast.ResultsStepwise forward linear regression showed a negative association between breast size index and lactose concentration in breast milk (β = −.242, p = .003). The final model, which includes breast size index, feeding frequency, and maternal energy intake together explained around 13% of the variance in breast milk lactose content (R2adj = .126, p < .001). No statistically significant relationship was found between breast size index and milk's energy density, protein, and fat content.ConclusionThis is the first study that shows a negative relationship between breast size during fully established lactation and lactose concentration in milk in a large sample size. No relationship between other macronutrients and breast size indicates that large breast size is not necessary for adequate milk production; however, it may contribute to an altered lactose concentration.
Speech and language in DDX3X‐neurodevelopmental disorder: A call for early augmentative and alternative communication intervention
Authors: Forbes Elana J. , Morison Lottie D. , Lelik Fatma , Howell Tegan , Debono Simone , Goel Himanshu , Burger Pauline , Mandel Jean‐Louis , Geneviève David , Amor David J. , Morgan Angela T. 
Published: February 2024

AbstractPathogenic variants in DDX3X are associated with neurodevelopmental disorders. Communication impairments are commonly reported, yet specific speech and language diagnoses have not been delineated, preventing prognostic counseling and targeted therapies. Here, we characterized speech and language in 38 female individuals, aged 1.69–24.34 years, with pathogenic and likely pathogenic DDX3X variants (missense, n = 13; nonsense, n = 12; frameshift, n = 7; splice site, n = 3; synonymous, n = 2; deletion, n = 1). Standardized speech, language, motor, social, and adaptive behavior assessments were administered. All participants had gross motor deficits in infancy (34/34), and fine motor deficits were common throughout childhood (94%; 32/34). Intellectual disability was reported in 86% (24/28) of participants over 4 years of age. Expressive, receptive, and social communication skills were, on average, severely impaired. However, receptive language was significantly stronger than expressive language ability. Over half of the assessed participants were minimally verbal (66%; 22/33; range = 2 years 2 months–24 years 4 months; mean = 8 years; SD = 6 years) and augmented speech with sign language, gestures, or digital devices. A quarter of the cohort had childhood apraxia of speech (25%; 9/36). Despite speech and language impairments, social motivation was a relevant strength. Many participants used augmentative and alternative communication (AAC), underscoring the need for early, tailored, and comprehensive AAC intervention.
Concentration‐Driven Evolution of Adaptive Artificial Ion Channels or Nanopores with Specific Anticancer Activities
Authors: Chen Zhiqing , Xie Xiaopan , Jia Chunyan , Zhong Qishuo , Zhang Qiuping , Luo Daoxin , Cao Yin , Mu Yuguang , Ren Changliang 
Published: February 2024

AbstractIn nature, ceramides are a class of sphingolipids possessing a unique ability to self‐assemble into protein‐permeable channels with intriguing concentration‐dependent adaptive channel cavities. However, within the realm of artificial ion channels, this interesting phenomenon is scarcely represented. Herein, we report on a novel class of adaptive artificial channels, Pn‐TPPs, based on PEGylated cholic acids bearing triphenylphosphonium (TPP) groups as anion binding motifs. Interestingly, the molecules self‐assemble into chloride ion channels at low concentrations while transforming into small molecule‐permeable nanopores at high concentrations. Moreover, the TPP groups endow the molecules with mitochondria‐targeting properties, enabling them to selectively drill holes on the mitochondrial membrane of cancer cells and subsequently trigger the caspase 9 apoptotic pathway. The anticancer efficacies of Pn‐TPPs correlate with their abilities to form nanopores. Significantly, the most active ensembles formed by P5‐TPP exhibits impressive anticancer activity against human liver cancer cells, with an IC50 value of 3.8 μM. While demonstrating similar anticancer performance to doxorubicin, P5‐TPP exhibits a selectivity index surpassing that of doxorubicin by a factor of 16.8.
Ring‐Opening Terpolymerisation of Elemental Sulfur Waste with Propylene Oxide and Carbon Disulfide via Lithium Catalysis
Authors: Gallizioli Cesare , Battke David , Schlaad Helmut , Deglmann Peter , Plajer Alex J. 
Published: February 2024

AbstractElemental sulfur, a waste product of the oil refinement process, represents a promising raw material for the synthesis of degradable polymers. We show that simple lithium alkoxides facilitate the polymerisation of elemental sulfur S8 with industrially relevant propylene oxide (PO) and CS2 (a base chemical sourced from waste S8 itself) to give poly(monothiocarbonate‐alt‐Sx) in which x can be controlled by the amount of supplied sulfur. The in situ generation of thiolate intermediates obtained by a rearrangement, which follows CS2 and PO incorporation, allows to combine S8 and epoxides into one polymer sequence that would otherwise not be possible. Mechanistic investigations reveal that alkyl oligosulfide intermediates from S8 ring opening and sulfur chain length equilibration represent the better nucleophiles for inserting the next PO if compared to the trithiocarbonates obtained from the competing CS2 addition, which causes the sequence selectivity. The polymers can be crosslinked in situ with multifunctional thiols to yield reprocessable and degradable networks. Our report demonstrates how mechanistic understanding allows to combine intrinsically incompatible building blocks for sulfur waste utilisation.
Sulfur in Waste‐Free Sustainable Synthesis: Advancing Carbon–Carbon Coupling Techniques
Authors: Shlapakov Nikita S. , Kobelev Andrey D. , Burykina Julia V. , Cheng Yuan‐Zheng , You Shu‐Li , Ananikov Valentine P. 
Published: February 2024

AbstractThis review explores the pivotal role of sulfur in advancing sustainable carbon‐carbon (C−C) coupling reactions. The unique electronic properties of sulfur, as a soft Lewis base with significant mesomeric effect make it an excellent candidate for initiating radical transformations, directing C−H‐activation, and facilitating cycloaddition and C−S bond dissociation reactions. These attributes are crucial for developing waste‐free methodologies in green chemistry. Our mini‐review is focused on existing sulfur‐directed C−C coupling techniques, emphasizing their sustainability and comparing state‐of‐the‐art methods with traditional approaches. The review highlights the importance of this research in addressing current challenges in organic synthesis and catalysis. The innovative use of sulfur in photocatalytic, electrochemical and metal‐catalyzed processes not only exemplifies significant advancements in the field but also opens new avenues for environmentally friendly chemical processes. By focusing on atom economy and waste minimization, the analysis provides broad appeal and potential for future developments in sustainable organic chemistry.
Research of aging test on high Tg colorless polyimide
Authors: Li Yulin , Jiang Sirui , Li Fu , Chen Cheng 
Published: February 2024

AbstractFor the past few years, colorless polyimide (CPI) has been drawn much attention for its application in transparent electronics. The high temperature (even to 450°C) process of the preparation of organic light‐emitting diode display (OLED) device may have huge challenges on the properties of CPI, so we designed a series of aging test experiments to study the influence of test temperature and atmosphere on the high transparency percentages (Tr%) of CPI films with structure of Glass/SiO2/CPI/SiO2. As the aging temperature increased from 430 to 450°C and then to 470°C, the Tr% of the film decreased significantly. Comparing with the sample without aging, the transmission losses were 0.22%, 1.42%, and 4.82% for the films aging with 430, 450, and 470°C in N2 atmosphere, respectively. Additionally, aging in nitrogen resulted in less Tr% loss (1.22%) compared with air (1.42%). This research offers insights into how to maintain the high Tr% of CPI films during high‐temperature processing. Furthermore, it supports the development of more durable and reliable CPI‐based components for OLED displays and other transparent electronic devices. This can lead to advancements in the performance of these devices, potentially extending their lifespan and broadening their range of applications.
A g‐C3N4/PANI S‐scheme heterojunction with face‐to‐face structure to improve the anticorrosion property on Q235 steel and enhanced mechanism study
Authors: Ma Yongning , Li Panpan , Wu Peihan , Guo Mingyuan , Yang Yuhao , Li Xiaolong 
Published: February 2024

AbstractIn photocatalytic anticorrosion perspective, the migration rate of excited electrons from surface layers to substrate steels restricted the performance of g‐C3N4 due to the high resistance between interface of g‐C3N4 layers and adhesive layers. Herein, an S‐scheme g‐C3N4/polyaniline (PANI) heterojunction with face‐to‐face structure was established by a secondary calcining method. The as‐prepared heterojunctions were applied to protect Q235 carbon steel, and the results showed that the anticorrosion performance of S‐scheme g‐C3N4/PANI heterojunction is much higher than that of g‐C3N4 and PANI coating layers according to salt spray test. Photocurrent intensity indicated that the optimum amounts of g‐C3N4 and PANI were 0.06 and 0.09 mL/cm2, which are benefit for the transport of excited electrons due to the optimum thickness of coating layers. Furthermore, the S‐scheme g‐C3N4/PANI heterojunction can promote the separation rate of charge carriers and suppress the recombination rate at the same time, which are inferred from photocurrent intensity, electrochemical impedance spectra, super‐depth‐of‐field microscope, and photoluminescence investigation. In the last, the enhanced anticorrosion performance of S‐scheme g‐C3N4/PANI heterojunction with face‐to‐face structure was deduced according to mentioned characterization.
Robust poly(p‐phenylene oxide) anion exchange membranes reinforced with pore‐filling technique for water electrolysis
Authors: Feng Zhiming , Gupta Gaurav , Mamlouk Mohamed 
Published: February 2024

AbstractMechanical robustness and durability are crucial for anion exchange membranes to guarantee the longevity and consistent performance of AEM water electrolysis (AEMWE) systems. In this study, a composite membrane based on the quaternized poly(p‐phenylene oxide) (QPPO)/polytetrafluoroethylene (PTFE) was developed. This membrane was fabricated by enhancing the QPPO‐based AEM through a pore‐filling technique within a porous PTFE structure. The tensile strength of the composite membrane was increased significantly from 16.5 to 31 MPa. The conductivity of the composite membrane was 6.25 mScm−1 lower than 30 mScm−1 of the QPPO‐based membrane at 20°C, resulting from the low volume fraction of QPPO in the composite membrane. At 40% RH, the net change mass of the composite membrane is 1.59%, much lower than that of QPPO‐based membrane (10.98%) at 40°C. The composite membrane demonstrated a significantly increased lifetime in the working electrolyzer (>200 h) compared with an otherwise identical electrolyzer assembled with a QPPO‐based membrane (50 h).
The modified boundary layer mechanism for the release between polyimide film and poly(ether ketone ketone) thermoplastics
Authors: Yang Zixuan , Dissevelt Tim , Li Nan , de Vries Erik , Grouve Wouter , Bao Ningzhong , de Rooij Matthijn , Akkerman Remko , Chu Liangyong 
Published: February 2024

AbstractSticking between the thermoplastic polymer and metal tool is a crucial issue, as it determines whether the manufactured part can be ejected from the metal mold. Polyimide (PI) release films have been widely used in the processing of fiber‐reinforced thermoplastic polymer composites. Compared with other release mediums such as release agents, PI release film has a higher release efficiency. However, the underlying release mechanism is still not well understood which is essential to improve their performance further and reduce the cost. In this paper, poly(ether ketone ketone) (PEKK) polymer was melted and cooled down between two PI films. The surface morphologies and chemical compositions of the PI film and PEKK were characterized both before and after release using atomic force microscope, x‐ray photoelectron spectroscopy, contact angle measurements, and confocal microscopy. It showed that a thin PI layer was transferred from the PI release film to the PEKK surface during the release process. Based on these experimental results, a modified boundary layer mechanism is proposed as a hypothesis to describe the release mechanism of PI films. Our results give a fundamental understanding of how PI film works for the release of thermoplastics with high processing temperatures and may help to improve the performance and reduce the costs of existing PI films and may give guidance to the design of new release media.
No identity connections without representation? Exploring associations between neighbourhood opportunities, ethnic–ideal alignment and well‐being in Black, Indigenous and other youths of colour in Canada
Authors: Debrosse Régine , Boatswain‐Kyte Alicia , David Syndie , Gooding Gregory , Vaval Pierreson , Lafortune Gina 
Published: February 2024

AbstractIn Canada, Black, Indigenous and other youths of colour often have high aspirations, but many are not sure that they are attainable. Context can signal what is in or out of reach to youths, particularly environments that send repeated and proximal signals, like neighbourhoods. Notably, the Social Identity Approach suggests that in neighbourhoods with people like them doing well socioeconomically or being well represented in leadership, youths may see a place for people similar to them, which in turn could benefit how they view their identities and experience well‐being. In this exploratory research, Black, Indigenous and other youths of colour in Montréal (n = 179) were surveyed about their neighbourhood, social and future identities and well‐being. Regressions suggest that youths' neighbourhoods predict the extent to which they perceive that opportunities are accessible to people like them. Youths who reported more opportunities for people similar to them in their neighbourhood tended to report higher alignment between their racial/ethnic and ideal future identities and higher flourishing. The findings highlight the connection between neighbourhood factors—such as cues about whether similar people are welcomed, valued, and have access to opportunities—and the identities and well‐being of Black, Indigenous and other youths of colour.
Relationship of market capitalization of the IBEX 35 to corporate social responsibility and transparency
Authors: Quesada Cristóbal Parra , Espada Manuela Cañizares 
Published: February 2024

AbstractThis paper seeks to determine whether the economic‐financial performance and value of the companies composing the IBEX 35 are related to the transparency with which these companies publish their economic and social data. Our goal is ultimately to establish the degree (if any) to which Spain's largest listed companies' commitments to transparency and CSR are related to their market capitalization volumes. We also evaluate the effectiveness—relative to the economic data and to each other—of the transparency and Corporate Social Responsibility (CSR) rankings prepared by Transparency International Spain and the Corporate Social Responsibility Observatory. The results indicate a high correlation of market capitalization to the transparency and CSR indexes, and a positive evaluation of using these tools for future lines of research in Spain.
A hybrid amplifier topology for low‐noise direct‐coupled front ends
Authors: Spinelli Enrique M. , Haberman Marcelo A. , Guerrero Federico N. 
Published: February 2024

SummaryHybrid amplifiers combine discrete transistors with operational amplifiers (OAs) achieving superior characteristics compared with commercially available OAs, while keeping simple structures and a reduced number of parts. A single‐ended amplifier topology based on a junction field‐effect transistor (JFET) is proposed as a means of achieving very low input noise levels, both in current and voltage. It is direct‐coupled and allows to place a high‐pass filter at its input to preserve input range, or at its output to optimize noise. The proposed topology results in a low input capacitance and low input‐current noise, making it suitable for applications where multiple amplifiers are connected in parallel to achieve ultra‐low noise levels. The amplifier's gain is set by a resistor ratio, being suitable for instrumentation front ends. The circuit analysis and design equations are provided to adapt it for different applications and, as an example, an amplifier with a gain of 40 dB and a bandwidth from DC to 1 MHz was designed, built, and tested. The dominant noise contribution of the amplifier was the JFET (a JFE2140 device), featuring an input noise voltage of
, that is reduced to
when two amplifiers are connected in parallel.