bluuebunny/crossref_metadata_2025_split huggingface dataset:
Open‐shell Poly(3,4‐dioxythiophene) Radical for Highly Efficient Photothermal Conversion
Authors: Wei Qi , Huang Jiaxing , Meng Qiao , Zhang Zesheng , Gu Sichen , Li Yuan 
Published: September 2024

AbstractOpen‐shell organic radical semiconductor materials have received increasing attention in recent years due to their distinctive properties compared to the traditional materials with closed‐shell singlet ground state. However, their poor chemical and photothermal stability in ambient conditions remains a significant challenge, primarily owing to their high reactivity with oxygen. Herein, a novel open‐shell poly(3,4‐dioxythiophene) radical PTTO2 is designed and readily synthesized for the first time using low‐cost raw material via a straightforward BBr3‐demethylation of the copolymer PTTOMe2 precursor. The open‐shell character of PTTO2 is carefully studied and confirmed via the signal‐silent 1H nuclear magnetic resonance spectrum, highly enhanced electron spin resonance signal compared with PTTOMe2, as well as the ultra‐wide ultraviolet‐visible‐near nfraredUV–vis–NIR absorption and other technologies. Interestingly, the powder of PTTO2 exhibits an extraordinary absorption range spanning from 300 to 2500 nm and can reach 274 °C under the irradiation of 1.2 W cm−2, substantially higher than the 108 °C achieved by PTTOMe2. The low‐cost PTTO2 stands as one of the best photothermal conversion materials among the pure organic photothermal materials and provides a new scaffold for the design of stable non‐doped open‐shell polymers.
Enhanced Reliability and Self‐Compliance of Synaptic Arrays for Multibit Encoded Neuromorphic Systems
Authors: Kim Sungjoon , Ji Hyeonseung , Kim Sungjun , Choi Woo Young 
Published: September 2024

AbstractUtilizing memristors to increase the density of crossbar arrays requires reducing dependency on transistors. This paper presents an approach where the current limiting function is integrated within the memristor by inducing an AlOx/TaOx layer, thereby limiting overshoot current during filament formation. The reaction between TaOx and Al can be accelerated through annealing, which optimizes the on/off ratio and reduces device‐to‐device variation. Additionally, AlN is inserted to inhibit the movement of oxygen ions to the bottom electrode, improving conductive filament reoxidation. Furthermore, biological synaptic properties are examined using electrical pulse schemes, revealing multibit characteristics of >5‐bit. After the structure optimization, 24 × 24 crossbar arrays are fabricated, allowing 100% of cells to achieve self‐compliance filament formation without hard breakdown. Moreover, the crossbar array demonstrates an on/off ratio of over 4 × 102. Additionally, a multibit‐encoded neuromorphic system is proposed based on the device's multibit capability. The number of synapses can be significantly reduced by grouping input data into a single memristor device. When comparing classification accuracies, 97.14% and 95.54% are observed without and with encoding. The improvements in device structure and encoding method presented in this study enable highly integrated crossbar arrays and efficient neuromorphic systems.
Personalizing progressive changes to brain structure in Alzheimer's disease using normative modeling
Authors: Verdi Serena , Rutherford Saige , Fraza Charlotte , Tosun Duygu , Altmann Andre , Raket Lars Lau , Schott Jonathan M. , Marquand Andre F. , Cole James H. ,   for the Alzheimer's Disease Neuroimaging Initiative
Published: September 2024

AbstractINTRODUCTIONNeuroanatomical normative modeling captures individual variability in Alzheimer's disease (AD). Here we used normative modeling to track individuals’ disease progression in people with mild cognitive impairment (MCI) and patients with AD.METHODSCortical and subcortical normative models were generated using healthy controls (n ≈ 58k). These models were used to calculate regional z scores in 3233 T1‐weighted magnetic resonance imaging time‐series scans from 1181 participants. Regions with z scores < –1.96 were classified as outliers mapped on the brain and summarized by total outlier count (tOC).RESULTStOC increased in AD and in people with MCI who converted to AD and also correlated with multiple non‐imaging markers. Moreover, a higher annual rate of change in tOC increased the risk of progression from MCI to AD. Brain outlier maps identified the hippocampus as having the highest rate of change.DISCUSSIONIndividual patients’ atrophy rates can be tracked by using regional outlier maps and tOC.Highlights
Neuroanatomical normative modeling was applied to serial Alzheimer's disease (AD) magnetic resonance imaging (MRI) data for the first time.
Deviation from the norm (outliers) of cortical thickness or brain volume was computed in 3233 scans.
The number of brain‐structure outliers increased over time in people with AD.
Patterns of change in outliers varied markedly between individual patients with AD.
People with mild cognitive impairment whose outliers increased over time had a higher risk of progression from AD.
Outstanding Circularly Polarized TADF in Chiral Cu(I) Emitters: From Design to Application in CP‐TADF OLEDs
Authors: Petyuk Maxim Yu. , Meng Lingqiang , Ma Zihao , Agafontsev Alexander M. , Bagryanskaya Irina Yu. , Berezin Alexey S. , Zhang Jingzhi , Chu Anlea , Rakhmanova Mariana I. , Meng Hong , Tkachev Alexey V. , Yam Vivian Wing‐Wah , Artem'ev Alexander V. 
Published: September 2024

AbstractLow‐cost molecular emitters that merge circularly polarized luminescence (CPL) and thermally activated delayed fluorescence (TADF) properties are attractive for many high‐tech applications. However, the design of such emitters remains a difficult task. To address this challenge, here, we propose a simple and efficient strategy, demonstrated by the design of pseudochiral‐at‐metal complexes [Cu(L*)DPEPhos]PF6 bearing a (+)/(−)‐menthol‐derived 1,10‐phenanthroline ligand (L*). These complexes exhibit a yellow CP‐TADF with a record‐high quantum yield (close to 100 %) and high dissymmetry factor (|glum|~1×10−2). Remarkably, the above compounds also show a negative thermal‐quenching (NTQ) of luminescence in the 300–77 K range. Exploiting the designed Cu(I) emitters, we fabricated efficient CP‐TADF OLEDs displaying mirror‐imaged CPL bands with high |gEL| factors of 1.5×10−2 and the maximum EQE of 6.15 %. Equally important, using the (+)‐[Cu(L*)DPEPhos]PF6 complex, we have discovered that an external magnetic field noticeably suppresses CP‐TADF of Cu(I) emitters. These findings are an important contribution to the CPL phenomenon and provide access to highly efficient, low‐cost and robust CP‐TADF emitters.
Cleavage of the Robust Silicon–Fluorine σ‐Bond Allows Silicon–Carbon Bond Formation: Synthetic Strategies Toward Ortho‐Silyl Aryl Phosphonates
Authors: Ji Suhyun , Kim Soomin , Lee Jae Kyun , Lee Duck‐Hyung , Han Seo‐Jung 
Published: September 2024

AbstractA straightforward, mild, and transition‐metal‐free three‐component coupling reaction involving arynes, phosphites, and silyl fluorides was developed through Si−F bond activation. Although the Si−F bond is one of the strongest bonds, Si−C bond formation via Si−F bond cleavage with the assistance of bidentate silicon and phosphonium Lewis acids has been successfully achieved. This unprecedented strategy provides a facile approach for synthesizing ortho‐silyl‐substituted aryl phosphonates. Notably, this method allows the use of not only dialkylarylsilyl fluorides and diarylalkylsilyl fluorides but also triarylsilyl fluorides as coupling partners, which is uncommon in the field of arylsilane synthesis. Furthermore, a variety of ortho‐silyl‐substituted aryl phosphonates were produced in moderate to good yields with broad functional group tolerance. Additionally, the versatility of ortho‐silyl‐substituted aryl phosphonates was demonstrated by the elaboration of the products into a range of silicon‐containing compounds.
Synthesis and Characterization of Fe3O4@SiO2@APIDSO3H as a Novel and Efficient Magnetic Nanocatalyst in Pechmann Condensation
Authors: Aghashiri Zohre , Ghassamipour Soheila , Jamalian Arezu , Emadi Masoomeh 
Published: September 2024

ABSTRACTFe3O4@APIDSO3H as a novel and magical magnetic nanocatalyst was designed, synthesized, and characterized by different spectroscopic techniques such as Fourier transform infrared (FT‐IR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), x‐ray diffraction (XRD), energy‐dispersive x‐ray (EDX), thermogravimetric analysis (TGA), and vibrating sample magnetometer (VSM). The loading percentage of sulfonic acid on the magnetic nano catalyst was calculated using CHNS analysis. Then, the potential use of it was investigated for the synthesis of various coumarins by Pechmann condensation. The corresponding products were synthesized and isolated in 60%–99% yields. The catalyst was recycled and reused for four times without loss in catalytic activity.
CO2 capture for environmental remediation with hollow fibre membrane: Impact of air gap and bore fluid ratio onto the morphology and performance
Authors: Zainuddin Muhd Izzudin Fikry , Ahmad Abdul Latif , Shah Buddin Meor Muhammad Hafiz , Adnan Mohamad Alif 
Published: September 2024

AbstractHollow fibre membrane (HFM) is favourable for carbon dioxide (CO2) due to its high packing density and high volume to area ratio. In this study, the effect of air gap and bore fluid ratio is explored to study its influence on the morphology and separation performance. With high dope extrusion rate (DER), the shear‐induced polymer orientation can be preserved with low air gap which come with the cost of deformed lumen. As such, the coagulant activity of the bore fluid can be reduced by introducing solvent, which in turn reduces rate of phase inversion to prevent sudden contraction of polymer at low air gap, thus allowing proper formation of lumen. With the presence of solvent, the flowability of the dope solution increased due to reduced viscosity as the bore fluid with high solvent content make contact the external coagulant. HFM spun with low air gap with the presence of solvent in the bore fluid shows increased stretched ratio due to the influence of gravitational pull upon being extruded from the spinneret. This in turn improved the polymer chain orientation due to the stretch across the spinning line. Subsequently, HFM spun with 80 wt.% of N‐methyl‐2‐pyrollidone (NMP) in the bore fluid using narrow gap spinneret with 5‐cm air gap shows the highest ideal CO2/N2 and CO2/CH4 selectivity at 23.4 and 28 respectively, even though it also exhibit the lowest CO2 permeance at only 3.1 GPU which was ascribed to the formation of dense skin layer. Meanwhile, when HFM was spun with a bigger annulus gap, the ideal CO2/N2 and CO2/CH4 selectivity slightly dropped, however the CO2 permeance exhibit increment.
Effect of side chain modification on edge‐on oriented dithienobenzodithiophene‐based non‐fullerene acceptors for organic solar cells
Authors: In Kim Da , Kim Kyungsik , Park Byoungwook , Kim Jehan , Kim Yun‐Hi , Lee Kwanghee , Kwon Soon‐Ki , Lee Jinho 
Published: September 2024

AbstractTwo non‐fullerene acceptors (NFAs), DTBDT‐ICN and DTBDT‐SEH, based on dithienobenzodithiophene (DTBDT) and a 2‐(3‐oxo‐2,3‐dihydroinden‐1‐ylidene) malononitrile (IC) with different side chains of alkylthienyl and alkylthio‐thienyl, respectively, were designed and used as electron acceptors in organic solar cells (OSCs). Both NFAs provide suitable energy level configurations that ensure efficient charge transfer with the donor polymer PBDB‐T, as confirmed by significant photoluminescence reduction in the blend films. However, due to the high planarity together with strong π‐π stacking interactions, the DTBDT‐ICN presented significant aggregation and phase separation in the blend films, leading to suboptimal charge generation. In addition, grazing incidence wide‐angle x‐ray scattering measurements revealed a predominance of edge‐on molecular orientations, which are unfavorable for vertical charge transport. On the other hand, DTBDT‐SEH exhibited less pronounced molecular aggregation and edge‐on orientation properties compared to DTBDT‐ICN, resulting in improved carrier mobility (μe of 3.86 × 10−6 compared to 7.59 × 10−7) and mitigated recombination losses (1.19 kT/q compared to 1.21 kT/q) in OSC devices. The improved morphological features of PBDB‐T:DTBDT‐SEH led to a high power conversion efficiency of 3.31%, which is three times higher than that of PBDB‐T:DTBDT‐ICN‐based devices (1.55%). Furthermore, paired with the high performance polymer PM6, PM6:DTBDT‐SEH demonstrated an enhanced efficiency, reaching 7.03%.
PVA/titanate nanotube nanocomposites: Evaluating the required structural properties for their performance as macromolecule delivery systems
Authors: Factori Irina M. , da Silva Emerson R. , Gerbelli Barbara B. , Liberato Michelle S. , de Araujo Daniele Ribeiro , Alves Wendel A. 
Published: September 2024

AbstractBiopolymer‐based nanocomposites are gaining prominence in the fabrication of biomedical devices, with polyvinyl alcohol (PVA) being widely used in smart dressings for drug and protein integration. This study introduces electrospun mats composed of partially hydrolyzed PVA and sodium titanate nanotubes (TiNTs). The investigation involved mats with TiNT concentrations ranging from 0% to 5% at room temperature. The morphological and structural changes resulting from adding TiNTs were examined in detail. The inclusion of TiNTs impacted parameters such as mean fiber diameter (130–190 nm), crystallinity degree (30–50%), and porosity (70–55%) and was closely associated with the viscoelastic properties of the mats. Higher TiNT concentrations led to reductions in either the storage modulus, from 350 to 220 MPa, or in the loss modulus, from 30 to 25 MPa, unveiling an increase in tenacity. Furthermore, in vitro release tests were conducted using bovine serum albumin (BSA) in Franz cells over 48 h. The results indicated that release profiles were best fitted by the Higuchi model (0.95 > R2 > 0.99) for both PVA mats (0% and 5.0% TiNTs), with the 5% TiNTs‐PVA membrane demonstrating greater BSA diffusion when compared to pure PVA. The release constant 𝐾rel, representing the rate of drug diffusion, was found to be 0.006 for 5% TiNT‐PVA mats and 0.002 μg h‐1/2 for pure PVA, respectively. These results suggest the potential of these materials in designing controlled transdermal delivery systems that could significantly improve the efficacy and safety of drug applications.
Impact of sterilization technique on electrospun poly(4‐hydroxybutyrate) membranes for biomedical application
Authors: Chen Qi , Yuan Shuaishuai , Xu Yuanjing , Zhang Fengxiang , Wang Kaiti , Yan Shunjie , Li Chunming , Li Zhibo 
Published: September 2024

AbstractBioabsorbable poly(4‐hydroxybutyrate) (P4HB) electrospun membrane has been widely used in various biomedical applications due to its biocompatibility and unique mechanical properties. When commercialization is envisaged, a sterilization procedure aiming to prevent bacterial contamination of biomedical devices is indispensable. Herein, P4HB membranes were sterilized by using different sterilization techniques. It's observed that ethylene oxide (EO), ultraviolet radiation (UV), and electron beam (E‐beam) irradiation do not influence the morphology of fiber membranes. Analysis of the data revealed that E‐beam irradiation sterilization can induce chain scission of P4HB. The EO sterilization process can increase the melting point of P4HB electrospun membranes. None of the sterilization methods showed a significant effect on the hemocompatibility of the P4HB membranes. Furthermore, the cytocompatibility experiment indicated that none of the P4HB membranes had any toxic effects on L929 cells. Taken together, selecting a suitable sterilization method that effectively sterilizes and does less damage during the sterilization process is critical to P4HB membranes for biomedical application.
Autistic‐relevant behavioral phenotypes of a mouse model of cyclin‐dependent kinase‐like 5 deficiency disorder
Authors: Mottolese Nicola , Coiffard Oceane , Ferraguto Celeste , Manolis Athanasios , Ciani Elisabetta , Pietropaolo Susanna 
Published: September 2024

AbstractCyclin‐dependent kinase‐like 5 (CDKL5) deficiency disorder (CDD) is a neurodevelopmental disease caused by mutations in the X‐linked CDKL5 gene and characterized by early‐onset epilepsy, intellectual disability, and autistic features. To date, the etiological mechanisms underlying CDD are largely unknown and no effective therapies are available. The Cdkl5 knock‐out (KO) mouse has been broadly employed in preclinical studies on CDD; Cdkl5‐KO mice display neurobehavioral abnormalities recapitulating most CDD symptoms, including alterations in motor, sensory, cognitive, and social abilities. However, most available preclinical studies have been carried out on adult Cdkl5‐KO mice, so little is known about the phenotypic characteristics of this model earlier during development. Furthermore, major autistic‐relevant phenotypes, for example, social and communication deficits, have been poorly investigated and mostly in male mutants. Here, we assessed the autistic‐relevant behavioral phenotypes of Cdkl5‐KO mice during the first three post‐natal weeks and in adulthood. Males and females were tested, the latter including both heterozygous and homozygous mutants. Cdkl5 mutant pups showed qualitative and quantitative alterations in ultrasonic communication, detected first at 2 weeks of age and confirmed later in adulthood. Increased levels of anxiety‐like behaviors were observed in mutants at 3 weeks and in adulthood, when stereotypies, reduced social interaction and memory deficits were also observed. These behavioral effects of the mutation were evident in both sexes, being more marked and varied in homozygous than heterozygous females. These findings provide novel evidence for the autistic‐relevant behavioral profile of the Cdkl5 mouse model, thus supporting its use in future preclinical studies investigating CDD pathology and autism spectrum disorders.
Dangerous liaisons: Loss of keratinocyte control over melanocytes in melanomagenesis
Authors: Green Kathleen J. , Pokorny Jenny , Jarrell Brieanna 
Published: September 2024

AbstractMelanomas arise from transformed melanocytes, positioned at the dermal‐epidermal junction in the basal layer of the epidermis. Melanocytes are completely surrounded by keratinocyte neighbors, with which they communicate through direct contact and paracrine signaling to maintain normal growth control and homeostasis. UV radiation from sunlight reshapes this communication network to drive a protective tanning response. However, repeated rounds of sun exposure result in accumulation of mutations in melanocytes that have been considered as primary drivers of melanoma initiation and progression. It is now clear that mutations in melanocytes are not sufficient to drive tumor formation—the tumor environment plays a critical role. This review focuses on changes in melanocyte‐keratinocyte communication that contribute to melanoma initiation and progression, with a particular focus on recent mechanistic insights that lay a foundation for developing new ways to intercept melanoma development.
A novel thiourea‐based fluorescent turn‐on sensor for rapidly detecting hypochlorite through a desulfurization reaction
Authors: Choi Boeun , Kim Soyeon , Kim Cheal 
Published: September 2024

AbstractExcess hypochlorite (ClO−) is harmful to living organisms and can cause various oxidative diseases in the human body. Owing to the toxicity of ClO−, the development of efficient fluorescence sensors to track ClO− is necessary. In this work, we report a novel thiourea‐based fluorescent turn‐on sensor 1‐(9‐ethyl‐9H‐carbazol‐3‐yl)‐3‐(naphthalen‐1‐yl)thiourea (ECNT) for recognizing ClO−. ECNT can detect ClO− with high selectivity, relatively low interference with other analytes, and a significantly fast response time (<1 s) through a desulfurization reaction. The detection limit of ECNT for ClO− is calculated as 5.59 μM. Of note, ECNT is a chemosensor that reacts the fastest with ClO− among the reported thiourea‐based fluorescence turn‐on sensors for detecting ClO−. The response mechanism of ECNT to ClO− is demonstrated through 1H NMR titration, ESI mass, and density functional theory calculations.
Mental health in people living with and beyond colorectal cancer: A patient‐oriented constructivist grounded theory
Authors: Cheng Vicki , McTaggart‐Cowan Helen , Loree Jonathan M. , Murphy Rachel A. , Barnes Mikaela , Bechthold Haydn , Jansen Norman , De Vera Mary A. 
Published: September 2024

AbstractBackgroundWith the burden of colorectal cancer in Canada, there is a need to address the psycho‐oncologic challenges, including mental health. This study aims to explore the lived mental health experiences in patients with CRC across the phases of the CRC care continuum.MethodsWe employed a patient‐oriented constructivist grounded theory design and recruited English speaking participants ≥18 years, diagnosed with CRC within the last 10 years, residing in Canada. We collected data through semi‐structured individual interviews using a guide co‐constructed with patient research partners. Data collection and analysis were iterative, employed theoretical sampling, and culminated in a theoretical model.ResultsTwenty‐eight participants diagnosed with CRC (18 females, 10 males), aged 18–63 years at time of diagnosis were interviewed, with representation across all CRC stages. There were 10 participants (36%) in treatment, 12 participants (43%) in follow‐up, and 6 participants (21%) in the beyond phase. We constructed a patient‐oriented theory illustrating the dynamic nature between one's self‐identity and their mental health experiences across the CRC care continuum. Mental health experiences encompass emotional and cognitive‐behavioral responses, expressed differently across phases. Mental health care experiences are also shaped by barriers, facilitators, and individual contextual factors, all of which influence their access to care.ConclusionOur theory provides insight into the mental health experiences of patients with CRC across phases of the CRC care continuum. Understanding patients' emotional and cognitive‐behavioral responses and care experiences can help identify opportunities to integrate mental health into CRC care.
Detection of Micromolar Glucose Levels in Human Sweat Using an Organic Transistor‐Based Enzymatic Sensor
Authors: Sasaki Yui , Ohshiro Kohei , Kato Miyuki , Haba Daijiro , Nakagami Gojiro , Minami Tsuyoshi 
Published: September 2024

AbstractSweat glucose serves as a significant biomarker of health, necessitating accurate determination at the micromolar level for noninvasive monitoring. To address this need, we design an organic field‐effect transistor (OFET)‐based enzymatic sensor to quantify glucose levels in human sweat. The extended‐gate structure of the OFET device ensures stable analyte detection in human sweat owing to its isolated configuration. The extended‐gate‐type OFET has been functionalized with glucose oxidase and an N‐ethylphenazonium‐based mediator‐attached monolayer. This configuration facilitates electron relay, enabling accurate and reproducible glucose detection. Leveraging the amplification ability of the OFET, the enzymatic sensor exhibited highly sensitive glucose detection, achieving a low limit of detection (2.9 μM) suitable for sweat analysis requirements. In addition, the sensor exhibited high discriminability in detecting glucose amidst interferents commonly found in sweat, indicating its practical feasibility for sweat analysis. Validation of glucose recovery rates (95–105 %) in human sweat, without pretreatment, was performed using established instrumental analysis methods.