bluuebunny/crossref_metadata_2025 huggingface dataset:
GPR120: Mechanism of action, role and potential for medical applications
Authors: Karakuła-Juchnowicz Hanna , Róg Joanna , Juchnowicz Dariusz , Morylowska-Topolska Justyna
Published: November 2017

G protein-coupled receptors (GPCRs) constitute a family of transmembrane proteins that mediate many cellular processes. GPR120/FFAR4, a receptor from this family that is activated by fatty acids, has received considerable attention recently.
This paper presents a literature review concerning the role of GPR120 and its mechanism of action
in animal and human studies as well as the potential use of GPR120 for the treatment of chronic
diseases.
Two electronic databases – Medline and Google Scholar – were searched for available studies
addressing the review topic that were written in English and published from 2000 to June 2017.
The following key terms were used in the search: GPR120, FFA4, GPR120 agonist, PUFAs, EPA, DHA,
adipocyte, obesity, hyperlipidemia, inflammation, cancer, diabetes, insulin resistance, taste, atherogenesis,
hepatis, central nervous system.
In humans, GPR120 expression is expressed in macrophages, eosinophils, and adipose tissue, in cells
of the tongue, liver, lungs, small and large intestine, gastric mucosa, and pancreas, in the central
nervous system and placental microvilli.
Medium- and long-chain fatty acids act as ligands for the receptor.
Through the internalization of beta-arrestin-2 complex and the inhibition of NF-κB, GPR120 mediates
the activation of the cell’s anti-inflammatory mechanisms.
The receptor is also involved in the maturation of adipocytes, the modulation of insulin signalling
pathways, the regulation of glucose metabolism, and the secretion of intestinal hormones.
GPR120 is a promising target for the treatment of numerous diseases, whose pathophysiology
is associated with low-grade inflammation. As a result of intensive searches, a likely group of
synthetic agonists of the receptor was determined with potential therapeutic applications in
conditions such as obesity, impaired carbohydrate metabolism, inflammatory bowel diseases,
cancer, mental disorders.
Deceptively simple: An outsider's perspective on natural language processing
Authors: KhudaBukhsh Ashiqur R.
Published: October 2024

This article highlights a collection of ideas with an underlying deceptive simplicity that addresses several practical challenges in computational social science and generative AI safety. These ideas lead to (1) an interpretable and quantifiable framework for political polarization; (2) a language identifier robust to noisy social media text settings; (3) a cross‐lingual semantic sampler that harnesses code‐switching; and (4) a bias audit framework that uncovers shocking racism, antisemitism, misogyny, and other biases in a wide suite of large language models.
Assessing the robustness of dose distributions in carbon ion prostate radiotherapy using a fast dose evaluation system
Authors: Tsubouchi Toshiro , Shiomi Hiroya , Suzuki Osamu , Hamatani Noriaki , Takashina Masaaki , Yagi Masashi , Wakisaka Yushi , Ogawa Atsuhiro , Terasawa Ayumi , Akino Yuichi , Ogawa Kazuhiko , Kanai Tatsuaki
Published: October 2024

Purpose

We developed a software program for swiftly calculating dose distributions for carbon ion beams. This study aims to evaluate the accuracy of dose calculations using this software and assess the robustness of dose distribution in treating prostate cancer.

Methods

At the Osaka Heavy Ion Therapy Center, markers are inserted into the prostate gland and used for position verification. To account for geometric changes along the beam path due to marker translation, a beam‐specific planning target volume (bsPTV) is set for each beam. To validate the accuracy of the dose calculations using the developed software, dose distributions for prostate and sarcoma cases were calculated and compared with the treatment planning system. To assess the robustness of the dose distribution, position verification data from 346 cases were utilized to reproduce dose distributions for three matching methods: bone matching, widely adopted in most particle therapy centers; marker translation, which involves direct translation to markers without bone matching; and marker translation after bone matching. The coverage of the target (D99 of clinical target volume (CTV)) was assessed to evaluate the robustness of the dose distribution. Additionally, statistical analyses were conducted for the dose distributions of each matching method.

Results

The dose calculation for a single condition can be completed very quickly. Statistical analysis revealed significant differences among dose distributions considering the three matching methods. When irradiation was performed with bone matching only, the D99 was reduced by more than 10% in approximately 7.5% of cases, making it as the poorest among the three matching methods. However, there was no significant reduction in target coverage with the other two methods.

Conclusion

We have demonstrated the accuracy of the developed software for rapidly calculating dose distributions for carbon ion beams and confirmed the robustness of the dose distributions based on the bsPTV.
Modulating NFO@N‐MWCNTs/CC Interfaces to Construct Multilevel Synergistic Sites (Ni/Fe‐O‐N‐C) for Multi‐Heavy Metal Ions Sensing
Authors: Wu Zhijun , Cheng Huan , Xu Lijia , He Qingxu , Kou Xin , Wang Yuchao , Huang Hui , Zhao Yongpeng
Published: October 2024

A hierarchical heterogeneous composite electrode of NiFe2O4@nitrogen‐doped multi‐walled carbon nanotubes/carbon cloth (NFO@N‐MWCNTs/CC) is prepared via a dip‐coating method, followed by a hydrothermal process. The flexible carbon cloth (CC) substrate provides robust support and the cross‐linked nitrogen‐doped multi‐walled carbon nanotubes (N‐MWCNTs) on the CC form a highly porous network with a large specific area that facilitates electron‐transfer. The stable support strengthens the framework and prevents pore structure disorder within the porous network, that could lead to the structural instability of the active sites. The decorated NiFe2O4 nanoparticles offer abundant active sites for enhanced electrocatalytic activity. Benefiting from the synergistic effect of the 3D hierarchical heterogeneous microstructure and multilevel bimetallic oxide active site (Ni/Fe‐O‐N‐C) constructs, the NFO@N‐MWCNTs/CC electrode achieves stable detection of multiple heavy metal ions (HMIs) with high reproducibility. The modified electrode allowed stable detection of multiple heavy metal ions with high reproducibility. The sensitivities of the electrode for Cd(II), Pb(II), Bi(III), and Hg(II) are 344.98, 441.02, 176.484, and 371.099 µA µm−1, respectively. The assay recoveries ranged from 95.3% to 106.8%, highlighting its practical applicability. This study provides innovative composites and theoretical insights to facilitate further advances in the simultaneous high‐performance detection of heavy metal ions.
Bridging to Commercialization: Record‐Breaking of Ultra‐Large and Superior Cyclic Stability Tungsten Oxide Electrochromic Smart Window
Authors: Tian Maofei , Zheng Rongzong , Jia Chunyang
Published: October 2024

Electrochromic smart windows (ESWs) can significantly reduce energy consumption in buildings, but their cost‐effective, large‐scale production remains a challenge. In this study, the instability of black phosphorus is leveraged to induce the growth of the tungsten oxide film through its decomposition process, inspired by the 2D material‐assisted in situ growth (TAIG) method. This approach results in the preparation of large‐scale, high‐performance WO3‐x·nH2O (n < 2) films. Characterization techniques and DFT calculations confirm efficient regulation of structural water and oxygen vacancies during TAIG preparation. The WO3‐x·nH2O films exhibit excellent electrochromic (EC) properties, including high transmittance modulation (74.2%@1100 nm), fast switching time (tc = 5.5 s, tb = 3.8 s), high coloration efficiency (124.7 cm2 C−1), and superior cyclic stability (transmittance modulation retained 94.7% after 20 000 cycles). Ultra‐large WO3‐x·nH2O film are prepared via a simple immersion process, and fabricated into a large‐area ESW under facile laboratory conditions, demonstrating the economic and practical feasibility of this approach in industrial‐scale production. Operated by the intelligent control circuit,  the ESW exhibits remarkable EC properties and cyclic stability This research represents a milestone in improving the performance and industrial‐scale production of ESWs, bridging the gap to the commercialization of EC technology.
Kirigami‐Inspired Three‐Dimensional Metamaterials with Programmable Isotropic and Orthotropic Thermal Expansion
Authors: Gu Yuanqing , Wei Zhibo , Wei Guowu , You Zhong , Ma Jiayao , Chen Yan
Published: October 2024

Mechanical metamaterials with specifically designed cells can provide unusual thermal expansion properties for diverse applications. Limited by very few available cell topologies and complicated non‐linear structural deformation, most existing thermal expansion metamaterials can only achieve orthogonally isotropic negative/zero/positive thermal expansion (NTE/ZTE/PTE) within a mild range, especially the 3D ones. Here, based on one‐degree‐of‐freedom kirigami polyhedrons proposed with a kinematic design strategy, a family of 3D isotropic and orthotropic metamaterials capable of programmable NTE, PTE, and even ZTE over ultra‐wide range is developed. Incorporating bi‐material strips as creases for isotropic polyhedrons, NTE and PTE metamaterials with coefficients of thermal expansion (CTEs) ranging from −2354.3 to 3006.7 ppm/°C are designed and programmed by the theoretical model. Meanwhile, isotropic ZTE metamaterials are constructed by either homogeneous tessellation of ZTE cells or hybrid tessellation of NTE and PTE cells. Furthermore, by allowing distinct geometric parameters in the three orthogonal directions of the kirigami polyhedrons while preserving the kinematic motion, orthotropic metamaterials, in which each of the three directions can be assigned with an independently programmed NTE, ZTE, or PTE, are also achieved. This study paves a novel pathway for the development of thermal expansion metamaterials with potential applications for space optical systems, MEMS, and so on.
Neuron‐Inspired Flexible Phase Change Materials for Ambient Energy Harvesting and Respiration Monitoring
Authors: Luo Tianwen , Kong Lingli , Lu Junjie , Xie Man , Lin Baofeng , Fu Lihua , Huang Bai , Xu Chuanhui
Published: October 2024

The global energy crisis and climate change pose unprecedented challenges. Wearable devices with personal thermoregulation and energy harvesting hold great promise for achieving energy savings and human thermal comfort. Here, inspired by neurons, a novel phase change material (PCM) is reported for efficient energy harvesting and respiratory monitoring via a self‐assembly strategy. The use of gum arabic (GA) enabled the encapsulation of polyethylene glycol (PEG) and the targeted distribution of carboxylated multi‐walled carbon nanotubes (cMWCNTs) simultaneously in poly (ethylene vinyl acetate) (EVA) matrix. The material exhibits an outstanding toughness value of 14.88 MJ m−3 and high elongation at a break of 565.67%, exhibiting remarkable flexibility. The material with sufficient melting enthalpy (71.11 J g−1) demonstrates high photothermal conversion efficiency (95.27%) under 808 nm laser irradiation (105 mW cm−2). In addition, due to the synergistic effect of GA and PEG, especially the formation of microdome structures on the surface, the material demonstrates ultrasensitive humidity responsiveness for respiratory monitoring with high precision, excellent repeatability, and fast response/recovery time (50.4/50.5 ms). Notably, it shows great potential for moisture‐electric generators (MEGs) with the function of non‐contact sensing. This material opens the path toward next‐generation wearable devices in energy conversion and health monitoring.
Oxidative Passivation of FAPbI3 via Femtosecond Laser for Enhanced Photoluminescence and Photoresponse Performance
Authors: Huang Ziyuan , Li Yixuan , Zhou Rongxue , Li Ying , Xing Jun , Zou Tingting , Yang Jianjun , Li Wei , Yu Weili
Published: October 2024

The presence of uncoordinated Pb atoms in perovskite materials, acting as non‐radiative recombination centers, significantly degrades the performance of perovskite‐based photoelectronic devices. Addressing this issue by passivating these deep energy level defects is essential for enhancing device performance. By now, the passivation methods are largely proposed by chemical additive engineering methods, which involve the oxidation of Pb through chemical additives. However, chemical passivation methods are often plagued by issues such as prolonged processing times, uncontrollable passivation regions uncontrollable, and environmental contamination. Here, a novel femtosecond laser oxidative passivation (FsLOP) technique for FAPbI3 is proposed, evidenced by X‐ray photoelectron spectroscopy (XPS) revealing the formation of Pb─O bonds. The role of peroxide anions in oxidation passivation is highlighted as pivotal. The oxidative passivation effect is further corroborated by a four‐fold increase in photoluminescence (PL) intensity and an exceptional improvement in photoresponse performance, achieving a detectivity of 6.77 × 1012 Jones. This work provides a deeper insight into the interaction between femtosecond lasers and perovskite materials, proposing an efficient, precisely controlled, and environmentally friendly way to improve the performance of perovskite photoelectronic devices.
Validating the Novel Electron Transport Layer with the Use of Experimentally Studied D18:Y6 Bulk Heterojunction Solar Cell
Authors: Karuppaiah Chandrasekar , Azhakanantham Dheebanathan , Selvamani Muthamizh , Perumal Sathish Kumar , Alotaibi Majed A. , Kesavan Arul Varman
Published: October 2024

Organic solar cells (OSC) are showing steady efficiency improvement due to the development in the materials synthesis, sophisticated characterization techniques, in‐depth understanding of materials and devices. In the recent years, bulk heterojunction OSC with a non‐fullerene acceptor /polymer acceptor shows significant enhancement in efficiency (≈19%). Efficiency of the polymer acceptor OSCs is much higher than the fullerene derivative‐based acceptors. In this work, OSC simulations are done using D18 donor and Y6 acceptor bulk heterojunction as a photoactive layer. As a first step, validity of the experimental results for ITO/PEDOT:PSS/D18:Y6/PDIN/Ag structure is done. To investigate efficiency, 2,8,15‐trifluoro‐3,9,14‐tris(heptylsulfonyl)diquinoxalino[2,3‐a:2′,3′‐c]phenazine (HATNASO2C7‐Cs) electron transport layer is validated in place of PDIN in the following device structure, ITO/PEDOT:PSS/D18:Y6/HATNASO2C7‐Cs/Ag. Energy level matching of the HATNASO2C7‐Cs is well aligned compared with PDIN at the cathode interface. Device simulation optimization are carried out for various photoactive layer, ETL and HTL condition. Highest efficiency of 20.99% is obtained for ITO/PEDOT:PSS/D18:Y6/HATNASO2C7‐Cs/Ag when the HATNASO2C7‐Cs thickness, bandgap, electron affinity, carrier mobility, and defect density is matched for ≈30 nm, ≈2.8 eV, ≈4.16 eV, ≈2 × 10−3 cm2 V−1 s−1, and 1014 cm−3 respectively. Obtained results are discussed in details and results will be helpful for preliminary understanding of the system.
A Programmable Handheld Extrusion‐Based Bioprinting Platform for In Situ Skin Wounds Dressing: Balance Mobility and Customizability
Authors: Wang Chenmin , Hu Chengwei , Cheng Haojin , Qi Weichen , Wang Liangliang , Wu Tianchi , Wu Jun , Cui Xu , Xu Jiake , Pan Haobo , Bian Shaoquan , Lu Weijia William , Zhao Xiaoli
Published: October 2024

Bioprinting technology plays a crucial role for constructing tissue substitutes. However, the mismatched scaffold shapes and the poor treatment timeliness limit its clinical translational application. In situ printing technology that prints bioregenerants directly inside patient's body can meet the needs of specific tissue repair. This study develops a smartphone controlled handheld bioprinter for in situ skin wounds dressing. The mini bioprinter can be handheld and placed on any printing surface to create strips, complex patterns, and 3D structures, and can be equipped with microchannel needles to expand functionality. The size of the strips as well as the printing path can be programmed and controlled by the smartphone to ensure the precision of the printed product quality. Furthermore, the device not only allows for smooth switching between different bioinks for printing heterogeneous structure, but also allows for fast and uniform coverage of large wound surfaces. When dealing with complex wounds in vitro & vivo, the printer can effectively fill and precisely close wounds, promoting wound healing. The programmable handheld bioprinter can balance mobility and customizability in the management of skin wounds and is expected to realize its potential for emergency medical treatment in condition‐constrained scenarios, such as battlefields or disaster areas.
Engineered Protein Fibers with Reinforced Mechanical Properties Via β‐Sheet High‐Order Assembly
Authors: Li Ming , Qin Dawen , Chen Jing , Jia Bo , Wei Zheng , Zhang Yi , Cheng Wenhao , Liu Qianqian , Wang Fan , Li Jingjing , Zhang Hongjie , Liu Kai
Published: October 2024

Protein fibers are ideal alternatives to synthetic polymers due to their unique mechanical properties, biocompatibility, and sustainability. However, engineering biomimetic protein fibers with high mechanical properties remains challenging, particularly in mimicking the high molecular weight of natural proteins and regulating their complex hierarchical structures. Here, a modular design and multi‐scale assembly strategy is developed to manufacture robust protein fibers using low‐ or medium‐molecular‐weight proteins. The distinct functional and structural properties of flexible, rigid, and cross‐linked domains in modular proteins are skillfully harnessed. By regulating the ratio of rigid to flexible domains, the formation of high‐order β‐sheet crystals aligned along the fiber axis is promoted, enhancing both strength and toughness. Furthermore, the dynamic imine cross‐linking network, formed by the aldehyde‐amine condensation reaction of the cross‐linked domains, further reinforces the protein fibers. Remarkably, fibers spun from modular proteins significantly smaller than natural spidroin exhibit outstanding mechanical properties, surpassing those of protein fibers with same or even higher molecular weights. This strategy offers a promising pathway for fabricating protein fibers suitable for diverse applications.
Halogen‐Bonded Hole‐Transport Material Enhances Open‐Circuit Voltage of Inverted Perovskite Solar Cells
Authors: Chen Zhaoyang , Zhang Jiakang , Chen Zilong , Yao Ze‐Fan , Liu Kai‐Kai , Zhou Zhongmin , Zhang Haichang , Liu Maning
Published: October 2024

Interfacial properties of a hole‐transport material (HTM) and a perovskite layer are of high importance, which can influence the interfacial charge transfer dynamics as well as the growth of perovskite bulk crystals particularly in inverted structure. The halogen bonding (XB) has been recognized as a powerful functional group to be integrated with new small molecule HTMs. Herein, a carbazole‐based halo (iodine)‐functional HTM (O1), is synthesized for the first time, demonstrating a high hole mobility and suitable energy levels that align well with those of perovskites. The strong interaction between O1 and perovskite, i.e., I···I−, induces the formation of an ordered interlayer, which are verified by both theoretical and experimental studies. Compared to the reference HTM (O2) without any halo‐function, the XB‐induced interlayer effectively enhances the interfacial charge extraction efficiency, while significantly hindering the non‐radiative charge recombination by reducing the surface traps upon the strong passivation effect. This is reflected as a big increase in the open‐circuit voltage by up to 114 mV in the fabrication of inverted devices with the highest power conversion efficiency of 22.34%. Moreover, the ordered XB‐driven interlayer at the interface of O1 and perovskite is mainly responsible for the extended lifespan under the operational conditions.
Out‐Diffusion and Uphill‐Diffusion of Mg in Czochralski‐Grown (100) β‐Ga2O3 Under High‐Temperature Annealing and Its Influence on Lateral MOSFET Devices
Authors: Chou Ta‐Shun , Tran Thi Thuy Vi , Peelaers Hartwin , Tetzner Kornelius , Hilt Oliver , Rehm Jana , Bin Anooz Saud , Fiedler Andreas , Galazka Zbigniew , Albrecht Martin , Popp Andreas
Published: October 2024

In this work, the out‐diffusion and uphill‐diffusion of Mg inside (100) β‐Ga2O3 epilayers and substrates are reported. The Mg accumulates toward the (100) surface upon annealing under an oxidizing environment, whereas the concentration profile changes with annealing temperatures and durations. Furthermore, the out‐diffusion of Mg from the substrate into the epilayer is observed at temperatures above 800 °C, which continues during the film growth. The substitutional‐interstitial‐diffusion (SID) mechanism is suggested to be the driving mechanism for the former, and the latter is related to the diffusion of mobile Mg interstitials. The accumulation profile of Mg can be used to identify the interface between the epilayer and the substrate. Furthermore, significant differences in device performance are observed for power transistors fabricated on annealed and non‐annealed epitaxial β‐Ga2O3 wafers. Increased breakdown voltages of annealed samples are attributed to the Mg diffusion into the first few nanometers of the epitaxial layer close to the interface to the semi‐insulating substrate, leading to compensation of residual dopants (donors) in that region.
Separator‐Supported Electrode Configuration for Ultra‐High Energy Density Lithium Secondary Battery
Authors: Kim Ju Young , Seo Min Young , Choi Jaecheol , Lee Yoon Ho , Kim YongJoo , Kang Seok Hun , Lee Yong Min , Lee Young‐Gi
Published: October 2024

Significant efforts are being made to develop high‐performance battery materials, particularly active materials. However, material‐dependent strategies for increasing energy density face challenges such as raw material costs and supply limitations, reducing their versatility to some extent. In this regard, the development of efficient battery designs can be a universal approach to increasing the energy density of lithium‐ion batteries with relatively low dependence on material properties. Herein, a novel configuration of an electrode‐separator assembly is presented, where the electrode layer is directly coated on the separator, to realize lightweight lithium‐ion batteries by removing heavy current collectors. Even on the hydrophobic separator, a poly(vinyl alcohol) binder enables uniform and scalable coating of aqueous electrode slurries through molecular interactions with the separator surface. Moreover, carbon nanotubes are utilized to reinforce the electronic conduction of the electrode, providing consistent electronic pathways regardless of SEI formation. Furthermore, owing to the superior permeability of liquid electrolytes through this electrode‐separator assembly, a multilayered electrode‐separator assembly can be suggested to further increase energy density when combined with a lithium metal anode. This lithium metal battery can achieve an areal capacity of ≈30 mAh cm−2 and an enhanced energy density of over 20% compared to conventional battery configurations.
“Ardor and diligence”: Quantifying the faculty effort needed in emergency medicine graduate medical education
Authors: Burkhardt John C. , Jordan Jaime , Cranford James A. , Gallahue Fiona E. , Kocher Keith E. , Murano Tiffany , Weizberg Moshe , Hopson Laura R.
Published: October 2024

Objectives

Regulatory requirements around protected faculty effort to support graduate medical education (GME) programs have changed. The amount of labor required to run a GME program is unknown. We sought to describe the work performed by program leadership and core faculty in emergency medicine (EM).

Methods

We performed a prospective survey study of core faculty in EM. Participants completed a demographic questionnaire followed by quarterly time surveys, covering activities in eight domains: evaluation, teaching and education, scholarly activity, service, interview/recruitment, clinical supervision, student responsibilities, and wellness and administration. We collected data from April 2022 to March 2023. We calculated descriptive statistics and used analyses of variance (ANOVA) to assess differences by faculty role and quarter.

Results

A total of 596 physicians completed the demographic questionnaire and 347 (58.2%) completed at least one quarterly time survey including 142 (41%) females, 48 (14%) program directors (PDs), 84 (24%) assistant/associate program directors (APDs), and 215 (62%) general core faculty (GCF). The mean number of hours per week spent on nonclinical education work was 60 h for PDs, 47 h for APDs, and 44 h for GCF. ANOVA found significant differences in mean hours per week and faculty role in domains of evaluation (p < 0.001), service (p = 0.007), and interview/recruitment (p < 0.001). We detected differences in mean hours per week and quarter in domains of evaluation (p < 0.001), teaching and education (p < 0.001), interview and recruitment (p < 0.001), and clinical supervision (p < 0.001).

Conclusions

Running a residency program requires many hours of faculty work, which can vary based on faculty role and time of year. These results can inform decisions regarding faculty support.
Directed image review technique (DIRT): A framework for ultrasound image assessment and interpretation
Authors: Broadstock Arthur T. , Baez Jessica , Minges Patrick G. , Frederick Meaghan , Stolz Lori A.
Published: October 2024

Use of point‐of‐care ultrasound (POCUS) is integral to the practice of emergency medicine, and POCUS education is a required component of emergency medicine training. Developing POCUS skills requires iterative deliberate practice of image acquisition and interpretation. Providing feedback to learners regarding ultrasound image interpretation can be challenging for emergency medicine clinician educators. We present a framework called the directed image review technique. This framework guides learner ultrasound image interpretation and provides educators with a similar structured approach to evaluate a learner's ultrasound competency and provide targeted feedback regarding image acquisition and interpretation.
Iron accumulation/overload and Alzheimer's disease risk factors in the precuneus region: A comprehensive narrative review
Authors: Mohammadi Sana , Ghaderi Sadegh , Fatehi Farzad
Published: October 2024

Alzheimer's disease (AD) is a neurodegenerative disease that is characterized by amyloid plaques, neurofibrillary tangles, and neuronal loss. Early cerebral and body iron dysregulation and accumulation interact with AD pathology, particularly in the precuneus, a crucial functional hub in cognitive functions. Quantitative susceptibility mapping (QSM), a novel post‐processing approach, provides insights into tissue iron levels and cerebral oxygen metabolism and reveals abnormal iron accumulation early in AD. Increased iron deposition in the precuneus can lead to oxidative stress, neuroinflammation, and accelerated neurodegeneration. Metabolic disorders (diabetes, non‐alcoholic fatty liver disease (NAFLD), and obesity), genetic factors, and small vessel pathology contribute to abnormal iron accumulation in the precuneus. Therefore, in line with the growing body of literature in the precuneus region of patients with AD, QSM as a neuroimaging method could serve as a non‐invasive biomarker to track disease progression, complement other imaging modalities, and aid in early AD diagnosis and monitoring.
Noise aware parameter estimation in bioprocesses: Using neural network surrogate models with nonuniform data sampling
Authors: Weir Lauren , Mathias Nigel , Corbett Brandon , Mhaskar Prashant
Published: October 2024

This article demonstrates a parameter estimation technique for bioprocesses that utilizes measurement noise in experimental data to determine credible intervals on parameter estimates, with this information of potential use in prediction, robust control, and optimization. To determine these estimates, the work implements Bayesian inference using nested sampling, presenting an approach to develop neural network‐ (NN) based surrogate models. To address challenges associated with nonuniform sampling of experimental measurements, an NN structure is proposed. The resultant surrogate model is utilized within a Nested Sampling Algorithm that samples possible parameter values from the parameter space and uses the NN to calculate model output for use in the likelihood function based on the joint probability distribution of the noise of output variables. This method is illustrated against simulated data, then with experimental data from a Sartorius fed‐batch bioprocess. Results demonstrate the feasibility of the proposed technique to enable rapid parameter estimation for bioprocesses.
Parsaclisib for the treatment of primary autoimmune hemolytic anemia: Results from a phase 2, open‐label study
Authors: Barcellini Wilma , Pane Fabrizio , Patriarca Andrea , Murakhovskaya Irina , Terriou Louis , DeSancho Maria T. , Hanna Wahid T. , Leopold Lance , Rappold Erica , Szeto Ke , Wei Shaoceng , Jäger Ulrich
Published: October 2024

Autoimmune hemolytic anemia (AIHA) is a group of acquired autoimmune disorders characterized by red blood cell hemolysis. In a phase 2, open‐label, multicenter study, adults with warm AIHA, cold agglutinin disease, or mixed‐type AIHA were administered once‐daily 1.0 or 2.5 mg parsaclisib (selective phosphoinositide 3‐kinase δ inhibitor) orally for 12 weeks, followed by an extension period. Dose increases (for AIHA worsening) or decreases (for tolerability) were permitted. Primary efficacy endpoint was the proportion of patients with complete (≥12 g/dL hemoglobin [Hgb]) or partial (10–12 g/dL Hgb or ≥2 g/dL increase from baseline) response at any visit during weeks 6–12 not attributable to transfusion. Among 25 enrolled patients (median age, 63 y), 16 (64%) achieved a partial or complete Hgb response during weeks 6–12. Responses were observed by week 1 in 52.0% of patients with incremental improvements during weeks 6–12 and sustained responses during the extension period. Responses were higher among patients with warm AIHA versus other types (75.0% vs. 44.4%). Clinically meaningful improvements in Functional Assessment of Chronic Illness Therapy‐Fatigue scores were observed at weeks 6 and 12. All patients had treatment‐emergent adverse events (TEAEs), most commonly diarrhea (32.0%) and pyrexia (28.0%). Grade ≥3 TEAEs occurred in 13 patients (52.0%). TEAEs considered possibly related to treatment occurred in 11 patients (44.0%). No dose reductions were required; six patients (24%) discontinued for a TEAE. In summary, parsaclisib was well tolerated and resulted in substantial improvements in Hgb response at week 1, with durable responses through the extension period.

Clinical trial registration

This trial was registered at ClinicalTrials.gov (NCT03538041).
Genetic ancestry in Puerto Rican afro‐descendants illustrates diverse histories of African diasporic populations
Authors: Nieves‐Colón Maria A. , Ulrich Emma C. , Chen Lijuan , Torres Colón Gabriel A. , Clemente Maricruz Rivera , (COPI) La Corporación Piñones Se Integra , Benn Torres Jada
Published: October 2024

Objectives

Genetic studies of contemporary Puerto Ricans reflect a demographic history characterized by admixture between Indigenous American, African, and European peoples. While previous studies provide genetic perspectives on the general Puerto Rican population, less is known about the island's sub‐populations, specifically Afro‐Puerto Ricans.

Materials and Methods

In this study, the genetic ancestry of Afro‐Puerto Ricans is characterized and compared to other Caribbean populations. Thirty DNA samples collected among self‐identified Puerto Ricans of African descent in Loíza (n = 2), Piñones (n = 13), San Juan (n = 2), Mayagüez (n = 9), and Ponce (n = 4), were genotyped at 750,000 loci on the National Geographic Genochip. We then applied unsupervised clustering and dimensionality‐reduction methods to detect continental and subcontinental African and European genetic ancestry patterns.

Results

Admixture analyses reveal that on average, the largest genetic ancestry component for Afro‐Puerto Ricans is African in origin, followed by European and Indigenous American genetic ancestry components. African biogeographic origins of Afro‐Puerto Ricans align most closely with contemporary peoples of Lower Guinea and the Bight of Biafra, while the European genetic ancestry component is most similar to contemporary Iberian, Italian, and Basque populations. These findings contrast with the biogeographic origins of comparative Barbadian and Puerto Rican populations.

Discussion

Our results suggest that while there are similarities with regard to general patterns of genetic ancestry among African descendants in the Caribbean, there is previously unrecognized regional heterogeneity, including among Puerto Rican sub‐populations. These results are also consistent with available historical sources, while providing depth absent from the documentary record, particularly with regard to African ancestry.
Making the most of a captive audience: Do specialist teams in custodial settings offer a way to assist people to access the NDIS?
Authors: Bates Shona , Katz Ilan , Whitten Tyson
Published: October 2024

While the National Disability Insurance Scheme (NDIS) has been operating in Australia for 10 years, numerous eligible people with disability have not accessed the scheme, many of whom are in prison. The South Australian Government, in partnership with the National Disability Insurance Agency (NDIA), implemented a pilot programme to assist people in prison to access the NDIS as having NDIS supports on release may reduce the risk of returning to custody. This qualitative study, drawing on interviews with 20 stakeholders, explores the enablers and barriers of assisting people with disability in prison access the NDIS. Our findings show that while custodial settings provide opportunities to assist people with disability to have their eligibility for the NDIS assessed, prisons are difficult settings in which to undertake subsequent assessment and planning processes to determine the supports available on release. People with disability exiting prison also face significant challenges accessing suitable accommodation and support services, particularly when their needs are complex. Further work is required to ensure planning and assessment processes meet the needs of this group. The findings provide useful insights to both justice and other institutional settings and respond to many of the questions raised by recent public inquiries and reviews.
Polyethylene Recycling via Water Activation by Ball Milling
Authors: Li Linfeng , Leutzsch Markus , Hesse Phil , Wang Chuanhao , Wang Bolun , Schüth Ferdi
Published: October 2024

Polyethylene (PE) is the most prevalent type of plastic waste and also the most challenging to depolymerize because of its inert carbon‐carbon (C−C) bonds.[1] High temperature and noble metals are usually required for depolymerization.[2] To avoid using noble metals, costly reagents and harsh reaction conditions, it is worthwhile but challenging to explore new reaction pathways.[3] We report an unprecedented mechanochemical reaction of PE and water to result in shorter‐chain alkanes, alkenes, alcohols, and ketones (Cn, where n≲50), with above 80 % of starting carbon converted into these products, which could be a valuable feedstock for re‐entering chemical value chains. This reaction is driven solely by ball milling, without heating and pressurizing. No costly catalysts are used. Instead, only earth‐abundant Al2O3 was milled with reactants.
Kinetic Control over Social and Narcissistic Self‐Sorting from Multicomponent Mixtures in Seed‐Initiated Supramolecular Polymerization by Fine‐Tuning of Steric Effects
Authors: Matsumoto Kentaro , Bäumer Nils , Ogi Soichiro , Yamaguchi Shigehiro
Published: October 2024

Supramolecular polymers offer an intriguing possibility to transfer molecular properties from the nano‐ to the mesoscale. Towards this achievement, seed‐initiated supramolecular polymerization has emerged as a powerful tool, as it prevents unlimited growth and enables size control of the assembly outcome. However, the potential application of the seeding method in the context of complex supramolecular systems is hitherto unclear. Herein we demonstrate that minute differences in molecular design in direct proximity to intermolecular recognition sites govern the molecular packing and in turn dictate the efficacy of seeded polymerization processes. We introduce a stepwise increase in steric demand in the central amino acid residue of a diamide system, which gradually increases the rotational displacement within the aggregated state. This fine‐tuning of the molecular packing directly affects the propensity of the different aggregates to act as seeds for the other supramolecular synthons. In turn this allows us to selectively target specific trapped monomer states in binary mixtures for social or narcissistic seeded polymerization.
Engineering Active Sites of Metal/Metal Oxide Catalysts by Oxide Ligand Overlayers
Authors: Zhou Jiahua , Yang Piaoping , Caratzoulas Stavros , Zheng Weiqing , Vlachos Dionisios G.
Published: October 2024

Engineering sites of supported metal catalysts is essential to enhancing activity and selectivity. Such enhancement is typically achieved by particle size modification, surface alloying, or attaching molecular ligands. Yet, control strategies for complex, multifunctional molecules and catalysts, where selectivity is crucial, are lacking. Here, we demonstrate that submonolayer WOx with tunable coverage preferentially decorates well‐coordinated Pt terrace sites as a stable ligand. By combining experimental kinetics with probe molecules, in situ spectroscopies, and first‐principles modeling, we show that the WOx coverage on Pt modifies the metal‐to‐acid site balance while retaining the acid strength intact and results in optimal reactivity for metal‐acid catalyzed reactions at a specific metal, size, and support‐dependent WOx coverage. The oxide can also alter the reactant adsorption mode, reversing selectivity and pathways from terrace‐ to step‐dominated, as evidenced in furfural decarbonylation and hydrogenation. The insights open avenues for improving metal/metal oxide catalysts beyond the specific system.
Organic Circularly Polarized Room‐Temperature Phosphorescence: Strategies, Applications and Challenges
Authors: Zou Xin , Gan Nan , Gao Yaru , Gu Long , Huang Wei
Published: October 2024

Organic circularly polarized luminescence (CPL) plays crucial roles in chemistry and biology for the potential in chiral recognition, asymmetric catalysis, 3D displays, and biological probes. The long‐lived luminescence, large Stokes shift, and unique chiroptical properties make organic circularly polarized room‐temperature phosphorescence (CPP) a new research hotspot in recent years. Nevertheless, achieving high‐performance organic CPP is still challenging due to the sensitivity and complexity of integrating triplet excitons and polarization within organic materials. This review summarizes the latest advances in organic CPP, ranging from design strategies and photophysical properties to underlying luminescence mechanisms and potential applications. Specifically, the design strategies for generating CPP are systemically categorized and discussed according to the interactions between chiral units and chromophores. The applications of organic CPP in organic light‐emitting diodes, sensing, chiral recognition, afterglow displays, and information encryption are also illustrated. In addition, we present the current challenges and perspectives on developing organic CPP. We expect this review to provide some instructive design principles to fabricate high‐performance organic CPP materials, offering an in‐depth understanding of the luminescence mechanism and paving the way toward diverse practical applications.
Activation and C−C Coupling of Aryl Iodides via Bismuth Photocatalysis
Authors: Mato Mauro , Stamoulis Alexios , Cleto Bruzzese Paolo , Cornella Josep
Published: October 2024

Within the emerging field of bismuth redox catalysis, the catalytic formation of C−C bonds using aryl halides would be highly desirable; yet such a process remains a synthetic challenge. Herein, we present a chemoselective bismuth‐photocatalyzed activation and subsequent coupling of (hetero)aryl iodides with pyrrole derivatives to access C(sp2)−C(sp2) linkages through C−H functionalization. This unique reactivity is the result of the bismuth complex featuring two redox state‐dependent interactions with light, which 1) activates the Bi(I) complex for oxidative addition via MLCT, and 2) promotes the homolytic cleavage of aryl Bi(III) intermediates through a LLCT process.
Visible Light Excitation of Poly‐(para‐Phenylene Ethynylene) Enables Heterogeneous Photocatalytic Oxidations of Amines in Flow
Authors: Weyl Basile , Goujon Gabriel , Raggio Lucas , Demey Emmanuelle , Vinh Joelle , d'Espinose de Lacaillerie Jean‐Baptiste , Krafft Jean‐Marc , Laroche Benjamin
Published: October 2024

Heterogeneous visible light photocatalysis is a compelling approach to address sustainability in synthetic photochemistry. However, the use of solid‐state photocatalysts remains very unpopular in organic synthesis because of their limited accessibility and the black‐box effect associated to the lack of rational between their molecular structure and their photochemical properties. Herein, we disclose the synthesis, characterization, photocatalytic properties and synthetic applications of a simple and readily available solid‐state conjugated organic polymer, poly‐(para‐phenylene ethynylene) 1, which exhibits a strong oxidative power upon irradiation with visible light (E(1*/1⋅−)=+1.67 V vs SCE). Comparisons with structural analogues highlighted the superior photocatalytic activity of this linear semiconductor, on account of its fully conjugated architecture. The associated excited‐state reactivity enabled the transformation of various amines into imines in batch and continuous flow reactors together with straightforward photocatalyst recycling. Mechanistic investigations revealed concomitant photoredox and energy transfer pathways, that led to the formation of the desired products. Ultimately, the inline generation of imines was exploited in telescoped three‐component Ugi reactions (3CR) in batch and flow toward biologically relevant α‐acylaminoamides.
The Synthesis and Application of Chitosan@Ag2O@Mn3O4 Three‐Phase Nanocomposite as a Heterogeneous Catalyst in the Synthesis of 2‐Hydroxynaphthalenepyrimidine Trione
Authors: Kaboutarkhani Bahareh Hassani , Sheikhhosseini Enayatollah , Yahyazadehfar Mahdieh
Published: October 2024

The catalyst is often the most expensive element in a chemical process, rather than the reactants or products. Apart from the financial benefits, it is equally crucial to recover and reuse the catalyst to prevent waste and enhance the process's greenness. This study successfully synthesized the new, superior, and recyclable heterogeneous chitosan@Ag2O@Mn3O4 three‐phase nanocatalyst with high surface area and stability using Ag2O and Mn3O4 nanoparticles that stabilized on chitosan by copreparation method and was characterized by Fourier transform infrared (FT‐IR), scanning electron microscopy (SEM), energy dispersive X‐ray (EDX), transmission electron microscopy (TEM), surface mapping (mapping), X‐ray diffraction (XRD), Brunner–Emmett–Teller (BET), thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC) techniques in detail. Following, the efficiency of the synthesized nanocatalyst in the preparation of 2‐hydroxynaphthalenepyrimidine triones using the reaction of aromatic aldehydes, β‐naphthol, and barbituric acid derivatives was investigated and proved. The advantages of this method include performing reactions at room temperature, green media, short reaction times, and the easy purification of the products.
Beef tallow/high oleic sunflower oil shortenings produced by chemical interesterification optimized by response surface methodology (RSM): Effect of processing conditions on physical properties
Authors: Ramos‐Ramos María Regina , Cevallos Velastegui Leslie Pamela , García Londoño Víctor Alonso , Aguirre‐Calvo Tatiana Rocío , Borroni Virginia , Herrera María Lidia
Published: October 2024

Response surface methodology (RSM) was used to obtain two shortenings (IEA and IEB) by chemical interesterification (CI) of beef tallow (BT) and high oleic sunflower oil (HOSFO) with melting points of 35.5°C and 38.5°C, higher OOO and SOO contents, and lower PPP, SOS, POS, and POP percentages than BT. The maximum percentage of HOSFO in the formulations and the optimum time, temperature, and catalyst concentrations to achieve the desired physicochemical properties for the shortenings were determined from the model. The shortenings were characterized, and the effects of processing and storage conditions were explored. HPLC/MS analysis showed that the mono and di‐unsaturated triacylglycerols (TAGs) had unsaturated fatty acids at the sn‐2 position. The changes in chemical composition due to the interesterification process were mostly differences in percentages more than in the type of TAGs present. IEA and IEB showed profiles of solid fat content versus temperature and G' values similar to those reported for soft and firm margarine, respectively. Under static cooling conditions, for BT, BA, BB, and IEB, the α‐form was the main polymorph, whereas the β′‐tendency increased with increasing temperature and slow cooling rate. IEA crystallized in the β′‐form between 20 and 32°C. Under dynamic cooling conditions, nucleation was impeded at fast cooling rate and promoted at slow rate as evidenced by induction times of crystallization. Interesterification decreased the MP, increased the β′ tendency that lasted at least 8 months at 25°C, and improved the nutritional value of shortening making them suitable as trans‐fat alternatives.
Strong Non‐Reciprocal Chiroptical Properties in Thin Films of Chiral Alkylthio‐Decorated 1,4‐Phenylene/Thiophene Dyes
Authors: Bertuolo Marco , Zinna Francesco , Aronica Laura Antonella , Pescitelli Gennaro , Di Bari Lorenzo , Albano Gianluigi
Published: October 2024

In the context of chiral π‐conjugated materials, the use of enantiopure alkylthio appendages represents a valid alternative to conventional alkoxy groups: sulphur atom is bigger and more electron‐rich than oxygen, thus allowing for higher polarizability, greater flexibility, larger bulkiness and lower structural anisotropy. In light of these considerations, here we report two new chiral alkylthio‐decorated 1,4‐phenylene/thiophene dyes, obtained by simple synthetic strategies involving Pd‐catalyzed cross‐coupling protocols, looking for strong non‐reciprocal chiroptical features in thin films. In particular, for the chiral alkylthio‐decorated 1,4‐phenylene–bis(thiophenylpropynone) (Thio‐PTPO) dye, which proved to be the most promising for our purpose, a detailed investigation in thin films was carried out, involving optical and chiroptical spectroscopies in absorption and emission, as well as optical microscopy techniques.