bluuebunny/crossref_metadata_2025 huggingface dataset:
To Know the Indigenous Other: A Century of Indians in Canadian History
Authors: Downey Allan
Published: November 2023

Celebrating its centenary in 2022, the Journal of the Canadian Historical Association (JCHA) has been home to scores of articles on Indigenous history within the colonial borders of Canada. Offering a historiography of the past one-hundred years of scholarship appearing in the journal focused on Indigenous topics, this article argues that the JCHA offers a unique case study of the history of the field. While the journal has offered a dearth of scholarship on people of colour, leading to the erasure of Black Canadians as prominent actors in Canada’s past, the zealous study of “Indians” within the journal’s pages is salient. However, much like the larger field of Canadian history, the journal has a fraught and contentious past with Indigenous Peoples, stories, and methods. Unlike the erasure of Black Canadians, the fervent focus on “Indians” in Canadian history has had the significant effect of Canadians coming to “know” the Indians who were produced within the power structures of Canadian imperialism, settler colonialism, and the academy as they sought to identify, classify, and organize the Other. More recently however, there has been a slow trickle of articles produced by historians of Indigenous history that is contributing to an intellectual sovereignty that situates Indigenous history as an independent and unique course of study not tied exclusively or directly to the nation-states of the United States and Canada.
Public-Private Partnerships for the UN Sustainable Development Goals achievement
Authors: Eremin Viktor
Published: November 2023

The subject of the study is public relations emerging in the implementation of public-private partnership projects aimed at achieving the sustainable development goals developed by the UN. The object of the study is a set of financial and institutional conditions for the implementation of public-private partnership (PPP) projects based on PPP agreements with a special focus on the UNECE model law “PPP for the benefit of people” being developed. Thus, the proposed approach to PPP for the benefit of people as a separate type of PPP has been criticized. The author, through the prism of sustainable development goals, describes the possibility of improving the proposed international legal norms and rules developed for the implementation of PPP projects. The article also discusses the possibility of introducing the sustainable development agenda through PPP agreements (lex PPPs). When writing the article, the following methods were used: logical, historical, theoretical-prognostic, formal-legal, systemic-structural, comparative law and legal modeling. The methodological apparatus consisted of the following dialectical techniques and methods of scientific knowledge: analysis, abstraction, induction, deduction, hypothesis, analogy, synthesis, typology, classification, systematization and generalization. The main conclusions of the study are that the concept of sustainable development and sustainable development goals are becoming increasingly popular in the practice of implementing investment projects, including those based on PPP. Further improvement of domestic legislation on PPP should be in line with the implementation of best practices, focused not just on the financial component and benefit of the investor and the state, but also on the benefit for people (PPP people first) and the planet (PPP for planet). The main results of the study include the fact that aspects were identified that slow down the advancement of the sustainable development agenda in the field of public-private partnership (contradiction of terms, lack of incentives for implementation for investors), a definition was given to public-private partnership for sustainable development, and It was also revealed that lex PPPs can become an effective tool for achieving sustainable development goals through their implementation in PPP agreements.
Functional ultrasound imaging of stroke in awake rats
Authors: Brunner Clément , Montaldo Gabriel , Urban Alan
Published: November 2023

Anesthesia is a major confounding factor in preclinical stroke research as stroke rarely occurs in sedated patients. Moreover, anesthesia affects both brain functions and the stroke outcome acting as neurotoxic or protective agents. So far, no approaches were well suited to induce stroke while imaging hemodynamics along with simultaneous large-scale recording of brain functions in awake animals. For this reason, the first critical hours following the stroke insult and associated functional alteration remain poorly understood. Here, we present a strategy to investigate both stroke hemodynamics and stroke-induced functional alterations without the confounding effect of anesthesia, i.e., under awake condition. Functional ultrasound (fUS) imaging was used to continuously monitor variations in cerebral blood volume (CBV) in +65 brain regions/hemispheres for up to 3 hr after stroke onset. The focal cortical ischemia was induced using a chemo-thrombotic agent suited for permanent middle cerebral artery occlusion in awake rats and followed by ipsi- and contralesional whiskers stimulation to investigate on the dynamic of the thalamocortical functions. Early (0–3 hr) and delayed (day 5) fUS recording enabled to characterize the features of the ischemia (location, CBV loss), spreading depolarizations (occurrence, amplitude) and functional alteration of the somatosensory thalamocortical circuits. Post-stroke thalamocortical functions were affected at both early and later time points (0–3 hr and 5 days) after stroke. Overall, our procedure facilitates early, continuous, and chronic assessments of hemodynamics and cerebral functions. When integrated with stroke studies or other pathological analyses, this approach seeks to enhance our comprehension of physiopathologies towards the development of pertinent therapeutic interventions.
RDET stacking classifier: a novel machine learning based approach for stroke prediction using imbalance data
Authors: Rehman Amjad , Alam Teg , Mujahid Muhammad , Alamri Faten S. , Ghofaily Bayan Al , Saba Tanzila
Published: November 2023

The main cause of stroke is the unexpected blockage of blood flow to the brain. The brain cells die if blood is not supplied to them, resulting in body disability. The timely identification of medical conditions ensures patients receive the necessary treatments and assistance. This early diagnosis plays a crucial role in managing symptoms effectively and enhancing the overall quality of life for individuals affected by the stroke. The research proposed an ensemble machine learning (ML) model that predicts brain stroke while reducing parameters and computational complexity. The dataset was obtained from an open-source website Kaggle and the total number of participants is 3,254. However, this dataset needs a significant class imbalance problem. To address this issue, we utilized Synthetic Minority Over-sampling Technique (SMOTE) and Adaptive Synthetic Sampling (ADAYSN), a technique for oversampling issues. The primary focus of this study centers around developing a stacking and voting approach that exhibits exceptional performance. We propose a stacking ensemble classifier that is more accurate and effective in predicting stroke disease in order to improve the classifier’s performance and minimize overfitting problems. To create a final stronger classifier, the study used three tree-based ML classifiers. Hyperparameters are used to train and fine-tune the random forest (RF), decision tree (DT), and extra tree classifier (ETC), after which they were combined using a stacking classifier and a k-fold cross-validation technique. The effectiveness of this method is verified through the utilization of metrics such as accuracy, precision, recall, and F1-score. In addition, we utilized nine ML classifiers with Hyper-parameter tuning to predict the stroke and compare the effectiveness of Proposed approach with these classifiers. The experimental outcomes demonstrated the superior performance of the stacking classification method compared to other approaches. The stacking method achieved a remarkable accuracy of 100% as well as exceptional F1-score, precision, and recall score. The proposed approach demonstrates a higher rate of accurate predictions compared to previous techniques.
As dimensões ESG aplicadas ao agronegócio: uma revisão sistemática de literatura
Authors: De Campos Filho Edinei Silva , De Oliveira Edenis Cesar
Published: November 2023

O agronegócio é um setor importante da economia global, e as práticas ESG estão ganhando importância cada vez maior nesse setor. Este estudo tem como objetivo analisar a produção científica sobre os aspectos ESG (Ambiental, Social e Governança) aplicados ao setor do agronegócio a partir de documentos indexados na base Web of Science e Periódicos CAPES, no período de jan./2013 – set./2023. A análise dos artigos selecionados foi realizada por meio de uma revisão sistemática da literatura, seguindo critérios rigorosos de inclusão e exclusão. A pesquisa foi realizada utilizando palavras-chave e operadores booleanos diretamente nas bases de pesquisas. Aplicados os “filtros”, restaram cinco artigos que atenderam os critérios estabelecidos. Os resultados indicam que o ESG desempenha um papel fundamental no setor do agronegócio, contribuindo para a sustentabilidade, responsabilidade social, rentabilidade e competitividade. No entanto, ainda existem desafios a serem enfrentados na implementação efetiva das práticas ESG, sendo necessária uma maior colaboração entre as partes interessadas.
Characteristics of a plastic scintillation detector in photon beam dosimetry
Authors: Das Indra J. , Sohn Jooyoung J. , Lim Sara N. , Sengupta Bishwambhar , Feijoo Marcos , Yadav Poonam
Published: November 2023

Background

Plastic scintillating detectors (PSD) have gained popularity due to small size and are ideally suited in small‐field dosimetry due to no correction needed and hence detector reading can be compared to dose. Likewise, these detectors are active and water equivalent. A new PSD from Blue Physics is characterized in photon beam.

Purpose

Innovation in small‐field dosimetry detector has led us to examine Blue Physics PSD (BP‐PSD) for use in photon beams from linear accelerator.

Methods

BP‐PSD was acquired and its characteristics were evaluated in photon beams from a Varian TrueBeam. Data were collected in a 3D water tank. Standard parameters; dose, dose rate, energy, angular dependence and temperature dependence were studied. Depth dose, profiles and output in a reference condition as well as small fields were measured.

Results

BP‐PSD is versatile and provides data very similar to an ion chamber when Cerenkov radiation is properly accounted. This device measures data pulse by pulse which very few detectors can perform. The differences between ion chamber data and PSD are < 2% in most cases. The angular dependence is a bit pronounces to 1.5% which is due to PSD housing. Depth dose and profiles are comparable within < 1% to an ion chamber. For small fields this detector provides suitable field output factor compared to other detectors and Monte Carlo (MC) simulated data without any added correction factor.

Conclusions

The characteristics of Blue Physics PSD is uniquely suitable in photon beam and more so in small fields. The data are reproducible compared to ion chamber for most parameters and ideally suitable for small‐field dosimetry without any correction factor.
Microstructural and Mechanical Characterizations of Mo/W and Mo/Graphite Joints with BNi2 Paste
Authors: Xu Biao , Cai Yuqi , Haider Julfikar , Khan Fahd Nawaz , Shehbaz Tauheed , Zhao Hongyang , Mao Yangwu
Published: November 2023

Brazing of Mo to W and to graphite is achieved using BNi2 paste (containing Ni, Cr, Si, and B). For the Mo/W or Mo/graphite joint, the joining area consists of a diffusion area and a brazing area. The diffusion area is composed of MoNi and Mo, which is formed by diffusion of the Mo substrate into the braze during brazing. The brazing area of the Mo/W joint contains Ni(ss) (solid solution), Cr(ss), Ni3B, CrB, and Ni4W, while the brazing area of the Mo/graphite joint mainly comprises Ni(ss), MoNi, Ni3B, and CrB. A continuous chromium carbide layer is formed at the brazing area/graphite interface in the Mo/graphite joint due to the reaction of Cr in the BNi2 braze with the graphite. Nanoindentation measurements of the joints show that the diffusion area exhibits the highest hardness and elastic modulus in the joints. The shear strengths of the Mo/W and Mo/graphite joints are 58.1 ± 16.0 and 13.0 ± 4.0 MPa, respectively. The Mo/W and Mo/graphite joints fracture after the shear tests in the W and graphite sides, respectively, near the joining area, indicating that both fractures are caused by the stress concentration in the corresponding areas.
3D Printed Design‐Assisted Multilayered Graphene Oxide‐Modified Polymer Glucose Sensor
Authors: Das Chirantan , Das Subham , Chugh Vibhas , Bhattacharjee Mitradip
Published: November 2023

This work investigates the capabilities of a platform for nonenzymatic glucose sensing employing a novel 3D printed three‐electrode mask‐embedded design. A reservoir‐on‐mask has been fabricated for smart sample insertion to avoid spillage. Working and counter silver electrodes are modified with three different material combinations such as graphene oxide (GO), poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), and GO + PEDOT:PSS, and their performance comparison is demonstrated. It is observed that the GO + PEDOT:PSS modification shows 94.57 and 71.01% higher sensitivity than GO and PEDOT:PSS, respectively, including a higher linearity compared to its counterparts. Glucose concentrations ranging from 50 to 300 mg dL−1 are detected by employing cyclic voltammetry and electrical impedance spectroscopic technique. Herein, a significantly high sensitivity of 18.8 μAmM−1 cm−2 and low limit of detection ≈ 0.4 mM has been achieved for the proposed sensor. The 3D printed mask structure provides 75% higher sample retention ability, greater reliability in terms of sample placement in the sensor and improved test performances. The proposed sensor can provide a stable and large‐scale deployable solution to future biosensing platforms.
Injectable Microporous Annealed Crescent‐Shaped (MAC) Particle Hydrogel Scaffold for Enhanced Cell Infiltration
Authors: Tang Rui‐Chian , Shang Lily , Scumpia Philip O. , Di Carlo Dino
Published: November 2023

Hydrogels are widely used for tissue engineering applications to support cellular growth, yet the tightly woven structure often restricts cell infiltration and expansion. Consequently, granular hydrogels with microporous architectures have emerged as a new class of biomaterial. Particularly, the development of microporous annealed particle (MAP) hydrogel scaffolds has shown improved stability and integration with host tissue. However, the predominant use of spherically shaped particles limits scaffold porosity, potentially limiting the level of cell infiltration. Here, a novel microporous annealed crescent‐shaped particle (MAC) scaffold that is predicted to have improved porosity and pore interconnectivity in silico is presented. With microfluidic fabrication, tunable cavity sizes that optimize interstitial void space features are achieved. In vitro, cells incorporated into MAC scaffolds form extensive 3D multicellular networks. In vivo, the injectable MAC scaffold significantly enhances cell infiltration compared to spherical MAP scaffolds, resulting in increased numbers of myofibroblasts and leukocytes present within the gel without relying on external biomolecular chemoattractants. The results shed light on the critical role of particle shape in cell recruitment, laying the foundation for MAC scaffolds as a next‐generation granular hydrogel for diverse tissue engineering applications.
Arresting Ion Migration from the ETL Increases Stability in Infrared Light Detectors Based on III‐V Colloidal Quantum Dots
Authors: Xia Pan , Zhu Tong , Imran Muhammad , Pina Joao M. , Atan Ozan , Najarian Amin Morteza , Chen Hao , Zhang Yangning , Jung Euidae , Biondi Margherita , Vafaie Maral , Li Chongwen , Grater Luke , Khatri Aayushi , Singh Ajay , Hoogland Sjoerd , Sargent Edward H.
Published: November 2023

III‐V colloidal quantum dots (CQDs) are of interest in infrared photodetection, and recent developments in CQDs synthesis and surface engineering have improved performance. Here this work investigates photodetector stability, finding that the diffusion of zinc ions from charge transport layers (CTLs) into the CQDs active layer increases trap density therein, leading to rapid and irreversible performance loss during operation. In an effort to prevent this, this work introduces organic blocking layers between the CQDs and ZnO layers; but these negatively impact device performance. The device is then, allowing to use a C60:BCP as top electron‐transport layer (ETL) for good morphology and process compatibility, and selecting NiOX as the bottom hole‐transport layer (HTL). The first round of NiOX‐based devices show efficient light response but suffer from high leakage current and a low open‐circuit voltage (Voc) due to pinholes. This work introduces poly[bis(4‐phenyl) (2,4,6‐trimethylphenyl)amine] (PTAA) with NiOX NC to form a hybrid HTL, an addition that reduces pinhole formation, interfacial trap density, and bimolecular recombination, enhancing carrier harvesting. The photodetectors achieve 53% external quantum efficiency (EQE) at 970 nm at 1 V applied bias, and they maintain 95% of initial performance after 19 h of continuous illuminated operation. The photodetectors retain over 80% of performance after 80 days of shelf storage.
High‐Brightness, Hundred‐Second Level Ultralong Afterglow Polymers Built via Ultrasound‐Synchronized B‐O‐Click Strategy
Authors: Chen Wei‐Guang , Wang Yan , Chen Zhi‐Jian , Wei Hai‐Jie , Dang Lei , Lin Ze‐Zhong , Chen Yu , Wang Yong
Published: November 2023

In recent years, there has been a growing interest in pure organic materials with ultralong room temperature phosphorescence (RTP) and afterglow duration time (tag) in the range of second level. However, it is extremely difficult to achieve tag >60 s in the polymer fields. Herein, this work proposes a highly versatile ultrasound‐synchronized B‐O‐Click strategy that can firmly immobilize various types of polycyclic aromatic boronic acids (PABAs) as single‐molecular states in a tight and rigid matrix of poly(vinyl alcohol) (PVA), achieving a series of record‐breaking ultralong afterglow polymeric RTP materials. Based on this approach, a polymeric material is reported exhibiting a record‐breaking tag = 130 s, accompanied with an ultralong lifetime of 7.24 s and a good phosphorescence efficiency of 14.26%. Three other polymeric materials with tag over 60 s are also realized via the same strategy by changing the phosphor. In addition, record‐breaking ultralong green (tag = 115 s) and red (tag = 80 s) afterglow are further achieved based on the phosphorescence resonance energy transfer (PRET) effect.
Mannich‐Type Condensation and Domino Quinazolinone‐Amidine Rearrangement Affords Ring‐Fused Mackinazolinones with Anti‐Amoebic Activity
Authors: Lish Matthew S. , Milanes Jillian E. , Sanders Kyana M. , Guzei Ilia A. , Morris James C. , Golden Jennifer E.
Published: November 2023

A three‐step synthesis of anti‐amoebic, ring‐fused mackinazolinones has been developed. A Mannich‐type reaction between quinazolin‐4‐ones and N‐Cbz propanal in the presence of AgOTf afforded quinazolinones (19–94% isolated yield) bearing a newly formed heterocycle with an alkylamine appendage that, upon N‐Cbz deprotection and basification, triggered a domino rearrangement to afford 45 separable, ring‐fused products. Several compounds inhibited growth of Naegleria fowleri parasites that can cause a lethal human brain infection. Thus, the methodology provides immediate access to a promising anti‐amoebic scaffold.
Identification of HLA‐restricted Cytotoxic T Lymphocyte Epitopes of B Cell Maturation Antigen as Promising Peptide Vaccine Candidates for Preventive and Therapeutic Strategies in Multiple Myeloma
Authors: Chiraphapphaiboon Wannasiri , Luangwattananun Piriya , Chieochansin Thaweesak , Samutpradit Danai , Hengswat Pranaidej , Areesawangkit Phurin , Phikulsod Ployploen , Sumransub Nuttavut , Sukpanichnant Sunya , Junking Mutita , Yenchitsomanus Pa‐thai
Published: November 2023

Multiple myeloma (MM) is an incurable hematologic malignancy for which curative treatment remains elusive. Consequently, immunotherapeutic strategies that selectively induce MM‐specific T cell responses by targeting MM‐associated antigens have emerged. This study aims to identify HLA‐restricted cytotoxic T lymphocyte (CTL) epitopes derived from B cell maturation antigen (BCMA) as potential peptide vaccine candidates to advance preventive and therapeutic interventions for MM. BCMA expression in bone marrow tissue samples from 96.8% of MM patients is observed, and the positive membrane BCMA expression is associated with inferior overall survival outcomes. Through an in silico model, four BCMA epitope peptides that exhibit in vitro concentration‐dependent binding to the HLA*A11:01 molecule are identified. Comparative analyses reveal that BCMA‐specific CTLs stimulated by BCMA‐2, BCMA‐3, and BCMA‐4 peptides exhibit significantly greater cytolysis of cancer cells, including BCMA‐overexpressing KMS‐20 and KKU‐055 cells, in comparison to an unpulsed condition or an irrelevant control peptide derived from human immunodeficiency virus‐1 (HIV‐1). Moreover, the observed cytolytic activities of these CTLs are significantly distinct when compared to corresponding BCMA‐negative cells, thereby indicating antigen‐specificity. This study highlights the promising potential of utilizing immunogenic HLA‐A*11:01‐restricted BCMA peptides as a viable approach for cancer vaccination and T cell‐based therapy in the context of MM.
Natural Multifunctional Silk Microcarriers for Noise‐Induced Hearing Loss Therapy
Authors: Zhang Hui , Chen Hong , Lu Ling , Wang Huan , Zhao Yuanjin , Chai Renjie
Published: November 2023

Noise‐induced hearing loss (NIHL) is a common outcome of excessive reactive oxygen species in the cochlea, and the targeted delivery of antioxidants to the inner ear is a potential therapeutic strategy. In this paper, a novel natural biomaterials‐derived multifunctional delivery system using silk fibroin‐polydopamine (PDA)‐composited inverse opal microcarriers (PDA@SFMCs) is presented for inner ear drug delivery and NIHL therapy. Due to their large specific surface area and interpenetrating nanochannels, PDA@SFMCs can rapidly load active biomolecules making them a convenient medium for the storage and delivery of such molecules. In addition, surface modification of PDA enables the microcarriers to remain in the round window niche, thus facilitating the precise local and directed delivery of loaded drugs. Based on these features, it is demonstrated here that n‐acetylcysteine‐loaded silk microcarriers have satisfactory antioxidant properties on cells and can successfully prevent NIHL in guinea pigs. These results indicate that the natural multifunctional silk microcarriers are promising agents for local inner ear drug delivery in the clinic.
Assembling of Polyaryls (Terphenyls, Tetraphenyls, Pentaphenyls, and Hexaphenyls) through Pd(II)‐catalyzed C−H Arylation of Biaryl Carboxamides with Iodobiaryls
Authors: Dalal Arup , Babu Srinivasarao Arulananda , Banga Shefali
Published: November 2023

A wide range of polyaryl compounds (π‐extended biaryls) including terphenyls, tetraphenyls, pentaphenyls, and hexaphenyls were assembled in a single operation of Pd(II)‐catalyzed C−H coupling of biaryl carboxamides and iodobiaryls. Traditionally, cross‐coupling protocols involving organometallic reagents were employed to assemble the core structure of π‐extended biaryls (polyphenylenes or polyaryls). The pre‐assembling of organometallic reagents is a limitation in investigations pertaining to the aryl‐aryl cross‐coupling reactions affording polyaryls (polyphenylenes). We report the application of Pd(II)‐catalyzed bidentate directing group (DG)‐aided C−H arylation method for constructing polyaryl motifs (π‐extended biaryls) using biaryl‐based carboxamides and iodobiaryls as the coupling partners in a single operation. The current investigation on the bidentate DG‐aided C−H arylation of biaryl carboxamides with iodobiaryls is expected to serve as a useful route to enrich the library of π‐extended biaryls (polyphenylenes or polyaryls).
Access to [6‐7‐6]‐Icetexanes through Sequential Cascade Cyclization and Biomimetic Ring Expansion
Authors: Le Thuy Quynh , Liaba Niaz , Jeong Da In , Lee Jeonghyo , Oh Chang Ho
Published: November 2023

We herein report an efficient synthetic method for preparing [6‐7‐6]‐icetexane derivatives. This approach employs our previously designed copper‐catalyzed intramolecular cyclization of enyne‐aryl carbonyl substrates to generate a [6‐6‐6]‐tricyclic abietane framework and a subsequent ring expansion protocol for the [6‐7‐6] scaffold. By synergizing these protocols, we established a highly efficient pathway for synthesizing icetexane compounds from readily available enyne‐aryl starting materials, exhibiting remarkable versatility in accommodating various functional groups while delivering consistently high yields.
Camera traps unveil demography, social structure, and home range of six unhabituated Western chimpanzee groups in the Moyen Bafing National Park, Guinea
Authors: Debetencourt Benjamin , Barry Mamadou Moussa , Arandjelovic Mimi , Stephens Colleen , Maldonado Nuria , Boesch Christophe
Published: November 2023

Precise estimates of population dynamics and social grouping patterns are required for effective conservation of wild animal populations. It is difficult to obtain such information on non‐human great apes as they have slow reproductive rates. To gain a better understanding of demography in these populations, previous research has typically involved habituation\, a process that requires years. Here, we collected data continuously over year‐long periods to monitor an unhabituated population of critically endangered Western chimpanzees (Pan troglodytes verus) in the Moyen Bafing National Park, Guinea. We used two arrays of 100 camera traps that were placed opportunistically in two distinct 100 km2 sites, named Bakoun and Koukoutamba. We identified 227 individuals in Bakoun and 207 in Koukoutamba through their unique facial features. Our camera trap data make clear that these individuals belong to six and seven closed groups, respectively. Six of those groups were near‐completely sampled with an average minimum size of 46.8 individuals (range: 37–58), and a mean adult sex ratio of 1.32 (range: 0.93–2.10). We described the demographic composition of these groups and use Bayesian social network analysis to understand population structure. The network analyses suggested that the social bonds within the two populations were structured by sex homophily, with male chimpanzees being more or equally likely to be observed together than other adult associations. Through estimation of minimum convex polygons, we described the minimum home range for those groups. Compared to other chimpanzee groups living in a similar environment (mosaic savanna‐forest), the Moyen Bafing region seems to host a high‐density of chimpanzees with small home ranges for their group size. Our research highlights the potential of camera traps for studying the demographic composition of chimpanzee populations with high resolution and obtaining crucial information on several groups in a time‐efficient and cost‐effective way.
Cations Determine the Mechanism and Selectivity of Alkaline Oxygen Reduction Reaction on Pt(111)**
Authors: Kumeda Tomoaki , Laverdure Laura , Honkala Karoliina , Melander Marko M. , Sakaushi Ken
Published: November 2023

The proton‐coupled electron transfer (PCET) mechanism of the oxygen reduction reaction (ORR) is a long‐standing enigma in electrocatalysis. Despite decades of research, the factors determining the microscopic mechanism of ORR‐PCET as a function of pH, electrolyte, and electrode potential remain unresolved, even on the prototypical Pt(111) surface. Herein, we integrate advanced experiments, simulations, and theory to uncover the mechanism of the cation effects on alkaline ORR on well‐defined Pt(111). We unveil a dual‐cation effect where cations simultaneously determine i) the active electrode surface by controlling the formation of Pt−O and Pt−OH overlayers and ii) the competition between inner‐ and outer‐sphere PCET steps. The cation‐dependent transition from Pt−O to Pt−OH determines the ORR mechanism, activity, and selectivity. These findings provide direct evidence that the electrolyte affects the ORR mechanism and performance, with important consequences for the practical design of electrochemical systems and computational catalyst screening studies. Our work highlights the importance of complementary insight from experiments and simulations to understand how different components of the electrochemical interface contribute to electrocatalytic processes.
Ultrapermeable Gel Membranes Enabling Superior Carbon Capture
Authors: Zhu Bin , Yang Yan , Guo Lei , Wang Kaifang , Lu Yanqiu , He Xuezhong , Zhang Sui , Shao Lu
Published: November 2023

Membrane technology is rapidly gaining broad attraction as a viable alternative for carbon capture to mitigate increasingly severe global warming. Emerging CO2‐philic membranes have become crucial players in efficiently separating CO2 from light gases, leveraging their exceptional solubility‐selectivity characteristics. However, economic and widespread deployment is greatly dependent on the boosted performance of advanced membrane materials for carbon capture. Here, we design a unique gel membrane composed of CO2‐philic molecules for accelerating CO2 transportation over other gases for ultrapermeable carbon capture. The molecular design of such soft membranes amalgamates the advantageous traits of augmented permeation akin to liquid membranes and operational stability akin to solid membranes, effectively altering the membrane's free volume characteristics validated by both experiments and molecular dynamics simulation. Surprisingly, gas diffusion through the free‐volume‐tuned gel membrane undergoes a 9‐fold improvement without compromising the separation factor for the superior solubility selectivity of CO2‐philic materials, and CO2 permeability achieves a groundbreaking record of 5608 Barrer surpassing the capabilities of nonfacilitated CO2 separation materials and exceeding the upper bound line established in 2019 even by leading‐edge porous polymer materials. Our designed gel membrane can maintain exceptional separation performance during prolonged operation, enabling the unparalleled potential of solubility‐selective next‐generation materials towards sustainable carbon capture.
Perovskite Oxide as A New Platform for Efficient Electrocatalytic Nitrogen Oxidation
Authors: Zheng Hui , Ma Ziwei , Liu Yunxia , Zhang Yizhe , Ye Jinyu , Debroye Elke , Zhang Longsheng , Liu Tianxi , Xie Yi
Published: November 2023

Electrocatalytic nitrogen oxidation reaction (NOR) offers an efficient and sustainable approach for conversion of widespread nitrogen (N2) into high‐value‐added nitrate (NO3−) under mild conditions, representing a promising alternative to the traditional approach that involves harsh Haber–Bosch and Ostwald oxidation processes. Unfortunately, due to the weak absorption/activation of N2 and the competitive oxygen evolution reaction, the kinetics of NOR process is extremely sluggish accompanied with low Faradaic efficiencies and NO3− yield rates. In this work, an oxygen‐vacancy‐enriched perovskite oxide with nonstoichiometric ratio of strontium and ruthenium (denoted as Sr0.9RuO3) was synthesized and explored as NOR electrocatalyst, which can exhibit a high Faradaic efficiency (38.6 %) with a high NO3− yield rate (17.9 μmol mg−1 h−1). The experimental results show that the amount of oxygen vacancies in Sr0.9RuO3 is greatly higher than that of SrRuO3, following the same trend as their NOR performance. Theoretical simulations unravel that the presence of oxygen vacancies in the Sr0.9RuO3 can render a decreased thermodynamic barrier toward the oxidation of *N2 to *N2OH at the rate‐determining step, leading to its enhanced NOR performance.
Exploring Superacid‐Promoted Skeletal Reorganization of Aliphatic Nitrogen‐Containing Compounds
Authors: Artault Maxime , Cantin Thomas , Longuet Mélissa , Vitse Kassandra , Mbengo Christ Daniel Matatu , Guégan Frédéric , Michelet Bastien , Martin‐Mingot Agnès , Thibaudeau Sébastien
Published: November 2023

Here we report a method to reorganize the core structure of aliphatic unsaturated nitrogen‐containing substrates exploiting polyprotonation in superacid solutions. The superelectrophilic activation of N‐isopropyl systems allows for the selective formal Csp3−H activation/cyclization or homologation / functionalization of nitrogen‐containing substrates. This study also reveals that this skeletal reorganization can be controlled through protonation interplay. The mechanism of this process involves an original sequence of C−N bond cleavage, isopropyl cation generation and subsequent C−N bond and C−C bond formation. This was demonstrated through in situ NMR analysis and labelling experiments, also confirmed by DFT calculations.
Enabling Carbonized Polymer Dots with Color‐tunable Time‐dependent Room Temperature Phosphorescence through Confining Carboxyl Dimer Association
Authors: Kang Chunyuan , Tao Songyuan , Yang Fan , Zheng Chengyu , Qu Zexing , Yang Bai
Published: November 2023

Developing a facile strategy to realize fine‐tuning of phosphorescence color in time‐dependent room temperature phosphorescence (RTP) materials is essential but both theoretically and practically rarely exploited. Through simultaneously confining carboxyl dimer association and isolated carboxyl into the particle via a simple hydrothermal treatment of polyacrylic acid, a dual‐peak emission of red phosphorescence (645 nm) and green phosphorescence (550 nm) was observed from carbonized polymer dots (CPDs). The ratio of the two luminescent species can be well regulated by hydrochloric acid inhibiting the dissociation of carboxyl to promote hydrogen bond. Due to comparable but different lifetimes, color‐tunable time‐dependent RTP with color changing from yellow to green or orange to green were obtained. Based on the crosslinking enhanced emission effect, the phosphorescence visible time was even extended to 7 s through introducing polyethylenimide. This study not only proposes a novel and facile method for developing CPDs with color‐tunable time‐dependent RTP, but also provides a bran‐new non‐conjugated red phosphorescence unit and its definite structure.
First Nations perspectives and approaches to engagement in infant‐family work: attending to cultural safety and service engagement
Authors: Elliott Alison , Slater Clarisse , Opie Jessica E. , McIntosh Jennifer E.
Published: November 2023

First Nations child and family practitioners, Alison Elliott and Clarisse Slater, yarn here with Jenn McIntosh about the cultural fit and importance of including infants in family therapy. They bring years of experience from the ‘Workin’ With the Mob' clinical program at The Bouverie Centre to bear on building safe and respectful engagement with First Nations peoples and families. They share a First Nations view of the call of the infant and their ancestry and their power to join in bringing healing to parent and family systems. They discuss safe engagement in attempting to build safety in the present, especially for new parents who carry childhood wounds. The baby's capacity to help reframe these conversations into opportunity for new hope and healing becomes central to systemic safety, rather than something to be avoided.
Thermal and structural behavior of mango (Mangifera indica L) kernel fat from three Ivorian varieties
Authors: Kouassi Alfred Kouakou , Alabi Taofic , Purcaro Giorgia , Moret Erica , Blecker Christophe , Danthine Sabine
Published: November 2023

Mango (Mangifera indica L.) seeds is an interesting source of fat, rich in stearic (St) and oleic (O) acid with three major triacylglycerols (TAG): StOSt, StOO, and StLSt. The kernel fat content and quality depend however on the varieties and their origin. The objective of this study was to investigate the crystallization and polymorphic behavior of mango kernel fat extracted from three selected Ivorian varieties which differ in terms of TAG composition: Kent (KT), Djakoumankoun (DN) and Brooks (BR). The isothermal crystallization behavior was examined at 15 and 20°C by pulsed nuclear magnetic resonance, differential scanning calorimetry, x‐ray diffraction (XRD) and polarized light microscope. Under static conditions, DN crystallized faster, followed by BR, then KT. At 15°C, an unusual evolution was observed for both DN and BR, which can be explained by a melt‐mediated polymorphic transition from α into more stable forms. Using a differential scanning calorimetry (DSC) stop‐and‐return technique, different crystallization behaviors were also observed. Isothermal XRD experiments confirmed that the kinetics of the polymorphic transformation was different within the three samples, even if the three fats were β‐3L‐tending. At 15°C, KT transformed from liquid state to stable form without passing through α‐form, while DN and BR crystallized first into α‐from which transformed further to β′, then into stable β‐form. At 20°C, DN and BR crystallized directly from liquid to β′, which later transformed into β‐form while KT did not crystallize under the same conditions. The huge differences observed result from the differences in the TAG profiles, mainly in the StOO and StOSt content.
In vivo hepatoprotective and nephroprotective effects ofStenocarpus sinuatusleaf extract against ifosfamide‐induced toxicity in rats
Authors: Younis Mai M. , Ayoub Iriny M. , George Mina Y. , Mostafa Nada M. , Eldahshan Omayma A.
Published: November 2023

Ifosfamide (IFOS) is a broad‐spectrum chemotherapeutic agent that has been extensively used for breast cancer and other solid tumors. Unfortunately, its use is associated with toxicities of several organs.Stenocarpus sinuatusis an Australian tree belonging to the Proteaceae family. In the current study, the phytochemical constituents ofS. sinuatusmethanol leaf extract (SSLE) were assessed. In addition, the protective effect of SSLE against IFOS‐induced nephrotoxicity and hepatotoxicity was evaluated. Rats were randomly divided into six groups: control, IFOS (50 mg/kg), IFOS + SSLE (100 mg/kg), IFOS + SSLE (200 mg/kg), IFOS + SSLE (400 mg/kg), and SSLE (400 mg/kg). Hepatoprotective and nephroprotective potency of SSLE was assessed using different biochemical parameters. The phytochemical investigation resulted in the isolation of four flavonoid glycosides (kaempferol 3‐O‐β‐d‐glucopyranosyl‐(1→2)‐α‐l‐rhamnopyranoside, kaempferol 3‐O‐α‐rhamnopyranoside, isorhamnetin 3‐O‐β‐d‐glucopyranosyl‐(1→2)‐α‐l‐rhamnopyranoside, and quercetin 3‐O‐β‐d‐glucopyranosyl‐(1→2)‐α‐l‐rhamnopyranoside) and a coumarin (scopoletin). This is the first report on the isolated compounds from the genusStenocarpus. SSLE showed enhancement of kidney and liver functions and reduction of oxidative stress and inflammation. The histopathology of the investigated organs confirmed the protective effect of SSLE. In conclusion, SSLE is considered as a promising candidate that can be used in defense against the toxic effects of IFOS after further clinical trials.
How technological knowledge management capability compliments knowledge‐intensive human resource management practices to enhance team outcomes: A moderated mediation analysis
Authors: Shahzad Khuram , De Sisto Marco , Ul‐Durar Shajara , Liu Wei
Published: November 2023

Although research establishes a link between knowledge‐intensive human resource (HR) practices (KIHRP) and knowledge‐intensive team (KIT) performance, knowledge is limited about the underlying mechanisms and boundary conditions that determine this relationship. This study integrates the ability–motivation–opportunity (AMO) framework and theory of team adaptation into an information processing perspective to present a cohesive model that explains the mediating role of team knowledge sharing and reflexivity processes, and moderation of organization's technological knowledge management (KM) capability to explain the effect of KIHRP on KIT performance. Data were collected in three waves and from three sources consisting of 380 knowledge workers from 123 teams in 74 organizations in Pakistan. The findings indicate that KIHRP relates positively to KIT performance directly as well as via team knowledge sharing and reflexivity processes where the organization's technological KM capability further strengthens this relationship.
Quantitative Analysis of 2D EXSY NMR Spectra of Strongly Coupled Spin Systems in Transmembrane Exchange
Authors: Shishmarev Dmitry , Fontenelle Clement Q. , Linclau Bruno , Kuprov Ilya , Kuchel Philip W.
Published: November 2023

Solute translocation by membrane transport proteins is a vital biological process that can be tracked, on the sub‐second timescale, using nuclear magnetic resonance (NMR). Fluorinated substrate analogues facilitate such studies because of high sensitivity of 19F NMR and absence of background signals. Accurate extraction of translocation rate constants requires precise quantification of NMR signal intensities. This becomes complicated in the presence of J‐couplings, cross‐correlations, and nuclear Overhauser effects (NOE) that alter signal integrals through mechanisms unrelated to translocation. Geminal difluorinated motifs introduce strong and hard‐to‐quantify contributions from non‐exchange effects, the nuanced nature of which makes them hard to integrate into data analysis methodologies. With analytical expressions not being available, numerical least squares fitting of theoretical models to 2D spectra emerges as the preferred quantification approach. For large spin systems with simultaneous coherent evolution, cross‐relaxation, cross‐correlation, conformational exchange, and membrane translocation between compartments with different viscosities, the only available simulation framework is Spinach. In this study, we demonstrate GLUT‐1 dependent membrane transport of two model sugars featuring CF2 and CF2CF2 fluorination motifs, with precise determination of translocation rate constants enabled by numerical fitting of 2D EXSY spectra. For spin systems and kinetic networks of this complexity, this was not previously tractable.
Hoechst‐Modification on Oligodeoxynucleotides for Efficient Transport to the Cell Nucleus and Gene Regulation
Authors: Makanai Hiroki , Nishihara Tatsuya , Nishikawa Makiya , Tanabe Kazuhito
Published: November 2023

Various artificial oligodeoxynucleotides (ODNs) that contribute to gene regulation have been developed and their diversity and multifunctionality have been demonstrated. However, few artificial ODNs are actively transported to the cell nucleus, despite the fact that gene regulation also takes place in both the cell nucleus and the cytoplasm. In this study, to prepare ODNs with the ability to accumulate in the cell nucleus, we introduced Hoechst molecules into ODNs that act as carriers of functional molecules to the cell nucleus (Hoe‐ODNs). We synthesized Hoe‐ODNs and confirmed that they bound strongly to DNA duplexes. When single‐stranded Hoe‐ODNs or double‐stranded ODNs consisting of Hoe‐ODNs and its complementary strand were administered into living cells, both ODNs were efficiently accumulated in the cell nucleus. In addition, antisense ODNs, which were tethered with Hoechst unit, were delivered into the cell nucleus and efficiently suppressed the expression of their target RNA. Thus, we constructed a delivery system that enables the transport of ODNs into cell nucleus.
Having a carotid in the throat: A rare case of internal carotid medialization‐induced dysphonia
Authors: De Stercke Antoine , Dequanter Didier , Rodriguez Alexandra
Published: November 2023

Key Clinical Message

Positional anomalies of the internal carotid artery are common. Often asymptomatic, they can cause dysphagia or dysphonia and can represent an important surgical risk. Knowing their existence is, therefore, essential for the ENT specialist.

Aberrant positions of the extracranial internal carotid artery (eICA) affect between 10 and 40% of the population and can present several forms that can bring them close to the pharyngeal walls. Although usually asymptomatic, some aberrant positions of eICA may cause symptoms such as cough or dysphagia but rarely dysphonia. Depending on their location, they can also represent a great risk during oro/hypopharyngeal interventions or intubations. We report here the case of a 72‐year‐old patient who presented for a first consultation with a little progressive chronic dysphonia without associated dysphagia or cough. The nasofibrostroboscopy revealed a pulsatile retrocricoid mass pushing the right arytenoid forward. Otherwise, the clinical examination of the ENT sphere was normal. A cervicofacial CT scan revealed a major medialization of the right carotid bifurcation and the eICA located within the retropharyngeal fatty space and causing a mass effect pushing forward and downward the right arytenoid and the piriform sinus, resulting in a loss of horizontality of the glottic plane. Given the absence of life‐threatening complications and the associated risk of surgery, no treatment was proposed. A follow‐up was established after discussion with the patient. The aim of this study was to describe a rare case of isolated dysphonia caused by right internal carotid medialization with mass effect on the arytenoid cartilage. It seems important for ENT to know these rare causes of dysphonia and/or dysphagia due to anatomical variations of eICA in order to avoid the operative risks associated with possible future therapeutic procedures in these patients.