bluuebunny/crossref_metadata_2025 huggingface dataset:
Trickery, mockery and the Scottish way of war
Authors: Macdonald Alastair J
Published: May 2023

Despite their prominence in later medieval Scottish narratives, the themes of trickery and mockery in the way war is presented have been subjected to little academic scrutiny. The current paper suggests that such scrutiny yields important insights. It is argued that trickery is given unusual weight in narrative sources to highlight Scottish ingenuity in defeating their more powerful English enemies in war. This is in turn reflective of actual Scottish military behaviour in which ruses of various sorts were practised, arguably more readily than in many other martial cultures. While this should not be taken to indicate that there was any significant Scottish departure from accepted ethics of war, it does highlight an element of distinctiveness both to the practice of war by the Scots and their martial self-perception. Mockery is often frequently deployed in sources depicting the Scots at war against the English. Often the intention is to subvert bombastic aristocratic attitudes, depicted as being typical of the English martial elite. This ties in with a representation of the Scots fighting a war that featured wide communal involvement and an earthier material culture. Again this is reflective of real reliance on a broad social spread participating in war, as necessitated by the realities of the Anglo-Scottish struggle and its significant imbalance of wealth and resources. By the time Hary's Wallace was composed, in the 1470s, suggestive shifts had taken place in how trickery and mockery in war were represented. There is in this text far less privileging of trickery, indicating a greater self-confidence among the Scots as the threat of English conquest became less sharp. Mockery has also changed in character, no longer seeking to puncture English aristocratic pretensions and instead offering a more generalised, and more brutal, attempt to highlight the complete moral depravity of the old enemy.
Prelims
Authors: - -
Published: May 2023

Front matter for Volume 143

Table of Contents

List of abbreviations commonly used in the Proceedings

Editorial board for the Proceedings Vol 143

Society of Antiquaries of Scotland Council from 1 December 2012

Patron and Honorary Fellows of the Society of Antiquaries of Scotland

Laws of the Society of Antiquaries of Scotland
Prelims
Authors: - -
Published: May 2023

Front matter for Volume 144

Table of Contents

List of abbreviations commonly used in the Proceedings

Editorial board for the Proceedings Vol 144

Society of Antiquaries of Scotland Council from 30 November 2013

Patron and Honorary Fellows of the Society of Antiquaries of Scotland

Laws of the Society of Antiquaries of Scotland
Alan Saville
Authors: Ralston Ian , Cowie Trevor
Published: May 2023

Alan Saville, the archaeologist and prehistorian and a former President of the Society of Antiquaries of Scotland, died in his adopted city of Edinburgh at the age of 69, following a long illness.
The land before symbol stones
Authors: Gondek Meggen , Noble Gordon , Ramsay Susan , Sheridan Alison
Published: May 2023

This article outlines the results of two related but distinct aspects of fieldwork: a geophysical survey of the Rhynie cropmark complex and a small targeted excavation conducted in 2005–6, which are both part of the Rhynie Environs Archaeological Project (REAP). The geophysical surveys included a substantial gradiometer and a smaller resistivity survey that aimed to characterise and explore the extent and survival of archaeology around the Craw Stane Pictish symbol stone (NJ42NE 35) and two other symbol stone findspots. The results showed several discrete anomalies; one of these was targeted by a small-scale excavation and proved to be a burnt Middle Bronze Age timber structure. This article describes the geophysical survey results and the excavation of the MBA structure and sets both within their landscape context.
Gods and monsters in Roman Scotland
Authors: Hunter Fraser
Published: May 2023

Recent finds of copper alloy and lead figural sculpture from Roman Scotland are presented and discussed. These are rare finds in this frontier area, and represent a significant addition to a small corpus. Discussion considers whether such finds offer clues to the location of shrines or other sacred places in the wider landscape, a question that has largely been ignored in research to date. The rarity of such finds among the Roman imports on Iron Age sites leads to a discussion of the uptake and impact of such naturalistic imagery on the local population. An appendix catalogues the finds.
The French cartographer and the clan chief
Authors: Keppie Lawrence
Published: May 2023

In June 1763 a Frenchman, identifiable as the cartographer Louis Stanislas De la Rochette, journeyed from Edinburgh into Perthshire in the company of Sir James Macdonald, eighth baronet of Sleat in Skye. Visits were made to the Roman sites at Ardoch, Kaims Castle, Strageath and Dalginross. Bound up with De la Rochette’s manuscript accounts of his journey to and sojourn in Scotland are a finished drawing of Ardoch and three of the fort and temporary camp at Dalginross, the latter valuably annotated with measurements, including those of the camp’s ‘Stracathro-type’ gates. The drawings can be compared with those made only a few years earlier by William Roy. De la Rochette, who had come to Scotland in 1763 ostensibly to see to the repatriation of French prisoners of war, became a well-known mapmaker in late 18th-century London.
The Knowe of Rowiegar, Rousay, Orkney
Authors: Hutchison Margaret , Curtis Neil , Kidd Ray
Published: May 2023

The Neolithic chambered cairn at Knowe of Rowiegar, Rousay, Orkney, was excavated in 1937 as part of a campaign that also saw excavations at sites such as Midhowe and the Knowe of Lairo. Not fully published at the time, and with only partial studies since, the human bone assemblage has now been largely re-united and investigated. This included an osteological study and AMS dating of selected bones from this site and other Rousay cairns in the care of University of Aberdeen Museums, as well as the use of archival sources to attempt a reconstruction of the site. It is suggested that the human remains were finally deposited as disarticulated bones and that the site was severely damaged at the time the adjacent Iron Age souterrain was constructed. The estimation of the minimum number of individuals represented in the assemblage showed a significant preponderance of crania and mandibles, suggesting the presence of at least 28 heads, along with much smaller numbers of other bones, while age and sex determinations showed a preponderance of adult males. Seven skulls showed evidence of violent trauma, while evidence from both bones and teeth indicates that there were high levels of childhood dietary deficiency. Although detailed analysis of the dates was hampered by the ‘Neolithic plateau’, a Bayesian analysis of the radiocarbon determinations suggests the use of the site during the period 3400 to 2900 cal bc. This is shown to be similar to that of other dated Orcadian Neolithic cairns and may represent different responses to two periods of severe climate deterioration.
Prelims
Authors: - -
Published: May 2023

Front matter for Volume 146

Table of Contents

List of abbreviations commonly used in the Proceedings

Editorial board for the Proceedings Vol 146

Society of Antiquaries of Scotland Council from 1 December 2015

Patron and Honorary Fellows of the Society of Antiquaries of Scotland, 2016-7

Laws of the Society of Antiquaries of Scotland
Prelims
Authors: - -
Published: May 2023

Front matter for Volume 148

Table of Contents

List of abbreviations commonly used in the Proceedings

Editorial board for the Proceedings Vol 148

Society of Antiquaries of Scotland Council from 1 December 2017

Patron and Honorary Fellows of the Society of Antiquaries of Scotland, 2018-9

Laws of the Society of Antiquaries of Scotland
Hayvanat Bahçesinde Oyunlaştırma: Bir Okul Dışı Öğrenme Etkinliği
Authors: ORHAN ÖZEN Sevil , DERİN Tarık , ATAN Zeynep
Published: May 2023

Araştırmada ilkokul öğrencileri için hayvanat bahçesinde oyunlaştırma destekli bir öğrenme etkinliği tasarlayıp yürütmek ve bunun katılımcılar üzerindeki yansımalarını incelemek amaçlanmıştır. Çalışma nitel araştırma yöntemlerinden durum çalışması ile gerçekleştirilmiştir. Katılımcıları belirlemek için ölçüt örnekleme kullanılmıştır. Okul yönetimi, öğretmen ve öğrenci velilerinin okul dışı geziler konusunda deneyimli ve gönüllü olması kriteri uygulanmıştır. Ölçüte göre araştırmanın katılımcılarını Türkiye'nin Uşak ilinde bulunan 19 ilkokul ikinci sınıf öğrencisi ve onların öğretmenleri oluşturmuştur. Öğretmenle yapılandırılmış görüşme formu, öğrencilerle odak grup görüşme formu kullanılmıştır. Ayrıca öğrenmeyi ölçmek için ön test ve son test olarak performans testi uygulanmıştır. Nitel veriler içerik analizi ile, performans puanları Wilcoxon işaretli sıralar testi ile analiz edilmiştir. Bu çalışmada ortaya çıkan önemli bir sonuç, hayvanat bahçesinde gerçekleştirilen oyunlaştırma destekli öğrenme etkinliğinin öğrencilerin ilgi ve motivasyonlarını yüksek tutmaya katkısıdır.
Excess Mortality and Years of Potential Life Lost Among the Black Population in the US, 1999-2020
Authors: Caraballo César , Massey Daisy S. , Ndumele Chima D. , Haywood Trent , Kaleem Shayaan , King Terris , Liu Yuntian , Lu Yuan , Nunez-Smith Marcella , Taylor Herman A. , Watson Karol E. , Herrin Jeph , Yancy Clyde W. , Faust Jeremy Samuel , Krumholz Harlan M.
Published: May 2023

Importance

Amid efforts in the US to promote health equity, there is a need to assess recent progress in reducing excess deaths and years of potential life lost among the Black population compared with the White population.

Objective

To evaluate trends in excess mortality and years of potential life lost among the Black population compared with the White population.

Design, setting, and participants

Serial cross-sectional study using US national data from the Centers for Disease Control and Prevention from 1999 through 2020. We included data from non-Hispanic White and non-Hispanic Black populations across all age groups.

Exposures

Race as documented in the death certificates.

Main outcomes and measures

Excess age-adjusted all-cause mortality, cause-specific mortality, age-specific mortality, and years of potential life lost rates (per 100 000 individuals) among the Black population compared with the White population.

Results

From 1999 to 2011, the age-adjusted excess mortality rate declined from 404 to 211 excess deaths per 100 000 individuals among Black males (P for trend <.001). However, the rate plateaued from 2011 through 2019 (P for trend = .98) and increased in 2020 to 395—rates not seen since 2000. Among Black females, the rate declined from 224 excess deaths per 100 000 individuals in 1999 to 87 in 2015 (P for trend <.001). There was no significant change between 2016 and 2019 (P for trend = .71) and in 2020 rates increased to 192—levels not seen since 2005. The trends in rates of excess years of potential life lost followed a similar pattern. From 1999 to 2020, the disproportionately higher mortality rates in Black males and females resulted in 997 623 and 628 464 excess deaths, respectively, representing a loss of more than 80 million years of life. Heart disease had the highest excess mortality rates, and the excess years of potential life lost rates were largest among infants and middle-aged adults.

Conclusions and relevance

Over a recent 22-year period, the Black population in the US experienced more than 1.63 million excess deaths and more than 80 million excess years of life lost when compared with the White population. After a period of progress in reducing disparities, improvements stalled, and differences between the Black population and the White population worsened in 2020.
Patterns of Manufacturer Coupon Use for Prescription Drugs in the US, 2017-2019
Authors: Kang So-Yeon , Liu Angela , Anderson Gerard , Alexander G. Caleb
Published: May 2023

Importance

Although manufacturer-sponsored coupons are commonly used, little is known about how patients use them within a treatment episode.

Objectives

To examine when and how frequently patients use manufacturer coupons during a treatment episode for a chronic condition, and to characterize factors associated with more frequent use.

Design, Setting, and Participants

This is a retrospective cohort study of a 5% nationally representative sample of anonymized longitudinal retail pharmacy claims data from October 1, 2017, to September 30, 2019, obtained from IQVIA’s Formulary Impact Analyzer. The data were analyzed from September to December 2022. Patients with new treatment episodes using at least 1 manufacturer coupon over a 12-month period were identified. This study focused on patients with 3 or more fills for a given drug and characterized the association of the outcomes of interest with patient, drug, and drug class characteristics.

Main Outcomes and Measures

The primary outcomes were (1) the frequency of coupon use, measured as the proportion of prescription fills accompanied by manufacturer coupon within the treatment episode, and (2) the timing of first coupon use relative to the first prescription fill within the treatment episode.

Results

A total of 36 951 treatment episodes accounted for 238 474 drug claims and 35 352 unique patients (mean [SD] age, 48.1 [18.2] years; 17 676 women [50.0%]). Among these episodes, nearly all instances (35 103 episodes [95.0%]) of first coupon use occurred within the first 4 prescription fills. Approximately two-thirds of treatment episodes (24 351 episodes [65.9%]) used a coupon for the incident fill. Coupons were used for a median (IQR) of 3 (2-6) fills. The median (IQR) proportion of fills with a coupon was 70.0% (33.3%-100.0%), and many patients discontinued the drug after the last coupon. After adjustment for covariates, there was no significant association between an individual’s out-of-pocket costs or neighborhood-level income and the frequency of coupon use. The estimated proportion of fills with a coupon was greater for products in competitive (19.5% increase; 95% CI, 2.1%-36.9%) or oligopolistic (14.5% increase; 95% CI, 3.5%-25.6%) markets than monopoly markets when there is only 1 drug in the therapeutic class.

Conclusions and Relevance

In this retrospective cohort analysis of individuals receiving pharmaceutical treatment for chronic diseases, the frequency of manufacturer-sponsored drug coupon use was associated with the degree of market competition, rather than patients’ out-of-pocket costs.
Yeast chaperones and ubiquitin ligases contribute to proteostasis during arsenite stress by preventing or clearing protein aggregates
Authors: Rodrigues Joana I. , Lorentzon Emma , Hua Sansan , Boucher Andrew , Tamás Markus J.
Published: May 2023

Arsenite causes proteotoxicity by targeting nascent proteins for misfolding and aggregation. Here, we assessed how selected yeast chaperones and ubiquitin ligases contribute to proteostasis during arsenite stress. Loss of the ribosome‐associated chaperones Zuo1, Ssz1, and Ssb1/Ssb2 reduced global translation and protein aggregation, and increased arsenite resistance. Loss of cytosolic GimC/prefoldin function led to defective aggregate clearance and arsenite sensitivity. Arsenite did not induce ribosomal stalling or impair ribosome quality control, and ribosome‐associated ubiquitin ligases contributed little to proteostasis. Instead, the cytosolic ubiquitin ligase Rsp5 was important for aggregate clearance and resistance. Our study suggests that damage prevention, by decreased aggregate formation, and damage elimination, by enhanced aggregate clearance, are important protective mechanisms that maintain proteostasis during arsenite stress.
Promoting retrieval practice use during self‐study in higher education: The effects of a compact strategy intervention with metacognitive support
Authors: Broeren Marloes , Verkoeijen Peter , Heijltjes Anita , Arends Lidia , Smeets Guus
Published: May 2023

Intensive training programs have successfully supported students in using cognitive learning strategies. This study investigated whether a compact intervention can promote students' retrieval practice use during self‐study for course‐relevant materials. In an experiment embedded in a reputation management course, students were either given strategy instructions on retrieval practice (RP condition), strategy instructions and metacognitive email support (RP++) or no support (control). Students' potential retrieval practice use during self‐study of key concepts was measured with an online learning environment. Results showed a small but significant effect on retrieval practice use for the RP++ condition as compared to control (p = .005, r = 0.39). No significant differences were found between RP++ and RP, and RP and control and no significant effects were found on a delayed performance test. With our compact intervention, we took a small step in fostering the use of retrieval practice as a learning strategy during self‐study.
Fluorinated Organic A‐Cation Enabling High‐Performance Hysteresis‐Free 2D/3D Hybrid Tin Perovskite Transistors
Authors: Yang Wonryeol , Park Geonwoong , Liu Ao , Lee Hock Beng , Kang Jae‐Wook , Zhu Huihui , Noh Yong‐Young
Published: May 2023

2D tin‐based perovskites have gained considerable attention for use in diverse optoelectronic applications, such as solar cells, lasers, and thin‐film transistors (TFTs), owing to their good stability and optoelectronic properties. However, their intrinsic charge‐transport properties are limited, and the insulating bulky organic ligands hinder the achievement of high‐mobility electronics. Blending 3D counterparts into 2D perovskites to form 2D/3D hybrid structures is a synergistic approach that combine the high mobility and stability of 3D and 2D perovskites, respectively. In this study, reliable p‐channel 2D/3D tin‐based hybrid perovskite TFTs comprising 3D formamidinium tin iodide (FASnI3) and 2D fluorinated 4‐fluoro‐phenethylammonium tin iodide ((4‐FPEA)2SnI4) are reported. The optimized FPEA‐incorporated TFTs show a high hole mobility of 12 cm2 V−1 s−1, an on/off current ratio of over 108, and a subthreshold swing of 0.09 V dec−1 with negligible hysteresis. This excellent p‐type characteristic is compatible with n‐type metal‐oxide TFT for constructing complementary electronics. Two procedures of antisolvent engineering and device patterning are further proposed to address the key concern of low‐performance reproducibility of perovskite TFTs. This study provides an alternative A‐cation engineering method for achieving high‐performance and reliable tin‐halide perovskite electronics.
Revisiting the Role of Sulfur Functionality in Regulating the Electron Distribution of Single‐Atomic Fe Sites Toward Enhanced Oxygen Reduction
Authors: Liu Heng , Jiang Luozhen , Sun Yanyan , Khan Javid , Feng Bin , Xiao Jiamin , Zhang Handong , Xie Haijiao , Li Lina , Wang Shuangyin , Han Lei
Published: May 2023

Introducing sulfur functionalities is reported as an efficacious route to regulate the electron distribution of single‐atomic Fe sites for improving the oxygen reduction reaction (ORR) activity, however, it remains controversial about the role of type of sulfur functionalities in enhancing the ORR activity. Herein, this study revisits the role of sulfur functionalities in regulating the electron distribution of single‐atomic Fe sites by the construction of single‐atomic Fe‐N4 sites with sulfur functionalities (FeSNC) using sulfur‐containing molecules with different molecular structures. X‐ray absorption spectroscopy and theoretical calculations confirm that thiophene S and oxidized S both possess the electron‐donating properties for regulating the electronic distribution of Fe‐N4 sites, which is beneficial to weaken the adsorption of the ORR intermediates. As expected, the optimal FeSNC has attractive ORR activity with half‐potential of 0.76 V in 0.5 m H2SO4 and 0.91 V in 0.1 m KOH along with remarkable Zn‐air battery performance. Moreover, the developed synthetic method has also been extended to construct B and P regulated FeNC catalysts.
Fluoride‐Catalyzed Siloxane Exchange as a Robust Dynamic Chemistry for High‐Performance Vitrimers
Authors: Tretbar Chase , Castro Jordan , Yokoyama Kosuke , Guan Zhibin
Published: May 2023

Sustainable development of new technologies requires materials having advanced physical and chemical properties while maintaining reprocessability and recyclability. Vitrimers are designed for this purpose; however, their dynamic covalent chemistries often have drawbacks or are limited to specialized polymers. Here, fluoride‐catalyzed siloxane exchange is reported as an exceptionally robust chemistry for scalable production of high‐performance vitrimers through industrial processing of commodity polymers such as poly(methyl methacrylate), polyethylene, and polypropylene. The vitrimers show improved resistance to creep, heat, oxidation, and hydrolysis, while maintaining excellent melt flow for processing and recycling. Furthermore, the siloxane exchange between different vitrimers during mechanical blending results in self‐compatibilized blends without any compatibilizers. This offers a general, scalable method for producing sustainable high‐performance vitrimers and a new strategy for recycling mixed plastic wastes.
3D Printing of Porous Degradable Scaffolds with Polylactic Acid‐Loaded Bioactive Glass and Calcium Sulfate Hemihydrate for Bone Defect Repair
Authors: Hu Huiqiang , Zhao Zheng , Sun Yanni , Zhao Jiawei , Chen Zhengqian , Li Jianyi , Kong Weiqing , Du Yukun , Shao Jiale , Zhu Xiaoyang , Lan Hongbo , Xi Yongming
Published: May 2023

Repair of bone defects, especially critical‐sized bone defects, remains a major clinical problem, and bone nonunion is the biggest challenge. Herein, melt‐extrusion 3D printing is applied to prepare biodegradable composite scaffolds containing bioactive glass (BAG), calcium sulfate hemihydrate (CSH), and polylactic acid (PLA). The compressive strength of scaffolds is similar to that of human bone tissue. In vitro and in vivo experiments show that the scaffolds have good biocompatibility. The scaffold can maintain the biomechanical stability of the bone defect area during the follow‐up period of 20 weeks and has no damage to liver and kidney in animal experiments. Scaffold degradation is accompanied by trabecular bone and vessel neogenesis. While the PLA group and control group cannot carry out effective bone defect repair, the bone defect repair effect of the PLA‐CSH‐BAG group is satisfactory. In conclusion, the biodegradable porous scaffold has been proposed as a safe and effective approach for the repair of bone defects.
Design of Bistable Soft Deployable Structures via a Kirigami‐Inspired Planar Fabrication Approach
Authors: Mungekar Mrunmayi , Ma Leixin , Yan Wenzhong , Kackar Vishal , Shokrzadeh Shyan , Jawed Mohammad Khalid
Published: May 2023

Fully soft bistable mechanisms have shown extensive applications ranging from soft robotics, wearable devices, and medical tools, to energy harvesting. However, the lack of design and fabrication methods that are easy and potentially scalable limits their further adoption into mainstream applications. Herein, a top–down planar approach is presented by introducing Kirigami‐inspired engineering combined with a pre‐stretching process. Using this method, Kirigami‐Pre‐stretched Substrate‐Kirigami trilayered precursors are created in a planar manner; upon release, the strain mismatch—due to the pre‐stretching of substrate—between layers will induce an out‐of‐plane buckling to achieve targeted 3D bistable structures. By combining experimental characterization, analytical modeling, and finite element simulation, the effect of the pattern size of Kirigami layers and pre‐stretching on the geometry and stability of resulting 3D composites is explored. In addition, methods to realize soft bistable structures with arbitrary shapes and soft composites with multistable configurations are investigated, which may encourage further applications. This method is demonstrated by using bistable soft Kirigami composites to construct two soft machines: (i) a bistable soft gripper that can gently grasp delicate objects with different shapes and sizes and (ii) a flytrap‐inspired robot that can autonomously detect and capture objects.
Organic Photonic Synaptic Devices with UV‐Stimulated Inhibition and Adaptive Short‐Term Plasticity
Authors: Zhu Chen‐Hui , Gao Xu , Huang Hai‐Tian , Li Li‐Xing , Xu Jian‐Long , Zhong Ya‐Nan , Tang Wei , Guo Xiao‐Jun , Wang Sui‐Dong
Published: May 2023

Bidirectional modulation of synaptic weight lays the basis for learning and memory in the brain, and the development of brain‐inspired photonic synaptic devices is hindered by deficient light‐stimulated inhibition. In this report, a type of organic thin film neuromorphic devices with a planar two‐terminal architecture, featuring as the inhibitory regulation of synaptic weight over two orders of magnitude upon selective UV illumination is developed. The in situ monitoring on the floating electrode potential and the corresponding simulation results demonstrate the effect of cumulative hole trapping in the polymer electret layer, which modulates the device conductance in a nonvolatile manner. Remarkably, UV‐induced long‐term depression is accompanied by enhanced short‐term potentiation in the device that may preserve a stable level of total synaptic activities. The UV‐stimulated inhibition and the adaptive short‐term plasticity, as well as the ON and OFF responses to light in the organic photonic synaptic device, suggest its potential applications in photonic neuromorphic computing.
Surface Acoustic Waves Equip Materials with Active De‐Icing Functionality: Unraveled Glaze Ice De‐Icing Mechanisms and Application to Centimeter‐Scale Transparent Surfaces
Authors: Jacob Stefan , Pandey Shilpi , Moral Jaime Del , Karimzadeh Atefeh , Gil‐Rostra Jorge , González‐Elipe Agustín R. , Borrás Ana , Winkler Andreas
Published: May 2023

Enabling active de‐icing functionality on low heat conductive and transparent materials is a requirement for several seminal industries in critical economic sectors. However, developing efficient and environmentally friendly de‐icing methods still fails because of compatibility problems with large‐scale devices and real‐world conditions. In this paper, de‐icing several square centimeters covered with thick layers of glaze ice is approached through nanoscale activation by surface acoustic waves (SAWs). De‐icing functionality is demonstrated with a self‐supported piezoelectric material (LiNbO3) and a piezoelectric film (ZnO) deposited on fused silica, the latter system proving the compatibility of the method with materials of practical relevance. Its applicability to large and transparent substrates is demonstrated by placing the interdigitated electrodes (IDTs) required for activation close to the substrate's edges, leaving most of the surface unaltered. The de‐icing mechanism of glaze ice by SAW activation is revealed by simulating the SAW propagation on ice‐covered surfaces and by experimental analysis of the ice melting process. This involves a combination of ice mechanical stress activation and heating through the initially formed water/ice front. Possible Joule effects due to ohmic losses in the IDTs have been discarded, monitoring local temperature variations during SAW activation at and out of resonance conditions.
Inclination‐Enabled Generalized Microfluid Rectifiers via Anisotropic Slippery Hollow Tracks
Authors: Zhu Suwan , Li Xin , Bian Yucheng , Dai Nianwei , Yong Jiale , Hu Yanlei , Li Jiawen , Wu Dong , Chu Jiaru
Published: May 2023

The power of spontaneous maneuvering of microfluids that allow gas or liquid to penetrate along a single direction, is usually endowed with the wettability gradient and the Laplace pressure difference through tailoring special solid‒gas interfacial geographies. Herein, inspired by the structures on rice leaves and the slippery surfaces of the pitcher plant, anisotropic slippery hollow tracks (ASHTs) are fabricated and thus propose a class of unique inclination‐enabled bubble “diode”, on which one‐way bubble penetration can be reversibly switched on/off. The minimum transition tilt angle is subject to the tract spacing and the infused oil amount. The underlying mechanism of bubble penetration is attributed to the competition between the variable buoyancy component and the interfacial energy gradient perpendicular to the samples. A wide spectrum of generalized microfluid maneuvering capabilities is further demonstrated, including heavy oil selective penetration, underwater CO2 gas collection, and even dry/wet environment management in smart buildings, which are challenging for conventional counterparts. This framework should facilitate the development of microfluid control with favorable retainability and wide applicability in multiple fluids.
Energy‐Saving High‐Bandwidth Perovskite Sub‐Micro‐Encoder
Authors: Liang Shuang , Zhong Yichi , Tang Bing , Wang Qiangqiang , Hu Yongsheng , Wang Zhenyu , Zhang Long , Dong Hongxing , Xie Wei , Xu Hongxing
Published: May 2023

Optical coding is widely applied in communication and data processing fields due to its practical and powerful characteristics, such as high transmission rate and operational convenience. However, improvements in the loading information capacity of optical encoders always result in increased energy consumption. It is a challenge to realize an optical encoder that combines energy savings, high bandwidth, and miniaturization. Here, both the concept and the demonstration of a perovskite sub‐micro‐encoder with an 84% energy‐saving efficiency and a tunable bandwidth of up to 200 GHz are reported. The way to code the radiative dynamics of the light source allows for the reduction of unnecessary energy consumption from the initial stage through the control of the radiation core. Moreover, the miniature encoder generates code sequences of good coherence, stimulating the development of perovskite‐based optical microchips for ultrafast information processing.
Personal Solar UV Monitoring based on Photoinduced Electron Transfers in Luminescent Materials
Authors: Yang Zetian , Joos Jonas J. , Hu Jieqi , Van der Heggen David , Pier Tim , Delaey Maxime , Vrielinck Henk , Jüstel Thomas , Smet Philippe F. , Poelman Dirk
Published: May 2023

The spectrally‐selective monitoring of doses of UV and visible light is crucial in numerous applications like photodynamic therapy and personal solar UV detection, due to the specific irradiation impact of light with different wavelengths and doses. Herein an approach to design wavelength‐specific integrating light dosimeters is demonstrated based on photo‐induced redox processes of certain lanthanides in phosphate compounds. Systematic experiments reveal that the reduction process is induced through ligand‐to‐metal charge transfer excitation while the oxidation process is achieved upon excitation of either the involved hole traps or 4fN‐4fN‐15d1 transitions of the created divalent dopants. These processes are rationalized in multi‐electron energy level diagrams for local electron transfer. The dose and wavelength‐dependent redox processes allow for selective UV and visible light dosimetry, and the spectral sensitivity of the dosimeter can be tailored by manipulating the dopant or the host. Particularly, the spectral sensitivity of Ba2.99Eu0.01(PO4)2 better matches the erythemal action spectrum of human skin than that of currently used benchmark polysulphone dosimeters, making it ideally suitable for personal solar UV radiation monitoring. These findings open the door to designing wavelength‐tunable light dosimeters according to the requirements of envisioned applications and are expected to benefit a wide range of luminescent functional devices.
Machine Learning Descriptors for Data‐Driven Catalysis Study
Authors: Mou Li‐Hui , Han TianTian , Smith Pieter E. S. , Sharman Edward , Jiang Jun
Published: May 2023

Traditional trial‐and‐error experiments and theoretical simulations have difficulty optimizing catalytic processes and developing new, better‐performing catalysts. Machine learning (ML) provides a promising approach for accelerating catalysis research due to its powerful learning and predictive abilities. The selection of appropriate input features (descriptors) plays a decisive role in improving the predictive accuracy of ML models and uncovering the key factors that influence catalytic activity and selectivity. This review introduces tactics for the utilization and extraction of catalytic descriptors in ML‐assisted experimental and theoretical research. In addition to the effectiveness and advantages of various descriptors, their limitations are also discussed. Highlighted are both 1) newly developed spectral descriptors for catalytic performance prediction and 2) a novel research paradigm combining computational and experimental ML models through suitable intermediate descriptors. Current challenges and future perspectives on the application of descriptors and ML techniques to catalysis are also presented.
Ruthenium Complexes of Bidentate N,N‐Ligand as Catalyst for Selective N‐Alkylation of Amines with Alcohols
Authors: Bhatt Surabhi , Rana Monika , Sharma Anuj K. , Joshi Hemant
Published: May 2023

This report describes the synthesis of a new N‐(4‐(benzo[d]thiazole‐2‐yl)phenyl)‐1‐(pyridine‐2‐yl)methanimine ligand (L1) by the reaction of 2‐(4‐aminophenyl)benzothiazole with pyridine‐2‐carboxaldehyde. The three new ruthenium(II) arene complexes were synthesized by the reaction of L1 with [RuCl2(p‐cymene)]2 (C1), [RuCl2(benzene)]2 (C2), and [RuCl2(hmb)]2 [hmb=hexamethylbenzene] (C3). The new ligand and complexes were characterized with the help of standard analytical techniques like 1H and 13C{1H} Nuclear Magnetic Resonance (NMR), Fourier Transform Infrared (FTIR), Ultraviolet‐visible (UV‐Visible), High‐Resolution Mass Spectrometry (HRMS), cyclic voltammetry, and elemental analysis techniques. The structure of ruthenium complex (C1) and its bonding mode with the ligand were authenticated with the help of single crystal X‐ray diffraction. The complex showed a pseudo‐octahedral half‐sandwich “piano‐stool” type geometry around the Ru center. The ruthenium arene complexes (C1–C3) were used to catalyze the N‐alkylation of aniline derivatives using aliphatic alcohols (EtOH, PrOH, MeOH). Among all three catalysts, C1 showed the highest yield of alkylated derivatives (up to 95%) with 1.0 mol% catalyst loading. The order of alkylation toward alcohol derivatives was EtOH = PrOH > MeOH. The alkylation reaction with ruthenium arene precursors showed poor yields (30–33%), demonstrating ligand design‘s potential in catalysis reactions. The proton NMR of the reaction mixture after 2 h shows the formation of Ru−H intermediate, which gave the desired alkylated products. Overall, these complexes are promising catalyst candidates for organic transformation.
Synthetic Studies to exo‐Ring‐Junction based Fused 5/5/n‐Tricyclic Systems: Access to A, B, C‐Ring System of Longeracinphyllin A, Himalenine D, and Daphnipaxiamine A.
Authors: Kotha Sambasivarao , Agrawal Arpit , Keesari Ramakrishna Reddy
Published: May 2023

We report a short synthetic approach to various tricyclic systems that are present in several diquinane‐based natural products starting with a readily available exo‐dicyclopentadiene‐1‐one. To this end, we have successfully assembled a fused 5/5/7‐tricyclic enone via ring‐rearrangement metathesis as a key step. The strategy has been further extended to synthesize the 1,3‐dihydroxy and then 1‐keto‐3‐hydroxy derivatives by utilizing regio‐ and stereoselective epoxidation and ring‐rearrangement metathesis reactions as key steps. All these target compounds are found to be present in diquinane‐based natural products such as longeracinphyllins A, himalenine D and daphnipaxianine A, etc. Moreover, the newly synthesized tricyclic compounds matches the exact ring‐junction stereochemistry (5/5‐exo) of these natural products. Hence, the synthetic studies disclosed here may be useful in the synthesis of biologically significant natural products and in the drug design. The newly synthesized molecules were characterized by NMR and HRMS data. Some of these structures were confirmed by a single crystal X‐ray diffraction studies.
Mothers of disabled infants had higher cortisol levels in a free‐ranging group of Japanese macaques (Macaca fuscata)
Authors: Turner Sarah E. , Fedigan Linda M. , Joyce Megan M. , Matthews H. Damon , Moriarity Robert J. , Nobuhara Hisami , Nobuhara Toshikazu , Stewart Brogan M. , Shimizu Keiko
Published: May 2023

Glucocorticoids (GCs) are hormones released in response to stressors and can provide insight into an organism's physiological well‐being. Experiencing chronic challenges to homeostasis is associated with significant deviations from baseline fecal GCs (fGCs) in many species, providing a noninvasive biomarker for assessing stress. In the group of free‐ranging Japanese macaques (Macaca fuscata) at the Awajishima Monkey Center in Japan, ~17% have congenital limb malformations. We collected 646 fecal samples from 27 females over three consecutive birth seasons (May–August) and analyzed them using enzyme immunoassay to extract fGCs. We explored the relationship between fGC levels and individual (physical impairment and reproductive status), social (dominance rank and availability of kin for social support), and ecological variables (exposure to potential predators, rainfall, and wild fruit availability). A disabled infant was associated significantly with higher fGC in the mother; however, physical impairment in adult females was not significantly related to fGC levels. Females with higher dominance rank had significantly lower fGC levels than lower ranking females. Other factors did not relate significantly to fGC. These results suggest that providing care that meets the support needs of disabled infants poses a physiological challenge for mothers and suggests that physically impaired adults are able to effectively compensate for their disabilities with behavioral plasticity. Once an individual with congenital limb malformations survives infancy through their mother's care, physical impairment does not appear to influence fGC values, while social variables like dominance rank significantly influenced cortisol values in free‐ranging female Japanese macaques.
Exploring effects of atmospheric conditions in hereditary hemorrhagic telangiectasia
Authors: Yusuf Hamzah M. , Rasheed Amna , Hetts Steven , Kim Helen , Loftus Patricia , Conrad Miles
Published: May 2023

Background

Hereditary hemorrhagic telangiectasia (HHT) is a rare autosomal dominant disorder characterized by recurrent epistaxis, telangiectasias, and visceral arteriovenous malformations. Individuals with HHT often identify low humidity and temperature as detrimental to epistaxis severity. We set out to assess the relationship between humidity and temperature on epistaxis severity in patients with HHT.

Methods

Retrospective cross‐sectional study at an academic hospital with an HHT center between July 1, 2014 and January 1, 2022. The primary outcome of this study was ESS. Pearson correlation analyses and multiple linear regression analyses were performed to test the association between weather variables and epistaxis severity scre (ESS). Results were reported as coefficient and 95% confidence interval (CI).

Results

Four hundred twenty‐nine patients were included in the analysis. Through a Pearson correlation analysis, neither humidity (regression coefficient = −0.01; 95% CI, −0.006 to 0.003; p = 0.50), daily low temperature (regression coefficient = 0.01; 95% CI, −0.011 to 0.016; p = 0.72), or daily high temperature (regression coefficient = 0.01; 95% CI, −0.004 to 0.013; p = 0.32) were significantly correlated with ESS. In a multiple linear regression analysis, adjusting for both daily low temperature and humidity, medications taken, demographics, and genotype, neither daily low temperature (regression coefficient = −0.02; 95% CI, −0.04 to 0.01; p = 0.14) nor humidity (regression coefficient = 0.01; 95% CI, −0.01 to 0.01; p = 0.64) were significantly associated with ESS.

Conclusion

We have shown in a large clinical sample that neither humidity nor temperature were strongly correlated with HHT patient epistaxis severity.
A review of artificial intelligence applications in manufacturing operations
Authors: Plathottam Siby Jose , Rzonca Arin , Lakhnori Rishi , Iloeje Chukwunwike O.
Published: May 2023

Artificial intelligence (AI) and machine learning (ML) can improve manufacturing efficiency, productivity, and sustainability. However, using AI in manufacturing also presents several challenges, including issues with data acquisition and management, human resources, infrastructure, as well as security risks, trust, and implementation challenges. For example, getting the data needed to train AI models can be difficult for rare events or costly for large datasets that need labeling. AI models can also pose security risks when integrated into industrial control systems. In addition, some industry players may be hesitant to use AI due to a lack of trust or understanding of how it works. Despite these challenges, AI has the potential to be extremely helpful in manufacturing, particularly in applications such as predictive maintenance, quality assurance, and process optimization. It is important to consider the specific needs and capabilities of each manufacturing scenario when deciding whether and how to use AI in manufacturing. This review identifies current developments, challenges, and future directions in AI/ML relevant to manufacturing, with the goal of improving understanding of AI/ML technologies available for solving manufacturing problems, providing decision‐support for prioritizing and selecting appropriate AI/ML technologies, and identifying areas where further research can yield transformational returns for the industry. Early experience suggests that AI/ML can have significant cost and efficiency benefits in manufacturing, especially when combined with the ability to capture enormous amounts of data from manufacturing systems.
Photocurrent Generation and Polarity Switching in Electrochemical Cells through Light‐induced Excited State Proton Transfer of Photoacids and Photobases**
Authors: Yucknovsky Anna , Shlosberg Yaniv , Adir Noam , Amdursky Nadav
Published: May 2023

Light is a common source of energy in sustainable technologies for photocurrent generation. To date, in such light‐harvesting applications, the excited electrons generate the photocurrent. Here, we introduce a new mechanism for photocurrent generation that is based on excited state proton transfer (ESPT) of photoacids and photobases that can donate or accept a proton, respectively, but only after excitation. We show that the formed ions following ESPT can either serve as electron donors or acceptors with the electrodes, or modify the kinetics of mass transport across the diffuse layer, both resulting in photocurrent generation. We further show that control of the current polarity is obtained by switching the irradiation between the photoacid and the photobase. Our study represents a new approach in photoelectrochemistry by introducing ESPT processes, which can be further utilized in light‐responsive energy production or energy storage.
An Integrated Dual‐Functional Nanotool Capable of Studying Single‐Cell Epigenetics and Programmable Gene Regulation
Authors: Shi Xiao‐Mei , Xu Yi‐Tong , Wang Bing , Li Zheng , Yu Si‐Yuan , Dong Hang , Zhao Wei‐Wei , Jiang Dechen , Chen Hong‐Yuan , Xu Jing‐Juan
Published: May 2023

Single‐cell epigenetics is envisioned to decipher manifold epigenetic phenomena and to contribute to our accurate knowledge about basic epigenetic mechanisms. Engineered nanopipette technology has gained momentum in single‐cell studies; however, solutions to epigenetic questions remain unachieved. This study addresses the challenge by exploring N6‐methyladenine (m6A)‐bearing deoxyribozyme (DNAzyme) confined within a nanopipette for profiling a representative m6A‐modifying enzyme, fat mass and obesity‐associated protein (FTO). Electroosmotic intracellular extraction of FTO could remove the m6A and cause DNAzyme cleavage, leading to the altered ionic current signal. Because the cleavage can release a DNA sequence, we simultaneously program it as an antisense strand against FTO‐mRNA, intracellular injection of which has been shown to induce early stage apoptosis. This nanotool thus features the dual functions of studying single‐cell epigenetics and programmable gene regulation.
Phosphine Oxide‐Functionalized Terthiophene Redox Systems
Authors: Käch Daniel , Gasser Aurelio C. , Wettstein Lionel , Schweinzer Clara , Bezdek Máté J.
Published: May 2023

Main group systems capable of undergoing controlled redox events at extreme potentials are elusive yet highly desirable for a range of organic electronics applications including use as energy storage media. Herein we describe phosphine oxide‐functionalized terthiophenes that exhibit two reversible 1e− reductions at potentials below −2 V vs Fc/Fc+ (Fc=ferrocene) while retaining high degrees of stability. A phosphine oxide‐functionalized terthiophene radical anion was synthesized in which the redox‐responsive nature of the platform was established using combined structural, spectroscopic, and computational characterization. Straightforward structural modification led to the identification of a derivative that exhibits exceptional stability during bulk 2 e− galvanostatic charge–discharge cycling and enabled characterization of a 2 e− redox series. A new multi‐electron redox system class is hence disclosed that expands the electrochemical cell potential range achievable with main group electrolytes without compromising stability.
Unlocking Migratory Insertion in Gold Redox Catalysis
Authors: Wang Wenliang , Ding Meiling , Zhao Chuan‐Gang , Chen Shuai , Zhu Chengjian , Han Jie , Li Weipeng , Xie Jin
Published: May 2023

Exploration of elementary reactions in organometallic catalysis is an important method with which to discover new reactions. In this article, we report a gold(I)‐catalyzed iodo‐alkynylation of benzyne involving the merging of challenging migratory insertion and an oxidative addition process in gold catalytic cycle. A wide range of structurally diverse alkynyl iodides are good coupling partners in this iodo‐alkynylation transformation. Both aliphatic and aromatic alkynyl iodides can react with benzynes smoothly to afford highly functionalized 1,2‐disubstituted aromatics in moderate to good yields. Its good functional group compatibility and late‐stage application of complex molecules demonstrate its synthetic robustness. Studies of the mechanism reveals the feasibility of oxidative addition and the DFT calculations demonstrate the possible migratory insertion of benzyne into AuIII‐carbon bonds in the AuI/AuIII redox catalytic cycle, representing an important step towards an elementary reaction in gold chemistry research.
Direct and Indirect Evolution of Photoluminescent Semiconductor CdS Magic‐Size Clusters through Their Precursor Compounds
Authors: Wang Dongqing , Liu Yuehui , Rowell Nelson , Wang Shanling , Zhang Chunchun , Zhang Meng , Luan Chaoran , Yu Kui
Published: May 2023

Colloidal semiconductor II–VI metal chalcogenide (ME) magic‐size clusters (MSCs) exhibit either an optical absorption singlet or doublet. In the latter case, a sharp photoluminescence (PL) signal is observed. Whether the PL‐inactive MSCs transform to the PL‐active ones is unknown. We show that PL‐inactive CdS MSC‐322 transforms to PL‐active CdS MSC‐328 and MSC‐373 in the presence of acetic acid (HOAc). MSC‐322 displays a sharp absorption at ≈322 nm, whereas MSC‐328 and MSC‐373 both have broad absorptions respectively around 328 and 373 nm. In a reaction of cadmium myristate and S powder in 1‐octadecene, MSC‐322 develops; with HOAc, MSC‐328 and MSC‐373 are present. We propose that the MSCs evolve from their relatively transparent precursor compounds (PCs). The PC‐322 to PC‐328 quasi‐isomerization involves monomer substitution, while monomer addition occurs for the PC‐328 to PC‐373 transformation. Our findings suggest that S dominates the precursor self‐assembly quantitatively, and ligand‐bonded Cd mainly controls MSC optical properties.