bluuebunny/crossref_metadata_2025 huggingface dataset:
Predicting Chronic Opioid Use Among Patients With Osteoarthritis Using Electronic Health Record Data
Authors: Mohl Jeff T. , Stempniewicz Nikita , Cuddeback John K. , Kent David M. , MacLean Elizabeth A. , Nicholls Lance , Kerrigan Christopher , Ciemins Elizabeth L.
Published: September 2022

Objective

To estimate the risk of a patient with osteoarthritis (OA) developing chronic opioid use (COU) within 1 year of a new opioid prescription by using electronic health record (EHR) data and predictive models.

Methods

We used EHR data from 13 health care organizations to identify patients with OA with an opioid prescription between March 1, 2017 and February 28, 2019 and no record of opioid use in the prior 6 months. We evaluated 4 machine learning models to estimate patients’ risk of COU (≥3 prescriptions ≥84 days, maximum gap ≤60 days). We also estimated the transportability of models to organizations outside the training set.

Results

The cohort consisted of 33,894 patients with OA, of whom 2,925 (8.6%) developed COU within 1 year. All models demonstrated good discrimination, with the best‐performing model (random forest) achieving an area under the receiver operating characteristic curve (AUC) of 0.728 (95% CI 0.711–0.745), but the simplest regression model performed nearly as well (AUC 0.717 [95% CI 0.699–0.734]). Predicted risk deciles spanned a range of 2% risk for the 10th percentile to 18% risk for the 90th percentile for well‐calibrated models. Models showed highly variable discrimination across organizations (AUC 0.571–0.842).

Conclusions

We found that EHR‐based predictive models could estimate the risk of future COU among patients with OA to help inform care decisions. Black‐box methods did not have significant advantages over more interpretable models. Care should be taken when extending all models into organizations not included in model training because of a high variability in performance across held‐out organizations.
Data‐Driven Magnetic Resonance Imaging Definitions for Active and Structural Sacroiliac Joint Lesions in Juvenile Spondyloarthritis Typical of Axial Disease: A Cross‐Sectional International Study
Authors: Weiss Pamela F. , Brandon Timothy G. , Lambert Robert G. , Biko David M. , Chauvin Nancy A. , Francavilla Michael L. , Jaremko Jacob L. , Herregods Nele , Kasapcopur Ozgur , Yildiz Mehmet , Hendry Alison M. , Maksymowych Walter P.
Published: September 2022

Objective

We aimed to determine quantitative sacroiliac (SI) joint magnetic resonance imaging (MRI) cutoffs for active and structural lesions that will be incorporated as imaging domains in classification criteria of axial disease in juvenile spondyloarthritis (SpA).

Methods

MRI scans from an international cross‐section of juvenile SpA patients were reviewed by 6 musculoskeletal imaging experts blinded to clinical details. Raters globally assessed the presence/absence of lesions typical of axial SpA and performed SI joint quadrant‐ or joint‐based scoring. Sensitivity and specificity of lesion cutoffs were calculated using a rater majority (≥4 of 6 raters) on a global assessment of the presence/absence of active or structural lesions typical of axial SpA with high confidence as the reference standard. Cutoffs were validated in an independent cohort.

Results

Imaging from 243 subjects, 61% male, median age 14.9 years, had sequences available for detailed MRI scoring. Optimal cutoffs for defining lesions typical of axial disease in juvenile SpA were: 1) inflammatory lesion: bone marrow edema in ≥3 SI joint quadrants across all SI joint MRI slices (sensitivity 98.6%, specificity 96.5%); 2) structural lesions: erosion in ≥3 quadrants or sclerosis or fat lesion in ≥2 SI joint quadrants or backfill or ankylosis in ≥2 joint halves across all SI joint MRI slices (sensitivity 98.6%, specificity 95.5%). Sensitivity and specificity of the optimal cutoffs in the validation cohort were excellent.

Conclusion

We propose data‐driven cutoffs for active inflammatory and structural lesions on MRI typical of axial disease in juvenile SpA that have high specificity and sensitivity using central imaging global assessment as the reference standard and excellent reliability.
Motion Artifact‐Resilient Zone for Implantable Sensors
Authors: Jeong Chanho , Koirala Gyan Raj , Jung Yei Hwan , Ye Yeong Sinn , Hyun Jeong Hun , Kim Tae Hee , Park Byeonghak , Ok Jehyung , Jung Youngmee , Kim Tae‐il
Published: September 2022

The miniaturization and flexibility of wearable and implantable devices allow humans to carry them directly on or in their bodies, thus enabling these devices to measure biometric signals in real‐time anywhere. However, as they are embedded or implanted into an actively moving human interface, motion artifact noise inevitably occurs. Typically, devices are laminated or implanted on body surfaces, but the positions of such devices cannot be designed without any discussion of the noise. Thus, this paper investigates an approach that minimizes the noise to achieve negligible motion artifacts in implantable micro‐devices that have a specific angle on the surface of the body, while maintaining the function of sensor. The device with a specific angle successfully detects the target signal, while motion artifacts—such as tension, compression, and bending—disturb the measurement. The pulse signal on a wrist is well measured while the hand is rotating, and artificial skin implanted on a rat can distinguish external pressure from the movement noise. A thermometer sensor that follows the same rule is further examined. Therefore, this approach is expected to be useful in numerous areas including human interface‐based medical devices, virtual reality, and health aids to improve quality of life.
Multifunctional DNA Hydrogel Enhances Stemness of Adipose‐Derived Stem Cells to Activate Immune Pathways for Guidance Burn Wound Regeneration
Authors: Zhou Liping , Zeng Zehua , Liu Songyang , Min Tiantian , Zhang Wenmin , Bian Xiaochun , Du Hongwu , Zhang Peixun , Wen Yongqiang
Published: September 2022

A grade 3 burn is a nonstatic fatal injury, which can lead to complete damage to the skin structure, accompanied by a series of symptoms such as persistent inflammation, pain, pruritus, ulcer, and peripheral neuropathy. Although the primary clinical burn treatment is skin grafting, it cannot comprehensively solve burn symptoms. Here, a multifunctional DNA hydrogel integrated system is conveniently obtained through dynamic cross‐linking of the DNA unit, polyacrylamide, and l‐ascorbate 2‐phosphate (l‐A2P) formation of dense hydrogen bonds. The DNA hydrogel is doped with borneol for pain and itch relief. The obtained DNA hydrogel provides a hotbed similar to the extracellular matrix structure in vivo for the growth and development of stem cells, which can regulate cell proliferation, maintain cell viability, and achieve perfect release in a suitable environment. Additionally, the pharmacological wound dressing shell features excellent mechanical behavior, tissue adhesion, and antibacterial properties. Beyond that, the multifunctional DNA hydrogel integrated system can promote macrophage transformation, angiogenesis, and neurogenesis. Notably, the system activates the phosphatidylinositol 3′‐kinase (PI3K)‐Akt signaling pathway, which helps to promote tissue regeneration. Therefore, the DNA hydrogel integrated system opens the cascade mode of effective integrated treatment of burn wounds, further driving the in‐depth study of clinical transformation mechanisms in the future.
Surface Structure Evolution and its Impact on the Electrochemical Performances of Aqueous‐Processed High‐Voltage Spinel LiNi0.5Mn1.5O4 Cathodes in Lithium‐Ion Batteries
Authors: He Jiarong , Melinte Georgian , Darma Mariyam Susana Dewi , Hua Weibo , Das Chittaranjan , Schökel Alexander , Etter Martin , Hansen Anna‐Lena , Mereacre Liuda , Geckle Udo , Bergfeldt Thomas , Sun Zhipeng , Knapp Michael , Ehrenberg Helmut , Maibach Julia
Published: September 2022

LiNi0.5Mn1.5O4 (LNMO) is a promising cathode in lithium‐ion batteries (LIBs) due to its high operating voltage and open Li+ diffusion framework. However, the instability of the electrode–electrolyte interface and the negative environmental impact of electrode fabrication processes limit its practical application. Therefore, switching electrode processing conditions to aqueous and understanding the accompanying surface structural evolution are imperative. Here, water‐treated, poly(acrylic acid) (PAA)‐treated, and H3PO4‐treated LNMO, labeled as W‐LNMO, A‐LNMO, and H‐LNMO, are studied systematically. W‐LNMO shows a high concentration of Mn3+ induced by Li loss while a conformal PAA layer formed on A‐LNMO reduces this phenomenon. H‐LNMO displays a second MnPO4∙H2O phase. Upon cycling, a fast capacity decay is observed in W‐LNMO while an extra plateau at ≈2.7 V appears in the initial charging, corresponding to a two‐phase transition. A surface reconstruction layer from a spinel to a rock‐salt phase with a reductive Mn2+ segregation is observed in W‐LNMO after 105 cycles. The PAA layer persists on A‐LNMO and alleviates the capacity decay. H‐LNMO delivers a relatively low capacity due to the formation of a MnPO4∙H2O phase. This study provides new insights into manipulating the surface chemistry of LNMO cathodes to enable aqueous, large‐scale processingin LIBs.
Liquid Confine‐Induced Gradient‐Janus Wires for Droplet Self‐Propelling Performances in High Efficiency
Authors: Zhong Lieshuang , Chen Huan , Zhu Lingmei , Zhou Maolin , Zhang Lei , Wang Shaomin , Han Xuefeng , Hou Yongping , Zheng Yongmei
Published: September 2022

Constructing surface wetting gradients usually involves complex physical or chemical methods. Here, a novel Gradient‐Janus wire (GJW) can be designed based on the theory of newly Liquid Confined Modification (LCM). In LCM theory, reaction difference will be generated by the confinement of reaction solution, which constructs wettability discrepancy on the same curve surface. Thus a unique continuous Gradient‐Janus wetting region can be constructed in a long range on a 1D wire. It is demonstrated that GJW can propel water droplets to transport the distance of ≈73 mm in 0.9 s, and liquid bridge to 85 mm (the longest among this kind of study) in 0.79 s with peak velocity high up to 237 mm s−1 (over 20 times faster than droplet transport on surface of Sarracenia trichome). The mechanism is attributed to cooperation between imbalanced Laplace pressure and surface tension force to generate the driving force act on droplet, liquid bridge, or column transport, respectively. LCM directs the large‐scale facile fabrication of GJWs within 20 s. A large‐scale GJW array can achieve the high‐efficient transport of water droplet in a wide volume range (few µL to 1 mL), making it potential in fogwater harvesting.
Biofabrication of Human Skin with Its Appendages
Authors: Hosseini Motaharesadat , Koehler Karl R. , Shafiee Abbas
Published: September 2022

Much effort has been made to generate human skin organ in the laboratory. Yet, the current models are limited due to the lack of many critical biological and structural features of the skin. Importantly, these in vitro models lack appendages and fail to recapitulate the whole human skin construction. Thus, engineering a human skin with the capacity to generate all components, including appendages, is a major challenge. This review intends to provide an update on the recent efforts underway to regenerate appendage‐bearing skin organs based on scaffold‐free and scaffold‐based bioengineering approaches. Although the mouse skin equivalents containing hair follicles, sebaceous glands, and sweat glands have been established in vitro, there has been limited success in humans. A combination of biofabricated matrices and cell aggregates, such as organoids, can pave the way for generating skin substitutes with human‐like biological, structural, and physical features. Accordingly, the formation of human skin organoids and reconstruction of vascularized skin equipped with immune cells prompt calls for more scientific research. The generation of appendage‐bearing skin substitutes can be applied in practice for wound healing, hair restoration, and scar treatment.
Nonequilibrium Lattice Dynamics in Photoexcited 2D Perovskites
Authors: Cuthriell Shelby A. , Panuganti Shobhana , Laing Craig C. , Quintero Michael A. , Guzelturk Burak , Yazdani Nuri , Traore Boubacar , Brumberg Alexandra , Malliakas Christos D. , Lindenberg Aaron M. , Wood Vanessa , Katan Claudine , Even Jacky , Zhang Xiaoyi , Kanatzidis Mercouri G. , Schaller Richard D.
Published: September 2022

Interplay between structural and photophysical properties of metal halide perovskites is critical to their utility in optoelectronics, but there is limited understanding of lattice response upon photoexcitation. Here, 2D perovskites butylammonium lead iodide, (BA)2PbI4, and phenethylammonium lead iodide, (PEA)2PbI4, are investigated using ultrafast transient X‐ray diffraction as a function of optical excitation fluence to discern structural dynamics. Both powder X‐ray diffraction and time‐resolved photoluminescence linewidths narrow over 1 ns following optical excitation for the fluence range studied, concurrent with slight redshifting of the optical bandgaps. These observations are attributed to transient relaxation and ordering of distorted lead iodide octahedra stimulated mainly by electron–hole pair creation. The c axis expands up to 0.37% over hundreds of picoseconds; reflections sampling the a and b axes undergo one tenth of this expansion with the same timescale. Post‐photoexcitation appearance of the (110) reflection in (BA)2PbI4 would suggest a transient phase transition, however, through new single‐crystal XRD, reflections are found that violate glide plane conditions in the reported Pbca structure. The static structure space group is reassigned as P212121. With this, a nonequilibrium phase transition is ruled out. These findings offer increased understanding of remarkable lattice response in 2D perovskites upon excitation.
Local Diverse Polarization Optimized Comprehensive Energy‐Storage Performance in Lead‐Free Superparaelectrics
Authors: Chen Liang , Wang Na , Zhang Zhifei , Yu Huifen , Wu Jie , Deng Shiqing , Liu Hui , Qi He , Chen Jun
Published: September 2022

Lead‐free dielectric ceramics with ultrahigh energy‐storage performance are the core components used in next‐generation advanced pulse power capacitors. However, the low energy storage density largely hinders their development towards miniaturization, lightweight, and integration. Here, an effective strategy of constructing local diverse polarization is designed in superparaelectrics to realize an ultrahigh energy storage density of ≈10.59 J cm−3 as well as a large efficiency of ≈87.6%. The excellent comprehensive energy‐storage performance is mainly attributed to the design of ultrasmall polar nanoregions with local diverse polarization configuration, confirmed by scanning transmission electron microscopy, leading to the reduced heat loss, substantially enhanced polarization, and breakdown electric field compared to ceramics with single polarization configuration. Benefiting from these features, outstanding temperature/frequency/cycling stability and superior charge/discharge performance (power density ≈187.5 MW cm−3, discharge energy density ≈3.52 J cm−3, discharge rate ≈77 ns) are also achieved. This work demonstrates that local diverse polarization is a super strategy to design new dielectric materials with high energy‐storage performance.
Multifunctionality of Li2SrNb2O7: Memristivity, Tunable Rectification, Ferroelasticity, and Ferroelectricity
Authors: Xu Xianghan , Huang Fei‐Ting , Du Kai , Cheong Sang‐Wook
Published: September 2022

Layered Li2SrNb2O7, an inorganic oxide in its bulk single‐crystalline form, is experimentally demonstrated to exhibit multiple structural facets such as ferroelasticity, ferroelectricity, and antiferroelectricity. The transition from a room temperature (RT) centrosymmetric structure to a low‐temperature out‐of‐plane ferroelectric and in‐plane antiferroelectric structure and the low‐temperature (LT) ferroelectric domain configuration are unveiled in TEM, piezoresponse force microscopy, and polarization loop studies. Li2SrNb2O7 also exhibits highly tunable ferroelasticity and excellent Li+ in‐plane conduction, which leads to a giant in‐plane memristor behavior and an in‐plane electronic conductivity increase by three orders of magnitude by electric poling at room RT). The accumulation of Li+ vacancies at the crystal–electrode interface is visualized using in situ optical microscopy. The Li‐ionic biased state shows a clear in‐plane rectification effect combined with a significant relaxation upon time at RT. Relaxation can be fully suppressed at LTs such as 200 K, and utilizing an electric field cooling, a stable rectification can be achieved at 200 K. The results shed light on the selective control of multifunctionalities such as ferroelasticity, ferroelectricity, and ionic‐migration‐mediated effects (a memristor effect and rectification) in a single‐phase bulk material utilizing, for example, different directions, temperatures, frequencies, and magnitudes of electric field.
Minimizing the Programming Power of Phase Change Memory by Using Graphene Nanoribbon Edge‐Contact
Authors: Wang Xiujun , Song Sannian , Wang Haomin , Guo Tianqi , Xue Yuan , Wang Ruobing , Wang HuiShan , Chen Lingxiu , Jiang Chengxin , Chen Chen , Shi Zhiyuan , Wu Tianru , Song Wenxiong , Zhang Sifan , Watanabe Kenji , Taniguchi Takashi , Song Zhitang , Xie Xiaoming
Published: September 2022

Nonvolatile phase‐change random access memory (PCRAM) is regarded as one of the promising candidates for emerging mass storage in the era of Big Data. However, relatively high programming energy hurdles the further reduction of power consumption in PCRAM. Utilizing narrow edge‐contact of graphene can effectively reduce the active volume of phase change material in each cell, and therefore realize low‐power operation. Here, it demonstrates that the power consumption can be reduced to ≈53.7 fJ in a cell with ≈3 nm‐wide graphene nanoribbon (GNR) as edge‐contact, whose cross‐sectional area is only ≈1 nm2. It is found that the polarity of the bias pulse determines its cycle endurance in the asymmetric structure. If a positive bias is applied to the graphene electrode, the endurance can be extended at least one order longer than the case with a reversal of polarity. In addition, the introduction of the hexagonal boron nitride (h‐BN) multilayer leads to a low resistance drift and a high programming speed in a memory cell. The work represents a great technological advance for the low‐power PCRAM and can benefit in‐memory computing in the future.
Performance of turf‐type bermudagrass cultivars in the upper and lower limits of the European transition zone
Authors: Gómez de Barreda Diego , Azcárraga Carlos , Pornaro Cristina , Macolino Stefano
Published: September 2022

Bermudagrass [Cynodon dactylon (L.) Pers.] is one of the most widely cultivated turfgrass species throughout the world. It has several important attributes, such as heat and drought tolerance, and one big disadvantage, which is susceptibility to cold temperatures. Although many seeded bermudagrass cultivars are widely used in Europe, research is warranted on new varieties released in recent decades. Two identical field studies were conducted in Valencia, Spain (39° N lat) and Legnaro, Italy (45° N lat) to evaluate the turfgrass quality, winter dormancy, and spring green‐up of two new bermudagrass releases in Europe (‘Arden 15’ and ‘MBG 002’) and three older bermudagrasses (‘Blackjack’, ‘Common’, and ‘Paul 1’). Even though bermudagrasses were successfully cultivated in the cooler temperature zone (45° N lat), cultivars exhibited poorer establishment and longer winter dormancy as a consequence of the lower temperatures compared with those grown in the warmer temperature zone (39° N lat). Cultivars Arden 15 and MBG 002 were able to mitigate the effects of low temperature that affected the older cultivars, especially during spring green‐up, which is an essential characteristic when growing bermudagrass in the upper limit of the transition zone.
Deep vicariance and frequent transoceanic dispersal shape the evolutionary history of a globally distributed fern family
Authors: Testo Weston L. , de Gasper André L. , Molino Sonia , Galán José María Gabriel y , Salino Alexandre , Dittrich Vinícius Antonio de Oliveira , Sessa Emily B.
Published: September 2022

Premise

The historical biogeography of ferns is typically expected to be dominated by long‐distance dispersal due to their minuscule spores. However, few studies have inferred the historical biogeography of a large and widely distributed group of ferns to test this hypothesis. Our aims were to determine the extent to which long‐distance dispersal vs. vicariance have shaped the history of the fern family Blechnaceae, to explore ecological correlates of dispersal and diversification, and to determine whether these patterns differ between the northern and southern hemispheres.

Methods

We used sequence data for three chloroplast loci to infer a time‐calibrated phylogeny for 154 of 265 species of Blechnaceae, including representatives of all genera in the family. This tree was used to conduct ancestral range reconstruction and stochastic character mapping, estimate diversification rates, and identify ecological correlates of diversification.

Results

Blechnaceae originated in Eurasia and began diversifying in the late Cretaceous. A lineage comprising most extant diversity diversified principally in the austral Pacific region around the Paleocene–Eocene Thermal Maximum. Land connections that existed near the poles during periods of warm climates likely facilitated migration of several lineages, with subsequent climate‐mediated vicariance shaping current distributions. Long‐distance dispersal is frequent and asymmetrical, with New Zealand/Pacific Islands, Australia, and tropical America being major source areas.

Conclusions

Ancient vicariance and extensive long‐distance dispersal have shaped the history of Blechnaceae in both the northern and southern hemispheres. The exceptional diversity in austral regions appears to reflect rapid speciation in these areas; mechanisms underlying this evolutionary success remain uncertain.
Elements of morphology: Standard terminology for the trunk and limbs
Authors: Biesecker Leslie G. , Adam Margaret P. , Chung Brian Hon‐Yin , Kosaki Kenjiro , Menke Leonie A. , White Susan M. , Carey John C. , Hennekam Raoul C. M.
Published: September 2022

An international group of clinicians working in the field of dysmorphology has initiated the standardization of terms used to describe human morphology. The goals are to standardize these terms and reach consensus regarding their definitions. In this way, we will increase the utility of descriptions of the human phenotype and facilitate reliable comparisons of findings among patients. Additional discussions with other workers in dysmorphology and related fields, such as developmental biology and molecular genetics, will become more precise. Here we introduce the anatomy of the trunk and limbs and define and illustrate the terms that describe the major characteristics of these body regions.
Copper‐catalyzed C(sp3)−H/N−H Cross Dehydrogenative Coupling Between Toluene Derivatives and Picolinamides
Authors: Ji Huihui , Zhan Hongju , Chen Shumin , Fang Zeguo , Zhang Qian , Li Dong
Published: September 2022

An efficient C−N bond formation method through copper‐catalyzed C(sp3)−H/N−H cross dehydrogenative coupling between toluene derivatives and picolinamides was developed. The N−H bond of picolinamides was activated by the direction of pyridyl group without influence of remote C−H bonds. The method was applicable to a broad range of substrates with good functional group compatibility, which provided a novel route to prepare N‐benzyl tertiary amides from cheap and readily available starting materials.
Young Australians' labour market engagement and job aspiration in the wake of the COVID‐19 pandemic
Authors: Dinku Yonatan , Yap Mandy
Published: September 2022

Young people tend to bear the brunt of adverse employment consequences of a crisis due mainly to the precarious nature of their job and their over‐representation among jobseekers who are having to find employment when jobs are scarce. Using quarterly welfare payment data for the period 2019–2021 from the Department of Social Services, we noted a marked increase in the percentage of 16‐ to 21‐year‐olds who received youth allowance (other) payments. While a greater proportion of Indigenous youth than non‐Indigenous youth received the payments from 2019 to 2021, the gap widened following the outbreak of the pandemic. Further, applying regression analysis to data from the 2019 and 2020 waves of the 2015 Cohort of the Longitudinal Study of Australian Youth (LSAY), we find no statistically significant change in individual‐level labour force status between 2019 and 2020. However, pandemic‐induced labour market crises appear to have been associated with reduced work hours, heightened career concerns and sustained nonemployment, where potential impacts are larger among traditionally vulnerable youth groups such as female, Indigenous and overseas‐born young persons. The study highlights the need for recognising the intersectionality of youth and other forms of identity (such as gender, Indigenous status and nativity) while designing labour market policies.
Dearomative (3+2) Cycloadditions between Indoles and Vinyldiazo Species Enabled by a Red‐Shifted Chromium Photocatalyst
Authors: Gall Bradley K. , Smith Avery K. , Ferreira Eric M.
Published: September 2022

A direct dearomative photocatalyzed (3+2) cycloaddition between indoles and vinyldiazo reagents is described. The transformation is enabled by the development of a novel oxidizing CrIII photocatalyst, its specific reactivity attributed to increased absorptive properties over earlier Cr analogs and greater stability than Ru counterparts. A variety of fused indoline compounds are synthesized using this method, including densely functionalized ring systems that are feasible due to base‐free conditions. Experimental insights corroborate a cycloaddition initiated by nucleophilic attack at C3 of the indole radical cation by the vinyldiazo species.
Affinity Bioorthogonal Chemistry (ABC) Tags for Site‐Selective Conjugation, On‐Resin Protein‐Protein Coupling, and Purification of Protein Conjugates
Authors: Scinto Samuel L. , Reagle Tyler R. , Fox Joseph M.
Published: September 2022

The site‐selective functionalization of proteins has broad application in chemical biology, but can be limited when mixtures result from incomplete conversion or the formation of protein containing side products. It is shown here that when proteins are covalently tagged with pyridyl‐tetrazines, the nickel‐iminodiacetate (Ni‐IDA) resins commonly used for His‐tags can be directly used for protein affinity purification. These Affinity Bioorthogonal Chemistry (ABC) tags serve a dual role by enabling affinity‐based protein purification while maintaining rapid kinetics in bioorthogonal reactions. ABC‐tagging works with a range of site‐selective bioconjugation methods with proteins tagged at the C‐terminus, N‐terminus or at internal positions. ABC‐tagged proteins can also be purified from complex mixtures including cell lysate. The combination of site‐selective conjugation and clean‐up with ABC‐tagged proteins also allows for facile on‐resin reactions to provide protein‐protein conjugates.
Quantum dots in the biomedical world: A smart advanced nanocarrier for multiple venues application
Authors: Singh Siddharth , Raina Deepika , Rishipathak Dinesh , Babu Kamesh R. , Khurana Riya , Gupta Yogesh , Garg Kartik , Rehan Farah , Gupta Shraddha M.
Published: September 2022

Quantum dots (QDs) are semiconducting nanoparticles having different optical and electrical properties when compared to larger particles. They exhibit photoluminescence when irradiated with ultraviolet light, which is due to the transition of an excited electron from the valence band to the conductance band followed by the return of the exciting electron back into the valence band. The size and material of QDs can affect their optical and other properties too. The QDs possess special attributes like high brightness, protection from photobleaching, photostability, color tunability, low toxicity, low production cost, a multiplexing limit, and a high surface‐to‐volume proportion, which make them a promising tool for biomedical applications. Here, in this study, we summarize the utilization of QDs in different applications including bioimaging, diagnostics, immunostaining, single‐cell analysis, drug delivery, and protein detection. Moreover, we discuss the advantages and challenges of using QDs in biomedical applications when compared with other conventional tools.
A Combined XPS and Computational Study of the Chemical Reduction of BMP‐TFSI by Lithium**
Authors: Forster‐Tonigold K. , Buchner F. , Bansmann J. , Behm R. J. , Groß A.
Published: September 2022

Employing density functional theory (DFT) calculations and X‐ray photoelectron spectroscopy (XPS), we identify products of the reaction of the ionic liquid N,N‐butylmethylpyrrolidinum bis(trifluoromethylsulfonyl)imide (BMP‐TFSI) with lithium in order to model the initial chemical processes contributing to the formation of the solid electrolyte interphase in batteries. Besides lithium oxide, sulfide, carbide and fluoride, we find lithium cyanide or cyanamide as possible, thermodynamically stable product in the Li‐poor regime, whilst Li3N is the stable product in the Li‐rich regime. The thermodynamically controlled reaction products as well as larger fragments of TFSI persisting due to kinetic barriers could be identified by a comparison of experimentally and computationally determined core level binding energies.
Live‐cell imaging of genomic loci with Cas9 variants
Authors: Ye Huiying , Jiang Chao , Li Lian , Li Hui , Rong Zhili , Lin Ying
Published: September 2022

Background

Endonuclease‐deactivated clustered regularly interspaced short palindromic repeats (CRISPR)‐associated nuclease (dCas9) has been repurposed for live‐cell imaging of genomic loci. Engineered or evolved dCas9 variants have been developed to increase the applicability of the CRISPR/dCas9 system. However, there have been no systematic comparisons of these dCas9 variants in terms of their performance in the visualization of genomic loci.

Main Methods and Major Results

Here we demonstrate that dSpCas9 and its variants deSpCas9(1.1), dSpCas9‐HF1, devoCas9, and dxCas9(3.7) can be used for CRISPR‐based live‐cell genomic imaging. dSpCas9 had the greatest utility, with a high labeling efficiency of repetitive sequences—including those with a low number of repeats—and good compatibility with target RNA sequences at the MUC4 locus that varied in length from 13 to 23 nucleotides. We combined CRISPR‐Tag with the dSpCas9 imaging system to observe the dynamics of the Tet promoter and found that its movement was restricted when it was active.

Conclusions and Implications

These novel Cas9 variants provide a new set of tools for investigating the spatiotemporal regulation of gene expression through live imaging of genomic sites.
Highly expressed carbohydrate sulfotransferase 11 correlates with unfavorable prognosis and immune evasion of hepatocellular carcinoma
Authors: Xiong Dan‐dan , Li Jian‐di , He Rong‐quan , Li Ming‐xuan , Pan Yan‐qing , He Xiao‐lian , Dang Yi‐wu , Chen Gang
Published: September 2022

Despite great advance has been made in multi‐modality treatments for HCC patients, the effectiveness is far from satisfactory with worse survival outcome, which may be partly explainable by the anti‐tumor deficiency of the immune system. It is necessary to clarify the molecular mechanism of HCC immunodeficiency. Here, we demonstrated that carbohydrate sulfotransferase 11 (CHST11) was upregulated in HCC and related to advanced TNM stage. HCC patients with TP53 mutation showed higher CHST11 expression. Survival analysis revealed that CHST11 was an independent prognostic biomarker in HCC. Cellular functional experiments indicated that knockdown of CHST11 in HCC inhibited cell proliferation and metastasis. Gene functional enrichment analyses indicated that CHST11 modulated pathways related to tumor growth, metastasis and immune regulation. Continuative immune‐related analyses revealed that CHST11 expression facilitated Tregs infiltration in HCC and promoted the expression of checkpoints PD‐L1/PD‐1, resulting in the immunosuppression of HCC. Targeting CHST11 may inhibit Tregs infiltration and enhance the antineoplastic effect of immune checkpoint inhibitors, which provides a novel insight into the combination immunotherapy with Treg‐modulating agents and PD‐L1/PD‐1 inhibitors.
Application of fault tree analysis: Failure mode and effect analysis to evaluate critical factors influencing non‐GM segregation in the US grain and feed supply chain
Authors: Gupta Priyanka , Hurburgh Charles R. , Bowers Erin L. , Mosher Gretchen A.
Published: September 2022

Background and Objective

Adventitious presence (AP) or unintentional commingling of genetically modified (GM) grain in non‐GM grain lots is a concern for stakeholders who wish to produce non‐GM grain and grain‐based products. AP that exceeds tolerance levels results in the loss of product marketability as “non‐GM” and subsequent loss of a premium market price. The objective of this study was to evaluate the US commodity corn supply chain using Fault Tree Analysis (FTA) and Failure Mode and Effect Analysis (FMEA) to assess factors contributing to AP in supply chains that handle both GM and non‐GM products.

Findings

Systematic analysis of the farm‐to‐feed supply chain identified key processes and actors involved. FTA identified 27 factors potentially contributing to AP along with their root causes. Ranking of factors using FMEA prioritized 14 factors as “critical” with a comparatively higher likelihood of occurrence and impact on AP levels.

Conclusions

AP contributing factors were found across the supply chain, indicating that successful segregation relies on all supply chain participants. Identification and prioritization of critical factors make it possible to target resources to a small number of significant factors to attain low AP levels rather than distributing resources across the entire set of factors.

Significance and Novelty

This study is an initial attempt to provide insights into the assessment and management of AP in the grain and feed supply chain with a novel application of FTA and FMEA techniques.
Carbon‐Supported Au Catalyst in Acetylene Hydrochlorination: Enhancing Catalytic Performance by Complexation of Dicarbonyl Ligands
Authors: Qiao Xianliang , Liu Xinyu , Yang Yang , Mao Zhenhua , Li Tianhe , Gao Lele , Zhao Chaoyue , Guan Qingxin , Li Wei
Published: September 2022

Carbon‐supported Au (Au/AC) has been proven to be one of the most promising catalysts in the field of acetylene hydrochlorination. However, the catalytic performance of conventional Au/AC catalyst is usually limited due to the unsatisfactory dispersion of active Au cation on the surface of the support, carbon deposition, and inevitable reduction to inactive Au nanoparticles. Herein, Au catalysts with highly dispersed Au cation were developed using the complexation of dicarbonyl ligand N‐chlorosuccinimide (NCS) and N‐methylsuccinimide (NMS). The obtained Au−NMS/AC and Au−NCS/AC catalysts with 0.1 wt.% Au loading possessed acetylene conversion of 98 % and 88 % at 180 °C and GHSV (C2H2) of 160 h−1, which were clearly better than that of pristine Au/AC. The characterization results showed that coordination between Au cation and ligands enhanced the dispersion of Au species, suppressed the reduction of Au cation, and reduced the formation of carbon deposits. Density functional theory (DFT) calculations suggest that Au−NMS/AC and Au−NCS/AC catalysts follow a HCl‐preferred concerted addition reaction mechanism with lower reaction energy barrier. This favors the high activity and nuclearity stability of the Au center. This study provides great potential for the use of dicarbonyl ligands on Au‐based catalysts in acetylene hydrochlorination.
Catalytic Dehydrogenation of Ethane over Mn Oxide Supported on Zeolite Chabazite
Authors: Pan Jian , Shi Song , Yuan Yong , Lobo Raul F.
Published: September 2022

A new class of Mn‐containing zeolites prepared by incipient wetness impregnation (IWI) have been found to catalyze the ethane dehydrogenation reaction with high selectivity (98 %+). Preparation by IWI leads to the formation of Mn2O3 nanoparticles on the external surface of the zeolite crystals and herein is shown that the primary active sites for the reaction are located on the surface of these particles. Propane dehydrogenation is also successfully catalyzed by this catalyst. Other Mn‐zeolites (MFI and BEA) also have high reactivity and selectivity towards light alkane dehydrogenation.
Banks retail clients' profiles and the gender gap in subjective financial literacy of spouses
Authors: Broihanne Marie‐Hélène
Published: September 2022

This article examines the gender gap in subjective financial literacy of retail clients of a large commercial bank in Europe. Under the European regulatory context (MiFID), clients of banks and financial institutions have to complete risk‐profiling questionnaires; these data are especially useful for financial advisors. Using a database of banking records and MiFID questionnaire answers of more than 50,000 retail clients, we find that the gender gap in subjective financial literacy is significantly higher for individuals living as part of a couple. We consider 7,382 dual‐income couples with matched‐partner data and find some heterogeneity in their gender gap in subjective financial literacy. We identify the couple characteristics that explain either a classical (i.e., women exhibit a significantly lower self‐assessed financial knowledge than men) or an inverse gap and point out that subjective financial literacy of spouses is related to their financial management styles.
Harnessing Water to Enhance Quadrupolar NMR Spectroscopy and Imaging
Authors: Martinho Ricardo P. , Frydman Lucio
Published: September 2022

17O and 14N are attractive targets for in vivo NMR spectroscopy and imaging, but low gyromagnetic ratios γ and fast spin relaxation complicate observations. This work explores indirect ways of detecting some of these sites with the help of proton‐detected double resonance techniques. As standard coherence transfer methods are of limited use for such indirect detection, alternative routes for probing the quadrupolar spectra on 1H were tested. These centered on modulating the broadening effects imparted onto protons adjacent to the low‐γ species through J couplings through either continuous wave or spin‐echo double‐resonance decoupling/recoupling sequences. As in all cases, the changes imparted by these double‐resonance strategies were small due to the fast relaxation undergone by the quadrupoles, the sensitivity of these approaches was amplified by transferring their effects onto the abundant water 1H signal. These amplifications were mediated by the spontaneous exchanges that the labile 1Hs bound to 17O or 14N undergo with the water protons. In experiments designed on the basis of double‐resonance spin echoes, these enhancements were imparted by looping the transverse encodings together with multiple longitudinal storage periods, leading to decoupling‐recoupling with exchange (D‐REX) sequences. In experiments designed on the basis of continuous on/off quadrupolar decoupling, these solvent exchanges were incorporated into chemical‐exchange saturation transfer schemes, leading to decoupling‐recoupling with saturation transfer (D‐REST) sequences. Both of these variants harnessed sizable proportions of the easily detectable water signals, in order to characterize the NMR spectra and/or to image with atomic‐site specificity the 17O and 14N species.
In‐Situ Hydrogen‐Bond Tailoring To Construct Ultrathin Bi2O2O/Bi2O2(OH)(NO3) Nanosheets: Interactive CO2RR Promotion and Bismuth‐Oxygen Moiety Preservation
Authors: Ma Jinjin , Yan Jing , Xu Junjie , Ni Jiaqi , Li Ruiling , Li Li , Lu Lilin
Published: September 2022

Bismuth–oxygen moieties are beneficial for high‐efficiency electrochemical CO2 reduction (CO2RR) to produce formate; however, preserving bismuth‐oxygen moieties while applying a cathodic potential is challenging. This work reports the preparation of ultrathin Bi2O2O/Bi2O2(OH)(NO3) nanosheets (BiON‐uts) by in‐situ tailoring of hydrogen bonds in a Bi2O2(OH)(NO3) precursor. The BiON‐uts exhibits a formate faradaic efficiency of 98 % with higher partial current density than that of most reported bismuth‐based catalysts. Mechanistic studies demonstrate that the ultrathin nanosheet morphology facilitates ion‐exchange between BiON‐uts and the electrolyte to produce Bi2O2CO3 as intermediate, and adsorption of CO2 with surface Bi2O2O. DFT calculations reveal that the rate‐limiting first electron transfer is effectively improved by the high electron affinity of Bi2O2CO3. More importantly, high‐efficiency CO2RR in turn protects the bismuth–oxygen moieties from being reduced and thus helps to maintain the excellent CO2RR activity. This work offers an interactive mechanism of CO2RR promotion and bismuth–oxygen moiety preservation, opening up new opportunities for developing high‐performance catalysts.
Nanomaterials Facilitating Conversion Efficiency Strategies for Microbial CO2 Reduction
Authors: Tian Shihao , Jiang Yu‐Jing , Cao Yue , Zhang Jian‐Rong , Zhou Yang , Wang Yuanyuan
Published: September 2022

Microbial electro‐ and photoelectrochemical CO2 reduction represents an opportunity to tackle the environmental demand for sustainable fuel production. Nanomaterials critically impact the electricity‐ and solar‐driven microbial CO2 reduction processes. This minireview comprehensively summarizes the recent developments in the configuration and design of nanomaterials for enhancement of the bacterial adhesion and extracellular electron transfer (EET) processes, based on the modification technologies of improving chemical stability, electrochemical conductivity, biocompatibility, and surface area. Furthermore, the investigation of incorporating non‐photosynthetic microorganisms using advanced light‐harvesting nanostructured photoelectrodes for solar‐to‐chemical conversion, as well as the current understanding of EET mechanisms occurring at photosynthetic semiconductor nanomaterials‐bacteria biohybrid interface is detailed. The crucial factors influencing the performance of microbial CO2 reduction systems and future perspectives are discussed to provide guidance for the realization of their large‐scale application.
Breaking the Glass Ceiling: Views of Women from the Second‐Wave Feminist Movement
Authors: Ng Eddy S. , McGowan Rosemary A.
Published: September 2022

This is a qualitative study of the career perspectives of early female leaders in Canada whose careers emerged from the second‐wave feminist movement and who ascended to executive leadership positions. Using a discourse analytic lens, we analyze their perspectives on women's limited presence in executive leadership roles. The research participants suggested that women lacked the necessary resilience or personality; women lacked requisite political skills; affirmative action policies have hindered women's career advancement; and women have been unable to put their careers over family in the way that is required for executive leadership. The views expressed by these participants are often contrarian to current thinking about gender and leadership but underline the gendered nature of persistent barriers to executive leadership past and present.
Recent Advance in Polymer Coatings Combating Bacterial Adhesion and Biofilm Formation†
Authors: Chu Xiaotang , Yang Fangping , Tang Haoyu
Published: September 2022

Comprehensive Summary

Implantable medical device‐associated infections (DAIs) originating from bacterial adhesion and biofilm formation have threatened to the health and life of patients. Antibacterial polymer coatings with antifouling and/or bactericidal properties have showed great potentials to combat DAI issues. In this review, we report recent advances in antibacterial polymer coatings fighting bacterial adhesion and biofilm formation on implantable biomaterial surfaces. We summarize the mechanisms of bacterial adhesion and biofilm formation, which provides guidance for the design of antibacterial coatings. We describe the polymer and coating preparation methods and discuss the structure‐property relationships of antibacterial polymer coatings. Applications of these polymer coatings in medical catheters, orthopaedic implants, and other applications are elaborated. Future challenges and prospects associated with antibacterial polymer coatings for implantable medical devices are discussed.
Drug‐Drug Interactions With the Hepatitis B Virus Capsid Assembly Modulator JNJ‐56136379 (Bersacapavir)
Authors: Vandenbossche Joris , Yogaratnam Jeysen , Hillewaert Vera , Rasschaert Freya , Talloen Willem , Biewenga Jeike , Snoeys Jan , Kakuda Thomas N. , Palmer Martyn , Nangosyah Julius , Biermer Michael
Published: September 2022

The capsid assembly modulator JNJ‐56136379 (bersacapavir) disrupts hepatitis B virus replication. It is metabolized via cytochrome P450 (CYP) 3A, but little is known about the drug‐drug interactions of JNJ‐56136379 when combined with drugs that inhibit or are metabolized by CYP3A. In a phase 1, open‐label trial (NCT03945539), healthy adults received 1 dose of JNJ‐56136379 with and without 21 days of prior exposure to itraconazole 200 mg (CYP3A inhibitor). In a second phase 1, open‐label trial (NCT03111511), healthy women received 1 dose of drospirenone/ethinyl estradiol and midazolam before and after 15 days of JNJ‐56136379. Itraconazole increased the area under the plasma concentration–time curve (AUC) of JNJ‐56136379 by 38%. JNJ‐56136379 reduced the maximum observed concentration and AUC of midazolam (CYP3A substrate) by 42%–54%, increased AUC of ethinyl estradiol by 1.6‐fold, but had no effect on drospirenone pharmacokinetics. Overall, these results demonstrated that a strong CYP3A inhibitor (itraconazole) modestly increased JNJ‐56136379 exposure. Furthermore, JNJ‐56136379 was a weak inducer of CYP3A (midazolam) and increased ethinyl estradiol exposure; coadministration of high‐dose estrogen‐based contraceptives and JNJ‐56136379 is not recommended.
Identification of Electrochemically Adsorbed Species via Electrochemical Microcalorimetry: Sulfate Adsorption on Au(111)
Authors: Schönig Marco , Frittmann Stefan , Schuster Rolf
Published: September 2022

The front cover artwork is provided by Dr. Marco Schönig from Prof. Rolf Schuster's group at the Karlsruhe Institute of Technology. The image shows a gold surface under electrochemical control covered by two different, unspecified adsorbed species. In the inset, we present the result of our heat of reaction measurements, which showed that for Au(111) in sulfuric acid solutions the adsorbing anionic species is sulfate. Read the full text of the Research Article at 10.1002/cphc.202200227.