bluuebunny/crossref_metadata_2025 huggingface dataset:
Synthesis of a 2,5‐Bis(tert‐butyldimethylsilyloxy)furan and its Reaction with Benzyne
Authors: Budwitz Jessica E. , Newton * Christopher G.
Published: August 2024

This chapter presents the procedure for synthesis of a 2,5‐bis(tert‐butyldimethylsilyloxy)furan and its reaction with benzyne. Ring forming strategies for para‐hydro‐ and para‐benzoquinone synthesis include the Wulff–Dötz reaction, Moore–Liebeskind rearrangement, Hauser–Kraus annulation, oxidative Bergman cyclization, and variants of the Diels–Alder reaction utilizing oxygenated furans as dienes. In analogy to the ring‐opening chemistry of 2‐oxy‐substituted furans, treatment of the cycloadducts with aqueous NaF provided the corresponding para‐hydroquinones in up to 98% yield. Conceptually, these furans can be considered as vicinal bisketene equivalents for application as dienes in the Diels–Alder reaction. Representative para‐hydroquinones synthesized from 2,5‐bis(tert‐butyldimethylsilyloxy)furan include indole, silyl enol ether, and BiPhePhos‐inspired derivative. Reaction with acetylenic dienophiles yield the corresponding para‐benzoquinones (with no evidence for para‐hydroquinone formation), and illustrative examples prepared by reaction with arynes.
Discussion Addendum for: Indium‐Catalyzed Heteroaryl–Heteroaryl Bond Formation through Nucleophilic Aromatic Substitution: Preparation of 2‐Methyl‐3‐(thien‐2‐yl)‐1H‐indole
Authors: Tsuchimoto Teruhisa
Published: August 2024

One of the most frequently utilized strategies for constructing bonds on heteroaryl scaffolds is transition metal catalysis, where diverse types of bonds can now be constructed on heteroaryl rings. Another option for functionalizing heteroaryl rings is the nucleophilic aromatic substitution reaction. The C–C bond cleavage is observed during the indium‐catalyzed three‐component alkylation of pyrroles or indoles with alkynes or carbonyl compounds and nucleophiles. The electron‐rich compound that is next focused on is an amine, thereby allowing the synthesis of a broad range of heteroarylamines. This chapter describes Nitrogen–Heteroaryl Bond‐Forming reaction followed by Carbon–Heteroaryl Bond‐Forming Annulation. The chemistry of the indium–heteroarene π‐complex can be further applied to a distinct type of reaction: indium‐catalyzed formal N‐arylation and N‐alkylation of pyrroles. This transformation involves a unique nitrogen–nitrogen exchange strategy, or in other words, a pyrrole‐ring opening–closing strategy.
Preparation of 4‐(5‐(p‐Tolyl)‐3‐(trifluoromethyl)‐1H‐pyrazol‐1‐yl)benzenesulfonyl fluoride (ArSO
2
F)
Authors: Wagner Lucas , Ghiazza Clément , Cornella Josep
Published: August 2024

This chapter presents the procedure for preparation of 4‐(5‐(p‐Tolyl)‐3‐(trifluoromethyl)‐1H‐pyrazol‐1‐yl)benzenesulfonyl fluoride. Sulfonyl fluorides are highly coveted compounds by practitioners of both medicinal chemistry and chemical biology. Importantly, aryl sulfonyl fluorides are particularly stable towards hydrolysis compared to their chlorinated analogues, thus paving the way for a plethora of applications in biological domains. For instance, sulfonyl chlorides are particularly attractive as they readily react with simple fluoride sources. It should be mentioned that sulfonyl chlorides are highly unstable towards hydrolysis, thus prohibiting the widespread use of this strategy. As sulfonamides are usually made from the parent sulfonyl chloride or fluoride, one can consider this approach counter‐intuitive. However, the chemical stability of sulfonamides enables their incorporation at the early stages of a synthetic route and can be therefore regarded as a masked handle to selectively prepare bio‐relevant sulfonyl fluorides.
Advances in the Science and Engineering of Metal Matrix Nanocomposites: A Review
Authors: Cao Chezheng , Killips Alexander , Li Xiaochun
Published: August 2024

Metal matrix nanocomposites (MMNCs) are an emerging class of metals with nanosized reinforcements and have been investigated extensively in recent decades due to their promising properties for widespread applications such as aerospace, automotive, biomedical, and electronics. In this article, a comprehensive review is presented on the science and engineering aspects of MMNCs, especially the processing, microstructures, and properties of MMNCs. Common processing and manufacturing approaches and post‐processing of MMNCs are discussed. Recent advances in the unusual mechanical, physical, and chemical properties of MMNCs are reviewed. Furthermore, the latest progress on the fundamental study of interactions between nanoparticles and metals, including dispersion, pushing, and engulfment during solidification, nucleation, and phase control, is presented. It is worth noting that the exciting opportunities of nanotechnology‐enabled metallurgy (nanotech metallurgy), which have grown out of the domain of MMNCs recently, are also presented briefly.
Outstanding Room‐Temperature Thermoelectric Performance of n‐type Mg3Bi2‐Based Compounds Through Synergistically Combined Band Engineering Approaches
Authors: Cho Hyunyong , Back Song Yi , Sato Naoki , Liu Zihang , Gao Weihong , Wang Longquan , Nguyen Hieu Duy , Kawamoto Naoyuki , Mori Takao
Published: August 2024

Thermoelectric cooling materials based on Bi2Te3 have a long history of unsurpassed performance near room temperature. Recently, research into price‐competitive Mg3(Bi, Sb)2‐based materials are focused on replacing traditional cooling materials. Here, the thermoelectric properties of Mg3.2Bi1.998−xSbxTe0.002Cu0.005 (x = 0.0, 0.1, 0.2, 0.3, 0.4, and 0.5) polycrystalline compounds are investigated. In all temperature regions, electrical resistivity and Seebeck coefficient are increased with Sb concentration. The electronic transport properties of Sb‐alloyed compounds are maximized by synergistically combined band engineering approaches such as band structure change caused by lattice strain, increased electronic density of states, and chemical potential shift, leading to exceptionally high‐power factor values of over 3.0 mW m−1 K−2 at room temperature. Furthermore, with increasing Sb content, thermal conductivity values are systematically reduced due to the promotion of alloy scattering of phonons and suppression of the bipolar contribution. Consequently, these multiple approaches significantly enhance thermoelectric performance, resulting in an enhancement of thermoelectric figure‐of‐merit zT above 1.1 at 348–423 K. Additionally, a zTavg of 1.1 is recorded at 300–450 K, making it an unrivaled value among the reported n‐type Mg3Bi2‐based thermoelectric materials. Overall, this work demonstrates that Mg3Bi2‐based materials are more promising for thermoelectric cooling applications compared to Bi2Te3‐based materials.
Photodetector Array Based on Perovskite Thin Film Enhanced by Thioacetamide for Imaging and Integrated In‐Sensor Encryption
Authors: He Zhenhui , Liu Zhanwei , Luo Xuehu , Chen Yanting , Ruan Yuhao , Lei Dengyun , Cai Shuting , Li Guijun , Kwok Hoi‐Sing , Zhang Jianfeng , Liu Yuan
Published: August 2024

With the growing number of sensor nodes at edge devices, it is critical to guarantee the security of private data transmitted over the Internet of Things (IoT), especially in image and video applications. Traditional software‐based encryption schemes are vulnerable to advanced attacks based on machine learning or quantum computing, leading to the exploration of hardware‐based solutions. This study proposes a novel in‐sensor encryption technique using a perovskite photodetectors (PDs) array to integrate image acquisition and encryption functions within a single hardware platform. The technique exploits the inherent physical disorder and randomness of perovskite PDs to provide an optimal source of entropy for the generation of cryptographic keys. The MAPbI3 perovskite PDs array is fabricated by a convenient method and passivated by thioacetamide (TAA) to improve the performance in photoresponsivity, response time, spectra response, and stability, enabling sensitive imaging and reliable key generation. The improved perovskite PDs array exhibits remarkable optoelectronic properties and stability, highlighting its potential for in‐sensor encryption and the creation of trustworthy hardware security systems for imaging terminals.
Asymmetric [3+3] Cycloaddition of N‐Vinyl Oxindole Nitrones with 2‐Indolylmethanols to Prepare Spirooxindole[1,2]oxazines
Authors: Zou Ning , Wu Yu‐Zheng , Zhong Xin‐Yi , Wei Cui , Liao Li‐Min , Mo Dong‐Liang , Zhou Wen‐Jun
Published: August 2024

We describe a chiral phosphoric acid (CPA) catalyzed asymmetric [3+3] cycloaddition of N‐viny oxindole nitrones with 2‐indolylmethanols to prepare various spirooxindole[1,2]oxazines in 43–93% yields and 88:12–97:3 enantiomeric ratios. Experimental results revealed that the addition of hexafluoroisopropanol (HFIP) played important roles to help CPA control the reaction reactivity and enantioselectivity. The present method features the construction of a tetrasubstituted chiral carbon stereocenter and the example of N‐vinyl nitrones in asymmetric [3+3] cycloaddition.
The immediate metabolomic effects of whole‐genome duplication in the greater duckweed, Spirodela polyrhiza
Authors: Wu Tian , Bafort Quinten , Mortier Frederik , Almeida‐Silva Fabricio , Natran Annelore , Van de Peer Yves
Published: August 2024

Premise

In plants, whole‐genome duplication (WGD) is a common mutation with profound evolutionary potential. Given the costs associated with a superfluous genome copy, polyploid establishment is enigmatic. However, in the right environment, immediate phenotypic changes following WGD can facilitate establishment. Metabolite abundances are the direct output of the cell's regulatory network and determine much of the impact of environmental and genetic change on the phenotype. While it is well known that an increase in the bulk amount of genetic material can increase cell size, the impact of gene dosage multiplication on the metabolome remains largely unknown.

Methods

We used untargeted metabolomics on four genetically distinct diploid‐neoautotetraploid pairs of the greater duckweed, Spirodela polyrhiza, to investigate how WGD affects metabolite abundances per cell and per biomass.

Results

Autopolyploidy increased metabolite levels per cell, but the response of individual metabolites varied considerably. However, the impact on metabolite level per biomass was restricted because the increased cell size reduced the metabolite concentration per cell. Nevertheless, we detected both quantitative and qualitative effects of WGD on the metabolome. Many effects were strain‐specific, but some were shared by all four strains.

Conclusions

The nature and impact of metabolic changes after WGD depended strongly on the genotype. Dosage effects have the potential to alter the plant metabolome qualitatively and quantitatively, but were largely balanced out by the reduction in metabolite concentration due to an increase in cell size in this species.
Amyloid PET disclosure in subjective cognitive decline: Patient experiences over time
Authors: Hendriksen Heleen M. A. , de Rijke Tanja J. , Fruijtier Agnetha , van de Giessen Elsmarieke , van Harten Argonde C. , van Leeuwenstijn‐Koopman Mardou S. S. A. , van der Schaar Jetske , Trieu Calvin , Visser Denise , Smets Ellen M. A. , Visser Leonie N. C. , van der Flier Wiesje M.
Published: August 2024

INTRODUCTION

We disclosed amyloid positron emission tomography (PET) results in individuals with subjective cognitive decline (SCD) and studied patient experiences and outcomes over a 6‐month period.

METHODS

Fifty‐seven participants from the Subjective Cognitive Impairment Cohort (SCIENCe) (66 ± 8 years, 21 [37%] F, Mini‐Mental State Examination 29 ± 1, 15 [26%] amyloid positive [A+]) completed questionnaires 1 week prior (T0), 1 day after (T1), and 6 months after amyloid PET disclosure (T2). Questionnaires addressed patient‐reported experiences and outcomes.

RESULTS

Independent of amyloid status, participants were satisfied with the consultation (scale 1–10; 7.9 ± 1.7) and information provided (scale 1–4; T1: 3.3 ± 0.9, T2: 3.2 ± 0.8). After 6 months, A+ participants reported more information needs (45% vs. 12%, p = 0.02). Independent of amyloid status, decision regret (scale 1–5; A+: 1.5 ± 0.9, A−: 1.4 ± 0.6, p = 0.53) and negative emotions (negative affect, uncertainty, anxiety) were low (all p > 0.15 and Pinteraction > 0.60).

DISCUSSION

Participants with SCD valued amyloid PET disclosure positively, regardless of amyloid status. The need for information after 6 months, which was stronger in A+ individuals, underscores the importance of follow‐up.

Highlights

Participants with subjective cognitive decline (SCD) positively valued amyloid positron emission tomography (PET) disclosure.

Participants with SCD experienced low levels of decision regret.

We did not observe an increase in negative emotions.

After 6 months, amyloid‐positive individuals wanted more information.
Photothermal Synergistic Effect Induces Bimetallic Cooperation to Modulate Product Selectivity of CO2 Reduction on Different CeO2 Crystal Facets
Authors: Ren Yuqi , Si Yitao , Du Mingyue , You Changjun , Zhang Chunyang , Zhu Yuan‐Hao , Sun Zhenkun , Huang Kai , Liu Maochang , Duan Lunbo , Li Naixu
Published: August 2024

Product selectivity of solar‐driven CO2 reduction and H2O oxidation reactions has been successfully controlled by tuning the spatial distance between Pt/Au bimetallic active sites on different crystal facets of CeO2 catalysts. The replacement depth of Ce atoms by monatomic Pt determines the distance between bimetallic sites, while Au clusters are deposited on the surface. This space configuration creates a favourable microenvironment for the migration of active hydrogen species (*H). The *H is generated via the activation of H2O on monatomic Pt sites and migrate towards Au clusters with a strong capacity for CO2 adsorption. Under concentrated solar irradiation, selectivity of the (100) facet towards CO is 100 %, and the selectivity of the (110) and (111) facets towards CH4 is 33.5 % and 97.6 %, respectively. Notably, the CH4 yield on the (111) facet is as high as 369.4 μmol/g/h, and the solar‐to‐chemical energy efficiency of 0.23 % is 33.8 times higher than that under non‐concentrated solar irradiation. The impacts of high‐density flux photon and thermal effects on carriers and *H migration at the microscale are comprehensively discussed. This study provides a new avenue for tuning the spatial distance between active sites to achieve optimal product selectivity.
High‐Throughput Absorbance‐Activated Droplet Sorting for Engineering Aldehyde Dehydrogenases
Authors: Jain Ankit , Teshima Mariko , Buryska Tomas , Romeis Dennis , Haslbeck Magdalena , Döring Manuel , Sieber Volker , Stavrakis Stavros , de Mello Andrew
Published: August 2024

Recent decades have seen a dramatic increase in the commercial use of biocatalysts, transitioning from energy‐intensive traditional chemistries to more sustainable methods. Current enzyme engineering techniques, such as directed evolution, require the generation and testing of large mutant libraries to identify optimized variants. Unfortunately, conventional screening methods are unable to screen such large libraries in a robust and timely manner. Droplet‐based microfluidic systems have emerged as a powerful high‐throughput tool for library screening at kilohertz rates. Unfortunately, almost all reported systems are based on fluorescence detection, restricting their use to a limited number of enzyme types that naturally convert fluorogenic substrates or require the use of surrogate substrates. To expand the range of enzymes amenable to evolution using droplet‐based microfluidic systems, we present an absorbance‐activated droplet sorter that allows droplet sorting at kilohertz rates without the need for optical monitoring of the microfluidic system. To demonstrate the utility of the sorter, we rapidly screen a 105‐member aldehyde dehydrogenase library towards D‐glyceraldehyde using a NADH mediated coupled assay that generates WST‐1 formazan as the colorimetric product. We successfully identify a variant with a 51 % improvement in catalytic efficiency and a significant increase in overall activity across a broad substrate spectrum.
Influence of monomer structure and catalyst concentration on topological transition and dynamic properties of dicarboxylic acid‐epoxy vitrimers
Authors: Shen Shouqi , Thakur Vijay K. , Skordos Alexandros A.
Published: August 2024

This study delineates the dependence of thermophysical behavior of acid‐epoxy vitrimers on their formulation. The stress relaxation due to the bond exchange reaction and the glass transition temperature of acid epoxy vitrimers are investigated, with respect to the influence of catalyst content and acid chain length. This is carried out for a range of dicarboxylic acids and catalyst concentrations formulated and characterized using calorimetry and dynamic mechanical analysis. The influence of acid chain length on the bond exchange rate, topological transition, and glass transition temperatures of the vitrimers is found to be significant. The activation energy of the exchange reaction varies over a wide range from 73 to 104 kJ/mol and the topology freezing temperature from 66 to 136°C with the behavior governed by the interplay between crosslinking density, network flexibility and density and distance of functional groups, with an increase of catalyst concentration leading to lower topological transition temperature and the dependence on chain length showing non‐monotonic behavior. The glass transition decreases by about 30°C as the carbon chain length increases from 6 to 14 carbons due to enhanced monomer flexibility and is not affected by the concentration of catalyst.
Exploration of cytotoxicity of iodoquinazoline derivatives as inhibitors of both VEGFR‐2 and EGFRT790M: Molecular docking, ADMET, design, and syntheses
Authors: Alsulaimany Marwa , El‐Hddad Sanadelaslam S. A. , Akrim Zuhir S. M. , Aljohani Ahmed K. B. , Almohaywi Basmah , Alatawi Omar M. , Almadani Sara A. , Alharbi Hussam Y. , Aljohani Majed S. , Miski Samar F. , Alghamdi Read , El‐Adl Khaled
Published: August 2024

Novel inhibitors of epidermal growth factor receptor (EGFR)T790M/vascular endothelial growth factor receptor‐2 (VEGFR‐2) were synthesized based on the iodoquinazoline scaffold linked to different heteroaromatic, aromatic, and/or aliphatic moieties. The novel derivatives were in vitro examined for anticancer activities against A549, HCT116, michigan cancer foundation‐7 (MCF‐7), and HepG2 cells. Molecular modeling was applied to discover their orientation of binding with both VEGFR‐2 and EGFR active sites. Compounds 8d, 8c, 6d, and 6c indicated the highest cytotoxicity with IC50 = 6.00, 6.90, 6.12 and 6.24 µM, 7.05, 7.35, 6.80, and 6.80 µM, 5.75, 7.50, 6.90, and 6.95 µM, and 6.55, 7.88, 7.44, and 7.10 µM against the A549, HepG2, HCT116, and MCF‐7 cell lines, correspondingly. The cytotoxicity against normal VERO (normal african green monkey kidney cells) of the extremely active eight compounds 6a–d and 8a–d was evaluated. Our compounds exhibited low toxicity concerning normal VERO cells with IC50 = 45.66–51.83 μM. Furthermore, inhibition assays for both the EGFRT790M and VEGFR‐2 enzymes were done for all compounds. Remarkable inhibition of EGFRT790M activity was achieved with compounds 6d, 8d, 6c, and 8c at IC50 = 0.35, 0.42, 0.48, and 0.50 µM correspondingly. Moreover, remarkable inhibition of VEGFR‐2 activity was achieved with compounds 8d, 8c, 6d, and 6c at IC50 = 0.92, 0.95, 1.00, and 1.20 µM correspondingly. As planned, derivatives 6d, 8d, 6c, and 8c presented exceptional inhibition of both EGFRT790M/VEGFR‐2 activities. Finally, in silico absorption, distribution, metabolism, excretion and toxicity (ADMET) studies were made for the highly active four compounds 6c, 6d, 8c, and 8d in comparison with erlotinib and sorafenib as reference standards.
Features Associated With Different Inflammatory Phenotypes of Calcium Pyrophosphate Deposition Disease: A Study Using Data From the International American College of Rheumatology/EULAR Calcium Pyrophosphate Deposition Classification Criteria Cohort
Authors: Pascart Tristan , Latourte Augustin , Tedeschi Sara K. , Dalbeth Nicola , Neogi Tuhina , Adinolfi Antonella , Arad Uri , Andres Mariano , Becce Fabio , Bardin Thomas , Cipolletta Edoardo , Ea Hang‐Korng , Filippou Georgios , Filippucci Emilio , FitzGerald John , Iagnocco Annamaria , Jansen Tim L. , Janssen Matthijs , Lioté Frédéric , So Alexander , McCarthy Geraldine M. , Ramonda Roberta , Richette Pascal , Rosenthal Ann , Scirè Carlo , Silvagni Ettore , Sirotti Silvia , Sivera Francisca , Stamp Lisa K. , Taylor William J. , Terkeltaub Robert , Choi Hyon K. , Abhishek Abhishek
Published: August 2024

Objective

The study objective was to examine the disease, demographic, and imaging features associated with different inflammatory phenotypes of calcium pyrophosphate deposition (CPPD) disease, ie, recurrent acute calcium pyrophosphate (CPP) crystal arthritis, chronic CPP crystal inflammatory arthritis, and crowned dens syndrome (CDS).

Methods

Data from an international cohort (assembled from 25 sites in 7 countries for the development and validation of the 2023 CPPD classification criteria from the American College of Rheumatology/EULAR) that met the criteria were included. Three cross‐sectional studies were conducted to determine the phenotypic characteristics of recurrent acute CPP crystal arthritis, chronic CPP crystal inflammatory arthritis, and CDS. Multivariable logistic regression analysis was used to calculate adjusted odds ratio (aOR) and 95% confidence interval (CI) to examine the association between potential risk factors and the inflammatory phenotype.

Results

Among the 618 people included (56% female; mean age [standard deviation] 74.0 [11.9] years), 602 (97.4%) had experienced acute CPP crystal arthritis, 332 (53.7%) had recurrent acute arthritis, 158 (25.6%) had persistent inflammatory arthritis, and 45 (7.3%) had had CDS. Recurrent acute CPP crystal arthritis associated with longer disease duration (aOR 2.88 [95% CI 2.00–4.14]). Chronic CPP crystal inflammatory arthritis was associated with acute wrist arthritis (aOR 2.92 [95% CI 1.81–4.73]), metacarpophalangeal joint osteoarthritis (aOR 1.87 [95% CI 1.17–2.97]), and scapho‐trapezo‐trapezoid (STT) joint osteoarthritis (aOR 1.83 [95% CI 1.15–2.91]), and it was negatively associated with either metabolic or familial risk for CPPD (aOR 0.60 [95% CI 0.37–0.96]). CDS was associated with male sex (aOR 2.35 [95% CI 1.21–4.59]), STT joint osteoarthritis (aOR 2.71 [95% CI 1.22–6.05]), and more joints affected with chondrocalcinosis (aOR 1.46 [95% CI 1.15–1.85]).

Conclusion

CPPD disease encompasses acute and chronic inflammatory phenotypes, each with specific clinical and imaging features that need to be considered in the diagnostic workup.
Bisphenol A in Water Systems: Risks to Polycystic Ovary Syndrome and Biochar‐Based Adsorption Remediation: A Review
Authors: Michenzi Cinzia , Myers Samuel H. , Chiarotto Isabella
Published: August 2024

Access to clean and safe water sadly remains an issue in the 21st century. Water reservoirs, whether groundwater or surface water, are routinely contaminated by various harmful Emerging Contaminants (ECs). One of most prevalent pollutants among these pollutants is Bisphenol A, which is classified as an Endocrine Disrupting Compound (EDC). This substance adversely interferes with the endocrine system, primarily by mimicking estrogen, and has been considered a potential contributor to Polycystic Ovary Syndrome (PCOS) with 82.70 % of 1,391 women studied showing a positive correlation between BPA exposure and PCOS. PCOS is currently the most prevalent endocrine disorder affecting women of reproductive age; however, its pathogenesis remains unclear, complicating diagnosis and subsequently patient care. In this review, these topics are thoroughly examined, with particular emphasis on biochar, a new promising method for large‐scale water purification. Biochar, derived from various organic waste materials, has emerged as a cost‐effective substance with remarkable adsorption properties achieving up to 88 % efficiency over four cycles of reuse, similar to that of activated carbon. This review interrogates the suitability of biochar for counteracting the issue of EDC pollutants.
Advances in Evolved T7 RNA Polymerases for Expanding the Frontiers of Enzymatic Nucleic Acid Synthesis
Authors: Shu Liu , Yang Lijuan , Nie Zhou , Lei Chunyang
Published: August 2024

In vitro RNA synthesis technologies are crucial in developing therapeutic RNA drugs, such as mRNA vaccines and RNA interference (RNAi) therapies. Enzymatic RNA synthesis, recognized for its sustainability and efficiency, enables the production of extensive RNA sequences under mild conditions. Among the enzymes utilized, T7 RNA polymerase is distinguished by its exceptional catalytic efficiency, enabling the precise and rapid transcription of RNA from DNA templates by recognizing the specific T7 promoter sequence. With the advancement in clinical applications of RNA‐based drugs, there is an increasing demand for the synthesis of chemically modified RNAs that are stable and resistant to nuclease degradation. To this end, researchers have applied directed evolution to broaden the enzyme's substrate scope, enhancing its compatibility with non‐canonical substrates and reducing the formation of by‐products. This review summarizes the progress in engineering T7 RNA polymerase for these purposes and explores prospective developments in the field.
Atypical posterior reversible encephalopathy syndrome: A lentiform fork sign following transplantation
Authors: Appiani Franco E. , Claverie Carlos S. , Klein Francisco R.
Published: August 2024

Key Clinical Message

Posterior Reversible Encephalopathy Syndrome, typically characterized by parieto‐occipital vasogenic edema, can present atypically, as a bilateral symmetrical vasogenic edema in the basal ganglia, featuring the called “lentiform fork sign.” Prompt recognition of such variations is crucial for accurate diagnosis and tailored management, highlighting the complexity of this syndrome's manifestations.

Posterior Reversible Encephalopathy Syndrome (PRES) manifests as transient neurological symptoms and cerebral edema, commonly associated with immunosuppressive drugs (ISDs) in transplant recipients. ISDs can lead to endothelial dysfunction and compromise the blood–brain barrier. Typically, PRES exhibits identifiable MRI patterns, often demonstrating vasogenic edema in the bilateral parieto‐occipital white matter. Identifying unique presentations, such as the recently observed “lentiform fork sign,” commonly seen in uremic encephalopathy, emphasizes this syndrome's broad spectrum manifestations. A 19‐year‐old male, who underwent bilateral lung and liver transplantation, experienced a bilateral tonic–clonic seizure of unknown onset 47 days post‐surgery. MRI findings revealed an unconventional PRES pattern, featuring the “lentiform fork sign” as bilateral symmetrical vasogenic edema in the basal ganglia, surrounded by a hyperintense rim outlining the lentiform nucleus bilaterally. Subsequent management, including ISD modification and magnesium supplementation, resulted in clinical and neuroimaging resolution. An almost complete clinical and radiological resolution was achieved after 14 days. The occurrence of PRES in transplant recipients highlights the intricate interplay among ISDs, physiological factors, and cerebrovascular dynamics, potentially involving direct neurovascular endothelial toxicity and disruption of the blood–brain barrier. Neuroimaging plays a pivotal role in diagnosis. The distinctive “lentiform fork sign” was observed in this patient despite the absence of typical metabolic disturbances. Management strategies usually involve reducing hypertension, discontinuing ISDs, correcting electrolyte imbalances, and initiating antiseizure drugs if necessary. Identifying the presence of the “lentiform fork sign” alongside typical PRES edema in a patient lacking renal failure emphasizes that this manifestation is not solely indicative of uremic encephalopathy. Instead, it might represent the final common pathway resulting from alterations in the blood–brain barrier integrity within the deep white matter. Understanding such atypical imaging manifestations could significantly aid earlier and more precise diagnosis, influencing appropriate management decisions.
An unusual presentation of orbital encephalocele following a self‐inflicted gunshot wound injury: A case report and literature review
Authors: Levine Marc , Noel Olivier F. , Patel Shivam , Park Haejoe , Weller Christopher L. , Lighthall Jessyka G.
Published: August 2024

Key Clinical Message

While orbital encephaloceles secondary to orbital roof fractures, in the setting of gunshot wound injuries, are rare, it is important to discuss diagnosis, treatment, and outcomes. This comprehensive manuscript aims to accomplish these objectives.
Hypokalemic quadriplegia in Sjogren's syndrome: A case report
Authors: Mehdipour Dalivand Mahsa , Abdolazimi Rezvan , Alikhani Majid
Published: August 2024

Key Clinical Message

In managing Sjogren's syndrome, a thorough patient history, proper lab tests, and imaging are crucial. Clinicians should prioritize checking electrolyte levels in cases of muscle weakness, as early detection of hypokalemia can prevent severe complications. Proactive monitoring can avert renal tubular acidosis and improve patient outcomes.

Distal renal tubular acidosis (dRTA) occurs in approximately one‐third of patients with Sjogren's syndrome, a systemic autoimmune disorder characterized by lymphocytic infiltration of exocrine glands, leading to dryness of mucous membranes. Hypokalemic paralysis, a well‐documented but rare complication of dRTA, typically manifests as symmetric proximal muscle weakness of the extremities. We present the case of a 38‐year‐old woman with a history of Sjogren's syndrome diagnosed 3 years prior, who ceased her medication without medical supervision. She presented with quadriplegia, initially beginning unilaterally. This particular presentation is seldom documented in the literature. Laboratory investigations revealed hypokalemia and normal anion gap metabolic acidosis, consistent with dRTA‐induced hypokalemic paralysis. Intravenous potassium chloride was administered, resulting in complete recovery of muscle strength. Hypokalemic paralysis associated with dRTA is typically reversible; however, delays in diagnosis and treatment can lead to life‐threatening complications such as respiratory failure and arrhythmias. Therefore, clinicians should maintain a high index of suspicion for this condition in patients presenting with muscle weakness. Prompt and precise history takingand screening, and initiating appropriate management to prevent adverse outcomes.
The efficacy of the novel “wall pierce” technique for common femoral access in endovascular therapy
Authors: Mori Shinsuke , Kobayashi Norihiro , Tsutsumi Masakazu , Ito Yoshiaki
Published: August 2024

Key Clinical Message

Under challenging common femoral artery access scenarios, the “wall PIERCE” technique, which utilizes a larger puncture needle to pierce the vessel wall along the guidewire, facilitates sheath insertion. This method proved successful in two cases without any complications, presenting a valuable addition to strategies for addressing challenging sheath insertion scenarios.
Improvement of Asymmetric Reactions via Remote Electronic Tuning of N‐Heterocyclic Carbene Catalysts
Authors: Inokuma Tsubasa , Yamada Ken‐ichi
Published: August 2024

Aminoindanol‐derived N‐heterocyclic carbene catalysts have been widely used to achieve highly enantioselective reactions. Recently, substitution at the indane moiety of the catalysts has been found to have a great impact on the outcome of some reactions, even though the substituted position is distant from the carbene catalytic center. Especially, the introduction of an electron‐withdrawing group improves the yield and enantioselectivity. This review provides an overview of recent reports on the improvement of N‐heterocyclic‐carbene‐catalyzed asymmetric reactions by introducing electron‐withdrawing remote substituents.
A Highly Efficient Cross‐Coupling Mode via the Release of Small Molecules: Transition Metal‐Catalyzed Unimolecular Fragment Coupling (UFC)
Authors: Tian Tian , Uei Shuhei , Li Zhiping , Nishihara Yasushi
Published: August 2024

As a recently developed redox‐neutral coupling reaction, transition‐metal‐catalyzed unimolecular fragment coupling (UFC) has been extensively investigated over the past decade. In comparison to conventional cross‐coupling reactions, cross‐electrophilic coupling (XEC) and cross‐dehydrogenative coupling (CDC) protocols eliminate the need for stoichiometric organometallic reagents, reductants, or oxidants. Additionally, it produces only minimal molecular by‐products for the formation of a series of C−C bonds and C−X bonds with high atom efficiency. This review presents a summary and classification of the research progress made over the past decade in this field. The research is classified into four main categories, decarbonylation, decarboxylation, desulfonylation, and deisocyanation, according to the type of small molecule that is liberated from the reaction system. This facilitates the implementation of more practical, straightforward, and expedient reaction operations. It is noteworthy that the reaction employs carbonyl compounds (aldehydes, ketones, carboxylic acid derivatives, etc.), sulfones, and amides, which are typically inexpensive and accessible, as reaction substrates. This groundbreaking synthetic approach has since yielded a plethora of outcomes and novel research avenues in related fields, while also offering benefits to other related fields.
Copper‐Polyphenol Nanocomplexes with Peroxidase‐Like Activity for Enhanced Fungal Eradication
Authors: Liu Fang , Chen Yongcheng , Huang Yue , Jin Qiao
Published: August 2024

The increasing severity of fungal infections globally and the limited availability of effective treatments necessitate novel therapeutic strategies. In this study, we prepared copper‐polyphenol nanocomplexes (CPE NPs) through a one‐step synthetic process by the coordination self‐assembly of copper sulfate (CuSO4), protocatechuic acid (PA), and ϵ‐poly‐L‐lysine (EPL). CPE NPs demonstrated peroxidase‐like activities, which could catalyze H2O2 to generate hydroxyl radicals (⋅OH) to effectively eradicate fungi. CPE NPs were stable in a physiological neutral environment. However, since metal‐phenolic coordination interaction was unstable in acidic pH, CPE NPs could be dissociated in acidic environments, such as fungal infection sites, leading to effective release of Cu2+ and EPL, thereby exerting antifungal effects. CPE NPs exhibited excellent fungicidal ability at both pH 7.4 and 6.0 against Candida albicans and Aspergillus flavus. More importantly, CPE NPs could effectively eradicate fungi in 20 % Sabouraud dextrose broth (SDB) medium containing rich inorganic salts and proteins, in which dissociative Cu2+ completely lost its fungicidal ability. In summary, CPE NPs could effectively deliver Cu2+ to fungal surface for enhanced fungal eradication by generating ⋅OH, highlighting their great potential as a promising nano‐therapeutic agent for the treatment of fungal infections.
Ultrathin (15 nm) Carbon Sheets with Surface Oxygen Functionalization for Efficient Pseudocapacitive Na‐ion Storage
Authors: Etacheri Vinodkumar , Maça Rudi Ruben , Avvaru Venkata Sai , Hong Chulgi Nathan , Alazemi Abdullah , Pol Vilas G.
Published: August 2024

Disordered carbon is the state of the art anode material for Na‐ion batteries due to their increased interlayer spacing and good electronic conductivity. However, its practical application is hindered by average specific capacity, poor rate performance, low coulombic efficiency and limited cycling stability. Herein, we report the superior pseudocapacitance enhanced Na‐ion storage of in situ surface functionalized carbon nanosheets. Anodes composed of ultrathin (~15 nm) carbon nanosheets demonstrated excellent reversible specific capacity (375 mAh/g at 25 mA/g), rate performance (150 mAh/g at 2 A/g), long‐term cycling performance (1000 cycles at 1 A/g) and coulombic efficiency (~100 %). Considerably higher pseudocapacitance (up to ~78 %) is also identified in this case compared to amorphous carbon particles. Spectroscopic and electrochemical studies proved Na‐ion intercalation in to the disordered carbon and pseudocapacitive storage driven by oxygen‐containing surface functional groups. Outstanding electrochemical performance is credited to the synergy between diffusion limited intercalation and pseudocapacitive surface Na‐ion storage. The demonstrated synthetic method of in situ functionalized carbon nanosheets is inexpensive and scalable. The strategy of functional group and morphology induced pseudocapacitive Na‐ion storage offer new prospects to design high‐performance Na‐ion battery electrodes.
Unraveling the Role and Impact of Alumina on the Nucleation and Reversibility of β‐LiAl in Aluminum Anode Based Lithium‐Ion Batteries
Authors: Wells Lucas , Pham Thien An , Eshetu Gebrekidan Gebresilassie , Seidlmayer Stefan , Ceccio Giovanni , Cannavo Antonino , Vacík Jiří , Mikitisin Adrian , Müller‐Buschbaum Peter , Gilles Ralph , Figgemeier Egbert
Published: August 2024

Aluminum, due to its high abundance, very attractive theoretical capacity, low cost, low (de−) lithiation potential, light weight, and effective suppression of dendrite growth, is considered as a promising anode candidate for lithium‐ion batteries (LIBs). However, its practical application is hindered due to multiple detrimental challenges, including the formation of an amorphous surface oxide layer, pulverization, and insufficient lithium diffusion kinetics in the α‐phase. These outstanding intrinsic challenges need to be addressed to facilitate the commercial production of Al‐based batteries. The native passivation layer, Al2O3, plays a critical role in the nucleation and reversibility of lithiating aluminum and is thoroughly investigated in this study using high precision electrochemical micro calorimetry. The enthalpy of crystallization of β‐LiAl is found to be 40.5 kJ mol−1, which is in a strong agreement with the value obtained by calculation using Nernst equation (40.04 kJ mol−1). Surface treatment of the active material by the addition of 25 nm of alumina increases the nucleation energy barrier by 83 % over the native oxide layer. After the initial nucleation, the added alumina does not negatively impact the reversibility at 0.1 C rate, suggesting the removal of alumina is not necessary for improving the cyclability of aluminum anode based lithium‐ion batteries. Moreover, the coulombic efficiencies are also found to be slightly higher in the alumina treated samples compared to the untreated ones.
Methanol, the ICE Green Maker
Authors: Dobberkau Maximilian , Werner Ronny , Atzler Frank
Published: August 2024

Green methanol is a renewable fuel with great advantages when used in a spark ignition combustion process. Methanol has a comparatively high enthalpy of vaporization, leading to lower combustion temperatures as compared to gasoline combustion, and, hence, lower wall heat losses as well as a reduced tendency to pre‐ignition. Therefore, a brake efficiency of more than 40 % (this is comparable to diesel engines!) and furthermore minimal emissions, even at cold start, are possible. The serial combination with an electric powertrain provides a disconnection of the load demand of the powertrain and the operating point of the combustion engine. In this case, a high volumetric and gravimetric power density, easy energy storage and proven infrastructure of fuel distribution are combined with electric driving, high efficiencies, minimal emissions, and a closed carbon cycle for the energy provision.
Variable selection in modelling clustered data via within‐cluster resampling
Authors: Ye Shangyuan , Yu Tingting , Caroff Daniel A. , Huang Susan S. , Zhang Bo , Wang Rui
Published: August 2024

In many biomedical applications, there is a need to build risk‐adjustment models based on clustered data. However, methods for variable selection that are applicable to clustered discrete data settings with a large number of candidate variables and potentially large cluster sizes are lacking. We develop a new variable selection approach that combines within‐cluster resampling techniques with penalized likelihood methods to select variables for high‐dimensional clustered data. We derive an upper bound on the expected number of falsely selected variables, demonstrate the oracle properties of the proposed method and evaluate the finite sample performance of the method through extensive simulations. We illustrate the proposed approach using a colon surgical site infection data set consisting of 39,468 individuals from 149 hospitals to build risk‐adjustment models that account for both the main effects of various risk factors and their two‐way interactions.
Advancing Anode Performance in Aqueous Zinc‐Ion Batteries: A Review of Metal‐Organic Framework‐Based Strategies
Authors: Li Juanyun , Wang Bin , Wang Siyuan , Li Wenqi , Chen Ding
Published: August 2024

Aqueous zinc‐ion batteries (AZIBs) are garnering substantial research interest in electric vehicles, energy storage systems, and portable electronics, primarily for the reason that the inexpensive cost, high theoretical specific capacity, and environmental sustainability of zinc metal anodes, which are an essential component to their design. Nonetheless, the progress of AZIBs is hindered by significant obstacles, such as the occurrence of anodic side reactions (SR) and the formation of zinc dendrites. Metal‐organic framework (MOF)‐based materials are being explored as promising alternatives owing to homogeneous porous structure and large specific surface areas. There has been a rare overview and discussion on strategies for protecting anodes using MOF‐based materials. This review specifically aims to investigate cutting‐edge strategies for the design of highly stable MOF‐based anodes in AZIBs. Firstly, the mechanisms of dendrites and SR are summarized. Secondly, the recent advances in MOF‐based anodic protection including those of pristine MOFs, MOF composites, and MOF derivatives are reviewed. Furthermore, the strategies involving MOF‐based materials for zinc anode stabilization are presented, including the engineering of surface coatings, three‐dimensional zinc structures, artificial solid electrolyte interfaces, separators, and electrolytes. Finally, the ongoing challenges and prospective directions for further enhancement of MOF‐based anodic protection technologies in AZIBs are highlighted.
Design and Synthesis of Sb‐Doped CuS@C Hollow Nanocubes as Efficient Anode Materials for Sodium‐Ion Battery
Authors: Zheng Xiang , Zhang Zining , Li Zhiqian , Shi Chaohong , Zhao Jianqing , Tang Jing
Published: August 2024

Copper sulfide has received widespread attention for application as anode materials in sodium‐ion batteries due to their potent capabilitiess and eco‐friendly properties. However, it is a challenge to achieve a high rate capability and long cycle stability owing to the heterogeneous transfer of sodium ions during charge‐discharge, the interior poor electron conductivity and repeated volumetric expansion of copper sulfide. In this study, Sb‐doped copper sulfide hollow nanocubes coated with carbon shells (Sb‐CuS@C) was designed and constructed as anode nanomaterials in sodium‐ion batteries. Thanks to the intrinsic good electron conductivity and chemical stability of carbon shells, Sb‐CuS@C possesses a higher overall electron transfer as anode material, avoids agglomeration and structural destruction during the cycling. As a result, the synthesized Sb‐CuS@C achieved an excellent reversible capacity of 595 mA h g−1 after 100 cycles at 0.5 A g−1 and a good rate capability of 340 mA h g−1 at a higher 10 A g−1. DFT calculations clarify that the uniformly doped Sb would act as active sodiophilic nucleation sites to help adsorbing sodium‐ion during discharging and leading uniform sodium deposition. This work provides a new insight into the structural and componential modification for common transition‐metal sulfides towards application as anode materials in sodium‐ion battery.
Diversity of assessment practices and student perceptions of assessment in Finland
Authors: Nieminen Juuso Henrik , Atjonen Päivi , Tolvanen Asko
Published: August 2024

Educational policies and curriculum documents largely emphasise the idea that assessment should be diverse: that teachers should use versatile assessment practices such as tests, self‐ and peer‐assessment and portfolios instead of mainly drawing on uniform practices, such as examinations. In this study, we examined the diversity of assessment in the low‐stakes assessment culture of Finland where the national curriculum emphasises the ethos of Assessment for Learning. We were interested in how the diversity of assessment (or the lack of thereof) is related to student perceptions of assessment. We utilised both multilevel and person‐oriented methods in our analysis of a national evaluation dataset of 187 Finnish primary and lower secondary teachers and their 2370 students. First, we noted that according to the teachers’ responses, classroom assessment in Finland is not particularly diverse. At the same time, students did not find assessment particularly helpful for their learning. Second, a multilevel analysis revealed varying correlations between the prevalence of various assessment practices and students’ perceived usefulness of the corresponding practices. Third, we explored teacher subgroups in terms of their ‘assessment menu’ through a latent class analysis. All identified teacher subgroups drew heavily on closed‐book examinations. Finally, we analysed whether the assessment perceptions of students differ according to their teacher's latent class. The students whose teachers used the most diverse assessment menu reported the most pressure in assessment. We suggest these findings stem from the socio‐historical context of pedagogical conservatism in Finland, combined with the low stakes of assessment. We discuss the importance of widening teachers’ assessment practices in order to promote sustainable student perceptions of assessment, yet such assessment diversity must be valued in the educational system, and it needs to be based on sound pedagogical design.