bluuebunny/crossref_metadata_2025 huggingface dataset:
Evaluating stereotactic accuracy with patient‐specific MRI distortion corrections for frame‐based radiosurgery
Authors: Knill Cory , Halford Robert , Sandhu Raminder , Loughery Brian , Shamim Sharjil , Junn Fred , Lee Kuei , Almahariq Muayad , Seymour Zachary
Published: July 2024

Purpose

This study examines how MRI distortions affect frame‐based SRS treatments and assesses the need for clinical distortion corrections.

Methods

The study included 18 patients with 80 total brain targets treated using frame‐based radiosurgery. Distortion within patients' MRIs were corrected using Cranial Distortion Correction (CDC) software, which utilizes the patient's CT to alter planning MRIs to reduce inherent intra‐cranial distortion. Distortion was evaluated by comparing the original planning target volumes (PTVORIG) to targets contoured on corrected MRIs (PTVCORR). To provide an internal control, targets were also re‐contoured on uncorrected (PTVRECON) MRIs. Additional analysis was done to assess if 1 mm expansions to PTVORIG targets would compensate for patient‐specific distortions. Changes in target volumes, DICE and JACCARD similarity coefficients, minimum PTV dose (Dmin), dose to 95% of the PTV (D95%), and normal tissue receiving 12 Gy (V12Gy), 10 Gy (V10Gy), and 5 Gy (V5Gy) were calculated and evaluated. Student's t‐tests were used to determine if changes in PTVCORR were significantly different than intra‐contouring variability quantified by PTVRECON.

Results

PTVRECON and PTVCORR relative changes in volume were 6.19% ± 10.95% and 1.48% ± 32.92%. PTVRECON and PTVCORR similarity coefficients were 0.90 ± 0.08 and 0.73 ± 0.16 for DICE and 0.82 ± 0.12 and 0.60 ± 0.18 for JACCARD. PTVRECON and PTVCORR changes in Dmin were –0.88% ± 8.77% and −12.9 ± 17.3%. PTVRECON and PTVCORR changes in D95% were −0.34% ± 5.89 and −8.68% ± 13.21%. The 1 mm expanded PTVORIG targets did not entirely cover 14 of the 80 PTVCORR targets. Normal tissue changes (V12Gy, V10Gy, V5Gy) calculated with PTVRECON were (−0.09% ± 7.39%, −0.38% ± 5.67%, −0.08% ± 2.04%) and PTVCORR were (−2.14% ± 7.34%, −1.42% ± 5.45%, −0.61% ± 1.93%). Except for V10Gy, all PTVCORR changes were significantly different (p < 0.05) than PTVRECON.

Conclusion

MRIs used for SRS target delineation exhibit notable geometric distortions that may compromise optimal dosimetric accuracy. A uniform 1 mm expansion may result in geometric misses; however, the CDC algorithm provides a feasible solution for rectifying distortions, thereby enhancing treatment precision.
Development of an Ultrasound Imaging Atlas for Grading Osteoarthritis in the First Metatarsophalangeal Joint
Authors: Molyneux Prue , Bowen Catherine , Ellis Richard , Rome Keith , Fitzgerald Kate , Clark Phillip , Whittaker Jackie L. , Dando Charlotte , Gee Richard , Carroll Matthew
Published: July 2024

Objective

Ultrasound (US) imaging may play a fundamental role in the earlier detection and assessment of first metatarsophalangeal joint (MTPJ) osteoarthritis (OA) because of its ability to depict tissue‐specific morphologic changes before the point of irreversible structural damage. However, the role of US in supporting the diagnosis of OA in foot joints has not been clearly defined. The aims of this study were to develop a semiquantitative US atlas (the AUT ultrasound imaging [AUTUSI] atlas) to grade the degree of osteoarthritic change in the first MTPJ and to evaluate the intraexaminer and interexaminer reproducibility of using the atlas.

Methods

US images were obtained from 57 participants (30 participants with radiographically confirmed first MTPJ OA). The AUTUSI atlas supports the examination of grading joint effusion, synovial hypertrophy, synovitis, osteophytes, joint space narrowing, and cartilage thickness. Six examiners used the atlas to independently grade 24 US images across 2 sessions. Intraexaminer and interexaminer reproducibility were determined using percentage agreement and Gwet's AC2.

Results

Observations using the AUTUSI atlas demonstrated almost perfect‐to‐perfect interexaminer agreement (percentage agreement ranged from 96% to 100%, and Gwet's AC2 values ranged from 0.81 to 1.00) and moderate‐to‐perfect intraexaminer agreement (percentage agreement ranged from 67% to 100%, and Gwet's AC2 values ranged from 0.54 to 1.00).

Conclusion

The AUTUSI atlas demonstrated excellent intraexaminer and interexaminer reproducibility for evaluating first MTPJ joint effusion, synovial hypertrophy, synovitis, joint space narrowing, osteophytes, and cartilage thickness. The AUTUSI atlas affords an opportunity to detect prognostic markers of OA earlier in the disease cascade and has the potential to advance understanding of the pathologic process of first MTPJ OA.
Nanostructured Titanium with Ultrafine‐Grained Structure as Advanced Engineering Material for Biomedical Application
Authors: Rezyapova Luiza R. , Safargalina Zarema A. , Usmanov Emil I. , Valiev Roman R. , Minasov Timur B. , Valiev Ruslan Z.
Published: July 2024

Titanium and its alloys are popular materials for medical application, particularly in implant devices, where high mechanical properties and osseointegration are critical factors for successful implantation. In this work, the progress in the studies of nanostructured commercially pure Grade 4 titanium (nanoTi) is demonstrated, in which an ultrafine‐grained structure with nanoscale grain size is formed using severe plastic deformation processing. Nanostructured Grade 4 Ti has a very high strength, and its physical nature and strengthening mechanisms are analyzed herein. NanoTi proved also to have very high osseointegration during in vivo experiments. At the same time, the highest biofunctionality is demonstrated by the etched nanoTi samples with pronounced surface roughness, the latter being revealed from precise roughness measurements. The present study provided convincing evidence of accelerated bone formation on nanoTi, which is very promising for manufacture of dental and maxillofacial implants.
Effect of CeO2@Ni on the Oxidation Resistance of in Situ TiC/Ni Composite Applied for Intermediate Temperature Solid Oxide Fuel Cell Interconnects
Authors: Zheng Kaiyue , Qi Qian , Wang Lujie , Zhu Yuanyang , Zhao Yueyang
Published: July 2024

The TiC/Ni composites with different CeO2 or CeO2@Ni content are fabricated by pressureless reactive sintering, and the CeO2@Ni particles are prepared by electroless plating technique. The results show that the continuous Ni layer is prepared on CeO2 particles, leading to the decrease of contact angle between CeO2 and Ni from about 116° to 65°. The relative density of composites with 1 wt% CeO2 increases from 85.79% to 96.45% by Ni layer on CeO2 particles. The CeO2 or CeO2@Ni particles exhibit no obvious influence on the microstructure of composites, and Ce atoms of CeO2 diffuse into TiC particles during the reactive sintering process. The mass gain of composite decreases from 7.4709 to 4.9075 mg cm−2 by addition of 1 wt% CeO2@Ni. The Ce‐doped in NiO and TiO2 would restrict the inward diffusion of O atoms and outward diffusion of Ni atoms, resulting in the improvement of oxidation resistance of composite. With the increase of CeO2@Ni content from 0 to 1 wt%, the surface specific resistance of composite decreases from 3.16 to 0.56 Ω cm2 at 800 °C due to the thinner oxide scale and lower bandgap of TiO2 by Ce doping.
Visible Light‐Responsive Polyphenolic Bio‐Glues for Oral Mucosal Wound Healing
Authors: Zhang Hengjie , Zhang Jianhua , Wang Tianyou , Li Haotian , Zhang Rong , Chen Xianchun , Gu Zhipeng , Li Yiwen
Published: July 2024

Although bio‐adhesives have achieved many progresses, creating robust bio‐glues that could withstand the complex physiological microenvironment remains a significant challenge such as limited bioadhesion strength and stability, as well as slow adhesion speed caused by pH, enzymes, salt, and bacteria. Herein, a series of strong bio‐glues are successfully fabricated using a polyphenol–acrylamide–ruthenium crosslinking (PARC) reaction under visible light irradiation, involving acrylamides radical polymerization, polyphenols (extracts) coupling reaction, and ruthenium‐mediated photochemistry. The resulting bio‐glues underwent rapid sol–gel transition and exhibited adhesive properties within a short of time (≈5 s), which could quickly bond to various bio‐tissues. Moreover, these bioadhesives demonstrate high adhesion strength and stability with mucosal tissue in the oral environment, effectively promoting rat and pig oral mucosal wound healing. It is anticipated that this class of visible light‐responsive polyphenolic bio‐glues could serve as a robust tool for addressing oral mucosal defects in the clinic, offering a promising alternative to traditional treatments for oral mucosal disorders.
Zwitterion‐Separated Ion Pair Dominated Additive‐Electrolyte Structure for Ultra‐Stable Aqueous Zinc Ion Batteries
Authors: Deng Siting , Sun Yilun , Yang Zimin , Wu Mingqiang , Tong Hao , Nie Xinbin , Su Yifan , Li Jianwei , Chai Guoliang
Published: July 2024

Aqueous zinc ion batteries (AZIBs) are promising for large‐scale energy storage due to the advantages of high safety, high theoretical capacity, and cost‐effectiveness. However, the stability of AZIBs is poor (generally 50–100 cycles) at low current densities due to side reactions. Here, choline glycerophosphate (CGP) is introduced as a zwitterion additive to improve performance of AZIBs. The CGP helps to form a new solvated structure of Zn2+, named zwitterion‐separated ion pair (ZSIP) structure that can link OTf− ion and repel H2O molecular. In addition, CGP can be adsorbed on anode to suppress formation of by‐products ZnxOTfy(OH)2x‐y·nH2O, and on cathode to inhibit Zn3(OH)2V2O7·2H2O phase generation. Consequently, the Zn||Cu cell shows an excellent average Coulombic efficiency of 99.79% over 800 cycles at 1 mA cm−2 and 0.5 mAh cm−2. Impressively, the Zn//NH4V4O10 battery demonstrates exceptional capacity retention of 95% along with a high specific capacity of 409.3 mAh g−1 after 350 cycles under a trickle (dis)charge process (0.2 A g−1) and an ultra‐long lifespan of 14 000 cycles at 5 A g−1 along with a high specific capacity of 217 mAh g−1. The concept of ZSIP opens a new avenue for developing aqueous batteries with high performance and long stability in the future.
Nanotechnology‐Mediated Immunomodulation Strategy for Inflammation Resolution
Authors: Li Ying , Liu Wen , Wang Yuanchao , Liu Taotao , Feng Yakai
Published: July 2024

Inflammation serves as a common characteristic across a wide range of diseases and plays a vital role in maintaining homeostasis. Inflammation can lead to tissue damage and the onset of inflammatory diseases. Although significant progress is made in anti‐inflammation in recent years, the current clinical approaches mainly rely on the systemic administration of corticosteroids and antibiotics, which only provide short‐term relief. Recently, immunomodulatory approaches have emerged as promising strategies for facilitating the resolution of inflammation. Especially, the advanced nanosystems with unique biocompatibility and multifunctionality have provided an ideal platform for immunomodulation. In this review, the pathophysiology of inflammation and current therapeutic strategies are summarized. It is mainly focused on the nanomedicines that modulate the inflammatory signaling pathways, inflammatory cells, oxidative stress, and inflammation targeting. Finally, the challenges and opportunities of nanomaterials in addressing inflammation are also discussed. The nanotechnology‐mediated immunomodulation will open a new treatment strategy for inflammation therapy.
Smart Response Biomaterials for Pain Management
Authors: Zhang Xinyu , Guan Mengtong , Yi Weiwei , Li Xinhe , Ding Xiaoqian , He Yi , Han Wang , Wang Zijie , Tang Qiuyu , Liao Bo , Shen Jieliang , Han Xiaoyu , Bai Dingqun
Published: July 2024

The intricate nature of pain classification and mechanism constantly affects the recovery of diseases and the well‐being of patients. Key medical challenges persist in devising effective pain management strategies. Therefore, a comprehensive review of relevant methods and research advancements in pain management is conducted. This overview covers the main categorization of pain and its developmental mechanism, followed by a review of pertinent research and techniques for managing pain. These techniques include commonly prescribed medications, invasive procedures, and noninvasive physical therapy methods used in rehabilitation medicine. Additionally, for the first time, a systematic summary of the utilization of responsive biomaterials in pain management is provided, encompassing their response to physical stimuli such as ultrasound, magnetic fields, electric fields, light, and temperature, as well as changes in the physiological environment like reactive oxygen species (ROS) and pH. Even though the application of responsive biomaterials in pain management remains limited and at a fundamental level, recent years have seen the examination and debate of relevant research findings. These profound discussions aim to provide trends and directions for future research in pain management.
Regenerating Chemotherapeutics through Copper‐Based Nanomedicine: Disrupting Protein Homeostasis for Enhanced Tumor Therapy
Authors: Wu Xubo , Wu Qinghe , Hou Mengfei , Jiang Yifei , Li Meng , Jia Guoping , Yang Huizhen , Zhang Chunfu
Published: July 2024

The bis‐(diethyldithiocarbamate)‐copper (CuET), the disulfiram (DSF)‐Cu complex, has exhibited noteworthy anti‐tumor property. However, its efficacy is compromised due to the inadequate oxidative conditions and the limitation of bioavailable copper. Because CuET can inactivate valosin‐containing protein (VCP), a bioinformatic pan‐cancer analysis of VCP is first conducted in this study to identify CuET as a promising anticancer drug for diverse cancer types. Then, based on the drug action mechanism, a nanocomposite of CuET and copper oxide (CuO) is designed and fabricated utilizing bovine serum albumin (BSA) as the template (denoted as CuET‐CuO@BSA, CCB). CCB manifests peroxidase (POD)‐mimicking activity to oxidize the tumor endogenous H2O2 to generate reactive oxygen species (ROS), enhancing the chemotherapy effect of CuET. Furthermore, the cupric ions released after enzymatic reaction can regenerate CuET, which markedly perturbs intracellular protein homeostasis and induces apoptosis of tumor cells. Meanwhile, CCB triggers cuproptosis by inducing the aggregation of lipoylated proteins. The multifaceted action of CCB effectively inhibits tumor progression. Therefore, this study presents an innovative CuET therapeutic strategy that creates an oxidative microenvironment in situ and simultaneously self‐supply copper source for CuET regeneration through the combination of CuO nanozyme with CuET, which holds promise for application of CuET for effective tumor therapy.
Exploring the Possibility of Thermally Assisted Creation and Annihilation of Anti‐Frenkel Defects in a Multiferroic Oxide for Tuning Interfacial Ferroelectricity
Authors: Yeo Youngki , Kim Jihun , Suh Jeonghun , Jang Jinhyuk , Kang Kyungrok , Schoenherr Peggy , Kim Kwang‐Tak , Kim Yong‐Jin , Kim Kee Hoon , Ulrich Clemens , Seidel Jan , Choi Si‐Young , Yang Chan‐Ho
Published: July 2024

Lattice defects such as oxygen vacancies, interstitials, and their complexes are present in crystalline oxide materials. In particular, anti‐Frenkel defects, which refer to charge‐neutral anion vacancy‐interstitial pairs, are strongly coupled with ferroelectric and dielectric properties as electric dipoles. However, in order to observe their macroscopic manifestation, delicate defect controls are required to the extent that electronic and ionic charges are almost completely suppressed. Here, the thermal cycle dependence of dielectric and piezoelectric properties is scrutinized in the strain‐driven morphotropic phase boundaries of multiferroic La‐substituted BiFeO3 thin films. Electrochemical impedance spectroscopy provides the Warburg feature that is considered evidence of the ionic origin. The observations are discussed based on anti‐Frenkel defects that are created or annihilated reversibly by thermal cycles through high‐temperature structural phase transition temperature or magnetic Néel temperature. The defect dipoles are spontaneously aligned by the flexoelectric effect in the phase boundaries inducing a metastable interfacial ferroelectric phase. The findings offer useful insight into defect dipoles.
Bunte Salts for Electrochemical Deuteroalkylthiolation of Heteroarenes
Authors: Lu Ruhan , Tao Qisheng , Qian Qing , Li Bo , Zhang Yuhuan , Gao Yongyuan
Published: July 2024

This study presents a strategy for the electrochemical deuteroalkylthiolation of heteroarenes, using Bunte salt as a deuterium‐alkylthio source. This reaction occurs in an undivided cell without the need for catalysts, oxidants, or electrolytes, yielding a variety of deuteroalkylthiolated heteroarenes.
Advances in α‐Hydroxylation of β‐Dicarbonyl Compounds
Authors: Peng Shuai , Su Fangyao , Yin Shuting , Sun Baoguo , Tian Hongyu , Liang Sen
Published: July 2024

The α‐hydroxy‐β‐dicarbonyl motif is essential in many biologically active compounds, sparking significant interest in their synthesis. This review comprehensively examines the advancements in the α‐hydroxylation of β‐dicarbonyl compounds, systematically categorizing the methods based on the types of oxidants employed and highlighting advances in asymmetric α‐hydroxylation. It evaluates the substrate scope, advantages, and disadvantages of each approach, summarizing the possible intermediates involved and the types of reaction mechanisms.
Cathode Modification of Sodium‐Ion Batteries for Improved energy Density: A Review
Authors: Wan Xiaoyuan , Li Yanlin , Chen Shenghua , Duan Wenyuan , Lei Wanying
Published: July 2024

In recent years, with the large‐scale commercial application of lithium‐ion batteries, the shortage of lithium resource reserves and the rising price limit its development. The sodium‐ion batteries as a new type of secondary chemical power supply, with ample resources, high safety, as well as great electrochemical performance, are expected to form complementary with Lithium‐ion batteries in the domain of extensive electrochemical energy storage and low‐velocity electric vehicles. However, due to its low energy density, it remains challenging to develop high‐performance sodium‐ion batteries. As is well‐known, the cathode material is the essential factor affecting the performance of sodium‐ion batteries. In order to solve these questions, cathode modification of sodium‐ion batteries aroused wide concern for improving the electrochemical performance. Here, the authors first discuss the challenges of sodium‐ion batteries, and review the energy storage mechanism and the causes of the low energy density. Then, recent studies on cathode modification are summarized based on the mainstream cathode materials in sodium‐ion batteries including sodium‐based transition‐metal oxides, polyanionic compounds, and Prussian blue analogues. Finally, the prospects of sodium‐ion batteries are proposed, which provides promising strategies for the development and practical application of cathode materials in the future.
MEN1 Deficiency‐Driven Activation of the β‐Catenin‐MGMT Axis Promotes Pancreatic Neuroendocrine Tumor Growth and Confers Temozolomide Resistance
Authors: Xu Junfeng , Lou Xin , Wang Fei , Zhang Wuhu , Xu Xiaowu , Ye Zeng , Zhuo Qifeng , Wang Yan , Jing Desheng , Fan Guixiong , Chen Xuemin , Zhang Yue , Zhou Chenjie , Chen Jie , Qin Yi , Yu Xianjun , Ji Shunrong
Published: July 2024

O6‐methylguanine DNA methyltransferase (MGMT) removes alkyl adducts from the guanine O6 position (O6‐MG) and repairs DNA damage. High MGMT expression results in poor response to temozolomide (TMZ). However, the biological importance of MGMT and the mechanism underlying its high expression in pancreatic neuroendocrine tumors (PanNETs) remain elusive. Here, it is found that MGMT expression is highly elevated in PanNET tissues compared with paired normal tissues and negatively associated with progression‐free survival (PFS) time in patients with PanNETs. Knocking out MGMT inhibits cancer cell growth in vitro and in vivo. Ectopic MEN1 expression suppresses MGMT transcription in a manner that depends on β‐Catenin nuclear export and degradation. The Leucine 267 residue of MEN1 is crucial for regulating β‐Catenin‐MGMT axis activation and chemosensitivity to TMZ. Interference with β‐Catenin re‐sensitizes tumor cells to TMZ and significantly reduces the cytotoxic effects of high‐dose TMZ treatment, and MGMT overexpression counteracts the effects of β‐Catenin deficiency. This study reveals the biological importance of MGMT and a new mechanism by which MEN1 deficiency regulates its expression, thus providing a potential combinational strategy for treating patients with TMZ‐resistant PanNETs.
Nitrogen Bicoupled Carbon Bonding for Electrocatalysis of CO2 and Nitrobenzene via Engineering Hydroxyl Assisted Cobalt Single Atom
Authors: Zheng Jingui , Xu Shaohan , Sun Lingzhi , Pan Xun , Xie Qihao , Li Lina , Cai Junzhuo , Zhao Guohua
Published: July 2024

The coupling of CO2 and nitrogen‐containing species nitrobenzene has become an appealing and sustainable strategy for synthesizing high‐valuable organic nitrides. However, how to realize the nitrogen bicoupled carbon bonding (C─N─C) between two CO2 and nitrobenzene has been an insurmountable challenge. Hydroxyl‐assisted cobalt single atom (CoN2O2‐(OH)2) is engineered to achieve C─N─C bonding for N, N‐dimethylaniline synthesis. The CO2 is adsorbed through hydroxyl groups, that can be reduced and C─N coupling with nitrobenzene reduction intermediate on nearby Co site, and the vacant hydroxyl group continues to adsorb next CO2, which is sequentially coupled with an intermediate of C─N coupling, achieving C─N─C bonding for synthesis N, N‐dimethylaniline. Herein, first, C─N─C bonding is achieved for green synthesis of N, N‐dimethylaniline via electrocatalytic reduction of nitrobenzene and CO2 in an aqueous phase, with a yield of 505.2 µmol L−1 h−1 on CoN2O2‐(OH)2. In situ characterizations and DFT calculations together demonstrated that the key of C─N─C bonding is that *PhNCH3 intermediate of C─N bonding continues to couple with *CO achieving C─N─C bonding to generate *PhNCOCH3 for N, N‐dimethylaniline synthesis with a much lower free energy is far easier to take place on CoN2O2‐(OH)2. This work provides inspiring new insight into the green synthesis of long‐chain organic nitrides.
Exploring the Feasibility of Copper Incorporation in Halide Perovskites: Impact on CO2 Photoreduction Performance
Authors: Tailor Naveen Kumar , Singh Shreya , Singh Nikhil , Nayak Pabitra Kumar , Saini Saurabh K. , Das Srimanta , Venkanna Guguloth , Senanayak Satyaprasad P , Kumar Mahesh , Ghosh Dibyajyoti , Tripathi Komal , Pant Kamal Kishore , Satapathi Soumitra
Published: July 2024

Double perovskite have attracted substantial attention as prospective materials for applications in optoelectronics and photocatalysis. Significant efforts are devoted to modulating the properties of double perovskites to improve their performance. One promising approach involves substituting silver (Ag) with copper (Cu), which offers favorable electronic characteristics. Despite promising theoretical predictions, the experimental synthesis of copper‐based double perovskites has presented notable challenges. Here, the challenges of Cu incorporation in double perovskites and the subsequent – impact of Cu on the photocatalytic activity of halide perovskites toward CO2 reduction are explored. Combining detailed computational thermodynamic studies, it is found that Cu does not form the traditional double perovskite structure that is Cs2CuBiCl6; it stays as an interstitial dopant in its pristine Cs3Bi2Cl9 structure. The Cu‐Cs3Bi2Cl9 are found to exhibit enhanced CO2 photoreduction activity than the pristine Cs3Bi2Cl9. Further, transient absorption results show that Cu dopants enhance the carrier generation because of introduced sub‐bandgap states, and it is found that carrier decay lifetime is elevated in Cu‐Cs3Bi2Cl9, which can enhance the participation of carriers in CO2 photoreduction. The study explores the challenges and opportunities of copper doping in halide perovskites, offering the potential for developing efficient CO2 reduction photocatalysts.
Longer‐term surveillance imaging and endoscopy critical for majority of patients in detection of sinonasal malignancy recurrence
Authors: Kwiecien Catherine , Workman Alan D. , Wilensky Jadyn , Lerner David K. , Rathi Vinay K. , Douglas Jennifer E. , Kohanski Michael A. , Kuan Edward C. , Palmer James N. , Adappa Nithin D.
Published: July 2024

Background

Sinonasal malignancy surveillance paradigms are often based on Head and Neck National Comprehensive Cancer Network guidelines, which do not recommend standard surveillance imaging beyond 6 months without concerning symptomatology or physical examination findings.

Methods

This was a retrospective analysis of all patients who underwent resection of sinonasal malignancy at a tertiary care center over a 20‐year period from 2000 to 2020, with an ensuing surveillance period demonstrating recurrence.

Results

Fifty‐two patients with sinonasal malignancy recurrence were included, with an average time to recurrence of 30.9 months and a follow‐up period of over 60 months. Recurrence was diagnosed by routine imaging or endoscopy in asymptomatic patients in a majority (60%) of cases, while the remaining minority of diagnoses followed new symptomatology. Asymptomatic recurrence was associated with perineural spread of tumor at initial resection (p = 0.025), but not with age (p = 0.85) or stage at diagnosis (p = 0.68). Expectedly, positron emission tomography/computed tomography (CT) more often detected regional or distant recurrence, while structural imaging (CT/magnetic resonance imaging) demonstrated more frequent detection of recurrence in those with perineural spread of tumor (p = 0.01).

Conclusions

Our findings support high rates of asymptomatic recurrence in sinonasal malignancy, with the majority of recurrences diagnosed by routine endoscopy or imaging. Tailored and extended surveillance guidelines are necessary relative to those utilized for other head and neck mucosal cancers, and are especially appropriate when features such as perineural spread are present.
Diagnostic criteria for eosinophilic chronic rhinosinusitis: Comparative analysis and novel scoring system
Authors: Lee Jae Yoon , Kim Do Hyun , Kim Sung Won , Im Yeon Hee , Park Chan Soon , Kim Dong Hyun , Alkhars Zainab , Kim Soo Whan
Published: July 2024

Background

Accurate identification of eosinophilic chronic rhinosinusitis is essentialg because its treatment and prognosis substantially differ from other subtypes.

Methods

This retrospective observational study included 640 patients who underwent endoscopic sinus surgery for chronic rhinosinusitis in a single tertiary center from January 2021 to December 2022. Receiver operating characteristic curves were generated to compare accuracy, sensitivity, specificity of the novel scoring system, and previous diagnostic criteria (Japanese Epidemiological Survey of Refractory Eosinophilic Chronic Rhinosinusitis, European Forum for Research and Education in Allergy and Airway Diseases, European Position Paper on Rhinosinusitis and Nasal Polyps, and Sakuma et al.) for predicting eosinophilic chronic rhinosinusitis (ECRS) by tissue eosinophil count ≥70 per high power field.

Results

Patients were randomly divided into estimation (n = 430) and validation (n = 210) groups. The area under the receiver operating characteristic curve for the novel score was 0.753 (95% confidence interval [CI], 0.670–0.835) in the estimation group, 0.729 (0.629–0.830) in the validation group, and 0.661 (0.584–0.738) in the 20‐fold cross‐validation with the entire dataset.

Conclusions

We propose a novel scoring system that incorporates three key parameters: “novel score = blood eosinophil (%) + total Lund–Mackay score of anterior ethmoid sinuses + 2 if nasal polyp present” greater than 7 can be reliably used for diagnosing ECRS. This system can facilitate decision‐making processes regarding the administration of oral steroids and biologics targeting type 2 inflammation prior to surgical intervention.
Reasons for undergoing amyloid imaging among diverse enrollees in the A4 study
Authors: Magana‐Ramirez Christina M. , Irizarry‐Martinez Gimarie , Gillen Daniel L. , Grill Joshua D.
Published: July 2024

INTRODUCTION

Understanding attitudes toward participation among diverse preclinical Alzheimer's disease (AD) trial participants could yield insights to instruct future recruitment.

METHODS

Using data from the Anti‐Amyloid Treatment in Asymptomatic AD (A4) Study, we examined differences among mutually exclusive racial and ethnic groups in views and perceptions of amyloid imaging (VPAI), a measure of motivations to undergo amyloid biomarker testing in the setting of preclinical AD. We used linear regression to quantify differences at baseline.

RESULTS

Compared to non‐Hispanic or Latino (NH) White participants, Hispanic or Latino (3.52 points, 95% confidence interval [CI]: [2.61, 4.42]); NH Asian (2.97 points, 95% CI: [1.71, 4.22]); and NH Black participants (2.79 points, 95% CI: [1.96, 3.63]) participants demonstrated higher levels of endorsement of the VPAI items at baseline.

DISCUSSION

Differences may exist among participants from differing ethnic and racial groups in motivations to undergo biomarker testing in the setting of a preclinical AD trial.

Highlights

Representative samples in AD clinical trials are vital to result in generalizability.

We assessed motivations to undergo amyloid imaging in a preclinical AD trial.

Racial and ethnic minority groups showed higher endorsement of VPAI items.

Differences were driven by perceived risk, plan/prepare, and curiosity domains.

Few observations among racial and ethnic groups changed after biomarker disclosure.
Predicting continuous amyloid PET values with CSF tau phosphorylation occupancies
Authors: Wisch Julie K. , Gordon Brian A. , Barthélemy Nicolas R. , Horie Kanta , Henson Rachel L. , He Yingxin , Flores Shaney , Benzinger Tammie L. S. , Morris John C. , Bateman Randall J. , Ances Beau M. , Schindler Suzanne E.
Published: July 2024

INTRODUCTION

Cerebrospinal fluid (CSF) tau phosphorylation at multiple sites is associated with cortical amyloid and other pathologic changes in Alzheimer's disease. These relationships can be non‐linear. We used an artificial neural network to assess the ability of 10 different CSF tau phosphorylation sites to predict continuous amyloid positron emission tomography (PET) values.

METHODS

CSF tau phosphorylation occupancies at 10 sites (including pT181/T181, pT217/T217, pT231/T231 and pT205/T205) were measured by mass spectrometry in 346 individuals (57 cognitively impaired, 289 cognitively unimpaired). We generated synthetic amyloid PET scans using biomarkers and evaluated their performance.

RESULTS

Concentration of CSF pT217/T217 had low predictive error (average error: 13%), but also a low predictive range (ceiling 63 Centiloids). CSF pT231/T231 has slightly higher error (average error: 19%) but predicted through a greater range (87 Centiloids).

DISCUSSION

Tradeoffs exist in biomarker selection. Some phosphorylation sites offer greater concordance with amyloid PET at lower levels, while others perform better over a greater range.

Highlights

Novel pTau isoforms can predict cortical amyloid burden.

pT217/T217 accurately predicts cortical amyloid burden in low‐amyloid individuals.

Traditional CSF biomarkers correspond with higher levels of amyloid.
Anticoagulation Use and Endovascular Thrombectomy in Patients with Large Core Stroke: A Secondary Analysis of the SELECT2 Trial
Authors: Pujara Deep K. , Hussain M. Shazam , Abraham Michael G. , Ortega‐Gutierrez Santiago , Chen Michael , Kasner Scott E. , Churilov Leonid , Sitton Clark W. , Blackburn Spiros , Sundararajan Sophia , Hu Yin C. , Herial Nabeel A. , Budzik Ronald F. , Hicks William J. , Arenillas Juan F. , Tsai Jenny P. , Kozak Osman , Cordato Dennis J. , Manning Nathan W. , Hanel Ricardo A. , Aghaebrahim Amin N. , Wu Teddy Y. , Cardona Portela Pere , Pérez de la Ossa Natalia , Schaafsma Joanna D. , Blasco Jordi , Sangha Navdeep , Warach Steven , Gandhi Chirag D. , Al‐Mufti Fawaz , Kleinig Timothy J. , Al‐Shaibi Faisal , Duncan Kelsey R. , Shaker Faris , Johns Hannah , Xiong Wei , DeGeorgia Michael , Opaskar Amanda , Sunshine Jeffrey , Ray Abhishek , Jabbour Pascal , Bambakidis Nicholas , Sila Cathy , Nguyen Thanh N. , Grotta James C. , Hassan Ameer E. , Ribo Marc , Hill Michael D. , Campbell Bruce C. , Sarraj Amrou ,   For SELECT2 Investigators
Published: July 2024

Endovascular thrombectomy (EVT) safety and efficacy in patients with large core infarcts receiving oral anticoagulants (OAC) are unknown. In the SELECT2 trial (NCT03876457), 29 of 180 (16%; vitamin K antagonists 15, direct OACs 14) EVT, and 18 of 172 (10%; vitamin K antagonists 3, direct OACs 15) medical management (MM) patients reported OAC use at baseline. EVT was not associated with better clinical outcomes in the OAC group (EVT 6 [4–6] vs MM 5 [4–6], adjusted generalized odds ratio 0.89 [0.53–1.50]), but demonstrated significantly better outcomes in patients without OAC (EVT 4 [3–6] vs MM 5 [4–6], adjusted generalized odds ratio 1.87 [1.45–2.40], p = 0.02). The OAC group had higher comorbidities, including atrial fibrillation (70% vs 17%), congestive heart failure (28% vs 10%), and hypertension (87% vs 72%), suggesting increased frailty. However, the results were consistent after adjustment for these comorbidities, and was similar regardless of the type of OACs used. Whereas any hemorrhage rates were higher in the OAC group receiving EVT (86% in OAC vs 70% in no OAC), no parenchymal hemorrhage or symptomatic intracranial hemorrhage were observed with OAC use in both the EVT and MM arms. Although we did not find evidence that the effect was due to excess hemorrhage or confounded by underlying cardiac disease or older age, OAC use alone should not exclude patients from receiving EVT. Baseline comorbidities and ischemic injury extent should be considered while making individualized treatment decisions. ANN NEUROL 2024;96:887–894
A Modular Dual‐Catalytic Aryl‐Chlorination of Alkenes
Authors: Li Bo , Bunescu Ala , Drazen Daniel , Rolph Katherine , Michalland Jean , Gaunt Matthew J.
Published: July 2024

Alkyl chlorides are a class of versatile building blocks widely used to generate C(sp3)‐rich scaffolds through transformation such as nucleophilic substitution, radical addition reactions and metal‐catalyzed cross‐coupling processes. Despite their utility in the synthesis of high‐value functional molecules, distinct methods for the preparation of alkyl chlorides are underrepresented. Here, we report a visible‐light‐mediated dual catalysis strategy for the modular synthesis of highly functionalized and structurally diverse arylated chloroalkanes via the coupling of diaryliodonium salts, alkenes and potassium chloride. A distinctive aspect of this transformation is a ligand‐design‐driven approach for the development of a copper(II)‐based atom‐transfer catalyst that enables the aryl‐chlorination of electron‐poor alkenes, complementing its iron(III)‐based counterpart that accommodates non‐activated aliphatic alkenes and styrene derivatives. The complementarity of the two dual catalytic systems allows the efficient aryl‐chlorination of alkenes bearing different stereo‐electronic properties and a broad range of functional groups, maximizing the structural diversity of the 1‐aryl, 2‐chloroalkane products.
Enzymmaschinerie für bakteriellen Glucosidmetabolismus über einen konservierten nicht‐hydrolytischen Abbauweg
Authors: Kastner Klara , Bitter Johannes , Pfeiffer Martin , Grininger Christoph , Oberdorfer Gustav , Pavkov‐Keller Tea , Weber Hansjörg , Nidetzky Bernd
Published: July 2024

Flexible Substrataufnahme aus Nährstoffreservoirs ist für Mikroorganismen entscheidend, um sich in kompetitiven natürlichen Umgebungen durchzusetzen. Zur Aufnahme von Glucose aus verschiedenen Glucosid‐ und Disaccharid‐Substraten haben viele frei‐ und symbiotisch lebende Bakterien, neben der Hydrolyse, einen nicht‐hydrolytischen Stoffwechselweg entwickelt. Dieser besteht aus vier biochemischen Schritten und wird von einem distinkten Genlocus (glycoside utilization locus, GUL) codiert. Mechanistisch integriert der Stoffwechselweg die Oxidation und Reduktion am Glucosyl/Glucose‐C3 mit der eliminativen Spaltung der glycosidischen Bindung und der Addition von Wasser an das Eliminationsprodukt in zwei aufeinanderfolgenden, von Lyasen katalysierten Reaktionen. In dieser Studie zeigen wir, basierend auf der Untersuchung von Enzymen des Pflanzenpathogens Agrobacterium tumefaciens, ein konserviertes Aktivitätszentrum in beiden Lyasen, welches um ein zentrales Mn2+ Metallion angeordnet ist. Weiters identifizieren wir die strukturellen Voraussetzungen für die spezifische Katalyse der 3‐Ketoglucosid Eliminierung zu 2‐Hydroxy‐3‐ketoglycal und der Hydratisierung des Glycal zu 3‐Ketoglucose. Die Erweiterung unserer Suche nach GUL‐codierten putativen Lyasen auf das menschliche darmkommensale Bakterium Bacteroides thetaiotaomicron führte uns zur Entdeckung eines Ca2+‐koordinierten Aktivitätszentrums in einem Glycosidase‐ähnlichen Protein. Das Enzym katalysiert die eliminative Spaltung von 3‐Ketoglucosiden entgegengesetzter (α) anomerer Konfiguration im Vergleich zu den von der A. tumefaciens Lyase präferierten Substraten (β). Strukturelle und biochemische Vergleiche zeigen die molekular‐mechanistische Basis der Stereokomplementarität der beiden 3‐Ketoglucosid Lyasen. Unsere Ergebnisse identifizieren ein grundlegendes Set von GUL‐codierten Lyasen für den Glucosidmetabolismus und erlauben es, der Gendiversität von GULs in der Domäne von Bakterien physiologische Bedeutung zuzuschreiben.
Facilitating Formate Selectivity via Optimizing eg* Band Broadening in NiMn Hydroxides for Ethylene Glycol Electro‐Oxidation
Authors: Wang Zhen , Li Junhua , Zhang Qi , Wu Chao , Meng Haoyan , Tang Ying , Zou Anqi , Zhang Yiming , Ma Rui , Lv Xiang , Yu Zhigen , Xi Shibo , Xue Junmin , Wang Xiaopeng , Wu Jiagang
Published: July 2024

Ethylene glycol electro‐oxidation reaction (EGOR) on nickel‐based hydroxides (Ni(OH)2) represents a promising strategy for generating value‐added chemicals, i.e. formate and glycolate, and coupling water‐electrolytic hydrogen production. The high product selectivity was one of the most significant area of polyols electro‐oxidation process. Yet, developing Ni(OH)2‐based EGOR electrocatalyst with highly selective product remains a challenge due to the unclear cognition about the EGOR mechanism. Herein, Mn‐doped Ni(OH)2 catalysts were utilized to investigate the EGOR mechanism. Experimental and calculation results reveal that the electronic states of eg* band play an important role in the catalytic performance and the product selectivity for EGOR. Broadening the eg* band could effectively enhance the adsorption capacity of glyoxal intermediates. On the other hand, this enhanced adsorption could lead to reduced side reactions associated with glycolate formation, simultaneously promoting the cleavage of C−C bonds. Consequently, the selectivity for formate was notably augmented by these enhancements. This work offers new insights into the regulation of catalyst electronic states for improving polyol electrocatalytic activity and product selectivity.
Solvent Attenuation of London Dispersion in Polycyclic Aromatic Stacking
Authors: Elmi Alex , Bąk Krzysztof M. , Cockroft Scott L.
Published: July 2024

Solvent competition for London dispersion attenuates its energetic significance in molecular recognition processes. By varying both the stacked contact area and the solvent, here we experimentally deconvolute solvent attenuation using molecular balances. Experimental stacking energies (phenyl to pyrene) correlated strongly with calculations only when dispersion was considered. Such calculations favoured stacking by up to −27 kJ mol−1 in the gas phase, but it was weakly disfavoured in our solution‐phase experiments (+0.5 to +4.6 kJ mol−1). Nonetheless, the propensity for stacking increased with contact area and in solvents with lower bulk polarisabilities that compete less for dispersion. Experimental stacking energies per unit change in solvent accessible area ranged from −0.02 kJ mol−1 Å−2 in CS2, to −0.05 kJ mol−1 Å−2 in CD2Cl2, but were dwarfed by the calculated gas‐phase energy of −0.6 kJ mol−1 Å−2. The results underscore the challenge facing the exploitation of dispersion in solution. Solvent competition strongly but imperfectly cancels dispersion at molecular recognition interfaces, making the energetic benefits difficult to realise.
Insulator‐Transition‐Induced Degradation of Pyrochlore Ruthenates in Electrocatalytic Oxygen Evolution and Stabilization through Doping
Authors: Liu Tongtong , Guo Hengyu , Zhang Qingren , Fujishige Masatsugu , Endo Morinobu , Zhang Zhengping , Wang Feng
Published: July 2024

Ru‐based pyrochlores (e.g., Y2Ru2O7−δ) are promised to replace IrO2 in polymer electrolyte membrane (PEM) electrolyzers. It is significant to reveal the cliff attenuation on the oxygen evolution reaction (OER) performance of these pyrochlores. In this work, we monitor the structure changes and electrochemical behavior of Y2Ru2O7−δ over the OER process, and it is found that the reason of decisive OER inactivation is derived from an insulator transition occurred within Y2Ru2O7−δ due to its inner “perfecting” lattice induced by continuous atom rearrangement. Therefore, a stabilization strategy of the Ir‐substituted Y2Ru2O7−δ is proposed to alleviate this undesirable behavior. The double‐exchange interaction between Ru and Ir in [RuO6] and [IrO6] octahedra leads the charge redistribution with simultaneous spin configuration adjustment. The electronic state in newly formed octahedrons centered with Ru 4d3 (with the state of eg′↑↑a1g↑ eg0) and Ir 5d6 (eg′↑↓↑↓a1g↑↓ eg0) relieves the uneven electron distributions in [RuO6] orbital. The attenuated Jahn–Teller effect alleviates atom rearrangement, represented as the mitigation of insulator transition, surface reconstruction, and metal dissolution. As results, the Ir‐substituted Y2Ru2O7−δ presents the greatly improved OER stability and PEM durability. This study unveils the OER degradation mechanism and stabilization strategy for material design of Ru‐based OER catalysts for electrochemical applications.
Exploring the Complex Chemistry and Degradation of Ascorbic Acid in Aqueous Nanoparticle Synthesis
Authors: Roy Debashree , Johnson Hannah M. , Hurlock Matthew J. , Roy Kingshuk , Zhang Qiang , Moreau Liane M.
Published: July 2024

Ascorbic acid (AA) is the most widely used reductant for noble metal nanoparticle (NP) synthesis. Despite the synthetic relevance, its aqueous chemistry remains misunderstood, due in part to various assumptions about its reduction pathway which are insufficiently supported by experimental evidence. This study aims to provide an understanding of the complex chemistry associated with AA under aqueous conditions. We demonstrate that (i) AA undergoes appreciable degradation in alkaline solution on a timescale relevant to NP synthesis, (ii) contrary to popular belief, AA does not degrade into dehydroascorbic acid (DHA), nor is DHA the oxidized product of AA under noble metal NP synthetic conditions, (iii) DHA, which readily degrades under alkaline conditions, can also effectively reduce metal salt precursors to metal NPs, (iv) neither ascorbate nor dehydroascorbate act as surface capping agents post‐synthetically on the NPs (v) AA degradation time greatly affects the morphology and polydispersity of the resultant NP. Results from our mechanistic investigation enabled us to utilize purposefully‐aged reductants to achieve control over shape yield and monodispersity in the seed‐mediated synthesis of Au nanorods. Our findings have important implications for achieving monodispersed products in the many metal NP synthesis reactions that make use of AA as a reducing agent.
Synthesis of Alkene Atropisomers with Multiple Stereogenic Elements via Catalytic Asymmetric Rearrangement of 3‐Indolylmethanols
Authors: Wu Ping , Zhang Wen‐Tao , Yang Ji‐Xiang , Yu Xian‐Yang , Ni Shao‐Fei , Tan Wei , Shi Feng
Published: July 2024

Catalytic enantioselective preparation of alkene atropisomers with multiple stereogenic elements and discovery of their applications have become significant but challenging issues in the scientific community due to the unique structures of this class of atropisomers. We herein report the first catalytic atroposelective preparation of cyclopentenyl[b]indoles, a new kind of alkene atropisomers, with stereogenic point and axial chirality via an unusual rearrangement reaction of 3‐indolylmethanols under asymmetric organocatalysis. Notably, this novel type of alkene atropisomers have promising applications in developing chiral ligands or organocatalysts, discovering antitumor drug candidates and fluorescence imaging materials. Moreover, the theoretical calculations have elucidated the possible reaction mechanism and the non‐covalent interactions to control the enantioselectivity. This approach offers a new synthetic strategy for alkene atropisomers with multiple stereogenic elements, and represents the first catalytic enantioselective rearrangement reaction of 3‐indolylmethanols, which will advance the chemistry of atropisomers and chiral indole chemistry.
Enzyme Machinery for Bacterial Glucoside Metabolism through a Conserved Non‐hydrolytic Pathway
Authors: Kastner Klara , Bitter Johannes , Pfeiffer Martin , Grininger Christoph , Oberdorfer Gustav , Pavkov‐Keller Tea , Weber Hansjörg , Nidetzky Bernd
Published: July 2024

The flexible acquisition of substrates from nutrient pools is critical for microbes to prevail in competitive environments. To acquire glucose from diverse glycoside and disaccharide substrates, many free‐living and symbiotic bacteria have developed, alongside hydrolysis, a non‐hydrolytic pathway comprised of four biochemical steps and conferred from a single glycoside utilization gene locus (GUL). Mechanistically, this pathway integrates within the framework of oxidation and reduction at the glucosyl/glucose C3, the eliminative cleavage of the glycosidic bond and the addition of water in two consecutive lyase‐catalyzed reactions. Here, based on study of enzymes from the phytopathogen Agrobacterium tumefaciens, we reveal a conserved Mn2+ metallocenter active site in both lyases and identify the structural requirements for specific catalysis to elimination of 3‐keto‐glucosides and water addition to the resulting 2‐hydroxy‐3‐keto‐glycal product, yielding 3‐keto‐glucose. Extending our search of GUL‐encoded putative lyases to the human gut commensal Bacteroides thetaiotaomicron, we discover a Ca2+ metallocenter active site in a putative glycoside hydrolase‐like protein and demonstrate its catalytic function in the eliminative cleavage of 3‐keto‐glucosides of opposite (α) anomeric configuration as preferred by the A. tumefaciens enzyme (β). Structural and biochemical comparisons reveal the molecular‐mechanistic origin of 3‐keto‐glucoside lyase stereo‐complementarity. Our findings identify a basic set of GUL‐encoded lyases for glucoside metabolism and assign physiological significance to GUL genetic diversity in the bacterial domain of life.
Gold‐Catalyzed Alkoxy‐Carbonylation of Aryl and Vinyl Iodides
Authors: Bhoyare Vivek W. , Bera Asish , Gandon Vincent , Patil Nitin T.
Published: July 2024

Herein, for the first time, we disclose the gold‐catalyzed alkoxy‐carbonylation of aryl and vinyl iodides utilizing ligand‐enabled Au(I)/Au(III) redox catalysis. The present methodology is found to be general, efficient, employs mild reaction conditions and showcases a broad substrate scope even with structurally complex molecules. Density functional theory (DFT) calculations revealed mechanistic pathways distinct from those of conventional transition metal‐catalyzed carbonylation reactions.