bluuebunny/crossref_metadata_2025 huggingface dataset:
Quantitative Cardiac Positron Emission Tomography: The Time Is Coming!
Authors: Sciagrà Roberto
Published: September 2012

In the last 20 years, the use of positron emission tomography (PET) has grown dramatically because of its oncological applications, and PET facilities are now easily accessible. At the same time, various groups have explored the specific advantages of PET in heart disease and demonstrated the major diagnostic and prognostic role of quantitation in cardiac PET. Nowadays, different approaches for the measurement of myocardial blood flow (MBF) have been developed and implemented in user-friendly programs. There is large evidence that MBF at rest and under stress together with the calculation of coronary flow reserve are able to improve the detection and prognostication of coronary artery disease. Moreover, quantitative PET makes possible to assess the presence of microvascular dysfunction, which is involved in various cardiac diseases, including the early stages of coronary atherosclerosis, hypertrophic and dilated cardiomyopathy, and hypertensive heart disease. Therefore, it is probably time to consider the routine use of quantitative cardiac PET and to work for defining its place in the clinical scenario of modern cardiology.
Traumatic Cervical Spinal Cord Injury and Income and Employment Status
Authors: Jaffe Rachael H. , Coyte Peter C. , Chan Brian C.-F. , Hancock-Howard Rebecca L. , Malhotra Armaan K. , Ladha Karim , Wilson Jefferson R. , Witiw Christopher D.
Published: June 2024

Importance

Spinal cord injury (SCI) causes drastic changes to an individual’s physical health that may be associated with the ability to work.

Objective

To estimate the association of SCI with individual earnings and employment status using national administrative health databases linked to income tax data.

Design, Setting, and Participants

This was a retrospective, national, population-based cohort study of adults who were hospitalized with cervical SCI in Canada between January 2005 and December 2017. All acute care hospitalizations for SCI of adults ages 18 to 64 years were included. A comparison group was constructed by sampling from individuals in the injured cohort. Fiscal information from their preinjury years was used for comparison. The injured cohort was matched with the comparison group based on age, sex, marital status, province of residence, self-employment status, earnings, and employment status in the year prior to injury. Data were analyzed from August 2022 to January 2023.

Main outcomes and Measures

The first outcome was the change in individual annual earnings up to 5 years after injury. The change in mean yearly earnings was assessed using a linear mixed-effects differences-in-differences regression. Income values are reported in 2022 Canadian dollars (CAD $1.00 = US $0.73). The second outcome was the change in employment status up to 5 years after injury. A multivariable probit regression model was used to compare proportions of individuals employed among those who had experienced SCI and the paired comparison group of participants.

Results

A total of 1630 patients with SCI (mean [SD] age, 47 [13] years; 1304 male [80.0%]) were matched to patients in a preinjury comparison group (resampled from the same 1630 patients in the SCI group). The mean (SD) of preinjury wage earnings was CAD $46 000 ($48 252). The annual decline in individual earnings was CAD $20 275 (95% CI, −$24 455 to −$16 095) in the first year after injury and CAD $20 348 (95% CI, −$24 710 to −$15 985) in the fifth year after injury. At 5 years after injury, 52% of individuals who had an injury were working compared with 79% individuals in the preinjury comparison group. SCI survivors had a decrease in employment of 17.1 percentage points (95% CI, 14.5 to 19.7 percentage points) in the first year after injury and 17.8 percentage points (14.5 to 21.1 percentage points) in the fifth year after injury.

Conclusions and Relevance

In this study, SCI was associated with a decline in earnings and employment up to 5 years after injury for adults aged 18 to 64 years in Canada.
Clinical Outcomes for BRCA Pathogenic Variant Carriers With Breast Cancer Undergoing Breast Conservation
Authors: Wanis Kerollos Nashat , Kuerer Henry M. , Sun Susie X. , Hunt Kelly K. , Glencer Alexa C. , Teshome Mediget , Lucci Anthony , Weiser Roi , Johnson Helen , Smith Benjamin D. , Gutierrez Angelica M. , Shaitelman Simona F. , Arun Banu K.
Published: June 2024

Importance

Although most women with BRCA-associated breast cancer choose bilateral mastectomy, current guidelines support breast-conserving therapy as an option. As the indications for genetic testing expand and targeted therapies emerge, understanding the outcomes of breast-conserving therapy in the population of patients choosing breast conservation is important.

Objective

To describe the clinical outcomes of women with BRCA-associated breast cancer who were treated with breast-conserving therapy, including the risks of ipsilateral and contralateral cancer events and bilateral mastectomy-free survival.

Design, Setting, and Participants

This cohort study conducted at a single-institution academic national comprehensive cancer center included 172 women identified from a prospectively maintained database who had pathogenic BRCA1/2 variants and were treated with breast-conserving therapy from January 1, 1977, to December 31, 2021.

Main Outcomes and Measures

Clinical and pathologic characteristics for patients with BRCA1 and BRCA2 were compared, and estimates of overall survival, bilateral mastectomy-free survival, distant disease-free survival, risk of ipsilateral breast cancer, and risk of contralateral cancer were computed.

Results

The cohort included 172 women (mean [SD] age, 47.1 [11.7] years), with 42 (24.4%) receiving a diagnosis of breast cancer prior to 40 years of age. Compared with BRCA2 variant carriers (80 [46.5%]), women with BRCA1 variants (92 [53.5%]) were younger at breast cancer diagnosis and tended to have more advanced tumors, which were more likely to be hormone receptor negative and higher grade. At a median follow-up of 11.8 years (IQR, 5.7-18.2 years), estimates of 10-year survival and risk were: overall survival, 88.5% (95% CI, 83.1%-94.2%); bilateral mastectomy-free survival, 70.7% (95% CI, 63.3%-78.9%); risk of an ipsilateral breast cancer event, 12.2% (95% CI, 5.8%-18.2%); and risk of contralateral cancer, 21.3% (95% CI, 13.3%-28.6%). Risks continued to increase after 10 years of follow-up.

Conclusions and Relevance

In this cohort study, although women with breast cancer and pathogenic BRCA1/2 variants treated with breast-conserving therapy had above-average risks of ipsilateral and contralateral breast cancer events, most did not have another cancer event and remained bilateral mastectomy free. These findings may be useful for informing patients with BRCA variants choosing breast conservation.
Review of source models for reproducing and predicting strong motions by empirical Green's function method
Authors: Dan Kazuo
Published: June 2024

Short‐period ground motions from earthquakes are calculated by semiempirical methods such as the empirical Green's function method or the stochastic Green's function method. In this review paper, I summarized source models developed for reproducing and predicting ground motions in the theoretical methods at first, and then reviewed the source models applied to reproducing and predicting ground motions in the empirical Green's function method in these about 40 years. Finally, I showed some issues to be solved about source modeling in order to predict accurate short‐period motions in the near‐fault regions.
Real-time triplex loop-mediated isothermal amplification (LAMP) using a turbidimeter for detection of shrimp infectious hypodermal and hematopoietic necrosis virus (IHHNV)
Authors: Arunrut Narong , Jitrakorn Sarocha , Tondee Benyatip , Saksmerprome Vanvimon , Kiatpathomchai Wansika
Published: June 2024

Objective

The World Organization for Animal Health still regulates the infectious hypodermal and hematopoietic necrosis virus (IHHNV) in shrimp. The existing disease identification approach is time consuming, necessitates expensive equipment, and requires specialized expertise, thereby limiting the accessibility of shrimp disease screening on farms. Loop-mediated isothermal amplification (LAMP) is recognized for its ability to detect inhibitory substances with high sensitivity and specificity.

Methods

We developed a real-time triplex LAMP assay that combines the simplicity of point-of-care testing with the accuracy of a turbidimeter. Using a set of three LAMP primers, our technology enables rapid DNA amplification in a single reaction within 45 min and with a low detection limit (10 copies/reaction).

Result

We tested 192 shrimp samples from different sources and demonstrated the clinical utility of our method, achieving 100% specificity (95% confidence interval = 93.40–100.00%), 100% sensitivity (97.36–100.00%), and 100% accuracy (98.10–100.00%) in detecting IHHNV DNA, with a high Cohen's kappa value (1) compared to the standard quantitative polymerase chain reaction assay.

Conclusion

The high technology readiness level of our method makes it a versatile platform for any real-time LAMP assay, and its low cost and simplicity make it well suited for fast deployment and use in shrimp farming.

Abstract

Impact statement Introducing our real-time triplex LAMP assay, a game-changer in shrimp disease detection. Combining simplicity with precision, our technology delivers results in under 45 min, enabling timely disease management. With high sensitivity and specificity, it outperforms quantitative polymerase chain reaction, offering a cost-effective and versatile solution for shrimp farming.
A robust index for metal artifact quantification in computed tomography
Authors: Cammin Jochen
Published: June 2024

Background

Objective assessment of metal artifact strength and the effectiveness of metal artifact reduction algorithms in computed tomography requires a quantitative metric. Metrics described in the literature are typically employed to compare the artifact strength in images reconstructed from the same raw data, but their robustness against varying scan conditions and repeated scans over time as it occurs in periodic quality assurance has not been investigated.

Purpose

A new robust metric for quantifying metal artifacts in computed‐tomography images is proposed and compared to other commonly used metrics.

Methods

The proposed artifact metric is based on the location parameter of the Gumbel distribution, described previously in the literature, but normalized to the location parameter in a background region‐of‐interest to obtain a noise‐independent artifact metric. The metric was compared to three other quantitative metal artifact metrics (artifact‐index, contrast‐to‐noise ratio, Gumbel‐evaluation method) by evaluating metals artifacts in phantom scans and in clinical images. Robustness of the artifact metrics was evaluated using repeated scans with varying noise and against small variations in the selected regions‐of‐interest.

Results

The proposed artifact metric was independent of the underlying image noise and could be reproduced more consistently under slight changes of the region‐of‐interest within the artifact than the other investigated methods. The coefficient‐of‐variation was 5.7% on average with varying regions‐of‐interest in phantom scans and 2.5% in patient scans compared to 9.2% in phantoms scans and 9.9% in patient scans for the next‐best performing noise‐independent metric. Setup reproducibility was better than 5% and was comparable to the other metrics. The new metric correlated linearly with the artifact strength. The contrast‐to‐noise ratio, although often used in artifact quantification, was found to be an inadequate metric due to its lack of robustness against minute changes in the position, size, and pixel values of the region‐of‐interest chosen for calculating the metric and because it showed no correlation with the artifact strength.

Conclusions

A new metal artifact metric has been proposed that is robust under changing scan conditions and less sensitive to user‐dependent choices of the region‐of‐interest than other metrics. The new metric is straightforward to calculate and simple to implement in software commonly used for evaluation of medical imaging systems.
Perspective of Dutch Patients with Gout on Continuation or Discontinuation of Urate‐Lowering Therapy During Remission: A Mixed‐Methods Study
Authors: Peeters Iris Rose , Veenstra Frouwke , Wanten Sophie A. C. , Vriezekolk Johanna E. , van den Ende Cornelia H. , den Broeder Alfons A. , van Herwaarden Noortje , Verhoef Lise M. , Flendrie Marcel
Published: June 2024

Objective

Long‐term gout management is based on reducing serum urate by using urate‐lowering therapy (ULT). A lifelong treat‐to‐target approach is advocated, although a ULT (taper to) stop attempt can be considered (treat‐to‐avoid symptoms approach) during remission. Exploring the beliefs of patients with gout on long‐term ULT strategies during remission is important for optimizing gout management. We aimed to identify factors that influence the decision for continuation or discontinuation of ULT and to determine their relative importance according to patients with gout in remission.

Methods

A mixed‐methods design was used. First, semistructured interviews (substudy 1) were conducted to identify barriers and facilitators for the (dis)continuation of ULT using inductive thematic analysis. Afterwards, these barriers/facilitators were summarized into neutrally phrased items and used in a maximum difference scaling study (substudy 2) to determine their relative importance using the rescaled probability score.

Results

Substudies 1 and 2 included 18 and 156 patients, respectively. Substudy 1 yielded 22 items within 10 overarching themes. Substudy 2 revealed that the perceived risk of joint damage and gout flares and that ULT use gives some assurance were the most important items. The costs, ease of receiving ULT, and its practical use were the least important items.

Conclusion

These results can aid shared decision‐making and provide input for what is important to discuss with patients with gout in remission when they consider ULT discontinuation. The emphasis should be on the risk of having gout flares and joint damage, not so much on facilitating how easily medication is received.
Wide‐Angled Pragmatic Dielectric Chiral Meta‐Platform for Spin‐ and Wavelength‐Multiplexed Holography in the Ultraviolet and Visible
Authors: Asad Aqsa , Seong Junhwa , Khaliq Hafiz Saad , Lee Jae‐Won , Jeon Youngsun , Cabrera Humberto , Mehmood Muhammad Qasim , Gao Lei , Kim Hak‐Rin , Rho Junsuk
Published: June 2024

A chiral meta‐optics platform that incorporates hologram‐multiplexing with low phase distortion and wide‐incident angle tolerance over the broad spectral range of the ultraviolet‐visible (UV–vis) regimes holds great potential for photonic‐encryption‐based applications, particularly in next‐generation 3D displays, high‐resolution biomedical imaging, holographic anti‐counterfeiting labeling, and multi‐channel optical communication. However, the design incorporating giant chirality from UV–vis wavelengths coupled with wide‐incident‐angle tolerance and cost‐effective fabrication is still challenging. Here, the study introduces a pragmatic multifunctional dielectric chiral meta‐platform designed for simultaneous spin‐ and wavelength‐multiplexing of optical information in the UV–vis spectrum. The unit cell comprises a dimer structure based on wide‐bandgap silicon nitride (SiNx), ensuring substantial dual‐spectrum chiro‐optical effects. The meticulously engineered chiral meta‐platform offers an incident angle tolerance of up to 40 degrees, coupled with significant chiro‐optical transmission. To demonstrate the concept, two distinct phase profiles are embedded in the meta‐platform, utilizing the spin and wavelength of incident light as keys to unlock the specific holographic information. The chiral meta‐platform is experimentally validated for oblique illumination angles, showcasing its adaptability across the UV–vis spectrum. The demonstrated meta‐device with dual‐spectrum visual encryption can be applied in various anti‐counterfeiting and security applications.
Atomic Co/Cu Dual‐Metal for Rapid Conversion of 5‐Hydroxymethylfurfural under Ambient Pressure
Authors: Jing Tianyun , Yang Shaokang , Li Tingting , Wan Yangyang , Jia Huimin , Feng Yonghai , Zuo Yunpeng , Rao Dewei
Published: June 2024

Atomic scaling of cobalt‐based catalysts is the feasible and sustainable approach for selective oxidation of biomass‐derived 5‐hydroxymethylfurfural (HMF) to produce bio‐plastic monomer of 2,5‐furandicarboxylic acid (FDCA) under mild conditions. Here, a high‐efficiency dual single‐atomic Co/Cu supported on nitrogen‐doped carbon (a‐Co/Cu‐NC) is constructed. Leveraging exceptional oxygen activation ability, the Co/Cu dual‐atomic‐sites can accelerate the HMF oxidation, suppressing by‐product formation mediated by reactive oxygen species (ROS) in low‐oxygen environments. This leads to enhanced FDCA selectivity with a yield of 98% and a production rate of 298.8 mmolFDCA gmetal−1 h−1 under ambient conditions. Comprehensive experiments and density functional theory (DFT) calculations demonstrate that long‐range interactions between Co and Cu sites optimize reactant adsorption and lower energy barriers for •O2− and HMFCA formation.
Achieving Ultra‐Broadband Sunlight‐Like Emission in Single‐Phase Phosphors: The Interplay of Structure and Luminescence
Authors: Liu Shuifu , Li Liyi , Qin Xinghui , Du Rongkai , Sun Yifan , Xie Shixing , Wang Jiaqi , Molokeev Maxim S. , Xi Shibo , Bünzli Jean‐Claude G. , Zhou Lei , Wu Mingmei
Published: June 2024

The quest for artificial light sources mimicking sunlight has been a long‐standing endeavor, particularly for applications in anticounterfeiting, agriculture, and color hue detection. Conventional sunlight simulators are often cost‐prohibitive and bulky. Therefore, the development of a series of single‐phase phosphors Ca9LiMg1‐xAl2x/3(PO4)7:0.1Eu2+ (x = 0‐0.75) with sunlight‐like emission represents a welcome step towards compact and economical light source alternatives. The phosphors are obtained by an original heterovalent substitution method and emit a broad spectrum   spanning from violet to deep red. Notably, the phosphor with x = 0.5 exhibits an impressive full width at half‐maximum of 330 nm. A synergistic interplay of experimental investigations and theory unveils the mechanism behind sunlight‐like emission due to the local structural perturbations introduced by the heterovalent substitution of Al3+ for Mg2+, leading to a varied distribution of Eu2+ within the lattice. Subsequent characterization of a series of organic dyes combining absorption spectroscopy with convolutional neural network analysis convincingly demonstrates the potential of this phosphor in portable photodetection devices. Broad‐spectrum light source testing empowers the model to precisely differentiate dye patterns. This points to the phosphor being ideal for mimicking sunlight. Beyond this demonstrated application, the phosphor's utility is envisioned in other relevant domains, including visible light communication and smart agriculture.
High‐Performance Ceramic Catalyst Filters with Textured Waveguides for Efficient Removal of Volatile Organic Compounds
Authors: Kim Jawon , Park Jeonghyeon , Koo Min Seok , Cho Won Seok , Moon Seokho , Hwang Inyong , Kim Jaerim , Park Jae Yong , Ham Dong Jin , Lee Hyun Chul , Kim Jong Kyu
Published: June 2024

The cordierite‐based ceramic catalyst filter (CCF) has attracted considerable attention as a promising future air purification system due to its ability to filtrate particulate matter (PM), as well as decompose volatile organic compounds (VOCs) through ultraviolet (UV)‐activated photocatalytic reactions. Its performance, however, is strictly limited because majority of UV photons are absorbed near the entrance of the high‐aspect‐ratio air‐flow channels, thus, only a limited portion of photocatalysts is activated during the flow of polluted air. In this study, a high‐performance CCF is presented featuring textured waveguides (TWs) aligned with an array of UV light‐emitting diodes (LEDs) emitting at a peak wavelength of 365 nm, which are inserted into an array of high‐aspect‐ratio channels. TWs ensure the delivery of UV photons deep inside channels via total internal reflection and scattering, enabling the activation of majority of photocatalysts, resulting in remarkable improvement in VOCs removal efficiency. The proposed CCF system exhibits much higher formaldehyde (HCHO) removal efficiency by 70% compared to conventional CCF systems even subjected to much lower UV light power densities. It is strongly believed that it is possible to further improve the removal efficiency, while maintaining effective PM filtering and ultralow electrical power consumption, by optimization of the geometry of the CCF system with TWs.
Stability of Free and Liposomal Encapsulated RNA on a Mucoadhesive PVA Polymer for Esophageal RNA Drug Targeting Using the EsoCap System
Authors: Weide Aileen , Brokmann Friederike , Appel Bettina , Rosenbaum Christoph , Krause Julius , Janke Una , Delcea Mihaela , Weitschies Werner , Müller Sabine
Published: June 2024

The development of RNA and oligonucleotide‐based therapeutics is a longstanding goal and is currently gaining significant attention. Several RNA‐based drugs are approved for clinical use. Others are under investigation or in preclinical trials. This study have initiated the development of RNA drugs for localized use in the esophagus, utilizing the EsoCap System. This system's core component is a mucoadhesive film that carries the RNA drug and is precisely applied to the esophagus. Research into the stability and properties of naked and liposomal‐encapsulated RNA on mucoadhesive polymer film reveals that RNAs remain stable in various conditions without degradation, RNA leakage, or liposome fusion observed. The liposome size also remains constant after application on the film, drying, and rehydration. These findings pave the way for RNA drug development for esophageal diseases and their administration via the EsoCap system.
Gold Nanostructures for an Effective Bone Cancer Therapy: Numerical Simulation and Experimental Investigation
Authors: Mohammadzadeh Mahsa , Labbaf Sheyda , Kermanpur Ahmad
Published: June 2024

Gold nanostructures play a crucial role in medical applications, harnessing size and shape‐dependent properties. A prominent area of research is cancer treatment through the photothermal approach. Here, numerical simulation is explored to study the impact of gold nanostructure size, shape, and laser parameters on spatiotemporal temperature patterns during photothermal therapy (PTT). Spherical, rod, star, bipyramid, and cubic nanostructures in small, medium, and large sizes underwent 150 s of laser irradiation. COMSOL software, incorporating bioheat physics, precisely gauged thermal variations. The structural characteristics notably influence the temperature profiles, with medium‐sized rod, star, and bipyramid gold nanoparticles exhibiting superior thermal properties. Experimental validation of simulations focuses on the optimal nanostructure, synthesizing through the seed growth method. Transmission electron microscopy, UV‐visible spectroscopy, and X‐ray diffraction analysis confirm its proposed characteristics. Results demonstrate a robust correlation between experimental and simulation parameters, affirming precision. Findings showcase photothermal properties in line with theoretical predictions. The aim of this study is to determine the optimal gold nanostructure for bone cancer treatment using PTT, addressing the challenges presented by the dense and resilient nature of bone tissue and deep tumor locations. By utilizing multi‐physical modeling and simulations facilitated by COMSOL software, a novel method for pre‐clinical estimation is introduced. This research provides insights into each nanoparticle‐based PTT process prior to ex vivo and in vivo studies, offering a comprehensive understanding of the interplay between nanostructure characteristics and PTT outcomes. The approach contributes to advancing the field of cancer treatment by enhancing the predictability and effectiveness of nanoparticle‐mediated PTT.
Application of Physical Statistical Modeling in the Adsorption of the Drug Ketoprofen and the 2,4‐D Herbicide using the Bark Campomanesia Guazumifolia Forest Species Modified with H2SO4 as an Adsorbent
Authors: Aouaini Fatma , Dhaouadi Fatma , Georgin Jordana , Franco Dison S. P. , Alyousef Haifa , Erto Alessandro , Lamine Abdelmottaleb Ben
Published: June 2024

Emerging pollutants are a widespread environmental concern, andadsorption represents one of the choices available for the removal of suchcompounds from polluted waters. However, the set‐up of a new adsorption system requiresthe experimental determination of adsorption isotherms and their thoroughmodelling, for the sake of a convenient optimization. In this work, the Campomanesia guazumifolia biomass is adopted as precursor for the synthesis of anew adsorbent and then tested for the adsorption of KTP and 2,4‐D. Theadsorption performances of this biomass are significantly improved through atreatment with sulfuric acid, which allows obtaining higher removal efficiency ofthe target organic molecules. The experimental isotherms are measured at 298 – 328 K and pH 2. An ETAM model is employed for amodeling analysis of the experimental data, for the comprehension of theoccurring adsorption mechanism. Results demonstrated that adsorption of KTP isendothermic and occurs in multilayer with a multimolecular process, in whichthe molecular aggregation can be predicted. On the contrary, the adsorption of 2,4‐D on this functionalized biomass is exothermic. The adsorption energiesresulted to be < 40 kJ mol−1, indicating that physical adsorption forces are involved inthe removal of these organic molecules.
A Network Toxicology Approach for Mechanistic Modelling of Nanomaterial Hazard and Adverse Outcomes
Authors: del Giudice Giusy , Serra Angela , Pavel Alisa , Torres Maia Marcella , Saarimäki Laura Aliisa , Fratello Michele , Federico Antonio , Alenius Harri , Fadeel Bengt , Greco Dario
Published: June 2024

Hazard assessment is the first step in evaluating the potential adverse effects of chemicals. Traditionally, toxicological assessment has focused on the exposure, overlooking the impact of the exposed system on the observed toxicity. However, systems toxicology emphasizes how system properties significantly contribute to the observed response. Hence, systems theory states that interactions store more information than individual elements, leading to the adoption of network based models to represent complex systems in many fields of life sciences. Here, they develop a network‐based approach to characterize toxicological responses in the context of a biological system, inferring biological system specific networks. They directly link molecular alterations to the adverse outcome pathway (AOP) framework, establishing direct connections between omics data and toxicologically relevant phenotypic events. They apply this framework to a dataset including 31 engineered nanomaterials with different physicochemical properties in two different in vitro and one in vivo models and demonstrate how the biological system is the driving force of the observed response. This work highlights the potential of network‐based methods to significantly improve their understanding of toxicological mechanisms from a systems biology perspective and provides relevant considerations and future data‐driven approaches for the hazard assessment of nanomaterials and other advanced materials.
Exploring Structural Evolution Behaviors of Ligand‐Defect‐Rich Ferrocene‐Based Metal‐Organic Frameworks for Electrochemical Oxygen Evolution via Operando X‐Ray Absorption Spectroscopy
Authors: Sun Fengzhan , Li Zhao , Xu Hao , Fu Yang , Li Hui , Yao Yingying , Ren Li , He Xiaoqian , Li Yinghui , Yang Rui , Zhang Nian , Hu Zhigang , Ma Tianyi , Zou Jianxin
Published: June 2024

Metal‐organic frameworks (MOFs) have exhibited encouraging catalytic activity for the oxygen evolution reaction (OER), a crucial process for water electrolysis to produce green hydrogen. Nonetheless, distinguishing the source of catalytic activity and establishing the structure‐composition‐property relationships of MOFs during OER processes remain challenging. Here, for the first time, operando X‐ray absorption spectroscopy (XAS) is utilized to monitor the structural evolution and identify the active components of ferrocene‐based MOFs (Ni‐Fc) for OER. Ligand‐defect‐rich Ni‐Fc is synthesized via the co‐deposition method. After electrochemical activation, Ni‐Fc exhibits superior electrocatalytic activity (228 mV at 10 mA cm−2 in 0.1 m KOH), which is highly competitive compared with state‐of‐the‐art electrocatalysts. Operando XAS analysis and ex‐situ characterizations reveal the structural reconstruction of Ni‐Fc into amorphous NiFe‐catalysts (a‐NiFe) during the activation process, and further into real catalytic phases (a‐NiFe‐C) under catalytic potential greater than 1.45 V (vs RHE). In catalytic phases, in‐situ formed deprotonated and oxygen‐defected Ni oxyhydroxide analogues act as catalytic sites, while Fe hydroxide analogues derived from ligands optimize the electronic structure of Ni sites for improving OER activity. Density functional theory (DFT) analysis indicates a reduced energy barrier in a‐NiFe‐C compared to pristine MOFs, supporting the improved catalytic activity of the latter.
In‐Situ Laser Synthesis of Molecularly Dispersed and Covalently Bound Phosphorus‐Graphene Adducts as Self‐Standing 3D Anodes for High‐Performance Fast‐Charging Lithium‐Ion Batteries
Authors: Daffan Gil , Kothuru Avinash , Eran Assaf , Patolsky Fernando
Published: June 2024

Phosphorus shows promise as a next‐generation anode material due to its high theoretical capacity of 2596 mAh g−1. However, challenges such as low conductivity, severe volume expansion, and the dissolution and migration of electrolyte‐soluble lithium polyphosphides hamper high‐performance capabilities. While carbon composites are widely researched as a solution through the physical encapsulation of micro‐nano‐phosphorus domains, anodes still exhibit low cycling stability and rate performance. In response, this work proposes a new approach, focusing on chemical anchoring and molecular dispersion of phosphorus within the carbon host. Through laser irradiation of a red phosphorus/phenolic resin blend, in‐situ covalent binding of molecular phosphorus adducts to the as‐forming laser‐induced graphene is observed; directly synthesizing an additive‐free, flexible and 3‐dimensional mesoporous composite anode with high phosphorus content (33 wt.%), specific surface area (163.4 m2 g−1) and intrinsic conductivity (12 S cm−1). These anodes demonstrate remarkable cycling stability, with capacity retention of 98% after 3000 cycles at a high current density of 2 A g−1 and capacity of 673 mAh g−1.   The high cycling stability is further confirmed through the complete inhibition of lithium polyphosphide “shuttle effect” by chemical anchoring of the molecularly dispersed active material. Furthermore, scale‐up prospects utilizing laser‐assisted additive manufacturing are investigated.
Flexible healable electromagnetic‐interference‐shielding bioelastic hydrogel nanocomposite for machine learning‐assisted highly sensitive sensing bioelectrode
Authors: Zhang Yunfei , Li Zehui , Xu Zhishan , Xiao Mingyue , Yuan Yue , Jia Xiaolong , Shi Rui , Zhang Liqun , Wan Pengbo
Published: June 2024

The prosperous evolution of conductive hydrogel‐based skin sensors is attracting tremendous attention nowadays. Nevertheless, it remains a great challenge to simultaneously integrate excellent mechanical strength, desirable electrical conductivity, admirable sensing performance, and brilliant healability in hydrogel‐based skin sensors for high‐performance diagnostic healthcare sensing and wearable human‐machine interface, as well as robust photothermal performance for promptly intelligent photothermal therapy followed by the medical diagnosis and superior electromagnetic interference (EMI) shielding performance for personal protection. Herein, a flexible healable MXene hydrogel‐based skin sensor is prepared through a delicate combination of MXene (Ti3C2Tx) nanosheets network with the polymeric network. The as‐prepared skin sensor is featured with significantly enhanced mechanical, conducting, and sensing performances, along with robust self‐healability, good biocompatibility, and reliable injectability, enabling ultrasensitive human motion monitoring and teeny electrophysiological signals sensing. As a frontier technology in artificial intelligence, machine learning can facilitate to efficiently and precisely identify the electromyography signals produced by various human motions (such as variable finger gestures) with up to 99.5% accuracy, affirming the reliability of the machine learning‐assisted gesture identification with great potential in smart personalized healthcare and human‐machine interaction. Moreover, the MXene hydrogel‐based skin sensor displays prominent EMI shielding performance, demonstrating the great promise of effective personal protection.
Spending, utilization, and coverage for chronic rhinosinusitis with nasal polyposis therapies among Medicare Advantage beneficiaries
Authors: Bhat Akash M. , Soler Zachary M. , Rathi Vinay K. , Schlosser Rodney J.
Published: June 2024

Key points

CRSwNP‐specific mean total annual spending ranged from $5,837 (EDS‐FLU) to $28,058 (dupilumab).

Most CRSwNP patients receiving biologics had comorbid asthma and did not undergo sinus surgery.

While biologics were covered by most Medicare Part D plans, only 37% of plans covered EDS‐FLU.
Ab Initio Investigation of the Relativistic Effect in the Physical Properties of Intermetallic Superconductor TlBi2${\rm TlBi}_2$ with AlB2${\rm AlB}_2$‐Type Hexagonal Layer Structure
Authors: Tütüncü H. M. , Baǧcı Sadık , Uzunok Hüseyin Yasin , Srivastava G. P.
Published: June 2024

In this work, the role of spin‐orbit coupling (SOC) in the physical properties of is reported. These electronic calculations reveal that the heavy elements Tl and Bi promote strong spin‐orbit coupling, lifting some of the degeneracies at the high‐symmetry points. The presence of SOC causes significant decreases in both elastic constants and elastic moduli, which in turn improve the compatibility of the calculated Debye temperature ( = 80 K) with the recent experimental data of 83 K. Furthermore, our quasi‐static harmonic approximation calculation, like this elastic constant calculation, confirms that taking SOC into account improves agreement with the experiment by decreasing value of Debye temperature from 95 to 85 K. Activating the SOC causes significant modifications in the phonon spectrum and the density of phonon states, as well as in the Eliashberg spectral function. As a result of these modifications, the electron–phonon coupling parameter () increases from 1.178 to 1.259, by . The calculated values of both with and without SOC imply that can be treated as phonon‐mediated superconductor with strong coupling. The SOC‐induced increase in brings the superconducting transition temperature of from 6.076 to 6.211 K, which is almost equal to the recent experimental value of 6.2 K.
Chromium‐ and Metal‐Reductant‐Free Asymmetric Nozaki–Hiyama–Kishi (NHK) Reaction Enabled by Metallaphotoredox Catalysis
Authors: Gu Pei , Ding Linlin , Fang Xiaowu , Zhu Jie , Kang Shuyu , Wu Bingcheng , Zhang Jie , Zhao Yue , Shi Zhuangzhi
Published: June 2024

Chiral allylic alcohols are highly prized in synthetic chemistry due to their versatile reactivity stemming from both alkenyl and hydroxyl functionalities. While the Nozaki–Hiyama–Kishi (NHK) reaction is a widely used method for the synthesis of allylic alcohols, it suffers from drawbacks such as the use of toxic chromium salts, high amounts of metal reductants, and poor enantiocontrol. To address these limitations, we present a novel approach involving a metallaphotoredox‐catalyzed asymmetric NHK reaction for the production of chiral allylic alcohols. This method marries alkenyl (pseudo)halides with aldehydes, leveraging a synergistic blend of a chiral nickel catalyst and a photocatalyst. This innovative technique enables both oxidative addition and insertion just using nickel, diverging significantly from the conventional NHK reaction pathway mediated by nickel and chromium salts. The adoption of this methodology holds immense promise for crafting a spectrum of intricate compounds, particularly those of significance in pharmaceuticals. Detailed experimental investigations have shed light on the metallaphotoredox process, further enhancing our understanding and enabling further advancements.
Enhancement of Low Temperature Superionic Conductivity by Suppression of Li Site Ordering in Li7Si2–xGexS7I
Authors: Han Guopeng , Daniels Luke M. , Vasylenko Andrij , Morrison Kate A. , Corti Lucia , Collins Chris M. , Niu Hongjun , Chen Ruiyong , Roberston Craig M. , Blanc Frédéric , Dyer Matthew S. , Claridge John B. , Rosseinsky Matthew J.
Published: June 2024

Ge4+ substitution into the recently discovered superionic conductor Li7Si2S7I is demonstrated by synthesis of Li7Si2–xGexS7I, where x≤1.2. The anion packing and tetrahedral silicon location of Li7Si2S7I are retained upon substitution. Single crystal X‐ray diffraction shows that substitution of larger Ge4+ for Si4+ expands the unit cell volume and further increases Li+ site disorder, such that Li7Si0.88Ge1.12S7I has one Li+ site more (sixteen in total) than Li7Si2S7I. The ionic conductivity of Li7Si0.8Ge1.2S7I (x=1.2) at 303 K is 1.02(3)×10−2 S cm−1 with low activation energies for Li+ transport demonstrated over a wide temperature range by AC impedance and 7Li NMR spectroscopy. All sixteen Li+ sites remain occupied to temperatures as low as 30 K in Li7Si0.88Ge1.12S7I as a result of the structural expansion. This differs from Li7Si2S7I, where the partial Li+ site ordering observed below room temperature reduces the ionic conductivity. The suppression of Li+ site depopulation by Ge4+ substitution retains the high mobility to temperatures as low as 200 K, yielding low temperature performance comparable with state‐of‐the‐art Li+ ion conducting materials.
Catalytic Atroposelective Synthesis of C−N Axially Chiral Aminophosphines via Dynamic Kinetic Resolution
Authors: Rodríguez‐Franco Carlos , Roldán‐Molina Esther , Aguirre‐Medina Alberto , Fernández Rosario , Hornillos Valentín , Lassaletta José M.
Published: June 2024

A ruthenium‐catalyzed reductive amination via asymmetric transfer hydrogenation (ATH) has been used to perform an efficient dynamic kinetic resolution (DKR) of N‐aryl 2‐formyl pyrroles decorated with a phosphine moiety positioned at the ortho’ position. The strategy relies on the labilization of the stereogenic axis in the substrate facilitated by a transient Lewis acid‐base interaction (LABI) between the carbonyl carbon and the phosphorus center. The reaction features broad substrate scope of aliphatic amines and N‐aryl pyrrole scaffolds, and proceeds under very mild conditions to afford P,N atropisomers in good to high yields and excellent enantioselectivities (up to 99 % ee) for both diphenyl and dicyclohexylphosphino derivatives.
Formal High‐Order Cycloadditions of Donor‐Acceptor Cyclopropanes with Cycloheptatrienes
Authors: Borisov Denis D. , Platonov Dmitry N. , Sokolov Nikita A. , Novikov Roman A. , Tomilov Yury V.
Published: June 2024

The design of various cycloaddition/annulation processes is one of the most intriguing challenges in the development of donor‐acceptor (D–A) cyclopropane chemistry. In this work, a new class of formal high‐order [6+n]‐cycloaddition and annulation processes of D–A cyclopropanes with cycloheptatriene systems has been designed and reported, to fill a significant gap in the chemistry of D–A cyclopropanes. The reactivity of methylated cycloheptatrienes from Me1 to Me5 as well as unsubstituted cycloheptatriene was studied in detail under GaCl3 activation conditions, which makes it possible to efficiently generate gallium 1,2‐zwitterionic complexes or 1,3‐zwitterionic intermediates starting from D–A cyclopropanes, while other Lewis acids are ineffective and non‐selective. New examples of formal [6+2]‐, [6+3]‐, [6+4]‐, [6+1]‐, and [4+2]‐cycloaddition and annulation reactions with cycloheptatrienes along with more complex processes were discovered. Cycloheptatriene itself can also successfully act as a hydride anion donor, which allows the ionic hydrogenation of D–A cyclopropanes to be performed under mild conditions. As a result, a number of efficient and highly diastereoselective protocols for the synthesis of seven‐membered carbocycles has been developed.
Anchoring Cs+ Ions on Carbon Vacancies for Selective CO2 Electroreduction to CO at High Current Densities in Membrane Electrode Assembly Electrolyzers
Authors: Sun Yanhui , Chen Junxiang , Du XueMei , Cui Jiwei , Chen Xin , Wu Chenhe , Yang Xinmin , Liu Lequan , Ye Jinhua
Published: June 2024

Electrolyte cations have been demonstrated to effectively enhance the rate and selectivity of the electrochemical CO2 reduction reaction (CO2RR), yet their implementation in electrolyte‐free membrane electrode assembly (MEA) electrolyzer presents significant challenges. Herein, an anchored cation strategy that immobilizes Cs+ on carbon vacancies was designed and innovatively implemented in MEA electrolyzer, enabling highly efficient CO2 electroreduction over commercial silver catalyst. Our approach achieves a CO partial current density of approximately 500 mA cm−2 in the MEA electrolyzer, three‐fold enhancement compared to pure Ag. In situ Raman and theoretical analyses, combined with machine learning potentials, reveal anchored Cs induces an electric field that significantly promotes the adsorption of *CO2− intermediates through performing muti‐point energy calculations on each structure. Furthermore, reduced adsorption of *OH intermediates effectively hampers competing hydrogen evolution reaction, as clarified by disk electrode experiments and density functional theory studies. Additionally, coupling our system with commercial polysilicon solar cells yields a notable solar‐to‐CO energy conversion efficiency of 8.3 %. This study opens a new avenue for developing effective cation‐promoting strategy in MEA reactors for efficient CO2RR.
Harnessing Cooperative Multivalency in Thioguanine for Surface‐Enhanced Raman Scattering (SERS)‐Based Differentiation of Polyfunctional Analytes Differing by a Single Functional Group
Authors: Nguyen Lam Bang Thanh , Tan Emily Xi , Leong Shi Xuan , Koh Charlynn Sher Lin , Madhumita Murugan , Phang In Yee , Ling Xing Yi
Published: June 2024

Small‐molecule receptors are increasingly employed to probe various functional groups for (bio)chemical analysis. However, differentiation of polyfunctional analogs sharing multiple functional groups remains challenging for conventional mono‐ and bidentate receptors because their insufficient number of binding sites limits interactions with the least reactive yet property‐determining functional group. Herein, we introduce 6‐thioguanine (TG) as a supramolecular receptor for unique tridentate receptor‐analyte complexation, achieving ≥97 % identification accuracy among 16 polyfunctional analogs across three classes: glycerol derivatives, disubstituted propane, and vicinal diols. Crucially, we demonstrate distinct spectral changes induced by the tridentate interaction between TG's three anchoring points and all the analyte's functional groups, even the least reactive ones. Notably, hydrogen bond (H‐bond) networks formed in the TG‐analyte complexes demonstrate additive effects in binding strength originating from good bond linearity, cooperativity, and resonance, thus strengthening complexation events and amplifying the differences in spectral changes induced among analytes. It also enhances spectral consistency by selectively forming a sole configuration that is stronger than the respective analyte‐analyte interaction. Finally, we achieve 95.4 % accuracy for multiplex identification of a mixture consisting of multiple polyfunctional analogs. We envisage that extension to other multidentate non‐covalent interactions enables the development of interference‐free small molecule‐based sensors for various (bio)chemical analysis applications.
Closed‐Loop Recyclable and Totally Renewable Liquid Crystal Networks with Room‐Temperature Programmability and Reconfigurable Functionalities
Authors: Zhang Chenxuan , Zhang Zhuoqiang , Liu Xiaokong
Published: June 2024

Dynamic covalent liquid crystal networks (DCv‐LCNs) with straightforward (re)programmability, reprocessability, and recyclability facilitates the manufacture of sophisticated LCN actuators and intelligent robots. However, the DCv‐LCNs are still limited to heat‐assisted programming and polymer‐to‐polymer reprocessing/recycling, which inevitably lead to deterioration of the LCN structures and the actuation performances after repeated programming/processing treatments, owing to the thermal degradation of the polymer network and/or external agent interference. Here, a totally renewable azobenzene‐based DCv‐LCN with room‐temperature programmability and polymer‐to‐monomers chemical recyclability is reported, which was synthesized by crosslinking the azobenzene‐containing dibenzaldehyde monomer and the triamine monomer via the dynamic and dissociable imine bonds. Thanks to the water‐activated dynamics of the imine bonds, the resultant DCv‐LCN can be simply programmed, upon water‐soaking at room temperature, to yield a UV/Vis light‐driven actuator. Importantly, the reported DCv‐LCN undergoes depolymerization in an acid‐solvent medium at room temperature because of the acid‐catalyzed hydrolysis of the imine bonds, giving rise to easy separation and recovery of both monomers in high purity, even with tolerance to additives. The recovered pure monomers can be used to regenerate totally new DCv‐LCNs and actuators, and their functionalities can be reconfigured by removing old and introducing new additives, by implementing the closed‐loop polymer‐monomers‐polymer recycling.
Clinical Issues — July 2024
Authors: Seeman Kristyn , Caso Jamie
Published: June 2024

THIS MONTH

Cleaning surgical instruments after use in a procedure involving chemotherapeutic medications

Key words: deactivation, decontamination, cleaning, disinfection, chemotherapeutic medication.

Paper count sheets sterilized inside instrument sets

Key words: count sheets, instrument sets, printer ink, toner, toxicity.

Off‐label use of dental devices during direct laryngoscopy

Key words: mouth guard, dental injury, direct laryngoscopy, anesthesia, intubation.

Using intermittent pneumatic compression devices on patients in lithotomy position

Key words: mechanical compression devices, compartment syndrome, lithotomy, venous thromboembolism, thromboprophylaxis.