bluuebunny/crossref_metadata_2025 huggingface dataset:
Associations Between New York Heart Association Classification, Objective Measures, and Long-term Prognosis in Mild Heart Failure
Authors: Rohde Luis E. , Zimerman André , Vaduganathan Muthiah , Claggett Brian L. , Packer Milton , Desai Akshay S. , Zile Michael , Rouleau Jean , Swedberg Karl , Lefkowitz Martin , Shi Victor , McMurray John J. V. , Solomon Scott D.
Published: December 2022

Importance

Heart failure (HF) treatment recommendations are centered on New York Heart Association (NYHA) classification, such that most apparently asymptomatic patients are not eligible for disease-modifying therapies.

Objectives

To assess within-patient variation in NYHA classification over time, the association between NYHA class and an objective measure of HF severity (N-terminal pro–B-type natriuretic peptide [NT-proBNP] level), and their association with long-term prognosis in the PARADIGM-HF trial.

Design, Setting, and Participants

All patients in PARADIGM-HF were in NYHA class II or higher at baseline and were treated with sacubitril-valsartan during a 6- to 10-week run-in period before randomization. Patients classified as NYHA class I, II, and III in PARADIGM-HF were compared at randomization.

Exposures

NYHA class at randomization after 6 to 10 weeks of the run-in period.

Main Outcomes and Measures

Primary outcome was cardiovascular death or first HF hospitalization. Logistic regression models, areas under the receiver operating characteristic curve (AUC), kernel density estimation overlaps, and Cox proportional hazards models were used.

Results

The analysis included 8326 patients with known NYHA classification at randomization. Of 389 patients in NYHA class I, 228 (58%) changed functional class during the first year after randomization. Level of NT-proBNP was a poor discriminator of NYHA classification: for NYHA class I vs II, the AUC was 0.51 (95% CI, 0.48-0.54). For NT-proBNP level, estimated kernel density overlap was 93% between NYHA class I vs II, 79% between NYHA I vs III, and 83% between NYHA II vs III. Patients classified as NYHA III displayed a distinctively higher rate of cardiovascular events (NYHA III vs I, hazard ratio [HR], 1.84; 95% CI, 1.44-2.37; NYHA III vs II, HR, 1.49; 95% CI, 1.35-1.64). Patients in NYHA class I and II revealed lower event rates (NYHA II vs I, HR, 1.24; 95% CI, 0.97-1.58). Stratification by NT-proBNP level (<1600 pg/mL or ≥1600 pg/mL) identified subgroups with distinctive risk, such that NYHA class I patients with high NT-proBNP levels (n = 175) had a numerically higher event rate than patients with low NT-proBNP levels from any NYHA class (vs I, HR, 3.43; 95% CI, 2.03-5.87; vs II, HR, 2.12; 95% CI, 1.58-2.86; vs III, HR, 1.37; 95% CI, 1.00-1.88).

Conclusions and Relevance

In this study, patients in NYHA class I and II overlapped substantially in objective measures and long-term prognosis. Physician-defined “asymptomatic” functional class concealed patients who were at substantial risk for adverse outcomes. NYHA classification might be limited to differentiate mild forms of HF.

Trial Registration

ClinicalTrials.gov Identifier: NCT01035255
Apathy and Functional Impairment in the Course of Behavioral Variant Frontotemporal Dementia
Authors: Zhu Carolyn W. , Grossman Hillel T. , Sano Mary
Published: December 2022

This cohort study analyzes patterns of apathy and functional impairment in patients with progressive severity of behavioral variant frontotemporal dementia.
Trends in Episode-of-Care Spending for Cancer-Directed Surgery Among US Medicare Beneficiaries From 2011 to 2019
Authors: Melamed Alexander , Lin Yu-Li , Hassan Abbas M. , Rauh-Hain J. Alejandro , Herring Bradley , Keating Nancy L. , Offodile Anaeze C.
Published: December 2022

This cross-sectional study examines trends in the number of cancer-directed surgeries from 2011 to 2019 among US patients aged 65 years or older and in Medicare spending for those surgeries overall and by inpatient vs outpatient sites of care.
Slippage at the initiation of RNA synthesis by Qβ replicase results in a periodic polyG pattern
Authors: Lobodin Kirill V. , Chetverina Helena V. , Chetverin Alexander B.
Published: December 2022

The repetitive copying of template nucleotides due to transcriptional slippage has not been reported for RNA‐directed RNA polymerases of positive‐strand RNA phages. We unexpectedly observed that, with GTP as the only substrate, Qβ replicase, the RNA‐directed RNA polymerase of bacteriophage Qβ, synthesizes by transcriptional slippage polyG strands, which on denaturing electrophoresis produce a ladder with at least three clusters of bolder bands. The ≈ 15‐nt‐long G15, the major product of the shortest cluster, is tightly bound by the enzyme but can be released by the ribosomal protein S1, which, as a Qβ replicase subunit, normally promotes the release of a completed transcript. 7‐deaza‐GTP suppresses the polyG synthesis and abolishes the periodic pattern, suggesting that the N7 atom is needed for the initiation of RNA synthesis and the formation of the structure recognized by protein S1. The results provide new insights into the mechanism of RNA synthesis by the RNA‐directed RNA polymerase of a single‐stranded RNA phage.
Changes and Associations Between Gait Biomechanics and Knee Inflammation After Aspiration and Glucocorticoid Injection for Knee Osteoarthritis
Authors: Pinto Ryan F. , Birmingham Trevor B. , Philpott Holly T. , Primeau Codie A. , Leitch Kristyn M. , Arsenault Dominique A. , Appleton C. Thomas
Published: December 2022

Objective

Although knee inflammation is thought to adversely affect joint function in patients with knee osteoarthritis (OA), the effects of reducing knee inflammation on gait biomechanics and strength are unknown. Our objectives were to compare ultrasound (US) measures of knee inflammation, gait biomechanics, knee extension and flexion strength, and pain before and after knee aspiration and glucocorticoid injection, and to explore associations among changes.

Methods

Forty‐nine patients (69 knees) with symptomatic knee OA and synovitis were tested before and 3–4 weeks after US‐guided knee aspiration and glucocorticoid injection. At each visit, participants completed US assessments for inflammatory features of knee OA, 3D gait analysis, isokinetic knee extension and flexion strength tests, and Knee Osteoarthritis Outcome Score (KOOS) pain subscales. Linear and polynomial mixed‐effects regression models were used to investigate changes and their associations.

Results

Changes were observed for the synovitis score (unstandardized β [post‐injection minus pre‐injection] –0.55/9 [95% confidence interval (95% CI) –0.97, –0.12]), effusion depth (–1.05 mm [95% CI –1.07, –0.39]), KOOS pain (unstandardized β 5.91/100 [95% CI 1.86, 9.97]), peak external knee flexion and extension moments (KFM; 3.33 Nm [95% CI 0.45, 6.22]), KEM (–2.99 Nm [95% CI –5.93, –0.05]), and knee extension strength (4.70 Nm [95% CI 0.39, 9.00]) and flexion strength (3.91 Nm [95% CI 1.50, 6.81]). The external KFM increased during 13–38% and 76–89% of stance post‐injection. When controlled for time, greater synovitis was associated with lower knee extension strength, while lower pain was associated with increased knee extension and flexion strength.

Conclusion

In patients with knee OA and synovitis, reduced inflammation and pain after aspiration and glucocorticoid injection are associated with changes in knee gait biomechanics and strength.
Distributed adaptive neural network fixed‐time leader‐follower attitude consensus control for multiple rigid spacecraft
Authors: Qi Wen‐Nian , Wu Ai‐Guo , Dong Rui‐Qi
Published: December 2022

In this paper, the problem of fixed‐time attitude consensus control is addressed for a group of rigid spacecraft in the presence of inertia uncertainties and external disturbances. By applying the adaptive technique and neural network approximation technique to handle the disturbances and uncertainties, an adaptive neural network‐based distributed protocol is proposed to achieve attitude consensus control for multiple rigid spacecraft. The proposed distributed attitude consensus protocol is composed of a group of distributed fixed‐time observers for followers to estimate the leader's information and an adaptive neural network‐based fixed‐time sliding mode control law to realize attitude tracking control. Rigorous proofs are provided to demonstrate that the estimation errors of the proposed observers are convergent in a fixed time. Further, it is also proven that attitude tracking errors reach some adjustable regions in a fixed time under the proposed attitude consensus protocol. Numerical simulations are conducted to illustrate the performance of the proposed distributed attitude consensus protocol.
Aluminum‐Doped ZnO Weld Silver Nanowires‐Based High Transmittance, Low Sheet Resistance, and Tough Composite Transparent Conductive Films
Authors: Bin Peng-Shuai , Geng Wen-Hao , Wang Tao , Zhu Qiangxia , Li Min , Liu Xiang-Le , Qian Peng-Fei , Bao Ze-Long , Yang Zhi-Xian , Geng Hong-Zhang
Published: December 2022

Herein, silver nanowires (AgNWs) and aluminum‐doped zinc oxide (AZO) are prepared by polyol and gel–sol method, respectively. Then bendable, strong adhesion, flat, and high optical transmittance AgNWs:AZO composite transparent conductive film (TCF) is prepared in an all‐solution method. By spinning the AZO to the upper layer of the AgNW networks and annealing at 120 °C for 20 min, the junctions of the AgNW networks are welded by the capillary force in the solvent evaporation and AZO crystallization process. The sheet resistance of the TCF is as low as 12.9 Ω sq−1 at an optical transmittance of 92.1% (@550 nm), which is comparable to the indium tin oxide film on glass. The root means square roughness is reduced from 30.1 to 8.48 nm to match the criteria as anode for organic light emitting diodes (OLEDs). Furthermore, the adhesion between the AgNW networks and the substrate has been significantly improved. Finally, a flexible green OLED device with AgNW:AZO TCF as the anode is successfully prepared. The maximum luminous intensity of the prepared OLED is 10 060 cd m−2, and the maximum current efficiency is 6.43 cd A−1, which proves the great potential of the film in flexible electronics.
The Opportunity of Negative Capacitance Behavior in Flash Memory for High‐Density and Energy‐Efficient In‐Memory Computing Applications
Authors: Kim Taeho , Kim Giuk , Lee Young Kyu , Ko Dong Han , Hwang Junghyeon , Lee Sangho , Shin Hunbeom , Jeong Yeongseok , Jung Seong‐Ook , Jeon Sanghun
Published: December 2022

Flash memory is a promising candidate for use in in‐memory computing (IMC) owing to its multistate operations, high on/off ratio, non‐volatility, and the maturity of device technologies. However, its high operation voltage, slow operation speed, and string array structure severely degrade the energy efficiency of IMC. To address these challenges, a novel negative capacitance‐flash (NC‐flash) memory‐based IMC architecture is proposed. To stabilize and utilize the negative capacitance (NC) effect, a HfO2‐based reversible single‐domain ferroelectric (RSFE) layer is developed by coupling the flexoelectric and surface effects, which generates a large internal field and surface polarization pinning. Furthermore, NC‐flash memory is demonstrated for the first time by introducing a RSFE and dielectric heterostructure layer in which the NC effect is stabilized as a blocking layer. Consequently, an energy‐efficient and high‐throughput IMC is successfully demonstrated using an AND flash‐like cell arrangement and source‐follower/charge‐sharing vector‐matrix multiplication operation on a high‐performance NC‐flash memory.
Highly Stretchable, Responsive Flexible Dual‐Mode Magnetic Strain Sensor
Authors: Guo Xiaohui , Hong Weiqiang , Zhang Tianxu , Li Hongjin , Zhu Tong , Hong Qi , Wang Di , Liu Long , Zhao Yunong , Wang Dandan , Mai Zhihong , Wang Ming , Yan Feng , Meng Yuan , Xu Yaohua , Xing Guozhong
Published: December 2022

Stretchable strain sensors with high stability, high responsiveness, and low detection limit provide the broad potential for intelligent robots and electronic skin. However, developing low‐cost strain sensors with contact and non‐contact sensing modes remains a significant challenge. In this study, a flexible magnetic strain sensor based on a sandwich structure is proposed to address this challenge. The proposed structure utilizes the coordination between carbon black and Fe3O4 microparticles in the silicone rubber matrix to enhance the sensor's sensitivity to external strain and magnetic stimuli. The sensor exhibits excellent tensile properties with a strain range of up to 180%, fast response/recovery time (78 ms/65 ms), high stability, and durability after 9000 cycles. Moreover, the flexible magnetic strain sensors can detect micro‐vibration and micro‐strain signals. It can also be performed as electronic skin to precisely sense human movements. Furthermore, the newly developed sensor can accurately sense oncoming objects and bicycle riding speed/distance, and a flexible magnetic keyboard is conceived. Consequently, the dual‐modal magnetic strain sensor exhibits an excellent ability to identify contact and non‐contact states and has broad application prospects in next‐generation intelligent products.
Utilizing Breakdown Discharge of Self‐Powered Triboelectric Nanogenerator to Realize Multimodal Sterilization
Authors: Chen Junhuan , Li Jiawei , Wang Peng , Peng Yating , Wang Congyu , Wang Junlei , Zhang Dun
Published: December 2022

Triboelectric nanogenerator (TENG) is regarded as an efficient electrical energy generation technology for powering sterilization and disinfection systems. However, TENG‐based sterilization systems usually involve special materials and additional equipments. Additionally, the energy dissipation in TENG application, especially the breakdown discharge phenomenon, also restricts its practicability. In this work, based on the newly optimized high‐performance soft‐contact freestanding rotary TENG and “undesired” breakdown discharge, the self‐powered sterilizer is presented. The experiments demonstrate that this self‐powered sterilizer can effectively inactivate representative bacteria and mixed bacteria. Meanwhile, the analysis of active bacteria density and antibacterial rate reveal the effects of the system airtightness and the flow velocity of bacterial solution on sterilization performance. Furthermore, the investigations on bacterial morphology and solution composition demonstrate that the superior sterilization efficiency of self‐powered sterilizer is caused by the current‐induced deformation of bacteria membranes, and the generation of active chlorine and superoxide in sterilization system. As a result, the air breakdown‐based multimodal sterilization endows the self‐powered sterilizer with wide antibacterial spectrum without the emergence of drug resistance. This work not only provides an effective and straightforward strategy for developing self‐powered sterilization systems but also offers useful insights for the optimal use of TENG‐based energy resources.
Insights into the Effect of Catalytic Intratumoral Lactate Depletion on Metabolic Reprogramming and Immune Activation for Antitumoral Activity
Authors: Zhao Junlong , Tian Zhimin , Zhao Shoujie , Feng Dayun , Guo Zhixiong , Wen Liangzhi , Zhu Yejing , Xu Fenghua , Zhu Jun , Ma Shouzheng , Hu Jie , Jiang Tao , Qu Yongquan , Chen Dongfeng , Liu Lei
Published: December 2022

Lactate, a characteristic metabolite of the tumor microenvironment (TME), drives immunosuppression and promotes tumor progression. Material‐engineered strategies for intratumoral lactate modulations demonstrate their promise for tumor immunotherapy. However, understanding of the inherent interconnections of material‐enabled lactate regulation, metabolism, and immunity in the TME is scarce. To address this issue, urchin‐like catalysts of the encapsulated Gd‐doped CeO2, syrosingopine, and lactate oxidase are used in ZIF‐8 (USL, where U, S, and L represent the urchin‐like Gd‐doped CeO2@ZIF‐8, syrosingopine, and lactate oxidase, respectively) and orthotopic tumor models. The instructive relationships of intratumoral lactate depletion, metabolic reprogramming, and immune activation for catalytic immunotherapy of tumors is illustrated. The catalysts efficiently oxidize intratumoral lactate and significantly promote tumor cell apoptosis by in situ‐generated ·OH, thereby reducing glucose supply and inducing mitochondrial damage via lactate depletion, thus reprogramming glycometabolism. Subsequently, such catalytic metabolic reprogramming evokes both local and systemic antitumor immunity by activating M1‐polarizaed macrophages and CD8+ T cells, leading to potent antitumor immunity. This study provides valuable mechanistic insights into material‐interfered tumor therapy through intratumoral lactate depletion and consequential connection with metabolic reprogramming and immunity remodeling, which is thought to enhance the efficacy of immunotherapy.
Pure Tin Halide Perovskite Solar Cells: Focusing on Preparation and Strategies
Authors: Liu Hairui , Zhang Zuhong , Zuo Weiwei , Roy Rajarshi , Li Meng , Byranvand Mahdi Malekshahi , Saliba Michael
Published: December 2022

Metal halide perovskite solar cells (PSCs) have emerged as an important direction for photovoltaic research. Although the power conversion efficiency (PCE) of lead‐based PSCs has reached 25.7%, still the toxicity of Pb remains one main obstacle for commercial adoption. Thus, to address this issue, Pb‐free perovskites have been proposed. Among them, tin‐based perovskites have emerged as promising candidates. Unfortunately, the fast oxidation of Sn2+ to Sn4+ leads to low stability and efficiency. Many strategies have been implemented to address these challenges in Sn‐based PSCs. This work introduces stability and efficiency improvement strategies for pure Sn‐based PSCs by optimization of the crystal structure, processing and interfaces as well as, implementation of low‐dimension structures. Finally, new perspectives for further developing Sn‐based PSCs are provided.
CO2 solubility in aqueous N‐methylcyclohexylamine (MCA) and N‐cyclohexyl‐1,3‐propanediamine (CHAP) solutions
Authors: Tzirakis Fragkiskos , Papadopoulos Athanasios I. , Seferlis Panos , Tsivintzelis Ioannis
Published: December 2022

N‐methylcyclohexylamine (MCA) and N‐cyclohexyl‐1,3‐propanediamine (CHAP) have been suggested, in mixtures with lipophilic amines, as potential phase change solvents for CO2 capture applications, and subsequently studied as promising alternatives to monoethanolamine (MEA) for minimizing the desorber's energy requirements. In this study, new high pressure experimental data were obtained for the solubility of CO2 in aqueous solutions containing MCA or CHAP at 313 and 333 K. The obtained data were used to parameterize the modified Kent–Eisenberg model. In this direction, CHAP was modeled assuming a “principle of independent reactivity,” that is, that the reactivity of each amine group does not depend on the potential reaction of the other one. It was shown that through this approach the model can be successfully applied to diamines using the relevant equations of amine mixtures.
Financial impact of a specialized Down syndrome clinic: Implications and support for institutional support of specialty care clinics
Authors: VanZant J. Seth , Vellody Kishore
Published: December 2022

Individuals with Down syndrome (DS) have specific health care needs and require additional screening and surveillance for commonly associated conditions. The American Academy of Pediatrics (AAP) Committee on Genetics has provided clinical guidance in “Health Supervision for Children and Adolescents with Down Syndrome.” Many DS specialty centers (DSC) have been created, in part, to help ensure adherence to these guidelines. The primary purpose of this work is to determine the financial impact of a specialized DSC. A retrospective chart review was completed for all patients seen in DSC for fiscal year 2018 (June 2018–June 2019). Charts were reviewed to ascertain the financial impact of a DSC to a healthcare system by calculating total downstream charges (using CMS Chargemaster) as a surrogate marker for financial impact. Five‐hundred‐seventy‐four patient encounters were conducted; 99 were new patient visits. Annual charges totaled $1,399,450. The 1–5‐year‐old age group accounted for greater than half of all charges. The greatest proportion of charges resulted from sleep studies and other diagnostic testing (55%). DS clinics are extremely helpful in ensuring that children receive guideline‐based care. Taking into account downstream revenue, specialized DSCs are also financially beneficial to the institutions with whom they are affiliated.
Barriers to applying to the NDIS for Australians with psychosocial disability: A scoping review
Authors: Mellifont Damian , Hancock Nicola , Scanlan Justin Newton , Hamilton Deborah
Published: December 2022

The National Disability Insurance Scheme (NDIS) was designed to support Australians living with disability. However, public data evidence the low number of people with psychosocial disability in the Scheme. One reason for these low numbers is that many people with psychosocial disability have still not applied to receive NDIS support. The aim of this review was to analyse and synthesise previously reported barriers preventing people with psychosocial disability applying to the Scheme. A search of seven databases identified 61 relevant documents including peer‐reviewed research, published expert opinion pieces, newspaper articles and government and independent enquiries and reports. Thematic analysis revealed five overarching barriers to applying: social inequities acting as barriers to applying; stigma, trauma and previous negative experiences; barriers to finding supports needed to apply; challenges understanding the relevance of the Scheme; and experiences and symptoms of mental illness extend and exacerbate barriers. These barriers signpost problems inherent within an application process designed without engaging or being responsive to the expertise of and insights into people living with psychosocial disability. Resolution of these substantial barriers will not be a small task. It will require commitment to redesigning the Scheme's application process through a genuinely codesigned approach.
Brain vitamin D forms, cognitive decline, and neuropathology in community‐dwelling older adults
Authors: Shea M. Kyla , Barger Kathryn , Dawson‐Hughes Bess , Leurgans Sue E. , Fu Xueyan , James Bryan D. , Holland Thomas M. , Agarwal Puja , Wang Jifan , Matuszek Gregory , Heger Nicholas E. , Schneider Julie A. , Booth Sarah L.
Published: December 2022

Introduction

Vitamin D purportedly protects against cognitive decline and dementia based on observational data using circulating 25‐hydroxyvitamin D (25(OH)D). Little is known about vitamin D in the human brain and the association with dementia or neuropathology.

Methods

Decedents of the Rush Memory and Aging Project (n = 290) had vitamin D concentrations measured in four brain regions. Associations with cognitive and neuropathological outcomes were estimated using linear and logistic regression.

Results

The main form of vitamin D in all brain regions measured was 25(OH)D3. Higher brain 25(OH)D3 concentrations were associated with a 25% to 33% lower odds of dementia or mild cognitive impairment (MCI) at the last visit before death (all P ≤ .031). However, brain 25(OH)D concentrations were not associated with any post‐mortem neuropathology outcome studied.

Discussion

Higher brain 25(OH)D3 concentrations were associated with better cognitive function prior to death. Additional research is needed to clarify the specific mechanisms underlying this potentially protective relationship.
Recent Advances in Oral and Transdermal Protein Delivery Systems
Authors: Yang Yinxian , Zhou Ruyi , Wang Yanfang , Zhang Yuqi , Yu Jicheng , Gu Zhen
Published: December 2022

Protein and peptide drugs are predominantly administered by injection to achieve high bioavailability, but this greatly compromises patient compliance. Oral and transdermal drug delivery with minimal invasiveness and high adherence represent attractive alternatives to injection administration. However, oral and transdermal administration of bioactive proteins must overcome biological barriers, namely the gastrointestinal and skin barriers, respectively. The rapid development of new materials and technologies promises to address these physiological obstacles. This review provides an overview of the latest advances in oral and transdermal protein delivery, including chemical strategies, synthetic nanoparticles, medical microdevices, and biomimetic systems for oral administration, as well as chemical enhancers, physical approaches, and microneedles in transdermal delivery. We also discuss challenges and future perspectives of the field with a focus on innovation and translation.
Elektrochemische Synthese von Pyrazolinen und Pyrazolen via [3+2] dipolarer Cycloaddition
Authors: Linden Martin , Hofmann Silja , Herman Antonia , Ehler Nicole , Bär Robin M. , Waldvogel Siegfried R.
Published: December 2022

Pyrazoline und Pyrazole sind häufige und wichtige Bestandteile vieler Pharmaka und Agrochemikalien. Diese Arbeit zeigt den ersten elektrochemischen Ansatz zu deren direkter Synthese aus leicht zugänglichen Hydrazonen und Dipolarophilen bis in den Dekagrammbereich. Die Anwendung eines zweiphasigen Systems (wässrig/organisch) ermöglicht auch die Umsetzung hochempfindlicher Alkene, wobei kostengünstiges Natriumiodid gleichzeitig als Leitsalz und Mediator eingesetzt wird. Darüber hinaus wurden entscheidende Zwischenstufen isoliert, die einen Einblick in den Reaktionsmechanismus geben. Die Relevanz der vorgestellten Reaktion wird durch die Synthese des kommerziellen Herbizidsafeners Mefenpyr‐Diethyl in guter Ausbeute unterstrichen.
Rational Positioning of Metal Ions to Stabilize Open Tin Sites in Beta Zeolite for Catalytic Conversion of Sugars
Authors: Sun Pengyao , Liu Chong , Wang Haiyong , Liao Yuhe , Li Xuning , Liu Qiying , Sels Bert F. , Wang Chenguang
Published: December 2022

Via hydrothermal synthesis of Sn‐Al gels, mild dealumination and ion exchange, a bimetallic Sn‐Ni‐Beta catalyst was prepared which can convert glucose to methyl lactate (MLA) and methyl vinyl glycolate (MVG) in methanol at yields of 71.2 % and 10.2 %, respectively. Results from solid‐state magic‐angle spinning nuclear magnetic resonance, X‐ray photoelectron spectroscopy, transmission electron microscopy, spectroscopic analysis, probe‐temperature‐programmed desorption, and density functional theory calculations conclusively reveal that the openness of the Sn sites, such as by the formation of [(SiO)3−Sn−OH] entities, is governed by an adjacent metal cation such as Ni2+, Co2+, and Mn2+. This relies on the low structure‐defective pore channel, provided by the current synthesis scheme, and the specific silica hydroxyl anchor point is associated with the incorporation of Sn for additional and precise metal ion localization. The presence of metal cations significantly improved the catalytic performance of Sn‐Ni‐Beta for glucose isomerization and conversion to MLA of sugar compared with Sn‐Beta.
Cadmium‐Doped and Pincer Ligand‐Modified Gold Nanocluster for Catalytic KA2Reaction
Authors: Fan Ji‐Qiang , Yang Ying , Tao Cheng‐Bo , Li Man‐Bo
Published: December 2022

A gold nanocluster Au17Cd2(PNP)2(SR)12(PNP=2,6‐bis(diphenylphosphinomethyl)pyridine, SR=4‐MeOPhS) consisting of an icosahedral Au13kernel, two Au2CdS6staple motifs, and two PNP pincer ligands has been designed, synthesized and well characterized. This cadmium and PNP pincer ligand co‐modified gold nanocluster showed high catalytic efficiency in the KA2reaction, featuring high TON, mild reaction conditions, broad substrate scope as well as catalyst recyclability. Comparison of the catalytic performance between Au17Cd2(PNP)2(SR)12and the structurally similar single cadmium (or PNP) modified gold nanoclusters demonstrates that the co‐existence of the cadmium and PNP on the surface is crucial for the high catalytic activity of the gold nanocluster. This work would be enlightening for developing efficient catalysts for cascade reactions and discovering the catalytic potential of metal nanoclusters in organic transformations.
Atomically Dispersed Zn‐Pyrrolic‐N4 Cathode Catalysts for Hydrogen Fuel Cells
Authors: Sun Panpan , Qiao Zelong , Wang Shitao , Li Danyang , Liu Xuerui , Zhang Qinghua , Zheng Lirong , Zhuang Zhongbin , Cao Dapeng
Published: December 2022

To achieve practical application of fuel cell, it is vital to develop highly efficient and durable Pt‐free catalysts. Herein, we prepare atomically dispersed ZnNC catalysts with Zn‐Pyrrolic‐N4 moieties and abundant mesoporous structure. The ZnNC‐based anion‐exchange membrane fuel cell (AEMFC) presents an ultrahigh peak power density of 1.63 and 0.83 W cm−2 in H2‐O2 and H2‐air (CO2‐free), and also exhibits long‐term stability with more than 120 and 100 h for H2‐air (CO2‐free) and H2‐O2, respectively. Density functional calculations further unveil that the Zn‐Pyrrolic‐N4 structure is the origin of high activity of as‐synthesized ZnNC catalyst, while the Zn‐Pyridinic‐N4 moiety is inactive for oxygen reduction reaction (ORR), which successfully explain the puzzle why most Zn‐metal‐organic framework ‐derived ZnNC catalysts in previous reports did not present good ORR activity because of their Zn‐Pyridinic‐N4 moieties. This work offers a new route for speeding up development of AEMFCs.
ZnF2‐Riched Inorganic/Organic Hybrid SEI: in situ‐Chemical Construction and Performance‐Improving Mechanism for Aqueous Zinc‐ion Batteries
Authors: Xie Dan , Sang Yuan , Wang Dan‐Hong , Diao Wan‐Yue , Tao Fang‐Yu , Liu Chang , Wang Jia‐Wei , Sun Hai‐Zhu , Zhang Jing‐Ping , Wu Xing‐Long
Published: December 2022

Uncontrolled dendrites growth and serious parasitic reactions in aqueous electrolytes, greatly hinder the practical application of aqueous zinc‐ion battery. On the basis of in situ‐chemical construction and performance‐improving mechanism, multifunctional fluoroethylene carbonate (FEC) is introduced into aqueous electrolyte to construct a high‐quality and ZnF2‐riched inorganic/organic hybrid SEI (ZHS) layer on Zn metal anode (ZMA) surface. Notably, FEC additive can regulate the solvated structure of Zn2+ to reduce H2O molecules reactivity. Additionally, the ZHS layer with strong Zn2+ affinity can avoid dendrites formation and hinder the direct contact between the electrolyte and anode. Therefore, the dendrites growth, Zn corrosion, and H2 evolution reaction on ZMA in FEC‐included ZnSO4 electrolyte are highly suppressed. Thus, ZMA in such electrolyte realize a long cycle life over 1000 h and deliver a stable coulombic efficiency of 99.1 % after 500 cycles.
Pore Geometry and Surface Engineering of Covalent Organic Frameworks for Anhydrous Proton Conduction
Authors: Hao Liqin , Jia Shuping , Qiao Xueling , Lin En , Yang Yi , Chen Yao , Cheng Peng , Zhang Zhenjie
Published: December 2022

Developing new materials for anhydrous proton conduction under high‐temperature conditions is significant and challenging. Herein, we create a series of highly crystalline covalent organic frameworks (COFs) via a pore engineering approach. We simultaneously engineer the pore geometry (generating concave dodecagonal nanopores) and pore surface (installing multiple functional groups such as −C=N−, −OH, −N=N− and −CF3) to improve the utilization efficiency and host–guest interaction of proton carriers, hence benefiting the enhancement of anhydrous proton conduction. Upon loading with H3PO4, COFs can realize a proton conductivity of 2.33×10−2 S cm−1 under anhydrous conditions, among the highest values of all COF materials. These materials demonstrate good stability and maintain high proton conductivity over a wide temperature range (80–160 °C). This work paves a new way for designing COFs for anhydrous proton conduction applications, which shows great potential as high‐temperature proton exchange membranes.
Water‐Harvesting Metal–Organic Frameworks with Gigantic Al24Units and their Deconstruction into Molecular Clusters
Authors: Xu Huoshu , Wu Yichen , Yang Lingyi , Rao Yin , Wang Junyi , Peng Shuyin , Li Qiaowei
Published: December 2022

In contrast to the vast Al‐oxo molecular cluster chemistry, Al‐based building units for metal–organic framework (MOF) construction are limited in structural diversity and complexity. Synthesis of single crystalline MOFs based on this “hard” metal is further complicated by the poor reversibility of the Al‐organic coordination linkages. Here, a strategy to employ two kinds of linkages with distinct strength—strong Al‐carboxylate linkage and weak Cu‐pyrazol N linkage—gives FDM‐91 (FDM=Fudan Materials) with gigantic Al24‐based units. After replacing the weak moieties with organic linkers post‐synthetically, two new stable MOFs with exceptional water harvesting capacity (up to 0.53 g g−1) and outstanding cycling performance are developed. Linkage‐selective dissociation of FDM‐91 further leads to the isolation of the Al24molecular clusters. The versatile chemistry performed here to reinforce or deconstruct MOFs provides a new way to make important extended and discrete structures.
Electrochemical Synthesis of Pyrazolines and Pyrazoles via [3+2] Dipolar Cycloaddition
Authors: Linden Martin , Hofmann Silja , Herman Antonia , Ehler Nicole , Bär Robin M. , Waldvogel Siegfried R.
Published: December 2022

Pyrazolines and pyrazoles are common and important motifs of pharmaceutical agents and agrochemicals. Herein, the first electrochemical approach for their direct synthesis from easily accessible hydrazones and dipolarophiles up to decagram scale is presented. The application of a biphasic system (aqueous/organic) even allows for the conversion of highly sensitive alkenes, wherein inexpensive sodium iodide is employed in a dual role as supporting electrolyte and mediator. In addition, mechanistic insight into the reaction is given by the isolation of key step intermediates. The relevance of the presented reaction is underlined by the synthesis of commercial herbicide safener mefenpyr‐diethyl in good yields.
sn‐1 Specificity of Lysophosphatidylcholine Acyltransferase‐1 Revealed by a Mass Spectrometry‐Based Assay
Authors: Zhao Xue , Liang Jiaqi , Chen Ziye , Jian Ruijun , Qian Yao , Wang Yunfang , Guo Zhiying , Zhang Wenpeng , Zhang Ying , Yin Hang , Xia Yu
Published: December 2022

Lysophosphatidylcholine acyltransferase‐1 (LPCAT1) plays a critical role in the remodeling of phosphatidylcholines (PCs) in cellular lipidome. However, evidence is scarce regarding its sn‐selectivity, viz. the preference of assembling acyl‐Coenzyme A (CoA) at the C1 or C2‐hydroxyl on a glycerol backbone because of difficulty to quantify the thus‐formed PC sn‐isomers. We have established a multiplexed assay to measure both sn‐ and acyl‐chain selectivity of LPCAT1 toward a mixture of acyl‐CoAs by integrating isomer‐resolving tandem mass spectrometry. Our findings reveal that LPCAT1 shows exclusive sn‐1 specificity regardless of the identity of acyl‐CoAs. We further confirm that elevated PC 18 : 1/16:0 relative to its sn‐isomer results from an increased expression of LPCAT1 in human hepatocellular carcinoma (HCC) tissue as compared to normal liver tissue. MS imaging via desorption electrospray ionization of PC 18 : 1/16:0 thus enables visualization of HCC margins in human liver tissue at a molecular level.
Overall Carbon‐neutral Electrochemical Reduction of CO2 in Molten Salts using a Liquid Metal Sn Cathode
Authors: Jing Shuangxi , Sheng Ren , Liang Xinxin , Gu Dong , Peng Yuhao , Xiao Juanxiu , Shen Yijun , Hu Di , Xiao Wei
Published: December 2022

An overall carbon‐neutral CO2 electroreduction requires enhanced conversion efficiency and intensified functionality of CO2‐derived products to balance the carbon footprint from CO2 electroreduction against fixed CO2. A liquid Sn cathode is herein introduced into electrochemical reduction of CO2 in molten salts to fabricate core–shell Sn−C spheres (Sn@C). An in situ generated Li2SnO3/C directs a self‐template formation of Sn@C. Benefitting from the accelerated reaction kinetics from the liquid Sn cathode and the core–shell structure of Sn@C, a CO2‐fixation current efficiency higher than 84 % and a high reversible lithium‐storage capacity of Sn@C are achieved. The versatility of this strategy is demonstrated by other low melting point metals, such as Zn and Bi. This process integrates energy‐efficient CO2 conversion and template‐free fabrication of value‐added metal‐carbon, achieving an overall carbon‐neutral electrochemical reduction of CO2.
Amphiphilic drug slow release microspheres fabricated using polyvinyl alcohol, 10‐Undecen‐1‐ol, and multi‐walled carbon nanotubes
Authors: Tian Pan , Liu Wanjing , Yang Shengdu , Zhang Junhua
Published: December 2022

In this paper, novel embolic microspheres with efficient drug delivery and slow drug release properties were developed, which have potential applications in transarterial chemoembolization (TACE). The microspheres were prepared by suspension polymerization using vinyl acetate, 10‐Undecen‐1‐ol (UO), multi‐walled carbon nanotubes, and crosslinking agent (1,4‐butanediol divinyl ether). In the process, porous titanium tubes are used to control the particle size of the microspheres. In addition, the introduction of long‐chain (UO) makes the microsphere good swelling property in acetone. Multi‐walled carbon nanotubes modified by hexadecyltrimethoxysilane (HDTMS) are helpful for increasing both spherical morphology stabilization and swelling properties in acetone as well (C‐PVA‐2UO/CNT). Target drug was dissolved in acetone and the mcirospheres were dispersed in acetone to realize drug load. In vitro biocompatibility analysis showed that C‐PVA‐2UO/CNT is non‐cytotoxic and hemocompatible. The sustained drug release properties of C‐PVA‐2UO/CNT were confirmed by drug indomethacin (IMC) loading and release experiments. These findings suggest that the newly developed C‐PVA‐2UO/CNT has great potential to be used as a drug‐loaded embolization agent.
BTX production by breaking down lignin: Current status and future prospects
Authors: Ramirez Brenes Ricardo G , Alhadeff Eliana M. , Bojorge Ninoska , Trales Luiz E. M. , Pazos Gabrielle A. D.
Published: December 2022

Nowadays, lignin is a byproduct of the agricultural and cellulose pulp mill. Lignin is a sustainable, renewable raw material alternative to petroleum‐based chemicals, mainly for the benzene–toluene–xylene (BTX) production of commodities and the sequential secondary, tertiary and manufactured products in the petrochemical industry. It can be mass produced and is used for renewable energy biorefinery or high‐value‐added products. This review aims to outline the important lignin depolymerization technologies and the feasibility of imposing these transforming technologies on a large scale. Finally, this review examines the market prospects for BTX, revealing its R&D progress. However, the harmful effects of BTX and unfavorable conditions resulting from the COVID‐19 pandemic comprise roadblocks to its growth. However, the increasing use of biobased BTX is expected to open new market opportunities. © 2022 Society of Chemical Industry and John Wiley & Sons, Ltd.
Brazilian agricultural and livestock substrates used in co‐digestion for energy purposes: Composition analysis and valuation aspects
Authors: Mendes Fabrício Bruno , Lima Brenno Vinicius de Medeiros , Volpi Maria Paula Cardeal , Albarracin Lorena Torres , Lamparelli Rubens Augusto Camargo , Moraes Bruna de Souza
Published: December 2022

Brazil's agriculture and livestock annually generates enormous amounts of biomass, which varies in its biochemical composition. Many studies have pointed out the benefits of using this biomass as a substrate for biogas production through anaerobic digestion (AD), mostly via the co‐digestion (co‐AD) pathway. The agriculture and livestock of southeastern Brazil – sugarcane, orange, corn, soybean, coffee, cattle, swine, and poultry – have together demonstrated their potential for producing biomass that can be used for maximizing methane production. Filter cake, vinasse, straws, bagasse, mucilage, pulp, washing water, thin stillage, and manures also have specific organic matter and nutrient content that can be evaluated from an economic perspective as co‐products of biorefineries. Some are costless but others have acquisition costs in the agricultural market. Comparing the recent biochemical compositions cited in scientific literature (technical parameter) and to know the costs (valuation parameter) is crucial for farmers and investors make decisions in large‐scale. This study conducted a bibliographical survey of biomass generated in Brazilian agroindustry as a co‐substrate for energy production. The analysis summarized two tables: 1‐ a compilation of biochemical composition of the main co‐substrates, and 2‐ the acquisition or opportunity costs, discussing innovative aspects in the context of biogas production. © 2022 Society of Chemical Industry and John Wiley & Sons, Ltd.
Solubility, Extraction, and Nanoparticles Production in Supercritical Carbon Dioxide: A Mini‐Review
Authors: Sodeifian Gholamhossein , Usefi Mohammad Mahdi Behvand
Published: December 2022

Supercritical carbon dioxide (SC‐CO2) is CO2 that is stored beyond its critical point of 7.4 MPa and 31.1 °C. Given the request for consumption of a green solvent for the environment, SC‐CO2 is widely utilized in chemical, food, and pharmaceutical industries. To design material and drug production processes using supercritical fluid (SCF) technology, knowledge of their solubility is important. Temperature and pressure are the main factors in the study of solubility. Solubility data are then evaluated using equation of state, semi‐empirical, and intelligence models to establish suitable correlations. SC‐CO2 is one of the most important materials used in SCFs to study solubility. Another application of SC‐CO2 is in the field of material extraction to reduce the consumption of organic solvents. Nanoparticles production in drug industry is another advantage of SC‐CO2. Micro and nanoparticles can be produced using SCF techniques. In this review, the applications of SC‐CO2 in drug solubility, extraction of valuable materials, and nanoparticles production for pharmaceutical processes are reported and discussed. Finally, the main challenges are explained.
Minimalist transcatheter aortic valve replacement misses paravalvular regurgitation: Incidence and echocardiographic distribution of missed paravalvular regurgitation
Authors: Zaid Syed , Haniyeh Ahmed Abu , Rosenzveig Akiva , Malik Aaqib , Goldberg Joshua B. , Undemir Cenap , Spevack Daniel , Lansman Steven L. , Tang Gilbert H. L. , Ahmad Hasan
Published: December 2022

Background

Paravalvular regurgitation (PVR) may be missed intraoperatively with transthoracic echocardiography (TTE) guided minimalist TAVR. We sought to determine the incidence and echocardiographic distribution of PVR missed on intra‐op TTE, but detected on predischarge TTE.

Methods

From July 2015 to 2020, 475 patients with symptomatic severe native aortic stenosis underwent TTE‐guided minimalist TAVR. Missed PVR was defined as predischarge PVR that was ≥1 grade higher than the corresponding intra‐op PVR severity. PVR was classified as anterior or posterior on the four standard TTE views; parasternal short‐axis (PSAX), parasternal long‐axis (PLAX), apical 3‐chamber (A3C), and 5‐chamber (A5C). Location‐specific risk of missed PVR was then determined.

Results

Mild or greater PVR was seen in 55 (11.5%) cases intra‐op and 91 (19.1%) at predischarge, with no severe PVR. Among the 91 patients with ≥mild predischarge PVR, missed PVR was present in 42 (46.2%). Compared to the corresponding anterior jets, missed PVR rate was significantly higher for posterior jets in PLAX (62.5% vs. 25.0%, p = 0.005), A5C (56.9% vs. 25.0%, p = 0.009), PSAX (66.7% vs. 24.3%, 0.001), but not A3C (58.5% vs. 40.0%, p = 0.28).

Conclusions

Intraoperative TTE‐guided minimalist TAVR either misses nearly half of ≥mild PVR or underestimates PVR by ≥1 grade when compared to predischarge TTE. Posterior PVR jets are more likely to be missed. Transesophageal echo guidance may help minimize missing PVR. Further studies are warranted.
Radial and ulnar approach for carotid artery stenting with Roadsaver™ double layer micromesh stent: Early and long‐term follow‐up
Authors: Petkoska Danica , Zafirovska Biljana , Vasilev Ivan , Novotni Gabriela , Bertrand Olivier F. , Kedev Sasko
Published: December 2022

Aims

We aimed to evaluate the feasibility and safety of carotid artery stenting (CAS) with a newly designed double‐layer micromesh stent using wrist approach in patients with significant carotid disease.

Materials and Methods

Between January 2016 and December 2021, 105 patients undergoing CAS with Roadsaver™ stent were enrolled in a single center prospective study. Follow‐up assessments included neurological exams, duplex ultrasound (DUS), and 12‐lead ECG. The primary endpoint was the 30‐day composite rate of stroke, death, and myocardial infarction. Secondary endpoints included procedure success, access site complications, device success, target lesion revascularization, and in‐stent restenosis evaluated with DUS. Long‐term outcomes up to 72 months of follow‐up were assessed in all eligible patients.

Results

The study population was predominantly male (69.5%) with a median age of 68 ± 8 years. Patients were symptomatic in 80% of the cases, and 35% fulfilled the high‐risk criteria for surgical endarterectomy. The right internal carotid artery was the target artery in 56 (53.4%), and the left in 49 (46.6%) of the cases. All procedures were successfully completed from the right wrist, with right radial access in 94 (89.5%) cases and ulnar artery access with previous radial artery occlusion in 11 (10.5%) cases. All patients were treated successfully with the study device. The primary endpoint was met with a 30‐day major adverse event rate of 0.9% (1/105). Up to 72 months of follow‐up (median 30 ± 20 months) there were no strokes, neurological deaths, or target lesion revascularization of the treated lesion. Doppler ultrasound examination revealed nonsignificant in‐stent restenosis in two asymptomatic patients. There was no hand ischemia detected in any patient.

Conclusion

Results from this study demonstrate the radial and ulnar access for CAS with double layer micromesh Roadsaver™ stent is safe and feasible and associated with favorable early and long‐term follow‐up.
Electronic Tuning of Iminotriphenolate Ligands for Titanium(IV)‐catalyzed Ring‐opening Copolymerization of Cyclic Anhydrides and Epoxides
Authors: Jeong Yeolib , Cho Min Ki , Seo Sanghyup , Cho Heyjin , Son Kyung‐sun , Kim Hyunwoo
Published: December 2022

Alternating ring‐opening copolymerization (ROCOP) is a versatile synthetic method for preparing polyesters using relatively inexpensive and readily available monomers, epoxides and cyclic anhydrides. In this study, a new type of titanium (IV) complex coordinated with iminophenolate ligands was developed as an efficient catalyst for alternating ROCOP. As found in the crystal structures, iminophenolate titanium (IV) complexes exhibited octahedral geometries owing to geometrical constraints. Electronic tuning of iminophenolate ligands revealed that chloro‐substituted ligands are more efficient than other ligands with electron‐withdrawing or electron‐donating ligands. Density functional theory computation provided reaction profiles where octahedral intermediates and transition states were stabilized, and the chlorine substituent was the most efficient in stabilizing the transition state for the epoxide opening step.