bluuebunny/crossref_metadata_2025 huggingface dataset:
New Concept of Co-Agents for Scorch Delay and Property Improvement in Peroxide Vulcanization
Authors: Grima M. M. Alvarez , Talma A. G. , Datta R. N. , Noordermeer J. W. M.
Published: February 2011

Peroxide cure is an important and widely used cure system for rubber. Several properties obtained via peroxide vulcanization are superior and not achievable with sulfur vulcanization, e.g.: aging resistance, no reversion and low compression set. However, other properties such as tensile strength and dynamic properties, are inferior to those of sulfur vulcanizates. The use of co-agents in peroxide cure leads to a certain extent to improvement in mechanical properties such as tensile strength. Nevertheless the properties are still inferior with respect to mechanical/dynamical properties of sulfur-cured articles. If these properties can be improved, the range of applications of peroxide cure in the rubber industry can be significantly broadened. Scorch is a common problem in peroxide cure, especially for injection molding and extrusion applications. Several additives can help to improve scorch safety, however, they always result in a lower peroxide efficiency, thus inferior vulcanizate properties. In the present study a new concept of co-agents for peroxide vulcanization is introduced. This new concept consists of the use of a combination of a bismaleimide type co-agent, like N,N′-m-phenylenedimaleimide (BMI-MP), and a sulfur containing compound, like dipentamethylenethiuram tetrasulfide (DPTT). This combination provides scorch safety and at the same time improves the mechanical properties of the vulcanizates. Within the bismaleimide type co-agents N,N′-p-phenylenedimaleimide (BMI-PP) provides better mechanical properties than BMI-MP. The concentration of co-agent and sulfur containing compound have a big influence on the scorch time and on the mechanical properties. Optimal properties are reached with 4 phr of co-agent and 0.7 to 0.96 phr of sulfur containing compound.
Preparation and Characterization of Radiopaque Natural Rubber
Authors: Nisha V. S. , Joseph Rani
Published: February 2011

Currently radiopaque polymers are of great interest to medicine and dentistry because of their wide area of applications such as catheters, surgical tools, dental products, radiation shielders etc. Lead has historically been used as the shielding material, but not without health and environmental concerns. In this work, we have prepared radiopaque materials from natural rubber (NR) through different routes. Natural rubber was iodinated and characterized using UV-VIS spectroscopy, thermo gravimetric analysis and clinical X-ray techniques. The physical properties of Iodinated NR compounds prepared at ambient and high temperatures were studied. The low temperature cured samples showed better radiopacity and conductivity than high temperature cured samples. Radiopaque NR was prepared using radiopacifiers like barytes, barium sulphate, zinc oxide and active zinc oxide. The physical properties of the NR vulcanizates with different radiopacifiers were studied. Clinical X-ray techniques have been used to confirm the radiopacity. The optical density of the samples were measured and compared with that of conventionally used lead shield.
Characterization of Adhesion Interlayer Between Rubber and Brass by a Novel Method of Sample Preparation
Authors: Hotaka Takeshi , Ishikawa Yasuhiro , Mori Kunio
Published: February 2011

Instrumental characterization of an adhesion interface in a rubber-brass system often faces a difficulty in exposing a clean surface due to a stick of rubber residue on a brass surface. We have succeeded in isolating an interface from the rubber matrix by inserting a filter paper between rubber and brass during the vulcanization. Clean interface was obtained by removing the filter paper after the vulcanization, enabling a detailed characterization of the interface by XPS and SEM-EDX from a practical rubber formulation. Formulation of cobalt naphthenate did not contribute to a formation of adhesion interlayer in an initial stage of cure, but greatly affected the composition of copper sulfide during the vulcanization. It was found that a dosage of cobalt improved a growth of interface at aging. Copper sulfide particles were found to be spherical at the interface for unaged specimens. It was revealed that excess growth of copper sulfide was a main feature at a humidity aging, while the growth of zinc oxide was eminent under a hot water aging. Scheme of an aging reaction was considered to depend on an interaction between brass and external factors such as heat, water, and oxygen.
International Rubber Science Hall of Fame Inductee
Authors: Holden Geoff
Published: February 2011

Citation* - American scientist, chemist. Dr. Ralph Milkovich was a pioneer in anionic polymerization and heterophase polymer science. He demonstrated the concept of living anionic polymerization. He prepared the first poly(styrene-block-isoprene-block-styrene) thermoplastic elastomer, exhibiting the properties of a vulcanized rubber but processible as a thermoplastic. He also prepared a new class of polymeric materials, macromonomers, useful for the syntheses of well-defined, comb-type graft copolymers.
Equi-Biaxial Fatigue of Elastomers: The Effect of Oil Swelling on Fatigue Life
Authors: Jerrams Steve , Hanley John , Murphy Niall , Ali Hassan
Published: February 2011

The effect of oil swelling on the fatigue life of ethylene propylene diene monomer rubber (EPDM) has been studied under conditions of equi-biaxial cycling using dynamic bubble inflation. Specimens were subjected to varying degrees of swelling in reference mineral oils and fatigued at constant engineering stress amplitudes. The reference oils used for swelling the EPDM had known aniline points, allowing the rubber-oil compatibility to be determined. The inflation fluid for fatigue testing was selected with a solubility parameter that would produce a desired level of incompatibility with the test specimens, thereby limiting the amount of additional swelling during cycling. Wöhler (S-N) plots were generated for dry and swollen specimens and the changes in complex elastic modulus E* and dynamic stored energy were analyzed. Specimen fractures were analyzed using scanning electron microscopy. The fractures in the swollen samples show that the failure surfaces flowed more readily over each other than did those of the dryer specimens.
Reactive Compatibilization of Recycled Polyethylenes and Scrap Rubber in Thermoplastic Elastomers: Chemical and Radiation-Chemical Approach
Authors: Grigoryeva O. , Fainleib A. , Grenet J. , Saiter J. M.
Published: February 2011

Reactive compatibilization of recycled low- or high-density polyethylenes (LDPE and HDPE, respectively) and ground tire rubber (GTR) via chemical interactions of pre-functionalized components in their blend interface has been carried out. Polyethylene component was functionalized with maleic anhydride (MAH); as well, the rubber component was modified via functionalization with MAH or acrylamide (AAm) using chemically or irradiation (γ-rays) induced grafting techniques. The grafting degree and molecular mass distribution of the functionalized polymers have been measured via FTIR and Size Exclusion Chromatography (SEC) analyses, respectively. Additional coupling agents such as p-phenylene diamine (PDA) and polyamide fiber were used for producing some thermoplastic elastomer (TPE). Thermoplastic elastomer materials based on synthesized reactive polyethylenes and GTR as well as ethylene-propylenediene monomer rubber (EPDM) were prepared by dynamic vulcanization of the rubber phase inside thermoplastic (polyethylene) matrix and their phase structure, and main properties have been studied using DSC, DMTA and mechanical testing. As a result, high performance thermoplastic elastomers based on functionalized polyethylene and ground rubber with improved mechanical properties have been developed.
Filler Phase Distribution in Rubber Blends Characterized by Thermogravimetric Analysis of the Rubber-Filler Gel
Authors: Le H. H. , Ilisch S. , Kasaliwal G. R. , Radusch H-J.
Published: February 2011

The analysis of the rubber-filler gel of carbon black filled rubber compounds and blends provides useful information about the mixing process taking place inside the internal mixer. A new measure technique named wetting rate was introduced to describe the wetting behavior of the rubber onto the filler. Natural rubber (NR)/styrene-butadiene rubber (SBR) blends has been used for experimental investigation. NR shows a significantly higher wetting rate than SBR. The wetting rate does not only depend on the viscosity of rubber but strongly on the functionalization of it. Using the data determined from the thermogravimetric analysis (TGA) of rubber-filler gel, a new method was developed to characterize the kinetics of carbon black (CB) localization in the phases of heterogeneous rubber blends. During the first mixing stage, the CB localization is affected strongly by the wetting rate ratio of the blend components. In the second mixing stage, the rubber-filler interaction dominantly influences the distribution kinetics of the filler to the phases. Because of the higher wetting rate of the NR component, in the investigated NR/SBR blends more CB is found in the NR phase than in the SBR phase. The effect of the matrix viscosity and polarity on the phase specific CB distribution was systematically investigated.
Role of Compatibilization in Polymer Nanocomposites
Authors: Kroshefsky Robert D. , Price Jack L. , Mangaraj Duryodhan
Published: February 2011

Polymeric nanocomposites based on nanoclay, nanosilica, carbon nanotubes, and ceramic or mineral nanoparticles have been developed for a variety of applications. The large surface-to-mass ratios of these particles require good adsorption of the polymeric material on the particle surface to provide the adhesion levels between the filler and matrix resin necessary for improved performance. We review the basic principles underlying these surface interactions and their application in the preparation of a variety of these nanocomposites, as well as in explaining their performance. We demonstrate that the principles underlying the compatibilization of polymer blends and alloys can be successfully used to design nanocomposites and understand their performance.
Poly(alkylene Oxide) Rubbers
Authors: Hendrickson J. G. , Gurgiolo A. E. , Prescott W. E.
Published: February 2011

A high grade rubber was made by vulcanizing copolymers of propylene oxide and allyl glycidyl ether. The crude polymer contained both crystalline and amorphous fractions. The total polymer could be sulfur cured without fractionation or removing the catalyst—a partly hydrolized ferric alkoxide, resulting from the reaction of FeCl3 with propylene oxide. Variables in the vulcanization recipe were studied, and a tensile strength of 1980 psi with 560% elongation was obtained. Improved tear and oil resistance were observed as compared with SBR rubber. Other physical properties compared favorably with commencal rubbers, except for compression set.
The Dependence of Dielectric Properties on Crosslink Density of Rubbers
Authors: Bakule R. , Havránek A.
Published: February 2011

The dielectric properties of natural rubber, synthetic polyisoprene, andpolybutadiene samples crosslinked with sulfur and of natural rubber samplescrosslinked simultaneously with sulfur and dicumyl peroxide were studied. Inthe investigated systems, the number of polar groups in unit volume and thecrosslink density may be changed independently over relatively wide ranges.The measurements were performed in the frequency range from 101 to 105 Hzat various temperatures, and macroscopic parameters describing the dielectricproperties of the samples were evaluated. The position and intensity of thedielectric dispersion peak in the main transition zone is only slightly dependenton the crosslink density of the samples. These two values are mainly influencedby the amount of combined sulfur, or more generally, by the number and thedipole moments of polar groups in the sample. The influence of crosslink densityon the width of the absorption curve is very strong; the width increases withincreasing crosslink density. The possibility of explaining this effect in termsof the dependence of the free volume distribution function on crosslink densityis discussed.
A Family of Mappings Associated with Hadamard's Inequality on a Hypercube
Authors: Wang FuLi
Published: February 2011

This paper provides a method to generalize and refine the Hadamard's inequality on a hypercube in -dimensional Euclidean space by establishing a family of mappings.
Cancer Treatment Before and After Physician-Pharmacy Integration
Authors: Kanter Genevieve P. , Ozluk Pelin , Chi Winnie , Fisch Michael J. , Debono David , Parikh Ravi B. , Jacobson Mireille , Bekelman Justin E. , DeVries Andrea
Published: May 2024

Importance

Integration of pharmacies with physician practices, also known as medically integrated dispensing, is increasing in oncology. However, little is known about how this integration affects drug use, expenditures, medication adherence, or time to treatment initiation.

Objective

To examine the association of physician-pharmacy integration with oral oncology drug expenditures, use, and patient-centered measures.

Design, Setting, and Participants

This cohort study used claims data from a large commercial insurer in the US to analyze changes in outcome measures among patients treated by pharmacy-integrating vs nonintegrating community oncologists in 14 states between January 1, 2011, and December 31, 2019. Commercially insured patients were aged 18 to 64 years with 1 of the following advanced-stage diagnoses: breast cancer, colorectal cancer, kidney cancer, lung cancer, melanoma, or prostate cancer. Data analysis was conducted from May 2023 to March 2024.

Exposure

Treatment by a pharmacy-integrating oncologist, ascertained by the presence of an on-site pharmacy or nonpharmacy dispensing site.

Main Outcomes and Measures

Oral, intravenous (IV), total, and out-of-pocket drug expenditures for a 6-month episode of care; share of patients prescribed oral drugs; days’ supply of oral drugs; medication adherence measured by proportion of days covered; and time to treatment initiation. The association between an oncologist’s pharmacy integration and each outcome of interest was estimated using the difference-in-differences estimator.

Results

Between 2012 and 2019, 3159 oncologists (745 females [27.1%], 2002 males [72.9%]) treated 23 968 patients (66.4% female; 53.4% aged 55-64 years). Of the 3159 oncologists, 578 (18.3%) worked in practices that integrated with pharmacies (with a low rate in 2011 of 0% and a high rate in 2019 of 31.5%). In the full sample (including all cancer sites), after physician-pharmacy integration, no significant changes were found in oral drug expenditures, IV drug expenditures, or total drug expenditures. There was, however, an increase in days’ supply of oral drugs (5.96 days; 95% CI, 0.64-11.28 days; P = .001). There were no significant changes in out-of-pocket expenditures, medication adherence, or time to treatment initiation of oral drugs. In the breast cancer sample, there was an increase in oral drug expenditures ($244; 95% CI, $41-$446; P = .02) and a decrease in IV drug expenditures (–$4187; 95% CI, –$8293 to –$80; P = .05).

Conclusions and Relevance

Results of this cohort study indicated that the integration of oncology practices with pharmacies was not associated with significant changes in expenditures or clear patient-centered benefits.
First-in-Human Hyperpolarized MRI for Tumor Metabolism in HNSCC
Authors: Lai Stephen Y. , Sandulache Vlad C. , Schellingerhout Dawid , Fuller Clifton D. , Chen Yunyun , Walker Christopher M. , Bankson James A.
Published: May 2024

This case report describes the use of hyperpolarized magnetic resonance imaging (MRI) in a patient with head and neck squamous cell carcinoma (HNSCC) to demonstrate its translational viability.
Research on the correction method for radiotherapy verification plans based on displaced electronic portal imaging device
Authors: Guo Jian , Zhou Leyuan , Zeng Haibin
Published: May 2024

Background

It has been observed that under the single isocenter conditions, the potential shifts of the electronic portal imaging devices (EPID) may be introduced when executing portal dosimetry (PD) plans for bilateral breast cancer, pleural mesothelioma, and lymphoma. These shifts are relative to the calibration positions of EPID and result in significant discrepancies in the plan verification results.

Purpose

To explore methods including correction model and specific correction matrices to revise the data obtained from displaced EPID.

Methods

Two methods, the correction model and the specific correction matrices, were applied to correct the data. Five experiments were designed and conducted to build correction model and to validate the effectiveness of these two methods. Gamma passing rates were calculated and data profiles along X‐axis and Y‐axis were captured.

Results

The gamma passing rates for the EPID‐displaced IMRT validation plans after applying correction model, along with the application of specific correction matrices to VMAT and IMRT validation plans, exhibit results that are comparable to the cases with non‐displaced EPID. Except for the VMAT plans applied correction model which showed larger discrepancies (0.041 ± 0.028, 0.049 ± 0.030), the other three exhibit minimal differences in discrepancy values. In all profiles, the corrected data from displaced EPID exhibit a high level of agreement with data obtained from non‐displaced EPID. Good consistency is observed in actual application of the correction model and the specific correction matrices between gamma passing rates of data corrected and those of non‐displaced data.

Conclusions

The proposed methods involving correction model and specific correction matrices can correct the data collected from the displaced EPID, and the gamma passing rates of the corrected data show results that are comparable to some extent with those of non‐displaced data. Particularly, the results corrected by specific correction matrices closely resemble the data from non‐displaced EPID.
Outlier‐resistant state estimation for complex networks with random false data injection attacks under encoding–decoding mechanism
Authors: Liu Yufeng , Hu Jun , Jia Chaoqing , Chen Cai , Chi Kun
Published: May 2024

This article focuses on the outlier‐resistant state estimation problem for discrete time‐varying complex networks (TVCNs) affected by random false data injection attacks (FDIAs) under an encoding–decoding mechanism (EDM). From the perspective of information security, a uniform‐quantization‐based EDM is employed to encrypt the transmitted data. During the data transmission process, a set of independent random variables governed by Bernoulli distribution is introduced to characterize the occurrence of random FDIAs. For the purpose of alleviating the passive impact of potential measurement outliers, a saturation structure is adopted during the estimator design. The gain matrix is given by minimizing the upper bound of estimation error covariance. According to the stochastic analysis method, it is shown that the state estimation error is bounded exponentially in mean‐square sense by providing new sufficient condition. It should be noted that we make the first attempt to develop new outlier‐resistant state estimation method with performance evolution criterion in the time‐varying perspective for TVCNs with random FDIAs under EDM. Finally, a simulation example with comparative experiment is presented to illustrate the effectiveness of the newly presented outlier‐resistant estimation algorithm.
Interfaces Between Nanoparticle and Biomacromolecular Network: Dynamic Behaviors, Confinement and Entropy
Authors: Zhang Xuanyu , Dai Xiaobin , Wan Haixiao , Jiao Zheng , Chen Wenlong , Wei Wenjie , Li Jiaqi , Liu Kai , Yang Zhenzhong , Yan Li‐Tang
Published: May 2024

Biomacromolecular networks, crucial components of biological systems, are of great importance in biological and nanomedical science, in which the interfaces between nanoparticle and macromolecular networks are intriguing and drawing great attention. Herein, this review seeks to present the state‐of‐art progress and perspective of the dynamic behaviors, confinement and entropy at the nanoparticle‐biomacromolecular network interfaces. The basic biomacromolecular networks in living systems, recent research on networks with dynamic bonds and various diffusion behaviors of nanoparticles within biomacromolecular networks are summarized. In particular, entropic effects in the confined environments of biological networks are discussed, along with how they impact the mechanical properties and dynamical behaviors. The interesting research and findings included in this review might offer the scientific community a better understanding of how this field has developed thus far, and are anticipated to trigger more systematic and fundamental research to elucidate the underlying physics and broaden the potential applications of macromolecular networks, biological and artificial.
Lipid Nanoparticles: Versatile Drug Delivery Vehicles for Traversing the Blood Brain Barrier to Treat Brain Cancer
Authors: Cai Xudong , Drummond Calum J. , Zhai Jiali , Tran Nhiem
Published: May 2024

The blood‐brain barrier (BBB) poses a significant challenge in delivering therapeutic agents for brain diseases due to its high selectivity against foreign substances. This limitation greatly hampers the effectiveness of conventional chemotherapeutic drugs in treating brain cancers. In response, lipid‐based nanoparticles (LNPs) have emerged as a promising approach, offering opportunities for targeted drug delivery by conjugating targeting ligands onto their surface. This review provides a comprehensive overview of recent advancements in utilizing LNPs to traverse the BBB for enhanced transport of bioactive compounds into the brain, specifically for cancer treatments. Beginning with an exploration of the biological structure and functions of the BBB and the blood‐brain tumor barrier (BBTB), the review highlights the advantages presented by LNPs. Subsequently, it delves into strategies for surface modification of nanoparticles to enhance BBB targeting and improve efficacy in brain cancer treatment. Finally, the review offers insights into future prospects for designing the next generation of LNPs. The review presented herein aims to contribute to the ongoing efforts in overcoming the challenges associated with BBB penetration, ultimately advancing therapeutic strategies for brain cancer and other neurological disorders.
Lyophilizable Stem Cell‐Hybrid Liposome with Long‐Term Stability and High Targeting Capacity
Authors: Zhang Tianyuan , Zheng Xixi , Lin Ruyi , Sun Hao , Wu Honghui , Zhang Jinsong , Chen Shihan , Li Yaosheng , Xu Donghang , Gao Jianqing
Published: May 2024

The hybridization of liposome with stem cell membranes is an emerging technology to prepare the nanovehicle with the capacity of disease‐responsive targeting. However, the long‐term storage of this hybrid liposome has received limited attention in the literature, which is essential for its potential applicability in the clinic. Therefore, the preservation of long‐term activity of stem cell‐hybrid liposome using freeze‐drying is investigated in the present study. Mesenchymal stem cell‐hybrid liposome is synthesized and its feasibility for freeze‐drying under different conditions is examined. Results reveal that pre‐freezing the hybrid liposome at −20 °C in Tris buffer solution (pH 7.4) containing 10% trehalose can well preserve the liposomal structure for at least three months. Notably, major membrane proteins on the hybrid liposome are protected in this formulation and CXCR4‐associated targeting capacity is maintained both in vitro and in vivo. Consequently, the hybrid liposome stored for three months demonstrates a comparable tumor inhibition as the fresh‐prepared one. The present study provides the first insights into the long‐term storage of stem cell hybrid liposome using lyophilization, which may make an important step forward in enhancing the long‐term stability of these promising biomimetic nanovehicle and ease the logistics and the freeze‐storage in the potential clinical applications.
Enhanced Infrared Vision by Nonlinear Up‐Conversion in Nonlocal Metasurfaces
Authors: Valencia Molina Laura , Camacho Morales Rocio , Zhang Jihua , Schiek Roland , Staude Isabelle , Sukhorukov Andrey A. , Neshev Dragomir N.
Published: May 2024

The ability to detect and image short‐wave infrared light has important applications in surveillance, autonomous navigation, and biological imaging. However, the current infrared imaging technologies often pose challenges due to large footprint, large thermal noise and inability to augment infrared and visible imaging. Here, infrared imaging is demonstrated by nonlinear up‐conversion to the visible in an ultra‐compact, high‐quality‐factor lithium niobate resonant metasurface. Images with high conversion efficiency and resolution quality are obtained despite the strong nonlocality of the metasurface. The possibility of edge‐detection image processing augmented with direct up‐conversion imaging for advanced night vision applications is further shown.
Information Density Enhancement Using Lossy Compression in DNA Data Storage
Authors: Seo Seongjun , Tandon Anshula , Lee Keun Woo , Lee Jee‐Hyong , Park Sung Ha
Published: May 2024

This study develops two deoxyribonucleic acid (DNA) lossy compression models, Models A and B, to encode grayscale images into DNA sequences, enhance information density, and enable high‐fidelity image recovery. These models, distinguished by their handling of pixel domains and interpolation methods, offer a novel approach to data storage for DNA. Model A processes pixels in overlapped domains using linear interpolation (LI), whereas Model B uses non‐overlapped domains with nearest‐neighbor interpolation (NNI). Through a comparative analysis with Joint Photographic Experts Group (JPEG) compression, the DNA lossy compression models demonstrate competitive advantages in terms of information density and image quality restoration. The application of these models to the Modified National Institute of Standards and Technology (MNIST) dataset reveals their efficiency and the recognizability of decompressed images, which is validated by convolutional neural network (CNN) performance. In particular, Model B2, a version of Model B, emerges as an effective method for balancing high information density (surpassing over 20 times the typical densities of two bits per nucleotide) with reasonably good image quality. These findings highlight the potential of DNA‐based data storage systems for high‐density and efficient compression, indicating a promising future for biological data storage solutions.
Bioinspired Mechanochromic Liquid Crystal Materials: From Fundamentals to Functionalities and Applications
Authors: Chen Xinyu , Chen Jingyu , Song Xinyue , Du Tongji , Deng Xinrui , Deng Zhaoping , Hu Xiang‐Guo , Zeng Xingping , Yang Zhen , Yang Huai , Lan Ruochen
Published: May 2024

Inspired by intriguing color changeable ability of natural animals, the design and fabrication of artificial mechanochromic materials capable of changing colors upon stretching or pressing have attracted intense scientific interest. Liquid crystal (LC) is a self‐organized soft matter with anisotropic molecular alignment. Due to the sensitivity to various external stimulations, LC has been considered as an emerging and appealing responsive building block to construct intelligent materials and advanced devices. Recently, mechanochromic LC materials have becoming a hot topic in multifields from flexible artificial skins to visualized sensors and smart biomimetic devices. In this review, the recent progress of mechanochromic LCs is comprehensively summarized. Firstly, the mechanism and functionalities of mechanochromic LC is introduced, followed by preparation of various functional materials based on mechanochromic LCs. Then the applications of mechanochromic LCs are provided. Finally, the conclusion and outlooks of this field is given. This overview is hoped to provide inspiration in fabrication of advanced functional soft materials for scientists and engineers from multidisciplines including materials science, elastomers, chemistry, and physical science.
Highly‐Solvating Electrolyte Enables Mechanically Stable and Inorganic‐Rich Cathode Electrolyte Interphase for High‐Performing Potassium‐Ion Batteries
Authors: Zhao Shuoqing , Li Guohao , Zhang Bohan , Zhang Shipeng , Liu Youxing , Zhou Jinhui , Luo Mingchuan , Guo Shaojun
Published: May 2024

Cathode–electrolyte interphase (CEI) is crucial for the reversibility of rechargeable batteries, yet receives less attention compared to solid–electrolyte interphase (SEI). The prevalent weakly‐solvating electrolyte is usually proposed from the standing point of obtaining robust SEI, however, the resultant weak ion‐solvent interaction gives rise to excessive free solvents and forms thick CEI with high kinetic barriers, which is disadvantageous for interfacial stability at the high working voltage. Herein, a highly‐solvating electrolyte is reported to immobilize free solvents by generating stable ternary complexes and facilitate the growth of homogeneous and ultrathin CEI to boost the electrochemical performances of potassium‐ion batteries (PIBs). Through time‐of‐flight secondary ion mass spectrometry and cryogenic transmission electron microscopy, It is revealed that the deliberately coordinated complexes are the key to forming mechanically stable and inorganic‐rich CEI with superior diffusion kinetics for high‐performing PIBs. Coupling with a K0.5MnO2 cathode and a soft carbon (SC) anode, a high energy density (202.3 Wh kg−1) is achieved with an exceptional cycle lifespan (92.5% capacity retention after 500 cycles) in a SC||K0.5MnO2 full cell, setting new performance benchmarks for PIBs.
Gas Permeation through V2O5 Nanoribbons‐Based Membrane
Authors: Chevrier Sarah M. , Goh Kunli , Chuah Chong Yang , Gabriel Jean‐Christophe P.
Published: May 2024

Membrane separation processes play a crucial role in gas separation applications, with the need for ongoing development to fulfill new needs for today's challenges. For this purpose, novel 2D nanomaterials are progressively showing promise over conventional polymer‐based membrane material, exhibiting excellent molecular transport properties. Beyond the 2D materials already studied in this field, this article presents the first gas separation performances of vanadium pentoxide membrane. Brand new in gas separation topic, 2D van der Waals nanoribbons of V2O5 are successfully synthesized and layered on an anodic aluminum oxide substrate. Gas permeation analysis of He, N2, and CO2 are performed on various membranes made from different quantities of the nanomaterial. Gas permeance results suggest a deviation from an expected Knudsen diffusion mechanism of the V2O5‐based membrane for He separation. The ideal selectivities of He/N2 and He/CO2 are compared to Robeson's upper bound for polymeric membranes. V2O5 membranes, prepared with the highest V2O5 quantity, exceeded the upper bound from 2008 for He/N2 and 2019 (the most recent) for He/CO2, demonstrating the interesting potential of V2O5 2D materials for gas separation.
Deciphering the Role of Native Defects in Dopant‐Mediated Defect Engineering of Carbon Electrocatalysts
Authors: Li Ning , Li Mengyang , Guo Kun , Guo Ziqian , Wang Ruijie , Bao Lipiao , Hou Gao‐Lei , Lu Xing
Published: May 2024

Doping–dedoping chemistry lays the cornerstone for converting heteroatom dopants into intrinsic defects as the emerging active sites of carbon catalysts, but the defect content is yet hindered by inadequate doping efficiencies. Comprehending crucial factors behind the doping of pristine carbon and their correlation to the catalytic properties of dedoped carbon is thus of high significance. Here, the overlooked impact of native defects in pristine carbon on dopant‐mediated defect engineering of carbon catalysts is explicitly unveiled. Intact fullerene (C60), C60‐derived carbon, and carbon black in distinct pentagon/edge defect states are employed as respective precursors to undergo a nitrogen doping–dedoping treatment. Theoretical and experimental evidence consistently indicates that native pentagons change the preferred N doping site from the edge to the basal plane, leading to a substantially higher doping level. Importantly, in addition to pentagons from the removal of zigzag‐edged pyridinic N, N dopants in in‐plane pentagons are more easily dedoped than those in hexagons, generating even more pentagons in a new pentagon–heptagon–pentagon structure as oxygen reduction active sites. The optimized defect‐rich carbon gives an outstanding half‐wave potential of 0.834 V (0.846 V for Pt/C) via the four‐electron pathway, excellent long‐term durability, and prospective applicability in zinc–air batteries.
Complementary technology adoption and smallholder commercialization: Panel data evidence from Ethiopia
Authors: Tabe‐Ojong Martin Paul , Geffersa Abebayehu Girma
Published: May 2024

Agricultural transformation involves the transition from subsistence agriculture marked by cultivating crops for auto‐consumption to cultivating crops for output markets. This transition from subsistence agriculture to market‐oriented agriculture can be a key policy boost to economic development, but evidence on the key entry points to increasing smallholder commercialization remains scarce. We examine the relationship between the adoption of improved maize varieties (IMVs), inorganic fertilizers, and smallholder commercialization. We model commercialization as a two‐step decision process involving market participation and the extent of participation (sales quantity) conditional on participation. Given these two related steps, we estimate a double‐hurdle model in both linear and non‐linear forms. Employing a three‐wave panel dataset from Ethiopia, we use the household fixed effects and correlated random effects model with the control function approach. We find the adoption of IMVs to be significantly associated with both market participation and the extent of participation. This relationship is also true for fertilizers, where we show a positive association between fertilizer use and commercialization. Given the seeming complementarity in the use of both IMVs and fertilizers, we further estimate their joint adoption. We use the multinomial endogenous switching regression model where we show greater commercialization gains under joint adoption. These findings are in line with a growing literature supporting the bundling of agricultural technologies. Given these insights, we provide empirical and policy support to the scaling of agricultural technologies as they have the potential to induce agricultural transformation by unlocking market opportunities.
Design of Soft Microjoint to Improve Robotic Cell Micromanipulation Flexibility
Authors: Zhang Youchao , Wang Fanghao , Chen Guang , Li Zhijun , Knoll Alois , Ying Yibin , Zhou Mingchuan
Published: May 2024

Dexterity micromanipulation is a significant topic in the field of robotics. Herein, a novel robotic rotating microjoint controlled by an exogenous magnetic field based on magnetic programmable soft materials, which brings more dexterity to the micromanipulation task is proposed. First, the magnetic soft material is synthesized and the microjoint is manufactured. The maximum rotation angle and response time are characterized. Then the force analysis of the microjoint in a uniform magnetic field is performed and the relationship between the deformation bending angle of a microjoint and the magnetic field magnitude is first proposed. A sliding mode controller based on the deformation mechanism of microjoints and radial basis function neural network (DMRSMC) is proposed to achieve robust deformation control of the microjoint. The experiment that depicts the microjoint is able to achieve a maximum rotation angle of 22.16° and a response time of 16 ms. The DMRSMC controller performs angle control with higher accuracy than conventional SMC and PID controllers. Finally, a dexterous suction mechanism is developed by combining the microjoint with a soft micropipette needle to achieve dexterous grasping of zebrafish embryos with a 97% success rate and an orientation adjustment error is 1.36°.
Exploring the diverse clinical and variant spectrum of CEP78‐associated syndrome: Novel pathogenic variants identified in a case series
Authors: Zhai Yi , Ballios Brian G.
Published: May 2024

Dual sensory impairment, commonly referred to as combined hearing and vision loss, can stem from a diverse spectrum of conditions, each presenting with its unique set of clinical characteristics. Our understanding of dual sensory impairment has expanded significantly in the past decade, broadening the scope of genetic differential diagnoses, including genes such as CEP250, ARSG, TUBB4B, CEP78, and ABHD12. A case series including three patients from two families with genetically diagnosed CEP78‐associated cone–rod dystrophy was identified. We collected and reviewed their clinical records, imaging data, and genetic testing results. In addition, a comprehensive literature review was conducted on the phenotype and the genetic testing modality employed in all published CEP78 cases through a PubMed search using the keyword “CEP78.” A retinal dystrophy panel detected a novel homozygous CEP78 pathogenic variant (c.1447C>T, p.Arg483*) in siblings—Cases 1 and 2—from Family 1. Both teenagers have a clinical diagnosis of cone–rod dystrophy with presumed normal hearing. Case 3 from Family 2, diagnosed with cone–rod dystrophy and early‐onset hearing loss, was found to carry a CEP78 pathogenic variant (c.1206‐2A>C) and a likely pathogenic variant (c.856_857del, p.Leu286Glyfs*12) also through panel‐based genetic testing. Intriguingly, neither of these variants was reported in an affected sibling's clinical whole‐exome sequencing (WES) report when performed in 2015. A review of CEP78‐related literature unveiled that the initial report linking CEP78 to cone–rod dystrophy and hearing loss was published in September 2016. Any pathogenic variant found in CEP78 before 2016 would have been categorized as a “clearly disruptive variant in a gene of uncertain significance (GUS)” and might not have been reported in the WES report. It is important to acknowledge that our understanding of genotype–phenotype associations is undergoing rapid expansion. It is also crucial to recognize that repeat genetic testing may represent a fundamentally different approach, given the technological advancements not only in the coverage of the sequencing but also in the more comprehensive understanding of genotype–phenotype associations. This case series also enriches the existing CEP78 literature by providing phenotypic details of the youngest case of CEP78‐associated retinopathy reported in the literature (Case 2), which expands our perspective on the natural history of disease in this disorder.
Clusters of cognitive performance predict long‐term cognitive impairment in elderly patients with subjective memory complaints and healthy controls
Authors: Jiménez‐Huete Adolfo , Villino‐Rodríguez Rafael , Ríos‐Rivera Mirla M. , Rognoni Teresa , Montoya‐Murillo Genoveva , Arrondo Carlota , Zapata Carolina , Rodríguez‐Oroz María Cruz , Riverol Mario ,   for the Alzheimer's Disease Neuroimaging Initiative
Published: May 2024

INTRODUCTION

Patients with subjective memory complaints (SMC) may include subgroups with different neuropsychological profiles and risks of cognitive impairment.

METHODS

Cluster analysis was performed on two datasets (n: 630 and 734) comprising demographic and neuropsychological data from SMC and healthy controls (HC). Survival analyses were conducted on clusters. Bayesian model averaging assessed the predictive utility of clusters and other biomarkers.

RESULTS

Two clusters with higher and lower than average cognitive performance were detected in SMC and HC. Assignment to the lower performance cluster increased the risk of cognitive impairment in both datasets (hazard ratios: 1.78 and 2.96; Plog‐rank: 0.04 and <0.001) and was associated with lower hippocampal volumes and higher tau/amyloid beta 42 ratios in cerebrospinal fluid. The effect of SMC was small and confounded by mood.

DISCUSSION

This study provides evidence of the presence of cognitive clusters that hold biological significance and predictive value for cognitive decline in SMC and HC.

Highlights

Patients with subjective memory complaints include two cognitive clusters.

Assignment to the lower performance cluster increases risk of cognitive impairment.

This cluster shows a pattern of biomarkers consistent with incipient Alzheimer's disease pathology.

The same cognitive cluster structure is found in healthy controls.

The effect of memory complaints on risk of cognitive decline is small and confounded.
Tight Bounds from Multiple‐Observable Entropic Uncertainty Relations
Authors: Riccardi Alberto , Chesi Giovanni , Macchiavello Chiara , Maccone Lorenzo
Published: May 2024

The additivity properties for both bipartite and multipartite systems are investigated by using entropic uncertainty relations (EUR) defined in terms of the joint Shannon entropy of probabilities of local measurement outcomes. In particular, state‐independent and state‐dependent entropic inequalities are introduced. Interestingly, the violation of these inequalities is strictly connected with the presence of quantum correlations. It is shown that the additivity of EUR holds only for EUR that involve two observables, while this is not the case for inequalities that consider more than two observables or the addition of the von Neumann entropy of a subsystem. They are applied to bipartite systems and to several classes of states of a three‐qubit system.
Unlocking Single Particle Anisotropy in Real‐Time for Photoelectrochemistry Processes at the Nanoscale
Authors: Lu Si‐Min , Wang Hao‐Wei , Chen Mengjie , Xie Bao‐Kang , Long Yi‐Tao
Published: May 2024

The key to rationally and rapidly designing high‐performance materials is the monitoring and comprehension of dynamic processes within individual particles in real‐time, particularly to gain insight into the anisotropy of nanoparticles. The intrinsic property of nanoparticles typically varies from one crystal facet to the next under realistic working conditions. Here, we introduce the operando collision electrochemistry to resolve the single silver nanoprisms (Ag NPs) anisotropy in photoelectrochemistry. We directly identify the effect of anisotropy on the plasmonic‐assisted electrochemistry at the single NP/electrolyte interface. The statistical collision frequency shows that heterogeneous diffusion coefficients among crystal facets facilitate Ag NPs to undergo direction‐dependent mass transfer toward the gold ultramicroelectrode. Subsequently, the current amplitudes of transient events indicate that the anisotropy enables variations in dynamic interfacial electron transfer behaviors during photothermal processes. The results presented here demonstrate that the measurement precision of collision electrochemistry can be extended to the sub‐nanoparticle level, highlighting the potential for high‐throughput material screening with comprehensive kinetics information at the nanoscale.
Dual‐Locked Fluorescent Probes Activated by Aminopeptidase N and the Tumor Redox Environment for High‐Precision Imaging of Tumor Boundaries
Authors: Shen Yang , Li Wei , Zhou Zhixuan , Xu Junchao , Li Yuhang , Li Haiyan , Zheng Xudong , Liu Sulai , Zhang Xiao‐Bing , Yuan Lin
Published: May 2024

Clear delineation of tumor margins is essential for accurate resection and decreased recurrence rate in the clinic. Fluorescence imaging is emerging as a promising alternative to traditional visual inspection by surgeons for intraoperative imaging. However, traditional probes lack accuracy in tumor diagnosis, making it difficult to depict tumor boundaries accurately. Herein, we proposed an offensive and defensive integration (ODI) strategy based on the “attack systems (invasive peptidase) and defense systems (reductive microenvironment)” of multi‐dimensional tumor characteristics to design activatable fluorescent probes for imaging tumor boundaries precisely. Screened out from a series of ODI strategy‐based probes, ANQ performed better than traditional probes based on tumor unilateral correlation by distinguishing between tumor cells and normal cells and minimizing false‐positive signals from living metabolic organs. To further improve the signal‐to‐background ratio in vivo, derivatized FANQ, was prepared and successfully applied to distinguish orthotopic hepatocellular carcinoma tissues from adjacent tissues in mice models and clinical samples. This work highlights an innovative strategy to develop activatable probes for rapid diagnosis of tumors and high‐precision imaging of tumor boundaries, providing more efficient tools for future clinical applications in intraoperative assisted resection.
Integrated Design for Discrete Sulfur@Polymer Nanoreactor with Tandem Connection as Lithium–Sulfur Battery Cathodes
Authors: Wang Bin , Wang Yu , Lan Yudong , Lu Guiling , Liu Ling , Tang Tao , Li Ming , Cheng Yong , Xiao Jianrong , Li Xinyu
Published: May 2024

Apart from electrode material modification, architecture design and optimization are important approaches for improving lithium–sulfur battery performance. Herein, an integrated structure with tandem connection is constructed by confining nanosulfur (NS) in conductive poly(3,4‐ethylenedioxythiophene) (PEDOT) reaction chambers, forming an interface of discrete independent nanoreactor units bonded onto carbon nanotubes (noted as CNT/NS@PEDOT). The unique spatial confinement and concentration gradients of sulfur@PEDOT nanoreactors (SP‐NRs) can promote reaction kinetics while facilitating rapid polysulfide transformation and minimizing dissolution and diffusion losses. Meanwhile, overall ultrahigh energy input and output are achieved through tandem connection with carbon nanotubes, isolation with PEDOT coating, and synergistic multiplicative effects among SP‐NRs. As a result, it delivers a high initial discharge capacity of 1246 mAh g−1 at 0.1 C and 918 mAh g−1 at 1 C, the low capacity decay rate per lap of 0.011 % is achieved at a current density of 1 C after 1000 cycles. This research emphasizes the innovative structural design to provide a fresh trajectory for the further advancement of high‐performance energy storage devices.
Reactivity and Steric Parameters from 2D to 3D Bulky Pyridines: Increasing Steric Demand at Nitrogen with Chiral Azatriptycenes
Authors: Saida Ali Ben , Mahaut Damien , Tumanov Nikolay , Wouters Johan , Champagne Benoît , Vanthuyne Nicolas , Robiette Raphaël , Berionni Guillaume
Published: May 2024

Sterically hindered pyridines embedded in a three‐dimensional triptycene framework have been synthesized, and their resolution by chiral HPLC enabled access to unprecedented enantiopure pyridines exceeding the known steric limits. The design principles for new axially chiral pyridine derivatives are then described. To rationalize their associations with Lewis acids and transition metals, a comprehensive determination of the steric and electronic parameters for this new class of pyridines was performed. This led to the general parameterization of the steric parameters (percent buried volume %VBur, Tolman cone angle θ, and He8_steric descriptor) for a large set of two‐ and three‐dimensional pyridine derivatives. These parameters are shown to describe quantitatively their interactions with carbon‐ and boron‐centered Lewis acids and were used to predict the ΔG° of association with the prototypical B(C6F5)3 Lewis acid widely used in frustrated Lewis pair catalysis. This first parameterization of pyridine sterics is a fundamental basis for the future development of predictive reactivity models and for guiding new applications of bulky and chiral pyridines in organocatalysis, frustrated Lewis pairs, and transition‐metal catalysis.