bluuebunny/crossref_metadata_2025 huggingface dataset:
Colored Silicon Heterojunction Solar Cells Exceeding 23.5% Efficiency Enabled by Luminescent Down‐Shift Quantum Dots
Authors: Jiang Conghui , Zhang Guohua , Hong Zhiwei , Chen Jiangyu , Li Ya , Yuan Xianrong , Lin Yinyue , Yu Cao , Wang Tao , Song Tao , Wang Yusheng , Sun Baoquan
Published: November 2022

Colored solar panels, realized by depositing various reflection layers or structures, are emerging as power sources for building with visual aesthetics. However, these panels suffer from reduced photocurrent generation due to the less efficient light harvesting from visible light reflection and degraded power conversion efficiency (PCE). Here, color‐patterned silicon heterojunction solar cells are achieved by incorporating luminescent quantum dots (QDs) with high quantum yields as light converters to realize an asthenic appearance with high PCE. It is found that large bandgap (blue) QD layers can convert UV light into visible light, which can notably alleviate the parasitic absorption by the front indium tin oxide and doped amorphous silicon. Additionally, a universal optical path model is proposed to understand the light transmission process, which is suitable for luminescent down‐shift devices. In this study, solar cells with a PCE exceeding 23.5% are achieved using the combination of a blue QD layer and a top low refractive index anti‐reflection layer. Based on our best knoledge,the obtained PCE is the highest for a color‐patterned solar cell. The results suggest an enhanced strategy involving incorporation of luminescent QDs with an optical path design for high‐performance photovoltaic panels with visual aesthetics.
Interfacial Instability‐Induced (3I) Adhesives through “Mediator” Solvent Diffusion for Robust Underoil Adhesion
Authors: Wan Xizi , Zhang Feilong , Zhang Ke , Liu Xi , Xu Xuetao , Liu Mingqian , Jiang Lei , Wang Shutao
Published: November 2022

Underoil adhesives are intensively needed in case of oil spill caused by pipeline rupture, but remain a challenge owing to the obstruction of oil layer or their swelling in oil. Herein, a general solvent diffusion principle is demonstrated by introducing dual‐soluble “mediator” solvents to develop a new type of interfacial instability‐induced (3I) adhesives, achieving effective underoil adhesion on various substrates and blocking the oil leakage within seconds. Microscopic characterization reveals a fast and dynamic solvent exchange process that destroys the oil layer by liquid–liquid interfacial diffusion between the “mediator” solvent and oil, enabling 3I adhesives to contact the solid surfaces directly. The principle of interfacial instability‐induced liquid replacement is quite different from typical immiscible liquid replacement and is not restricted by the surface tension of solvents, surface energy, and roughness of solid surfaces, successfully directing the construction of a series of effective 3I adhesives with commercially available feedstocks. This study provides a unique clue for the design of next‐generation adhesives in complex environments.
Triboelectric Fluid Sensors: Principles, Development, and Perspectives
Authors: Wang Zheng , Wang Yingting , Gao Qi , Bao Gang , Cheng Tinghai , Wang Zhong Lin
Published: November 2022

Fluid energy is one of the most common, widely distributed, and significant renewable energy sources globally, which generally exists in gases and liquids such as wind energy, airflow energy, droplet energy, water flow energy, and wave energy. Since Wang's research group first invented the triboelectric nanogenerators (TENGs) in 2012, it has been widely utilized and developed rapidly as a new energy conversion method and as a promising sensing technology. Especially in fluid sensing, the TENGs get a lot of attention. This paper comprehensively reviews the latest research on triboelectric fluid sensors (TFSs). First, the fundamental theories and basic operation modes of TFSs are briefly introduced. Then, the research status of TFSs in different functions, structural design, and output performance is summarized according to the form of fluid energy (gas‐based, liquid‐based, and multi‐phase flow‐based). In addition, the application of TFSs in different fields is also discussed in this paper. Finally, this research presents its views on the challenges and future development trends of TFSs.
A Facile Au Dot‐Based Nanodrug for Enhanced Redox Dyshomeostasis in Chemodynamic Therapy
Authors: Wang Huafeng , Zhang Min , Wang Zhaoyin , Lu Yuxiao , Liu Xinhe , Wei Tianxiang , Dai Zhihui
Published: November 2022

Insufficient hydrogen peroxide (H2O2) in tumor microenvironment severely limits the therapeutic effect of chemodynamic therapy (CDT), while excessive glutathione (GSH) scavenges the generated hydroxyl radical (•OH) to reduce oxidative stress, making the CDT consequence even poorer. Herein, a facile yet vigorous therapeutic nanodrug, which integrates polyethylene glycol (PEG)‐functionalized gold nanodots (Au NPs) with ferrocene (Fc), is fabricated for enhanced CDT by redox dyshomeostasis with both GSH depletion and boosted oxidative stress. The constructed Au NPs‐PEG‐Fc (APF) nanodrug depletes GSH by competitive binding, catalyzes glucose to generate H2O2 with its glucose oxidase‐mimicking activity, and further catalyzes H2O2 to generate •OH through the Fc‐based Fenton reaction. Finally, it enhances redox dyshomeostasis through both the depletion of GSH and generation of •OH. Both in vitro and in vivo results show that the APF nanodrug can elevate oxidative stress to enhance the efficacy of CDT. Overall, this study provides a promising strategy for disrupting the redox balance to enhance the efficacy of CDT.
Investigation for Carbonation Mechanism of Tobermorite 9 Å: A Combination of DFT and Ab Initio Molecular Dynamics Study
Authors: Liu Xiaotong , Bai Xiaolin , Zhong Wei , Deng Xiangsheng , Liang Tianshui
Published: November 2022

Hydrated calcium silicate carbonation leads to reinforcement corrosion and strength reduction. The carbonation mechanism of Tobermorite 9 Å is researched by density functional theory calculation and ab initio molecular dynamics (AIMD). Results show that the lowest surface energy of Tobermorite 9 Å (001) slab is (001) surface. The bridge position of Ca1─Ca5 atom is the most stable adsorption position for carbon dioxide molecules. In terms of charge density difference, the results show that the Ca atom loses electrons and the O atom gains electrons. In terms of partial density of states, the results show that there are unobvious hybridization orbitals between Ca d‐ and O p‐orbitals, which leads to the formation of a very weak Ca─O bond. In terms of AIMD simulation at the temperature of 1073 K, the results show that the carbon dioxide gradually develops from adsorption to desorption on the Tobermorite 9 Å (001) surface. These findings provide profound views in understanding the carbonation of hydrated calcium silicate.
Nature of Zinc‐Derived Dendrite and Its Suppression in Mildly Acidic Aqueous Zinc‐Ion Battery
Authors: Kim Hee Jae , Kim Sun , Heo Kwang , Lim Jae‐Hong , Yashiro Hitoshi , Myung Seung‐Taek
Published: November 2022

Aqueous zinc‐ion batteries (ZIBs) are attractive in energy storage due to the use of aqueous electrolytes that ensures safety and ease of handling all parts in air. However, catastrophic zinc dendritic growth on zinc metal anodes impedes their practical application. Herein, Zn3(PO4)3·4H2O (ZP)‐coated zinc metal anode is introduced to effectively suppress the dendrite growth and the chemical state of the dendrites that are composed of metallic Zn0, ZnO, and Zn(OH)2is elucidated first. Significant improvement is observed for the ZP‐coated zinc metal symmetric cell. Operando synchrotron tomography demonstrates that the ZP‐coating layer ensures uniform deposition of zinc‐derived compounds by the ZP layer that scarifies itself through decomposition to P2O5, Zn0, and Zn(OH)2. Meanwhile, the local reaction between P2O5and H2O reproduces H3PO4, which provides a condition to reproduce Zn3(PO4)2·4H2O via a reaction between H3PO4and metallic Zn on the Zn metal anode. This cyclic reformation of Zn3(PO4)2·4H2O progressively prevents dendrites over the long‐term, even at high rates. The compatibility is verified in NaV3O8||ZP‐coated zinc anode cell over 1000 cycles. As a result, this finding presents a practical way for uniform deposition of Zn that can be applicable to aqueous and nonaqueous ZIBs.
Epidemiology of occupational injuries in construction workers between 2009 and 2018 in South Korea
Authors: Jung Saemi , Kim Tae‐Kyoung , Kim Yoon‐Ji , Kim Young‐Ki , Kang Dongmug , Kim Se‐Yeong
Published: November 2022

Background

This study aimed to investigate the characteristics of occupational injuries based on fatality, sex, and classification of occupations among construction workers using workers' compensation (WC) insurance data in South Korea.

Methods

We collected WC insurance data from the Korea Workers' Compensation & Welfare Service for all construction workers between 2009 and 2018. Data from 158,947 accepted claims for occupational injury were extracted, and the demographic features, occupational injury types, and annual trends were analyzed for fatal and nonfatal cases. The annual incidence and mortality trends of occupational injury were estimated using negative binomial regression and Poisson regression models, for injury incidence and mortality respectively.

Results

Among a total of 158,947 occupational injury cases, there were 155,772 (98%) nonfatal injuries and 3175 (2%) fatal injuries. For all occupational injuries, Construction Elementary Workers (6th Korean Standard Classification of Occupations (KSCO) 910; 45.7%) was the most frequent occupation, followed by Construction‐Related Technical Workers (6th KSCO 772; 39.2%). The most frequent injury type was a fracture, followed by ruptures or lacerations and contusions. The incidence of all occupational injuries increased from 700.36 per 100,000 persons in 2009 to 1,195.98 per 100,000 persons in 2018. Further, deaths from injuries at work followed a significantly increasing annual trend [mortality rate ratio 1.04 (95% CI: 1.03–1.05)] from 2009 to 2018.

Conclusion

The over two‐thirds increased incidence of occupational injuries and significantly increasing mortality trends for occupational injuries during the last 10 years indicate the need for aggressive intervention in occupational safety and health management within the Korean construction industry.
CuI Catalyzed Regio‐ and Stereo‐selective Hydroboration of Ynamides: α‐ and β‐Borylation via Hydro‐Cupration and Borylation
Authors: Roy Subhra , Mishra Archana , Sekhar Pati Subhransu , Behera Minati , Prakash Das Jaya
Published: November 2022

A CuI‐catalyzed hydrocupration and borylation protocol for the regio‐ and stereoselective borylation of ynamides utilizing pinacolatoborane (HBpin) as the borylating agent has been developed. The reaction features mild conditions, good substrate scope and functional group tolerance‐representing a highly efficient and practical method for the synthesis of regio‐ and stereoselective tri‐substituted alkenylboronates from readily available ynamides. The regioselectivity is controlled by altering substituents on the ynamides (alkyl vs aryl) and utilizing a catalytic species [LCuH] generated in situ from HBpin and [LCuX]. Suzuki coupling and other transformations highlight the synthetic utility of the method.
Primary sinonasal lymphoma: A multi‐institutional experience of clinical presentation, treatment, and outcomes
Authors: Eide Jacob G. , Kshirsagar Rijul S. , Birkenbeuel Jack L. , Abello Eric H. , Hobday Sara , Herzberg Sabrina , Wang Beverly Y. , Palmer James N. , Adappa Nithin D. , Kuan Edward C.
Published: November 2022

Background

Sinonasal lymphoma (SL) is a heterogeneous, underrecognized neoplastic disorder with limited outcomes data. We sought to better define outcomes by subtype and treatment at 2 referral centers over the past 2 decades.

Methods

Demographics, clinicopathologic data, and treatment outcomes for patients treated for SL were queried from January 1, 2000 to December 31, 2021 at 2 tertiary academic medical centers.

Results

Eighty‐four patients were included, with an average age at diagnosis of 63.4 ± 15 years. There were 34 females (40.5%). The majority of patients had an Eastern Cooperative Oncology Group (ECOG) score of <2 (76.2%) and the most common presenting symptom was facial swelling/pain (26.2%). The most common primary site was the nasal cavity (36.9%). Diffuse large B‐cell lymphoma was the most common subtype (46.4%), followed by extranodal NK/T‐cell lymphoma (17.9%). Chemotherapy was the most common treatment strategy (n = 59, 70.2%), followed by radiation therapy (n = 35, 41.7%) and immunotherapy (n = 24, 28.6%). Disease‐specific survival rates at 1, 5, and 10 years were 85.7%, 73.6%, and 58.6%, respectively. Eighteen patients (21.4%) developed recurrence. On multivariate analysis, higher ECOG score (p < 0.0001) and history of head and neck radiation (p = 0.048) were associated with worse survival. Younger age was associated with greater risk of recurrence (p = 0.022) and male sex was associated with more treatment side effects (p = 0.012).

Conclusion

This is the largest multi‐institutional analysis of SL characteristics and outcomes. Our work suggests that, although disease control in the first 5 years is reasonable, 10‐year outcomes remain challenging. Further studies are needed to investigate new treatment paradigms and risk stratification.
Disease progression model using the integrated Alzheimer's Disease Rating Scale
Authors: Gueorguieva Ivelina , Chua Laiyi , Willis Brian A. , Sims John R. , Wessels Alette M.
Published: November 2022

Introduction

An Alzheimer's disease (AD) dementia disease progression model was developed based on the integrated Alzheimer's Disease Rating Scale (iADRS).

Methods

Data from 3483 placebo participants in six AD trials were used to develop the disease progression model with NONMEM (version 7.4.2) and examined for mild cognitive impairment, and mild and moderate dementia due to AD.

Results

Baseline iADRS score was significantly influenced by AD symptomatic medication use, EXPEDITION2 enrollment (included moderate AD participants), age, and baseline Mini‐Mental State Examination (MMSE) score. Rate of disease progression increased across disease stage and was significantly influenced by AD medication use, age, and baseline MMSE score. Apolipoprotein E ε4 carrier status did not influence baseline iADRS score or disease progression.

Discussion

These results demonstrate a disease progression model describing the time course of the iADRS across the AD severity spectrum. This model can assist future clinical trials in study design optimization and treatment effect interpretation.

Highlights

A disease progression model described the integrated Alzheimer's Disease Rating Scale (iADRS) time course in mild cognitive impairment to moderate Alzheimer's disease.

Using the linear regression model, iADRS scores can be calculated for Mini‐Mental State Examination scores.

Results can help optimize future clinical trial design and aid in understanding treatment effects.
Layered β‐ZrNBr Nitro‐Halide as Multifunctional Photocatalyst for Water Splitting and CO2 Reduction
Authors: Bao Yunfeng , Du Shiwen , Shibata Kengo , Guo Xiangyang , Kamakura Yoshinobu , Feng Zhaochi , Huang Yanqiang , Ishitani Osamu , Maeda Kazuhiko , Zhang Fuxiang
Published: November 2022

Developing mixed‐anion semiconductors for solar fuel production has inspired extensive interest, but the nitrohalide‐based photocatalyst is still in shortage. Here we report a layered nitro‐halide β‐ZrNBr with a narrow band gap of ca. 2.3 eV and low defect density to exhibit multifunctionalities for photocatalytic water reduction, water oxidation and CO2 reduction under visible‐light irradiation. As confirmed by the results of electron paramagnetic resonance (EPR) and density functional theory (DFT) calculations, the formation of anion vacancies in the nitro‐halide photocatalyst was inhibited due to its relatively high formation energy. Furthermore, performance of β‐ZrNBr can be effectively promoted by a simple exfoliation into nanosheets to shorten the carrier transfer distance as well as to promote charge separation. Our work extends the territory of functional photocatalysts into the nitro‐halide, which opens a new avenue for fabricating efficient artificial photosynthesis.
Exploring Helical Peptides and Foldamers for the Design of Metal Helix Frameworks: Current Trends and Future Perspectives
Authors: Bajpayee Nikhil , Vijayakanth Thangavel , Rencus‐Lazar Sigal , Dasgupta Sneha , Desai Aamod V. , Jain Rahul , Gazit Ehud , Misra Rajkumar
Published: November 2022

Flexible and biocompatible metal peptide frameworks (MPFs)derived from short and ultra‐short peptides have been explored for the storage of greenhouse gases, molecular recognition, and chiral transformations. In addition to short flexible peptides, peptides with specifically folded conformations have recently been utilized to fabricate a variety of metal helix frameworks (MHFs). The secondary structures of the peptides govern the structure‐assembly relationship and thereby control the formation of three‐dimensional (3D)‐MHFs. Particularly, the hierarchical structural organization of peptide‐basedMHFshas not yet been discussed in detail. Here, we describe the recent progress of metal‐driven folded peptide assembly to construct 3D porous structures for use in future energy storage, chiral recognition, and biomedical applications, which could be envisioned as an alternative to the conventional metal‐organic frameworks (MOFs).
Boraalkenes Made by a Hydroboration Route: Cycloaddition and B=C Bond Cleavage Reactions
Authors: Jie Xiaoming , Chen Chaohuang , Daniliuc Constantin G. , Kehr Gerald , Erker Gerhard
Published: November 2022

Hydroboration of styrene or vinylcyclohexane with the IMes(C6F5)BH+ cation followed by deprotonation provided a convenient synthetic entry to the [B]=CHCH2R boraalkenes 9 a and 9 b. The in situ generated IMes(SCN)BH+ system reacted similarly with 1,1‐diphenylethene followed by deprotonation to give the isothiocyanato substituted boraalkene 9 c. The boraalkenes underwent [2+2] cycloaddition reactions with a small series of heterocumulenes to give the respective four‐membered heterocycles. The [B]=CHCH2R+CO2 cycloadducts 13 a and 13 b added the borane HB(C6F5)2 with cleavage of the central B−C σ‐bond. CS2 underwent an unusual reaction with the boraalkenes, namely insertion into the B=C bond with formation of the borylated dithioketene acetal under complete rupture of the strong B=C double bond. The intermediate dithiobora‐β‐lactone type intermediate was isolated in the case of the isothiocyanato‐boraalkene reaction and characterized by X‐ray diffraction.
Unsymmetrically Chlorinated Non‐Fused Electron Acceptor Leads to High‐Efficiency and Stable Organic Solar Cells
Authors: Ma De‐Li , Zhang Qian‐Qian , Li Chang‐Zhi
Published: November 2022

Searching the cost‐effective organic semiconductors is strongly needed in order to facilitate the practice of organic solar cells (OSCs), yet to be fulfilled. Herein, we have succeeded in developing two non‐fused ring electron acceptors (NFREAs), leading to the highest efficiency of 16.2 % for the NFREA derived OSCs. These OSCs exhibit the superior operational stabilities under one sun equivalent illumination without ultraviolet (UV) filtration. It is revealed that the modulation of halogen substituents on aromatic side chains, as the new structural tool to tune the intermolecular interaction and optoelectronic properties of acceptors, not only promotes the interlocked tic‐tac‐toe frame of three‐dimensional stacks in solid, but also improves charge dynamics of acceptors to enable high‐performance and stable OSCs.
Synthesis of Highly Luminescent Chiral Nanographene
Authors: Li Ji‐Kun , Chen Xing‐Yu , Zhao Wen‐Long , Guo Yun‐Long , Zhang Yi , Wang Xin‐Chang , Sue Andrew C.‐H. , Cao Xiao‐Yu , Li Meng , Chen Chuan‐Feng , Wang Xiao‐Ye
Published: November 2022

Chiral nanographenes with both high fluorescence quantum yields (ΦF) and large dissymmetry factors (glum) are essential to the development of circularly polarized luminescence (CPL) materials. However, most studies have been focused on the improvement ofglum, whereas how to design highly emissive chiral nanographenes is still unclear. In this work, we propose a new design strategy to achieve chiral nanographenes with highΦFby helical π‐extension of strongly luminescent chromophores while maintaining the frontier molecular orbital (FMO) distribution pattern. Chiral nanographene with perylene as the core and two dibenzo[6]helicene fragments as the wings has been synthesized, which exhibits a record highΦFof 93 % among the reported chiral nanographenes and excellent CPL brightness (BCPL) of 32 M−1 cm−1.
Nickel‐Catalyzed Cross‐Electrophile 1,2‐Silyl‐Arylation of 1,3‐Dienes with Chlorosilanes and Aryl Bromides
Authors: Pan Qiu‐Quan , Qi Liangliang , Pang Xiaobo , Shu Xing‐Zhong
Published: November 2022

Catalytic, three‐component, cross‐electrophile reactions have recently emerged as a promising tool for molecular diversification, but studies have focused mainly on the alkyl‐carbonations of alkenes. Herein, the scope of this method has been extended to conjugated dienes and silicon chemistry through silylative difunctionalization of 1,3‐dienes with chlorosilanes and aryl bromides. The reaction proceeds under mild conditions to afford 1,2‐linear‐silylated products, a selectivity that is different to those obtained from conventional methods via an intermediary of H(C)‐η3‐π‐allylmetal species. Preliminary mechanistic studies reveal that chlorosilane reacts with 1,3‐diene first and then couples with aryl bromide.
Halide Perovskite Single Crystals and Nanocrystal Films as Electron Donor‐Acceptor Heterojunctions
Authors: Shahjahan M. D. , Okamoto Takuya , Chouhan Lata , Sachith Bhagyashree Mahesha , Pradhan Narayan , Misawa Hiroaki , Biju Vasudevanpillai
Published: November 2022

Halide perovskites are materials for future optical displays and solar cells. Electron donor‐acceptor perovskite heterostructures with distinguishing halide compositions are promising for transporting and harvesting photogenerated charge carriers. Combined e‐beam lithography and anion exchange are promising to develop such heterostructures but challenging to prepare multiple heterojunctions at desired locations in single crystals. We demonstrate swift laser trapping‐assisted band gap engineering at the desired locations in MAPbBr3microrods, microplates, or nanocrystal thin films. The built‐in donor‐acceptor double and multi‐heterojunction structures let us transport and trap photogenerated charge carriers from wide‐band gap bromide to narrow‐band gap iodide domains. We discuss the charge carrier transport and trapping mechanisms from the viewpoints of engineered bands and band continuity. This work offers a convenient method for designing single‐, double‐ and multi‐heterojunction donor‐acceptor halide perovskites for photovoltaic, photonic, and electronic applications.
Interbacterial Chemical Communication‐Triggered Nascent Proteomics
Authors: Liu Weibing , Tang Qi , Meng Liying , Hu Shufan , Sun De‐en , Li Shan , Dai Peng , Chen Xing
Published: November 2022

Metabolic labeling with clickable noncanonical amino acids has enabled nascent proteome profiling, which can be performed in a cell‐type‐specific manner. However, nascent proteomics in an intercellular communication‐dependent manner remains challenging. Here we develop communication‐activated profiling of protein expression (CAPPEX), which integrates the LuxI/LuxR quorum sensing circuit with the cell‐type‐specific nascent proteomics method to enable selective click‐labeling of newly synthesized proteins in a specific bacterium upon receiving chemical signals from another reporter bacterium. CAPPEX reveals that E. coli competes with Salmonella for tryptophan as the precursor for indole, and the resulting indole suppressed the expression of virulence factors in Salmonella. This tryptophan‐indole axis confers attenuation of Salmonella invasion in host cells and living mice. The CAPPEX strategy should be widely applicable for investigating various interbacterial communication processes.
Stable Luminescent [Cu(NN)(PP)]+ Complexes Incorporating a β‐Cyclodextrin‐Based Diphosphane Ligand with Metal‐Confining Properties
Authors: Phan Tuan‐Anh , Armaroli Nicola , Saavedra Moncada Alejandra , Bandini Elisa , Delavaux‐Nicot Béatrice , Nierengarten Jean‐François , Armspach Dominique
Published: November 2022

A β‐cyclodextrin‐based diphosphane with metal‐confining properties was efficiently synthesized thanks to an unprecedented Smiles‐like rearrangement of diphenyl‐(2‐phosphanylphenyl)phosphane in the presence of excess n‐BuLi. The cis‐chelating bidentate ligand is capable of forming very stable heteroleptic [Cu(NN)(PP)]+ complexes in which a metal‐bound diimine ligand (bpy, phen, or mmp) is located within the cyclodextrin cavity. As a result of ligand encapsulation, flattening of the metal tetrahedral geometry in the excited state is disfavored, thereby resulting in enhanced luminescent properties.
Manganese‐Catalyzed Hydrogenative Desulfurization of Thioamides
Authors: Wang Zelong , Chen Silin , Chen Chao , Yang Yunhui , Wang Congyang
Published: November 2022

Earth‐abundant transition metal catalysis has emerged as an important alternative to noble transition metal catalysis in hydrogenation reactions. However, there has been no Earth‐abundant transition metal catalyzed hydrogenation of thioamides reported so far, presumably due to the poisoning of catalysts by sulfur‐containing molecules. Herein, we described the first manganese‐catalyzed hydrogenative desulfurization of thioamides to amines or imines. The key to success is the use of MnBr(CO)5instead of commonly‐employed pincer‐manganese catalysts, together with simple NEt3and CuBr. This protocol features excellent selectivity on sole cleavage of the C=S bond of thioamides, in contrast to the only known Ru‐catalyzed hydrogenation of thioamides, and unprecedented chemo‐selectivity tolerating vulnerable functional groups such as nitrile, ketone, aldehyde, ester, sulfone, nitro, olefin, alkyne and heterocycle, which are usually susceptible to common hydride‐type reductive protocols.
Designing Thiophene‐Enriched Fully Conjugated 3D Covalent Organic Framework as Metal‐Free Oxygen Reduction Catalyst for Hydrogen Fuel Cells
Authors: Bao Rui , Xiang Zhehao , Qiao Zelong , Yang Yongping , Zhang Yuting , Cao Dapeng , Wang Shitao
Published: November 2022

The application of three‐dimensional (3D) covalent organic frameworks (COFs) in renewable energy fields is greatly limited due to their non‐conjugated skeletons. Here, we design and successfully synthesize a thiophene‐enriched fully conjugated 3D COF (BUCT‐COF‐11) through an all‐thiophene‐linked saddle‐shaped building block (COThTh‐CHO). The BUCT‐COF‐11 exhibits excellent semiconducting property with intrinsic metal‐free oxygen reduction reaction (ORR) activity. Using the COF as cathode catalyst, the assembled anion‐exchange membrane fuel cells (AEMFCs) exhibited a high peak power density up to 493 mW cm−2. DFT calculations reveal that thiophene introduction in the COF not only improves the conductivity but also optimizes the electronic structure of the sample, which therefore boosts the ORR performance. This is the first report on the application of COFs as metal‐free catalysts in fuel cells, demonstrating the great potential of fully conjugated 3D COFs as promising semiconductors in energy fields.
Crystallization behavior of milk fat, palm oil, palm kernel oil, and cocoa butter with and without the addition of cannabidiol
Authors: Cooney Joseph , Hilton Isaac , Marsh Melissa , Jones Annalisa , Martini Silvana
Published: November 2022

The objective of this study was to evaluate the effect of cannabidiol (CBD) on the crystallization behavior and physical properties of various fats. Anhydrous milk fat (AMF), palm oil (PO), palm kernel oil (PKO), and cocoa butter (CB) were chosen for this study, for their unique crystallization behaviors. CBD was added at 1 and 2.5% wt/wt to these fats, and the crystallization behavior was evaluated at 26°C for AMF and PO and at 22°C for PKO and CB. Control samples with no CBD were prepared and evaluated as well. Results show that CBD delayed the crystallization of all fats with the least effect observed for the PO. Slight increases in crystal size were observed with the addition of CBD for all samples. CBD did not affect the melting profile of AMF or CB, but it increased the peak temperature of PO and decreased the enthalpy of PKO. Similarly, hardness was only affected by CBD in PO samples, with harder materials obtained for samples containing 2.5% CBD. The same trend was observed for elasticity. In addition, the elasticity of AMF increased with the addition of CBD but not its hardness. Overall, this study indicates that the effect of CBD on fat crystallization is highly dependent on the type of fat used. Producers of fat‐based products that are willing to include CBD in their formulations must carefully control processing conditions to ensure product quality.
Sustained antioxidant properties of epigallocatechin gallate loaded halloysite for PLA as potentially durable materials
Authors: Yao Zhongyang , Gong Weiguang , Li Chenyang , Deng Zhaopeng , Jin Yi , Meng Xin
Published: November 2022

Halloysite nanotube (HNT) was etched by hydrochloric acid, and epigallocatechin gallate (EGCG) was loaded into the etched HNT (HH) to prepare loaded antioxidant (HH‐E) for polylactic acid (PLA) with improved thermal‐oxidative stability. The loading process was confirmed by TGA and FT‐IR, and the loading capacity was 16.15%. The presence of EGCG on the surface of etched HNT was further confirmed by nitrogen adsorption and TEM. The effect of loaded EGCG on thermal‐oxidative stability of PLA was characterized by the change in OOT values of PLA after the aging process under 140°C. The results showed that HH‐E increased OOT values of PLA from 231.2°C to 293.6°C at first, indicating that HH‐E provided PLA with excellent thermal‐oxidative stability. Furthermore, as can be seen from the trend of OOT changing over aging time, during the 14 days aging process, OOT values of PLA composites with HH‐E decreased more slowly than that of PLA composites with EGCG alone, endowing PLA with sustainable thermal‐oxidative stability. Further kinetic analysis showed that the apparent activation energy of the degradation process (Ea) of PLA composites with HH‐E changed less than that of PLA composites with EGCG alone, which showed that the loading system provided PLA better sustainable stability. Moreover, the isothermal crystallization process of modified PLA was characterized by DSC and POM. The results showed that HH‐E provided heterogeneous crystal nucleus for PLA, reducing the half crystallization time (t0.5) and improvement of crystallization rate for PLA. These results prove that HH‐E exhibited excellent performance in improving the thermal stability and crystallization property of PLA, showing multifunctional characterization.
Polyphenylalanine ionic liquid for the extraction and determination of Allura red in food samples
Authors: Song Hanyang , Yang Jing , Zhu Xiashi
Published: November 2022

Poly amino acids ionic liquid {3‐(3‐(7‐(diethylamino)‐2‐carbonyl‐2 h‐amino‐3‐propyl)‐1‐ethyl Bromo imidazole P[Phe][EMI]} was synthesized and characterized with Fourier transform infrared spectroscopy (FTIR), hydrogen nuclear magnetic resonance (1H‐NMR), and scanning electron microscopy (SEM). A novel method based on solid‐phase extraction and high‐performance liquid chromatography for the detection of Allura red (AR) was established. Under optimized conditions, the linear range of AR was 0.01–10.00 μg ml−1, the limit of detection (LOD) was 0.004 μg ml−1 and the enrichment factor was 12.5 (volume of solution/volume of elution). The isothermal adsorption, kinetic model, and Gaussian calculation model was explained by the adsorption mechanism of AR on P[Phe][EMI]. The method was applied to the analysis of real samples with recoveries of 92.0%–102.2% and relative standard deviations of 1.0%–4.6%.
Design and properties of dynamic self‐healing polyurea molecule based on disulfide bonds
Authors: Wen Jie , Wang Lin , Li Rui , Tang Qin , Yan Jinyuan , Song Dayu
Published: November 2022

Although thermosetting polymer materials have excellent mechanical properties, they are less self‐healing, recycling than thermoplastic polymer materials, which may cause a serious waste of resources. Herein, a series of polyurea materials with high mechanical strength, good properties of self‐healing and recycling are prepared by adjusting the ratio of polyether polyol and introducing disulfides into the synthesis of polyurea prepolymer in an innovative way. The composite polyurea (FHPUA) materials with tensile strength over 47 MPa and elongation at break of 720% are prepared. The experimental results show that by adjusting the content of aromatic disulfide, the tensile strength is further increased to 52 MPa, and the heat resistance of the material is improved. Through five self‐healing experiments, the surface of the material recovers as before even after continuous heating at 70°C for 1 h. In addition, the tensile strength of the material recovers 86.56% and the elastic modulus recovers 70.21% after four recycling experiments. In practical application, it is expected to fill the shortcomings of traditional polyurea such as micro cracks, short service life and poor performance, and have great potential applications in the fields of coating layer of heavy‐duty conveyor belts, encapsulation film of electronic devices and building facade coating.
Effect of ultrasound treatment on bacteriostatic activity of piezoelectric PHB‐TiO2 hybrid biodegradable scaffolds prepared by electrospinning technique
Authors: Sarıipek Fatma Bayram , Özaytekin İlkay , Erci Fatih
Published: November 2022

In this study, biodegradable piezoelectric poly(3‐hydroxybuthyrate) (PHB) and PHB‐TiO2 as well as non‐piezoelectric poly(ε‐caprolactone) (PCL) fibrous scaffolds were successfully fabricated. First, TiO2 nanoparticles (NPs) with various content (1%, 2%, and 3% wt) were loaded into the PHB matrix to improve its tensile and wettability properties as well as piezoelectric performances. The piezoelectric property of the fibrous scaffolds was examined and a significant improvement in the piezoelectric property of hybrid fibrous scaffolds compared to pure PHB was detected. For the PHB‐2%TiO2 sample, a maximum of in the range 4.5–5 V electricity production from a height of 10 cm and a mass drop of 35 g was observed after 150°C heat treatment. Then, an in vitro bactericidal analysis was carried out to test the bacteriostatic effect of the produced piezoelectric biomaterials against E‐cherichia coli (E coli) under ultrasound treatment. It was observed that E. coli appeared to be the most sensitive to the PHB‐%2TiO2 sample and consequently the antibacterial activity of all the samples against E. coli was dependent on the piezoelectric properties of the samples. The results indicated that the fabricated fibrous scaffolds could be considered as a promising piezoelectric biomaterial with ultrasonically‐controlled bacteriostatic activity for various tissue engineering applications.
Virus removal from aqueous environments with polyelectrolyte coatings on a polypropylene fleece
Authors: Schulze Maiko , Nie Chuanxiong , Hartmann Greta , Nickl Philip , Kulka Michaël W. , Ballauff Matthias , Haag Rainer
Published: November 2022

The adsorption of viruses from aqueous solution is frequently performed to detect viruses. Charged filtration materials capture viruses via electrostatic interactions, but lack the specificity of biological virus‐binding substances like heparin. Herein, we present three methods to immobilize heparin‐mimicking, virus‐binding polymers to a filter material. Two mussel‐inspired approaches are used, based on dopamine or mussel‐inspired dendritic polyglycerol, and post‐functionalized with a block‐copolymer consisting of linear polyglycerol sulfate and amino groups as anchor (lPGS‐b‐NH2). As third method, a polymer coating based on lPGS with benzophenone anchor groups is tested (lPGS‐b‐BPh). All three methods yield dense and stable coatings. A positively charged dye serves as a tool to quantitatively analyze the sulfate content on coated fleece. Especially lPGS‐b‐BPh is shown to be a dense polymer brush coating with about 0.1 polymer chains per nm2. Proteins adsorb to the lPGS coated materials depending on their charge, as shown for lysozyme and human serum albumin. Finally, herpes simplex virus type 1 (HSV‐1) and severe acute respiratory syndrome coronavirus type 2 (SARS‐CoV‐2) can be removed from solution upon incubation with coated fleece materials by about 90% and 45%, respectively. In summary, the presented techniques may be a useful tool to collect viruses from aqueous environments.
Effects of mechanical recycling on optical properties and microstructure of recycled high‐density polyethylene pellets and bottles
Authors: Zeng Shao‐Fu , Guo Pan , Hu Chang‐Ying , Wang Zhi‐Wei
Published: November 2022

The demand for recycling high‐density polyethylene (HDPE) utilizing mechanical recycling technologies is currently felt strongly by both society and industry. However, thermal oxidation of the polymer during the recycling process may lead to irreversible changes in the material properties of recycled high‐density polyethylene (rHDPE). The effects of mechanical recycling on the optical characteristics and microstructure of rHDPE pellets and bottles were investigated in this study. The results revealed that the apparent color of the rHDPE became more yellow and gray compared to the virgin HDPE (vHDPE), and showed a signal at 670–680 nm in the solar reflectance spectrum. The thermal oxidation of rHDPE considerably raised the absorption intensities of carbonyl, ester, and hydroxyl groups in attenuated total reflection Fourier transform infrared spectrum. In addition, the presence of carbonyl and hydroxyl unsaturated chemicals might make it challenging to recognize the distinctive peaks of vHDPE in the ultraviolet–visible diffuse reflectance (UV–Vis‐DIR) spectra at wavelengths less than 400 nm. Thermal oxidation of rHDPE was also confirmed in the COH, CO, and OCO valence structures of C1s and O1s. A characteristic valence band (VB) profile at 25 eV can be used as the recognizable information for the oxidation of rHDPE. The microstructure of the surface of rHDPE pellets exhibited rough and uneven morphological defects. The higher recycled content made rHDPE bottles' surface morphology rougher and their cross‐section microstructure thinner and more porous than vHDPE bottles.
Amino‐terminated hyperbranched polymer functionalized graphene oxide with in situ trapped silver nanoparticles for high‐performance antibacterial nonwoven fabric
Authors: Zhou Jiahui , Yan Yi , Zhang Yue , Zhang Yufan , Zhang Desuo , Lin Hong , Chen Yuyue , Zhao Bing , Xiong Jiaqing
Published: November 2022

Antibacterial fabric with high thermal stability and mechanical strength is important for personalized protection, especially under the background of coronavirus pandemic (COVID‐19). This paper presents a facile approach toward high‐efficient antibacterial polypropylene spunbonded nonwoven fabrics (SNFs), which are decorated by a composite of graphene oxide embedded with silver nanoparticles (AgNPs/GO) through dip‐coating and in situ reduction effect of pre‐introduced amino‐terminated hyperbranched polymer (HBP‐NH2). Typically, HBP‐NH2 was grafted onto the GO nanosheets, then silver ions were trapped and self‐reduced by the HBP‐NH2 to generate silver nanoparticles decorated GO. The produced AgNPs are uniformly dispersed on the GO with a size of 13 nm. As an antibacterial coating, the Ag/GO composite could tightly wrap the SNFs fibers through the dip‐padding method, capable of enhancing the thermal stability and mechanical property of SNFs. The treated SNFs exhibited excellent antibacterial activities (~99.9%) against both Echerisia coli and Staphylococcus aureus, promising important potential for biomedical and personal protection applications.
Temperature dependent charge transport in electrostatically doped poly[benzimidazobenzophenanthroline] thin films
Authors: Cruz‐Arzon Alejandro J. , Serrano‐Garcia William , Pinto Nicholas J. , Gupta Nikita , Johnson Alan T. Charlie
Published: November 2022

Charge transport in electrostatically doped poly[benzimidazobenzophenanthroline]‐BBL thin films in a field‐effect transistor geometry were investigated in the temperature range 150 K < T < 370 K. At low temperatures activation and hopping transport mechanisms dominated, while phonon scattering dominated at high temperatures. The activation energies (EA) were found to lie in the range 140 meV < EA < 400 meV implying the existence of deep traps within the polymer bandgap of 1.8 eV. Two quasi‐linear dependencies of EA on the gate voltage (Vg) were observed with EA decreasing as Vg increased. An unexpected “metallic‐like” transport characteristic appeared for T > 335 K which depended on Vg. Enhanced electron delocalization combined with increased carrier density could be responsible for this “metallic‐like” behavior. Our results show that the existence of deep traps with multiple energy distributions, combined with increased carrier density led to the unusual temperature dependence of charge transport observed in BBL.
Highly moisture resistant super gas barrier polyelectrolyte complex thin film
Authors: Chiang Hsu‐Cheng , Iverson Ethan T. , Schmieg Kendra , Stevens Daniel L. , Grunlan Jaime C.
Published: November 2022

Polyelectrolyte complex (PEC) thin films have demonstrated remarkable oxygen barrier properties, but the moisture sensitivity from the hydrophilic nature of polyelectrolytes is a significant drawback. In this study, various molar ratios (1:1, 1:2, and 1:3) of branched polyethyleneimine (PEI) and poly(acrylic acid) (PAA) were prepared as one‐pot coating solutions, which can be deposited via a simple dip‐coating process and cured with a citric acid buffer solution, which increases the charge density of PEI and triggers complexation. As‐prepared conformal thin films impart excellent gas barrier, high modulus, and high moisture resistance. Undetectable oxygen transmission rate (OTR), at both 0% and 90% RH, can be achieved with a PEI:PAA molar ratio of 1:1 and buffer curing at pH 3. The strong complexation from ionic crosslinking creates an unusually dense thin film that is promising for various packaging applications (food, electronics, etc.). This thin film exhibits one of the best‐ever polymer‐based oxygen barriers at high humidity.
Large size, sensitive response thermally expandable microspheres for the manufacture of suede‐like leather
Authors: Wei Huan , Luo Haihang , Li Jing , Fan Haojun , Xiang Jun , Chen Yi , Yan Jun
Published: November 2022

A large size, sensitive response thermally expandable microspheres (TEMs) for suede‐like leather manufacture was prepared by suspension polymerization using acrylonitrile (AN), methyl methacrylate (MMA) and vinyl acetate (VAC) as the shell monomers and iso‐pentane as the foaming component. The effect of the interfacial tension and viscosity of polymerization system on the particle size of TEMs, and in turn, the effect of the particle size of TEMs on the expansion temperature, expansion ratio and thermal response performance were investigated in detail. The results showed that increasing the interface tension and viscosity of the polymerization system was beneficial for preparing large size TEMs. Under the optimized conditions of 300 rpm, 25 wt% iso‐pentane dosage, and 9:3:1 mass ratio of AN/MAA/VAC, the TEMs shown above 100 μm particle size and 4 times expansion ratio at 150°C. Moreover, TEMs with 18% encapsulation ratio (Er) of the foaming component can complete foaming in the narrow temperature range (ΔT ≤ 10°C), showing a sensitive thermal response. The mixture of waterborne polyurethane and quantitative TEMs was coated on the surface of synthetic leather base, and a new type of suede‐like leather was obtained after foaming, which can substitute genuine suede leather.
Low‐intensity low‐frequency ultrasound mediates riboflavin delivery during corneal crosslinking
Authors: Sun Zhe , Li Zhiming , Chung Jin Teng , Lau Laurence Chi Ming , Jhanji Vishal , Chau Ying
Published: November 2022

We employed the mechanical effect from 40 kHz ultrasound (US) to improve the delivery of riboflavin into corneal stroma for collagen crosslinking, which can benefit the treatment of keratoconus and other corneal ectasias. Experiments were conducted, first with porcine corneas ex vivo and then with New Zealand white rabbits in vivo, at varying mechanical index (MI) and sonication time. Results showed that 15 min of US applied on the cornea at MI = 0.8 in the presence of 0.5% of riboflavin solution enabled its delivery to deeper corneal stroma. Excessive heat was removed by a cooling setup to negate the thermal effect. The corneal absorption amount and penetration of riboflavin through cornea as detected by fluorotron, as well as the enhancement of corneal stiffness as measured by Young's modulus, were comparable to the conventional approach that requires complete corneal epithelium debridement. Histological analysis revealed minor exfoliation of superficial cell layers of corneal epithelium and loss of ZO‐1 tight junctions immediately after US. Full recovery of the corneal epithelium and restoration of tight junctions occurred in 3–4 days. The study shows that low‐intensity low‐frequency ultrasound (LILF US) is a less invasive alternative to the conventional epithelium‐off method for delivering riboflavin into the corneal stroma.
Endocrine therapy initiation and overall survival outcomes with omission of radiation therapy in older Medicare patients with early‐stage hormone‐receptor‐positive breast cancer
Authors: Shen Chan , Li Ning , Zhou Shouhao , Stahl Kelly , Dodge Daleela , Zhao Hui
Published: November 2022

Background

Guidelines allow for the omission of radiotherapy in older women with early‐stage, hormone‐receptor‐positive breast cancer, given that the patients receive adequate endocrine therapy (ET). However, the initiation of ET and survival outcomes after forgoing radiation therapy among these patients have not been well‐studied.

Methods

We identified patients aged 70 to 90 years old newly diagnosed in 2010–2015 with early‐stage, hormone receptor positive, and human epidermal growth factor receptor 2 (HER2) negative (HR+/Her2−) breast cancer who received lumpectomy and omitted radiation therapy using the SEER‐Medicare database. We examined the initiation of ET and the utilization patterns of ET using a multivariable logistic regression. We further examined the overall survival outcomes using Kaplan–Meier estimation and Cox proportional hazard model with inverse probability weighting.

Results

Of the 2618 patients, 808 (30.9%) received no ET. The multivariable logistic regression showed that more recent years had better ET initiation (2013–2015 vs. 2010–2012: OR = 1.39, 95% CI:[1.16, 1.66]), while older patients (81–90 vs. 70–80: OR = 0.45, 95% CI:[0.38, 0.54]) were less likely to receive ET. Both the Kaplan–Meier estimation (log‐rank p‐value<0.0001) and the Cox proportional hazard model with inverse probability weighting (HR = 0.76, 95% CI:[0.58, 0.99]) showed that receiving ET was associated with better overall survival.

Conclusion

This population‐based study suggests that a sizable proportion of patients who omitted radiation did not receive endocrine therapy and receiving endocrine therapy was beneficial among these patients. Although ET initiation has improved in more recent years, certain patient groups were still especially susceptible to no endocrine therapy.