bluuebunny/crossref_metadata_2025_split huggingface dataset:
Defect Passivation in Air‐Stable Tin(IV)‐Halide Single Crystal for Emissive Self‐Trapped Excitons
Authors: Zhou Lei , Zhang Lei , Li Hui , Shen Wei , Li Ming , He Rongxing 
Published: September 2021

AbstractTin(IV)‐based metal halides are promising optoelectronic materials due to their robust structure and eco‐friendly nature, but these materials exhibit poor photoluminescence (PL) properties and the underlying mechanisms are still elusive. Here, a novel air‐stable hybrid Sn4+‐halide material (C8H22N2Cl)2SnCl6 that is resistant to moisture (>70% relative humidity) for >1 year is reported. The inferior PL property of (C8H22N2Cl)2SnCl6 is limited by the lattice defects and robust crystal structure, which however could be effectively improved by introducing Sb3+ ion with stereoactive 5s2 lone pair. As a result, Sb3+‐doped (C8H22N2Cl)2SnCl6 exhibits a superbly stable room‐temperature PL centered at 690 nm with an unprecedented quantum yield (QY) of 41.76% from self‐trapped excitons, which is the highest PLQY of hybrid tin(IV)‐based perovskite materials. The improved PL efficiency is attributed to the defect passivation and remarkable structure distortion induced by Sb3+ dopants. This dopant‐induced defect passivation and exciton self‐trapping approach offers an avenue to improve optoelectronic material performance.
Injectable Natural Polymer Hydrogels for Treatment of Knee Osteoarthritis
Authors: Lin Xiaojie , Tsao Ching Ting , Kyomoto Masayuki , Zhang Miqin 
Published: September 2021

AbstractOsteoarthritis (OA) is a serious chronic and degenerative disease that increasingly occurs in the aged population. Its current clinical treatments are limited to symptom relief and cannot regenerate cartilage. Although a better understanding of OA pathophysiology has been facilitating the development of novel therapeutic regimen, delivery of therapeutics to target sites with minimal invasiveness, high retention, and minimal side effects remains a challenge. Biocompatible hydrogels have been recognized to be highly promising for controlled delivery and release of therapeutics and biologics for tissue repair. In this review, the current approaches and the challenges in OA treatment, and unique properties of injectable natural polymer hydrogels as delivery system to overcome the challenges are presented. The common methods for fabrication of injectable polysaccharide‐based hydrogels and the effects of their composition and properties on the OA treatment are detailed. The strategies of the use of hydrogels for loading and release cargos are also covered. Finally, recent efforts on the development of injectable polysaccharide‐based hydrogels for OA treatment are highlighted, and their current limitations are discussed.
Nickelate Superconductivity without Rare‐Earth Magnetism: (La,Sr)NiO2
Authors: Osada Motoki , Wang Bai Yang , Goodge Berit H. , Harvey Shannon P. , Lee Kyuho , Li Danfeng , Kourkoutis Lena F. , Hwang Harold Y. 
Published: September 2021

AbstractThe occurrence of unconventional superconductivity in cuprates has long motivated the search for manifestations in other layered transition metal oxides. Recently, superconductivity is found in infinite‐layer nickelate (Nd,Sr)NiO2 and (Pr,Sr)NiO2 thin films, formed by topotactic reduction from the perovskite precursor phase. A topic of much current interest is whether rare‐earth moments are essential for superconductivity in this system. In this study, it is found that with significant materials optimization, substantial portions of the La1−xSrxNiO2 phase diagram can enter the regime of coherent low‐temperature transport (x = 0.14 ‐ 0.20), with subsequent superconducting transitions and a maximum onset of ≈9 K at x = 0.20. Additionally, the unexpected indication of a superconducting ground state in undoped LaNiO2 is observed, which likely reflects the self‐doped nature of the electronic structure. Combining the results of (La/Pr/Nd)1−xSrxNiO2 reveals a generalized superconducting dome, characterized by systematic shifts in the unit cell volume and in the relative electron‐hole populations across the lanthanides.
Atomic Scale Control and Visualization of Topological Quantum Phase Transition in π‐Conjugated Polymers Driven by Their Length
Authors: González‐Herrero Héctor , Mendieta‐Moreno Jesús I. , Edalatmanesh Shayan , Santos José , Martín Nazario , Écija David , de la Torre Bruno , Jelinek Pavel 
Published: September 2021

AbstractQuantum phase transitions (QPTs) driven by quantum fluctuations are transitions between distinct quantum phases of matter. At present, they are poorly understood and not readily controlled. Here, scanning tunneling microscopy (STM) and noncontact atomic force microscopy (nc‐AFM) are used to explore atomic scale control over quantum phase transitions between two different topological quantum states of a well‐defined π‐conjugated polymer. The phase transition is driven by a pseudo Jahn–Teller effect that is activated above a certain polymer chain length. In addition, theoretical calculations indicate the presence of long‐lasting coherent fluctuations between the polymer's two quantum phases near the phase transition, at finite temperature. This work thus presents a new way of exploring atomic‐scale control over QPTs and indicates that emerging quantum criticality in the vicinity of a QPT can give rise to new states of organic matter.
Sono‐Controllable and ROS‐Sensitive CRISPR‐Cas9 Genome Editing for Augmented/Synergistic Ultrasound Tumor Nanotherapy
Authors: Pu Yinying , Yin Haohao , Dong Caihong , Xiang Huijing , Wu Wencheng , Zhou Bangguo , Du Dou , Chen Yu , Xu Huixiong 
Published: September 2021

AbstractThe potential of the cluster regularly interspaced short palindromic repeat (CRISPR)‐associated protein 9 (Cas9)‐based therapeutic genome editing is severely hampered by the difficulties in precise regulation of the in vivo activity of the CRISPR‐Cas9 system. Herein, sono‐controllable and reactive oxygen species (ROS)‐sensitive sonosensitizer‐integrated metal–organic frameworks (MOFs), denoted as P/M@CasMTH1, are developed for augmented sonodynamic therapy (SDT) efficacy using the genome‐editing technology. P/M@CasMTH1 nanoparticles comprise singlet oxygen (1O2)‐generating MOF structures anchored with CRISPR‐Cas9 systems via 1O2‐cleavable linkers, which serve not only as a delivery vector of CRISPR‐Cas9 targeting MTH1, but also as a sonoregulator to spatiotemporally activate the genome editing. P/M@CasMTH1 escapes from the lysosomes, harvests the ultrasound (US) energy and converts it into abundant 1O2 to induce SDT. The generated ROS subsequently trigger cleavage of ROS‐responsive thioether bonds, thus inducing controllable release of the CRISPR‐Cas9 system and initiation of genome editing. The genomic disruption of MTH1 conspicuously augments the therapeutic efficacy of SDT by destroying the self‐defense system in tumor cells, thereby causing cellular apoptosis and tumor suppression. This therapeutic strategy for synergistic MTH1 disruption and abundant 1O2 generation provides a paradigm for augmenting SDT efficacy based on the emerging nanomedicine‐enabled genome‐editing technology.
Cation‐Free siRNA Micelles as Effective Drug Delivery Platform and Potent RNAi Nanomedicines for Glioblastoma Therapy
Authors: Jiang Tong , Qiao Yonghan , Ruan Weimin , Zhang Dongya , Yang Qingshan , Wang Guoying , Chen Qunzhi , Zhu Fengping , Yin Jinlong , Zou Yan , Qian Rongjun , Zheng Meng , Shi Bingyang 
Published: September 2021

AbstractNanoparticle‐based small interfering RNA (siRNA) therapy shows great promise for glioblastoma (GBM). However, charge associated toxicity and limited blood–brain‐barrier (BBB) penetration remain significant challenges for siRNA delivery for GBM therapy. Herein, novel cation‐free siRNA micelles, prepared by the self‐assembly of siRNA‐disulfide‐poly(N‐isopropylacrylamide) (siRNA‐SS‐PNIPAM) diblock copolymers, are prepared. The siRNA micelles not only display enhanced blood circulation time, superior cell take‐up, and effective at‐site siRNA release, but also achieve potent BBB penetration. Moreover, due to being non‐cationic, these siRNA micelles exert no charge‐associated toxicity. Notably, these desirable properties of this novel RNA interfering (RNAi) nanomedicine result in outstanding growth inhibition of orthotopic U87MG xenografts without causing adverse effects, achieving remarkably improved survival benefits. Moreover, as a novel type of polymeric micelle, the siRNA micelle displays effective drug loading ability. When utilizing temozolomide (TMZ) as a model loading drug, the siRNA micelle realizes effective synergistic therapy effect via targeting the key gene (signal transducers and activators of transcription 3, STAT3) in TMZ drug resistant pathways. The authors’ results show that this siRNA micelle nanoparticle can serve as a robust and versatile drug codelivery platform, and RNAi nanomedicine and for effective GBM treatment.
Immunotherapy and Prevention of Cancer by Nanovaccines Loaded with Whole‐Cell Components of Tumor Tissues or Cells
Authors: Ma Lin , Diao Lu , Peng Zuofu , Jia Yun , Xie Huimin , Li Baisong , Ma Jianting , Zhang Meng , Cheng Lifang , Ding Dawei , Zhang Xuenong , Chen Huabing , Mo Fengfeng , Jiang Honglv , Xu Guoqiang , Meng Fenghua , Zhong Zhiyuan , Liu Mi 
Published: September 2021

AbstractTumor tissues/cells are the best sources of antigens to prepare cancer vaccines. However, due to the difficulty of solubilization and delivery of water‐insoluble antigens in tumor tissues/cells, including water‐insoluble antigens into cancer vaccines and delivering such vaccines efficiently to antigen‐presenting cells (APCs) remain challenging. To solve these problems, herein, water‐insoluble components of tumor tissues/cells are solubilized by 8 m urea and thus whole components of micrometer‐sized tumor cells are reasssembled into nanosized nanovaccines. To induce maximized immunization efficacy, various antigens are loaded both inside and on the surface of nanovaccines. By encapsulating both water‐insoluble and water‐soluble components of tumor tissues/cells into nanovaccines, the nanovaccines are efficiently phagocytosed by APCs and showed better therapeutic efficacy than the nanovaccine loaded with only water‐soluble components in melanoma and breast cancer. Anti‐PD‐1 antibody and metformin can improve the efficacy of nanovaccines. In addition, the nanovaccines can prevent lung cancer (100%) and melanoma (70%) efficiently in mice. T cell analysis and tumor microenvironment analysis indicate that tumor‐specific T cells are induced by nanovaccines and both adaptive and innate immune responses against cancer cells are activated by nanovaccines. Overall, this study demonstrates a universal method to make tumor‐cell‐based nanovaccines for cancer immunotherapy and prevention.
Highly Selective Adsorption of Carbon Dioxide over Acetylene in an Ultramicroporous Metal–Organic Framework
Authors: Shi Yanshu , Xie Yi , Cui Hui , Ye Yingxiang , Wu Hui , Zhou Wei , Arman Hadi , Lin Rui‐Biao , Chen Banglin 
Published: September 2021

AbstractSeparating carbon dioxide from fuel gases like hydrocarbons by physical adsorbents is industrially important and more energy‐efficient than traditional liquid extraction or cryogenic distillation methods. It is very important while very challenging to develop CO2‐selective adsorbents, considering CO2 is less polarizable than light hydrocarbon molecules, particularly those simultaneously with almost identical molecular dimensions and physical properties, such as acetylene. Herein, an ultramicroporous metal–organic framework constructed from copper(II) and 5‐fluoropyrimidin‐2‐olate, termed Cu‐F‐pymo, is carefully studied under different activations for inverse separation of CO2 from C2H2. The partially desolvated Cu‐F‐pymo can exclusively capture CO2 over C2H2 with very high selectivity exceeding 105 under ambient conditions, the highest ever reported. Sorption experiments and modeling studies reveal that such molecular sieving effect is attributed to the suppression of C2H2 adsorption from the blockage of the preferential sites for C2H2 by residual water molecules. The inverse separation is further confirmed by column breakthrough studies given that highly pure acetylene (>99.9%) can be directly harvested from the gas mixture. Cu‐F‐pymo also shows remarkable stability under harsh conditions.
Facile Two‐Step van der Waals Epitaxial Growth of Bi2S3/ReS2 Heterostructure with Improved Saturable Absorption
Authors: Lu Chunhui , Luo Mingwei , Yang Dan , Ma Jingyao , Qi Mei , Xu Xinlong 
Published: September 2021

Abstract2D van der Waals (vdW) heterostructure provides a novel platform to modulate linear and nonlinear optical (NLO) properties for optical devices by interface engineering. However, NLO properties and mechanisms based on vdW heterostructures are far from complete understanding. Herein, two‐step vdW vapor epitaxial growth by either physical or chemical vapor deposition methods is successfully demonstrated to synthesize uniform Bi2S3/ReS2 vdW heterostructures in large area. Type‐II band‐alignment of these heterostructures is confirmed by X‐ray photoelectron spectroscopy combined with the UV–Vis spectra. The enhanced NLO response of Bi2S3/ReS2 films is observed with high saturable absorption coefficient (≈−445 cm GW−1), large modulation depth (≈10.5%), and low saturation intensity (≈105 GW cm−2). Energy level model based on type‐II charge transfer process is used successfully to understand the optical physics process at the interface of the vdW heterostructures. Constructing heterostructures with two‐step vdW vapor epitaxial growth provides a new method to design high‐performance nonlinear photonic devices with 2D materials.
A Tetraarylpyrrole‐Based Phosphine Ligand for the Palladium‐Catalyzed Amination of Aryl Chlorides
Authors: Sai Masahiro 
Published: September 2021

AbstractA tetraarylpyrrole‐based phosphine ligand L1 in combination with Pd(dba)2 provided a catalyst for the Buchwald‐Hartwig amination reaction. A variety of amines were rapidly coupled with aryl chlorides at a Pd loading of 0.5 mol%. The selective monoarylation of aliphatic primary amines was achieved in the presence of 0.8 equiv. water. Comparison experiments were also conducted, which revealed that the catalytic activity of L1 is superior to representative phosphine ligands in the Pd‐catalyzed C−N coupling of various amines.magnified image
Base Metal‐Catalyzed C‐Methylation Reactions Using Methanol
Authors: Sarki Naina , Goyal Vishakha , Natte Kishore , Jagadeesh Rajenahally V. 
Published: September 2021

AbstractC‐methylation is a vitally important reaction applicable in chemical synthesis and structure‐based drug design. Notably, the “magic methyl” effect has become decisive in medicinal chemistry and drug discovery for the modulation of bio‐active properties in life science molecules. In this regard, C‐methylation reaction is widely applied chemical modification in various biomolecules, pharmaceuticals, and natural products. In general, this reaction often relies on activated, hazardous and uneconomical methyl sources such as diazomethane, dimethyl sulfate, and methyl halides. To achieve methylation reactions in a sustainable and cost‐effective manner, the use of ‘ideal’ C1 source is crucial. In this regard, methanol constitutes an expedient −CH3 source because this simple alcohol is less‐hazardous, inexpensive, and abundantly available platform chemical as well as it produces only water as the by‐product in methylation processes. Regarding potential catalysts to perform C‐methylation using methanol by hydrogen borrowing methodology, non‐noble metal‐based catalysts are highly preferable due to their unique advantages such as more abundance, inexpensive and low‐toxicity. In recent years, chemists made significant contributions towards catalytic valorization of methanol as C1 source to insert methyl groups via C−H activation in a variety of compounds and life science molecules. Consequently, in this minireview we summarize the C‐methylation process using methanol by applying Fe‐, Mn‐, Co‐ and Ni‐based catalysts as well as metal free catalysts.magnified image
Cognitive load and processes during chest radiograph interpretation in the emergency department across the spectrum of expertise
Authors: Morra Michael , Braund Heather , Hall Andrew K. , Szulewski Adam 
Published: September 2021

AbstractBackgroundIn the emergency department (ED), chest radiographs (CXRs) provide essential information for clinical diagnostic reasoning. Errors in interpretation by emergency physicians can lead to negative patient outcomes. To aid in teaching this important skill, an understanding of cognitive processes and cognitive load (CL) in CXR interpretation in emergency medicine (EM) personnel is warranted.MethodsThis study adopted a concurrent mixed‐methods research design. Participant groups included medical students (M), junior (J) and senior (S) EM residents, and attending emergency physicians (P) in the ED at an academic hospital. To elucidate cognitive processes, a real‐time cognitive task analysis during CXR interpretation was performed. Interviews were audio recorded, transcribed verbatim, and analyzed thematically. The interview was followed by a questionnaire, where participants rated their CL, stress, and confidence level.ResultsLevels of CL (M vs. S and M vs. P, p = 0.002; J vs. S, p = 0.004; J vs. P, p = 0.005) and stress (J vs. P, p = 0.002) decreased, while confidence levels increased (M vs. S, p = 0.006; J vs. S, p ≤ 0.001; J vs. P, p = 0.003) as experience level increased. Qualitative analysis of interviews revealed four themes: checking behavior, information reduction, pattern recognition versus systematic viewing, and recognizing scope of practice. Experts commonly utilized checking behavior (e.g., comparison to prior radiographs) and deprioritized task irrelevant data. Experts used a general overview technique as their initial approach as opposed to a systematic viewing approach, and they more readily recognized an EM physicians’ scope of practice in this task.ConclusionThis study characterized differences in cognition that led to increased CL, stress, and lower level of confidence in EM learners during CXR interpretation and provided insight into expertise development in this important skill.
Modeling phase formation on catalyst surfaces: Coke formation and suppression in hydrocarbon environments
Authors: Wang Peng , Senftle Thomas P. 
Published: September 2021

AbstractWe develop a simulation toolset employing density functional theory in conjunction with grand canonical Monte Carlo (GCMC) to study coke formation on Fe‐based catalysts during propane dehydrogenation (PDH). As expected, pure Fe surfaces develop stable graphitic coke structures and rapidly deactivate. We find that coke formation is markedly less favorable on Fe3C and FeS surfaces. Fe‐Al alloys display varying degrees of coke resistance, depending on their composition, suggesting that they can be optimized for coke resistance under PDH conditions. Electronic structure analyses show that both electron‐withdrawing effects (on Fe3C and FeS) and electron‐donating effects (on Fe‐Al alloys) destabilize adsorbed carbon. On the alloy surfaces, a geometric effect also isolates Fe sites and disrupts the formation of graphitic carbon networks. This work demonstrates the utility of GCMC for studying the formation of disordered phases on catalyst surfaces and provides insights for improving the coke resistance of Fe‐based PDH catalysts.
Recent Advances in Metal‐ and Organocatalyzed Asymmetric Functionalization of Pyrroles
Authors: Borah Biplob , Dwivedi Kartikey Dhar , Chowhan L. Raju 
Published: September 2021

AbstractThe wide occurrence of pyrroles in natural products and pharmaceuticals calls for novel synthetic methodologies for the efficient synthesis of enantiopure pyrroles. Owing to their highly reactive nature and wide‐ranging chemical landscape, enormous efforts have been dedicated not only to their synthesis but also to the development of reactions using them as a platform and their utilization in the stereocontrolled synthesis of diverse molecules. In sharp contrast to the extensive studies devoted toward indoles, the asymmetric functionalization of pyrroles was less explored. Nevertheless, the attractiveness of pyrroles for their selective functionalization to access natural product analogy, and medicinally useful architectures have witnessed tremendous growth in the last few years. Their effectiveness under both metal‐ and organocatalytic conditions currently encompasses a vast majority of enantioselective transformations. This review article aims to present a comprehensive overview of the catalytic asymmetric C−H as well as N−H functionalization of pyrroles reported from 2010 to now.
The growth rates of solitary gallbladder polyps compared to multi‐polyps: A quantitative analysis
Authors: Diep Raymond , Lombardo Paul , Schneider Michal 
Published: September 2021

AbstractObjectivesSeveral studies suggest solitary gallbladder polyps (GBPs) have an increased malignancy risk compared to multi‐polyps. Furthermore, some malignant GBPs possessed faster growth rates compared to benign GBPs. To our knowledge, no study has established a relationship between GBP number and growth rates. Hence, this study aims to: (i) determine whether there is a statistical significance in growth rates between solitary GBPs versus multi‐polyps; (ii) determine, in a four‐year period, the proportion of GBPs in this study’s total cohort that exhibit growth compared to previous studies.MethodsA retrospective, quantitative, cohort study was implemented utilising 100 consecutive patient records from three private radiology clinics. These were assessed against the eligibility criteria and allocated into the solitary or multi‐polyp study group, depending on number of GBPs detected on initial and follow‐up ultrasound examinations conducted 6–48 months later. Patient age, GBP sizes, time interval between initial and follow‐up ultrasound examinations and GBP growth rates were compared between the study groups utilising Student’s t tests.ResultsNo statistically significant difference was found between the study groups according to gender, age, GBP size and time between ultrasound examinations. Furthermore, there was no statistically significant difference between the growth rates of solitary and multi‐polyp groups (P = 0.77). Most GBPs [92/100 (92%)] grew <2 mm in maximal diameter, while 8/100 (8%) of GBPs grew ≥2 mm in maximal diameter at follow‐up.ConclusionsThe large majority of GBPs maintained size stability at follow‐up. On average, solitary GBPs did not grow faster than multi‐polyps, although further research is recommended to reinforce this.