bluuebunny/crossref_metadata_2025 huggingface dataset:
Side‐Chain Engineering of Aggregation‐Induced Emission Molecules for Boosting Cancer Phototheranostics
Authors: Song Shanliang , Zhao Yue , Kang Miaomiao , Zhang Zhijun , Wu Qian , Fu Shuang , Li Youmei , Wen Haifei , Wang Dong , Tang Ben Zhong
Published: September 2021

The ingenious construction of versatile cancer phototheranostics involving ﬂuorescence imaging (FLI) and photodynamic and photothermal therapies (PDT, PTT) concurrently has attracted great interest. By virtue of their inherent twisted structures and plentiful motion moieties, aggregation‐induced emission luminogens (AIEgens) have been proven to be perfect templates for the development of multimodal phototheranostic systems as their diverse energy consumption pathways can be ﬂexibly regulated through tuning the intramolecular motions. Side‐chain engineering is generally accepted as a useful regulation strategy for intramolecular motions through altering the side‐chain structure of the molecule, but has rarely been reported for the construction of AIE‐active multimodal phototheranostics. Herein, by taking full advantage of the side‐chain engineering strategy, an AIE‐active multifunctional phototheranostic system (TBFT2 nanoparticles) is successfully constructed by intentionally manipulating the length of side chains. Bearing the longest alkyl chain, all of those three energy dissipation pathways including radiative decay, nonradiative thermal deactivation, and intersystem crossing process of TBFT2 are retained simultaneously and controllably in the aggregate state. In vitro and in vivo evaluations verify that TBFT2 nanoparticles perform well in terms of FLI‐guided PDT and PTT synergistic cancer therapy. This study thus provides new insight into the exploration of superior versatile phototheranostics through side‐chain engineering.
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

Tin(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

Osteoarthritis (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

The 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

Quantum 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

The 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

Nanoparticle‐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

Tumor 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

Separating 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

2D 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.
Vacuum–Sublimable Ionic Yellow Phosphorescent Iridium(III) Complexes with Broad Emission for White Electroluminescence
Authors: Tao Peng , Zheng Xiao-Kang , Lee Yuk-Ki , Wang Guo-Liang , Li Fei-Yang , Li Zi-Kang , Zhao Qiang , Miao Yan-Qin , Wong Wai-Yeung
Published: September 2021

The exploration of efficient yellow emitters featuring broad emission band plays an essential role for the complementary‐color‐based white organic light‐emitting devices (OLEDs). Herein, two new yellow ionic iridium(III) complexes (Ir1 and Ir2) having excellent sublimation ability are designed and prepared by the incorporation of chlorine‐modified 2‐phenylquinoline ligand and introduction of bulky counter ion. At room temperature, these ionic iridium(III) complexes show bright yellow phosphorescence in both solid and solution states due to the presence of bulky counter ion. They share the same emission wavelength (538 and 573 nm as the emission shoulder) with extremely high quantum yields (as high as 0.91) in Ar‐saturated CH2Cl2. Notably, those complexes also exhibit very broad full width at half maximum (FWHM) (up to 100 nm) attributed to almost the same intensities of emission maximum and shoulder, making them excellent candidates for white electroluminescence. The as‐prepared yellow OLEDs show high external quantum efficiency (EQE) of 11.6% and broad FWHM of 105 nm. The two‐color‐based white OLED is prepared with peak EQE of 9.2%, the 1931 CIE coordinate of (0.29, 0.31), and color rendering index of 79, proving that these new ionic iridium(III) complexes show a great potential for white electroluminescence.
A Tetraarylpyrrole‐Based Phosphine Ligand for the Palladium‐Catalyzed Amination of Aryl Chlorides
Authors: Sai Masahiro
Published: September 2021

A 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.

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Base Metal‐Catalyzed C‐Methylation Reactions Using Methanol
Authors: Sarki Naina , Goyal Vishakha , Natte Kishore , Jagadeesh Rajenahally V.
Published: September 2021

C‐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.

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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

Background

In 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.

Methods

This 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.

Results

Levels 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.

Conclusion

This 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

We 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

The 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

Objectives

Several 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.

Methods

A 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.

Results

No 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.

Conclusions

The 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.
Relation of Pre‐Stroke Aspirin Use With Cerebral Infarct Volume and Functional Outcomes
Authors: Ryu Wi‐Sun , Schellingerhout Dawid , Hong Keun‐Sik , Jeong Sang‐Wuk , Kim Beom Joon , Kim Joon‐Tae , Lee Kyung Bok , Park Tai Hwan , Park Sang‐Soon , Park Jong‐Moo , Kang Kyusik , Cho Yong‐Jin , Park Hong‐Kyun , Lee Byung‐Chul , Yu Kyung‐Ho , Oh Mi Sun , Lee Soo Joo , Kim Jae Guk , Cha Jae‐Kwan , Kim Dae‐Hyun , Lee Jun , Han Moon‐Ku , Park Man Seok , Choi Kang‐Ho , Nahrendorf Matthias , Lee Juneyoung , Bae Hee‐Joon , Kim Dong‐Eog
Published: September 2021

Objective

We investigated (1) the associations of pre‐stroke aspirin use with thrombus burden, infarct volume, hemorrhagic transformation, early neurological deterioration (END), and functional outcome, and (2) whether stroke subtypes modify these associations in first‐ever ischemic stroke.

Methods

This multicenter magnetic resonance imaging (MRI)‐based study included 5,700 consecutive patients with acute first‐ever ischemic stroke, who did not undergo intravenous thrombolysis or endovascular thrombectomy, from May 2011 through February 2014. Propensity score‐based augmented inverse probability weighting was performed to estimate adjusted effects of pre‐stroke aspirin use.

Results

The mean age was 67 years (41% women), and 15.9% (n = 907) were taking aspirin before stroke. Pre‐stroke aspirin use (vs nonuse) was significantly related to a reduced infarct volume (by 30%), particularly in large artery atherosclerosis stroke (by 45%). In cardioembolic stroke, pre‐stroke aspirin use was associated with a ~50% lower incidence of END (adjusted difference = −5.4%, 95% confidence interval [CI] = −8.9 to −1.9). Thus, pre‐stroke aspirin use was associated with ~30% higher likelihood of favorable outcome (3‐month modified Rankin Scale score < 3), particularly in large artery atherosclerosis stroke and cardioembolic stroke (adjusted difference = 7.2%, 95% CI = 1.8 to 12.5 and adjusted difference = 6.4%, 95% CI = 1.7 to 11.1, respectively). Pre‐stroke aspirin use (vs nonuse) was associated with 85% less frequent cerebral thrombus‐related susceptibility vessel sign (SVS) in large artery atherosclerosis stroke (adjusted difference = −1.4%, 95% CI = −2.1 to −0.8, p < 0.001) and was associated with ~40% lower SVS volumes, particularly in cardioembolic stroke (adjusted difference = −0.16 cm3, 95% CI = −0.29 to −0.02, p = 0.03). Moreover, pre‐stroke aspirin use was not significantly associated with hemorrhagic transformation (adjusted difference = −1.1%, p = 0.09).

Interpretation

Pre‐stroke aspirin use associates with improved functional independence in patients with first‐ever ischemic large arterial stroke by reducing infarct volume and/or END, likely by decreasing thrombus burden, without increased risk of hemorrhagic transformation. ANN NEUROL 2021;90:763–776
Direct, Site‐Selective and Redox‐Neutral α‐C−H Bond Functionalization of Tetrahydrofurans via Quantum Dots Photocatalysis
Authors: Qiao Jia , Song Zi‐Qi , Huang Cheng , Ci Rui‐Nan , Liu Zan , Chen Bin , Tung Chen‐Ho , Wu Li‐Zhu
Published: September 2021

As one of the most ubiquitous bulk reagents available, the intrinsic chemical inertness of tetrahydrofuran (THF) makes direct and site‐selective C(sp3)−H bond activation difficult, especially under redox neutral condition. Here, we demonstrate that semiconductor quantum dots (QDs) can activate α‐C−H bond of THF via forming QDs/THF conjugates. Under visible light irradiation, the resultant alkoxyalkyl radical directly engages in radical cross‐coupling with α‐amino radical from amino C−H bonds or radical addition with alkene or phenylacetylene, respectively. In contrast to stoichiometric oxidant or hydrogen atom transfer reagents required in previous studies, the scalable benchtop approach can execute α‐C−H bond activation of THF only by a QD photocatalyst under redox‐neutral condition, thus providing a broad of value added chemicals starting from bulk THFs reagent.
Iodide‐Induced Fragmentation of Polymerized Hydrophilic Carbon Nitride for High‐Performance Quasi‐Homogeneous Photocatalytic H2O2 Production
Authors: Che Huinan , Gao Xin , Chen Juan , Hou Jun , Ao Yanhui , Wang Peifang
Published: September 2021

Polymeric carbon nitride (PCN) as a class of two‐electron oxygen reduction reaction (2 e− ORR) photocatalyst has attracted much attention for H2O2 production. However, the low activity and inferior selectivity of 2 e− ORR greatly restrict the H2O2 production efficiency. Herein, we develop a new strategy to synthesize hydrophilic, fragmented PCN photocatalyst by the terminating polymerization (TP‐PCN) effect of iodide ions. The obtained TP‐PCN with abundant edge active sites (AEASs), which can form quasi‐homogeneous photocatalytic system, exhibits superior H2O2 generation rate (3265.4 μM h−1), far surpassing PCN and other PCN‐based photocatalysts. DFT calculations further indicate that TP‐PCN is more favorable for electron transiting from β spin‐orbital to the π* orbitals of O2, which optimizes O2 activation and reduces the energy barrier of H2O2 formation. This work provides a new concept for designing functional photocatalysts and understanding the mechanism of O2 activation in ORR for H2O2 production.
Fe3O4/CuO/ZnO@MWCNT MNCs as an efficient organometallic nanocatalyst promoted synthesis of new 1,2,4‐triazolpyrimidoazepine derivatives: Investigation of antioxidant and antimicrobial activity
Authors: Shirangi Hannaneh Sadat , Varasteh Moradi Ali , Ahmadi Golsefidi Maziar , Hossaini Zinatossadat , Jalilian Hamid Reza
Published: September 2021

In this study, we synthesized new 1,2,4‐triazolpyrimidoazepine derivatives in high yields using multicomponent reactions of isatins, alkyl bromides, activated acetylenic compounds, guanidine, aldehydes, and hydrazonoyl chloride in the presence of Fe3O4/CuO/ZnO@MWCNT as a high performance catalyst in water at room temperature. The Fe3O4/CuO/ZnO@MWCNT synthesizes using Petasites hybridus rhizome water extract as a green media and moderate base. As well Fe3O4/CuO/ZnO@MWCNT MNCs show a good improvement in the yield of the product and displayed significant reusable activity. Investigation of antioxidant ability of synthesized compounds using radical trapping of diphenyl‐picrylhydrazine (DPPH) and ferric reduction power experiment is another purpose in this research. Also, the antimicrobial activity of some synthesized compounds proved by employing the disk diffusion test on Gram‐positive and Gram‐negative bacteria. This procedure has some benefits such as short reaction time, product with excellent yields, simple catalyst, and products separation.
Polymorphic fingerprint as an approach to authenticate Iberian pig categories
Authors: Bayés‐García Laura , Colomer‐Llombart Eduard , Aguilar‐Jiménez Mercedes , Calvet Teresa
Published: September 2021

High‐commercial‐value products are often susceptible to food fraud. Among them, Iberian dry‐cured ham is highly appreciated due to its particular and sensory, but also nutritional, properties. There are four different Iberian ham categories (namely bellota, recebo, cebo de campo and cebo), which directly depend on the rearing system of the pig during the last stage of the fattening phase. However, there is still a lack of a normalized and robust method capable of authenticating the different product categories and, therefore, preventing mislabeling. In the present work, we characterized the polymorphic behavior of raw (before curing) lipid extracts belonging to the four categories of Iberian pig. A total of 80 different samples were analyzed by DSC, and synchrotron radiation XRD experiments were carried out for selected ones. The results obtained showed that bellota and recebo categories exhibited essentially the same crystallization and polymorphic behavior and this was significantly different (p < 0.05) from that of cebo de campo and cebo. The latter exhibited higher crystallization and melting temperatures than bellota and recebo samples, due to the occurrence of an additional β′‐2L polymorphic form. By considering the differences in rearing systems of pigs belonging to the different categories, we concluded that the key factor which determined the polymorphism of Iberian pig lipid extracts was not the physical exercise practiced by the pig, but the inclusion of acorns in the feeding system. This work demonstrated that thermal and crystallographic techniques, like DSC and XRD, may be promoted to be used as fingerprinting tools for the authentication of high‐value food products.
Understanding the effect of processing temperature and carbon nanotube addition on the viscoelastic response of polyurethane foams
Authors: Bhinder Jasdeep , Agnihotri Prabhat K.
Published: September 2021

We experimentally demonstrate a strategy to design the microstructure and hence viscoelastic behavior of polyurethane (PU) foams. PU foams are fabricated at two temperatures (room and −5°C) and reinforced with varying concentrations of oxidized carbon nanotubes (CNTs). Hierarchical pores, thicker cell walls, higher density, and low porosity are recorded in PU foams processed at −5°C. The addition of CNTs improves the cell wall stiffness and thermal stability of PU foams. Master curves constructed from dynamic mechanical analysis show that processing at −5°C and addition of 1.6 wt.% oxidized CNTs enhance the storage modulus of PU foams over a wide temperature and frequency range. Prony series analysis reveals that PU foams fabricated at −5°C have significantly lower relaxation time. Moreover, the elastic modulus of PU foams processed using optimized conditions shows stronger rate dependency in comparison to other types of PU foams fabricated in this work.
Thin‐layer photodegradable polyrotaxane gel‐immobilized surfaces for photoregulation of surface properties and cell adhesiveness
Authors: Kang Tae Woong , Tamura Atsushi , Arisaka Yoshinori , Yui Nobuhiko
Published: September 2021

Thin‐layer photodegradable polyrotaxane (PRX) gel‐immobilized surfaces were fabricated to investigate the photoregulation of surface properties. Photodegradable PRXs comprising α‐cyclodextrin as a cyclic molecule, poly(ethylene glycol) as a polymer axel, and bulky trithiocarbonate as a photolabile stopper molecule (PRX‐MTP) were utilized for the fabrication of thin‐layer gels. PRX‐MTP gels were prepared on the surface of the glasses, where the surfaces were treated with an isocyanate group‐containing silane coupling agent to allow the covalent immobilization of the PRX‐MTP gels. This PRX‐MTP gel layer was disappeared upon irradiation with ultraviolet (UV; 365 nm) or visible light (465 nm) for 2 h due to the photodegradation of PRX‐MTPs. The surface wettability and roughness were changed owing to the photodegradation of the PRX‐MTP gel layer. When cells were seeded on the PRX‐MTP gel surfaces, adhesion was not observed. However, visible light irradiation of the PRX‐MTP gel layer resulted in cell adhesion on the irradiated surfaces. Consequently, it was determined that the surface properties and cell adhesiveness of the PRX‐MTP gel surfaces could be regulated by visible light irradiation. The photodegradable PRX‐MTP gel surfaces could be utilized for research on cell patterning, cell function control, and advanced cell culture system.
Distribution and establishment of the alien Australian redclaw crayfish, Cherax quadricarinatus, in the Zambezi Basin
Authors: Madzivanzira Takudzwa C. , South Josie , Ellender Bruce R. , Chalmers Russell , Chisule Gethings , Coppinger Christine R. , Khaebeb Fernandu H. , Jacobs Francois J. , Chomba Machaya , Musando Bumango , Mwale Chanda , Nhiwatiwa Tamuka , Rennie Craig L. , Richardson Naomi , Weyl Olaf L. F.
Published: September 2021

Crayfish are invasive polytrophic keystone species, which are phylogenetically unique on the African continent. The Australian redclaw crayfish Cherax quadricarinatus is invasive in southern African freshwater systems including the Zambezi River Basin. Surveys conducted across the Zambezi Basin (Botswana, Zimbabwe, Namibia and Zambia) between 2017 and 2019 showed that C. quadricarinatus is broadly distributed across the Upper and Middle Zambezi and is rapidly spreading through natural and human‐mediated means across several ecoregions.

The probability of capture (Pcapture), catch per unit effort (CPUE) and population characteristics of C. quadricarinatus from the recent Barotse floodplain invasion were compared with older invasions from Lake Kariba and Kafue River.

The Pcapture and CPUE of C. quadricarinatus in the recently invaded region of the Barotse floodplain were similar to those of the older invasions. Mass and carapace length of C. quadricarinatus from the Barotse floodplain were significantly lower than those of C. quadricarinatus from the older invasions. Sex ratios differed significantly between the three invasive populations. The Barotse floodplain population had a disproportionate investment in females (65.3%) and intersex individuals (8.4%). No crayfish were detected in the Zambezian Headwaters or the Okavango Floodplains ecoregions, but current spread rates are 49 km yr−1 downstream and 12 km yr−1 upstream.

Investment in population management and the prevention of spread will have high conservation value across the invaded regions in order to restrict crayfish ecological impacts via direct predation and competition. In areas where crayfish are in high abundance, existing fisheries are affected through damage to nets, leading to increased net abandonment and ghost gear pollution in invaded regions.

The emphasis should be on developing cohesive transboundary biosecurity policies in southern Africa to limit further spread that will threaten the integrity of freshwater ecosystems. However, long‐term monitoring is needed to gauge invasion risk to sensitive areas such as the Okavango Floodplains ecoregion and determine field‐based ecological impacts.
Bygone theatres of events: A history of human anatomy and dissection
Authors: Brenna Connor T. A.
Published: September 2021

Over the last four millennia, the discipline of anatomy and its relationships with medicine and society have evolved dramatically. Human dissection, the perennial tool for anatomical discovery and education, has both guided this evolution and matured alongside it. Soon after the first cadaveric dissections recorded in ancient Greece, China, India, and Persia, clear endorsements of its practice fell largely silent in the anatomical record for 1,500 years before reappearing in Europe at the dawn of the Renaissance. Between the 13th and 18th centuries CE, the performance of anatomical dissection became a popular form of education and public entertainment, and the demand for human cadavers steadily increased among European anatomical schools while supply remained limited by legal statute. This gave rise to an informal group of amateur and professional body snatchers called the Resurrectionists and, later, inspired the Anatomy Act of 1832 CE. In the 20th and 21st centuries CE, voluntary body bequeathal programs have enabled the practice of human dissection to continue in academic centers as a cornerstone of anatomical education, now with a newfound focus on the development of affective skills. This article provides an abridged account of anatomy's development, highlighting key moments in its growth, the valuable contributions of many different societies to the discipline, and the important roles of several luminary anatomists of antiquity. Within the broader context of this history, it offers an overview of anatomical dissection's evocative past, spanning from its inception to its present‐day practice.
LncRNA DLGAP1‐AS1 accelerates glioblastoma cell proliferation through targeting miR‐515‐5p/ROCK1/NFE2L1 axis and activating Wnt signaling pathway
Authors: Wang Zixuan , Han Yipeng , Li Qifeng , Wang Baocheng , Ma Jie
Published: September 2021

Introduction

Glioblastoma (GBM), the primary malignant tumor in the central nervous system, features high aggressiveness and mortality. Long noncoding RNAs (lncRNAs) can exert the crucial function in regulating various human diseases, including GBM. However, the function and mechanism of lncRNA DLGAP1 antisense RNA 1 (DLGAP1‐AS1) in GBM remain still unknown.

Methods

DLGAP1‐AS1 expression in GBM cells was detected by RT‐qPCR. Functional assays were conducted to determine GBM cell proliferation and apoptosis. RIP, RNA pull down, and luciferase reporter assay were applied for measuring the interplay of DLGAP1‐AS1 with other RNAs.

Results

DLGAP1‐AS1 was distinctly upregulated in GBM cells. DLGAP1‐AS1 depletion inhibited cell proliferation, but induced apoptosis. MiR‐515‐5p could be sponged by DLGAP1‐AS1 in GBM cells and to repress cell proliferation in GBM. Further, Rho‐associated coiled‐coil containing protein kinase 1 (ROCK1) and Nuclear factor erythroid‐2 like 1 (NFE2L1) were confirmed as the target gene of miR‐515‐5p. Wnt signaling pathway could be activated by DLGAP1‐AS1 via regulating ROCK1 and NFE2L1 expression. Rescue assays proved that overexpression of both ROCK1 and NFE2L1 could totally reverse the inhibitory effect of silencing DLGAP1‐AS1 on GBM cell proliferation.

Conclusion

LncRNA DLGAP1‐AS1 accelerated cell proliferation in GBM via targeting miR‐515‐5p/ROCK1/NFE2L1 axis and activating Wnt signaling pathway.
Tractography of the ansa lenticularis in the human brain
Authors: Li Mengjun , Ribas Eduardo Carvalhal , Zhang Zhiping , Wu Xiaolong , Wang Xu , Liu Xiaohai , Liang Jiantao , Chen Ge , Li Mingchu
Published: September 2021

The aim of this study was to make a thorough investigation of the trajectory of the ansa lenticularis (AL) and its subcomponents using high‐resolution fiber‐tracking tractography. The subcomponents of the AL were reconstructed from one region of interest (ROI) in the area of the globus pallidus combined with another ROI in the red nucleus, substantia nigra, subthalamic nucleus, or thalamus. This fiber‐tracking protocol was tested in an HCP‐1065 template, 35 healthy subjects from Massachusetts General Hospital (MGH), and 20 healthy subjects from the human connectome project (HCP) using generalized q‐sampling imaging (GQI)‐based tractography. Quantitative anisotropy and fractional anisotropy were also computed for the AL subcomponents. The subcomponents of the AL could be reconstructed in the HCP‐1065 template, 35 MGH healthy subjects, and 20 HCP healthy subjects. The AL descends from the globus pallidus and joins the ansa peduncularis for a short distance, subdividing later into fibers that continue separately to the red nucleus, substantia nigra, subthalamic nucleus, and thalamus. The study demonstrated the trajectory of the ansa lenticularis and its subcomponents using GQI‐based tractography, improving our understanding of the anatomical connectivity between the globus pallidus and the thalamo‐subthalamic region in the human brain. One Sentence Summary The investigation of the ansa lenticularis and its subcomponents using high‐resolution diffusion images based tractography.
Association of dietary fat intake and hepatocellular carcinoma among US adults
Authors: Moussa Iman , Day Rena S. , Li Ruosha , Kaseb Ahmed , Jalal Prasun K. , Daniel‐MacDougall Carrie , Hatia Rikita I. , Abdelhakeem Ahmed , Rashid Asif , Chun Yun Shin , Li Donghui , Hassan Manal M.
Published: September 2021

Background and Aims

The role of dietary fat consumption in the etiology of hepatocellular carcinoma (HCC) remains unclear. We investigated the associations of total fat and fatty acids with risk of HCC among US adults in a hospital‐based case–control study.

Methods

We analyzed data from 641 cases and 1034 controls recruited at MD Anderson Cancer Center during 2001–2018. Cases were new patients with a pathologically or radiologically confirmed diagnosis of HCC; controls were cancer‐free spouses of patients with cancers other than gastrointestinal, lung, liver, or head and neck. Cases and controls were frequency‐matched by age and sex. Dietary intake was assessed using a validated food frequency questionnaire. Odds ratios (ORs) and corresponding confidence intervals (CIs) were computed using unconditional logistic regression with adjustment for major HCC risk factors, including hepatitis B virus and hepatitis C virus infection.

Results

Monounsaturated fatty acid (MUFA) intake was inversely associated with HCC risk (highest vs. lowest tertile: OR, 0.49; 95% CI, 0.33–0.72). Total polyunsaturated fatty acid (PUFA) intake was directly associated with HCC risk (highest vs. lowest tertile: OR, 1.82; 95% CI, 1.23–2.70). Omega‐6 PUFA was directly associated with HCC risk (highest vs. lowest tertile: OR 2.29; 95% CI, 1.52–3.44). Long‐chain omega‐3 PUFA (eicosapentaenoic acid and docosahexaenoic acid) intake was also inversely associated with HCC risk (highest vs. lowest tertile: OR, 0.50; 95% CI, 0.33–0.70). No association was observed for saturated fat and HCC risk.

Conclusion

Our findings support a direct association of omega‐6 PUFA intake with HCC and an inverse association of MUFA and long‐chain omega‐3 PUFA intake with HCC.