bluuebunny/crossref_metadata_2025_split huggingface dataset:
Changes in ambulance departures for assault calls during COVID‐19 pandemic restrictions
Authors: Pisl Vojtech , Vevera Jan , Štěpánek Lubomír , Volavka Jan 
Published: October 2022

AbstractRestrictions related to COVID‐19 changed the daily behavior of people, including the expression of violence. Although an increased incidence of violent behavior, especially domestic violence, was expected during the pandemic, retrospective analyses have yielded mixed results. Records of ambulance departures to address injuries caused by assaults in the Pilsen region, Czech Republic, during the restrictive measures during the national state of emergency were compared to data from 3 previous years using general linear models. The number and severity of assaults were analyzed for the whole sample and separately for patients of either sex, for residential or nonresidential locations, and for domestic violence. Controlling for the seasonal effects, the number of assaults decreased by 39% during the pandemic restrictions compared to the 3 previous years. No difference was found between the effects of restrictions on assaults resulting in an injury of a male or female patient. The decrease was specifically pronounced in the sample of assaults in nonresidential locations, while no effect of restrictions was observed in assaults in residential locations and domestic assaults. Pandemic restrictions were associated with a decreased incidence of violent assaults that required ambulance services. Although the incidence decreased especially in those assaulted outside of their homes, we found no support for an increase in domestic violence or violence against women. Pandemic restrictions may have served as a protective rather than a risk factor for assaults severe enough to warrant a call for ambulance services.
Hybrid Block Copolymer/Perovskite Heterointerfaces for Efficient Solar Cells
Authors: Sun Jianguo , Li Bin , Hu Long , Guo Junjun , Ling Xufeng , Zhang Xuliang , Zhang Chi , Wu Xianxin , Huang Hehe , Han Chenxu , Liu Xinfeng , Li Youyong , Huang Shujuan , Wu Tom , Yuan Jianyu , Ma Wanli 
Published: October 2022

AbstractSolution processable semiconductors like organics and emerging lead halide perovskites (LHPs) are ideal candidates for photovoltaics combining high performance and flexibility with reduced manufacturing cost. Moreover, the study of hybrid semiconductors would lead to advanced structures and deep understanding that will propel this field even further. Herein, a novel device architecture involving block copolymer/perovskite hybrid bulk heterointerfaces is investigated, such a modification could enhance light absorption, create an energy level cascade, and provides a thin hydrophobic layer, thus enabling enhanced carrier generation, promoting energy transfer and preventing moisture invasion, respectively. The resulting hybrid block copolymer/perovskite solar cell exhibits a champion efficiency of 24.07% for 0.0725 cm2‐sized devices and 21.44% for 1 cm2‐sized devices, respectively, together with enhanced stability, which is among the highest reports of organic/perovskite hybrid devices. More importantly, this approach has been effectively extended to other LHPs with different chemical compositions like MAPbI3 and CsPbI3, which may shed light on the design of highly efficient block copolymer/perovskite hybrid materials and architectures that would overcome current limitations for realistic application exploration.
Lanthanide(III)‐Cu4I4 Organic Framework Scintillators Sensitized by Cluster‐Based Antenna for High‐Resolution X‐ray Imaging
Authors: Liu Xiangmei , Li Ruhua , Xu Xueli , Jiang Yangyang , Zhu Wenjuan , Yao Yu , Li Feiyang , Tao Xiaofang , Liu Shujuan , Huang Wei , Zhao Qiang 
Published: October 2022

AbstractScintillator‐based X‐ray imaging has attracted great attention from industrial quality inspection and security to medical diagnostics. Herein, a series of lanthanide(III)‐Cu4I4 heterometallic organic frameworks (Ln‐Cu4I4 MOFs)‐based X‐ray scintillators are developed by rationally assembling X‐ray absorption centers ([Cu4I4] clusters) and luminescent chromophores (Ln(III) ions) in a specific manner. Under X‐ray irradiation, the heavy inorganic units ([Cu4I4] clusters) absorb the X‐ray energy to populate triplet excitons via halide‐to‐ligand charge transfer (XLCT) combined with the metal‐to‐ligand charge‐transfer (MLCT) state (defined as the X/MLCT state), and then the 3X/MLCT excited state sensitizes Tb3+ for intense X‐ray‐excited luminescence via excitation energy transfer. The obtained Tb‐Cu4I4 MOF scintillators exhibit high resistance to humidity and radiation, excellent linear response to X‐ray dose rate, and high X‐ray relative light yield of 29 379 ± 3000 photons MeV−1. The relative light yield of Tb‐Cu4I4 MOFs is ≈3 times higher than that of the control Tb(III) complex. X‐ray imaging tests show that the Tb‐Cu4I4 MOFs‐based flexible scintillator film exhibits a high spatial resolution of 12.6 lp mm−1. These findings not only provide a promising design strategy to develop lanthanide‐MOF‐based scintillators with excellent scintillation performance, but also exhibit high‐resolution X‐ray imaging for biological specimens and electronic chips.
Characterization of a Ferryl Flip in Electronically Tuned Nonheme Complexes. Consequences in Hydrogen Atom Transfer Reactivity
Authors: Dantignana Valeria , Pérez‐Segura M. Carmen , Besalú‐Sala Pau , Delgado‐Pinar Estefanía , Martínez‐Camarena Álvaro , Serrano‐Plana Joan , Álvarez‐Núñez Andrea , Castillo Carmen E. , García‐España Enrique , Luis Josep M. , Basallote Manuel G. , Costas Miquel , Company Anna 
Published: October 2022

AbstractTwo oxoiron(IV) isomers (R2a and R2b) of general formula [FeIV(O)(RPyNMe3)(CH3CN)]2+ are obtained by reaction of their iron(II) precursor with NBu4IO4. The two isomers differ in the position of the oxo ligand, cis and trans to the pyridine donor. The mechanism of isomerization between R2a and R2b has been determined by kinetic and computational analyses uncovering an unprecedented path for interconversion of geometrical oxoiron(IV) isomers. The activity of the two oxoiron(IV) isomers in hydrogen atom transfer (HAT) reactions shows that R2a reacts one order of magnitude faster than R2b, which is explained by a repulsive noncovalent interaction between the ligand and the substrate in R2b. Interestingly, the electronic properties of the R substituent in the ligand pyridine ring do not have a significant effect on reaction rates. Overall, the intrinsic structural aspects of each isomer define their relative HAT reactivity, overcoming changes in electronic properties of the ligand.
Native Amide‐Directed C(sp3)−H Amidation Enabled by Electron‐Deficient RhIII Catalyst and Electron‐Deficient 2‐Pyridone Ligand
Authors: Wakikawa Takumi , Sekine Daichi , Murata Yuta , Bunno Youka , Kojima Masahiro , Nagashima Yuki , Tanaka Ken , Yoshino Tatsuhiko , Matsunaga Shigeki 
Published: October 2022

AbstractTrivalent group‐9 metal catalysts with a cyclopentadienyl‐type ligand (CpMIII; M=Co, Rh, Ir, Cp=cyclopentadienyl) have been widely used for directed C−H functionalizations, albeit that their application to challenging C(sp3)−H functionalizations suffers from the limitations of the available directing groups. In this report, we describe directed C(sp3)−H amidation reactions of simple amide substrates with a variety of substituents. The combination of an electron‐deficient CpERh catalyst (CpE=1,3‐bis(ethoxycarbonyl)‐substituted Cp) and an electron‐deficient 2‐pyridone ligand is essential for high reactivity.
A General Method to Edit Histone H3 Modifications on Chromatin Via Sortase‐Mediated Metathesis
Authors: Yang Qingyun , Gao Yingxiao , Liu Xia , Xiao Yihang , Wu Mingxuan 
Published: October 2022

AbstractThe post‐translational modifications (PTMs) on the tail of histone H3 control chromatin structure and influence epigenetics and gene expression. The current chemical methods including unnatural amino acid incorporation and protein splicing enable preparations of the histone with diverse PTMs in cellular contexts, but they are not applicable to edit native chromatin. The manipulation of histone‐modifying enzymes alter the endogenous histone PTMs but the lack of specificity of most histone‐modifying enzymes prevents precise control of specific H3 tail PTM patterns. Here we report a new method to edit the N‐tail of histone H3 via sortase mediated metathesis (SMM). The sortase can install desired PTM patterns into histone H3 on nucleosomes in vitro and in cellulo. This study expands the application scope of sortase from ligation to metathesis in live cells using cell‐penetrating peptides (CPPs). In addition, it offers a strategy to edit PTMs of cellular histone H3 with potential for the development of precise epigenome editing.
Spatiotemporally Controlled Formation and Rotation of Magnetic Nanochains In Vivo for Precise Mechanotherapy of Tumors
Authors: Fu Qinrui , Feng Hongjuan , Liu Luntao , Li Ziqiao , Li Jianjie , Hu Jing , Hu Chengzhi , Yan Xiaohui , Yang Huanghao , Song Jibin 
Published: October 2022

AbstractSystemic cancer therapy is always accompanied with toxicity to normal tissue, which has prompted concerted efforts to develop precise treatment strategies. Herein, we firstly develop an approach that enables spatiotemporally controlled formation and rotation of magnetic nanochains in vivo, allowing for precise mechanotherapy of tumor. The nanochain comprised nanocomposites of pheophorbide‐A (PP) modified iron oxide nanoparticle (IONP) and lanthanide‐doped down‐conversion NP (DCNP). In a permanent magnetic field, the nanocomposites would be aligned to form nanochain. Next, MnO2 NPs were subsequently administered to accumulate in tumor as suppliers of Mn2+, which coordinates with PP to immobilize the nanochain. In a rotating magnetic field, the nanochain would rapidly rotate, leading to apoptosis/necrosis of tumor cell. The nanochain showed high T2‐MR and NIR‐II fluorescence imaging signals, which facilitated guided therapy. The strategy has great potential in practical applications.
Observation of an Alternate Charge‐Polarization State in a One‐Dimensional Pt−Pt−I Chain Compound with a Bulky Pendant Ligand
Authors: Moriyama Hayato , Otsubo Kazuya , Sugimoto Kunihisa , Kawaguchi Shogo , Kitagawa Hiroshi 
Published: October 2022

AbstractA one‐dimensional (1D) halogen‐bridged dinuclear‐metal complex (MMX‐chain) exhibits various electronic states based on a mixed‐valence metal‐dimer system. This report deals with the synthesis and physical properties of a new MMX‐chain with a bulky pendant ligand, Pt2(mcc‐HexCS2)4I (mcc‐HexCS2=trans‐4‐(methoxycarbonyl)cyclohexanedithiocarboxylate). The steric hindrance caused by the bulky substituent induces a strain in its 1D chain, achieving at ambient condition the first pure alternate charge‐polarization (ACP) state (−Pt2+−Pt3+−I−−Pt3+−Pt2+−I−−), a kind of spin‐Peierls state, as confirmed by X‐ray diffraction and its conducting and magnetic properties. The strain effect is also manifested as a very large linear thermal expansion along the chain direction, which is quite different from conventional MMX‐chains without a bulky ligand. The design of low‐dimensional materials with ligand variations is expected to lead to the emergence of new electron–lattice coupled electronic states.
Effects of biofilm heterogeneity on the apparent mechanical properties obtained by shear rheometry
Authors: Li Mengfei , Nahum Yanina , Matouš Karel , Stoodley Paul , Nerenberg Robert 
Published: October 2022

AbstractRheometry is an experimental technique widely used to determine the mechanical properties of biofilms. However, it characterizes the bulk mechanical behavior of the whole biofilm. The effects of biofilm mechanical heterogeneity on rheometry measurements are not known. We used laboratory experiments and computer modeling to explore the effects of biofilm mechanical heterogeneity on the results obtained by rheometry. A synthetic biofilm with layered mechanical properties was studied, and a viscoelastic biofilm theory was employed using the Kelvin–Voigt model. Agar gels with different concentrations were used to prepare the layered, heterogeneous biofilm, which was characterized for mechanical properties in shear mode with a rheometer. Both experiments and simulations indicated that the biofilm properties from rheometry were strongly biased by the weakest portion of the biofilm. The simulation results using linearly stratified mechanical properties from a previous study also showed that the weaker portions of the biofilm dominated the mechanical properties in creep tests. We note that the model can be used as a predictive tool to explore the mechanical behavior of complex biofilm structures beyond those accessible to experiments. Since most biofilms display some degree of mechanical heterogeneity, our results suggest caution should be used in the interpretation of rheometry data. It does not necessarily provide the “average” mechanical properties of the entire biofilm if the mechanical properties are stratified.
Costimulatory molecule‐related lncRNA model as a potential prognostic biomarker in non‐small cell lung cancer
Authors: Yao Yuanshan , Yang Fuzhi , Chen Anna , Hua Qingwang , Gao Wen 
Published: October 2022

AbstractObjectiveCostimulatory molecules have been demonstrated to exert essential roles in multiple cancers. However, their role in lung cancer remains elusive. Here, we sought to identify costimulatory molecule‐related lncRNAs in non‐small cell lung cancer (NSCLC) and establish a prognostic signature to predict the prognosis of patients with NSCLC.MethodsA total of 535 lung adenocarcinoma (LUAD) and 502 lung squamous cell carcinoma (LUSC) patients from the cancer genome atlas (TCGA) database were recruited. A novel costimulatory molecule‐based lncRNA prognostic model was constructed using the least absolute shrinkage and selection operator (LASSO) algorithm to predict the overall survival. The Homo_sapiens.GRCh38 data set was set as a reference file for probe annotation.ResultsA total of 593 costimulatory molecule‐related lncRNAs were extracted. After analysis, six costimulatory molecule‐related lncRNAs (AC084859.1, AC079949.2, HSPC324, LINC01150, LINC01150, and AC090617.5) were screened. A prognostic model based on the six lncRNAs was established using systematic bioinformatics analyses. The prognostic model had a prognostic value in NSCLC patients. Furthermore, a prognostic nomogram was established based on clinical parameters and a risk‐score model. Patients with different risk scores had considerably different tumor‐infiltrating immune cells, somatic mutational loading, clinical outcomes, signaling pathways, and immunotherapy efficacy. In addition, LINC01137 was associated with unfavorable disease outcomes and fueled tumor progression in NSCLC.ConclusionTaken together, our study demonstrated that a costimulatory molecule‐related lncRNA model could be a potential prognostic biomarker in NSCLC. Moreover, LINC01137 could facilitate the proliferation and invasion of lung cancer.
Diterpenoids from Strophioblachia glandulosa and Their NLRP3 Inflammasome Inhibitory Effects
Authors: Sakah Kaunda Joseph , Xu Yao‐Jun , Zhang Rui‐Han , Zhang Xing‐Jie , Li Xiao‐Li , Xiao Wei‐Lie 
Published: October 2022

AbstractOur study on the roots and leaves of the never‐hitherto‐chemically studied S. glandulosa led to the isolation of five new diterpenes, referred to as stroglandulons A–E (1–5), alongside 18 known constituents (6–23). The structures of the new compounds were elucidated on the basis of their spectroscopic data, while the known ones were determined based on the comparison of their data with the literature values. Compounds 1–5 were evaluated for their inhibitory effects against NLRP3 inflammasome activation; compound 5 showed inhibition by an IC50 value of 6.12±0.03 μM.
Influence of Pore Size in Benzoin Condensation of Furfural Using Heterogenized Benzimidazole Organocatalysts
Authors: Miletto Ivana , Meazza Marta , Paul Geo , Cossi Maurizio , Gianotti Enrica , Marchese Leonardo , Rios Ramon , Pera‐Titus Marc , Raja Robert 
Published: October 2022

AbstractA designed N‐heterocyclic carbene (NHC) catalyst was covalently anchored on a range of mesoporous and hierarchical supports, to study the influence of pore size in the benzoin condensation of furfural. The structural and spectroscopic characteristics of the anchored catalysts were investigated, also with the help of molecular dynamics simulations, in order to rationalize the degree of stability and recyclability of the heterogenized organocatalysts. Quantitative yields (99 %) and complete recyclability were maintained after several cycles, vindicating the design rationale.
Dual‐Readout of the Mechanical Response of a Bis‐acridinium [2]Rotaxane
Authors: Hu Johnny , Adrouche Sonia , Gauthier Etienne S. , Le Breton Nolwenn , Cecchini Marco , Gourlaouen Christophe , Choua Sylvie , Heitz Valérie , Jacquot de Rouville Henri‐Pierre 
Published: October 2022

AbstractA [2]rotaxane built around a multi‐responsive bis‐acridinium macrocycle has been synthesized. Structural investigation has confirmed the interlocked nature of the molecule, and MD simulations illuminated its conformational dynamics with atomic resolution. Both halochromic and redox‐switching properties were explored to shed light on the mechanical response and electronic changes that occur in the bis‐acridinium [2]rotaxane. The topology of the rotaxane led to different mechanical behaviors upon addition of hydroxide ions or reduction that were easily detected by UV/Vis spectroscopy and electrochemistry.
Stereodivergent Total Syntheses of (+)‐Mycaperoxides C, D, G Methyl Ester and (−)‐Mycaperoxide B**
Authors: Kerim Mansour D. , Evanno Laurent , Ferrié Laurent 
Published: October 2022

AbstractMycaperoxides are natural endoperoxides isolated from different Mycale genus sponges, showing significant antiviral or antibacterial activities. We report herein the first total syntheses of representative congeners of this family from sclareol using a stereodivergent approach. Thus, an innovative oxidative ring expansion of cyclobutanol was used to bring the 1,2‐dioxane subunit, and a Mukaiyama aldol reaction on peroxycarbenium species was utilized to install the propionic acid subunit. During the study toward (+)‐mycaperoxide D methyl ester (2), the isolation of the eight possible diastereomers under their ethyl thioester form allowed to build a pertinent database for further NMR assignment studies. Thus, we completed the total syntheses of (+)‐mycaperoxides D, C, G methyl ester, and (−)‐mycaperoxide B in 11 to 15 steps, confirming their original assignment.
Iron‐Catalysed Carbene Transfer to Isocyanides as a Platform for Heterocycle Synthesis
Authors: Roose Thomas R. , Preschel H. Daniel , Mayo Tejedor Helena , Roozee Jasper C. , Hamlin Trevor A. , Maes Bert U. W. , Ruijter Eelco , Orru Romano V. A. 
Published: October 2022

AbstractAn iron‐catalysed carbene transfer reaction of diazo compounds to isocyanides has been developed. The resulting ketenimines are trapped in situ with various bisnucleophiles to access a range of densely functionalized heterocycles (pyrimidinones, dihydropyrazolones, 1H‐tetrazoles) in a one‐pot process. The electron‐rich Hieber anion ([Fe(CO)3NO]−) facilitates efficient catalytic carbene transfer from acceptor‐type α‐diazo carbonyl compounds to isocyanides, providing a cost‐efficient and benign alternative to similar noble metal‐catalysed processes. Based on DFT calculations a plausible reaction mechanism for activation of the α‐diazo carbonyl carbene precursor and ketenimine formation is provided.
Accomplishing Scalability by Using Plate‐Based Freeze and Thaw Technologies
Authors: Jenewein Roland , Breitrainer Michael 
Published: October 2022

AbstractControlling the freezing behavior of bulk drug substance opens doors to process reproducibility and consistent quality of the final drug product by maintaining uniform conditions for the biopharmaceuticals during freezing, and consequently for frozen storage and shipment. This simplifies the commercial bulk production, particularly when manufacturing different drug substances at different sensitivities and temperature set points and enables scalability. The leverage of the ice front growth speed had a significant impact on controllability and, as a result, on the protein quality.
Automation of Integrated Perfusion Control Simplifying Process Intensification of Mammalian Biomanufacturing in Single‐Use Bioreactors
Authors: Schulze Markus , Kues Dominic , Gao Wei , Houser Matthew , Scheibenbogen Karl‐Heinz , Husemann Bernward , Husemann Ute , Greller Gerhard 
Published: October 2022

AbstractProduction of biopharmaceuticals needs to become faster, more flexible, and efficient. Perfusion processes allow to operate cell cultivations at higher cell concentrations, shorten their process time and increase their productivity. Still, either customized software solutions or third‐party stand‐alone control devices are often used for perfusion control. Its integration into a bioreactor automation platform will simplify the implementation and application of perfusion processes in the future. In this study, the automation of an integrated perfusion control strategy for a scalable single‐use bioreactor family is demonstrated. The control strategy is illustrated by means of a CHO cell N–1 perfusion process in a 50‐L bioreactor. Accurate control allowed to achieve 80 · 106 c mL−1 within five days. Furthermore, also DO and pH setpoints were precisely controlled throughout the N–1 perfusion process. Finally, the advantage of this process strategy is exemplified by comparing fed‐batch processes inoculated from N–1 perfusion vs. N–1 batch processes.
A Triethyleneglycol C60 Mono‐adduct Derivative for Efficient Electron Transport in Inverted Perovskite Solar Cells†
Authors: Fakharuddin Azhar , Armadorou Konstantina‐Kalliopi , Zorba Leandros P. , Tountas Marinos , Seewald Tobias , Soultati Anastasia , Tsipas Polychronis , Schütz Emilia R. , Tzoganakis Nikolaos , Panagiotakis Stylianos , Yannakopoulou Konstantina , Dimoulas Athanasios , Psycharis Vassilis , Kymakis Emmanuel , Yusoff Abd Rashid bin Mohd , Aidinis Konstantinos , Schmidt‐Mende Lukas , Vougioukalakis Georgios C. , Nazeeruddin Mohammad Khaja , Vasilopoulou Maria 
Published: October 2022

Comprehensive SummaryInverted perovskite solar cells (PSCs) have attracted increasing attention in recent years owing to their low‐temperature fabrication proces s. However, they suffer from a limited number of electron transport materials available with [6,6]‐phenyl C61 butyric acid methyl ester (PCBM) to be the most widely studied based on its appropriate energy levels and high electron mobility. The low relative permittivity and aggregation tendency upon illumination of PCBM, however, compromises the solar cell efficiency whereas its modest hydrophobicity negatively impacts on the device stability. Alternative electron transport materials with desired properties and appropriate degree of hydrophobicity are thus desirable for further developments in inverted PSCs. Herein, we synthesize a triethyleneglycol C60 mono‐adduct derivative (termed as EPF03) and test it as a novel electron transport material to replace PCBM in inverted PSCs based on a quadruple cation (RbCsMAFA) perovskite. We also compare this derivative with two novel fullerenes decorated with two (EPF01) or one dodecyl (EPF02) long side chains. The latter two fail to perform efficiently in inverted PSCs whereas the former enabled a power conversion efficiency of 18.43%, which represents a 9% improvement compared to the reference device using PCBM (17.21%). The enhanced performance mainly stems from improved electron extraction and reduced recombination enabled by the insertion of the large relative permittivity amongst other properties of EPF03. Furthermore, our results indicate that triethylene glycol side chains can also passivate perovskite trap states, suppress ion migration and enhance photostability and long‐term stability of EPF03 based perovskite solar cells.