bluuebunny/crossref_metadata_2025_split huggingface dataset:
Monitoring Transformations of Catalytic Active States in Photocathodes Based on MoSx Layers on CuInS2 Using In Operando Raman Spectroscopy
Authors: Chae Sang Youn , Yoon Noyoung , Joo Oh shim , Park Eun Duck 
Published: December 2022

AbstractThe electrochemical activation of CuInS2/MoSx for photoelectrochemical (PEC) H2 production was revealed for the first time through in operando Raman spectroscopy. During the activation process, the initial metallic MoSx phase was transformed to semiconducting MoSx, which facilitates charge carrier transfer between CuInS2 and MoSx. Ex situ X‐ray photoelectron spectroscopy and Raman spectroscopy suggest the existence of MoO3 after the activation process. However, apart from contradicting these results, in operando Raman spectroscopy revealed some of the intermediate steps of the activation process.
The Highly Controlled and Efficient Polymerization of Ethylene
Authors: Goller Alexander , Obenauf Johannes , Kretschmer Winfried P. , Kempe Rhett 
Published: December 2022

AbstractThe highly controlled and efficient polymerization of ethylene is a very attractive but challenging target. Herein we report on a Coordinative Chain Transfer Polymerization catalyst, which combines a high degree of control and very high activity in ethylene oligo‐ or polymerization with extremely high chain transfer agent (triethylaluminum) to catalyst ratios (catalyst economy). Our Zr catalyst is long living and temperature stable. The chain length of the polyethylene products increases over time under constant ethylene feed or until a certain volume of ethylene is completely consumed to reach the expected molecular weight. Very high activities are observed if the catalyst elongates 60 000 or more alkyl chains and the polydispersity of the strictly linear polyethylene materials obtained are very low. The key for the combination of high control and efficiency seems to be a catalyst stabilized by only one strongly bound monoanionic N‐ligand.
Impact of Mineralizing Agents on Aluminum Distribution and Acidity of ZSM‐5 Zeolites
Authors: Al‐Nahari Shadi , Dib Eddy , Cammarano Claudia , Saint‐Germes Etienne , Massiot Dominique , Sarou‐Kanian Vincent , Alonso Bruno 
Published: December 2022

AbstractIntensive research on improving the catalytic properties of zeolites is focused on modulating their acidity and the distribution of associated Al sites. Herein, by studying a series of ZSM‐5 zeolites over a broad range of Al content, we demonstrate how the nature of the mineralizing agent (F− or OH−) used in hydrothermal syntheses directly impacts Al sites distribution. The proportions of Al sites, probed by 27Al NMR, depend on the Si/Al ratio for F−, but remain identical for OH− (from Si/Al=30 to 760). This leads to contrasting variations in weak and strong acidities. Such opposite effect of mineralizers is explained by the spatial location of negative charges and the resulting balance between short‐ and long‐range electrostatic interactions. This understanding paves the way for additional and simple opportunities to control zeolites’ acidity.
Expanded Conformations of Monomeric Tau Initiate Its Amyloidogenesis**
Authors: Fernández‐Ramírez María del Carmen , Ng Kevin Kan‐Shing , Menéndez Margarita , Laurents Douglas V. , Hervás Rubén , Carrión‐Vázquez Mariano 
Published: December 2022

AbstractUnderstanding early amyloidogenesis is key to rationally develop therapeutic strategies. Tau protein forms well‐characterized pathological deposits but its aggregation mechanism is still poorly understood. Using single‐molecule force spectroscopy based on a mechanical protection strategy, we studied the conformational landscape of the monomeric tau repeat domain (tau‐RD244‐368). We found two sets of conformational states, whose frequency is influenced by mutations and the chemical context. While pathological mutations Δ280K and P301L and a pro‐amyloidogenic milieu favored expanded conformations and destabilized local structures, an anti‐amyloidogenic environment promoted a compact ensemble, including a conformer whose topology might mask two amyloidogenic segments. Our results reveal that to initiate aggregation, monomeric tau‐RD244‐368 decreases its polymorphism adopting expanded conformations. This could account for the distinct structures found in vitro and across tauopathies.
Visible light‐induced metal‐free atom transfer radical (co)polymerization of maleimides using commercial organocatalysts
Authors: Liao Daohong , Chen Ao , Pang Wenmin , Tan Chen , Bashir Muhammad Sohail 
Published: December 2022

AbstractMetal‐free photocontrolled atom transfer radical polymerization (ATRP) has recently received increasing attention due to its ability to avoid heavy metal contamination. However, the polymerization of 1,2‐disubstituted olefin monomers by photocontrolled ATRP has rarely been reported. In this contribution, visible light‐induced metal free atom transfer radical (co)polymerization of maleimides (MI) by using several commercial organocatalysts was investigated in both batch and continuous flow processes. It was shown that the combination of the commercial dye eosin Y (EY) and cocatalyst N,N′,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) can mediate controlled and selective ATRP of various N‐alkyl substituted MI monomers. The effect of polymerization time, initiators and catalysts are discussed. The results revealed that molecular weight (Mn) of the obtained polymers was increased by increase in monomers conversion with their narrow polydispersities (PDI ≤1.2). MIs alternating copolymerization with styrenes (St) under irradiation of visible light was also done which generated the polymaleimide resins with ultrahigh glass transition temperatures (Tg up to 259°C). Moreover, continuous flow process was also used for the co‐polymerization of MI and St by using a tubular reactor to get polymaleimide resins. Thus, this work provides an effective strategy to obtain copolymers of MI monomers and styrenes via both batch and continuous flow processes, enabling technical advantages for potential large‐scale applications.
Frequency analysis of random fatigue: Setup for an experimental study
Authors: Sgamma Michele , Chiocca Andrea , Bucchi Francesco , Frendo Francesco 
Published: December 2022

AbstractThe frequency‐domain approach to fatigue life estimation in random loading has been largely investigated due to its computational advantages, and several methods for the frequency translation of the most common time‐domain methods have been proposed. Between the most known frequency methods, there are Bendat's method, valid for narrow‐band signals, and Dirlik's formula, which ifis considered the best result for wide‐band signals. However, a great part of the frequency methods takes the rainflow count as a reference time‐domain method and uses the rainflow damage computation as the exact value to emulate. Therefore, very few experimental data for the fatigue life of mechanical components subject to random loads are available in the literature. This work presents the setup for a series of experimental tests for specimens subjected to random loads, aiming at achieving experimental data to compare with the results provided by frequency methods. After a brief description of the materials used for the setup, the two‐step test concept is described: first, the specimen will be subjected to random loads obtained by a certain power spectral density for an amount of time which should nominally cause a 30% of damage; then, the fatigue test will be ended on a resonance testing machine to compute the actual residual fatigue life of the specimen; this two‐step testing also allows to reduce the time requested for the tests. The test bench developed for the experimental investigation is described in the paper, together with the results of some preliminary tests, aimed at verifying the feasibility of the conceived procedure.
Sequential Methods for Di‐ and Tetrahydro‐Pyranone Synthesis Enable Concise Access to Tuscolid δ‐Lactone
Authors: Gao Xin , Menche Dirk 
Published: December 2022

AbstractTwo novel tandem sequences for stereoselective synthesis of elaborate hydropyranones are reported. The first one relies on an aldol‐lactonization procedure of a chiral enolate with an unprotected aldehyde, while the second one is based on a challenging dienolate ketone addition with concomitant cyclization and substrate controlled reduction. Both approaches proceed with high efficiency and stereoselectivity and enable very short accesses to the authentic pyranone subunit of the complex polyketide tuscolid and will be important to develop a first total synthesis of this structurally unique macrolide and to evaluate the tuscolid‐tuscoron rearrangement.
Analysis of polymeric nanoparticle properties for siRNA/DNA delivery in a tumor xenograft tissue slice air–liquid interface model
Authors: Karimov Michael , Scherer Marlene , Franke Heike , Ewe Alexander , Aigner Achim 
Published: December 2022

AbstractBackgroundClassical two‐dimensional (2D) cell culture as a drug or nanoparticle test system only poorly recapitulates in vivo conditions. Animal studies are costly, ethically controversial, and preclude large‐scale testing.Methods and ResultsWe established a three‐dimensional (3D) tissue slice air–liquid interface (ALI) culture model for nanoparticle testing. We developed an optimized procedure for the reproducible generation of large sets of tissue slices from tumor xenografts that retain their tissue architecture. When used for the analysis of nanoparticles based on chemically modified polyethylenimines (PEIs) to deliver siRNA or DNA, differences in transfection efficacy and cytotoxicity between nanoparticles were observed more clearly than in 2D cell culture. While nanoparticle efficacies between cell culture and the tissue slice model overall correlated, the tissue slice model also identified particularly suitable candidates whose efficacy was underestimated in 2D cell culture and had already been shown in previous in vivo studies.ConclusionThe ex vivo 3D tissue slice ALI culture model is a powerful system that allows the effective evaluation of biological nanoparticle efficacy and biocompatibility in an intact tissue environment. It is comparably inexpensive, time‐saving, and follows the 3R principle, while allowing the identification of critical nanoparticle properties and optimal candidates for in vivo applications.
A dialysis medium refreshment cell culture set‐up for an osteoblast‐osteoclast coculture
Authors: Vis Michelle Anna Maria , de Wildt Bregje Wilhelmina Maria , Ito Keita , Hofmann Sandra 
Published: December 2022

AbstractCulture medium exchange leads to loss of valuable auto‐ and paracrine factors produced by the cells. However, frequent renewal of culture medium is necessary for nutrient supply and to prevent waste product accumulation. Thus it remains the gold standard in cell culture applications. The use of dialysis as a medium refreshment method could provide a solution as low molecular weight molecules such as nutrients and waste products could easily be exchanged, while high molecular weight components such as growth factors, used in cell interactions, could be maintained in the cell culture compartment. This study investigates a dialysis culture approach for an in vitro bone remodeling model. In this model, both the differentiation of human mesenchymal stromal cells (MSCs) into osteoblasts and monocytes (MCs) into osteoclasts is studied. A custom‐made simple dialysis culture system with a commercially available cellulose dialysis insert was developed. The data reported here revealed increased osteoblastic and osteoclastic activity in the dialysis groups compared to the standard nondialysis groups, mainly shown by significantly higher alkaline phosphatase (ALP) and tartrate‐resistant acid phosphatase (TRAP) activity, respectively. This simple culture system has the potential to create a more efficient microenvironment allowing for cell interactions via secreted factors in mono‐ and cocultures and could be applied for many other tissues.
Addressing multilevel barriers to clinical trial participation among Black and White men with prostate cancer through the PACCT study
Authors: Eggly Susan , Senft Nicole , Kim Seongho , Heath Elisabeth I. , Jang Hyejeong , Moore Tanina F. , Baidoun Fatmeh , Manning Mark A. , Penner Louis A. , Albrecht Terrance L. , Carducci Michael A. , Lansey Dina , Hamel Lauren M. 
Published: December 2022

AbstractBackgroundCancer clinical trial participation is low and inequitable. Partnering Around Cancer Clinical Trials (PACCT) addressed systemic and interpersonal barriers through an observational study of eligibility and an intervention to improve patient–physician communication and trial invitation rates.MethodsPhysicians at two comprehensive cancer centers and Black and White men with prostate cancer participated. Patients were followed for 2 years to determine whether they became potentially eligible for an available therapeutic trial. Potentially eligible patients were randomized to receive a trials‐focused Question Prompt List or usual care. Patient–physician interactions were video‐recorded. Outcomes included communication quality and trial invitation rates. Descriptive analyses assessed associations between sociodemographic characteristics and eligibility and effects of the intervention on outcomes.ResultsOnly 44 (22.1%) of participating patients (n = 199) became potentially eligible for an available clinical trial. Patients with higher incomes were more often eligible (>$80,000 vs. <$40,000, adjusted OR = 6.06 [SD, 1.97]; $40,000–$79,000 vs. <$40,000, adjusted OR = 4.40 [SD, 1.81]). Among eligible patients randomized to the intervention (n = 19) or usual care (n = 25), Black patients randomized to the intervention reported participating more actively than usual care patients, while White intervention patients reported participating less actively (difference, 0.41 vs. −0.34). Intervention patients received more trial invitations than usual care patients (73.7% vs. 60.0%); this effect was greater for Black (80.0% vs. 30.0%) than White patients (80.0% vs. 66.7%).ConclusionsFindings suggest the greatest enrollment barrier is eligibility for an available trial, but a communication intervention can improve communication quality and trial invitation rates, especially for eligible Black patients.
2‐Arylpropylamines from 1‐Propenylbenzenes in a New One‐Pot Metathesis–Hydroaminomethylation Protocol
Authors: Avendaño‐Villarreal Jesus A. , Delolo Fábio G. , Granato Artur V. , Gusevskaya Elena V. , dos Santos Eduardo N. 
Published: December 2022

Abstract2‐Arylpropylamines are useful as active pharmaceutical ingredients (APIs) and as synthetic building blocks in fine chemistry. Herein we report a new and efficient methodology to transform naturally occurring 1‐propenylbenzenes into 2‐arylpropylamines employing a one‐pot ethenolysis/hydroaminomethylation protocol. Four consecutive reactions must occur in the same reaction vessel and the careful selection of the reaction conditions was critical to obtain the desired products in high yields. The negative interference between the ethenolysis and the hydroaminomethylation (HAM) catalysts was circumvented by the appropriate adjustment on the molar ratio of the catalysts. As a result, nine 2‐arylpropylamines were obtained in yields ranging in 75–93 %.
Strain‐Sensitive On‐Surface Ladderization by Non‐Dehydrogenative Heterocyclization
Authors: Ma Yujing , Sugawara Kazuma , Ishigaki Yusuke , Sun Kewei , Suzuki Takanori , Kawai Shigeki 
Published: December 2022

AbstractOn‐surface cyclodehydrogenation recently became an important reaction to planarize π‐conjugated molecules and oligomers. However, the high‐activation barrier to cleave the C−H bond often requires high‐temperature annealing, consequently restricting structures of precursor molecules and/or leading to random fusion at their edges. Here, we present a synthesis of pyrrolopyrrole‐bridged ladder oligomers from 11,11,12,12‐tetrabromo‐1,4,5,8‐tetraaza‐9,10‐anthraquinodimethane molecules on Ag(111) with bond‐resolved scanning tunnelling microscopy. This non‐dehydrogenative cyclization between pyrazine and ethynylene/cumulene groups has a low‐activation barrier for forming intermediary dimeric oligomer containing dipyrazinopyrrolopyrrolopyrazine units, thus giving new insight into the strain‐sensitive in ladder‐oligomer formation.
Azatriseptanes: Strained Framework Analogs of [7,7,7]Circulenes
Authors: Zhang Kai , Hope Philip A. , El Bitar Nehme Mélissa , Linden Anthony , Spingler Bernhard , Rickhaus Michel 
Published: December 2022

AbstractThe synthesis and characterization of heptagon‐embedded polycyclic aromatic compounds are essential for understanding the effect of negative curvature on carbon allotropes such as fullerenes and graphenes that have applications in functional organic materials. However, owing to the synthetic difficulties in functionalizing and embedding seven‐membered rings, these strain‐challenged structures are relatively unexplored. We report here the synthesis, characterization, and properties of a triarylamine core bridged with ethano chains at the 2,2’‐positions. In doing so, we provide access to the first heterocycle containing three fused heptagon rings with a nitrogen at its core (BATA‐NHAc). X‐ray crystallographic analysis and DFT calculations revealed a remarkably strained structure wherein two of the bridged aryl units approach coplanarity, while the third ring is twisted out of plane at 70°. UV‐vis and emission spectroscopies identify red‐shifted absorption and concentration‐dependent emission profiles, respectively, as a result of the unique conformation and self‐assembly properties of BATA‐NHAc. Furthermore, cyclic voltammetry shows a decrease in the oxidation potential for BATA‐NHAc in comparison to the non‐bridged analog. This study opens new avenues in understanding the structure–property relationships of curved π‐aromatics and the construction of π‐frameworks of increasing complexity.
Bendamustine in the treatment of patients with indolent non‐Hodgkin lymphoma refractory or relapse to rituximab treatment: An open‐label, single‐agent, multicenter study in China
Authors: Gao Yan , Liu Yizhen , Wang Yafei , Zhang Qingyuan , Wu Depei , Ye Xu , Wu Jianqiu , Xu Wei , Zhou Jianfeng , Yang Yu , Cen Hong , Zhang Feng , Xiang Ying , Tang Xiaoqiong , Ding Kaiyang , Lin JinYing , Ma Lei , Wang Shunqing , Yu Hao , Zhao Yang , Song Bin , Lv Fangfang , Huang Huiqiang 
Published: December 2022

AbstractBackgroundThe optimal treatment strategy for refractory or relapse (R/R) indolent non‐Hodgkin lymphoma (iNHL) has not been fully identified. This study aims to investigate the efficacy and tolerance of bendamustine hydrochloride developed in native Chinese corporation in the treatment of patients with R/R iNHL.MethodsA total of 101 patients from 19 centers were enrolled in this study from July 2016 to February 2019. Bendamustine hydrochloride (120 mg/m2) was given on days 1 and 2 of each 21‐day treatment cycle for six planned cycles or up to eight cycles if tolerated. Parameters of efficacy and safety were analyzed.ResultsThe median age of the patients was 53.44 (range, 24.4–74.6) years old. A total of 56 (55.44%) patients completed at least six treatment cycles, and the relative dose intensity was 93.78%. The overall response rate was 72.28%, and the median duration of response was 15.84 months (95% confidence interval [CI], 13.77–27.48 months). Median progression‐free survival was 16.52 months (95% CI, 14.72–23.41 months), and the median overall survival was not reached. Grade 3 or 4 hematologic toxicities included neutropenia (77.22%), thrombocytopenia (29.70%), and anemia (15.84%). The most frequent nonhematologic adverse events (any grade) included nausea, vomiting, fatigue, fever, decreased appetite, and weight loss. Seven patients died during the trial, and four cases may be related to the investigational drug.ConclusionsThis study reveals that bendamustine hydrochloride is a feasible treatment option for the indolent B‐cell non‐Hodgkin lymphoma patient who has not remitted or relapsed after treatment with rituximab. All adverse events were predictable and manageable.
CRISPR‐Suppressor Scanning for Systematic Discovery of Drug‐Resistance Mutations
Authors: Ngan Kevin C. , Lue Nicholas Z. , Lee Ceejay , Liau Brian B. 
Published: December 2022

AbstractCRISPR‐Cas9 genome editing technologies have enabled complex genetic manipulations in situ, including large‐scale, pooled screening approaches to probe and uncover mechanistic insights across various biological processes. The RNA‐programmable nature of CRISPR‐Cas9 greatly empowers tiling mutagenesis approaches to elucidate molecular details of protein function, in particular the interrogation of mechanisms of resistance to small molecules, an approach termed CRISPR‐suppressor scanning. In a typical CRISPR‐suppressor scanning experiment, a pooled library of single‐guide RNAs is designed to target across the coding sequence(s) of one or more genes, enabling the Cas9 nuclease to systematically mutate the targeted proteins and generate large numbers of diverse protein variants in situ. This cellular pool of protein variants is then challenged with drug treatment to identify mutations conferring a fitness advantage. Drug‐resistance mutations identified with this approach can not only elucidate drug mechanism of action but also reveal deeper mechanistic insights into protein structure‐function relationships. In this article, we outline the framework for a standard CRISPR‐suppressor scanning experiment. Specifically, we provide instructions for the design and construction of a pooled sgRNA library, execution of a CRISPR‐suppressor scanning screen, and basic computational analysis of the resulting data. © 2022 Wiley Periodicals LLC.Basic Protocol 1: Design and generation of a pooled sgRNA librarySupport Protocol 1: sgRNA library design using command‐line CRISPORSupport Protocol 2: Production and titering of pooled sgRNA library lentivirusBasic Protocol 2: Execution and analysis of a CRISPR‐suppressor scanning experiment
Therapeutic role of Artemether in the prevention of hepatic steatosis through miR‐34a‐5p/PPARα pathway
Authors: Chen Li , Yu Shuang , Hong Shubing , Lin Xia , Zhu Xiaonan , Cao Xiaopei , Li Yanbing , Xiao Haipeng 
Published: December 2022

AbstractArtemether (ATM) is a natural antimalarial drug that can also regulate glucose and lipid metabolism. However, little is known regarding its pharmacological action in metabolic dysfunction‐associated fatty liver disease (MAFLD), and the underlying mechanisms remain undetermined. The aim of this study was to explore the therapeutic effects of ATM against hepatic steatosis and the possible mechanisms. ATM significantly decreased blood glucose levels, improved glucose tolerance, reduced inflammatory response, and alleviated hepatic steatosis in the ob/ob mouse model as well as the high‐fat diet‐fed mice. ATM also inhibited lipid accumulation in murine hepatocytes in vitro. Using RNA sequencing, miR‐34a‐5p and peroxisome proliferator‐activated receptor‐α (PPARα) were identified as important regulators during ATM treatment. ATM administration downregulated miR‐34a‐5p expression and miR‐34a‐5p abrogated the inhibitory effects of ATM on PO (palmitate + oleate)‐induced lipid accumulation as well as triglycerides levels in murine hepatocytes. Furthermore, the expression of PPARα, a target gene of miR‐34a‐5p, was upregulated by ATM and PPARα inhibitor MK‐886 abolished the positive effect of ATM. Consequently, PPARα agonist fenofibrate reversed the decreased mitochondrial fatty acid β‐oxidation induced by miR‐34a‐5p mimics after ATM treatment, thereby leading to attenuation of intracellular lipid accumulation. Taken together, ATM is a promising therapeutic agent against MAFLD that reduces lipid deposition by suppressing miR‐34a‐5p and upregulating PPARα.