bluuebunny/crossref_metadata_2025 huggingface dataset:
Discrete GPCR-triggered endocytic modes enable β-arrestins to flexibly regulate cell signaling
Authors: Barsi-Rhyne Benjamin , Manglik Aashish , von Zastrow Mark
Published: October 2022

β-Arrestins are master regulators of cellular signaling that operate by desensitizing ligand-activated G-protein-coupled receptors (GPCRs) at the plasma membrane and promoting their subsequent endocytosis. The endocytic activity of β-arrestins is ligand dependent, triggered by GPCR binding, and increasingly recognized to have a multitude of downstream signaling and trafficking consequences that are specifically programmed by the bound GPCR. However, only one biochemical ‘mode’ for GPCR-mediated triggering of the endocytic activity is presently known – displacement of the β-arrestin C-terminus (CT) to expose clathrin-coated pit-binding determinants that are masked in the inactive state. Here, we revise this view by uncovering a second mode of GPCR-triggered endocytic activity that is independent of the β-arrestin CT and, instead, requires the cytosolic base of the β-arrestin C-lobe (CLB). We further show each of the discrete endocytic modes is triggered in a receptor-specific manner, with GPCRs that bind β-arrestin transiently (‘class A’) primarily triggering the CLB-dependent mode and GPCRs that bind more stably (‘class B’) triggering both the CT and CLB-dependent modes in combination. Moreover, we show that different modes have opposing effects on the net signaling output of receptors – with the CLB-dependent mode promoting rapid signal desensitization and the CT-dependent mode enabling prolonged signaling. Together, these results fundamentally revise understanding of how β-arrestins operate as efficient endocytic adaptors while facilitating diversity and flexibility in the control of cell signaling.
Yo soy de p fkn r
Authors: Powell Derrek
Published: October 2022

Based in a sociophonetic analysis of lyrics performed by eight male Reggaeton artists of Puerto Rican origin, this study combines raciolinguistic and variationist frameworks to examine the frequency of occurrence and underlying linguistic, musicological, and poetic factors conditioning the distribution of the lateral variant of syllable- and word-final alveolar tap /ɾ/. Given that this trait is regarded as a distinctive characteristic of Puerto Rican Spanish capable of indexing in-group membership alongside positive assessments of Puerto Rican national identity, the study explores the implementation of this feature in popular performances of Puerto Ricanness in the context of global Latin Urban Music (Delgado Díaz et al. 2021, Medina Rivera 1997, Valentín Márquez 2015).The results show that lateralization is more frequently used by contemporary reggaetoneros like Bad Bunny and Ozuna, whose professional careers began in an era in which Reggaeton enjoyed global accessibility, contrasted to the pioneering artists of the genre such as Daddy Yankee and Nicky Jam, who use the variant significantly less frequently. Additionally, the results suggest that, while the most recent tracks performed by newer artists exhibit the highest rates of occurrence, the inverse is true for artists whose careers began in the early 2000s before the global consumption of Reggaeton, who are documented as decreasing use of [l] in what is interpreted as an attempt to distinguish their works from younger performers. This work contributes to the growing literature regarding the linguistic construction of performative identities permeating the popular music industry, offering insight into the racialization of [l] as a distinct Puerto Rican feature relative to expressions of ethnonational pride
Performance Analysis of Three-Phase Shunt Active Power Filter for Harmonic Mitigation
Authors: Yusuf Samson Dauda , Loko Abdulmumini Zubairu , Abdullahi Jibrin , Abdulhamid Aminu Alhaji
Published: October 2022

Aims: To carried out performance analysis of a shunt active power filter (SAPF) for harmonics mitigation.

Study Design: Experimental design through simulation studies using P-Q Theory and proportional integral controller.

Place and Duration of Study: Department of Physics, Nasarawa State University Keffi, main campus, Nigeria, between October 2020 and September 2021.

Methodology: Primary and secondary data were obtained using AVO Digital Multimeter and manufacturers’ datasheets from Schneider electric website to capture required system parameters, SAPF was designed using a Voltage Source Inverter model to represent the Three-Phase source, and P-Q Theory with PI Control was used for reference current extraction. The SAPF was modeled, designed and simulated using MATLAB-Simulink and analyzed under different nonlinear load conditions and harmonic spectrum to achieve low Total Harmonic Distortion (THD).

Results: The THD in the unbalanced system voltages before the application of SAPF was found to be 12.6%, 11.4% and 11.2%, while after the application of SAPF was 2.2%, 2.5% and 2.5% for phase voltages a, b and c respectively. The grid currents indicated THD of 27.2%, 30.9% and 31% before application of SAPF and 2.2%, 2.2% and 2.1% after application.

Conclusion: The use of non-linear loads; has adverse effects on the quality of electric power as well as phase voltage and frequency waveforms. The use of SAPF is of vital importance in improving electric power quality for reliable power supply and quality service delivery.
Hospital Rankings and Health Equity
Authors: Binger Tavia , Chen Harold , Harder Ben
Published: October 2022

This Viewpoint examines US News & World Report’s approach to evaluating and publicly reporting hospital performance in various aspects of health equity as well as describes several novel equity measures published as part of its “Best Hospitals” rankings program.
Removing Race From Hyperbilirubinemia Guidelines Is Not Enough
Authors: Ostfeld-Johns Sharon , Aragona Elena , Hart Louis
Published: October 2022

This Viewpoint discusses the complexities of race-conscious medicine and the importance of more explicit and attentive guidance in treatment recommendations.
Long‐Term Clinical and Radiographic Outcomes in Patients With Clinically Isolated Aortitis
Authors: Mayer Adam , Sperry Alexandra , Quimson Laarni , Rhee Rennie L.
Published: October 2022

Objective

The optimal management of patients with incidentally found clinically isolated aortitis (CIA) after aneurysm repair is unclear. This study compared long‐term surgical and clinical outcomes after surgical repair of thoracic aortic aneurysm between patients with CIA and patients with noninflammatory etiologies.

Methods

This is a matched cohort study. Patients with CIA were identified by histopathology following open thoracic aortic aneurysm repair. Two comparators without inflammation on pathology were matched to each patient by year of surgical repair. Outcomes included surgical complications, new vascular abnormalities on imaging, and death.

Results

One hundred sixty‐two patients were included: 53 with CIA and 109 matched comparators. Median follow‐up time was similar between groups (CIA 3.7 vs. comparator 3.3 years, P = 0.64). There was no difference in postoperative complications, surgical revision, or death between groups. Only 32% of patients with CIA saw a rheumatologist in the outpatient setting and 33% received immunosuppressive treatment. On surveillance imaging, no difference was seen in new or worsening aortic aneurysms, but there were significantly more vascular abnormalities in branch arteries of the thoracic aorta in patients with CIA (39% vs. 11%, P < 0.01).

Conclusion

Among patients who underwent surgical repair of a thoracic aortic aneurysm, patients with CIA were more likely than noninflammatory comparators to develop radiographic abnormalities in aortic branch arteries. Notably, there was no difference in risk of new aortic aneurysms or surgical complications despite most patients with CIA never receiving immunosuppression. This suggests that more selective initiation of immunosuppression in CIA may be considered after aortic aneurysm repair.
Sodium Ion Storage in Na4MnV(PO4)3@C Free‐Standing Electrode
Authors: Hu Ping , Zhu Ting , Cai Congcong , Mai Bo , Yang Chen , Ma Jianmin , Zhou Liang , Fan Hong Jin , Mai Liqiang
Published: October 2022

To enhance the energy density of batteries and explore intrinsic charge storage mechanism of the active materials, it is important to reduce or eliminate the use of non‐active materials in electrodes, such as binder and conductive additives. Herein, free‐standing Na4MnV(PO4)3@C (F‐NMVP@C) fiber membrane is fabricated and directly used as a sodium‐ion battery (SIB) cathode. In situ X‐ray diffraction reveals that the V3+/V4+ redox reaction occurs through a solid‐solution reaction while a two‐phase Mn2+/Mn3+ redox reaction is identified, and both are highly reversible. Meanwhile, ex situ electrochemical impedance spectroscopy reveals that both the ion diffusion coefficient and charge transfer resistance of F‐NMVP@C change reversibly during the Na+ intercalation/de‐intercalation. Battery full cells are assembled based on the free‐standing F‐NMVP@C cathodes and F‐Sb@C anodes, which manifests a high energy density (293 Wh kg−1) and good cyclability (87.5% after 100 cycles at 1 C). The high‐performance free‐standing cathodes and anodes shed light on the development of flexible SIBs.
Toward Unifying the Mechanistic Concepts in Electrochemical CO2 Reduction from an Integrated Material Design and Catalytic Perspective
Authors: Bagchi Debabrata , Roy Soumyabrata , Sarma Saurav Ch. , C. Peter Sebastian
Published: October 2022

Electrocatalytic CO2 reduction (eCO2RR) is one of the avenues with most potential toward achieving sustainable energy economy and global climate change targets by harvesting renewable energy into value‐added fuels and chemicals. From an industrial standpoint, eCO2RR provides specific advantages over thermochemical and photochemical pathways in terms of much broader product scope, high product specificity, and easy adaptability to the renewable electricity infrastructure. However, unlike water electrolyzers, the lack of suitable cathode materials for eCO2RR impedes its commercialization due to material design challenges. The current state‐of‐the‐art catalysts in eCO2RR suffer largely from low reaction rates, insufficient C2+ product selectivity, high overpotentials, and industrial‐scale stability. Overcoming the scientific and applied technical hurdles for commercial realization demands a holistic integration of catalytic designs, deep mechanistic understanding, and efficient process engineering. Special emphasis on mechanistic understanding and performance outcome is sought to guide the future design of eCO2RR catalysts that can play a significant role in closing the anthropogenic carbon loop. This article provides an integrative approach to understand principles of robust eCO2RR catalyst design superimposed with underlying mechanistic projections which strongly depend on experimental conditions viz. choice of electrolyte, reactor and membrane design, pH of the solvent, and partial pressure of the CO2.
Heterogeneous NASICON‐Type Composite as Low‐Cost, High‐Performance Cathode for Sodium‐Ion Batteries
Authors: Guo Jin‐Zhi , Zhang Hong‐Xia , Gu Zhen‐Yi , Du Miao , Lü Hong‐Yan , Zhao Xin‐Xin , Yang Jia‐Lin , Li Wen‐Hao , Kang Shuwen , Zou Weimin , Wu Xing‐Long
Published: October 2022

As promising cathode for sodium‐ion batteries, Na+ Superionic Conductor (NASICON)‐type materials have attracted attention owing to their excellent structural stability, superior ionic conductivity, and small volume expansion. However, the vanadium‐based NASICON‐type cathode with the biotoxicity and exorbitant price of V element and the iron‐based cathode with low mean working voltage as well as the intrinsic poor electronic conductivity of polyanionic compounds hinder their practical applications. Herein, a double‐carbon‐layer decorated heterogeneous composite, Na3V2(PO4)3‐Na3Fe2(PO4)(P2O7) (NVFPP/C/G), is successfully prepared for addressing these limitations. Due to their synergistic effect, NVFPP/C/G exhibits excellent electrochemical performance in half‐cell system and superior full‐cell performance when matched with hard carbon anode. Furthermore, the phase composition, electrode kinetics, and phase transition are confirmed by combined analyses of slow scanning power X‐ray diffraction, high‐resolution transmission electron microscopy, cyclic voltammetry with various scan rates, galvanostatic intermittent titration technique, ex situ X‐ray photoelectron spectra, and in situ X‐ray diffraction. This study portends a promising strategy to utilize composite structure engineering for developing advanced polyanionic cathodes.
Guanidinium‐Decorated Nanostructure for Precision Sonodynamic‐Catalytic Therapy of MRSA‐Infected Osteomyelitis
Authors: Cheng Yijie , Zhang Yufei , Zhao Zhe , Li Gang , Li Jie , Li Anran , Xue Yun , Zhu Baolin , Wu Zhongming , Zhang Xinge
Published: October 2022

Osteomyelitis caused by methicillin‐resistant Staphylococcus aureus (MRSA) biofilm infection is difficult to eradicate and can even be life‐threatening. Given that the infection is persistent and deep‐seated in the bone tissue, controlled and efficient treatment of osteomyelitis remains challenging. Herein, an activatable nanostructure (Au/TNT@PG) is presented for synergistic sonodynamic‐catalytic therapy of MRSA‐infected osteomyelitis. The Au/TNT@PG backbone is obtained by conjugating a guanidinium‐rich polymer (PG), a component that penetrates the biofilm matrix, onto ultrasound (US)‐absorbing gold‐doped titanate nanotubes (Au/TNTs). Under deep‐penetrating US irradiation, the nanocomposite generates 1O2 for sonodynamic therapy and catalyzes the decomposition of endogenous H2O2 into toxic •OH in the acidic infection microenvironment for catalytic therapy, leading to bacterial cell death. Its robust antibacterial effectiveness is attributable to its bacteria‐capturing ability, the biofilm penetrability of positively charged guanidinium, and the subsequent synergistic effect of sonodynamic‐catalytic action of Au/TNT. Such a remotely controlled approach potentiates the polarization of macrophages to M2‐type while suppressing the M1‐type, leading to topical inflammation resolution and enhanced osteoblast proliferation and differentiation to inhibit bone loss. Therefore, this study provides a generic nanotherapeutic approach for efficient sonodynamic‐catalytic therapy with respect to osteomyelitis.
Rational Screening of Artificial Solid Electrolyte Interphases on Zn for Ultrahigh‐Rate and Long‐Life Aqueous Batteries
Authors: Wang Dongdong , Liu Hongxia , Lv Dan , Wang Cheng , Yang Jian , Qian Yitai
Published: October 2022

Solid electrolyte interphase (SEI) on Zn anodes plays a pivotal role for high‐rate and long‐life aqueous batteries, because it effectively inhibits side reactions and dendritic growth. Many materials are explored as SEIs by a trial‐and‐error approach. Herein, an exercisable way is proposed to screen the potential SEIs on Zn anodes in view of dendrite‐suppressing ability and charge‐transfer property theoretically. As an output of this screening, Zn3(BO3)2 (ZBO) is checked experimentally. In symmetrical cells, Zn@ZBO runs over 250 h at an ultrahigh current density of 50 mA cm−2 for a large areal capacity 10 mAh cm−2. In full cells, Zn@ZBO||MnO2 shows an impressive cumulative capacity (≈406 mAh cm−2) under harsh conditions, i.e., a lean electrolyte condition (10 µL mAh−1), limited Zn supply (negative/positive electrode capacity ratio, N/P ratio = 2.3), and high areal capacity (5.0 mAh cm−2). The significance of this work lies in not only the first report of ZBO on Zn showing excellent electrochemical performance, but also a feasible way to screen the promising SEI materials for other metal anodes.
MOF Derived C/N Co‐Doped ZnO Modified through Facile In Situ Coupling with NixPy toward Photocatalytic H2O2 Production and H2 Evolution Reaction
Authors: Ray Asheli , Subudhi Satyabrata , Tripathy Suraj Prakash , Acharya Lopamudra , Parida Kulamani
Published: October 2022

Photocatalytic H2O2 and H2 evolution are the sustainable alternative to meet the energy crisis. To fabricate an efficacious photocatalyst, here a robust MOF‐derived porous C/N co‐doped ZnO nano‐granular particles modified via in situ coupling with NixPy cocatalyst is developed. C and N are doped in ZnO via calcination of Zn‐MOF that narrows the bandgap of ZnO as verified by UV–vis DRS. More in, NixPy acts as robust cocatalyst, which enhances light absorption ability in the visible region. The existence of C, N, and Ni–P components along with their tremendous charge carrier dynamics are confirmed from XPS, PL, TRPL, and electrochemical analysis, respectively, that enhances the photoctalytic activity effectively. Hence, the H2O2 production rate and H2 evolution rate for optimized composite C/N‐ZNP‐2 are observed to be 2495.1 ± 62.3 µmol h−1 g−1and 12265 ± 112.4 µmol h−1 g−1, which are 2.8 and 2.7 folds higher than C/N‐ZnO, respectively. Additionally, the PO bond helps in inhibiting the further decomposition of H2O2. Consequently, the porous nature as well as larger surface area along with the presence of NixPy cocatalyst in C/N‐ZnO facilitates the overall reaction mechanism, hence paving the path for a robust photo‐catalyst towards sustainable energy generation.
Fully Recyclable Liquid‐Metal‐Based Multi‐Layer Thermally Triggered Transient Electronic Devices
Authors: Teng Long , Li Li , Huang Jingxia , Li Shuai , Hu Renchao , Zhou Xuechang , Wang Hong
Published: October 2022

The emergent transient electronics that can be destroyed or degraded harmlessly under an environmental stimulus are attracting extensive attentions toward eco‐friendly electronic devices and confidential communication applications. However, currently available transient electronics are limited by the poor recyclability of components, which fails to meet the ever‐increasing demands of advanced electronic devices. Here, this work reports a fully recyclable transient electronic device based on a multi‐layered architecture, comprising a liquid metal (LM) as the conductor and a NaOH solution‐embedded paraffin composite (NPC) as the degradation agent. Upon thermally triggered by the bottom heater, the middle‐layer LM circuit and the top NPC layer melt, releasing the aqueous alkali to destroy the circuit at a quick transient rate (46 ± 4 s). Afterward, both the free LM and paraffin are recycled at extremely high efficiencies, that is, 98% for LM owing to the self‐aggregation and fluidic nature, 95% for paraffin arising from the low melting point and good recoverability. The successful integration of transience and recycling abilities dramatically improves the feasibility of transient electronics in real applications, as further demonstrated in a radio‐frequency transmission device and a remote destructible memristor, which hold great promises for confidential data storage devices and next‐generation electronics.
Ultrasensitive Perovskite Photodetector Achieved When Configured with a Si Metal Oxide Semiconductor Field‐Effect Transistor
Authors: Liu Jinbo , Haroldson Ross , Verkhogliadov Grigorii , Lin Dayang , Gu Qing , Zakhidov Anvar A. , Hu Walter , Young Chadwin D.
Published: October 2022

A novel photodetecting device architecture that combines the optoelectronic property advantages of a perovskite and the amplification properties of a Si metal–oxide–semiconductor field‐effect transistor (MOSFET) to innovate a photodetecting system with ultrahigh sensitivity, especially in low‐light intensity, is demonstrated. This perovskite‐based MOSFET photodetector (PM‐PD) can respond as low as 116 nW cm−2 with extremely high responsivity 4200 A W−1. The perovskite is part of the gate dielectric to modulate the MOSFET drain current when the light intensity is changed. A direct bandgap, organic–inorganic hybrid halide perovskite with a large optical absorption coefficient, can enhance photodetector performance. However, perovskite materials are not good conductors for transporting photogenerated electrons and holes compared with single‐crystal silicon. Therefore, the perovskite was utilized as a dielectric where the capacitance is used instead. In the proposed PM‐PD architecture, changing the width‐to‐length (W/L) ratio of perovskite capacitor electrodes, can modulate the dark current from picoamperes to microamperes providing a tunable parameter for optimizing photodetecting performance. Furthermore, the capacitance of the perovskite can be modulated by frequency, which facilitates matching the capacitance of perovskite and MOSFET gate oxide—another important requirement for optimal photodetecting performance. Finally, our novel PM‐PD is commensurate with potential 3D monolithic integration.
A Hybrid Amorphous/Crystalline TiO2 Material with Enhanced Photocatalytic Performance
Authors: Deng Hao , Yuan Liyong , Li Zijie , Wang Degao , Wang Xucong , Liang Pengliang , Wang Lin , Liu Yichuan , Fu Yajun , Chang Zhiyuan , Chai Zhifang , Gibson John K. , Shi Weiqun
Published: October 2022

Whereas crystalline TiO2 is widely used as a photocatalyst for solar energy conversion, the use of amorphous TiO2 is limited by diminished performance. Herein, the highly active photocatalyst composed of low‐crystalline TiO2 prepared by simple heat treatment of amorphous material is reported. Transmission electron microscopy, X‐ray diffraction, Raman, X‐ray absorption spectroscopy, and scanning transmission electron microscopy show that the low crystalline catalyst is hetero‐phase amorphous/anatase (mamorphous: manatase ≈ 2:3). Enhanced photocatalytic performance derives from the difference in conduction band potential between the phases, which promotes charge transfer and photochemical conversion. The photocatalyst calcined at 300 °C (T‐300) exhibits superior performance over commercial P25 (Degussa) for elimination of perrhenate, Re(VII), a surrogate for Tc(VII), and furthermore remains stable after several recycles. The high efficiency of Re(VII) removal by T‐300 is likely to correlate with active radicals ∙CO2− in the TiO2/HCOOH system. In addition to identifying a simple and effective photocatalyst, the results more generally elucidate titania‐based photocatalysis.
Engineering the Comfort‐of‐Wear for Next Generation Wearables
Authors: Shimura Tokihiko , Sato Shun , Zalar Peter , Matsuhisa Naoji
Published: October 2022

Wearable technologies are becoming important for the fields of information technology and healthcare, driven mainly by societal issues such as the aging society and the current pandemic. Recently developed flexible/stretchable wearable devices have demonstrated their ability for long‐term healthcare monitoring with improved signal integrity and multimodality. However, the adherence of wearers to such wearable devices cannot be determined only by the function. Here “comfort‐of‐wear” is identified as one of the most critical parameters for future wearables, similar to how clothes are chosen based on how comfortable they are. “Comfort‐of‐wear” is defined as the device's ability to not to disturb the wearers’ daily life. Several engineering approaches are introduced to improve the comfort‐of‐wear of devices—via strategies that include improving flexibility by utilizing a combination of structures, materials, and systems. Finally, the future of wearables enabled by cutting‐edge advanced electronic technologies is proposed.
Formation Mechanism and High Thermoelectric Performance of Cu5+3xFe1‐xS4 Icosahedral Nanoparticles with Distinctive Core‐Shell Structures
Authors: Zheng Sikang , Yang Xiaolong , Wang Huan , Zhang Bin , Xiong Xin , Lu Xu , Han Guang , Wang Guoyu , Zhou Xiaoyuan
Published: October 2022

Multiply twinned icosahedrons possess a diversity of unique functionalities well‐suited to various applications, such as thermoelectric conversion. Regarding chalcogenide icosahedron, an unconventional yet promising thermoelectric candidate, disclosing its growth mechanism is rather challenging. This study uncovers the formation mechanism of thermoelectric Cu5+3xFe1‐xS4 (0 ≤ x ≤ 0.4) core‐shell nano‐icosahedrons, which is distinct from that of well‐known metal icosahedrons. Electron microscopy and molecular dynamics simulations reveal that the evolution into icosahedrons, stemming from the fivefold twin formation in the center of Cu5FeS4 particle aggregates, is accompanied by the gradual formation of Fe‐rich orthorhombic‐structured core and Cu‐rich cubic‐structured shell, which provides a peculiar stress relaxation mechanism. Further identified by density functional theory calculations, Fe atoms have the tendency to transform cubic Cu5FeS4 to its orthorhombic phase and in turn result in varied crystal structures and lattice parameters in the core and shell. Importantly, by adjusting the Cu/Fe ratio of the precursors, the stress‐releasing process and potential energy of icosahedrons are controllably tuned, generating Cu5+3xFe1‐xS4 icosahedrons with tunable diameters. Accordingly, a significantly enhanced thermoelectric zT of 0.90, the largest value for Cu5FeS4, is realized. This study will shed light on the design strategy for Cu‐based ternary chalcogenide icosahedrons with enhanced thermoelectric properties.
Advection and dispersion induced by an interface between two immiscible fluids in a laminar flow
Authors: Dejam Morteza , Hassanzadeh Hassan
Published: October 2022

We report novel transport phenomena arising from an interface between two immiscible liquids in a laminar flow. In the context of the Taylor–Aris dispersion theory, we provide a quantitative description and demonstrate that the planar interface between two liquids in a laminar flow can lead to uphill advection and dispersion, dispersion barrier, as well as osmotic dispersion. The developed understanding of the newly identified transport phenomena paves the way for further research in this area and enables the insightful elucidation of mixing and separation processes in multiphase systems.
Minimum reflux calculation for multicomponent distillation in multi‐feed, multi‐product columns: Mathematical model
Authors: Jiang Zheyu , Tawarmalani Mohit , Agrawal Rakesh
Published: October 2022

Multi‐feed, multi‐product distillation columns are ubiquitous in multicomponent distillation systems. The minimum reflux ratio of a distillation column is directly related to its energy consumption and capital cost. Thus, it is a key parameter for distillation systems design, operation, and comparison. In this series, we present the first accurate shortcut based algorithmic method to determine the minimum reflux condition for any general multi‐feed, multi‐product (MFMP) distillation column separating any ideal multicomponent mixture. The classic McCabe‐Thiele or Underwood method is a special case of this general approach. Compared with existing techniques, this method does not involve any rigorous tray‐by‐tray calculation, nor does it require guessing of key components. In this first part of the series, we present the mathematical model for a general MFMP column, derive constraints for feasible separation and minimum reflux condition, discuss their geometric interpretations, and present an illustrative example to demonstrate the effectiveness of our approach.
Molecular predictors of immunophenotypic measurable residual disease clearance in acute myeloid leukemia
Authors: Stahl Maximilian , Derkach Andriy , Farnoud Noushin , Bewersdorf Jan Philipp , Robinson Troy , Famulare Christopher , Cho Christina , Devlin Sean , Menghrajani Kamal , Patel Minal A. , Cai Sheng F. , Miles Linde A. , Bowman Robert L. , Geyer Mark B. , Dunbar Andrew , Epstein‐Peterson Zachary D. , McGovern Erin , Schulman Jessica , Glass Jacob L. , Taylor Justin , Viny Aaron D. , Stein Eytan M. , Getta Bartlomiej , Arcila Maria E. , Gao Qi , Barker Juliet , Shaffer Brian C. , Papadopoulos Esperanza B. , Gyurkocza Boglarka , Perales Miguel‐Angel , Abdel‐Wahab Omar , Levine Ross L. , Giralt Sergio A. , Zhang Yanming , Xiao Wenbin , Pai Nidhi , Papaemmanuil Elli , Tallman Martin S. , Roshal Mikhail , Goldberg Aaron D.
Published: October 2022

Measurable residual disease (MRD) is a powerful prognostic factor in acute myeloid leukemia (AML). However, pre‐treatment molecular predictors of immunophenotypic MRD clearance remain unclear. We analyzed a dataset of 211 patients with pre‐treatment next‐generation sequencing who received induction chemotherapy and had MRD assessed by serial immunophenotypic monitoring after induction, subsequent therapy, and allogeneic stem cell transplant (allo‐SCT). Induction chemotherapy led to MRD− remission, MRD+ remission, and persistent disease in 35%, 27%, and 38% of patients, respectively. With subsequent therapy, 34% of patients with MRD+ and 26% of patients with persistent disease converted to MRD‐. Mutations in CEBPA, NRAS, KRAS, and NPM1 predicted high rates of MRD− remission, while mutations in TP53, SF3B1, ASXL1, and RUNX1 and karyotypic abnormalities including inv (3), monosomy 5 or 7 predicted low rates of MRD− remission. Patients with fewer individual clones were more likely to achieve MRD− remission. Among 132 patients who underwent allo‐SCT, outcomes were favorable whether patients achieved early MRD− after induction or later MRD− after subsequent therapy prior to allo‐SCT. As MRD conversion with chemotherapy prior to allo‐SCT is rarely achieved in patients with specific baseline mutational patterns and high clone numbers, upfront inclusion of these patients into clinical trials should be considered.
Low‐Toxicity ZnSe/ZnS Quantum Dots as Potent Photoreductants and Triplet Sensitizers for Organic Transformations
Authors: Nie Chengming , Lin Xuyang , Zhao Guohui , Wu Kaifeng
Published: October 2022

Colloidal quantum dots (QDs) can photocatalyze diverse organic reactions. However, reported QD‐photocatalysts often contain highly‐toxic elements Cd or Pb, and have not surpassed prototypical transition‐metal complexes in terms of their photoredox power or excited‐state energy. Here we report low‐toxicity ZnSe/ZnS core/shell QDs as potent visible photocatalysts to drive challenging organic transformations. To overcome the limitation of short excited‐state lifetime of the QDs, we functionalize their surfaces with benzophenone ligands which can rapidly extract electrons from photoexcited QDs and sustain long‐lived charge‐separated states. The benzophenone anions function as potent electron relay to drive dehalogenation of aryl chlorides and additive‐free polymerization of acrylates. Alternatively, the QDs are functionalized with biphenyl ligands to store energy in long‐lived, energetic triplets, enabling [2+2] homo‐cycloaddition of styrene and cycloaddition of carbonyls with alkenes.
Stereochemie steuert die Stärke der Diwasserstoffbrücken‐Bindungen in chiralen Amin‐Boran‐Addukten
Authors: Kemper Michael , Drost Deborah A. , Engelage Elric , Merten Christian
Published: October 2022

Das wachsende Interesse an der Nutzung neuartiger Konzepte nicht‐kovalenter Wechselwirkungen in Katalysatoren und in der supramolekularen Chemie hat uns veranlasst, eine besondere Art von Wasserstoffbrückenbindungen erneut aufzugreifen: die Diwasserstoffbrückenbindung (dihydrogen bond, DHB), die zwischen einem klassischen Wasserstoffbrückenbindungs‐Donor und einem hydridischen Wasserstoff als Akzeptor gebildet wird. In diesem Beitrag wird durch Vergleich der Strukturen und Bindungsenthalpien verschiedener chiraler Amin‐Boran‐Addukte untersucht wie die Stärke der N−Hδ+⋅⋅⋅δ−H−B‐Wechselwirkung und damit eine durch DHB‐getriebene Selbstaggregation von sterischen Effekte bestimmt wird. Für ein Amin‐Boran Diastereomerenpaar, das aus einem chiralen sekundären Amin hergestellt wurde, wird gezeigt, dass die Stereochemie am Stickstoff einen signifikanten Einfluss auf die Wechselwirkungsenthalpie hat. Basierend auf dieser Erkenntnis können N‐chirale Amin‐Borane als interessante, supramolekulare Bausteine zur Feinabstimmung der Bildungsdynamiken von Assemblierungen betrachtet werden.
Spatially Directed Biosynthesis of Quantum Dots via Spidroin Templating in Escherichia coli
Authors: Chen Meng‐Ting , Hu Chun‐Fei , Huang Hai‐Bo , Qian Zhi‐Gang , Xia Xiao‐Xia
Published: October 2022

Spatially directed synthesis of quantum dots (QDs) is intriguing yet challenging in organisms, due to the dispersed feature of templating biomolecules and precursors. Whether this task could be accomplished by biomolecular condensates, an emerging type of membraneless compartments in cells remains unknown. Here we report synthetic protein condensates for templated synthesis of QDs in bacterium Escherichia coli. This was realized by overexpression of spider silk protein to bind precursor ions and recruit other necessary components, which induced the spidroin to form more β‐sheet structures for assembly and maturation of the protein condensates. This in turn enabled formation and co‐localization of the fluorescent QDs to “light up” the condensates, and alleviated cytotoxicity of the precursor heavy metal ions and resulting QDs. Thus, our results suggest a new strategy for nanostructure synthesis and deposition in subcellular compartments with great potential for in situ applications.
Arylboration of Enecarbamates for the Synthesis of Borylated Saturated N‐Heterocycles
Authors: Trammel Grace L. , Kannangara Prashansa B. , Vasko Dmytro , Datsenko Oleksandr , Mykhailiuk Pavel , Brown M. Kevin
Published: October 2022

Two catalytic systems have been developed for the arylboration of endocyclic enecarbamates to deliver synthetically versatile borylated saturated N‐heterocycles in good regio‐ and diastereoselectivities. A Cu/Pd dual catalytic reaction enables the synthesis of borylated, α‐arylated azetidines, while a Ni‐catalysed arylboration reaction efficiently functionalizes 5‐, 6‐, and 7‐membered enecarbamates. In the case of the Cu/Pd‐system, a remarkable additive effect was identified that allowed for broader scope. The products are synthetically useful, as demonstrated by manipulations of the boronic ester to access biologically active compounds.
Hydrogen Drives Part of the Reverse Krebs Cycle under Metal or Meteorite Catalysis
Authors: Rauscher Sophia A. , Moran Joseph
Published: October 2022

Hydrogen (H2) is a geological source of reducing electrons that is thought to have powered the metabolism of the last universal common ancestor to all extant life, and that is still metabolized by various modern organisms. It has been suggested that H2drove a geochemical analogue of some or all of the reverse Krebs cycle at the emergence of the metabolic network, catalyzed by metals, but this has yet to be demonstrated experimentally. Herein, we show that three consecutive steps of the reverse Krebs cycle, converting oxaloacetate into succinate, can be driven without enzymes and in one‐pot by H2as the reducing agent under mild conditions compatible with biological chemistry. Low catalytic amounts of nickel (10–20 mol %) or platinum group metals (0.1–1 mol %) or even small amounts of ground meteorites were found to promote the reductive chemistry at temperatures between 5 and 60 °C and over a wide pH range, including pH 7. These results lend additional support to the hypothesis that geologically produced hydrogen and metal catalysts could have initiated early metabolic networks.
One‐dimensional metal–organic frameworks built by coordinating 2,4,6‐tris(4‐pyridyl)‐1,3,5‐triazine linker with copper nodes: CO2 adsorption properties
Authors: Portolés‐Gil Núria , Vallcorba Oriol , Fraile‐Sainz Julio , López‐Periago Ana M. , Domingo Concepción , Ayllón José A.
Published: October 2022

The reaction between 2,4,6‐tris(4‐pyridyl)‐1,3,5‐triazine (4‐tpt) and copper(II) hexafluoroacetylacetone (Cu(hfa)2) yields two different 1D metal–organic frameworks (MOFs), [(Cu(hfa)2)2(4‐tpt)]n (1) and [Cu(hfa)2(4‐tpt)]n (2). The Cu:4‐tpt ratio in the new MOFs is determined by the reaction medium, particularly, the solvent used. The two compounds have been fully characterized, including crystal structure elucidation. [(Cu(hfa)2)2(4‐tpt)]n (1), with a 2:1 Cu:4‐tpt ratio, could be precipitated in either 1,1,2‐trichloroethane or supercritical CO2. In (1), 4‐tpt shows a tritopic coordination mode, but only half of the Cu(hfa)2 subunits act as a node, thus connecting two 4‐tpt and giving a 1D network. The other half of Cu(hfa)2 subunits are connected only to one pyridine and thus protrude along the chains. The later Cu(hfa)2 fragments show a labile character and can be dissolved in diethyl ether to give the second MOF [Cu(hfa)2(4‐tpt)]n (2), with a 1:1 Cu:4‐tpt ratio. The compound (2) has also a 1D structure, with all the incorporated copper atoms acting as nodes. In this case, the packing of the chains defines accessible channels, which are perpendicular to the chain axis. After activation, N2 adsorption/desorption measurements at 77 K confirm the microporous character of (2) with an apparent surface area of 190 m2 g−1. Besides, at 273 K this material clearly shows a significant adsorption of CO2 prompted by noncoordinated nitrogen in the triazine linker.
An efficient new method for electrospinning chitosan and heparin for the preparation of pro‐angiogenic nanofibrous membranes for wound healing applications
Authors: Shahzadi Lubna , Ramzan Amna , Anjum Awais , Jabbar Faiza , Khan Ather Farooq , Manzoor Faisal , Shahzad Sohail Anjum , Chaudhry Aqif Anwar , Rehman Ihtesham ur , Yar Muhammad
Published: October 2022

Chronic skin wounds and surgical sutures need critical care and fast recovery, robust connection of blood vessels and effective restoration of circulation is necessary in progressive wound healing. Heparin is well known for its' anticoagulant properties, VEGF activation and antithrombosis action. Chitosan aid in the development of the vascular grafts due to its ECM like properties of blood vessels. For electrospinning of Heparin negatively charged and low molecular weight positively charges chitosan, the homogenous solution is required, they precipitate out during mixing due to opposite charges. In the current study, a an efficient strategy is developed for the electrospinning of chitosan and heparin in the presence of lysozyme. The insolubility/non‐homogenous solution formation for electrospinning from charged chitosan and heparin fast acting was solved by using a small amount of N‐cetyl‐N,N,N‐trimethyl ammonium bromide (CTAB) and the resulting solution produced very smooth nanofibers. Polycaprolactone (PCL) was found to be a suitable polymer for the electrospinning of chitosan and heparin using organic and inorganic solvents. Surface morphology of the synthesized fibers was investigated by scanning electron microscopy (SEM) and the presence of functional groups was investigated by FTIR. Degradation studies were performed which revealed that lysozyme loaded materials were degraded much faster as compared to other materials. The angiogenic and biocompatible potential of heparin with 1 mg/ml and 4 mg/ml lysozyme concentration was demonstrated by chorionic allantoic membrane (CAM) assay and it was estimated that 1 mg/ml (lysozyme) loaded CS/HA material was found to be an efficient biomaterial to stimulate angiogenesis.
Bond strength and bond mechanism of injection over‐molded woven carbon fiber/PEEK‐short carbon fiber/PEEK composite components
Authors: Deng Tianzhengxiong , Huang Zhigao , Zheng Bing , Jiang Wei , Chen Lu , Chen Cheng , Zhou Helezi , Zhou Huamin
Published: October 2022

A weak interface is formed between injected plastic and substrate during the injection over‐molding process. This study investigated the effects of mold temperature and melt temperature on the bond strength of injection over‐molded components, which were produced by injecting short carbon fiber reinforced polyether‐ether‐ketone (SCF/PEEK) onto the surface of woven carbon fiber reinforced PEEK (WCF/PEEK) laminate substrate. The results show that the interfacial laminar shear strength (ILSS) increases significantly from 15.8 to 50.0 MPa as the mold temperature raises from 190 to 260°C. The ILSS increases first and then decreases with melt temperature raises from 380 to 420°C, achieving a maximum value of 44.4 MPa at 410°C melt temperature. Crystallinity analysis and microscopic observations indicate different bonding modes are formed at the interface. The matrix tangling appears in the matrix enrichment area, interlocking, and tangling appear in the pits and weak tangling and cracks occur on the fiber surface. The mold temperature affects the ILSS by changing the crystallization property and the connection mode in the interface, while the melt temperature affects the ILSS by changing the area of the matrix entanglement. The relationship between the process conditions—interfacial microstructure—interfacial mechanical performance was discussed.
Photovoltaic performance of mixed cation K0.005MA0.995PbI3‐based perovskite solar module
Authors: Singh Harpreet , Dhakla Shweta , Deendyal Parvesh K. , Kumar Anand , Kumar Sarvesh , Kashyap Manish K.
Published: October 2022

Hybrid halide perovskites (HHPs) are attracting large attention due to their excellent photovoltaic characteristics. MAPbI3 (MA = CH3NH3) based solar cells are widely studied both on experimental and theoretical fronts. Alkali metal ion doping in the absorbing layer material (MAPbI3) of HHP solar cells is helpful for enhancing the photovoltaic performance and stability of the complete solar module. In present work, a complete perovskite solar module with K‐doped MAPbI3 absorbing layer has been simulated numerically. The effect of various parameters such as thickness, defect density, series, and shunt resistances on device performance has been studied. After optimizing these parameters, a device with the maximum possible efficiency (20.69%) has been reported. The reproducibility of solar cells before and after optimization has also been compared with respect to the variation in carrier mobilities in absorber layer material. Higher reproducibility of the optimized device has been obtained as compared to the pristine device. This present work contains adequate information to run an experimental trial for designing solar module containing K‐doped MAPbI3 absorbing layer.
Reset of Inflammatory Priming of Joint Tissue and Reduction of the Severity of Arthritis Flares by Bromodomain Inhibition
Authors: Friščić Jasna , Reinwald Christiane , Böttcher Martin , Houtman Miranda , Euler Maximilien , Chen Xi , Walker Kellie I. , Kirchner Philipp , Zhu Honglin , Wirth Benjamin , Weidner Daniela , Krüger René , Trajkovic Vladimir , Ekici Arif B. , Klein Kerstin , Mougiakakos Dimitrios , Ospelt Caroline , Schett Georg , Hoffmann Markus H.
Published: October 2022

Objective

We have recently shown that priming of synovial fibroblasts (SFs) drives arthritis flares. Pathogenic priming of SFs is essentially mediated by epigenetic reprogramming. Bromodomain and extraterminal motif (BET) proteins translate epigenetic changes into transcription. Here, we used a BET inhibitor (I‐BET151) to target inflammatory tissue priming and to reduce flare severity in a murine experimental arthritis model.

Methods

BALB/c mice were treated by intraperitoneal injection or by local injection in the paw with I‐BET151, which blocks the interaction of BET proteins with acetylated histones. We assessed the effects of I‐BET151 on acute arthritis and/or inflammatory tissue priming in a model of repeated injections of monosodium urate crystals or zymosan into the mouse paw. I‐BET151 was given before arthritis induction, at peak inflammation, or after healing of the first arthritis bout. We performed transcriptomic (RNA‐Seq), epigenomic (ATAC‐Seq), and functional (invasion, cytokine production, migration, senescence, metabolic flux) analyses of murine and human SFs treated with I‐BET151 in vitro or in vivo.

Results

Systemic I‐BET151 administration did not affect acute inflammation but abolished inflammatory tissue priming and diminished flare severity in both preventive and therapeutic treatment settings. I‐BET151 was also effective when applied locally in the joint. BET inhibition also inhibited osteoclast differentiation, while macrophage activation in the joint was not affected. Flare reduction after BET inhibition was mediated, at least in part, by rolling back the primed transcriptional, metabolic, and pathogenic phenotype of SFs.

Conclusion

Inflammatory tissue priming is dependent on transcriptional regulation by BET proteins, making them promising therapeutic targets for prevention of arthritis flares in previously affected joints.
The highest percentage of Gleason Pattern 4 is a predictor in intermediate‐risk prostate cancer
Authors: Sato Shun , Kimura Takahiro , Onuma Hajime , Egawa Shin , Shimoda Masayuki , Takahashi Hiroyuki
Published: October 2022

Objectives

This study aims to clarify the clinicopathological significance of several novel pathological markers, including the percentage of Gleason pattern 4 and small/non‐small cribriform pattern, in intermediate‐risk Gleason score 3 + 4 = 7 prostate cancer.

Subjects and Methods

Two‐hundred and twenty‐eight patients with Gleason score 3 + 4 = 7 intermediate‐risk prostate cancer who underwent radical prostatectomy between 2009 and 2019 at our institute were selected. Preoperative clinicopathological characteristics, including serum prostate‐specific antigen level, clinical T stage, percentage of cancer‐positive cores at biopsy, small/non‐small cribriform pattern, the highest percentage of Gleason pattern 4, the total length of Gleason pattern 4 and percentage of Gleason score 7 cores were examined in univariate/multivariate logistic regression analysis to determine their predictive value for postoperative adverse pathological findings, defined as an upgrade to Gleason score 4 + 3 = 7 or higher, pN1 or pT3b disease.

Results

Fifty‐four cases (23.7%) showed adverse pathological findings. Although a non‐small cribriform pattern, highest Gleason pattern 4 percentage and total length of Gleason pattern 4 were predictive of adverse pathological findings in univariate analysis, only the highest Gleason pattern 4 percentage was an independent predictive factor in multivariate analysis (odds ratio: 1.610; 95% confidence interval: 1.260–2.070; P = 0.0002).

Conclusion

The highest Gleason pattern 4 percentage was a potent predictive parameter for Gleason score 3 + 4 = 7 intermediate‐risk prostate cancer and should be considered in the risk classification scheme for prostate cancer.
The agony of choice: Impact of the host animal species on the enzyme‐linked immunosorbent assay performance for host cell protein quantification
Authors: Seisenberger Christina , Graf Tobias , Sticht Sarah , Haindl Markus , Mohn Ulrich , Wegele Harald , Wiedmann Michael , Wohlrab Stefanie
Published: October 2022

Host cell proteins (HCPs) are inevitable process‐related impurities in biotherapeutics commonly monitored by enzyme‐linked immunosorbent assays (ELISAs). Of particular importance for their reliable detection are the anti‐HCP polyclonal antibodies (pAbs), supposed to detect a broad range of HCPs. The present study focuses on the identification of suitable host animal species for the development of high‐performance CHO‐HCP ELISAs, assuming the generation of pAbs with adequate coverage and specificity. Hence, antibodies derived from immunization of sheep, goats, donkeys, rabbits, and chickens were compared concerning their amount of HCP‐specific antibodies, coverage, and performance in a sandwich ELISA. Immunization of sheep, goats, donkeys, and rabbits met all test criteria, whereas the antibodies from chickens cannot be recommended based on the results of this study. Additionally, a mixture of antibodies from the five host species was prepared to assess if coverage and ELISA performance can be improved by a multispecies approach. Comparable results were obtained for the single‐ and multispecies ELISAs in different in‐process samples, indicating no substantial improvement for the latter in ELISA performance while raising ethical and financial concerns.