bluuebunny/crossref_metadata_2025_split huggingface dataset:
3‐Ligated Phenothiazinyl‐terephthalonitrile Dyads and Triads ‐ Synthesis, Electronic Properties, Delayed Fluorescence and Electronic Structure
Authors: Kloeters Laura N. , Meissner Jan A. , Presser Lysander , Suta Markus , Meisner Jan , Müller Thomas J. J. 
Published: May 2023

AbstractThe bromine‐lithium exchange‐borylation‐Suzuki sequence efficiently furnishes phenothiazine‐terephthalonitrile donor‐acceptor dyads and triads in high yields. In contrast to most phenothiazine‐acceptor conjugates the title compounds are ligated in p‐position to the phenothiazine nitrogen atom. Moreover, the acceptors are either directly linked or ligated by an arylene bridge and p‐anisyl N‐substituents on the phenothiazine are chosen to lock the tricycle into an intra‐configuration. Cyclic voltammetry reveals effects of bridging and ligation of the N‐substituent. Optical spectroscopy likewise displays similar band gaps, large Stokes shifts and substantial to high quantum yields in solution, in the solid state and in PMMA matrix. Time‐resolved fluorescence spectroscopy indicates quite long fluorescence decay times in solution and emission components in the microsecond time range. TADF properties are further assessed by fluorescence increase in deoxygenated solution, gated emission spectroscopy and temperature‐dependent determination of phosphorescence. The nature of the electronically excited states is investigated by DFT/MRCI. While for the directly ligated dyad a singlet‐triplet energy gap Δ
of 0.24 eV can be estimated and is consistently confirmed by quantum chemical calculations on the lowest energy conformer, even lower
of 0.029 and 0.008 eV are estimated for the investigated dyads and the triad in the solid state and in PMMA matrix.
A Pyramidal Metal–Organic Frameworks‐Derived FeP@CoP Aluminium‐Ion Battery Cathode Displaying Low‐Temperature Tolerance and Fast Electron Transfer Kinetics
Authors: Bai Haiyuan , Tao Kehao , Yan Zicong , Zhan Xinju , Zhang Huigang , Han Tianli , Liu Jinyun , Li Jinjin 
Published: May 2023

AbstractAnhui Provincial Engineering Laboratory for Engineering appropriate cathode materials is significant for the development of high‐performance aluminum‐ion (Al‐ion) batteries. Here, a pyramidal metal–organic frameworks (MOFs)‐derived FeP@CoP composite was developed as cathode, which exhibits good stability and high capacity. FeP@CoP cathode maintains a high capacity of 168 mAh g−1 after 200 cycles, and displays a stable rate‐performance at both room and low temperatures of −10 °C. After three rounds of rate‐performance cycling, the FeP@CoP composite recovers 178.2 mAh g−1 at 0.3 A g−1. Moreover, density functional theory (DFT) calculations verify improved electron‐transfer kinetics with narrowed band gap and enhanced density of states. These findings inspire a broad set of studies on MOFs‐derived composites for high‐performance secondary batteries.
Degradation of wastewater from carbon capture plants using metal‐impregnated TiO2 photocatalyst
Authors: Bommavaram Kishore , Ali Feysal M. , Ibrahim Hussameldin 
Published: May 2023

AbstractAmine‐based carbon capture (ABCC) is an advanced and cost‐effective technology used to reduce the effects of climate change by capturing emitted from different sources. Although it has been demonstrated commercially, amine degradation poses a significant threat to humans and aquatic life. Amine degradation produces a wide variety of complex products such as nitrosamines and some organic acids. Some of these products are carcinogenic and mutagenic in nature and have demonstrated acute toxicity for laboratory animals. In order to mitigate the adverse impact of these compounds on human health and aquatic life, heterogeneous photocatalysis, an advanced oxidation process which can degrade a wide variety of chemical species with potent reactive hydroxyl radicals, was considered for the degradation of these compounds. The photocatalytic degradation of N‐nitrosodiethylamine (NDEA), acetic acid, and formic acid were tested using TiO2 and metal‐impregnated TiO2 catalysts such as Fe, Co, Ni, and Cu. Various techniques, such as thermogravimetric analysis (TGA), UV–Vis, X‐ray diffraction (XRD), Brunauer–Emmett–Teller (BET), scanning electron microscopy (SEM), and X‐ray fluorescence (XRF) were used to characterize these catalysts. The operational parameters for the photocatalytic degradation process were chosen as solution pH, catalyst dose, and metal impregnation percentage (imp%), and they were optimized using response surface methodology (RSM). pH was found as an important factor, and its impact on the photocatalytic degradation efficiency was more significant than the other operational parameters. The average degradation efficiency of the compounds reached 93.1% for Fe‐TiO2, 92.08% for Co‐TiO2, 89.09% for Ni‐TiO2, 88.81% for Cu‐TiO2, and 86.3% for TiO2 at the optimum conditions.
Passivation of Hematite Surface States to Improve Water Splitting Performance
Authors: Zhao Qingjiang , Huang Pengda , Hu Dong , Li TianBao , Xu Bingshe 
Published: May 2023

AbstractHematite is considered a promising photoanode material for solar water splitting; however, its photoelectrochemical (PEC) water splitting performance is limited by a high‐density surface state. In this study, we achieved passivation of a hematite surface using In2O3 nanoparticles. We characterized the passivation effect by analyzing the Mott‐Schottky curves. The resulting compound exhibited a negative shift of 0.1 eV in the onset potential compared to pure hematite, strongly indicating that the defect surface state of hematite was effectively passivated. Furthermore, the addition of NiFe(OH)x as a cocatalyst enhanced the oxygen evolution reaction kinetics. The optimal Ti−Fe2O3/In2O3/NiFe(OH)x compound photoanode achieved a superior photocurrent density of 2.6 mA cm−2 at 1.23 V vs. RHE, which is more than six times that of pure hematite (0.41 mA cm−2). This finding highlights a potential avenue for overcoming the issue of a high surface‐state density as the limiting condition for photoelectrodes.
Specificity and function of T cell subset identities using single‐cell sequencing
Authors: Liu Xuanqi , Zhu Zhenhua , Wang Xiangdong 
Published: May 2023

AbstractT cells, with numerous classifications, are vital components of the adaptive immune system, which function to maintain homeostasis to protect against pathogens. With the rapid development of single‐cell RNA sequencing (scRNA‐seq), the specificity and functions of high‐resolution characterizations and identities of T cells are continuously explored and discovered. The exact T cell identities provide new insights for deeply understanding the heterogeneity of T cells and for the identification of previously unrecognized cell subsets. The accuracy and specificity of T cell cluster and annotation are critical and important in scRNA‐seq analyses, even though the characters and numbers of T cell marker gene panels (MGPs) are to be furthermore improved and uncovered. In order to initiate the discussion on identities of T cell subsets/clusters and impacts of identity specificity in the understanding of immune function, the present review systematically summarized the T cell identities of MGPs and functional characteristics of distinct T cell identities in the scRNA‐seq analysis. We also discussed the critical gene differences among panels across T cell subsets, cell functional states, tissue types, and diseases, with a special focus on the significance and potential values of T cell MGP accuracy and specificity in clinical applications. We hope that the precise knowledge of T cell subsets/clusters benefit decision designs and makings of biomarker discoveries and therapeutic strategies to improve the outcomes of patients.
Dependent state space Student‐t processes for imputation and data augmentation in plasma diagnostics
Authors: Rath Katharina , Rügamer David , Bischl Bernd , von Toussaint Udo , Albert Christopher G. 
Published: May 2023

AbstractMultivariate time series measurements in plasma diagnostics present several challenges when training machine learning models: the availability of only a few labeled data increases the risk of overfitting, and missing data points or outliers due to sensor failures pose additional difficulties. To overcome these issues, we introduce a fast and robust regression model that enables imputation of missing points and data augmentation by massive sampling while exploiting the inherent correlation between input signals. The underlying Student‐t process allows for a noise distribution with heavy tails and thus produces robust results in the case of outliers. We consider the state space form of the Student‐t process, which reduces the computational complexity and makes the model suitable for high‐resolution time series. We evaluate the performance of the proposed method using two test cases, one of which was inspired by measurements of flux loop signals.
Design of an optimized traffic‐aware routing algorithm using integer linear programming for software‐defined networking
Authors: Eissa Menas Ebrahim , Abdel Azim Mohamed , Ata Mohamed Maher 
Published: May 2023

SummaryThe number of internet users and connected devices has dramatically expanded due to the recent technological boom and the benefits that the internet of things offers to ease our lives. Network scheduling, quality of service, resource allocation, and security issues are now being addressed via software‐defined networking (SDN). SDN has several benefits over traditional networks, including global centralized control, managing network traffic, and separating the forwarding and control plane. The work done in this paper aims to design and implement a traffic‐aware routing framework based on routing optimization presented as an integer linear programming (ILP) to improve heterogeneous traffic flows' quality of service (QoS) in a simulated SDN environment. With the knowledge that the routing problem is a nondeterministic polynomial‐time‐hard problem, the proposed scheme aims to decrease the computational routing time to make the ILP‐based routing system more suitable for real‐time processing. The simulation results illustrate that the proposed framework reduces the computational time by 23% and 49% for Abilene and Goodnet topology, respectively. Additionally, with 1000 flows in the network, the suggested scheme reduces the number of network flows that violate the QoS by 9% and 22% (with Abilene topology) and 16% and 51% (with Goodnet topology) as compared to the existing shortest path delay and sway methods, respectively.
Novel ester tethered dihydroartemisinin‐3‐(oxime/thiosemicarbazide)isatin hybrids as potential anti‐breast cancer agents: Synthesis, in vitro cytotoxicity and structure–activity relationship
Authors: Liu Shaohuan , Wang Shu , Xu Dan , Pan Bowen , Chen Linzhi , Zhao Shijia , Xu Zhi , Zhou Wei 
Published: May 2023

AbstractA series of ester tethered dihydroartemisinin‐3‐(oxime/thiosemicarbazide)isatin hybrids 7a–p were designed, synthesized, and assessed for their antiproliferative activity against MCF‐7, MDA‐MB‐231, MCF‐7/ADR, and MDA‐MB‐231/ADR breast cancer cell lines. Among them, hybrids 7a,f (IC50: 1.33–3.84 µM) showed potent activity against triple‐negative (MDA‐MB‐231 and MDA‐MB‐231/ADR) breast cancer cell lines, and hybrid 7f (IC50: 3.90 and 10.18 µM) also demonstrated promising activity against estrogen receptor‐positive breast cancer cells (MCF‐7 and MCF‐7/ADR), and the activity was superior to these of artemisinin, dihydroartemisinin, and ADR, revealing their potential to fight against both drug‐sensitive and drug‐resistant breast cancers. The enriched structure–activity relationships may facilitate further design of more active candidates.
Assessing impacts of sulfur deposition on aquatic ecosystems: A decision support system for the Southern Appalachians
Authors: Reynolds Keith M. , Hessburg Paul F. , Lakicevic Milena , Povak Nicholas A. , Salter R. Brion , Sullivan Timothy J. , McDonnell Todd C. , Cosby Bernard J. , Jackson William 
Published: May 2023

AbstractWith climate change and ongoing impacts from human development and resource extraction, US federal land management agencies are acutely concerned with managing for healthy aquatic ecosystems in the Southern Appalachian Mountain (SAM) Region. Here, we describe development of a spatial decision support application to assess the biological and ecological impacts of atmospheric S and N deposition on aquatic ecosystems of the region. We first summarize foundational published work to predict continuous maps of surface water acid neutralizing capacity (ANC) and soil base cation weathering (BCw). We use the predicted ANC and BCw maps to estimate steady‐state critical loads (CLs) of atmospheric S and N deposition. We included estimated CLs of atmospheric N to get a complete picture of CLs and potential exceedances. We then present a logic‐based decision support model for assessing effects of S and N deposition based on statistically modeled stream ANC and CL exceedance. The model is easily modified for continuous monitoring of CL exceedance patterns as new S and N deposition and ANC data become available. We present mapped model results for the SAM study area and an important subset of the region, the Great Smoky Mountains National Park. ANC modeling results revealed that predicted acid sensitivity was spatially variable, with areas of relatively low stream ANC (<50 μeq · L−1) and soil BCw (<50 meq · m−2 · year−1) predominantly found in certain critical areas. Within the Great Smoky Mountains National Park, evidence for S CL exceedance based on an ANC criterion of 50 μeq · L−1 was strong at locations where ambient S deposition was at least two times the CL. We also predicted likely impacts of CL exceedances on aquatic insect species richness and native fish abundance. Responses for insect species richness and fish impact showed variability similar to CL exceedance, with increasing impact positively correlated with elevation. Finally, we discuss ways that the decision support system can be used to prioritize management across the region.
Exploring friendship in hydropolitics: The case of the friendship dam on the Asi/Orontes river
Authors: Haemmerli Hannah , Bréthaut Christian , Ezbakhe Fatine 
Published: May 2023

Abstract“Friendship dams” are an explicit, yet underexplored, materialization of hydropolitics that illustrate the potential role of water in international cooperation. Via a case study analysis of the Syria‐Turkey Friendship Dam project proposed for the Asi/Orontes river, we trace the process of cooperation that led to the use of this notion of “friendship” in transboundary cooperation. Using a transversal analysis of different phases of cooperation and non‐cooperation, we consider broad, big‐picture political and diplomatic factors related to water and beyond. Our analysis shows that two key variables shaped how water was used as an instrument of cooperation in this case: (1) security and (2) the dynamics of international cooperation undertaken by the riparians, namely Turkey. The friendship dam label can be considered a manifestation of strategic international friendship that the two riparian countries invoked to achieve security and bilateral cooperation.
Catalysis for Oleochemical Platforms
Authors: Cucciolito Maria Elena , Di Serio Martino , Esposito Roberto , Melchiorre Massimo , Ruffo Francesco , Russo Vincenzo , Tesser Riccardo , Turco Rosa , Vitiello Rosa 
Published: May 2023

AbstractThe present review articles the most recent efforts, made in the Department of Chemical Sciences of the University of Naples Federico II, in the catalytic treatment of biomasses derived from vegetable oils. The review is focused on several technologies aimed at the production of either biofuels or valuable chemicals: (i) biodiesel production; (ii) esterification to obtain high‐added value products; (iii) epoxidation of vegetable oils; (iv) glycerol ketalization; (v) oxidative cleavage of unsaturated fatty acids. The results are critically summarized to highlight the scientific activities and the main results in the field of biorefinery concept.
Hierarchical Helicates Bearing Phosphorus‐Based Substituents in the Periphery
Authors: Wang Wei , Sturm Lisa , Sommer David , Oppel Iris , Albrecht Markus 
Published: May 2023

AbstractPhosphinate and phosphane substituted hierarchical helicates have been prepared, and the phosphinate derivatives could be characterized in the crystal. The helicate with phosphane substituents was submitted to an orientating study on catalysis, showing its potential to act as chelating ligand for the generation of active rhodium‐based hydrogenation catalysts.
A Comprehensive Study on Redox Behavior and Halogen Exchange in Telluropyran Derivatives
Authors: Liu Si , Chen Weinan , Yan Chuan , Zhou Fan , Zhou Zhanglang , Wang Min , Zhou Gang 
Published: May 2023

AbstractIncorporation of tellurium into polycyclic compounds may endow them with unique chemical and optoelectronic properties which are not observed in their lighter chalcogen analogues. Herein, a telluropyran‐containing polycyclic compound (T1) synthesized through a ring‐expansion reaction from the corresponding tellurophene analogue can be reversibly oxidized into halogen adducts T1•X2 (X=Cl, Br, I) with the formation of two Te−X bonds. Their chemical structures have been verified by two‐dimensional 1H‐1H correlation spectroscopy and single crystal X‐ray diffraction analysis. The halogen oxidations of T1 and the reverse thermal eliminations as well as the halogen exchange in halogen adducts T1•X2 have been systematically investigated and compared by UV‐vis absorption titration, electrochemical measurements, thermogravimetric analysis, and density functional calculations (DFT). The oxidation of Te(II) in T1 to Te(IV) in T1•X2 results in the switch from aromaticity to nonaromaticity for the six‐membered telluropyran ring, as revealed by nucleus‐independent chemical shift calculations. It is also found that the halides in the halogen adducts can be exchanged by lighter ones, but not vice versa. The stabilities of the oxidized products are in the order of T1•Cl2>T1•Br2>T1•I2, which are consistent with the calculated rate constants and energy barriers of the elimination reactions.
Ultralow‐power in‐memory computing based on ferroelectric memcapacitor network
Authors: Tian Bobo , Xie Zhuozhuang , Chen Luqiu , Hao Shenglan , Liu Yifei , Feng Guangdi , Liu Xuefeng , Liu Hongbo , Yang Jing , Zhang Yuanyuan , Bai Wei , Lin Tie , Shen Hong , Meng Xiangjian , Zhong Ni , Peng Hui , Yue Fangyu , Tang Xiaodong , Wang Jianlu , Zhu Qiuxiang , Ivry Yachin , Dkhil Brahim , Chu Junhao , Duan Chungang 
Published: May 2023

AbstractAnalog storage through synaptic weights using conductance in resistive neuromorphic systems and devices inevitably generates harmful heat dissipation. This thermal issue not only limits the energy efficiency but also hampers the very‐large‐scale and highly complicated hardware integration as in the human brain. Here we demonstrate that the synaptic weights can be simulated by reconfigurable non‐volatile capacitances of a ferroelectric‐based memcapacitor with ultralow‐power consumption. The as‐designed metal/ferroelectric/metal/insulator/semiconductor memcapacitor shows distinct 3‐bit capacitance states controlled by the ferroelectric domain dynamics. These robust memcapacitive states exhibit uniform maintenance of more than 104 s and well endurance of 109 cycles. In a wired memcapacitor crossbar network hardware, analog vector‐matrix multiplication is successfully implemented to classify 9‐pixel images by collecting the sum of displacement currents (I = C × dV/dt) in each column, which intrinsically consumes zero energy in memcapacitors themselves. Our work sheds light on an ultralow‐power neural hardware based on ferroelectric memcapacitors.
The impact of a mandatory universal drug insurance program on health behaviors and outcomes
Authors: Lebihan Laetitia 
Published: May 2023

AbstractThis paper investigates the effects of a mandatory, universal prescription drug insurance policy on health behaviors and outcomes within a public health care system providing physician and hospital services free of charge. Using Canadian longitudinal data, we show that the reform improved individuals' general health while reducing body mass index and smoking. However, the program also increased drinking and had no significant impact on mental health, physical activity, or preventive care. We also examine the mechanisms through which these effects can play a role, as well as the heterogeneous effects. Estimates suggest that the policy decreased SES‐based disparities in health.
Hypothalamic‐pituitary‐adrenal and autonomic response to psychological stress in abstinent alcohol use disorder individuals with and without depressive symptomatology
Authors: Syed Shariful A. , Sinha Rajita , Milivojevic Verica , MacDougall Alicia , LaValle Heather , Angarita Gustavo A. , Fox Helen C. 
Published: May 2023

AbstractBackgroundStress and depression have each been associated with relapse risk. In clinical practice, chronic alcohol use is often accompanied by poor emotional and self‐regulatory processes. Tonic and phasic changes in stress responsivity impact an individual's relapse risk to alcohol. A further complicating factor is the pervasive coexistence of depressive symptoms in those with Alcohol Use Disorder (AUD), where the contribution of depressive symptomatology to these processes is not well understood. Individuals with AUD (AD) (21 with and 12 without sub‐clinical depressive symptoms) and 37 social drinking controls (16 with and 21 without sub‐clinical depressive symptoms) as part of a more extensive study (Fox et al., 2019). All participants were exposed to two 5‐min personalized guided imagery conditions (stress and neutral) in a randomized and counterbalanced order across consecutive days. Alcohol craving, negative mood, Stroop performance, and plasma measures (cortisol, adrenocorticotrophic hormone, and salivary alpha‐amylase) were collected before and after imagery exposure.ResultsElevations in autonomic response (heart rate) to imagery (stress and neutral) were observed as a function of drinking (in both depressed and non‐depressed individuals with alcohol use disorder compared with depressed and non‐depressed social drinkers). Conversely, suppressed cortisol following stress was observed as a function of depressive symptomatology across both drinking groups. Individuals with comorbid AD and depressive symptoms demonstrated attenuated Adrenocorticotropic Hormone and poor Stroop performance compared with the other groups, indicating an interactive effect between drinking and depression on pituitary and inhibitory systems.ConclusionSub‐clinical depressive pathophysiology may be distinct from drinking severity and may alter relapse‐related stress adaptations during protracted abstinence from alcohol.
The Driven Liouville von Neumann Approach to Electron Dynamics in Open Quantum Systems
Authors: Hod Oded , Kronik Leeor 
Published: May 2023

AbstractThe driven Liouville von Neumann approach is a method to computationally explore electron dynamics and transport in nanoscale systems. It does so by imposing open boundary conditions on finite atomistic model systems, which drive them out of equilibrium. The approach is compatible with any underlying electronic structure treatment that can be phrased in terms of a single‐particle framework, ranging from simple tight‐binding descriptions to state‐of‐the‐art density functional theory treatments of the interacting system. In this perspective, we motivate the approach, discuss its theoretical foundations, explain its essential elements, overview recent extensions and applications, and present remaining challenges and opportunities.