bluuebunny/crossref_metadata_2025_split huggingface dataset:
Distinct Bimetallic Cooperativity Among Water Reduction Catalysts Containing [CoIIICoIII], [NiIINiII], and [ZnIIZnII] Cores
Authors: Morgan Fredricka , Schaugaard Richard , Anderson Dennis , Schlegel H. Bernhard , Verani Cláudio N. 
Published: February 2022

AbstractThree binuclear species [LCoIII2(μ‐Pz)2](ClO4)3 (1), [LNiII2(CH3OH)2Cl2]ClO4 (2), and [LZnII2Cl2]PF6 (3) supported by the deprotonated form of the ligand 2,6‐bis[bis(2‐pyridylmethyl) amino‐methyl]‐4‐methylphenol were synthesized, structurally characterized as solids and in solution, and had their electrochemical and spectroscopic behavior established. Species 1–3 had their water reduction ability studied aiming to interrogate the possible cooperative catalytic activity between two neighboring metal centers. Species 1 and 2 reduced H2O to H2 effectively at an applied potential of −1.6 VAg/AgCl, yielding turnover numbers of 2,820 and 2,290, respectively, after 30 minutes. Species 3 lacked activity and was used as a negative control to eliminate the possibility of ligand‐based catalysis. Pre‐ and post‐catalytic data gave evidence of the molecular nature of the process within the timeframe of the experiments. Species 1 showed structural, rather than electronic cooperativity, while species 2 displayed no obvious cooperativity. DFT methods complemented the experimental results determining plausible mechanisms.
Wavelength Orthogonal Photodynamic Networks
Authors: Truong Vinh X. , Ehrmann Katharina , Seifermann Maximilian , Levkin Pavel A. , Barner‐Kowollik Christopher 
Published: February 2022

AbstractThe ability of light to remotely control the properties of soft matter materials in a dynamic fashion has fascinated material scientists and photochemists for decades. However, only recently has our ability to map photochemical reactivity in a finely wavelength resolved fashion allowed for different colors of light to independently control the material properties of polymer networks with high precision, driven by monochromatic irradiation enabling orthogonal reaction control. The current concept article highlights the progress in visible light‐induced photochemistry and explores how it has enabled the design of polymer networks with dynamically adjustable properties. We will explore current applications ranging from dynamic hydrogel design to the light‐driven adaptation of 3D printed structures on the macro‐ and micro‐scale. While the alternation of mechanical properties via remote control is largely reality for soft matter materials, we herein propose the next frontiers for adaptive properties, including remote switching between conductive and non‐conductive properties, hydrophobic and hydrophilic surfaces, fluorescent or non‐fluorescent, and cell adhesive vs. cell repellent properties.
Synthesis of Intramolecular P/Al‐Based Frustrated Lewis Pairs via Aluminum‐Tin‐Exchange and their Reactivity toward CO2
Authors: Federmann Patrick , Müller Robert , Beckmann Fabian , Lau Caroline , Cula Beatrice , Kaupp Martin , Limberg Christian 
Published: February 2022

AbstractFrustrated Lewis pairs (FLPs) composed of acidic alane and basic phosphane functions, separated by a xanthene linker, can be prepared through the corresponding Me3Sn derivative and methyl aluminum compounds with elimination of Me4Sn. This way MeClAl‐, Cl2Al‐ and (C6F5)2Al‐ moieties could be introduced and the resulting FLPs are stabilized by a further equivalent of the alane precursors. In contact with the FLPs CO2 is bound via the C atom at the phosphane functions and the two O atoms at the Al centers. The residues at the latter determine the binding strength. Hence, in case of MeClAl CO2 capture occurs at higher pressure and under ambient conditions CO2 is released again, while for Cl2Al and (C6F5)2Al CO2 binding becomes irreversible. The results of DFT calculations rationalize these findings by the high thermodynamic stabilization in case of more electronegative residues, which concomitantly lead to higher barriers, and in case of (C6F5)2Al further stabilization is achieved through a low reorganization energy.
Dealing with the devil: Combined effects of destructive leadership and Dark Triad personality on revenge, happiness and psychological detachment
Authors: Syed Fauzia , Naseer Saima , Shamim Fatima 
Published: February 2022

AbstractUtilizing the cognitive appraisal theory of stress and coping, we examined the combined effects of destructive leadership and Dark Triad personality on revenge and employee outcomes (happiness and psychological detachment). Adopting a time‐lagged research design (three time lags), we collected data from 288 employees from the service sector in Pakistan. Using Process technique, our findings showed that revenge mediated the destructive leadership and outcomes relationship. We also found that the impact of destructive leadership on revenge was more substantial for individuals having high Dark Triad personality. The results supported our moderated mediation hypothesis, proving that revenge mediates the relationship between destructive leadership and outcomes for individuals with a high Dark Triad Personality.
A hybrid machine learning approach integrating recurrent neural networks with subspace identification for modelling HVAC systems
Authors: Hassanpour Hesam , Mhaskar Prashant , Risbeck Michael J. 
Published: February 2022

AbstractThis paper addresses the problem of system identification for heating, ventilation, and air conditioning (HVAC) systems using a relatively small amount of data for the zone under consideration, by leveraging larger datasets for similar zones. To this end, a hybrid machine learning approach is developed where a pre‐trained recurrent neural network (RNN) model, trained on a large amount of data from a representative zone, is leveraged to build models for the other zones using a smaller amount of data. This is achieved by developing a hybrid model that integrates the pre‐trained RNN model with the models built using the subspace identification (SubID) technique to predict the residuals (differences between the real outputs and the predicted outputs from the pre‐trained RNN model) in the other zones. The effectiveness of the proposed hybrid approach is shown using real data collected from a multi‐zone fitness centre. The results demonstrate the superior performance of the hybrid approach over the cases where individual RNN and SubID models are directly developed using only the data from the zones in question.
Development of Novel Phosphino‐Oxazoline Ligands and Their Application in Asymmetric Alkynlylation of Benzylic Halides
Authors: Guo Rui , Sang Jiale , Xiao Haijing , Li Junxia , Zhang Guozhu 
Published: February 2022

Comprehensive SummaryA new set of stereochemically diverse phosphino‐oxazoline ligands derived from simple L‐amino acids and 2‐(diphenylphosphaneyl)benzoic acid were developed. Those mono anionic tridentated N,N,P‐ligands promote the Cu‐catalyzed enantioselective radical coupling of terminal alkynes with a broad range of benzylic halides including benzo‐fused cyclic α‐halides and α‐silyl benzyl halides in high yield and excellent enantioselectivity under mild reaction conditions. With multi distinct sites for structural modification, a diverse pool of chiral N,N,P‐ligands is readily accessed, allowing for rapid optimization of the ligand structure for a specific substrate. Notably, the enantioselective alkynlylation of benzylic halides bonds in benzo‐cyclic molecules has also been realized for the first time.
Visual insights into the essence of homogeneous catalysis
Authors: Lüke Dennis , Oetken Marco 
Published: February 2022

AbstractFür die schulische Auseinandersetzung mit dem Themenfeld der Katalyse stehen Lehrkräften zahlreiche Modellexperimente zur Verfügung, die vornehmlich energetische Aspekte dieses Reaktionstyps in den Blick nehmen. Doch gerade im Anfangsunterricht des Faches Chemie scheint es didaktisch sinnvoll zu sein, auch phänomenologische Zugänge zum Reaktionsweg der Katalyse zu schaffen, da dieser als Ursache herabgesetzter Aktivierungsenergien gilt. Mit dem Spurenelement Molybdän als Katalysator lassen sich Zwischenverbindungen der Katalyse visuell identifizieren, sicher isolieren und auch im Schüler:innenversuch experimentell handhaben.
Complex pBAE Nanoparticle Cell Trafficking: Tracking Both Position and Composition Using Super Resolution Microscopy
Authors: Riera Roger , Tauler Jana , Feiner‐Gracia Natàlia , Borrós Salvador , Fornaguera Cristina , Albertazzi Lorenzo 
Published: February 2022

AbstractNanomedicine emerged some decades ago with the hope to be the solution for most unmet medical needs. However, tracking materials at nanoscale is challenging to their reduced size, below the resolution limit of most conventional techniques. In this context, we propose the use of direct stochastic optical reconstruction microscopy (dSTORM) to study time stability and cell trafficking after transfection of oligopeptide end‐modified poly(β‐aminoester) (OM‐pBAE) nanoparticles. We selected different combinations of cationic end oligopeptides (arginine – R; histidine – H; and lysine – K) among polymer libraries, since the oligopeptide combination demonstrated to be useful for different applications, such as vaccination and gene silencing. We demonstrate that their time evolution as well as their cell uptake and trafficking are dependent on the oligopeptide. This study opens the pave to broad mechanistic studies at nanoscale that could enable a rational selection of specific pBAE nanoparticles composition after determining their stability and cell trafficking.
Longitudinal stability of Social Cognition and Object Relations Scale—Global Rating Method dimensional ratings, score ranges and narrative ‘blandness’ in a clinical sample
Authors: Ridenour Jeremy M. , Lewis Katie C. , Siefert Caleb J. , Stein Michelle B 
Published: February 2022

AbstractWhile understanding how internalized representations of others (i.e., object relations) change over the course of treatment is essential for treatment planning and evaluation of progress, few studies have examined the nature of these changes through repeated psychological assessments. In this study, we applied the SCORS‐G to Thematic Apperception Test narratives for 61 adult patients with complex psychiatric problems undergoing residential treatment over an 18‐month period. Over the course of treatment, patient representations of self and others became more complex, indicating improvements in mentalization. Further, an analysis of default ratings (i.e., an aspect of story ‘blandness’) suggested that certain shifts in SCORS‐G dimensional scores over time were accounted for by greater degree of scorable content across time points, rather than changes specific to the dimensions themselves. Findings from novel exploratory analyses aimed at evaluating the test–retest reliability of both default rating proportion and several emerging alternative scoring approaches (including changes in minimum, maximum and range of scores on individual dimensions) are reported. While the magnitude of change across mean dimensional scores was found to be lower compared to those previously found in outpatient populations, our results suggest that the SCORS‐G remains capable of detecting changes in mentalization capacities in individuals contending with longstanding, severe psychiatric impairment and personality‐based psychopathology. Implications for treatment, assessment and future research are discussed.
How to Obtain High‐Quality Metaphase Spreads for Molecular Cytogenetics
Authors: Liehr Thomas , Weise Anja , Person Luisa , Padutsch Niklas , Kankel Stefanie 
Published: February 2022

AbstractInterphase or metaphase nuclei can be accessed in molecular cytogenetic analyses. Metaphase spreads are routinely studied by fluorescence in situ hybridization (FISH) to answer clinical genetic questions. Even though metaphase quality is essential for FISH studies, there is limited ability in clinical cases to improve the quality of cytogenetic preparations. However, the quality of preps is important for the exact localization of FISH signals, which is necessary to identify individual chromosomes and chromosomal sub‐regions using inverted DAPI banding. Here we present an efficient and easy‐to‐perform variant of standard slide pretreatment before a normal FISH procedure. This method reproducibly leads to solid, “steel,” nonfuzzy, and well‐DAPI‐banded metaphases. This protocol works in blood lymphocyte and amniotic fluid‐derived fibroblasts. © 2022 The Authors. Current Protocols published by Wiley Periodicals LLC.Basic Protocol: Slide pretreatment for high‐quality metaphases for molecular cytogenetics.
Flow cytometric immunophenotyping of plasma cells across the spectrum of plasma cell proliferative disorders: A fresh insight with pattern‐based recognition
Authors: Das Nupur , Dahiya Meetu , Gupta Ritu , Rai Sandeep , Singh Saroj , Prajapati Vijay K. , Kumar Lalit , Sharma Atul , Sahoo Ranjit K. , Gogia Ajay 
Published: February 2022

AbstractBackgroundThe expression pattern of common antigens including cytoplasmic kappa/lambda ratio (cyKLR) was evaluated by flow cytometric immunophenotyping (FCMI) to explore their relevance in discriminating normal and aberrant plasma cells (NPC and APC, respectively) across spectrum of plasma cell proliferative disorders (PCPD).MethodsIn this prospective analysis, 791 samples from PCPD (treatment naive = 455; partially treated = 336) were evaluated for expression of CD38, CD138, CD45, CD19, CD56, CD27, CD81, CD117, Cy‐kappa, and Cy‐lambda using FCMI.ResultsAmongst the entire cohort, 20.7% (n = 164) samples displayed only APC, 21% (n = 165) only NPC and 58% (n = 462) showed coexistence of NPC and APC. Using pattern‐based recognition (PBR) for three common patterns (CD19 vs. CD56; CD27 vs. CD56 and CD19 vs. CD27), APC was separable from NPC in 93% samples. In 6.5% samples, the gating markers contributed in APC–NPC differentiation and in the remaining 0.5% CD117 and CD81 proved useful. Clonality assessment was found to be crucial to label plasma cell compartment as completely normal or aberrant in 42% cases with either all NPC or all APC. Sixty one out of 462 cases (13%) revealed cyKLR within normal reference range and in these cases; abnormal cyKLR was demonstrable only after gating APC separately based on PBR.ConclusionFair discrimination between NPC and APC is achievable in all PCPD samples using eight markers (Gating: CD38, CD138, CD45; PBR:CD19, CD56, CD27; clonality: Cy‐kappa and Cy‐lambda). Thus, combined assessment of clonality and immunophenotypic aberrancies is required for accurate, reliable and precise assessment of NPC and APC compartments in PCPD.
A hybrid Harrison Hawk optimization based on differential evolution for the node localization problem in IoT networks
Authors: Baidar Lotfi , Rahmoun Abdellatif , Mihoubi Miloud , Lorenz Pascal , Birogul Serdar 
Published: February 2022

SummaryDespite the close of a tumultuous 2020 and the start of 2021, connected devices will continue to shape the future of numerous industries, and businesses are confident that the Internet of Things (IoT) will play a key role in the future success of their trade. The growing Internet of Things (IoT) is connecting devices to a variety of sensors, applications, and other IoT elements to automate business processes and support human efficiencies in business and the home. WSN along with node localization algorithms can play a critical role in IoT applications. Nevertheless, in IoT applications, the context of real‐time location‐based services is gaining an overwhelming interest. To do this, several approaches are proposed in the recent literature based mainly on computational intelligence algorithms. This paper proposes a node localization algorithm based on swarm intelligence algorithms, that is, a hybrid Harris Hawks optimization based on differential evolution (HHODE).HHODE algorithm relies on Euclidian Distance as objective function to evaluate best‐fit coordinates of sensor nodes in a wireless sensor network. Moreover, several experimentations are performed depending on the network size, communication range of sensors, geographical distribution, and the beacon nodes' density to demonstrate the efficiency of the HHODE algorithm. Compared to Standard DE, HOO, PSO, and Bat Algorithm, HHODE shows higher performance with regard to node localization.
Isotope hydrology to provide insights into the behaviour of temporary wetlands as a basis for developing sustainable ecohydrological management strategies in Mediterranean regions
Authors: Mattei Alexandra , Huneau Frédéric , Garel Emilie , Sorba Laurent , Orsini Sophie , Santoni Sébastien 
Published: February 2022

AbstractThe lack of hydrological considerations in the existing protection statutes for small temporary wetlands has recently been pointed out as the main cause of their rapidly increasing disappearance. In the present study, we aim to demonstrate the interest of using the tools of isotope hydrology to obtain a rapid and cost effective understanding of the hydrological connectivity of Mediterranean temporary wetlands in order to define the optimal environmental conditions needed to ensure their sustainability. By combining physical and isotope measurements, we have investigated the fragile balance of direct precipitation, subsurface water and groundwater influencing the hydroperiod of a typical Mediterranean temporary pond. The use of the water stable isotopes enabled us to demonstrate (i) the major role played by groundwater and subsurface water in the flooding phase of the temporary pond; (ii) the involvement of different water reservoirs in varying proportions over time to maintain the pond filled with water: precipitation, subsurface and groundwater by using d‐excess; (iii) the main role played by evaporation in starting the drying up phase; and (iv) the connection existing between a geographically isolated wetland and the regional groundwater body. These results highlight the urgent need to consider both surface and groundwater fluxes in specific protection statutes for wetlands. To this end, we recommend the use of the water stable isotopes to provide insights into the hydrological behaviour of the wetlands in order to dispose of additional cost‐effective arbitration arguments to help ensure their sustainability. The lack of hydrological considerations in existing protection statutes for small temporary wetlands has recently been pointed out as the main cause of their disappearance. Here, by combining physical and isotopes measurements, we first highlight the main role played by groundwater in the flooding phase of the temporary pond and the involvement of different water reservoirs in varying proportions over time to maintain the pond filled. These results demonstrate the connection existing between a geographically isolated wetland and the regional groundwater and highlight the urgent need to consider both surface and groundwater fluxes in specific protection statutes for wetlands.
The nuances of “the social cure” for people who experience psychosis
Authors: Hogg Lorna I. , Smith Laura G. E. , Morrison Anthony P. , Prosser Annayah M. B. , Kurz Tim 
Published: February 2022

AbstractPeople can derive health benefits from social group memberships. However, joining groups can be difficult for people experiencing psychosis due to the social impacts of the condition and public and internalised stigma. We interviewed a diverse group of 26 people experiencing psychosis and explored through thematic analysis their perceptions of how psychosis influenced social identity processes. Participants confirmed both the impact of psychosis on group processes and the value of group memberships for wellbeing. Empathy, understanding, and lack of judgement were perceived to be critical for group formation. Participants sought social validation in both pre‐existing and new relationships, including from others experiencing psychosis. A novel finding was the compartmentalising of the psychosis identity to facilitate periods of either greater connection or social mobility dependent on current mental state. Thus, this study suggests nuance to the application of the Social Cure for a highly stigmatised, yet fluctuating, condition such as psychosis.
What does implementing case‐centered teaching of evaluation look like in practice?
Authors: Kallemeyn Leanne M. , Roseveare Christine , Steinberg Marla , Tovey Tiffany L. S. 
Published: February 2022

AbstractRooted in the pedagogical literature, three evaluation educators, guided by a facilitator, engaged in reflective practice regarding case‐centered teaching and learning. We engaged in (D)escription, (A)nalysis, (T)heorizing, and (A)cting (DATA model) in relation to case‐centered teaching. Based on a cross‐case analysis, we identified five common actions in our teaching with cases: (1) Use case‐centered teaching in various contexts to support a variety of different learning outcomes for students from different backgrounds; (2) Choose cases intentionally; (3) Integrate student learning activities, supports, and materials; (4) Evaluate students’ learning experiences with cases; and (5) Engage in collaborative reflection to facilitate learning and improvement on instructional practices with case‐centered teaching.
Recent trends in fluorescent aptasensors for mycotoxin detection in food: Principles, constituted elements, types, and applications
Authors: Yan Xiaohai , Chen Hong , Du Gengan , Guo Qi , Yuan Yahong , Yue Tianli 
Published: February 2022

AbstractMycotoxins are the secondary metabolites of fungi in food and can be toxic to people. Therefore, developing simple, sensitive, and specific detection methods to detect mycotoxins in food is essential for ensuring food safety. Fluorescent aptasensors for the detection of mycotoxins in food have developed rapidly. They are simple and fast with high affinity and specificity. However, fluorescent aptasensors have not yet been applied in officially approved standards so far. This review elucidates fluorescent aptasensors for mycotoxin detection, including principles, constituted elements, types, and applications. Screening results of aptamers and each aptamer sequence used in fluorescent aptasensors are summarized to facilitate further research for later studies. We also focused on fluorescent probes, nanomaterials, and other strategies in the process of constructing fluorescent aptasensors. We then discuss current challenges and future perspectives in fluorescent aptasensors for mycotoxin detection.
Survival and disease progression following solitary locoregional recurrence after head and neck radiotherapy
Authors: Zhao Lucian , Day Andrew T. , Moon Dominic , Avkshtol Vladimir , Sumer Baran D. , Hughes Randall , Sher David J. 
Published: February 2022

AbstractPurposeThe management of solitary locoregional recurrence (sLRR) of head and neck squamous cell carcinoma (HNSCC) previously treated with radiotherapy (RT) is challenging. We aimed to identify characteristics associated with improved outcome.MethodsWe identified patients treated with non‐sinus, mucosal HNSCC who initially received IMRT. We characterized overall survival (OS) and locoregional control (LRC). Multivariable analysis (MVA) on survival and patterns‐of‐failure were performed using Cox and Fine‐Gray competing risks analysis.ResultsWe identified 90 patients with available follow‐up. In total, 67 (74%) patients received curative‐intent salvage, while 23 (26%) received palliative care. On MVA, significantly improved OS and LRC were associated with lower initial N‐classification and use of salvage total laryngectomy (TL) or neck dissection (ND).ConclusionA nontrivial number of patients with sLRR cannot undergo salvage. Among patients treated with curative intent, TL or ND were clearly associated with improved OS and LRC.