bluuebunny/crossref_metadata_2025_split huggingface dataset:
ATRP Enhances Structural Correlations In Polymerization‐Induced Phase Separation**
Authors: Sicher Alba , Whitfield Richard , Ilavsky Jan , Saranathan Vinodkumar , Anastasaki Athina , Dufresne Eric R. 
Published: February 2023

AbstractSynthetic methods to control the structure of materials at sub‐micron scales are typically based on the self‐assembly of structural building blocks with precise size and morphology. On the other hand, many living systems can generate structure across a broad range of length scales in one step directly from macromolecules, using phase separation. Here, we introduce and control structure at the nano‐ and microscales through polymerization in the solid state, which has the unusual capability of both triggering and arresting phase separation. In particular, we show that atom transfer radical polymerization (ATRP) enables control of nucleation, growth, and stabilization of phase‐separated poly‐methylmethacrylate (PMMA) domains in a solid polystyrene (PS) matrix. ATRP yields durable nanostructures with low size dispersity and high degrees of structural correlations. Furthermore, we demonstrate that the length scale of these materials is controlled by the synthesis parameters.
Substrate‐Bound Diarylethene‐Based Anisotropic Metal–Organic Framework Films as Photoactuators with a Directed Response
Authors: Jiang Yunzhe , Liu Yidong , Grosjean Sylvain , Bon Volodymyr , Hodapp Patrick , Kanj Anemar Bruno , Kaskel Stefan , Bräse Stefan , Wöll Christof , Heinke Lars 
Published: February 2023

AbstractMolecular machines and responsive materials open a plethora of new opportunities in nanotechnology. We present an oriented crystalline array of diarylethene (DAE)‐based photoactuators, arranged in a way to yield an anisotropic response. The DAE units are assembled, together with a secondary linker, into a monolithic surface‐mounted metal–organic framework (SURMOF) film. By Infrared (IR) and UV/Vis spectroscopy as well as by synchrotron X‐ray diffraction, we show that the light‐induced extension changes of the molecular DAE linkers multiply to yield mesoscopic and anisotropic length changes. Due to the special architecture and substrate‐bonding of the SURMOF, these length changes are transferred to the macroscopic scale, leading to the bending of a cantilever and performing work. This research shows the potential of assembling light‐powered molecules into SURMOFs to yield photoactuators with a directed response, presenting a path to advanced actuators.
Hydride‐containing 2‐Electron Pd/Cu Superatoms as Catalysts for Efficient Electrochemical Hydrogen Evolution
Authors: Brocha Silalahi Rhone P. , Jo Yongsung , Liao Jian‐Hong , Chiu Tzu‐Hao , Park Eunsaem , Choi Woojun , Liang Hao , Kahlal Samia , Saillard Jean‐Yves , Lee Dongil , Liu C. W. 
Published: February 2023

AbstractThe first hydride‐containing 2‐electron palladium/copper alloys, [PdHCu11{S2P(OiPr)2}6(C≡CPh)4] (PdHCu11) and [PdHCu12{S2P(OiPr)2}5{S2PO(OiPr)} (C≡CPh)4] (PdHCu12), are synthesized from the reaction of [PdH2Cu14{S2P(OiPr)2}6(C≡CPh)6] (PdH2Cu14) with trifluoroacetic acid (TFA). X‐ray diffraction reveals that the PdHCu11 and PdHCu12 kernels consist of a central PdH unit encapsulated within a vertex‐missing Cu11 cuboctahedron and complete Cu12 cuboctahedron, respectively. DFT calculations indicate that both PdHCu11 and PdHCu12 can be considered as axially‐distorted 2‐electron superatoms. PdHCu11 shows excellent HER activity, unprecedented within metal nanoclusters, with an onset potential of −0.05 V (at 10 mA cm−2), a Tafel slope of 40 mV dec−1, and consistent HER activity during 1000 cycles in 0.5 M H2SO4. Our study suggests that the accessible central Pd site is the key to HER activity and may provide guidelines for correlating catalyst structures and HER activity.
A promising low‐dielectric‐constant material with good comprehensive performance upon heating
Authors: Ma Yingyi , He Zian , Han Yuhang 
Published: February 2023

AbstractThe dielectric and other properties of low‐dielectric‐constant materials after heating are crucial to their performance and use, but rarely studied. In this article, sandwich‐type porous polyimide (PI) film in which porous structures located on both upper and lower surfaces of flat PI film was prepared through the simple, low‐cost and green microemulsion method. The porous structures were preserved after heating due to the usage of thermally stable fluorine‐contained PI (FPI) and PI as skeleton and substrate of the porous structure, respectively, but with the increase of pore size because of the removal of thermally unstable surfactant on the inner surface of the pores. More importantly, 2.89%–5.57% of reductions in the dielectric constant with the maintenance of low dielectric loss and water absorption and high mechanical strength were observed after heating. Therefore, the low dielectric properties of heated films were well preserved upon high humidity treatment. Moreover, the structure and properties of the heated films could be adjusted via controlling the parameters in the microemuslion method. These excellent properties after the high‐temperature treatment facilitate the application of the sandwich‐type porous PI film as dielectric materials in high‐temperature environment.
Circularity assessment of logistics activities for green business performance management
Authors: Berberoglu Yalcin , Kazancoglu Yigit , Sagnak Muhittin 
Published: February 2023

AbstractThe population of the world is increasing, and product demand is increasing, making a linear economy ineffective, and therefore, this situation makes the circular economy (CE) a requirement. Economic, social, and environmental factors all play a role in the CE. Also, logistics activities are critical parts of the CE. Hence, this study's goal is to create a framework for evaluating organizations' CE logistics performance. The main contribution of the study is the creation of a framework to assess the circularity performance, including various logistics activities, and measure the performance of logistics activities. To establish a list of criteria, 30 experts were interviewed. The criteria were ranked using fuzzy statements. The selected multi‐criteria decision‐making (MCDM) method, data envelopment analysis, is applied using IBM ILOG CPLEX Optimization Studio version 20.1.0.
Virtual scene generation promotes shadow puppet art conservation
Authors: Liang Hui , Dong Xiaohang , Pan Junjun , Zheng Xiangyu 
Published: February 2023

AbstractAs an ancient performing art, shadow puppetry is a treasure of Chinese art. However, with the development of society, shadow puppetry becomes less well‐known among the young generation. To preserve and further spread this traditional culture, the digitization of shadow puppets is playing an increasingly important role in shadow puppetry conservation. Despite this, the spread of shadow puppetry culture in modern times still faces many hindrances. In digitalized shadow puppet art, the virtual scenes in certain degree determine the artistic effect of shadow puppet performance. The commonly used method for digital shadow puppet scene construction is via artificially created models which are then placed in corresponding positions. Obviously, this is a cumbersome and time‐consuming task. Therefore, a semantic‐based scene generation method for digital shadow puppet performance scene is proposed in this paper. According to this method, the key information is extracted from the descriptive text using the Chinese text segmentation technology. Meanwhile, we generate semantic scene graphs and search the corresponding shadow puppet models in the model library to construct the virtual scenes of digital shadow puppet performance. In the evaluation experiment, we invited 30 volunteers (10 female and 20 male) who had been exposed to traditional shadow puppet play in their daily lives. As suggested by the experimental results, the digital shadow puppet performance scene generated in this paper exhibit advantages of convenient use and high availability, which largely enhance the effect of digital shadow puppet performance. It should nonetheless be noted that it's not easy to extract the spatial relations from complicated texts, which inevitably limits the effectiveness of our scene generation method. The research work of this paper aims to promote digital shadow puppet technology and provide insights for the inheritance and conservation of traditional shadow puppet art.
A Detailed View on Geosmin Biosynthesis
Authors: Xu Houchao , Dickschat Jeroen S. 
Published: February 2023

AbstractThe bacterial geosmin synthase is a fascinating bifunctional enzyme that has been discovered almost two decades ago. Several aspects of the cyclisation mechanism from FPP to geosmin are known, but a detailed picture of the stereochemical course of this reaction is unknown. This article reports on a deep investigation of the mechanism of geosmin synthase through isotopic labelling experiments. Furthermore, the effects of divalent cations on geosmin synthase catalysis were investigated. The addition of cyclodextrin to enzymatic reactions, a molecule that can capture terpenes, suggests that the biosynthetic intermediate (1(10)E,5E)‐germacradien‐11‐ol produced by the N‐terminal domain is passed to the C‐terminal domain not through a tunnel, but rather through release into the medium and uptake by the C‐terminal domain.
Organophotocatalytic Mechanisms: Simplicity or Naïvety? Diverting Reactive Pathways by Modifications of Catalyst Structure, Redox States and Substrate Preassemblies
Authors: Mandigma Mark John P. , Kaur Jaspreet , Barham Joshua P. 
Published: February 2023

AbstractPhotocatalysis is a powerful tool to assemble diverse chemical scaffolds, yet a bottleneck on its further development is the understanding of the multitude of possible pathways when practitioners rely only on oversimplified thermodynamic and optical factors. Recently, there is a growing number of studies in the field that exploit, inter alia, kinetic parameters and organophotocatalysts that are synthetically more programmable in terms of their redox states and opportunities for aggregation with a target substrate. Non‐covalent interactions play a key role that enables access to a new generation of reactivities such as those of open‐shell organophotocatalysts. In this review, we discuss how targeted structural and redox modifications influence the organophotocatalytic mechanisms together with their underlying principles. We also highlight the benefits of strategies such as preassembly and static quenching that overcome common reactivity issues (e. g., diffusion rate limits and energetic limits).
Calcium‐Modified PtSn/Al2O3 Catalyst for Propane Dehydrogenation with High Activity and Stability
Authors: Gao Xin‐Qian , Yao Zi‐Hao , Li Wen‐Cui , Deng Gao‐Ming , He Lei , Si Rui , Wang Jian‐Guo , Lu An‐Hui 
Published: February 2023

AbstractCatalytic dehydrogenation of propane to propylene and by‐product hydrogen is an atom‐economical and environmentally friendly route. PtSn/Al2O3 catalysts have been industrialized in this process, but still suffer from platinum sintering and coke deposition under reaction conditions. Herein, we design a calcium‐modified PtSn/Al2O3 catalyst showing a superior propane dehydrogenation performance. The presence of calcium combined with unsaturated aluminum and tin could consist of a new local microenvironment that promotes the dispersion of the platinum species and increases the electron density of the platinum species, which improves the catalytic activity, facilitates propylene desorption and inhibits coke formation. As a result, the achieved PtSnCa/Al2O3 catalyst exhibits a higher propylene formation rate and a lower coke‐accumulation rate compared to the catalyst without Ca addition. Moreover, the size of active phase clusters (∼1 nm) remained almost unchanged after the catalytic test, indicating a superior sintering resistance.
Characterization of Fragile X Mental Retardation Protein expression in human nociceptors and their axonal projections to the spinal dorsal horn
Authors: Mitchell Molly E. , Cook Lauren C. , Shiers Stephanie , Tavares‐Ferreira Diana , Akopian Armen N. , Dussor Gregory , Price Theodore J. 
Published: February 2023

AbstractFragile X Mental Retardation Protein (FMRP) regulates activity‐dependent RNA localization and local translation to modulate synaptic plasticity throughout the central nervous system. Mutations in the FMR1 gene that hinder or ablate FMRP function cause Fragile X Syndrome (FXS), a disorder associated with sensory processing dysfunction. FXS premutations are associated with increased FMRP expression and neurological impairments including sex dimorphic presentations of chronic pain. In mice, FMRP ablation causes dysregulated dorsal root ganglion (DRG) neuron excitability and synaptic vesicle exocytosis, spinal circuit activity, and decreased translation‐dependent nociceptive sensitization. Activity‐dependent, local translation is a key mechanism for enhancing primary nociceptor excitability that promotes pain in animals and humans. These works indicate that FMRP likely regulates nociception and pain at the level of the primary nociceptor or spinal cord. Therefore, we sought to better understand FMRP expression in the human DRG and spinal cord using immunostaining in organ donor tissues. We find that FMRP is highly expressed in DRG and spinal neuron subsets with substantia gelatinosa exhibiting the most abundant immunoreactivity in spinal synaptic fields. Here, it is expressed in nociceptor axons. FMRP puncta colocalized with Nav1.7 and TRPV1 receptor signals suggesting a pool of axoplasmic FMRP localizes to plasma membrane‐associated loci in these branches. Interestingly, FMRP puncta exhibited notable colocalization with calcitonin gene‐related peptide (CGRP) immunoreactivity selectively in female spinal cord. Our results support a regulatory role for FMRP in human nociceptor axons of the dorsal horn and implicate it in the sex dimorphic actions of CGRP signaling in nociceptive sensitization and chronic pain.
Development of urban underground space in coastal cities in China: A review
Authors: Yu Peng , Liu Honghua , Wang Zhongsheng , Fu Jiani , Zhang Hui , Wang Jia , Yang Qi 
Published: February 2023

AbstractThe development of urban underground space is a critical way to alleviate the lack of urban resources, and improve environmental conditions as well as residents' quality of life, which has important practical significance. As the most densely populated and economically developed areas, coastal cities face many challenges in underground space development owing to their unique environmental geological conditions. This study examined the current situation of underground space development, academic research, technology application, evaluation methods, planning, and legislation in coastal cities in China. On this basis, it analyzed the future development trends, and presented reasonable suggestions for the critical scientific and technical problems faced by the development of underground space in coastal cities. The key suggestions are as follows: it is necessary to define and clarify the critical geological issues, distributions, and hazards that affect underground space development and major engineering construction in coastal cities; the land‐sea integrated detection technology for sea crossing bridges and submarine tunnels needs to be studied; in evaluating the suitability of underground space in coastal cities, the land and sea area evaluation factors should be integrated; and the evaluation system of land‐sea integration needs to be established.
Can polycentric governance lower industrial greenhouse gas emissions: Evidence from the United States
Authors: Daley Dorothy M. , Abel Troy D. , Stephan Mark , Rai Saatvika , Rogers Ellen 
Published: February 2023

AbstractThe governance challenges embedded in climate change are daunting. Conventional logic holds that national and international action is necessary. While the United States is a major source of Greenhouse Gas (GHG) emissions – second only to China – national action on climate change has been lacking. However, hundreds of subnational US governments and thousands of industrial facilities are actively engaged in addressing climate change. Given the potential mismatch between the global nature of the problem and the policy reach of subnational governments, we evaluate the extent to which polycentric variation in subnational climate action is associated with changes in GHG emissions. We develop a unique data set that incudes facility‐level GHG emissions from major industrial sectors in the United States over 8 years and subnational climate governance action across all 50 states. This large‐N data set allows us to systematically test hypothesis from polycentric governance. This type of comparative analysis can help to better understand the conditions under which polycentric governance is associated with improved climate change outcomes, that is, declining GHG emissions. Our results suggest that even when controlling for past emissions, some elements of polycentric governance are associated with decreases in GHG emissions. Future research would benefit from augmenting the large N comparative analysis presented here with mixed methods research to more fully understand the dynamic processes shaping both climate policy and GHG emissions.
Statistical characterization of erosion and sediment transport mechanics in shallow tidal environments. Part 1: erosion dynamics
Authors: D'Alpaos Andrea , Tognin Davide , Tommasini Laura , D'Alpaos Luigi , Rinaldo Andrea , Carniello Luca 
Published: February 2023

Wave-induced bottom shear stress is one of the leading processes that
control sediment erosion dynamics in shallow tidal environments, because
it is responsible for sediment resuspension and, jointly with tidal
currents, for sediment reworking on tidal flats. Reliable descriptions
of erosion events are foundational to effective frameworks relevant to
the fate of tidal landscape evolution. However, the absence of
long-term, measured time series of bottom shear stress (BSS) prevents a
direct analysis of erosion dynamics. Here we adopted a fully-coupled,
bi-dimensional numerical model to compute BSS generated by both tidal
currents and wind waves in six historical configurations of the Venice
Lagoon in the last four centuries. The one-year-long time series of the
total BSS were analyzed based on the peak-over-threshold theory to
statistically characterize events that exceed a given erosion threshold
and investigate the effects of morphological modifications on spatial
and temporal erosion patterns. Our analysis suggests that erosion events
can be modeled as a marked Poisson process in the intertidal flats for
all the considered configurations of the Venice Lagoon, because
interarrival times, durations and intensities of the over-threshold
exceedances are well described by exponentially distributed random
variables. Moreover, while the intensity and duration of over-threshold
events are temporally correlated, almost no correlation exists between
them and interarrival times. The resulting statistical characterization
allows for a straightforward computation of morphological indicators,
such as erosion work, and paves the way to a novel synthetic, yet
reliable, approach for long-term morphodynamic modeling of tidal
environments.
Bioaccumulation Kinetics of Model Pharmaceuticals in the Freshwater Unionid Pondmussel, Sagittunio subrostratus
Authors: Burket S. Rebekah , Sims Jaylen L. , Dorman Rebecca , Kemble Nile , Brunson Eric , Steevens Jeffery A. , Brooks Bryan W. 
Published: February 2023

Abstract
Bioaccumulation of ionizable pharmaceuticals has been increasingly studied, with most reported aquatic tissue concentrations in field or laboratory experiments being from fish. However, higher levels of antidepressants have been observed in bivalves compared with fish from effluent-dominated and dependent surface waters. Such observations may be important for biodiversity because approximately 70% of freshwater bivalves in North America are considered to be vulnerable to extinction. Because experimental bioaccumulation information for freshwater bivalves is lacking, we examined accumulation dynamics in the freshwater pondmussel, Sagittunio subrostratus, following exposure to a model weak acid, acetaminophen (mean (±SD) = 4.9 ± 1 µg L–1), and a model weak base, sertraline (mean (±SD) = 1.1 ± 1.1 µg L–1) during 14-day uptake and 7-day depuration experiments. Pharmaceutical concentrations were analyzed in water and tissue using isotope dilution liquid chromatography–tandem mass spectrometry. Mussels accumulated two orders of magnitude higher concentrations of sertraline (31.7 ± 9.4 µg g–1) compared to acetaminophen (0.3 ± 0.1 µg g–1). Ratio and kinetic-based bioaccumulation factors of 28,836.4 (L kg–1) and 34.9 (L kg–1) were calculated for sertraline and for acetaminophen at 65.3 (L kg–1) and 0.13 (L kg–1), respectively. However, after 14 days sertraline did not reach steady-state concentrations, although it was readily eliminated by S. subrostratus. Acetaminophen rapidly reached steady-state conditions but was not depurated over a 7-day period. Future bioaccumulation studies of ionizable pharmaceuticals in freshwater bivalves appear warranted. Environ Toxicol Chem 2023;42:1183–1189. © 2023 SETAC. This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.
Mixed Germania‐Silica Films on Ru(0001): A Combined Experimental and Theoretical Study
Authors: Fuhrich Alexander , Paier Joachim , Tosoni Sergio , Leandro Lewandowski Adrián , Gura Leonard , Schneider Wolf‐Dieter , Pacchioni Gianfranco , Freund Hans‐Joachim 
Published: February 2023

AbstractTwo‐dimensional oxide films are potentially useful for future technological applications, but also important objects to study model catalyst systems on the more fundamental side. Here we study silica, germania, and mixed silica‐germania films supported on a metal single crystal surface Ru(0001). Those mixed films are interesting objects to systematically modify the properties of silica films, which may be used as membranes or covers for model studies in confined space, due to the modification of the rather stiff silica layers by incorporating germanium atoms replacing silicon atoms. Here we report a combined experimental and theoretical study of such layers, where we show how X‐ray photoelectron spectroscopy in combination with LEED and I/V LEEM measurements allow us to judge the formation of such mixed films.
Optimal design of a periodic‐move sprinkler irrigation system considering pump characteristics
Authors: Sithole Thandokuhle Nkululeko , Singh Rajesh P. , Mahar Pooran S. 
Published: February 2023

AbstractAn optimisation model is developed for designing a single‐ and two‐pipe size periodic‐move sprinkler lateral for various values of uniform upward and downward slopes. Two layouts are considered, and the optimisation model maximizes the length of the main line subject to a minimum desirable pump efficiency and an allowable pressure variation without throttling the pump at the lateral inlet. The step‐by‐step approach is used for computing the frictional head loss of the pipelines for analysis of sprinkler pressure heads. The head‐discharge characteristics of sprinkler heads, the pipe characteristics of the lateral and main lines and the pump characteristics are matched to determine the optimal diameter and length of the main line and diameter of the lateral line. The applicability of the optimisation models are illustrated by solving standard design problems using LINGO 18.0. Larger pipe diameters for single‐ and two‐pipe size laterals resulted in an increase in the length of the main line and, subsequently, the area. The developed optimisation model can be used for designing the periodic‐move sprinkler irrigation system for any given field and farmers conditions according to field shape, topography of the land and availability of sprinkler components, pipe sizes and pumps.