bluuebunny/crossref_metadata_2025_split huggingface dataset:
Thermal Paper and Time Temperature Integrators Made From a Structural Colored Polymer Crosslinked With Hydrogen Bonded Cyclohexanoic Acid Derivatives
Authors: Foelen Yari , van der Heijden Daniëlle A. C. , Verdurmen Anne M. J. , Mulder Dirk Jan , Lub Johan , Schenning Albert P. H. J. 
Published: August 2022

AbstractHydrogen‐bonded cyclohexanoic derivatives are applied in a structural colored cholesteric liquid crystal (CLC) helical polymer that demonstrates an extraordinary dual thermal response. Integration of the dynamic hydrogen‐bonded cyclohexanoic acid derivatives in the CLC polymer as supramolecular crosslinks yields an immediate and irreversible loss of the green structural color upon exposure to temperatures above the cholesteric‐to‐isotropic transition temperature (TNI) caused by the helical order loss. Exposure to temperatures below the TNI yields a gradual irreversible red color shift of the reflected wavelength over broad temperature and time ranges. Most likely due to polymerization confinement in combination with the dynamics of the carboxylic acid hydrogen bonds, helical unwinding takes place over time causing the red shift of the reflected wavelength. The temperature response can be programmed by altering the chemical composition of the liquid crystal mixture. Furthermore, the green, structural color of the polymer can also be easily changed making it possible to print different colored indicators combined with different respective temperature responses on a single substrate. The printed optical sensors can be easily delaminated by dissolving the non‐covalent crosslinked polymer. Such optical polymer materials are attractive for easy processable time–temperature integrators and thermal paper.
MXene‐Germanium Schottky Heterostructures for Ultrafast Broadband Self‐Driven Photodetectors
Authors: Xiong Guoliang , Zhang Gang , Yang Xiaozhan , Feng Wenlin 
Published: August 2022

AbstractA novel 2D layered material Ti3C2Tx (MXene) is favored by researchers in the application field of optoelectronics due to its tunable work function, great light transmittance, and excellent electrical conductivity. In this work, Ti3C2Tx/n‐germanium (MXene/n‐Ge) Schottky heterostructures are fabricated and investigated. Schottky contacts of MXene with n‐Ge are identified by ultraviolet photoelectron spectroscopy (UPS). Based on the MXene/n‐Ge Schottky junctions, an ultrafast, broadband, and self‐powered photodetector is demonstrated and studied. The MXene/n‐Ge device exhibits excellent photoresponse from ultraviolet to near‐infrared light illumination. In particular, it shows an excellent on/off ratio (≈104), a high responsivity (3.14 A/W), a larger specific detectivity (2.14 × 1011 Jones), and an ultrafast response speed (trise of 1.4 µs and tdecay of 4.1 µs). Moreover, the MXene/n‐Ge Schottky heterostructure photodetector also shows excellent low‐temperature work characteristics of 73 K. It is believed that this work will attract more researchers’ attention to MXene in the field of optoelectronic devices.
Determinants of downside risk exposure: An analysis of Korean rice farms using partial and quantile moments
Authors: Kulkarni Kedar , Rossi David 
Published: August 2022

AbstractThe past decade has seen a resurgence in methods such as the partial and quantile moments model for measuring downside risk exposure and downside risk aversion. However, mixed conclusions are drawn regarding the identification and determinants of downside risk exposure attributable to the methodological differences in the approaches to risk estimation. In this paper, we replicate Kim et al. (2014) who perform a quantile moments‐based analysis of risk exposure. Extending the original study, we address the methodological differences in approaches to measuring downside risk with further robustness checks, including alternative estimation approaches and a comparison to the partial moments model (Antle, 2010). Our results confirm the original finding of Kim et al. (2014) that around 90% of the cost of risk is attributable to downside risk exposure. However, this estimate is highly sensitive to the specification of the estimated mean production as well as the choice of the statistical estimator. Finally, our results suggest that both the quantile moments model and the partial moments model provide similar insights on the determinants of downside risk exposure as well as the cost of risk.
Modeling of deposit formation in mesoporous substrates via atomic layer deposition: Insights from pore‐scale simulation
Authors: Gu Hao , Lee Dennis T. , Corkery Peter , Miao Yurun , Kim Jung‐Sik , Yuan Yuchen , Xu Zhen‐liang , Dai Gance , Parsons Gregory N. , Kevrekidis Ioannis G. , Zhuang Liwei , Tsapatsis Michael 
Published: August 2022

AbstractAtomic layer deposition (ALD) has been a promising technique in fabricating membranes and tuning their properties with a precision at the atomic level. Fabrication of zeolitic imidazolate framework (ZIF) membranes using the ligand‐induced permselectivation (LIPS) method starts with the formation of an oxide in a mesoporous substrate by ALD and is followed by the transformation of this oxide to ZIF using imidazolate vapor treatment. The objective of the ALD step is to block the mesopores with a thin deposit, that is, one with small penetration depth and small thickness on the top surface of the substrate. Unlike typical ALD on nonporous substrates, where all available sites react per ALD cycle, thin deposit formation in a mesoporous substrate requires that only a small fraction of the available deposition sites (i.e., close to the substrate surface) is subjected to ALD. Consequently, reactant dosing and duration of pulses are important process variables which, together with diffusion and reaction kinetics determine the deposit structure. Quantitative understanding of the interplay of these variables and phenomena can enable the rational design of ALD within mesoporous substrates. Here, we extend our earlier modeling effort considering the coexistence of ALD both inside the pores and on the external surface of the substrate. Finite‐volume based models were developed and validated to simulate the two distinct modes of deposition cycle by cycle. The total mass uptake of the substrate with ALD cycles can be predicted using the combined surface deposition and pore reaction–diffusion models as affirmed by in situ quartz crystal microbalance experimental data. The ALD reactor model combined with the deposition model can accurately capture the number of ALD cycles needed to block the pores of the substrate. Based on the model, we designed a modified ALD process and examined the performance of the corresponding LIPS membranes. The present modeling work provides a new understanding of the deposit formation via ALD within mesoporous substrates for a variety of membrane applications.
The gendered relationship between cumulative exposure to lower community attachment and adolescent health
Authors: Park Gum‐Ryeong , Kim Jinho 
Published: August 2022

AbstractThis study examines whether the longitudinal association between cumulative exposure to lower community attachment and adolescent health differs by gender. Using seven waves of the Korean Children and Youth Panel Survey spanning 2010–2016, this study examines the association between cumulative exposure to lower community attachment and self‐rated health among Korean adolescents. This study estimated fixed‐effects models to account for unobserved confounders at the individual level. Fixed‐effects estimates revealed that cumulative exposure to lower community attachment is associated with a decreased likelihood of reporting excellent health. Starting from the initial exposure, girls’ self‐rated health continued to deteriorate over time. In contrast, boys’ self‐rated health decreased for up to 3 years of persistent exposure, but has since returned to pre‐exposure levels. The association between cumulative exposure to lower levels of community attachment and a decline in self‐rated health is more pronounced among girls than boys. Gender‐specific community‐based interventions during adolescence may be required to promote adolescent health and well‐being.
Dibenzo[b,f][1,4,5]chalcogenadiazepine Photoswitches: Conversion of Excitation Energy into Ring Strain
Authors: Shen Xin , Zhang Cefei , Lan Fengying , Su Zhishan , Zheng Yuanqin , Zheng Tingting , Xiong Qin , Xie Xinyu , Du Guangxi , Zhao Xiaohu , Hu Changwei , Deng Pengchi , Yu Zhipeng 
Published: August 2022

AbstractTetra‐ortho‐substituted, heteroaryl and cyclic azobenzenes have emerged as three key strategies on morphology design of photoswitch to diversify controllability. Cyclic azobenzene is of particular utilization in photo‐energy conversion due to rigid and ring‐strain structure. Despite the well‐recognized diazocine, the photo‐switching properties of seven‐membered cyclic azobenzenes (diazepines) have yet been exploited. Herein, we report a family of dibenzo[b,f][1,4,5]chalcogenadiazepines (DBChDs) and their T‐type photo‐switching nature with tunable relaxation rate. Based on experiments together with DFT calculations, we found that an unsymmetric 2‐bithiophenyl‐dibenzo[b,f][1,4,5]thiadiazepine exhibited an efficient response to 445 nm laser stimulation (quantum efficiency, ΦZ→E=0.71) with millisecond relaxation half‐life (t1/2=40 ms). Photo‐energy transduction efficiency was also exceptionally high with 29.1 % converted into ring‐strain energy mainly loaded on azo π‐bond.
Hydrophobicity Directed Chiral Self‐Assembly and Aggregation‐Induced Emission: Diacetylene‐Cored Pseudopeptide Chiral Dopants
Authors: Maurya Govind P. , Verma Deepak , Sinha Aloka , Brunsveld Luc , Haridas V. 
Published: August 2022

AbstractHere we delineate simple and tunable hydrophobically driven chiral functional assemblies of diacetylene cored pseudopeptides. These amino acid appended, rigid core dialkynes constitute promising chiral supramolecular building blocks for materials properties engineering. The chiral appended amino acid elements allow for simple tuning of solubility and interaction properties as well as governing chirality, while the central dialkyne core can impart hydrophobically driven assembly and Aggregation Induced Emission (AIE) properties. The self‐assembly of these rod‐like dialkynes can be regulated by tuning the solvent environment, with for example self‐assembly into vesicles in acetonitrile and into helical organization with AIE in a H2O/DMSO mixture. Of additional high interest, these supramolecular materials, themselves devoid of liquid crystal (LC) properties, can induce chirality into non‐chiral LC matrices with high helical twisting power.
Decarboxylative Sulfinylation Enables a Direct, Metal‐Free Access to Sulfoxides from Carboxylic Acids
Authors: Nguyen Viet D. , Haug Graham C. , Greco Samuel G. , Trevino Ramon , Karki Guna B. , Arman Hadi D. , Larionov Oleg V. 
Published: August 2022

AbstractThe intermediate oxidation state of sulfoxides is central to the plethora of their applications in chemistry and medicine, yet it presents challenges for an efficient synthetic access, limiting the structural diversity of currently available sulfoxides. Here, we report a data‐guided development of direct decarboxylative sulfinylation that enables the previously inaccessible functional group interconversion of carboxylic acids to sulfoxides in a reaction with sulfinates. Given the broad availability of carboxylic acids and the growing synthetic potential of sulfinates, the direct decarboxylative sulfinylation is poised to improve the structural diversity of synthetically accessible sulfoxides. The reaction is facilitated by a kinetically favored sulfoxide formation from the intermediate sulfinyl sulfones, despite the strong thermodynamic preference for the sulfone formation, unveiling the previously unknown and chemoselective radicalophilic sulfinyl sulfone reactivity.
Enantioselective Total Synthesis of (−)‐Limaspermidine and (−)‐Kopsinine by a Nitroaryl Transfer Cascade Strategy
Authors: Horst Brendan , Verdoorn Daniël S. , Hennig Sven , van der Heijden Gydo , Ruijter Eelco 
Published: August 2022

AbstractWe report an intramolecular conjugate addition/Truce‐Smiles/E1cb cascade of 2‐nitrobenzenesulfonamide‐functionalized cyclohexenones as a new entry to the core scaffold of monoterpene indole alkaloids. The method was applied to the asymmetric total synthesis of (−)‐limaspermidine, (−)‐kopsinilam, and (−)‐kopsinine, as well as the framework of the kopsifoline alkaloids, thus highlighting its complementarity to existing approaches involving the use of indole‐based starting materials or the interrupted Fischer indole synthesis. Furthermore, we show that the cascade tolerates various substituents on the nitroarene, opening the way to other natural products as well as non‐natural analogues.
Using Continuous Intraoperative Pressure Mapping to Describe Patterns of Tissue Interface Pressure
Authors: Al‐Majid Sadeeka , Vuncanon Barbara , Kiyohara Melody , Rakovski Cyril 
Published: August 2022

ABSTRACTThe purpose of this study was to describe patterns of intraoperative tissue interface pressure, identify the amount of time during which the pressure at four anatomical locations exceeded 32 mm Hg, and examine associations between patient‐ and surgery‐related variables and peak tissue interface pressure. We used a pressure mapping system to measure the intraoperative tissue interface pressure of 150 patients. We implemented linear mixed‐effects models to assess trends in the mean and peak tissue interface pressure. The percentage of time during which the interface pressure exceeded 32 mm Hg at the scapulae, interscapular area, and sacral area was 70%, 70%, and 90%, respectively. Body mass index, length of surgery, and intraoperative position were major predictors of increased pressure. Understanding patterns of tissue interface pressure of patients during surgery may help perioperative nurses develop strategies to attenuate pressure and protect skin integrity.
Analysis of the Magnetic Coupling in a Mn(II)‐U(V)‐Mn(II) Single Molecule Magnet
Authors: Dey Sourav , Rajaraman Gopalan , Bolvin Hélène 
Published: August 2022

Abstract[{Mn(TPA)I}{UO2(Mesaldien)}{Mn(TPA)I}]I formula (here TPA=tris(2‐pyridylmethyl)amine and Mesaldien=N,N’‐(2‐aminomethyl)diethylenebis(salicylidene imine)) reported by Mazzanti and coworkers (Chatelain et al. Angew. Chem. Int. Ed. 2014, 53, 13434) is so far the best Single Molecule Magnet (SMM) in the {3d–5f} class of molecules exhibiting barrier height of magnetization reversal as high as 81.0 K. In this work, we have employed a combination of ab initio CAS and DFT methods to fully characterize this compound and to extract the relevant spin Hamiltonian parameters. We show that the signs of the magnetic coupling and of the g‐factors of the monomers are interconnected. The central magnetic unit [UVO2]+ is described by a Kramers Doublet (KD) with negative g‐factors, due to a large orbital contribution. The magnetic coupling for the {Mn(II)‐U(V)} pair is modeled by an anisotropic exchange Hamiltonian: all components are ferromagnetic in terms of spin moments, the parallel component JZ twice larger as the perpendicular one J⊥. The spin density distribution suggests that spin polarization on the U(V) center favors the ferromagnetic coupling. Further, the JZ/J⊥ ratio, which is related to the barrier height, was found to correlate to the corresponding spin contribution of the g‐factors of the U(V) center. This correlation established for the first time offers a direct way to estimate this important ratio from the corresponding gS‐values, which can be obtained using traditional ab initio packages and hence has a wider application to other {3d–5f} magnets. It is finally shown that the magnetization barrier height is tuned by the splitting of the [UVO2]+ 5 f orbitals.
On the Oxidative Valorization of Lignin to High‐Value Chemicals: A Critical Review of Opportunities and Challenges
Authors: Abdelaziz Omar Y. , Clemmensen Ida , Meier Sebastian , Costa Carina A. E. , Rodrigues Alírio E. , Hulteberg Christian P. , Riisager Anders 
Published: August 2022

AbstractThe efficient valorization of lignin is crucial if we are to replace current petroleum‐based feedstock and establish more sustainable and competitive lignocellulosic biorefineries. Pulp and paper mills and second‐generation biorefineries produce large quantities of low‐value technical lignin as a by‐product, which is often combusted on‐site for energy recovery. This Review focuses on the conversion of technical lignins by oxidative depolymerization employing heterogeneous catalysts. It scrutinizes the current literature describing the use of various heterogeneous catalysts in the oxidative depolymerization of lignin and includes a comparison of the methods, catalyst loadings, reaction media, and types of catalyst applied, as well as the reaction products and yields. Furthermore, current techniques for the determination of product yields and product recovery are discussed. Finally, challenges and suggestions for future approaches are outlined.
Implications of preclinical Alzheimer's disease biomarker disclosure for US policy and society
Authors: Erickson Claire M. , Clark Lindsay R. , Ketchum Fred B. , Chin Nathaniel A. , Gleason Carey E. , Largent Emily A. 
Published: August 2022

AbstractDisclosure of Alzheimer's disease (AD) biomarkers to cognitively unimpaired adults are currently conducted only in research settings. Yet, US Food and Drug Administration approval of a disease‐modifying treatment for symptomatic individuals, improved understanding of the “preclinical” phase of disease, and advancements toward more accessible biomarker tests suggest such disclosure will increase in frequency, eventually becoming routine in clinical practice. The changing landscape in AD research to focus on biomarkers has generated debate on the validity and clinical utility of disclosure to cognitively unimpaired adults. This article explores the broader social implications of more widespread AD biomarker disclosure—that is, of individuals learning their risk for developing dementia caused by AD. We identify 10 challenges and offer preliminary solutions. As the field continues to evolve, it is essential to anticipate and address these broader ethical, legal, and social implications of disclosure.
Temporal stability of productivity is associated with complementarity and competitive intensities in intercropping
Authors: Wu Jinpu , Bao Xingguo , Zhang Jiudong , Lu Binglin , Zhang Weiping , Callaway Ragan M. , Li Long 
Published: August 2022

AbstractYear‐to‐year stability in crop production is a crucial aspect of feeding a growing global population. Evidence from natural ecosystems shows that increasing plant diversity generally increases the temporal stability of productivity; however, we have little knowledge of the mechanisms by which diversity affects stability. In fact, understanding the drivers of stability is a major knowledge gap in our understanding of biodiversity and ecosystem function in general. We varied resource inputs into crop monocultures and intercropping of maize/pea and maize/rapeseed for 3 years in field experiments to create a wide range of values for temporal stability, complementarity effects, selection effects, competition, and facilitation. We correlated whole‐system temporal stability in productivity with these values and the stability of competitively subordinate species and competitively dominant species in the intercrops. We then used structural equation modeling (SEM), which combines complex path models with latent variables, to estimate how interspecific interactions for water, nitrogen, and phosphorus affected the relationships between stability and these values. Intercropping treatments did not increase stability, but the wide range of stability created by our experiments allowed us to explore the relationship of many factors with stability. Complementarity correlated positively with the temporal stability of grain yield and aboveground biomass, suggesting that either facilitative interactions or niche partitioning shifted over time in ways that promoted stability. Furthermore, the temporal stability of total productivity of intercropping relied most on the stability of more productive species. However, facilitation tested by relative interaction index independently did not correlate with stability, but the temporal stability of the whole system increased as the competitive effects of competitively dominant species (pea and rapeseed) on competitively subordinate species (maize) decreased and was highest when these competitive effects were virtually zero. SEM indicated that as competition for soil nitrogen from competitively dominant species on competitively subordinate species decreased, the overall temporal stability of whole‐system aboveground biomass increased. This stability then led to greater stability in grain production. Our findings indicate that complex shifts in complementarity and competitive intensities are likely to be key mechanisms that maintain temporal stability in species‐diverse agriculture and, potentially, in natural systems.
Cobalt Catalysts Bearingortho‐(4,4′‐Dichlorobenzhydryl) Substituents and Their Use in Generating Narrowly Dispersed Polyethylene of High Linearity
Authors: Liu Tian , Liu Ming , Ma Yanping , Solan Gregory A. , Liang Tongling , Sun Wen‐Hua 
Published: August 2022

AbstractSix well‐defined examples ofortho‐(4,4′‐dichlorobenzhydryl)‐substituted 2,6‐diaryliminopyridine‐cobalt dichloride complex,Co1−Co6, have been prepared in reasonable yield by treatment of the corresponding free ligand (L1−L6) with cobalt(II) chloride hexahydrate. The molecular structures ofCo2andCo3highlight theirpseudo‐square pyramidal geometry, the nonsymmetrical properties of theN,N,N′‐chelating ligand and the steric shielding conferred by theortho‐(4,4′‐dichlorobenzhydryl) groups. On treatment with the aluminoxanes, MAO or MMAO, all cobalt complexes exhibited good to high productivities for ethylene polymerization (up to 8.96×106 g (PE) mol−1(Co) h−1at 60 °C) affording linear polyethylene with molecular weights in the range 28.8–250.2 kg mol−1. The steric properties of theortho‐substituents were found to exhibit significant effects on the activity and molecular weight of the resulting polymers. For example,Co1/MAO proved the most active and thermally stable, while the more sterically encumberedCo3in combination with either MAO or MMAO afforded the highest molecular weight polymer. All polymerizations were well‐controlled as is evidenced by the narrow dispersities displayed by the polymers, a feature that is characteristic of single‐site behavior. By comparison with theirortho‐benzhydryl‐substituted cobalt counterparts, the effect of thepara‐chloride substitution was to increase thermal stability, raise activity and depress polymer molecular weight.