bluuebunny/crossref_metadata_2025_split huggingface dataset:
Organocatalytic depolymerization of poly(trimethylene carbonate)
Authors: Fukushima Kazuki , Watanabe Yuya , Ueda Tetsuya , Nakai So , Kato Takashi 
Published: November 2022

AbstractAliphatic polycarbonates have attracted attention as degradable and sustainable materials contributing to the circular plastic economy. Their chemical recycling has not been sufficiently studied. In this study, the efficacy of organocatalysts for depolymerization of poly(trimethylene carbonate) (PTMC), a representative aliphatic polycarbonate, is investigated using several organic acids and bases. The hydrolysis of PTMC produces the water‐soluble degradates propane‐1,3‐diol (PD) and CO2. A phosphazene base P2‐t‐Bu shows high activity for the hydrolysis, yielding up to 31% and 89% of PD in the homogeneous reaction at around 27°C and the inhomogeneous reaction under the reflux condition, respectively. By contrast, 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD) exhibits exceptionally high catalytic activity for the methanolysis of PTMC, producing PD and dimethyl carbonate. This is because of dual hydrogen‐bonding activation, which completes the inhomogeneous reaction in a few hours at around 27°C while yielding more than 90% of PD. The reaction rate of the TBD‐catalyzed methanolysis depends on the concentration of the nucleophile and catalyst, and the ratio of the nucleophile to the substrate affects the PD yield. These results provide a highly promising standard for chemical recycling of functionalized aliphatic polycarbonates that could potentially be applied to sustainable materials in the future.
Stimuli‐responsive polypeptoid block copolymers containing o‐nitrobenzyl groups with extremely sharp transition
Authors: Lin Maosheng , Li Zenghao , Fu Xiaohui , Sun Jing 
Published: November 2022

AbstractBioinspired thermoresponsive polymers have received increasing attention for many applications. Here, we report a series of thermoresponsive polypeptoid block copolymers containing o‐nitrobenzyl groups, that is, poly(ethylene glycol)‐b‐poly[N‐[2‐[N‐(o‐nitrobenzyloxycarbonyl)‐amino]‐ethyl]‐glycine] (PEG‐b‐PN[oNB]G), prepared by ring‐opening polymerization. The polypeptoid block copolymers show reversible lower critical solution temperature (LCST)‐type behavior in water with tunable phase transition properties dependent on the pH values, chemical compositions, and concentrations of the copolymers. The dynamic light scattering results reveal the formation of spherical micelles and temperature‐induced aggregation of PEG‐b‐PN(oNB)G. Notably, the phase transition of the block copolymer solution upon heating appears extremely sharp (∆T < 1°C), superior to bench mark poly(N‐isopropylacrylamide). In addition, we present the removal of photo‐responsive o‐nitrobenzyl groups can result in the increased clouding point and even the loss of phase transition properties, acting as an excellent regulator to tune the LCST behavior. We demonstrate that the hydrogen‐bonding interaction may play a critical part on the LCST behavior. The prepared diblock copolymers show great potential for many applications and its structure–property may shed light on highly designable stimuli‐responsive polymeric materials.
A benzimidazolyl‐substituted cyclotriphosphazene and its application in benzoxazine: Curing behaviors, thermal properties, and fire safety
Authors: Wu Feifan , Wang Jun , Wang Jingsheng , Chen Kaiwen , Yang Shuang , Huo Siqi , Wang Hao 
Published: November 2022

AbstractIn this study, a well‐designed benzimidazolyl‐substituted cyclotriphosphazene (BICP) was used as a versatile additive to enhance the integrated performances of bisphenol A‐aniline based benzoxazine (BA‐a). Our results showed that the BA‐a/BICP systems possessed lower curing temperature than virgin BA‐a due to the catalytic action of tertiary amines in BICP. Moreover, the thermal resistance of BA‐a/BICP thermosets was better than that of BA‐a thermoset because of the rigid structure and high thermal stability of BICP. The introduction of BICP significantly enhanced the fire safety of BA‐a. For instance, the limiting oxygen index and UL‐94 rating of BA‐a/BICP‐11 sample with 11 wt% of BICP were up to 35.2% and V‐0. Compared with BA‐a, the total smoke production and peak smoke production rate of BA‐a/BICP‐17 sample with 17 wt% of BICP were reduced by 36.5% and 39.3%, respectively. The improved fire safety of BA‐a/BICP sample was mainly due to the condensed‐phase effect of BICP. This work provides a simple strategy for the development of advanced benzoxazine resins with low curing temperature, great thermal properties, and superior fire safety.
PocketOptimizer 2.0: A modular framework for computer‐aided ligand‐binding design
Authors: Noske Jakob , Kynast Josef Paul , Lemm Dominik , Schmidt Steffen , Höcker Birte 
Published: November 2022

AbstractThe ability to design customized proteins to perform specific tasks is of great interest. We are particularly interested in the design of sensitive and specific small molecule ligand‐binding proteins for biotechnological or biomedical applications. Computational methods can narrow down the immense combinatorial space to find the best solution and thus provide starting points for experimental procedures. However, success rates strongly depend on accurate modeling and energetic evaluation. Not only intra‐ but also intermolecular interactions have to be considered. To address this problem, we developed PocketOptimizer, a modular computational protein design pipeline, that predicts mutations in the binding pockets of proteins to increase affinity for a specific ligand. Its modularity enables users to compare different combinations of force fields, rotamer libraries, and scoring functions. Here, we present a much‐improved version––PocketOptimizer 2.0. We implemented a cleaner user interface, an extended architecture with more supported tools, such as force fields and scoring functions, a backbone‐dependent rotamer library, as well as different improvements in the underlying algorithms. Version 2.0 was tested against a benchmark of design cases and assessed in comparison to the first version. Our results show how newly implemented features such as the new rotamer library can lead to improved prediction accuracy. Therefore, we believe that PocketOptimizer 2.0, with its many new and improved functionalities, provides a robust and versatile environment for the design of small molecule‐binding pockets in proteins. It is widely applicable and extendible due to its modular framework. PocketOptimizer 2.0 can be downloaded at https://github.com/Hoecker-Lab/pocketoptimizer.
To twist or not to twist: From chromophore structure to dynamics inside engineered photoconvertible and photoswitchable fluorescent proteins
Authors: Krueger Taylor D. , Tang Longteng , Chen Cheng , Zhu Liangdong , Breen Isabella L. , Wachter Rebekka M. , Fang Chong 
Published: November 2022

AbstractGreen‐to‐red photoconvertible fluorescent proteins (FPs) are vital biomimetic tools for powerful techniques such as super‐resolution imaging. A unique Kaede‐type FP named the least evolved ancestor (LEA) enables delineation of the evolutionary step to acquire photoconversion capability from the ancestral green fluorescent protein (GFP). A key residue, Ala69, was identified through several steady‐state and time‐resolved spectroscopic techniques that allows LEA to effectively photoswitch and enhance the green‐to‐red photoconversion. However, the inner workings of this functional protein have remained elusive due to practical challenges of capturing the photoexcited chromophore motions in real time. Here, we implemented femtosecond stimulated Raman spectroscopy and transient absorption on LEA‐A69T, aided by relevant crystal structures and control FPs, revealing that Thr69 promotes a stronger π–π stacking interaction between the chromophore phenolate (P‐)ring and His193 in FP mutants that cannot photoconvert or photoswitch. Characteristic time constants of ~60–67 ps are attributed to P‐ring twist as the onset for photoswitching in LEA (major) and LEA‐A69T (minor) with photoconversion capability, different from ~16/29 ps in correlation with the Gln62/His62 side‐chain twist in ALL‐GFP/ALL‐Q62H, indicative of the light‐induced conformational relaxation preferences in various local environments. A minor subpopulation of LEA‐A69T capable of positive photoswitching was revealed by time‐resolved electronic spectroscopies with targeted light irradiation wavelengths. The unveiled chromophore structure and dynamics inside engineered FPs in an aqueous buffer solution can be generalized to improve other green‐to‐red photoconvertible FPs from the bottom up for deeper biophysics with molecular biology insights and powerful bioimaging advances.
Development and biological evaluation of nanoencapsulated‐based pyrethroids with synergists for resistance management of two soybean pests: insights for new insecticide formulations
Authors: Boff Jéssica S. , Reis Alexandre C. , de Oliveira Jhones L. , Gross Renata B. , Fraceto Leonardo F. , Melo Adriano A. , Bernardi Oderlei 
Published: November 2022

AbstractBackgroundChemical control is commonly used against Euschistus heros (F.) and Chrysodeixis includens (Walker) in soybean fields in South America. However, previous studies reported that these pests have reduced susceptibility to pyrethroids in Brazil. On this basis, we developed and evaluated nanoencapsulated‐based bifenthrin (BFT) and λ‐cyhalothrin (LAM) with the synergists piperonyl butoxide (PBO) and diethyl maleate (DEM) for insect resistance management (IRM).ResultsNanoformulations of BFT and LAM with PBO and DEM presented good physical–chemical characteristics and were stable. The spherical morphology of all systems and the encapsulation efficiency in nanostructured lipid carriers did not change when synergists were added. Nanoencapsulated BFT with DEM applied topically increased the susceptibility of E. heros to BFT by 3.50‐fold. Similarly, nanoencapsulated BFT and LAM with PBO in diet‐overlay bioassays increased the susceptibility of C. includens to both chemicals by up to 2.16‐fold. Nanoencapsulated BFT and LAM with synergists also improve control efficacy of both species, causing higher mortality than commercial products containing these chemistries.ConclusionsIt is possible to develop nanoencapsulated‐based formulations of BFT and LAM with PBO or DEM, and these nanoformulations have the potential to improve control of E. heros and C. includens with recognized low susceptibility to pyrethroids. This study provides updates for designing new insecticide formulations for IRM. © 2022 Society of Chemical Industry.
A reliability‐based robust optimization design for the drum brake using adaptive Kriging surrogate model
Authors: Yang Zhou , Pak Unsong , Kwon Cholu , Zhang Yimin 
Published: November 2022

AbstractTo decrease random parameters’ influence on the drum brake reliability, the reliability‐based robust optimization design (RBROD) of the electric vehicle brake is proposed. Based on the assumption that the maximum temperature of the brake cannot exceed the allowable temperature, a performance function model of thermal–mechanical coupling reliability of drum brakes is established by the adaptive Kriging method, and the analysis of reliability sensitivity and RBROD are conducted. The accuracy of the proposed model is verified by temperature measurement experiment under emergency braking condition. The robust optimization design improves the drum brake reliability to 0.99998 and reduce the influence of the design parameters on the reliability, with the absolute values of the reliability sensitivity and the weight of the drum brake are significantly smaller. Therefore, the objectives of reliability design, robustness design, and optimization design are simultaneously achieved by the proposed methods. Besides, the relative error of the proposed method is 0.373%, the number of function evaluations is 39, and the comparison with four meta‐model methods show that the proposed method holds high‐accuracy and high‐efficiency. This study provides a high‐precision theoretical explanation for the robust optimization design of drum brake.
Validation of a surgical workspace scale during robot‐assisted surgery
Authors: Alhusseinawi Hayder , Haase Rikke , Rasmussen Sten , Jensen Jørgen B. , Kingo Pernille S. 
Published: November 2022

AbstractBackgroundA sufficient surgical workspace is crucial to avoid complications. Within classic laparoscopy, many subjective surgical rating scales (SRSs) have previously been used to evaluate the surgical workspace. This study aimed to validate a modified version of the 5‐point SRS during robot‐assisted radical nephrectomy (RARN).MethodsThirty‐two intra‐operative videos of intraperitoneal spaces were recorded from eight patients who underwent RARN. To attain the visualisation of different types of workspaces, we recorded 20 s panoramic videos of different pneumoperitoneum, namely 3, 5, 7 and 12 mmHg. The videos were randomised and presented two times to eight experienced robotic surgeons to evaluate the workspace using our modified 5‐point SRS. Both inter‐and intra‐rater reliabilities were tested.ResultsThe results of the validation study showed moderate inter‐rater and good to excellent intra‐rater reliability.ConclusionThis is a valid tool that can be confidently used by future researchers in the field of robot‐assisted surgery.
The Financial Burden of Out-of-Pocket Healthcare Expenses on Caregivers of Children with Atopic Dermatitis in the United States
Authors: Chovatiya Raj , Begolka Wendy Smith , Thibau Isabelle J. , Silverberg Jonathan I. 
Published: November 2022

Abstract

Background
Atopic dermatitis (AD) is associated with elevated financial costs, including out-of-pocket (OOP) expenses. Yet, the full burden of OOP expenses in children with AD is poorly understood.

Objectives
We sought to characterise categories, impact, and associations of caregiver-reported OOP AD healthcare expenses for US children.

Methods
An online survey was administered to National Eczema Association members (N = 113 502). Inclusion criteria (US resident; respondent age ≥18; self or caregiver report of AD diagnosis) was met by 77.3% (1118/1447) of those who completed the questionnaire.

Results
Caregivers of children (&lt;18 years) with AD reported increased healthcare provider (HCP) visits, comorbid food allergy, cutaneous infections, and topical antimicrobial use (p &lt; 0.005 for all), and increased OOP expenses for hospitalisation, emergency room visits, emollients, hygiene/bathing products, childcare, and specialised cleaning products, and clothing/bedding (p &lt; 0.05 for all) compared to adults with AD. Children with AD had increased median total yearly OOP expenditures ($860 vs. $500, p = 0.002) and were more likely to spend ≥$1000 OOP per year (48.9% vs. 40.0%, p = 0.03). In children, yearly OOP expenses ≥$1000 were associated with increased AD severity, flares, HCP visits, prescription polypharmacy, and step-up therapy use (p &lt; 0.005 for all) compared with adults. Predictors of harmful financial impact among children included black race (adjusted OR [95% confidence interval]: 3.86 [1.66–8.98] p = 0.002) and ≥$1000 annual OOP expenditures (6.98 [3.46–14.08], p &lt; 0.0001).

Conclusion
Children with AD have unique and increased OOP expenses that are associated with significant disease burden. Strategies are needed to reduce OOP costs and improve clinical outcomes in children with AD.
Metabolic health disparities driven by financial stress: Behavioural adaptation or modification?
Authors: Kuo Wan‐Chin , Bratzke Lisa. C. , Hagen Erika W. , Hale Lauren , Brown Roger L. , Barnet Jodi H. , Peppard Paul E. 
Published: November 2022

AbstractFinancial stress has been linked to an increased risk of metabolic syndrome, yet, it remains unclear whether suboptimal sleep duration and physical inactivity are the adaptive responses to financial stress or effect modifiers in the association between financial stress and metabolic syndrome. Hence, this study aims to examine whether physical activity and sleep duration mediate or moderate the bivariate association between financial stress and metabolic syndrome. A prospective secondary analysis was conducted using data from the Wisconsin Sleep Cohort Study (N = 445, mean [SD] age = 64 [7] years). Baseline moderation effect was examined using subgroup analysis with model constraints; prospective mediation model was examined using bias‐corrected bootstrap confidence intervals. Results indicate that participants with higher financial stress were less likely to meet physical activity and sleep recommendations. Baseline moderation analysis indicates that meeting current recommendations of sleep duration and physical activity attenuated the association between financial stress and metabolic syndrome. In the prospective mediation analysis, weekly physical activity levels partially mediated the relationship between financial stress and metabolic syndrome, but sleep duration did not mediate this relationship. In conclusion, the joint effect of optimal sleep duration and physical activity disassociates financial stress from the risk of metabolic syndrome. Future interventions addressing metabolic risk might achieve better outcomes if clinicians and researchers factor in the behavioral adaptation of physical inactivity in financially stressed adults (Clinical Trial Registration: NCT00005557).
Pioneering digital platform ecosystems: The role of aligned capabilities and motives in shaping key choices and performance outcomes
Authors: Wormald Audra , Shah Sonali K. , Braguinsky Serguey , Agarwal Rajshree 
Published: November 2022

AbstractResearch SummaryWe inductively analyze rich qualitative and quantitative data on the global census of pioneering mobile money firms to examine how firm characteristics shape digital platform ecosystem configuration choices regarding (a) internal versus external integration and (b) the creation of network externalities through open versus closed end‐user access. In contrast to received wisdom, we find pioneering firms were equally likely to engage in external and internal integration; moreover, diversifying entrants were less likely to internally integrate than startups. We uncover the important role of motives, in addition to capabilities, for creating alignment between pioneering firms and their partners. Such alignment was key for addressing path‐dependent implementation challenges through experimentation and navigating nascent industry uncertainty for success.Managerial SummaryOur study showcases how enterprising firms pioneered and diffused mobile money, a digital platform that improves access to financial services. The successful take‐off and growth of this industry, as revealed by our inductive analysis, was contingent on aligned capabilities and motives among platform co‐providers and critical partners. We illuminate why and how pioneer capabilities and motives influenced key platform choices regarding internal versus external integration, and open versus closed end‐user access. These choices then created different implementation challenges. The successful pioneers navigated these challenges to create a robust ecosystem for network effects by engaging in two actions: they developed lasting partner relationships, and they experimented to determine distinct demand segments, identify unmet needs, and develop value propositions.
Entrapped Molecule‐Like Europium‐Oxide Clusters in Zinc Oxide with Nearly Unaffected Host Structure
Authors: Mukherjee Soham , Katea Sarmad Naim , Rodrigues Emille M. , Segre Carlo. U. , Hemmer Eva , Broqvist Peter , Rensmo Håkan , Westin Gunnar 
Published: November 2022

AbstractNanocrystalline ZnO sponges doped with 5 mol% EuO1.5are obtained by heating metal–salt complex based precursor pastes at 200–900 °C for 3 min. X‐ray diffraction, transmission electron microscopy, and extended X‐ray absorption fine structure (EXAFS) show that phase separation into ZnO:Eu andc‐Eu2O3takes place upon heating at 700 °C or higher. The unit cell of the clean oxide made at 600 °C shows only ≈0.4% volume increase versus undoped ZnO, and EXAFS shows a ZnO local structure that is little affected by the Eu‐doping and an average Eu3+ion coordination number of ≈5.2. Comparisons of 23 density functional theory‐generated structures having differently sized Eu‐oxide clusters embedded in ZnO identify three structures with four or eight Eu atoms as the most energetically favorable. These clusters exhibit the smallest volume increase compared to undoped ZnO and Eu coordination numbers of 5.2–5.5, all in excellent agreement with experimental data. ZnO defect states are crucial for efficient Eu3+excitation, whilec‐Eu2O3phase separation results in loss of the characteristic Eu3+photoluminescence. The formation of molecule‐like Eu‐oxide clusters, entrapped in ZnO, proposed here, may help in understanding the nature of the unexpected high doping levels of lanthanide ions in ZnO that occur virtually without significant change in ZnO unit cell dimensions.
Automated Folding of Origami Lattices: From Nanopatterned Sheets to Stiff Meta‐Biomaterials
Authors: van Manen Teunis , Ganjian Mahya , Modaresifar Khashayar , Fratila‐Apachitei Lidy E. , Zadpoor Amir A. 
Published: November 2022

AbstractFolding nanopatterned flat sheets into complex 3D structures enables the fabrication of meta‐biomaterials that combine a rationally designed 3D architecture with nanoscale surface features. Self‐folding is an attractive approach for realizing such materials. However, self‐folded lattices are generally too compliant as there is an inherent competition between ease‐of‐folding requirements and final load‐bearing characteristics. Inspired by sheet metal forming, an alternative route is proposed for the fabrication of origamilattices. This ‘automated‐folding’ approach allows for the introduction of sharp folds into thick metal sheets, thereby enhancing their stiffness. The first time realization of automatically folded origami lattices with bone‐mimicking mechanical properties is demonstrated. The proposed approach is highly scalable given that the unit cells making up the meta‐biomaterial can be arbitrarily large in number and small in dimensions. To demonstrate the scalability and versatility of the proposed approach, it is fabricated origamilattices with > 100 unit cells, lattices with unit cells as small as 1.25 mm, and auxetic lattices. The nanopatterned the surface of the sheets prior to folding. Protected by a thin coating layer, these nanoscale features remained intact during the folding process. It is found that the nanopatterned folded specimens exhibits significantly increased mineralization as compared to their non‐patterned counterparts.