bluuebunny/crossref_metadata_2025 huggingface dataset:
Autism Spectrum Disorder
Authors: Hirota Tomoya , King Bryan H.
Published: January 2023

Importance

Autism spectrum disorder (ASD), characterized by deficits in social communication and the presence of restricted, repetitive behaviors or interests, is a neurodevelopmental disorder affecting approximately 2.3% children aged 8 years in the US and approximately 2.2% of adults. This review summarizes evidence on the diagnosis and treatment of ASD.

Observations

The estimated prevalence of ASD has been increasing in the US, from 1.1% in 2008 to 2.3% in 2018, which is likely associated with changes in diagnostic criteria, improved performance of screening and diagnostic tools, and increased public awareness. No biomarkers specific to the diagnosis of ASD have been identified. Common early signs and symptoms of ASD in a child’s first 2 years of life include no response to name when called, no or limited use of gestures in communication, and lack of imaginative play. The criterion standard for the diagnosis of ASD is a comprehensive evaluation with a multidisciplinary team of clinicians and is based on semistructured direct observation of the child’s behavior and semistructured caregiver interview focused on the individual’s development and behaviors using standardized measures, such as the Autism Diagnostic Observation Schedule-Second Edition and the Autism Diagnostic Interview. These diagnostic measures have sensitivity of 91% and 80% and specificity of 76% and 72%, respectively. Compared with people without ASD, individuals with ASD have higher rates of depression (20% vs 7%), anxiety (11% vs 5%), sleep difficulties (13% vs 5%), and epilepsy (21% with co-occurring intellectual disability vs 0.8%). Intensive behavioral interventions, such as the Early Start Denver Model, are beneficial in children 5 years or younger for improvement in language, play, and social communication (small to medium effect size based on standardized mean difference). Pharmacotherapy is indicated for co-occurring psychiatric conditions, such as emotion dysregulation or attention-deficit/hyperactivity disorder. Risperidone and aripiprazole can improve irritability and aggression (standardized mean difference of 1.1, consistent with a large effect size) compared with placebo. Psychostimulants are effective for attention-deficit/hyperactivity disorder (standardized mean difference of 0.6, consistent with a moderate effect size) compared with placebo. These medications are associated with adverse effects including, most commonly, changes in appetite, weight, and sleep.

Conclusions and Relevance

ASD affects approximately 2.3% of children aged 8 years and approximately 2.2% of adults in the US. First-line therapy consists of behavioral interventions, while co-occurring psychiatric conditions, such as anxiety or aggression, may be treated with specific behavioral therapy or medication.
Timeliness and Modality of Treatment for New Cancer Diagnoses During the COVID-19 Pandemic in Canada
Authors: Fu Rui , Sutradhar Rinku , Li Qing , Hanna Timothy P. , Chan Kelvin K. W. , Irish Jonathan C. , Coburn Natalie , Hallet Julie , Dare Anna , Singh Simron , Parmar Ambica , Earle Craig C. , Lapointe-Shaw Lauren , Krzyzanowska Monika K. , Finelli Antonio , Louie Alexander V. , Hong Nicole J. Look , Witterick Ian J. , Mahar Alyson , Urbach David R. , McIsaac Daniel I. , Enepekides Danny , Tinmouth Jill , Eskander Antoine
Published: January 2023

Importance

The impact of COVID-19 on the modality and timeliness of first-line cancer treatment is unclear yet critical to the planning of subsequent care.

Objective

To explore the association of the COVID-19 pandemic with modalities of and wait times for first cancer treatment.

Design, Setting, and Participants

This retrospective population-based cohort study using administrative data was conducted in Ontario, Canada, among adults newly diagnosed with cancer between January 3, 2016, and November 7, 2020. Participants were followed up from date of diagnosis for 1 year, until death, or until June 26, 2021, whichever occurred first, to ensure a minimum of 6-month follow-up time.

Exposures

Receiving a cancer diagnosis in the pandemic vs prepandemic period, using March 15, 2020, the date when elective hospital procedures were halted.

Main Outcomes and Measures

The main outcome was a time-to-event variable describing number of days from date of diagnosis to date of receiving first cancer treatment (surgery, chemotherapy, or radiation) or to being censored. For each treatment modality, a multivariable competing-risk regression model was used to assess the association between time to treatment and COVID-19 period. A secondary continuous outcome was defined for patients who were treated 6 months after diagnosis as the waiting time from date of diagnosis to date of treatment.

Results

Among 313 499 patients, the mean (SD) age was 66.4 (14.1) years and 153 679 (49.0%) were male patients. Those who were diagnosed during the pandemic were less likely to receive surgery first (subdistribution hazard ratio [sHR], 0.97; 95% CI, 0.95-0.99) but were more likely to receive chemotherapy (sHR, 1.26; 95% CI, 1.23-1.30) or radiotherapy (sHR, 1.16; 95% CI, 1.13-1.20) first. Among patients who received treatment within 6 months from diagnosis (228 755 [73.0%]), their mean (SD) waiting time decreased from 35.1 (37.2) days to 29.5 (33.6) days for surgery, from 43.7 (34.1) days to 38.4 (30.6) days for chemotherapy, and from 55.8 (41.8) days to 49.0 (40.1) days for radiotherapy.

Conclusions and Relevance

In this cohort study, the pandemic was significantly associated with greater use of nonsurgical therapy as initial cancer treatment. Wait times were shorter in the pandemic period for those treated within 6 months of diagnosis. Future work needs to examine how these changes may have affected patient outcomes to inform future pandemic guideline development.
An evaluation of the use of DirectSPR images for proton planning in the RayStation treatment planning software
Authors: Sarkar Vikren , Paxton Adam , Su Fanchi , Price Ryan , Nelson Geoff , Szegedi Martin , James Sara St. , Salter Bill J.
Published: January 2023

An important source of uncertainty in proton therapy treatment planning is the assignment of stopping‐power ratio (SPR) from CT data. A commercial product is now available that creates an SPR map directly from dual‐energy CT (DECT). This paper investigates the use of this new product in proton treatment planning and compares the results to the current method of assigning SPR based on a single‐energy CT (SECT). Two tissue surrogate phantoms were CT scanned using both techniques. The SPRs derived from single‐energy CT and by DirectSPR™ were compared to measured values. SECT‐based values agreed with measurements within 4% except for low density lung and high density bone, which differed by 13% and 8%, respectively. DirectSPR™ values were within 2% of measured values for all tissues studied. Both methods were also applied to scanned containers of three types of animal tissue, and the expected range of protons of two different energies was calculated in the treatment planning system and compared to the range measured using a multi‐layer ion chamber. The average difference between range measurements and calculations based on SPR maps from dual‐ and single‐energy CT, respectively, was 0.1 mm (0.07%) versus 2.2 mm (1.5%). Finally, a phantom was created using a layer of various tissue surrogate plugs on top of a 2D ion chamber array. Dose measurements on this array were compared to predictions using both single‐ and dual‐energy CTs and SPR maps. While standard gamma pass rates for predictions based on DECT‐derived SPR maps were slightly higher than those based on single‐energy CT, the differences were generally modest for this measurement setup. This study showed that SPR maps created by the commercial product from dual‐energy CT can successfully be used in RayStation to generate proton dose distributions and that these predictions agree well with measurements.
High‐Throughput Fabrication of Size‐Controlled Pickering Emulsions, Colloidosomes, and Air‐Coated Particles via Clog‐Free Jetting of Suspensions
Authors: Jiang Jieke , Poortinga Albert T. , Liao Yuanyuan , Kamperman Tom , Venner Cornelis H. , Visser Claas Willem
Published: January 2023

Microcapsules with a liquid core and a solid shell composed of hydrophobic nanoparticles are broadly applied in food, pharmaceutics, and biotechnologies. For example, Pickering emulsions, colloidosomes, or antibubbles (droplets surrounded by air layers in water) enable controlled release of active agents, biocompatibility, and contact‐less liquid transportation. However, producing controlled nanoparticle‐ or polymer‐laden hydrophobic shells at scale is highly challenging, since bulk methods are polydisperse and microfluidic chips are prone to clogging and slow. Here, clog‐free coating of an aqueous jet with silica nanoparticle suspensions with concentrations up to 10% (w/v), as well as high concentrations of polymers (30% (w/v) poly(lactic acid) (PLA)), is demonstrated, enabling continuous generation of microcapsules at flow rates up to 4 mL min−1. Pickering emulsions are converted into capsules, providing hydrophobic shells consisting of nanoparticles for controlled release. As a highlight, the scalable fabrication of air‐coated capsules (antibubbles) in the sub‐millimeter range is demonstrated. The shell contains an air film that protects the liquid core for days yet enables ultrasound‐induced release within 3 min. By enabling rapid fabrication of controlled Pickering emulsions, colloidosomes, antibubbles, and biodegradable capsules, jetting through a liquid layer (JetALL) provides a versatile platform for advanced applications in food, pharmacy, and life science.
Atomically Dispersed Ni–Cu Catalysts for pH‐Universal CO2 Electroreduction
Authors: Zhang Libing , Feng Jiaqi , Liu Shoujie , Tan Xingxing , Wu Limin , Jia Shunhan , Xu Liang , Ma Xiaodong , Song Xinning , Ma Jun , Sun Xiaofu , Han Buxing
Published: January 2023

CO2 electroreduction is of great significance to reduce CO2 emissions and complete the carbon cycle. However, the unavoidable carbonate formation and low CO2 utilization efficiency in neutral or alkaline electrolytes hinder its application at commercial scale. The development of CO2 reduction under acidic conditions provides a promising strategy, but the inhibition of the hydrogen evolution reaction is difficult. Herein, the first work to design a Ni–Cu dual atom catalyst supported on hollow nitrogen‐doped carbon is reported for pH‐universal CO2 electroreduction to CO. The catalyst shows a high CO Faradaic efficiency of ≈99% in acidic, neutral, and alkaline electrolytes, and the partial current densities of CO reach 190 ± 11, 225 ± 10, and 489 ± 14 mA cm−2, respectively. In particular, the CO2 utilization efficiency under acidic conditions reaches 64.3%, which is twice as high as that of alkaline conditions. Detailed study indicates the existence of electronic interaction between Ni and Cu atoms. The Cu atoms push the Ni d‐band center further toward the Fermi level, thereby accelerating the formation of *COOH. In addition, operando characterizations and density functional theory calculation are used to elucidate the possible reaction mechanism of CO2 to CO under acidic and alkaline electrolytes.
A 3D‐Printed Proton Pseudocapacitor with Ultrahigh Mass Loading and Areal Energy Density for Fast Energy Storage at Low Temperature
Authors: Zhang Miaoran , Xu Tiezhu , Wang Di , Yao Tengyu , Xu Zhenming , Liu Qingsheng , Shen Laifa , Yu Yan
Published: January 2023

The sluggish ionic transport in thick electrodes and freezing electrolytes has limited electrochemical energy storage devices in lots of harsh environments for practical applications. Here, a 3D‐printed proton pseudocapacitor based on high‐mass‐loading 3D‐printed WO3 anodes, Prussian blue analog cathodes, and anti‐freezing electrolytes is developed, which can achieve state‐of‐the‐art electrochemical performance at low temperatures. Benefiting from the cross‐scale 3D electrode structure using a 3D printing direct ink writing technique, the 3D‐printed cathode realizes an ultrahigh areal capacitance of 7.39 F cm−2 at a high areal mass loading of 23.51 mg cm−2. Moreover, the 3D‐printed pseudocapacitor delivers an areal capacitance of 3.44 F cm−2 and excellent areal energy density (1.08 mWh cm−2). Owing to the fast ion kinetics in 3D electrodes and the high ionic conductivity of the hybrid electrolyte, the 3D‐printed supercapacitor delivers 61.3% of the room‐temperature capacitance even at −60 °C. This work provides an effective strategy for the practical applications of energy storage devices with complex physical structure at extreme temperatures.
Principles of Design and Synthesis of Metal Derivatives from MOFs
Authors: De Villenoisy Thibault , Zheng Xiaoran , Wong Vienna , Mofarah Sajjad S. , Arandiyan Hamidreza , Yamauchi Yusuke , Koshy Pramod , Sorrell Charles C.
Published: January 2023

Materials derived from metal–organic frameworks (MOFs) have demonstrated exceptional structural variety and complexity and can be synthesized using low‐cost scalable methods. Although the inherent instability and low electrical conductivity of MOFs are largely responsible for their low uptake for catalysis and energy storage, a superior alternative is MOF‐derived metal‐based derivatives (MDs) as these can retain the complex nanostructures of MOFs while exhibiting stability and electrical conductivities of several orders of magnitude higher. The present work comprehensively reviews MDs in terms of synthesis and their nanostructural design, including oxides, sulfides, phosphides, nitrides, carbides, transition metals, and other minor species. The focal point of the approach is the identification and rationalization of the design parameters that lead to the generation of optimal compositions, structures, nanostructures, and resultant performance parameters. The aim of this approach is to provide an inclusive platform for the strategies to design and process these materials for specific applications. This work is complemented by detailed figures that both summarize the design and processing approaches that have been reported and indicate potential trajectories for development. The work is also supported by comprehensive and up‐to‐date tabular coverage of the reported studies.
Modulating Interfacial Carrier Dynamics via Spatial Conformation toward Efficient and Stable Perovskite Solar Cells
Authors: Chen Weixian , Gong Cheng , Li Ru , Chen Jiangzhao , Zang Zhigang
Published: January 2023

Interfacial defects result in serious carrier nonradiative recombination. The correlation between spatial conformation of modifiers and interfacial carrier dynamics is scarcely revealed. Here, an effective interfacial carrier dynamics and defect passivation modulation strategy via controlling spatial conformation of modification molecules is reported. Two kinds of similar Lewis base ligand molecules, biuret (BU) and dithiobiuret (DTBU), are employed to modify the surface of perovskite films. BU and DTBU can effectively passivate interfacial defects but the former is more effective than the latter on account of higher electronegativity and more advantageous molecular spatial arrangement. The planar symmetrical BU molecules can arrange compactly and orderly on the surface of perovskite films while the adsorbed DTBU molecules with a twisted asymmetrical structure are relatively chaotic. BU modification reduces interfacial energy offset, ameliorates improved interfacial energy band alignment, and speeds up hole extraction. In contrast, a much thicker adsorbed layer is yielded after DTBU treatment, which impedes carrier extraction and transfer and accordingly leads to grievous nonradiative recombination. The spatial conformation difference produces an inverse influence on device performance (positive for BU and negative for DTBU). The power conversion efficiency is much enhanced from 21.66% to 23.54% after BU modification along with improved stability.
Structural Colors Based on Diamond Metasurface for Information Encryption
Authors: Gu Jiteng , Liu Yan , Meng Nannan , Sahmuganathan Vicknesh , Tan Sze Chieh , Sudijono John , Tang Jiecong , Venkatasubramanian Eswaranand , Mallick Abhijit , Tjiptoharson Febiana , Rezaei Soroosh Daqiqeh , Teo Siew Lang , Zhu Qiang , Chen Yunjie , Lin Ming , Dong Zhaogang , Loh Kian Ping
Published: January 2023

Structural colors based on dielectric metasurfaces are attractive because of their potential application in next‐generation color printing. However, the commonly used dielectric materials suffer from issues of high light absorption (e.g., Si at blue wavelength) and low resistance to corrosion (e.g., titanium oxide), which greatly limit their application as structural color for information encryption. Here, dielectric‐metasurface‐based structural color constructed on nanocrystalline diamond (NCD) film by using bias enhanced nucleation (BEN) technique is demonstrated. Owing to the formation of highly crystalline diamond by the BEN process, the synthesized NCD film with a thickness of ~500 nm exhibits excellent optical quality with a relatively high refractive index that produces a strong magnetic dipole mode by Mie resonance. To realize the dynamic functionalities of diamond‐metasurface color with high resolution, a periodic array of asymmetric diamond cuboids with high aspect ratio (≈3.1) is fabricated, which produces polarization‐dependent response due to the enhanced Mie resonance. By optimizing the configuration of the diamond‐metasurface system, the color performance is improved with high brightness and a relatively wide gamut. This work demonstrates for the first time that NCD can serve as a robust and highly tunable dielectric platform for application in information encryption.
An integrated chemical engineering approach to understanding microplastics
Authors: Bang Rachel S. , Bergman Michael , Li Tianyu , Mukherjee Fiona , Alshehri Abdulelah S. , Abbott Nicholas L. , Crook Nathan C. , Velev Orlin D. , Hall Carol K. , You Fengqi
Published: January 2023

Environmental and health risks posed by microplastics (MPs) have spurred numerous studies to better understand MPs' properties and behavior. Yet, we still lack a comprehensive understanding due to MP's heterogeneity in properties and complexity of plastic property evolution during aging processes. There is an urgent need to thoroughly understand the properties and behavior of MPs as there is increasing evidence of MPs' adverse health and environmental effects. In this perspective, we propose an integrated chemical engineering approach to improve our understanding of MPs. The approach merges artificial intelligence, theoretical methods, and experimental techniques to integrate existing data into models of MPs, investigate unknown features of MPs, and identify future areas of research. The breadth of chemical engineering, which spans biological, computational, and materials sciences, makes it well‐suited to comprehensively characterize MPs. Ultimately, this perspective charts a path for cross‐disciplinary collaborative research in chemical engineering to address the issue of MP pollution.
Bandgap‐Engineered Germanene Nanosheets as an Efficient Photodynamic Agent for Cancer Therapy
Authors: Ge Min , Guo Haiyan , Zong Ming , Chen Zhixin , Liu Zhuang , Lin Han , Shi Jianlin
Published: January 2023

Two‐dimensional (2D) monoelemental materials (Xenes) show considerable potential in bioapplications owing to their unique 2D physicochemical features and the favored biosafety resulting from their monoelemental composition. However, the narrow band gaps of Xenes prevent their broad applications in biosensors, bioimaging and phototherapeutics. In this study, it is demonstrated that 2D germanene terminated with −H via surface chemical engineering, shows a much broadened direct band gap of 1.65 eV, which enables the material to be used as a novel inorganic photosensitizer for the photodynamic therapy of singlet oxygen. Through theoretical analysis and in vitro studies, H‐germanene nanosheets demonstrate a substantially enlarged band gap and favorable biodegradability, demonstrating a substantial cancer treatment capacity. This study demonstrates the feasibility of constructing novel therapeutic photodynamic agents by surface covalent engineering for catalytic tumor therapy.
Ultramicroporous Covalent Organic Framework Nanosheets with Functionality Pair for Membrane C2H2/C2H4 Separation
Authors: Li Jialu , Cheng Zeliang , Wang Ziyang , Dong Junchao , Jiang Haicheng , Wang Wenjian , Zou Xiaoqin , Zhu Guangshan
Published: January 2023

Gas separation efficiency of covalent organic framework (COF) membrane can be greatly elevated through precise functionalization. A pair‐functionalized COF membrane of 1,3,5‐triformylphloroglucinol (TP) and isoquinoline‐5,8‐diamine (IQD) monomers in two and three nodes is designed and synthesized. TP‐IQD is crystallized in a two‐dimensional structure with a pore size of 6.5 Å and a surface area of 289 m2 g−1. This COF possesses N−O paired groups which cooperatively interact with C2H2 instead of C2H4. TP‐IQD nanosheets of ≈10 μm in width and ≈4 nm in thickness are prepared by mechanical exfoliation; they are further processed with 6FDA‐ODA polymer into a hybrid membrane. High porosity and functionality pair of TP‐IQD offer the membrane with significantly increased C2H2 permeability and C2H2/C2H4 selectivity which are 160 % and 430 % higher of pure 6FDA‐ODA. The boosted performance demonstrates high efficiency of the pair‐functionality strategy for the synthesis of separation‐led COFs.
Controlling the Photofunctionality of a Polyanionic Heteroleptic Copper(I) Photosensitizer for CO2 Reduction Using Its Ion‐pair Formation with Polycationic Ammonium in Aqueous Media
Authors: Sueyoshi Fumika , Zhang Xian , Yamauchi Kosei , Sakai Ken
Published: January 2023

A water‐soluble trianionic heteroleptic copper(I) photosensitizer having four sulfonate groups (CuPS3−) was found to afford the 1 : 2 ion‐pair adduct with dicationic alkylammonium (hexamethonium) cations (HM2+) in aqueous media, leading to exhibit excellent photophysical and photocatalytic performances owing to the substantial suppression of water‐derived non‐radiative decay of the photoexcited state.
Frustrated Lewis Pair Adduct of Atomic P(−1) as a Source of Phosphinidenes (PR), Diphosphorus (P2), and Indium Phosphide
Authors: Frenette Brandon L. , Trach Jonathan , Ferguson Michael J. , Rivard Eric
Published: January 2023

We report phosphinidenes (PR) stabilized by an intramolecular frustrated Lewis pair (FLP) chelate. These adducts include the parent phosphinidene, PH, which is accessed via thermolysis of coordinated HPCO. The reported FLP‐PH species acts as a springboard to other phosphorus‐containing compounds, such as FLP‐adducts of diphosphorus (P2) and InP3. Our new adducts participate in thermal‐ or light‐induced phosphinidene elimination (of both PH and PR, R=organic group), transfer P2units to an organic substrate, and yield the useful semiconductor InP at only 110 °C from solution.
A machine learning model and biometric transformations to facilitate European oyster monitoring
Authors: Pineda‐Metz Santiago E. A. , Merk Verena , Pogoda Bernadette
Published: January 2023

Ecosystem monitoring, especially in the context of marine conservation and management requires abundance and biomass metrics, condition indices, and measures of ecosystem services of key species, all of which can be calculated using biometric transformation factors.

Following ecosystem restoration measures in the North Sea and north‐east Atlantic waters, European oyster (Ostrea edulis) restoration and its monitoring have substantially increased over the past decade. Restoration activities are implemented by diverse approaches and practitioners ranging from governmental conservation agencies, research institutions and non‐governmental institutions to regional groups, including citizen science projects. Thus, tools for facilitating data acquisition and estimation with non‐destructive techniques can support monitoring quantitatively and qualitatively.

Weight‐to‐weight transformation factors for calculating dry weight of O. edulis from wet weight measurements are presented. Another important tool is the estimation of weight only from size measurements. The classical approach to achieve these transformation factors is the construction of allometric models, which, however, can greatly vary among regions and between years, making them extremely location/season specific.

Alternative and more flexible models constructed using random forests are proposed. This algorithm is a machine learning technique that is increasingly used in ecology, and has been proven to outperform other predictive models. From biometric variable measurements of 1,401 O. edulis individuals, allometric models were used to estimate total, shell and body wet weights, and compare them with 15 random forest models.

In general, the random forest models outperformed the allometric ones, with lower error when estimating weight. The developed random forest models can thus provide a tool for facilitating oyster restoration monitoring by increasing data acquisition without the need of sacrificing European oyster individuals. Their improvement can imply its implementation in other regions and support European oyster restoration and monitoring efforts throughout Europe.
Effects of inhaling essential oils of Citrus limonum L., Santalum album, and Cinnamomum camphora on human brain activity
Authors: Ueda Kazutaka , Horita Tatsushi , Suzuki Takeshi
Published: January 2023

Introduction

Essential oil inhalation has various effects on the human body. However, its effects on cognitive function and the neural basis remain unclear. We aimed to investigate the effects of inhaling lemon, sandalwood, and kusunoki essential oils on human brain activity and memory function using multichannel electroencephalography and brain source activity estimation.

Methods

Participants performed a letter 2‐back working memory task during electroencephalography measurements before and after essential oil inhalation. Brain activation, task difficulty, concentration degree, and task performance were compared among the essential oils and a fragrance‐free control.

Results

Task performance significantly improved after lemon essential oil inhalation. Lemon essential oil inhalation resulted in delta and theta band activation in the prefrontal cortex, including the anterior cingulate gyrus and orbitofrontal cortex, superior temporal gyrus, parahippocampal gyrus, and insula. During inhalation, persistent alpha band activation was observed in the prefrontal cortex, including the anterior cingulate gyrus. Sandalwood essential oil inhalation led to beta and gamma band activation in the prefrontal cortex, including the anterior cingulate gyrus.

Conclusion

Our findings demonstrate that different essential oils have specific effects on brain activity related to emotion and memory processing.
Understanding Rh‐catalysed Hydroformylation with Phosphite Ligands through Catalyst Speciation Analysis by Operando FlowNMR Spectroscopy
Authors: Bara‐Estaún Alejandro , Lyall Catherine L. , Lowe John P. , Pringle Paul G. , Kamer Paul C. J. , Franke Robert , Hintermair Ulrich
Published: January 2023

Phosphites are industrially important ligands for the Rh‐catalysed hydroformylation of olefins because they produce more active catalysts than phosphines, which is mainly due to their strong π‐acceptor properties facilitating CO dissociation from the metal centre. Herein, the effect of three prominent phosphite ligands (triphenylphosphite, Alkanox and BiPhePhos) on catalyst speciation during turnover is investigated using multi‐nuclear operando FlowNMR spectroscopy. The quantitative catalyst distribution maps derived explain activity trends across a range of catalytic reaction conditions that show how phosphites produce more active catalysts, including reduced formation of inactive Rh0 dimers in the absence of substrate during pre‐activation and at the end of the reaction. Additionally, [(alkanox)Rh(acac)] complexes have been found to be of high stability which can be exploited for post‐catalytic Rh recovery by simple addition of 2,4‐pentanediones.
Interfacial Polymerization Kinetics of Polyurea Microcapsules Formed Using Hexamethylene Diisocyanate Biuret Low Viscosity Isocyanate
Authors: Canamas Pablo , Gozzi Nathan , Du Jiupeng , Guichardon Pierrette
Published: January 2023

For cosmetic industrial applications, polyurea microcapsules were formed by using hexamethylene diisocyanate biuret low viscosity (HDB‐LV) and three different amines: ethylenediamine (EDA), guanidine (GUA), and hexamethylenediamine (HMDA). Toluene droplets containing dissolved HDB‐LV were formed by an oil‐in‐water emulsion before being poured into a water phase containing the required excess of amine. The pH of the aqueous phase was fitted through time to calculate the kinetic constant k' and the diffusion constant DB through the polyurea shell when possible. At 60 °C, EDA and HMDA follow a pure kinetic regime, whereas GUA follows a combination of kinetic and diffusion regimes. The presented kinetic data shows that HDB‐LV is a promising nontoxic isocyanate for cosmetic encapsulation.
Electrochemical and Structural Characterization of Soft Landed Tungsten‐Substituted Lindqvist Polyoxovanadate‐Alkoxides
Authors: Wilson Solita M. , Petel Brittney E. , Schreiber Eric , Maiola Michela L. , Su Pei , Matson Ellen M. , Laskin Julia
Published: January 2023

Lindqvist polyoxovanadate‐alkoxide (POV‐alkoxide) clusters are excellent candidates for applications in energy storage and conversion due to their rich electrochemical profiles. One approach to tune the redox properties of these cluster complexes is through substitutional cationic doping within the hexavanadate core. Here, we report the synthesis of a series of tungsten‐substituted POV‐alkoxide clusters with one and two tungsten atoms. Soft landing of mass‐selected ions was used to purify heterometal POV‐alkoxides that cannot be readily separated using conventional approaches. The soft landed POV‐alkoxides are characterized using infrared reflection‐absorption spectroscopy and electrospray ionization mass spectrometry. The redox properties of the isolated ions are examined using an in situ electrochemical cell which enables traditional in vacuo electrochemical measurements inside of an ion soft landing instrument. Although the overall cluster core retains redox activity after tungsten doping, vanadium‐based redox couples (VV/VIV) are shifted substantially, indicating a pronounced effect of a heteroatom on the electronic structure of the core.
Hierarchical Porous Carbon Spheres Loaded CoOX (CoOx/HPCS) for Efficient Oxygen Reduction Reaction in Alkaline Media
Authors: Hua Yani , Shi Hongwei , Liu Jiamei , Gao Zhan
Published: January 2023

The development of efficient non‐noble metal catalysts for oxygen reduction reaction (ORR) in alkaline media is vital for wide application of numerous energy conversion devices. In this work, the CoOx/HPCS catalysts are demonstrated to show excellent activity toward ORR with more positive peak potential, initial potential, and half‐wave potential than pure HPCS. Moreover, the CoOx/HPCS exhibits a long‐term stability and a stronger methanol resistance compared to 20% Pt/C. The outstanding ORR activity for CoOx/HPCS is owing to its excellent characteristics, like: 1) a good conductivity of the carbon matrix to improve the electron transfer ability; 2) the rich hierarchical hollow carbon matrix and high surface area conducive to providing more accessible active sites and improving mass transportation; 3) the defect caused by oxygen vacancy beneficial for enhancing catalytic activity; 4) the synergistic effect between CoOx and HPCS support being crucial for ORR, thence enhancing the electrochemical performance of CoOx/HPCS.
Tunnelling Dynamics of Kicked Systems: A Route to Tunnelling Control
Authors: Kar Susmita , Bhattacharyya Shankar Prasad
Published: January 2023

The effects of discontinuously time‐varying perturbations on the dynamics of a particle moving in harmonic, symmetric double well and symmetric triple well potentials, are investigated both classically and quantum mechanically. The quantum dynamics is followed using the time‐dependent Fourier grid Hamiltonian (TDFGH) method while the classical dynamics is analyzed within the framework of classical Hamiltonian mechanics. Depending on the spatial symmetry of the perturbation and the characteristic features of the reversal time
, different types of ‘phase space’ structures are observed in each of the potentials. For symmetric double and triple well potentials, quantum dynamics reveals that complete destruction of tunnelling (CDT) can be achieved in the presence of a time‐dependent spatially asymmetric perturbing field that is continuous in time. Any discontinuity in time‐variation of the perturbation may induce over the barrier transition. The relevance of these results in the context of (i) tunnelling control and (ii) quantum computing with 3‐state or 2‐state quantum registers is briefly discussed.
Recent Trends in Plasmon‐Assisted Photocatalytic CO2 Reduction
Authors: Ciocarlan Radu‐George , Blommaerts Natan , Lenaerts Silvia , Cool Pegie , Verbruggen Sammy W.
Published: January 2023

Direct photocatalytic reduction of CO2 has become an highly active field of research. It is thus of utmost importance to maintain an overview of the various materials used to sustain this process, find common trends, and, in this way, eventually improve the current conversions and selectivities. In particular, CO2 photoreduction using plasmonic photocatalysts under solar light has gained tremendous attention, and a wide variety of materials has been developed to reduce CO2 towards more practical gases or liquid fuels (CH4, CO, CH3OH/CH3CH2OH) in this manner. This Review therefore aims at providing insights in current developments of photocatalysts consisting of only plasmonic nanoparticles and semiconductor materials. By classifying recent studies based on product selectivity, this Review aims to unravel common trends that can provide effective information on ways to improve the photoreduction yield or possible means to shift the selectivity towards desired products, thus generating new ideas for the way forward.
Grafting and Solubilization of Redox‐Active Organic Materials for Aqueous Redox Flow Batteries
Authors: Chen Ruiyong , Zhang Peng , Chang Zhenjun , Yan Junfeng , Kraus Tobias
Published: January 2023

This study concerns the development of sustainable design strategies of aqueous electrolytes for redox flow batteries using redox‐active organic materials. A green spontaneous grafting reaction occurs between a redox‐active organic radical and an electrochemically activated structural modifier at room temperature through a simple mixing step. Then, a physical mixing method is used to formulate a structured aqueous electrolyte and enables aqueous solubilization of the organic solute from below 0.5 to 1.5 m beyond the conventional dissolution limit. The as‐obtained concentrated mixture can be readily used as catholyte for a redox flow battery. A record high discharge cell voltage (1.6 V onset output voltage) in aqueous non‐hybrid flow cell is attained by using the studied electrolytes.
Highly Stable Metal–Organic Framework with Redox‐Active Naphthalene Diimide Core as Cathode Material for Aqueous Zinc‐Ion Batteries
Authors: Liu Yongyao , Li Zhonglin , Han Yuejiang , Ji Zhenyu , Li Hengbo , Liu Yuanzheng , Wei Yifan , Chen Cheng , He Xiang , Wu Mingyan
Published: January 2023

Recently, metal–organic frameworks (MOFs) as the cathode materials for aqueous zinc‐ion batteries (ZIBs) received growing attention. Herein, a novel MOF, Ni‐Ndi‐trz (Ndi‐trz=2,7‐di(4H‐1,2,4‐triazol‐4‐yl)benzo[lmn][3,8]phenanthroline‐1,3,6,8(2H,7H)‐tetraone) was synthesized through a solvothermal method. Its rational design using a naphthalene diimide (Ndi) core allowed the formation of a four‐fold interpenetrated pcu (primitive cubic) topology. The as‐synthesized Ni‐Ndi‐trz is highly stable over a wide pH range (0–12) for 30 days, which is critical to ensure the decent cyclability of zinc‐ion batteries (ZIBs). When used as the cathode material of ZIBs, it shows a high initial specific capacity of 90.7 mAh g−1 and excellent cycling stability. Remarkably, three‐electrode system tests, ex situ FTIR, UV/Vis and XPS spectra revealed that the Ndi core of Ni‐Ndi‐trz undergoes a reversible interconversion between the keto and enol forms when interacting with Zn2+ ions. This work may shed light on the feasibility of designing novel MOFs and exploring their mechanisms for zinc ion batteries.
Electronic and Steric Effects on L‐Lactide Ring‐Opening Polymerization with NSSN‐type Zr(IV) Complexes
Authors: Ritacco Ida , Voccia Maria , Impemba Salvatore , Camellone Matteo Farnesi , Milione Stefano , Caporaso Lucia
Published: January 2023

In this work the mechanism of L‐lactide polymerization promoted by NSSN zirconium complexes was investigated through DFT methods with the aim to understand as the electronic and steric features of the ligand affect the energy reaction. It was observed that the rate determining step of the process is the opening of the L‐lactide ring and that by increasing the steric hindrance, evaluated by changing geometric parameters and topographic steric maps, or the electron‐withdrawing properties of the ligand, the corresponding energy barrier increases. On the other hand, calculations foresee that a small and electron‐releasing substituent on the nitrogen atom of the ligand, such as the methyl group, is desirable in order to obtain NSSN zirconium based catalysts with improved activity in the ROP of the L‐lactide.
Effects of hydrogen mixing ratio on combustion and emissions of natural gas‐diesel dual fuel engine with high natural gas substitution rate
Authors: Guo Baoxing , Xia Qi , Xu Yuanli , Xu Xiaofan , Zhang Mengyuan
Published: January 2023

In order to explore the feasibility of natural gas (NG)/diesel dual‐fuel engine with high NG substitution rate under medium and low load, the effects of hydrogen (H2) on the performance and emissions of the engine are studied numerically. The baseline engine is a four‐cylinder turbocharged diesel engine, which is modified into a diesel‐Natural Gas‐Hydrogen ternary fuels engine with port‐injected H2 and NG fuels and direct‐injected diesel fuel. The simulation is performed using GT‐Power software, and numerical results are validated with the experimental data. The percentage of diesel fuel is set at 10% and 20% (by energy). The engine speed decreases from high speed to medium speed and finally to low speed. The engine load decreases from medium load to low load. The H2 mixing ratio increases from 10% to 50%. The results show that, with the increase of H2 mixing ratio, the peak cylinder pressure (PCP), the peak cylinder temperature (PCT), the heat release rate (HRR) and the maximum pressure rise rate (MPRR) increase, while the indicated thermal efficiency (ITE) decreases under all working conditions. Among them, the MPRR increases by 4%~13% at medium load and 1%~2% at low load, but it does not exceed 0.6 MPa/ (°) CA. The indicated thermal efficiency decreases by 1%~4% at medium and low load. In terms of emissions, the carbon monoxide (CO) and the hydrocarbons (HC) decrease by 34%~43%, but the nitrogen oxide (NOX) increases by 58%~73%.
Numerical investigation of turbulent mixed convection flow and heat transfer characteristics of 2 × 2 subchannels with spacer grids
Authors: Long Jianping , Yang Bao‐Wen , Wu Ting , Zhang Bin
Published: January 2023

In turbulent mixed convection conditions, flow and heat transfer can deteriorate under specific conditions, thus affecting the performance of the safety of the system, which could imperil the safety of the nuclear reactor. In this paper, by analyzing the velocity, temperature distributions, and other thermal‐hydraulic parameters, the steady‐state computational fluid dynamics approach with the SST k–ω turbulence model used in this study was verified. Then, flow and heat transfer characteristics in turbulent mixed convection inside 2 × 2 subchannels with and without spacer grids were investigated. The results showed that the velocity profiles were distorted and the heat transfer capacity was impaired due to the influence of buoyancy. The Nusselt number ratio (Nu/Nuf) between turbulent mixed convection and forced convection increased with the increase of Reynolds number (Re) until unity but decreased with the increases of Grashof number (Gr) and Buoyancy parameter (Bo*).
Anchorage weakening effect of coal roadway sidewall with different destressing borehole diameters
Authors: Yin Yanchun , Zhou Hongjie , Zhang Yubao , Wang Chao , Deng Yanhui , Chen Biao
Published: January 2023

The pressure relief with large‐diameter boreholes is one of the effective methods to prevent coal bumps in deep coal roadway. An unreasonable pressure relief design can cause the rockbolt support failure and aggravate the deformation of the surrounding rocks. In this paper, a coupling model of roadway sidewall considering borehole pressure relief and rockbolt support was established. The influence of the destressing borehole diameter on the rockbolt located in the plastic zone and the roadway deformation was studied by theoretical calculation and numerical simulation. The results show that there is a critical zone of the borehole diameter for the influence on the rockbolt normal stress and roadway convergence. When the destressing borehole diameter exceeds the critical zone, the rockbolt normal stress decreases sharply. Considering the existence of the broken zone in the surrounding rock, the bolehole diameters in the critical zone increase with the increase of the distance between the borehole and the rockbolt, the residual strength, and decrease with the increase of initial stress. In the engineering analysis, with the increase of the destressing borehole diameter, the ultimate pullout force of rockbolt decrease, and the plastic zone of surrounding rock, the roadway deformation, the maximum axial force, and slippage of the rockbolt all increase. Therefore, to better keep the stability of the surrounding rock in coal roadway, the borehole pressure relief needs to be coordinated with the rockbolt support. The destressing borehole diameter in the pressure relief design should not be greater than the critical zone.
Low rates of rock organic carbon oxidation and anthropogenic cycling of rhenium in a slowly denuding landscape
Authors: Ogrič Mateja , Dellinger Mathieu , Grant Katherine E. , Galy Valier , Gu Xin , Brantley Susan L. , Hilton Robert G.
Published: January 2023

The oxidation of petrogenic organic carbon (OCpetro) is a source of carbon dioxide to the atmosphere over geological timescales. The rates of OCpetro oxidation in locations that experience low rates of denudation remain poorly constrained, despite these landscapes dominating Earth's continental surface area. Here, we track OCpetro oxidation using radiocarbon and the trace element rhenium (Re) in the deep weathering profiles, soils and stream waters of the Susquehanna Shale Hills Critical Zone Observatory (PA, USA). In a ridge‐top borehole, radiocarbon measurements reveal the presence of a broad OCpetro weathering front, with a first‐order assessment of ~40% loss occurring over ~6 m. However, the low OCpetro concentration (< 0.05 wt%) and inputs of radiocarbon throughout the deepest parts of the profile complicate the assessment of OCpetro loss. The OCpetro weathering front coincides with a zone of Re depletion (~90% loss), and we estimate that > 80% of Re in the rock is associated with OCpetro, based on Re/Na and Re/S ratios. Using estimates of long‐term denudation rates, the observed OCpetro loss and the Re proxy are equivalent to a low OCpetro oxidation yield of < 1.7 × 10−2 tC km−2 yr−1. This is consistent with the low OCpetro concentrations and low denudation rates at this location. In addition, we find the surface cycle of Re is decoupled from that of deep weathering, with an enrichment of Re in surface soils and elevated Re concentrations in stream water, precipitation, and shallow groundwater. A mass balance model shows that this can be explained by a historical anthropogenic contribution of Re through atmospheric deposition. We estimate that the topsoil Re pool could take decades to centuries to deplete and call for a renewed focus on anthropogenic perturbation of the surface Re cycle in low denudation rate settings.
Sample size calculation for clinical trials analyzed with the meta‐analytic‐predictive approach
Authors: Qi Hongchao , Rizopoulos Dimitris , van Rosmalen Joost
Published: January 2023

The meta‐analytic‐predictive (MAP) approach is a Bayesian method to incorporate historical controls in new trials that aims to increase the statistical power and reduce the required sample size. Here we investigate how to calculate the sample size of the new trial when historical data is available, and the MAP approach is used in the analysis. In previous applications of the MAP approach, the prior effective sample size (ESS) acted as a metric to quantify the number of subjects the historical information is worth. However, the validity of using the prior ESS in sample size calculation (i.e., reducing the number of randomized controls by the derived prior ESS) is questionable, because different approaches may yield different values for prior ESS. In this work, we propose a straightforward Monte Carlo approach to calculate the sample size that achieves the desired power in the new trial given available historical controls. To make full use of the available historical information to simulate the new trial data, the control parameters are not taken as a point estimate but sampled from the MAP prior. These sampled control parameters and the MAP prior based on the historical data are then used to derive the statistical power for the treatment effect and the resulting required sample size. The proposed sample size calculation approach is illustrated with real‐life data sets with different outcomes from three studies. The results show that this approach to calculating the required sample size for the MAP analysis is straightforward and generic.
Fruit quality and volatile compounds of greenhouse sweet peppers as affected by the LED spectrum of supplementary interlighting
Authors: Kim Dongpil , Ra Inseok , Son Jung Eek
Published: January 2023

BACKGROUND

Seasonal low light intensity and short photoperiods lead to decreased yield, size, and quality of fruits in the Northern Hemisphere. Recently, supplemental lighting using light‐emitting diodes (LEDs) has been introduced to overcome such problems. However, most studies have focused on plant growth or fruit yield but not on taste. This study aimed to evaluate the quality and volatile compounds of greenhouse sweet pepper fruits under three different lighting conditions: natural light only (NL), NL with red/blue interlighting (RB), and NL with red/blue/far‐red interlighting (RBFR).

RESULTS

The size, color, firmness, and soluble sugar concentration of the sweet pepper fruit were investigated, and sensory evaluation was conducted by nine trained panelists. Individual fruit fresh weights were higher in the order of RBFR, NL, and RB, with mean values of 219.1, 201.7, and 197.4 g, respectively. Additionally, the composition of volatile compounds demonstrated a distinct clustering pattern by light treatment, implying that the LED interlighting spectra affected the overall taste of sweet pepper fruits. Sensory evaluation indicated that sweetness was higher in the order of RBFR, RB, and NL, with values of 5.28, 4.36, and 3.72, respectively. The soluble sugar results showed the same order as that for the sensory evaluation of sweetness, i.e., RBFR, RB, and NL, with values of 5071, 4647, and 3978 μg −1 fresh weight, respectively.

CONCLUSION

Adding far‐red to RB interlighting could improve the fruit quality attributes, fruit taste perception, and soluble sugars of sweet peppers compared to those under RB or solely NL. © 2023 Society of Chemical Industry.