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Bulking Up the Bay-position Substituents Enables Enhanced Selectivity of C_(s)‑Symmetric Boron Subphthalocyanine−Subnaphthalocyanine Hybrids

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precision Chemistry 2024年第4期2卷 161-181页

作者： Nina F.Farac Alan j.Lough Timothy p.Bender Department of Chemical Engineering and Applied Chemistry University of TorontoTorontoOntario M5S 3E5Canada Department of Chemistry University of TorontoTorontoOntario M5S 3H6Canada Department of Materials Science and Engineering University of TorontoTorontoOntario M5S 3E4Canada Department of Mechanical and Industrial Engineering University of TorontoTorontoOntario M5S 3G8Canada

The precise synthesis of subporphyrinoid hybrids withπ-expanded topologies and unique material properties plays a promising role in the design of functional ***,selective,and controllable routes to boron subphthalocyanine−subnaphthalocyanine hybrids,Bsub(pc_(3‑p)-Nc_(p))s,are desirable for this purpose yet synthetically challenging due to random mixtures of C_(s-),C_(3v-),and,in some cases,C_(1)-symmetric compounds that form during traditional statistical mixed ***,we addressed this issue by developing a sterically driven mixed cyclotrimerization with enhanced selectivity for the targeted C_(s)-symmetric hybrid and complete suppression of sterically crowded macrocyclic *** process,coupled with a rationally designed precursor bearing bulky phenyl substituents,enabled the synthesis and characterization of bay-position phenylated ph_(2)-(R_(p))_(8)Bsub(pc_(2)-Nc_(1))hybrids with halogens(Rp=Cl or F)in their peripheral isoindole *** selectivity ranged between 59 and 72%with remarkable yields,significantly higher than that of conventional mixed *** findings were augmented by theoretical calculations on precursor Lewis basicity as guiding principles into hybrid macrocycle ***,the incorporation of unfused phenyl groups and halogen atoms into the hybrid framework resulted in fine-tuned optical,structural,electronic,and electrochemical *** straightforward approach achieved improved selectivity and controlled narrowing of the product distribution,affording the efficient synthesis of structurally sophisticated Bsub(pc_(2)-Nc_(1))*** then expands the library of 3-dimensionalπ-extended macrocycles for use in a range of applications,such as in optoelectronic devices with precisely tailored optical properties.

关键词： subphthalocyanine hybrids low-symmetry aromatic macrocycle selective cyclotrimerization sterically driven chemistry broad absorption material properties

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Optimization of chemistry and process parameters for control of intermetallic formation in Mg sludges

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journal of Magnesium and Alloys 2024年第4期12卷 1431-1448页

作者： Y.Fu G.G.Wang A.Hu Y.Li K.B.Thacker j.p.Weiler H.Hu Department of Mechanical Automotive and Materials EngineeringUniversity of Windsor401 Sunset AveWindsorOntario N9B 3P4Canada Global Technology Centre Meridian Lightweight Technologies25 MacNab AveStrathroyOntario N7G 4H6Canada

Intermetallic formation in sludge during magnesium(Mg)melting,holding and high pressure die casting practices is a very important ***,very often it is overlooked by academia,original equipment manufacturers(OEM),metal ingot producers and even die *** aim of this study was to minimize the intermetallic formation in Mg sludge via the optimization of the chemistry and process *** Al8Mn5 intermetallic particles were identified by the microstructure analysis based on the Al and Mn *** design of experiment(DOE)technique,Taguchi method,was employed to minimize the intermetallic formation in the sludge of Mg alloys with various chemical compositions of Al,Mn,Fe,and different process parameters,holding temperature and holding *** sludge yield(SY)and intermetallic size(IS)was selected as two *** optimum combination of the levels in terms of minimizing the intermetallic formation were 9 wt.%Al,0.15 wt.%Mn,0.001 wt.%(10 ppm)Fe,690℃ for the holding temperature and holding at 30 mins for the holding time,*** best combination for smallest intermetallic size were 9 wt.%Al,0.15 wt.%Mn,0.001 wt.%(10 ppm)Fe,630℃ for the holding temperature and holding at 60 mins for the holding time,*** groups of sludge factors,Chemical Sludge(CSF),physical Sludge(pSF)and Comprehensive Sludge Factors(and CpSF)were established for prediction of sludge yields and intermetallic sizes in Al-containing Mg *** CpSF with five independent variables including both chemical elements and process parameters gave high accuracy in prediction,as the prediction of the pSF with only the two processing parameters of the melt holding temperature and time showed a relatively large deviation from the experimental *** Chemical Sludge Factor was primarily designed for small ingot producers and die casters with a limited melting and holding capacity,of which process parameters could be fixed *** physical Sludge Factor could be used f

关键词： Magnesium sludge Al-Mn intermetallic Optimization Taguchi method Sludge factor Chemical composition process parameter

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Towards efficient strain engineering of 2D materials:A four-points bending approach for compressive strain

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Nano Research 2024年第6期17卷 5317-5325页

作者： Hao Li Félix Carrascoso Ana Borrás Gloria p.Moreno Francisco j.Aparicio Ángel Barranco Andrés Castellanos Gómez Campus de Cantoblanco Instituto de Ciencia de Materiales de MadridC.Sor Juana Inés de la Cruz328049 MadridSpain Nanotechnology on Surfaces and plasma Lab Instituto de Ciencia de Materiales de Sevilla(CSIC-Universidad de Sevilla).C/Americo Vespucio 49E-41092 SevilleSpain Departamento de Física Aplicada I Escuela Politécnica SuperiorUniversidad de Sevillac/Virgen deÁfrica 7E-41011 SevilleSpain

Strain engineering,as a powerful strategy to tune the optical and electrical properties of two-dimensional(2D)materials by deforming their crystal lattice,has attracted significant interest in recent years.2D materials can sustain ultra-high strains,even up to 10%,due to the lack of dangling bonds on their surface,making them ideal brittle *** remarkable mechanical resilience,together with a strong strain-tunable band structure,endows 2D materials with a broad optical and electrical response upon ***,strain engineering based on 2D materials is restricted by their nanoscale and strain quantification *** this study,we have modified a homebuilt three-points bending apparatus to transform it into a four-points bending apparatus that allows for the application of both compressive and tensile strains on 2D *** approach allows for the efficient and reproducible construction of a strain system and minimizes the buckling effect caused by the van der Waals interaction by adamantane encapsulation *** results demonstrate the feasibility of introducing compressive strain on 2D materials and the potential for tuning their optical and physical properties through this approach.

关键词： uniaxial compressive strain polymer encapsulation differential reflectance spectroscopy exciton tunability

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Strategy of preparing SmCo based films with high coercivity and remanence ratio achieved by temperature and chemical optimization

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journal of Rare Earths 2024年第7期42卷 1289-1297,I0004页

作者： Yansong Gong Zhaoguo Qiu Sizhe Liang Xinrui Zheng Hongxia Meng Zhigang Zheng Deyang Chen Shengfu Yuan Weixing Xia Dechang Zeng j.p.Liu School of Materials Science and Engineering South China University of TechnologyGuangzhou510640China Zhongshan R&D Center for Materials Surface and Thin Films Technology of the South China University of Technology Gent Materials Surface Technology(Guangdong)Co.Ltd.Zhongshan528437China Institute for Advanced Materials South China Academy of Advanced OptoelectronicsSouth China Normal UniversityGuangzhou510006China Yangjiang Branch Guangdong Laboratory Materials Science and Technology Yangjiang Advanced Alloys LaboratoryYangjiang529500China Laboratory of Rare-Earth Magnetic Functional Materials Ningbo Institute of Material Technology and EngineeringChinese Academy of SciencesNingbo315201China Department of physics University of Texas at ArlingtonArlingtonTX76019USA

SmCo based films with excellent intrinsic magnetic properties have promising applications in micro-electro-mechanical system(MEMS).However,due to the complexity of phase composition and uncontrollable crystallization degree of SmCo hard magnetic phase in the film,both the coercivity(Hc)and remanence(Mr)of films are difficult to enhance *** this paper,SmCo based films were deposited with a Cr underlayer and capping layer on single crystal Si substrates via magnetron sputtering *** effects of annealing parameters and Sm/Co atomic ratio on the phase structure and coercivity of films are *** adjusting the Sm/Co atomic ratio from 1:5 to 1:4,Co soft magnetic phase disappears and the single phase SmCo5 is obtained,leading to the increase of coercivity of the films from 30 to 34 *** influence of deposition temperature and Cu doping on magnetic properties of SmCo based films was *** the deposition temperature increases from room temperature to 250℃,the coercivity will further increase from 34 to 51 ***,a severe kink is observed in the demagnetization curves due to the poor exchanged *** analysis of transmission electron microscopy(TEM)confirms that the average size of non-hard magnetic amorphous phase exceeds the effective exchanged coupling length of SmCo5,which contributes to the decoupling and low remanence ***,doping Cu and applying a post-annealing process can significantly improve the crystallization degree of the *** the coercivity and the remanence ratio of the demagnetization curves are greatly *** propose a plausible strategy to prepare the SmCo based films with high coercivity and remanence ratio by temperature and chemical optimization,which can be utilized in high performed MEMS devices.

关键词： Rare earths SmCo based films phase composition Crystallization conditions Coercivity Remanence ratio

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HI in High Gas-phase Metallicity Dwarf Galaxy WISEA j230615.06+143927.9

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Research in Astronomy and Astrophysics 2024年第1期24卷 292-299页

作者： Yan Guo C.Sengupta T.C.Scott p.Lagos Y.Luo purple Mountain Observatory Chinese Academy of SciencesNanjing 210023China School of Astronomy and Space Sciences University of Science and Technology of ChinaHefei 230026China Institute of Astrophysics and Space Sciences(IA porto) Rua das Estrelas4150-762PortoPortugal

We present resolved Giant Metrewave Radio Telescope H I observations of the high gas-phase metallicity dwarf galaxy WISEA j230615.06+143927.9(z = 0.005)(hereafter j2306) and investigate whether it could be a Tidal Dwarf Galaxy(TDG) candidate. TDGs are observed to have higher metallicities than normal dwarfs. j2306 has an unusual combination of a blue g-r color of 0.23 mag, irregular optical morphology and high-metallicity(12 +log(O/H) = 8.68 ± 0.14), making it an interesting galaxy to study in more detail. We find j2306 to be an H I rich galaxy with a large extended, unperturbed rotating H I disk. Using our H I data we estimated its dynamical mass and found the galaxy to be dark matter(DM) dominated within its H I radius. The quantity of DM, inferred from its dynamical mass, appears to rule out j2306 as an evolved TDG. A wide area environment search reveals j2306 to be isolated from any larger galaxies which could have been the source of its high gas metallicity. Additionally, the H I morphology and kinematics of the galaxy show no indication of a recent merger to explain the *** detailed optical spectroscopic observations of j2306 might provide an answer to how a seemingly ordinary irregular dwarf galaxy achieved such a high level of metal enrichment.

关键词： galaxies:abundances galaxies:dwarf galaxies:irregular radio lines:galaxies radio lines:ISM

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Exploring the effects of anthropogenic disturbance on predator inspection activity in Trinidadian guppies

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Current Zoology 2024年第1期70卷 109-111页

作者： Alix j.p Brusseau Laurence E.A.Feyten Adam L.Crane Grant E.Brown Department of Biology Concordia UniversityMontrealQCH4B 1R6Canada Department of Biomedical Sciences WCVMUniversity of SaskatchewanSaskatoonSKCanada

prey animals are often faced with uncertainty due to having imperfect information regarding current local conditions,including predation risks and the availability of reliable foraging opportunities(Dall 2010).As this uncertainty increases,the probability of making costly behavioral errors also increases,leading to more risk averse behavioral tactics(Feyten et al.2019).For example,Trinidadian guppies poecilia reticulata are far more risk averse when faced with multiple unknown sources of risk assessment information than when faced with a mix of known and unknown cues(Feyten et al.2019).prey can reduce uncertainty by gathering and integrating private and social information regarding current risk levels within microhabitats(Dall 2010;Munoz and Blumstein 2012).

关键词： human disturbance information availability information reliability predator-prey interactions risk assessment uncertainty

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predicting Chemical Immunotoxicity through Data-Driven QSAR Modeling of Aryl Hydrocarbon Receptor Agonism and Related Toxicity Mechanisms

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Environment & Health 2024年第7期2卷 474-485页

作者： Nada j.Daood Daniel p.Russo Elena Chung Xuebin Qin Hao Zhu predicting Chemical Immunotoxicity through Data-Driven QSAR Modeling of Aryl Hydrocarbon Receptor Agonism and Related Toxicity Mechanisms Department of Chemistry and Biochemistry Rowan UniversityGlassboroNew Jersey 08028United States Center for Biomedical Informatics and Genomics Tulane University School of MedicineNew OrleansLouisiana 70112United States Tulane National primate Research Center Tulane University School of MedicineCovingtonLouisiana 70433United States

Computational modeling has emerged as a time-saving and cost-effective alternative to traditional animal testing for assessing chemicals for their potential ***,few computational modeling studies for immunotoxicity were reported,with few models available for predicting toxicants due to the lack of training data and the complex mechanisms of *** this study,we employed a data-driven quantitative structure–activity relationship(QSAR)modeling workflow to extensively enlarge the limited training data by revealing multiple targets involved in *** this end,a probe data set of 6,341 chemicals was obtained from a high-throughput screening(HTS)assay testing for the activation of the aryl hydrocarbon receptor(AhR)signaling pathway,a key event leading to *** this probe data set against pubChem yielded 3,183 assays with testing results for varying proportions of these 6,341 compounds.100 assays were selected to develop QSAR models based on their correlations to AhR *** individual QSAR models were built for each assay using combinations of four machine-learning algorithms and three molecular fingerprints.5-fold cross-validation of the resulting models showed good predictivity(average CCR=0.73).A total of 20 assays were further selected based on QSAR model performance,and their resulting QSAR models showed good predictivity of potential immunotoxicants from external *** study provides a computational modeling strategy that can utilize large public toxicity data sets for modeling immunotoxicity and other toxicity endpoints,which have limited training data and complicated toxicity mechanisms.

关键词： Immunotoxicity QSAR Machine learning Aryl hydrocarbon receptor Data mining

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particle elasticity influences polymeric artificial antigen presenting cell effectiveness in vivo via CD8+T cell activation,macrophage uptake,and the protein corona

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Nano Research 2024年第10期17卷 9052-9064页

作者： Savannah E.Est-Witte Sydney R.Shannon Dennis H.Gong Kaitlyn G.Calabresi jawaun j.Harris Kaitlyn Storm Edwin j.Yoo Ariel Isser Vivek p.jani Natalie K.Livingston Mary O.Omotoso Kelly Rhodes Elana Ben-Akiva Randall A.Meyer Zoe T.Hsieh Simone Sidoli Stephany Y.Tzeng jonathan p.Schneck jordan j.Green Translational Tissue Engineering Center Institute for NanobiotechnologyDepartment of Biomedical EngineeringJohns Hopkins School of Medicine400 N BroadwayBaltimoreMD 21231USA Institute for Cell Engineering Department of PathologyJohns Hopkins School of Medicine733 N BroadwayBaltimoreMD 21205USA Department of Biochemistry Albert Einstein College of MedicineThe BronxNew York CityNY 10461USA

Adoptive cell therapy(ACT)is an immunotherapy strategy for cancer that has seen widespread clinical *** ACT,patient-derived lymphocytes are stimulated with the antigen of interest ex vivo,proliferated,then returned to the patient to initiate an antigen-specific antitumor *** effective,this process is resource-intensive and logistically impossible for many *** artificial antigen presenting cells(aApCs)offer a potential“off-the-shelf”alternative to ex vivo *** particulate aApCs perform well in vitro,they have had limited success in vivo due to poor bioavailability after *** to bioavailability include rapid clearance,unfavorable biodistribution,and inadequate interactions with CD8+T cells at sites of *** properties such as elasticity have been shown to vastly impact the bioavailability and particle-cell interactions,but this has yet to be investigated in the context of aApCs for in vivo T-cell *** literature likewise indicates that biomaterial properties,especially elasticity,can modulate T-cell activation in *** the goal of creating a more biomimetic,next-generation particulate aApC,we developed a poly(ethylene)glycol hydrogel particle platform with tunable elasticity to investigate the impact of elasticity on antigen-specific T cell activation for in vivo adoptive *** this knowledge,we were able to gain more precise control over in vivo T cell activation and investigate possible mechanisms including the effects of aApC elasticity on T cell binding,macrophage uptake,and the protein corona.

关键词： adoptive cell therapy artificial antigen presenting cells particle drug delivery elasticity protein corona poly(ethylene glycol)

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A facile strategy for tuning the density of surface-grafted biomolecules for melt extrusion-based additive manufacturing applications

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Bio-Design and Manufacturing 2024年第3期7卷 277-291页

作者： I.A.O.Beeren G.Dos Santos p.j.Dijkstra C.Mota j.Bauer H.Ferreira Rui L.Reis N.Neves S.Camarero-Espinosa M.B.Baker L.Moroni Department of Complex Tissue Regeneration MERLN Institute for Technology-Inspired Regenerative MedicineMaastricht University6229 ER MaastrichtThe Netherlands 3B’s Research Group I3Bs–Research Institute on BiomaterialsBiodegradables and BiomimeticsHeadquarters of the European Institute of Excellence on Tissue Engineering and Regenerative MedicineUniversity of MinhoAveParkZona Industrial da Gandra4805-017 BarcoGuimarãesPortugal ICVS/3B’s-pT Government Associate Laboratory 4806-909 Braga/GuimarãesPortugal pOLYMAT University of the Basque Country UPV/EHU20018 Donostia/San SebastiánSpain IKERBASQUE Basque Foundation for Science48009 BilbaoSpain

Melt extrusion-based additive manufacturing(ME-AM)is a promising technique to fabricate porous scaffolds for tissue engi-neering ***,most synthetic semicrystalline polymers do not possess the intrinsic biological activity required to control cell *** of biomolecules on polymeric surfaces of AM scaffolds enhances the bioactivity of a construct;however,there are limited strategies available to control the surface ***,we report a strategy to tune the surface density of bioactive groups by blending a low molecular weight poly(ε-caprolactone)5k(pCL5k)containing orthogonally reactive azide groups with an unfunctionalized high molecular weight pCL75k at different *** porous three-dimensional(3D)scaf-folds were then fabricated using a high weight percentage(75 wt.%)of the low molecular weight pCL *** a proof-of-concept test,we prepared films of three different mass ratios of low and high molecular weight polymers with a thermopress and reacted with an alkynated fluorescent model compound on the surface,yielding a density of 201-561 pmol/cm^(2).Subsequently,a bone morphogenetic protein 2(BMp-2)-derived peptide was grafted onto the films comprising different blend compositions,and the effect of peptide surface density on the osteogenic differentiation of human mesenchymal stromal cells(hMSCs)was *** two weeks of culturing in a basic medium,cells expressed higher levels of BMp receptor II(BMpRII)on films with the conjugated *** addition,we found that alkaline phosphatase activity was only significantly enhanced on films contain-ing the highest peptide density(i.e.,561 pmol/cm^(2)),indicating the importance of the surface *** together,these results emphasize that the density of surface peptides on cell differentiation must be considered at the cell-material ***,we have presented a viable strategy for ME-AM community that desires to tune the bulk and surface functionality via blending of(m

关键词： Additive manufacturing Blending Surface functionalization Surface density Click chemistry Human

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From bibliometric analysis: 3D printing design strategies and battery applications with a focus on zinc‐ion batteries

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SmartMat 2024年第1期5卷 59-82页

作者： Xuan Gao Kejiang Liu Chang Su Wei Zhang Yuhang Dai Ivan p.parkin Claire j.Carmalt Guanjie He Christopher Ingold Laboratory Department of ChemistryUniversity College LondonLondonUK Electrochemical Innovation Lab(EIL) Department of Chemical EngineeringUniversity College LondonLondonUK Department of physics Hong Kong Baptist UniversityHong KongChina Nanyang Technopreneurship Center Nanyang Technological UniversitySingaporeSingapore

Three‐dimensional(3D)printing has the potential to revolutionize the way energy storage devices are designed and *** this paper,we explore the use of 3D printing in the design and production of energy storage devices,especially zinc‐ion batteries(ZIBs)and examine its potential advantages over traditional manufacturing methods.3D printing could significantly improve the customization of ZIBs,making it a promising strategy for the future of energy *** particular,3D printing allows for the creation of complex,customized geometries,and designs that can optimize the energy density,power density,and overall performance of ***,we discuss and compare the impact of 3D printing design strategies based on different configurations of film,interdigitation,and framework on energy storage devices with a focus on ***,3D printing enables the rapid prototyping and production of batteries,reducing leading times and costs compared with traditional manufacturing ***,there are also challenges and limitations to consider,such as the need for further development of suitable 3D printing materials and processes for energy storage applications.

关键词： 3D printing battery commercialization bibliometric analysis electrode configurations zinc‐ion battery

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