bluuebunny/crossref_metadata_2025_split huggingface dataset:
Importance of Electron Mediator Transparency: Photocatalytic Hydrogen Production from Polyoxometalate using Dye‐double‐layered Photocatalysts
Authors: Yoshimura Nobutaka , Tomita Osamu , Abe Ryu , Yoshida Masaki , Kobayashi Atsushi 
Published: January 2023

AbstractOne‐directional electron transfer is crucial for two‐step photoexcitation (Z‐scheme) water‐splitting photocatalysis. We investigated the hydrogen evolution activity of PS‐double‐layered photocatalysts (X‐DSP, X‐RuCP6‐Zr‐RuP6@Pt/KxH4‐xNb6O17; X=Zr4+, H+) in the presence of highly charged polyoxometalates‐K6[SiVIVW11O40] ⋅ nH2O (VIV‐POM) and K6[SiW11O39MnII(H2O)] ⋅ nH2O (MnII‐POM)‐as redox‐reversible electron donors, to induce effective photocatalyst‐donor electrostatic attraction. Surface‐phosphonate‐comprising H+‐DSP completely one‐electron oxidized VIV‐POM with 0.39 % apparent quantum yield in the initial hour (iAQY) in both HCl and phosphate buffer aqueous solutions. Conversely, the Zr4+‐DSP iAQY decreased to 0.05 % in HCl aq. Considering that the 0.39 % iAQY was retained when replacing VIV‐POM with MnII‐POM in HCl aq, we supposed that energy transfer deactivation from photoexcited PS* to surface‐immobilized VIV‐POM is the plausible origin of the lower iAQY, owing to the stronger visible‐light absorptivity of VIV‐POM. This suggests that accumulation of visible‐light‐transparent electron mediator on the photocatalyst surface is an effective approach for one‐directional electron transfer in Z‐scheme water‐splitting photocatalysis.
Synthesis of Nano CdZnS/SnS2/SnO2 Heterojunction for Photocatalytic Degradation of Rhodamine B
Authors: Li Lei , Du Yan , Sun Houxiang , Zhang Huabing , Zhong Zicong 
Published: January 2023

AbstractThe accumulation of organic dyes in water and their consequent detrimental effect to ecological environment have attracted worldwide extensive attention. It is urgent to develop rapid and efficient method to degrade organic dyes. In this paper, an efficient CdZnS/SnS2/SnO2 heterojunction is successfully prepared by sequential template approach and hydrothermal method. Comparison with CdZnS and SnS2/SnO2, the heterogeneous structure of CdZnS/SnS2/SnO2 greatly enhances the photocatalytic degradation ability of Rhodamine B (RhB). The apparent reaction rate of CdZnS/SnS2/SnO2 heterostructure is around 12.71 and 16.69 times higher than those of SnS2/SnO2 and CdZnS, respectively, reaching 0.0267 min−1. After CdZnS/SnS2/SnO2 photocatalysis of RhB solution, the BOD/COD ratio increases from 0.168 to 0.725, indicating that the biodegradability is greatly improved. It has been proved that ⋅OH, ⋅O2−, h+ and e− are the main active species involved in the degradation process. In addition, the CdZnS/SnS2/SnO2 exhibits good stability and reusability, with little change in the photocatalytic activity after five cycles. Its superior removal activity is mainly due to the formation of heterojunction improved light harvesting and enhanced separation efficiency. This work provides a new insight for photocatalytic degradation of organic dye wastewater by solar light.
Ammonia Decomposition in Electric Field over Ce‐based Materials
Authors: Maslova Valeriia , Fourré Elodie , Veryasov Gleb , Nesterenko Nikolai , Grishin André , Louste Christophe , Nassar Michelle , Guignard Nadia , Arrii Sandrine , Batiot‐Dupeyrat Catherine 
Published: January 2023

AbstractElectric field‐induced decomposition of ammonia into hydrogen and nitrogen was investigated over CeO2, Fe‐, Ru‐ deposited CeO2, CePO4 and Sr‐doped CePO4, and CeZrO4 in a packed bed down‐flow reactor. The effect of applied current, concentration of ammonia in a feed, and residence time was examined using CeO2 alone. The conversion of ammonia was also studied with respect to a reduction temperature, loading and a type of the deposited metal. The activity results have been analyzed in terms of surface, morphological and electrical characterization of the catalysts. Among metal‐deposited catalysts, ammonia decomposition result at 4 mA was the best for 1 wt % Fe/CeO2 reduced at 550 °C, showing 22 % of conversion with 0.18 mmol of converted ammonia per kJ of energy consumed. The activity of studied Ce‐based catalysts normalized per mass of loaded catalyst showed an accordance in activity‐porosity relation.
The Aldol‐Tishchenko Reaction of Butanone, Cyclobutanone and a 3‐Pentanone Derived Sulfinylimine and DFT Calculations of the Stereo‐determining Step
Authors: Alcock Emma , Mackey Pamela , Turlik Aneta , Bhatt Khushi , Light Mark E. , Houk Kendall N. , McGlacken Gerard P. 
Published: January 2023

AbstractHerein, we present a highly diastereoselective method to furnish acyclic 3‐amino‐1,5‐diol derivatives using a tandem double‐aldol‐Tishchenko protocol (dr up to >99 : 1) using a butanone derived sulfinylimine. In most cases only 1 diastereomer predominates, from a possible 16. The reaction is also regioselective. In addition, the highly challenging cyclobutanone and 3‐pentanone derivatives are also amenable to a double‐aldol‐Tishchenko reaction, although the dr values are modest. Despite that, clean single diastereomers can be isolated, which should prove very useful in medicinal chemistry and other areas. Detailed DFT calculations support the observed stereoselectivities in all cases, providing a rationale for the excellent dr values in the butanone series and the moderate values for the 3‐pentanone class.
Piezoelectric Metal‐Organic Frameworks Mediated Mechanoredox Borylation and Arylation Reactions by Ball Milling
Authors: Ding Rundong , Liu Qing , Zheng Lifei 
Published: January 2023

AbstractHerein, metal‐organic frameworks UiO‐66 and UiO‐66‐NH2were synthesized, and their piezoelectric properties were characterized by piezoresponse force microscopy. Under mechanical agitation, the highly polarized UiO‐66 and UiO‐66‐NH2can act as electron donors to reduce aryl diazonium salts, forming the aryl radical species, which further react with bis(pinacolato)diborane or heteroarenes to generate the desired products with broad substrate scope. For all substrates, it was found that the reactions mediated by UiO‐66‐NH2, which exhibited better piezoelectric property, were more efficient than those promoted by UiO‐66. Moreover, it was shown that the convenient regeneration of spent catalysts can be reused for promoting mechanoredox reactions without loss of activities by taking advantage of the unmatched repairability of metal‐organic frameworks. Mechanistic studies revealed that a radical pathway was involved in these transformations.
Substituent‐Dependent Photoexcitation Processes of π‐Stacked Ion Pairs
Authors: Tanaka Hiroki , Okayasu Yoshinori , Kobayashi Yoichi , Maeda Hiromitsu 
Published: January 2023

AbstractPorphyrin ion pairs, the charge of which is delocalized in core units, form tightly associated structures through iπ–iπ interactions. 5,10,15‐Triphenyl‐substituted porphyrin–AuIII complex, which is favorable for forming stacked structures in the form of a stable ion, has been synthesized. Ion‐pair metathesis based on the hard and soft acids and bases theory enabled combination with porphyrin anions possessing electronic states controlled by electron‐donating and electron‐withdrawing groups. Transient absorption spectroscopy suggested that the lifetimes of the radical pairs generated by photoinduced electron transfer of the ion pairs could be controlled by a judicious combination of the anions and cations.
Supramolecular Structure and Photo‐Thermo‐Electric Property of Hydrogen‐Bonded Liquid Crystalline Polymer Containing Poly(4‐vinylpridine) and Cyanostilbene Side Chains
Authors: Lv Xu‐Chen , Lu Lin , Zuo Xin‐Xiao , Achalkumar Ammathnadu S. , Zhao Ai‐Juan , Bermeshev Maxim V. , Wang Fu‐Min , Ngeontae Wittaya , Ren Xiang‐Kui 
Published: January 2023

AbstractA series of side‐chain liquid crystalline polymers P4VP(CN‐DBE)x, where x is the molar ratio of cyanostilbene (CN‐DBE) to poly(4‐vinylpyridine) (P4VP) repeating unit, was synthesized based on the intermolecular hydrogen bonding between P4VP and CN‐DBE. Their luminescent property, liquid crystalline structure and photo‐thermo‐electric property were elucidated using photoluminescence spectra, X‐ray diffraction, thermal imaging and thermoelectric experiments. With the increase of x, the supramolecular system can be changed from lamellar structure to hexagonal columnar structure. Moreover, the P4VP(CN‐DBE)x polymer with columnar structure exhibits more efficient photothermal effect. The temperature of P4VP(CN‐DBE)0.6 can rise to 130 °C within 10 s under the irradiation of ultraviolet lamp. In addition, the supramolecular system possesses unique photo‐thermo‐electric conversion ability, and 25 mA current can be detected in the circuit coupled with the thermoelectric module. This work broadens the potential applications of hydrogen‐bonded polymer, and provides a simple and facile strategy to prepare liquid crystalline polymers with photo‐thermo‐electric property.
In‐silico vinyl chloride suspension polymerization: Kinetic modelling, thermal runaway prediction, and prevention
Authors: Han Jian‐Peng , Yang Ya‐Nan , Zhao Chang‐Sen , Qian Ying‐Hui , Niu Qiang , Luo Zheng‐Hong , Zhou Yin‐Ning 
Published: January 2023

AbstractIn the present study, a combined kinetic and heat transfer model was developed to study the kinetics and predict thermal runaway of vinyl chloride (VC) suspension polymerization. Reactor temperature, monomer conversion, mole of initiator, radical concentrations in the two phases (i.e., VC‐rich phase and PVC‐rich phase), and average molecular properties were mapped during non‐isothermal processes. Meanwhile, the risk of thermal runaway was evaluated using S–Z (divergence) and H–J criteria. Simulation results show that a lower jacket temperature Tj and a larger heat transfer coefficient U are able to postpone or even avoid the risk of thermal runaway. Both of the criteria serve well for the prediction of thermal runaway during non‐isothermal processes. To prevent the occurrence of thermal runaway to the greatest extent, model‐based design of strategies for an isothermal polymerization process was done. Specifically, either jacket temperature Tj or heat transfer coefficient U can be fine‐tuned to maintain a 50°C isothermal process.
Sparse estimation within Pearson's system, with an application to financial market risk
Authors: Carey Michelle , Genest Christian , Ramsay James O. 
Published: January 2023

AbstractPearson's system is a rich class of models that includes many classical univariate distributions. It comprises all continuous densities whose logarithmic derivative can be expressed as a ratio of quadratic polynomials governed by a vector of coefficients. The estimation of a Pearson density is challenging, as small variations in can induce wild changes in the shape of the corresponding density . The authors show how to estimate and effectively through a penalized likelihood procedure involving differential regularization. The approach combines a penalized regression method and a profiled estimation technique. Simulations and an illustration with S&P 500 data suggest that the proposed method can improve market risk assessment substantially through value‐at‐risk and expected shortfall estimates that outperform those currently used by financial institutions and regulators.
Hydrazone‐Tethered 5‐(Pyridin‐4‐yl)‐4H‐1,2,4‐triazole‐3‐thiol Hybrids: Synthesis, Characterisation, in silico ADME Studies, and in vitro Antimycobacterial Evaluation and Cytotoxicity
Authors: Oderinlo Ogunyemi O. , Jordaan Audrey , Seldon Ronnett , Isaacs Michelle , Hoppe Heinrich C. , Warner Digby F. , Tukulula Matshawandile , Khanye Setshaba D. 
Published: January 2023

AbstractCompounds containing arylpyrrole‐, 1,2,4‐triazole‐ and hydrazone structural frameworks have been widely studied and demonstrated to exhibit a wide range of pharmacological properties. Herein, an exploratory series of new 1,2,4‐triazole derivatives designed by amalgamation of arylpyrrole and 1,2,4‐triazole structural units via a hydrazone linkage is reported. The synthesised compounds were tested in vitro for their potential activity against Mycobacterium tuberculosis (MTB) H37Rv strain. The most promising compound 13 – the derivative without the benzene ring appended to the pyrrole unit displayed acceptable activity (MIC90=3.99 μM) against MTB H37Rv, while other compounds from the series exhibited modest to weak antimycobacterial activity with MIC90 values in the range between 7.0 and >125 μM. Furthermore, in silico results, predicated using the SwissADME web tool, show that the prepared compounds display desirable ADME profile with parameters within acceptable range.
2‐Hydroxy‐4‐benzyloxylimine Resveratrol Derivatives as Potential Multifunctional Agents for the Treatment of Parkinson's Disease
Authors: Cao Zhongcheng , Zhang Tianlong , Fu Xianwu , Wang Xingyue , Xia Qian , Zhong Lei , Zhu Jiang 
Published: January 2023

AbstractA series of 2‐hydroxy‐4‐benzyloxylimine resveratrol derivatives was designed, synthesized and evaluated as multifunctional agents for the treatment of Parkinson's disease. The results revealed that most derivatives possessed good multifunctional activities. Among them, representative compound (E)‐5‐[(4‐fluorobenzyl)oxy]‐2‐{[(4‐hydroxyphenyl)imino]methyl}phenol (7 h) exhibited excellent MAO‐B inhibition (IC50=8.43×10−3 μM) and high antioxidant activity (ORAC=3.45 Trolox equivalent). Additionally, 7 h displayed good metal chelating ability, appropriate blood–brain barrier (BBB) permeability, significant neuroprotective effect, and great anti‐neuroinflammatory activity. Furthermore, 7 h can also ameliorate 1‐methyl‐4‐phenyl‐1,2,3,6‐tetrahydropyridine (MPTP)‐induced Parkinson's disease symptoms in mice. Therefore, compound 7 h was found to be a promising candidate for further development against PD.
Associations of breast cancer related exposures and gene expression profiles in normal breast tissue—The Norwegian Women and Cancer normal breast tissue study
Authors: Krum‐Hansen Sanda , Standahl Olsen Karina , Anderssen Endre , Frantzen Jan Ole , Lund Eiliv , Paulssen Ruth H. 
Published: January 2023

AbstractBackgroundNormal breast tissue is utilized in tissue‐based studies of breast carcinogenesis. While gene expression in breast tumor tissue is well explored, our knowledge of transcriptomic signatures in normal breast tissue is still incomplete. The aim of this study was to investigate variability of gene expression in a large sample of normal breast tissue biopsies, according to breast cancer related exposures (obesity, smoking, alcohol, hormone therapy, and parity).MethodsWe analyzed gene expression profiles from 311 normal breast tissue biopsies from cancer‐free, post‐menopausal women, using Illumina bead chip arrays. Principal component analysis andK‐means clustering was used for initial analysis of the dataset. The association of exposures and covariates with gene expression was determined using linear models for microarrays.ResultsHeterogeneity of the breast tissue and cell composition had the strongest influence on gene expression profiles. After adjusting for cell composition, obesity, smoking, and alcohol showed the highest numbers of associated genes and pathways, whereas hormone therapy and parity were associated with negligible gene expression differences.ConclusionOur results provide insight into associations between major exposures and gene expression profiles and provide an informative baseline for improved understanding of exposure‐related molecular events in normal breast tissue of cancer‐free, post‐menopausal women.
Quantitative Descriptions of Dewar‐Chatt‐Duncanson Bonding Model: A Case Study of Zeise and Its Family Ions
Authors: Yang Tao , Li Zhaoyang , Wang Xue‐Bin , Hou Gao‐Lei 
Published: January 2023

AbstractHistorically, Dewar‐Chatt‐Duncanson (DCD) model is a heuristic device to advance the development of organometallic chemistry and deepen our understanding of the metal‐ligand bonding nature. Zeise's ion, the first man‐made organometallic compound and a quintessential transition metal‐olefin complex, was qualitatively explained using the DCD bonding scheme in 1950s. In this work, we quantified the explicit contributions of the σ donation and π back‐donation to the metal‐ligand bonding in Zeise and its family ions, [PtX3L]− (X=F, Cl, Br, I, and At; L=C2H4, CO, and N2), using state‐of‐the‐art quantum chemical calculations and energy decomposition analysis. The relative importance of the σ donation and π back‐donation depends on both X and L, with [PtCl3(C2H4)]− being a critical case in which the σ donation is marginally weaker than the π back‐donation. The changes along this series are controlled by the energy levels of the correlated molecular orbitals of PtX3− and ligand L. This study deepens our understanding of the bonding properties for transition metal complexes beyond the qualitative description of the DCD model.
A Theoretical Account of the Coupling between Metal‐ and Ligand‐centred Spins
Authors: Roy Sriparna , Paul Satadal , Misra Anirban 
Published: January 2023

AbstractThis study addresses the magnetic interaction between paramagnetic metal ions and the radical ligands taking the [CuII(hfac)2(imVDZ)] and [MII(hfac)2(pyDTDA)] (imVDZ=1,5‐dimethyl‐3‐(1‐methyl‐2‐imidazolyl)‐6‐oxoverdazyl; hfac=(1,1,1,5,5,5)hexafluroacetylacetonate; pyDTDA=4‐(2′‐pyridyl)‐1,2,3,5‐dithiadiazolyl), (M=Cu, Ni, Co, Fe, Mn) compounds as reference systems. The coupling between the metal and ligand spins is quantified in terms of the exchange coupling constant (J) in the platform of density functional theory (DFT) and the wave function‐based complete active space self‐consistent field (CASSCF) method. Application of DFT and broken symmetry (BS) formalism results ferromagnetic coupling for all the transition metal complexes except the Mn(II) complex. This DFT‐BS prediction of magnetic nature matches with the experimental finding for all the complexes other than the Fe(II)‐pyDTDA complex, for which an antiferromagnetic coupling between high spin iron and the thiazyl ligand has been reported. However, evaluation of spin state energetics through the multiconfigurational wave function‐based method produces the S=3/2 ground spin state for the iron‐thiazyl in parity with experiment. Electronic structure analyses find the overlap between the metal‐ and ligand‐based singly occupied molecular orbitals (SOMOs) to be one of the major reasons attributing to different extent of exchange coupling in the systems under investigation.
Design, prototype validation, and reliability analysis of a multi‐input DC/DC converter for grid‐independent hybrid electric vehicles
Authors: Bairabathina Saikumar , Subramani Balamurugan 
Published: January 2023

SummarySignificantly, the performance of a grid‐independent hybrid electric vehicle (GIHEV) is decided by a multi‐input converter in it. This paper discusses the detailed mathematical modeling, design, prototype validation, and analysis of a multi‐input DC‐DC converter (MIC). This converter actively accommodates fuel cell and solar photovoltaic (PV) panel as sources and utilizes the concept of multiple switching frequencies to get wide regulation of output voltage and power flow. The average large‐signal modeling, small‐signal modeling, and steady‐state modeling are demonstrated to achieve accurate design and analysis. The reliability analysis of the proposed converter along with the respective mathematical background is discussed. The proposed system design is validated with the help of an experimental setup and tested effectively. The proposed converter promises higher gain and 95.58% efficiency with fewer switches, low voltage stress, and fewer circuit components.
A design of predictive manufacturing system in IoT‐assisted Industry 4.0 using heuristic‐derived deep learning
Authors: Murugiah Premkumar , Muthuramalingam Akila , Anandamurugan S. 
Published: January 2023

SummaryThe predictive maintenance function is ensured with the earlier detection of errors and faults in the machinery before reaching its critical stages. On the other hand, the challenges faced by Internet of things (IoT) devices are the security problem because they can be easily attacked by comparing the other devices such as computers or portable devices. It cannot solve the high‐dimensional issues and imbalanced data. The computation cost is very expensive when using the modern sampling method. In addition, the conventional methods for predictive maintenance are incorporated with a single method. So, the maintenance and prognostic tasks are very hard to address simultaneously. Thus, a new predictive manufacturing system in Industry 4.0 for examining the machines is proposed. In the initial stage, the data are collected from IoT industry sensors. Considerably, the data cleaning is carried out, and deep features are extracted through the “Multi‐Scale Dilation Attention Convolutional Neural Network (MSDA‐CNN).” Further, the deep, weighted features are extracted, where the weight is optimized using the hybrid algorithm named Probabilistic Beetle Swarm‐Butterfly Optimization (PBS‐BO). In the end, the weighted features are given to the Optimized Hybrid Fault Detection (OHFD) that is performed by the “Deep Neural Network (DNN) and Deep Belief Network (DBN).” Finally, if any faults in machines are predicted, then the system sends alerts to the industrialists for suitable decision‐making. The efficiency of the suggested model is evaluated on a set of real measurements in Industry 4.0.
Progress of small molecules for targeted protein degradation: PROTACs and other technologies
Authors: Zhao Hong‐Yi , Xin Minhang , Zhang San‐Qi 
Published: January 2023

AbstractRecent years have witnessed the rapid development of targeted protein degradation (TPD), especially proteolysis targeting chimeras. These degraders have manifested many advantages over small molecule inhibitors. To date, a huge number of degraders have been excavated against over 70 disease‐related targets. In particular, degraders against estrogen receptor and androgen receptor have crowded into phase II clinical trial. TPD technologies largely expand the scope of druggable targets, and provide powerful tools for addressing intractable problems that can not be tackled by traditional small molecule inhibitors. In this review, we mainly focus on the structures and biological activities of small molecule degraders as well as the elucidation of mechanisms of emerging TPD technologies. We also propose the challenges that exist in the TPD field at present.