bluuebunny/crossref_metadata_2025_split huggingface dataset:
Silver‐Templated γ‐Keggin Alkyltin‐Oxo Cluster: Electronic Structure and Optical Limiting Effect
Authors: Zhu Yu , Wang Zirui , Li Dejing , Zhu Yin‐Di , Li Qiao‐Hong , Li Dong‐Sheng , Zhang Lei 
Published: April 2022

AbstractAs one of the most representative polyoxometalate (POM) structures, Keggin clusters have attracted considerable attention. Nevertheless, the noble‐metal‐templated Keggin structure has not been reported to date. In this work, for the first time, a Ag atom was successfully incorporated to template the formation of a γ‐Keggin alkytin‐oxo cluster. Moreover, the central Ag atom has brought a significant heavy atom effect, showing the important influence on the electronic structure and optical properties. Theoretical calculations demonstrate that the Ag atom affects the frontier molecular orbitals and excited states of the AgSn12 cluster, and also the process of electron transfer. The solid structure of the AgSn12 cluster exhibits a significant third‐order nonlinear optical (NLO) response, and an excellent optical limiting effect has been experimentally verified. The success of this work opens the way for the construction and optical properties modulation of noble metal templated Keggin structures.
Saving the Energy Loss in Lithium‐Mediated Nitrogen Fixation by Using a Highly Reactive Li3N Intermediate for C−N Coupling Reactions
Authors: Chen Gao‐Feng , Savateev Aleksandr , Song Zihan , Wu Haoyu , Markushyna Yevheniia , Zhang Lili , Wang Haihui , Antonietti Markus 
Published: April 2022

AbstractDirect synthesis of N‐containing organic compounds from dinitrogen (N2) can make synthetic chemistry more sustainable. Previous bottlenecks in lithium‐mediated N2fixation were resolved by loading Li‐metal anodes covered with the typical Li+ion‐conducting solid electrolyte interface, which are subsequently allowed to react with N2. The developed strategy allowed us to reach high Faradaic efficiencies toward Li3N. These reactive Li3N were then contacted with acylchlorides. Surface nitride ions are more nucleophilic than amines which direct the two C−N coupling reactions toward formation of imides rather than amides, and an integrated current efficiency of 57–77 % could be realized. This study thereby not only provides a feasible electrochemical Li3N synthesis, but also delineates an economical and green synthesis of highly valuable N‐containing compounds from N2under mild conditions, just using commercial spare parts and processes from the omnipresent Li battery technology.
Controlling Reaction Routes in Noble‐Metal‐Catalyzed Conversion of Aryl Ethers
Authors: Schmid Julian , Wang Meng , Gutiérrez Oliver Y. , Bullock R. Morris , Camaioni Donald M. , Lercher Johannes A. 
Published: April 2022

AbstractHydrogenolysis and hydrolysis of aryl ethers in the liquid phase are important reactions for accessing functionalized cyclic compounds from renewable feedstocks. On supported noble metals, hydrogenolysis is initiated by a hydrogen addition to the aromatic ring followed by C−O bond cleavage. In water, hydrolysis and hydrogenolysis proceed by partial hydrogenation of the aromatic ring prior to water or hydrogen insertion. The mechanisms are common for the studied metals, but the selectivity to hydrogenolysis increases in the order Pd<Rh<Ir<Ru≈Pt in decalin and water; the inverse was observed for the selectivity to hydrolysis in water. Hydrogenolysis selectivity correlates with the Gibbs free energy of hydrogen adsorption. Hydrogenolysis has the highest standard free energy of activation and a weak dependence on H2 pressure, thus, the selectivity to hydrogenolysis is maximized by increasing temperature and decreasing H2 pressure. Selectivity to C−O bond cleavage reaches >95 % in water and alkaline conditions.
Site‐Selective Pyridylic C−H Functionalization by Photocatalytic Radical Cascades
Authors: Kim Myojeong , You Euna , Kim Jieun , Hong Sungwoo 
Published: April 2022

AbstractAn efficient pyridylic C(sp3)−H functionalization has been developed through photocatalytic radical‐mediated fluoroalkylation or cascade reactions. This method is enabled by the reversible formation of alkylidene dihydropyridine intermediates via the facile enolate formation of C4‐alkylN‐amidopyridinium salts in the absence of an external base, thereby establishing the conditions necessary for subsequent intermolecular radical trapping. Rapid structural diversification of the pyridylic site can be achieved through photocatalytic multicomponent cascade reactions involving alkene trifluoromethylation, SO2‐reincorporation, and sulfonyl radical addition. This operationally simple method features a broad substrate scope and high chemoselectivity and offers a unique approach for the rational modification of the heterobenzylic C−H bonds of pyridines and quinolines with uniform site‐selective control. Furthermore, experimental and theoretical studies were performed to elucidate the reaction mechanism.
Recent Breakthroughs in P4 Chemistry: Towards Practical, Direct Transformations into P1 Compounds
Authors: Scott Daniel J. 
Published: April 2022

AbstractFor several decades, academic researchers have been intensively studying the chemistry of white phosphorus (P4) in the hope of developing direct methods for its transformation into useful P‐containing products. This would bypass the hazardous, multistep procedures currently relied on by industry. However, while academically interesting P4 activation reactions have become well established, their elaboration into useful, general synthetic procedures has remained out of reach. Very recently, however, a series of independent reports has begun to change this state of affairs. Each shows how relatively simple and practical synthetic methods can be used to access academically or industrially relevant P1 compounds from P4 directly, in “one pot” or even in a catalytic fashion. These reports mark a step change in the field of P4 chemistry, and suggest its possible transition from an area of largely academic interest to one with the promise of true synthetic relevance.
Unravelling the Turn‐On Fluorescence Mechanism of a Fluorescein‐Based Probe in GABAA Receptors
Authors: Singer Nadja K. , Sánchez‐Murcia Pedro A. , Ernst Margot , González Leticia 
Published: April 2022

AbstractGABAA (γ‐aminobutyric acid type A) receptors are ligand‐gated ion channels mediating fast inhibitory transmission in the mammalian brain. Here we report the molecular and electronic mechanism governing the turn‐on emission of a fluorescein‐based imaging probe able to target the human GABAA receptor. Multiscale calculations evidence a drastic conformational change of the probe from folded in solution to extended upon binding to the receptor. Intramolecular ππ‐stacking interactions present in the folded probe are responsible for quenching fluorescence in solution. In contrast, unfolding within the GABAA receptor changes the nature of the bright excited state triggering emission. Remarkably, this turn‐on effect only manifests for the dianionic prototropic form of the imaging probe, which is found to be the strongest binder to the GABAA receptor. This study is expected to assist the design of new photoactivatable screening tools for allosteric modulators of the GABAA receptor.
Disorder–Order Conversion‐Induced Enhancement of Thermal Stability of Pyroxene Near‐Infrared Phosphors for Light‐Emitting Diodes
Authors: Wen Dawei , Liu Hongmin , Guo Yue , Zeng Qingguang , Wu Mingmei , Liu Ru Shi 
Published: April 2022

AbstractThe minimization of thermal quenching, which leads to luminescence loss at high temperatures, is one of the most important issues for near‐infrared phosphors. In the present work, we investigated the properties of near‐infrared Ca(Sc,Mg)(Al, Si)O6 : Cr3+ phosphors with a pyroxene‐type structure under blue light excitation. The CaScAlSiO6 : Cr3+ end member of Ca(Sc,Mg)(Al,Si)O6 : Cr3+ phosphor led to broadband emission at a full‐width half maximum of 215 nm, whereas the CaMgSi2O6 : Cr3+ end member exhibited high thermal stability at 150 °C, with an intensity of 88.4 % of that at room temperature. The structural analysis and density functional theory calculations revealed the absence of soft conformations and local space confinement contributed to the high structural rigidity and weakened the thermal quenching effect.
Neochamaejasmin B extracted from Stellera chamaejasme L. induces apoptosis through caspase‐10‐dependent way in insect neuronal cells
Authors: Gu Guirong , Jiang Mingfang , Hu Hanying , Qiao Weijie , Jin Hong , Hou Taiping , Tao Ke 
Published: April 2022

AbstractTo explore the toxicity mechanisms of neochamaejasmin B (NCB) extracted from Stellera chamaejasme L., we first evaluated its cytotoxicity in neuronal cells of Helicoverpa zea (AW1 cells). NCB inhibited cell growth and was cytotoxic to AW1 cells in a dose‐dependent manner. Further, transmission electron microscopy (TEM) was used to analyze the microstructure, and typical apoptotic characteristics were observed in AW1 cells treated with NCB. Moreover, the NCB‐induced apoptosis was dose dependent. Subsequently, we explored the mechanism of apoptosis. A decline in the mitochondrial membrane potential (MMP) was found. Also, the levels of Bax were increased with increases in drug concentration, but there was no statistical difference in Bcl‐2 levels at different NCB doses. Caspase‐3 and caspase‐10 activity was increased. These findings confirmed that NCB induced apoptosis in AW1 cells through a caspase‐10‐dependent mechanism. The results provide the basic information needed for understanding the toxicity and mechanisms of action of NCB, which could potentially be used to develop NCB as a new insecticide.
An Aluminum‐Benzo[1,2‐b:4,5‐b’]dithiophene‐4,8‐dione Organic Rechargeable Battery Featuring Low Self‐Discharge
Authors: Wang Yijia , Long Ng Kok , Azimi Gisele 
Published: April 2022

AbstractThe achievable cell‐level specific energy density of existing aluminum‐ion batteries (AIBs) employing AlCl4− intercalation type cathodes is intrinsically limited by the chloroaluminate anolyte. Towards achieving AIBs with higher specific energy, it is imperative to explore alternative cell chemistries that fundamentally tap the capacity of Al metal anode. Here, we report a benzo[1,2‐b:4,5‐b’]dithiophene‐4,8‐dione (BDTD) organic electrode material with favorable AlCl2+ intercalation mechanism. This BDTD cathode delivers a specific capacity of 143 mAh g−1, and the resulting battery exhibits a well‐defined voltage plateau at ∼1.2 V. This characteristic voltage plateau is mainly driven by the predominant diffusive charge storage in BDTD cathode, which accounts for up to 85 % of the total charge‐storage contribution. As a result, the BDTD cathode demonstrates exceptional self‐discharging resistance by recovering >95 % of its capacity upon 24‐h resting.
Boosting bacteria differentiation efficiency with multidimensional surface‐enhanced Raman scattering: the example of Bacillus cereus
Authors: Zhu Chengye , Liu Wen , Wang Dongmei , Gong Zhengjun , Fan Meikun 
Published: April 2022

AbstractSurface‐enhanced Raman scattering (SERS) is a powerful tool for constructing biomolecular fingerprints, which play a vital role in differentiation of bacteria. Due to the rather subtle differences in the SERS spectra among different bacteria, artificial intelligence is usually adopted and enormous amounts of spectral data are required to improve the differentiation efficiency. However, in many cases, large volume data acquisition on bacteria is not only technical difficult but labour intensive. It is known that surface modification of SERS nanomaterials can bring additional dimensionality (difference) of the SERS fingerprints. Here in this work, we show that the concept could be used to improve the bacteria differentiation efficiency. Ag NPs were modified with 11‐mercaptoundecanoic acid, 11‐mercapto‐1‐undecanol, and 1‐dodecanethiol to provide additional dimensionality. The modified NPs then were mixed with cell lysate from different strains of Bacillus cereus (B. cereus). Even by applying a simple PCA process to the resulting SERS spectra data, all the three modified Ag NPs showed superior differentiation results compared with bare Ag NPs, which could only separate Staphylococcus aureus (S. aureus) and B. cereus. It is believed that the multidimensional SERS could find great potential in bacteria differentiation.
From spores to fungal pellets: A new high‐throughput image analysis highlights the structural development of Aspergillus niger
Authors: Müller Henri , Barthel Lars , Schmideder Stefan , Schütze Tabea , Meyer Vera , Briesen Heiko 
Published: April 2022

AbstractMany filamentous fungi are exploited as cell factories in biotechnology. Cultivated under industrially relevant submerged conditions, filamentous fungi can adopt different macromorphologies ranging from dispersed mycelia over loose clumps to pellets. Central to the development of a pellet morphology is the agglomeration of spores after inoculation followed by spore germination and outgrowth into a pellet population, which is usually very heterogeneous. As the dynamics underlying population heterogeneity is not yet fully understood, we present here a new high‐throughput image analysis pipeline based on stereomicroscopy to comprehensively assess the developmental program starting from germination up to pellet formation. To demonstrate the potential of this pipeline, we used data from 44 sampling times harvested during a 48 h submerged batch cultivation of the fungal cell factory Aspergillus niger. The analysis of up to 1700 spore agglomerates and 1500 pellets per sampling time allowed the precise tracking of the morphological development of the overall culture. The data gained were used to calculate size distributions and area fractions of spores, spore agglomerates, spore agglomerates within pellets, pellets, and dispersed mycelia. This approach eventually enables the quantification of culture heterogeneities and pellet breakage.
Sustainable business models as successful drivers in equity crowdfunding
Authors: Caputo Andrea , Schiocchet Elisa , Troise Ciro 
Published: April 2022

AbstractEquity crowdfunding is a form of capital market concerning the online offering of private company securities to a group of people for investment. Over the years, it has emerged as a valid financing alternative for sustainability‐oriented startups to conventional sources of funding to support their establishment and growth. This research explores the role that the elements of sustainable business models (SBM), which creates, delivers, and captures value for all its stakeholders without depleting the natural, economic, and social resources it relies on, can play as success discriminants of equity crowdfunding campaigns. A configuration approach was selected, and Fuzzy Set Qualitative Comparative Analysis (fsQCA) was used to investigate the causal configurations of 33 crowdfunding campaigns posted on the six most popular Italian equity crowdfunding platforms from 2014 to 2020. The analysis revealed that the SBM elements, and combinations of them, can positively affect the outcome of a campaign. Results also show that negative outcomes may be primarily due to campaign‐related features, such as high minimum investment requirements and high funding target.
Fast Interlayer Charge Separation and Transmission in ZnIn2S4/CNTs/ZnS Heterojunctions for Efficient Photocatalytic Hydrogen Evolution
Authors: Zhang Chengming , Gao Kaiyue , Zhu Haibao , Liu Jingwei , Chen Jianli , Xie Fazhi , Xie Wenjie , Wang Xiufang 
Published: April 2022

AbstractThe construction of close contact heterojunction structures is crucial to modify photocatalytic performance. Here a series of heterojunction ZnIn2S4/CNTs/ZnS nanocomposites for photocatalytic hydrogen evolution were synthesized by a simple thermal reflux approach. The ideal ZnIn2S4/CNTs/ZnS sample has a photocatalytic hydrogen evolution rate of 0.9363 mmol ⋅ g−1 ⋅ h−1 with favorable cycle stability, which is about 16.9 and 5.5 times that of pure ZnIn2S4 and binary ZnIn2S4/ZnS. The tight interfacial contact between ZnIn2S4, ZnS, and CNTs raises photogenerated charge carrier separation efficiency. CNTs have a high electrical conductivity, which allows them to receive and transport photogenerated electrons effectively. Therefore, the recombination of photon‐generated charges may be efficaciously restrained, and the accepted electrons can be rapidly transported to reactive sites for production of hydrogen. Simultaneously, density functional theory (DFT) simulations show that introducing CNTs can enhance electronic characteristics and add additional charge carriers. This study shows that well‐designed CNTs‐based heterojunction structure can effectively promote charge separation in photocatalysis.
Glucose Induces Heme Leakage and Suppresses H2O2 Uptake of Chloroperoxidase in the Asymmetric Hydroxylation of Ethylbenzene
Authors: Wang Zheyu , Fu Zhongwang , Jian Yupei , Han Yilei , Xia Meng , Zhang Shuiwei , Yan Binhang , Jiang Guoqiang , Lu Diannan , Wu Jianzhong , Liu Zheng 
Published: April 2022

AbstractAs a basic feedstock for both natural life and chemical production, glucose is converted into various chemicals upon the help of peroxidase cascades composed of glucose oxidase (GOx) and peroxidases. However, little is known about the glucose effect on the structure and activity of peroxidases in a non‐natural environment. We report herein that glucose deactivates chloroperoxidase (CPO) used in the asymmetric hydroxylation of ethylbenzene into (R)‐1‐phenylethanol. Through both experiment and molecular simulation, we discover that glucose deactivates CPO through hydrophobic interaction with heme and hydrogen bonding with Glu183. These interactions lead to heme leakage and the reduction of H2O2 uptake thereby undermining the CPO activity. The mechanism appears generically applicable to other hemeproteins such as horseradish peroxidase, hemoglobin, and myoglobin. These findings may open new avenues for the design of peroxidase cascades for applications ranging from better diagnosis of diabetes to green synthesis of chemicals by direct functionalization of C−H bonds.
Demands, resources, meaningful work, and burnout of counselors‐in‐training
Authors: Um Byeolbee , Bardhoshi Gerta 
Published: April 2022

AbstractThis study examined the relationship between demands, resources, meaningful work, and burnout of counselors‐in‐training. The results of structural equation modeling indicated that demands and resources significantly predicted burnout of counselors‐in‐training, whereas meaningful work did not mediate the relationship between resources and burnout. Implications for counselor education are discussed.
Simulation of an Integrated Anaerobic Digestion and Combined Heat and Power System for Food Waste Utilization
Authors: Sidek Nailah Fasihah , Harun Noorlisa , Mohd Zamri Fatin Nur Liyana 
Published: April 2022

AbstractDemand for renewable energy such as biogas is increasing because it is considered a clean and environmentally friendly source of energy and has the potential for minimizing carbon emissions. Biogas production through anaerobic digestion (AD) of organic materials is considered one of the most sustainable ways. It can be utilized directly or indirectly to generate heat, electricity, or mechanical energy for transportation. One of the most effective ways to use biogas is the combined heat and power (CHP) system, especially in combination with simulation software to facilitate the whole process without an actual experimental setup, easing the evaluation and analysis process. This study aims to develop an integrated model of AD for biogas production from food waste and CHP plants, through simulation using Aspen Plus software. The simulated results show that the developed process model can predict the heat and power produced from food waste feedstock.
Near Infrared Circularly Polarized Luminescence From Water Stable Organic Nanoparticles Containing a Chiral Yb(III) Complex
Authors: Cavalli Enrico , Nardon Chiara , Willis Oliver G. , Zinna Francesco , Di Bari Lorenzo , Mizzoni Silvia , Ruggieri Silvia , Gaglio Salvatore C. , Perduca Massimiliano , Zaccone Claudio , Romeo Alessandro , Piccinelli Fabio 
Published: April 2022

AbstractWe report the first example of very efficient NIR Circularly Polarized Luminescence (CPL) (around 970 nm) in water, obtained thanks to the combined use of a chiral Yb complex and of poly lactic‐co‐glycolic acid (PLGA) nanoparticles. [YbL(tta)2]CH3COO (L=N, N’‐bis(2‐pyridylmethylidene)‐1,2‐(R,R+S,S) cyclohexanediamine and tta=2‐thenoyltrifluoroacetonate) shows good CPL in organic solvents, because the tta ligands efficiently sensitize Yb NIR luminescence and the readily prepared chiral ligand L endows the complex with the necessary dissymmetry. PLGA nanoparticles incorporate the complex and protect the metal ion from the intrusion of solvent molecules, while ensuring biocompatibility, water solubility and stability to the complex. Hydrophilic NIR‐CPL optical probes can find applications in the field of NIR‐CPL bio‐assays.
Large Enhancement of the Single‐Molecular Conductance of a Molecular Wire through a Radical Substituent
Authors: Yasui Ryuto , Shimizu Daiki , Matsuda Kenji 
Published: April 2022

AbstractInvited for the cover of this issue are Ryuto Yasui, Daiki Shimizu, and Kenji Matsuda at Kyoto University. The image depicts a comparison of the molecular conductance of radical‐substituted and non‐radical‐substituted molecular wires evaluated by STM. Read the full text of the article at 10.1002/chem.202104242.