bluuebunny/crossref_metadata_2025 huggingface dataset:
Opportunities, Challenges, and Strategies for Scalable Deposition of Metal Halide Perovskite Solar Cells and Modules
Authors: Khorasani Azam , Mohamadkhani Fateme , Marandi Maziar , Luo Huiming , Abdi‐Jalebi Mojtaba
Published: March 2024

Hybrid organic‐inorganic perovskite solar cells (PSCs) have rapidly advanced in the new generation of photovoltaic devices. As the demand for energy continues to grow, the pursuit of more stable, highly efficient, and cost‐effective solar cells has intensified in both academic research and the industry. Consequently, the development of scalable fabrication techniques that yield a uniform and dense perovskite absorber layer with optimal crystallization plays a crucial role to enhance stability and higher efficiency of perovskite solar modules. This review provides a comprehensive summary of recent advancements, comparison, and future prospects of scalable deposition techniques for perovskite photovoltaics. We discuss various techniques, including solution‐based and physical methods such as blade coating, inkjet printing (IJP), screen printing, slot‐die coating, physical vapor deposition, and spray coating that have been employed for fabrication of perovskite modules. The advantages and challenges associated with these techniques, such as contactless and maskless deposition, scalability, and compatibility with roll‐to‐roll processes, have been thoroughly examined. Finally, the integration of multiple subcells in perovskite solar modules is explored using different scalable deposition techniques.
Structure and Internal Dynamics of Short RNA Duplexes Determined by a Combination of Pulsed EPR Methods and MD Simulations
Authors: Gauger Maximilian , Heinz Marcel , Halbritter Anna‐Lena J. , Stelzl Lukas S. , Erlenbach Nicole , Hummer Gerhard , Sigurdsson Snorri Th. , Prisner Thomas F.
Published: March 2024

We used EPR spectroscopy to characterize the structure of RNA duplexes and their internal twist, stretch and bending motions. We prepared eight 20‐base‐pair‐long RNA duplexes containing the rigid spin‐label Çm, a cytidine analogue, at two positions and acquired orientation‐selective PELDOR/DEER data. By using different frequency bands (X‐, Q‐, G‐band), detailed information about the distance and orientation of the labels was obtained and provided insights into the global conformational dynamics of the RNA duplex. We used 19F Mims ENDOR experiments on three singly Çm‐ and singly fluorine‐labeled RNA duplexes to determine the exact position of the Çm spin label in the helix. In a quantitative comparison to MD simulations of RNA with and without Çm spin labels, we found that state‐of‐the‐art force fields with explicit parameterization of the spin label were able to describe the conformational ensemble present in our experiments. The MD simulations further confirmed that the Çm spin labels are excellent mimics of cytidine inducing only small local changes in the RNA structure. Çm spin labels are thus ideally suited for high‐precision EPR experiments to probe the structure and, in conjunction with MD simulations, motions of RNA.
Ultrathin Free‐Standing Porous Aromatic Framework Membranes for Efficient Anion Transport
Authors: Du Wenguang , Liu Lin , Yin Liying , Li Bo , Ma Yu , Guo Xiaoyu , Zang Hong‐Ying , Zhang Ning , Zhu Guangshan
Published: March 2024

Porous aromatic frameworks (PAFs) show promising potential in anionic conduction due to their high stability and customizable functionality. However, the insolubility of most PAFs presents a significant challenge in their processing into membranes and subsequent applications. In this study, continuous PAF membranes with adjustable thickness were successfully created using liquid‐solid interfacial polymerization. The rigid backbone and the stable C−C coupling endow PAF membrane with superior chemical and dimensional stabilities over most conventional polymer membranes. Different quaternary ammonium functionalities were anchored to the backbone through flexible alkyl chains with tunable length. The optimal PAF membrane exhibited an OH− conductivity of 356.6 mS ⋅ cm−1 at 80 °C and 98 % relative humidity. Additionally, the PAF membrane exhibited outstanding alkaline stability, retaining 95 % of its OH− conductivity after 1000 hours in 1 M NaOH. To the best of our knowledge, this is the first application of PAF materials in anion exchange membranes, achieving the highest OH− conductivity and exceptional chemical/dimensional stability. This work provides the possibility for the potential of PAF materials in anionic conductive membranes.
Lewis Acid Decorated Hexacyanodiborane(6) Dianion
Authors: Zapf Ludwig , Finze Maik
Published: March 2024

First examples of diborane(6) dianions decorated with weakly coordination B(C6F5)3 (BCF) groups and SiEt3+ moieties have been synthesized demonstrating the synthetic potential of the [B2(CN)6]2− dianion. [B2{CNB(C6F5)3}6]2− (1) was isolated as potassium and tetrabutylammonium salt. 1 is a rare example for a weakly coordinating dianion and it was used for the stabilization of the carbocation [Ph3C]+ and the oxonium acid [H(OEt2)2]+. Reaction of [Ph3C]21 with HSiEt3 resulted in the silylated neutral diborane(6) [B2{CNB(C6F5)3}4(CNSiEt3)2] (2) in which two BCF groups have been selectively replaced by SiEt3+ substituents, underscoring the stability and chemical versatility of the [B2(CN)6]2− dianion. The chemical properties and physicochemical data of 1 and 2 provide insight into electronic, coordinating, and steric properties of theses novel diborane(6) compounds.
Tumor‐targeted and microenvironment‐activatable iron‐based nMOF for synergistic inducing ferroptosis
Authors: Gao Fangxin , Xie Yaqing , Zhang Pan , Chang Qinghua , Zhang Enli , Shen Jingyi , Liang Lili , Zong Zhihui
Published: March 2024

Ferroptosis is a new form of cell death that relies on iron and involves an imbalance of intracellular reactive oxygen species (ROS), which is expected to help alleviate bottlenecks in tumor treatment. Herein, a sorafenib‐loaded folic acid‐armored iron‐based nMOF was designed for synergistic inducing ferroptosis of tumors. The particle size of the synthesized SM@F is about 210nm, and the drug loading rate is 24.74%. SM@F can be degraded and releases sorafenib and iron ions slowly, resulting in intracellular drug release and iron overload after being highly uptaken by SMMC‐7721 cells. SM@F can effectively inhibit the proliferation of SMMC‐7721 cells, and this effect can be significantly attenuated by ferroptosis inhibitors. Mechanistic investigations revealed that SM@F could increase the content of ROS, and lipid peroxides; decrease the content of glutathione (GSH); and down‐regulate the GXP4 expression in SMMC‐7721 cells. The results indicate that the synthesized SM@F could effectively inhibit the proliferation of tumor cells with synergistic inducing ferroptosis.
Dual cross‐linking of XNBR latex with epoxy‐functional calcium silicate particles for the production of accelerator‐free medical gloves
Authors: Grabmayer Theresa , Manhart Jakob , Fleischmann Darya , Kaiser Simon , Schaller Raimund , Holzner Armin , Schlögl Sandra
Published: March 2024

In this work, an innovative dual cross‐linking strategy for carboxylated nitrile butadiene rubber (XNBR) latex using epoxy‐modified calcium silicate particles is presented. In their role as dual cross‐linker, the particles are able to form covalent bonds (nucleophilic ring opening of epoxy moieties) as well as ionic cross‐links (calcium ions of the inorganic core) across the carboxylic acid groups of the rubber. To characterize the curing efficiency, thin elastomer films are prepared by using a conventional coagulant dipping process and their cross‐link densities, curing kinetics, and tensile properties are investigated as a function of the concentration of the cross‐linker and curing time. The results show that latex films containing 5 phr of epoxy‐functional particles give the highest tensile strength, which is further improved by pre‐vulcanizing the liquid latex compound at 60°C for 30 min. The latex formulations are stable over 3 days and the pre‐cured films exhibit a high resistance against gamma sterilization and subsequent accelerated aging. Moreover, sterile films do not cause any skin irritation or skin sensitization reactions, showing the high potential of epoxy‐functional particles in the production of accelerator‐free hypoallergenic gloves.
Surface modification of spherical silica micro‐powder using silane coupling agents and their application in epoxy resin‐based composite materials
Authors: Wang Daobei , Yu Mingdong , Wang Yining , Yao Zhiqiang , Xia Anqi , Li Lin , Wang Dongzhi
Published: March 2024

In recent years, the packaging industry has utilized electronic packaging materials with epoxy resin (EP) and high‐performance fillers, exhibiting superior mechanical properties and thermal conductivity. Spherical silica micro‐powder (SSP) is a critical thermal conductive filler but faces challenges due to its inorganic nature. Surface modification is essential to improve SSP's compatibility and dispersion in organic matrices for effective use in EP‐based composites. In this paper, the effects of the following four modification methods on SSP/EP composites were studied: (1) the processes include co‐modification with dimethyldimethoxysilane (DMDMS) and trimethylethoxysilane (MTES), (2) modification with NaOH, (3) co‐modification with DMDMS and MTES in an alkaline environment after NaOH modification, and (4) co‐modification with methyltrimethoxysilane (MTMS) and propyltrimethoxysilane (PTMOS). Through comprehensive characterization and evaluation, it is evident that modification schemes 1, 3, and 4 significantly enhance SSP's hydrophobicity, dispersibility, and compatibility with EP. This led to the improvement of thermal conductivity and stability of the composite, and modification scheme 4 showed the highest enhancement, with a 42.6% increase in thermal conductivity. Moreover, the mechanical properties of modified composite materials, such as bending strength, impact resistance, and tensile strength, surpass those of unmodified SSP/EP composite materials. The study provides valuable insights for reducing manufacturing costs and enhancing productivity in the electronic packaging sector.
A climatological analysis of northward‐moving typhoon in environments of the Northeast China cold vortex
Authors: Zhao Dajun , Yu Yubin , Wei Na , Song Jinjie , Chen Lianshou
Published: March 2024

This study investigates the influence of the Northeast China cold vortex (NCCV) on the northward‐moving typhoons (NTCs) over the western North Pacific (WNP). There is a significant inverse relationship between the NCCV during June–September and simultaneous NTCs during 1981–2021. Fewer (more) NTCs are observed during NCCV active (inactive) year a combination of less (more) NTC genesis, particularly over the central Pacific region of 10°–30° N and 130°–150° E, and fewer (more) NTCs moving northwestward and making landfall in coastal regions of the Yellow Sea and Bohai Sea. These regions are characterized by significantly decreased low‐level vorticity and mid‐level humidity, which impedes NTC genesis and notably enhances the deep‐layer subtropical straight westerly steering flow, thus blocking the northward movement of NTCs. These remarkable environmental changes during different NCCV years are clearly linked with the changes of an anomalous anticyclone in the subtropics (20°–30° N, 120°–160° E). In short, more (less) NCCV activity strengthens (weakens) the anomalous anticyclone, resulting in fewer (more) NTCs.
Identifying the Role of Electrolyte Additives for Lithium Plating on Graphite Electrode by Operando X‐ray Tomography
Authors: Klein Antoine , Sadd Matthew , Mozhzhukhina Nataliia , Olsson Martina , Broche Ludovic , Xiong Shizhao , Matic Aleksandar
Published: March 2024

The plating of lithium metal on the graphite electrode is a major degradation mechanism in lithium‐ion batteries (LIBs). It brings a significant risk of internal shortcircuit by penetration of dendritic lithium through the separator, leading to short cycle life and safety issues. Understanding how and when plating occurs is crucial for the development of mitigation strategies, e. g. tuning the electrolyte composition. Here we present an operando X‐ray tomographic microscopy (XTM) study to directly monitor the plating of lithium metal in a lithium/graphite cell. XTM enables a non‐destructive and quantitative characterization at operando conditions of lithium deposition on a graphite electrode at relevant conditions. In this work it allows us to probe the role of the electrolyte additives vinylene carbonate (VC) and lithium bis(fluorosulfonyl)imide (LiFSI) in the standard LIB electrolyte LP57 (base electrolyte without additives). The additives show overall better performances in terms of delayed onset of lithium plating which is important for the utilisation of the full capacity of graphite intercallaiton. We show that there is a transition during lithiation of the dominating mechanism, once lithium plating is initiated this rapidly becomes dominating and hinders further intercalation. For the base electrolyte a homogeneous and dense morphology of plated lithium is found, whereas a more dendritic morphology is observed in the presence of additives. During delithiation, there is a rapid stripping of some of the plated lithium followed by deintercalation. In addition, our work provides a general methodology to track the morphology of plated lithium, which is crucial for fundamental research about battery safety.
The T‐locus – inspiration and distraction?
Authors: Erickson Robert P.
Published: March 2024

The T/t locus was a major focus of study by mouse geneticists during the 20th century. In the 70s, as the study of cell surface antigens controlling transplantation antigens was taking off, several laboratories hypothesized that alleles of this locus would control cell surface antigens important for embryonic development. One such antigen, the embryonal carcinoma F9 antigen was said to be an example. Other antigens were described on sperm and embryos that were said to be controlled by alleles at the T/t complex. These findings were later found to be false. The history of the findings and their refutation is described.
A Review on the Traditional Applications, Phytochemistry, and Pharmacology of the Genus Physochlaina G. Don
Authors: Rasheed Tantray Younas , Jan Ishrat , Mohiuddin Irshad , Gorla Preeti , Anand Charul , Chandra Arya Jagdish , Ahmad Bhat Shahnawaz , Kumar Vijay , Narasimhaji Ch. Venkata , Nagayya Shiddamallayya , Acharya Rabinarayan
Published: March 2024

Physochlaina is a genus of flowering plants belonging to the family Solanaceae and consists of 10 species distributed in various Asian countries. The species of the genus have been traditionally used to cure a variety of illnesses due to their highly valuable medicinal properties, including cancer, asthma, cough, weakness, stomachache, diarrhea, swelling, spasms, toothache, boils, ulcers, rheumatic pain, chronic bronchitis, gastric problems, abdominal pain, palpitation, and insomnia. The species have gained significant attention due to their remarkable ethnopharmacological and ethnomedicinal significance. The researchers have isolated so far 71 biologically active secondary metabolites from different Physochlaina species, which include flavonoids, alkaloids, coumarins, phenolic acids, iridoids, and sterols. These compounds exhibit diverse biological activities, such as antibacterial, anti‐oxidant, anti‐inflammatory, cytotoxic, and anticancer properties. The present review has been compiled with the intention of providing a comprehensive overview of the botany, distribution, traditional uses, phytochemical profile, and biological activities of the genus Physochlaina for future exploration of plant‐based drugs and therapeutic approaches. The present review contributes to understanding the significant pharmacological potential of Physochlaina species and unraveling their chemical composition, highlighting their relevance in developing therapeutic agents. Till date, numerous pharmacological properties and isolated phytochemicals of Physochlaina species that support the species traditional and ethnobotanical history have been documented in a number of scientific publications. However, greater emphasis should be paid to in vivo investigations on various extracts and their phytoconstituents as well as mechanistic analysis to help drug developers better understand how to use Physochlaina species as significant therapeutic resources for herbal formulations using various techniques.
Advancements in Addressing Microcrack Formation in Ni–Rich Layered Oxide Cathodes for Lithium–Ion Batteries
Authors: Xu Tianmei , Wu Jingjing , Ding Juan , Huang Yingde , Huang Yudai , Zhao Wengao
Published: March 2024

Nickel–rich layered oxides of LiNi1–x–yCoxMn(Al)yO2 (where 1–x–y>0.6) are considered promising cathode active materials for lithium‐ion batteries (LIBs) due to their high reversible capacity and energy density. However, the widespread application of NCM(A) is limited by microstructural degradation caused by the anisotropic shrinkage and expansion of primary particles during the H2→H3 phase transition. In this mini–review, we comprehensively discuss the formation of microcracks, subsequent material degradation, and related alleviation strategies in nickel–rich layered NCM(A). Firstly, theories on microcracks′ formation and evolution mechanisms are presented and critically analyzed. Secondly, recent advancements in mitigation strategies to prevent degradation in Ni–rich NCM/NCA are highlighted. These strategies include doping, surface coating, structural optimization, and morphology engineering. Finally, we provide an outlook and perspective to identify promising strategies that may enable the practical application of Ni–rich NCM/NCA in commercial settings.
Anodic Oxidation of Aliphatic and Aromatic Amides, Bisamides and Related Derivatives
Authors: Becker James Y.
Published: March 2024

The current comprehensive review covers four main parts, of which some are presented in the form of a personal account. 1. Anodic oxidation of a) N‐alkyl and N,N‐diallyl carbonyl moieties, b) Azacycloalkyl amides and the effect of ring‐size on the outcome, c) Lactams, d) Sulfonamides, and e) The effect of a substituent R attached to carbonyl (N−CO−R) or sulfonamides (N−SO2R) on their oxidation potentials. 2. Anodic oxidation of aromatic amides, in particular of type Ph2CHCONHAr, lacking hydrogen(s) at the α‐position to nitrogen. They undergo three types of bond‐cleavage, yielding a variety of fragmentation products. 3. a) Anodic oxidation of symmetrical bisamides of type ZCONH(CH2)nNHCOZ (Z=Me, Ph, Ar; n=2–4) under constant current electrolysis, in methanol. For n=3, 4 they afford mostly mono‐ and dimethoxylation products. For n=2 they undergo ′CH2−CH2′ bond cleavage to yield fragmentation products. b) Anodic oxidation of symmetrical bisamides of type ArCONH(CH2)2NHCOAr under controlled potential electrolysis, in acetonitrile, leads togem‐unsymmetrical bisamides of type ArCONHCH2NHCOMe as the major product, in fair yields. 4. Utilization of the anodic process in organic synthesis to form C−C bonds by bothintra‐andinetrmolecular processes; as well as C−O and C−N bonds for generating heterocycles.
Functional Plasticity of a Viral Terpene Synthase, OILTS, that Shows Non–Specific Metal Cofactor Binding and Metal–Dependent Biosynthesis
Authors: Jung Youngcheol , Mitsuhashi Takaaki , Kikuchi Takashi , Fujita Makoto
Published: March 2024

OILTS is a viral class I terpene synthase found from the giant virus Orpheovirus IHUMI–LCC2. It exhibits a unique structure and demonstrates high plasticity to metal cofactors, allowing it to biosynthesize different cyclic terpene frameworks. Notably, while OILTS produces only (+)‐germacrene D–4–ol with the most common cofactor, Mg2+, it also biosynthesizes a different cyclic terpene, (+)‐cubebol, with Mn2+, Co2+, or Ni2+, presenting a rare instance of cofactor‐dependent enzyme catalysis. This is the first report of (+)‐cubebol biosynthesis, to our knowledge. In addition, OILTS can uptake Zn2+ as a cofactor, which is uncommon among ordinary terpene synthases. These findings suggest that OILTS′s functional plasticity may benefit the virus in diverse host environments, highlighting potential evolutionary implications.
Enhancing Intramolecular Ferromagnetic Coupling in Tetrathiafulvalene–Nitronyl Nitroxide‐Based Compounds through Spin Polarization Mechanism
Authors: Franquesa‐Viñas Pau , Ribas‐Ariño Jordi , Santiago Raul , Deumal Mercè
Published: March 2024

Spin‐polarized donor radicals based on tetrathiafulvalene (TTF) derivatives and nitronyl nitroxide (NN) radicals in which one‐electron oxidation involves the HOMO instead of the SOMO are well known for exhibiting magnetoresistance. In particular, BTBN consists of one dibromo‐TTF and one NN radical, which are linked by a phenyl coupler group. One of the key factors driving magnetoresistance is the presence of intramolecular ferromagnetic (FM) coupling between the oxidized π‐donor (TTF+⋅, D unit) and NN (R unit). Here, a theoretical study is carried out to assess suitable candidates with enhanced FM coupling with respect BTBN, which is thus used as a reference. The study is conducted via in silico chemical modification of the substituents of the BTBN basic functional units (D and R radicals, C coupler) to benefit from the spin polarization mechanism to boost the intramolecular FM coupling, aiming to distort the BTBN radical arrangement within the molecular crystal as little as possible, in the event the material can be synthesized. NICSiso(1) and Wiberg's Bond Order are analyzed to further assist in identifying promising potential candidates, since the decrease in aromaticity is expected to enhance the diradical character and give rise to a larger magnetic coupling value. The most favorable diradical building block to replace the BTBN moiety results from using a hydroxyl‐ethylene (−(H)C=C(OH)−) as a coupler preserving BTBN original radicals, namely, NN and TTF+⋅ units. This study aims at illustrating the feasibility of improving the intramolecular FM interaction between radical moieties, which is fully realized, as a first step towards the synthesis of new materials with (possibly) enhanced magnetoresistance properties.
Mono‐Ortho‐Beryllated Carbodiphosphoranes: Synthesis, Structure, Bonding and Reactivity
Authors: Buchner Magnus R. , Kreuzer Lukas K. , Thomas‐Hargreaves Lewis R. , Müller Matthias , Ivlev Sergei I. , Frenking Gernot , Pan Sudip
Published: March 2024

The reaction of organoberyllium compounds with hexaphenylcarbodiphosphorane yields mono‐ortho‐beryllated complexes, which feature a double dative Be=C bond. The bonding situation in these compounds together with a simple carbodiphosphorane and an N‐heterocyclic carbene adduct was analysed with energy decomposition analysis in combination with natural orbital for chemical valence as well as with quantum theory of atoms‐in‐molecules. Furthermore, the driving forces accountable for mono‐ortho‐beryllation were elucidated along with the reactivity of the Be=C bond.
Recovery of valuable metals from cathode materials of spent ternary lithium‐ion battery using natural product as reducing reagent
Authors: Dong Liping , Li Yongjian , Shi Pei , Tian Shichao , Ren Zhongqi , Zhou Zhiyong
Published: March 2024

In recent years, ternary lithium‐ion batteries (LIBs) have been vigorously promoted in the field of new energy vehicles for their excellent overall performance, and the rapid growth of battery production and sales has brought about a proliferation of spent LIBs. The recycling of cathode materials of spent ternary LIBs, which are rich in many valuable metal elements, will bring multiple environmental and economic benefits. In this paper, a systematic study of the key influencing factors in the wet leaching and recycling process was carried out. A natural product tea polyphenol was innovatively used as the reducing reagent, and a sulphuric acid–tea polyphenol leaching system was constructed for the reductive acid leaching of cathode materials of spent ternary LIBs. Under the optimum leaching conditions, the leaching efficiencies of lithium, nickel, cobalt, and manganese were 99.54%, 98.88%, 99.37%, and 98.45%, respectively. After leaching, a stepwise precipitation method was used to separate and recover the valuable metal ions from the leachate. In summary, an innovatively complete recycling process route for cathode materials of spent ternary LIBs was constructed, which provides a solid theoretical basis and technical support for the efficient and clean recycling of spent LIBs.
Pressure Induces Six‐fold Coordination for the Lighter Pnictides Phosphorus and Arsenic Triiodide
Authors: Gain Pranab , Mondal Soumya , Datta Ayan
Published: March 2024

In this study, we employ an evolutionary algorithm in conjunction with first‐principles density functional theory (DFT) calculations to comprehensively investigate the structural transitions, electronic properties, and chemical bonding behaviors of XI3 compounds, where X denotes phosphorus (P) and arsenic (As), across a range of elevated pressures. Our computational analyses reveal a distinctive phenomenon occurring under compression, wherein the initially trigonal structures of PI3 (P 63) and AsI3 (R‐3) undergo an intriguing transformation, leading to the emergence of six‐coordinated monoclinic phases (C2/m) at 6 GPa and 2 GPa for PI3 and AsI3, respectively. These high‐pressure phases exhibit their stability up to 10 GPa for PI3 and 12 GPa for AsI3. Notably, the resulting structures at elevated pressures bear striking resemblance to the widely recognized six‐coordinated octahedral BiI3 crystal configuration observed at ambient conditions. Our investigation further underscores the pivotal role of pressure‐induced reactivity of the lone‐pair electrons in PI3 and AsI3, facilitating their enhanced stereochemical reactivity and thereby enabling higher six‐fold coordination. Complementary analyses employing electron localization function (ELF) and density of states (DOS) effectively delineate the progression towards augmented coordination in PI3 and AsI3 with increasing pressure. While the phenomenon of heightened coordination is conventionally associated with heavier pnictide iodides such as SbI3 and BiI3 under ambient conditions due to heightened ionic character and relativistic effects in bismuth (Bi) and antimony (Sb), our findings accentuate that analogous structural transformations can also be induced in lighter elements like phosphorus (P) and arsenic (As) under the influence of pressure.
Possibilities and Limitations of Kinetic Studies in On‐Surface Synthesis by Real Time X‐ray Photoelectron Spectroscopy
Authors: Lackinger Markus
Published: March 2024

The kinetics of coupling reactions on surfaces can be quantitatively studied in real time by X‐ray Photoelectron Spectroscopy (XPS). From fitting experimental data, kinetic reaction parameters such as the rate constant's pre‐exponential and activation energy can be deduced and compared to quantum chemical simulations. To elucidate the possibilities and limitations of this approach, we propose studies in which experimental data are first simulated and subsequently fitted. Knowing the exact kinetic parameters used in the simulation allows one to evaluate the accuracy of the fit result. Here, several experimental influences, such as the data point density and the addition of noise, are explored for a model reaction with first‐order kinetics. The proposed procedure sheds light on the accuracy with which kinetic parameters can be derived and may also help in the design of future experiments.
Coarsening of Quasi Two‐Dimensional Emulsions Formed by Islands in Free‐Standing Smectic Films
Authors: Klopp Christoph , Trittel Torsten , Stannarius Ralf
Published: March 2024

We study the coarsening behavior of assemblies of islands on smectic A freely suspended films in ISS microgravity experiments. The islands can be regarded as liquid inclusions in a two‐dimensional fluid in analogy to liquid droplets of the discontinuous phase of an emulsion. The coarsening is effectuated by two processes, predominantly by island coalescence, but to some extend also by Ostwald ripening, whereby large islands grow at the expense of surrounding smaller ones. A peculiarity of this system is that the continuous and the discontinuous phases consist of the same material. We determine the dynamics, analyze the self‐similar aging of the island size distribution and discuss characteristic exponents of the mean island growth.
Tetrel Bonding of the Carbenium Ion Forms a Pentacoordinate Carbon Atom
Authors: Scheiner Steve
Published: March 2024

As a flat trigonal species, the CR3+ carbenium ion contains a pair of deep π‐holes above and below its molecular plane. In the case of CH3+ a first base will form a covalent bond with the central C, making the combined species tetrahedral. Approach of a second base to the opposite side results in a longer but rather strong noncovalent tetrel bond (TB). While CMe3+ can also form a similar asymmetric complex with a pair of bases, it also has the capacity to form a pair of nearly equivalent TBs, such that the resulting symmetric trigonal bipyramid configuration is only slightly higher in energy. When the three substituents on the central C are phenyl rings, the symmetric configuration with two TBs predominates. These tetrel bonds are quite strong, reaching up to 20 kcal/mol. Adding OPH2 or OCH substituents to the phenyl rings permits the formation of intramolecular C⋅⋅O TBs to the central C, very similar in many respects to the case where these TBs are intermolecular.
New Perspectives on Delocalization Pathways in Aromatic Molecular Chameleons
Authors: Leyva‐Parra Luis , Casademont‐Reig Irene , Pino‐Rios Ricardo , Ruiz Lina , Alonso Mercedes , Tiznado William
Published: March 2024

This study comprehensively analyzes the magnetically induced current density of polycyclic compounds labeled as “aromatic chameleons” since they can arrange their π‐electrons to exhibit aromaticity in both the ground and the lowest triplet state. These compounds comprise benzenoid moieties fused to a central skeleton with 4n π‐electrons and traditional magnetic descriptors are biased due to the superposition of local magnetic responses. In the S0 state, our analysis reveals that the molecular constituent fragments preserve their (anti)aromatic features in agreement with two types of resonant structures: one associated with aromatic benzenoids and the other with a central antiaromatic ring. Regarding the T1 state, a global and diatropic ring current is revealed. Our aromaticity study is complemented with advanced electronic and geometric descriptors to consider different aspects of aromaticity, particularly important in the evaluation of excited state aromaticity. Remarkably, these descriptors consistently align with the general features on the main delocalization pathways in polycyclic hydrocarbons consisting of fused 4n π‐electron rings. Moreover, our study demonstrates an inverse correlation between the singlet‐triplet energy difference and the antiaromatic character of the central ring in S0.
Turnover Number in Photoinduced Molecular Catalysis of Hydrogen Evolution: a Benchmarking for Catalysts?
Authors: Fortage Jérôme , Collomb Marie‐Noëlle , Costentin Cyrille
Published: March 2024

Development of devices for production of H2 using light and a sustainable source of electrons may require the design of molecular systems combining a molecular catalyst and a photosensitizer. Evaluation of the efficiency of hydrogen production is commonly performed in homogeneous solution with a sacrificial electron donor and the report of the maximal turnover number vs catalyst (
). This figure of merit is strongly dependent on deactivation pathways and does not by itself provide a benchmarking for catalysts. In particular, when the photosensitizer degradation is the primary source of limitation, a kinetic model, rationalizing literature data, shows that a decrease of the catalyst concentration leads to an increase of
. It indicates that exceptionally high
obtained at very low catalyst concentration shall not be considered as an indication of an exceptional catalytic system. We advocate for a systematic kinetic analysis in order to get a quantitative measure of the competitive pathways leading to
values and to provide keys for performance improvement.
Lisa Takami shares how she took her book proposal from life goal to published reality
Authors: Sutton Halley
Published: March 2024

Lisa Mednick Takami, Ed.D., has been a long‐time contributor to Women in Higher Education. In the fall of 2023, she published her first book with Wiley: Women in the Higher Education C‐Suite: Diverse Executive Profiles.
Improved carrier collection efficiency in CZTS solar cells by Li‐enhanced liquid‐phase‐assisted grain growth
Authors: Yuan Xiaojie , Li Jianjun , Sun Kaiwen , Huang Jialiang , Cui Xin , Wang Ao , Xie Bingqiao , Hoex Bram , Green Martin , Hao Xiaojing
Published: March 2024

The liquid‐phase‐assisted grain growth (LGG) process is a promising strategy to fabricate large‐grain pure sulfide Cu2ZnSnS4 (CZTS) layers that span the absorber thickness and improve the carrier collection efficiency in photovoltaic devices. Li doping is an effective route to promote such LGG process of Cu2ZnSn(S,Se)4 (CZTSSe) as it can provide liquid Li‐Se phase facilitating the growth of large‐grain CZTSSe. However, the detailed function of the added Li in grain growth has rarely been investigated in both CZTS and CZTSSe, as the reported in situ, and pre‐deposition doping strategies usually suffer from substantial Li losses during the spin‐coating process and/or the high‐temperature sulfurization process. Herein, by monitoring the temperature‐dependent Li loss during the sulfurization process, we demonstrate that a small proportion of the added Li can remain at the CZTS film from the early sulfurization stage and provide Li‐S flux to promote the LGG process. An encouraging efficiency of 10.53%, with a remarkably high short‐circuit current density of 22.6 mA/cm2 and open‐circuit voltage of 0.744 V, is achieved by a significantly enlarged grain size of 3 μm with Li addition. This work could enhance the knowledge of employing Li‐S as flux for growing large‐grain chalcogenide absorbers for high performance devices with better carrier transport.
Proteinase K is not essential for marine eDNA metabarcoding
Authors: Timmers Molly A. , Viehl Katherine , Angulo Cameron , Hoban Mykle L. , Toonen Robert J. , Walsh Cameron A. J. , Wishingrad Van , Bowen Brian W.
Published: March 2024

Proteinase K (ProK) is regarded as an essential ingredient in most DNA extraction protocols for protein‐rich sample types such as tissue, blood, and mucus. However, ProK is expensive and may be unnecessary when samples are protein‐limited, such as environmental DNA (eDNA) from oligotrophic seawater. To investigate this, we filtered seawater through Sterivex cartridges from a mesocosm receiving input from the adjacent coral reef slope at the Hawai‘i Institute of Marine Biology. We tested whether the addition of varying levels of ProK (0 μL, 25 μL, 50 μL, 100 μL, or 150 μL—20 mg/mL stock concentrations) to 1.8 mL of lysis buffer affected DNA yield and the diversity, community composition, and detection of known organisms within the mesocosm community based on zero‐width operational taxonomic units (ZOTUs) obtained from DNA metabarcoding. We found no significant differences in diversity metrics among ProK quantities and dominant ZOTUs were consistent across concentrations. Over 50% of detected ZOTUs were shared among samples and only two ZOTUs were unique to samples of a particular ProK concentration. While the community composition among ProK quantities differed, pairwise community comparisons between quantities were not statistically significant and matched the known species composition of the mesocosm. These results suggest that rare ZOTUs and eDNA patchiness are driving overall community differences as opposed to extraction ingredients. Our data show that ProK is not essential when assessing communities from oligotrophic marine environments using eDNA and that the reduction or elimination of ProK can decrease sample preparation time and costs while maintaining data integrity.
Role of Alkylated 2,6‐bis(tetrazol‐5‐yl)pyridyl Ligands and Iron(II) Salts in Selecting Spin Crossover Complexes
Authors: Mazzoni Rita , Baratti Stefano , Rustichelli Daniel , Stagni Stefano , Fiorini Valentina , Zacchini Stefano , Pinkowicz Dawid , Forni Alessandra , Plaisier Jasper R. , Gigli Lara , Rigamonti Luca
Published: March 2024

The substituents in 2,6‐bis(2‐R‐2H‐tetrazol‐5‐yl)pyridyl neutral ligands R2btp (R=Me, tBu) revealed a prominent effect when reacting with iron(II) salts, in combination with the nature of the anion. According to metal:ligand molar ratio, reaction of R2btp with FeCl2 led to isolate [FeII(R2btp‐κ3N,N’,N”)2](FeIIICl4)2, R=Me (1 a) and tBu (2 a), where the octahedral iron(II) centres bring two tridentate ligands in mer coordination mode, but also [FeII(tBu2btp‐κ3N,N’,N”)(tBu2btp‐κN)2(H2O‐κO)](FeIIICl4)2 (2 b), where one ligand is tridentate, while the other two coordinate the iron(II) through one tetrazolyl nitrogen atom, and the octahedral sphere is completed by one water molecule. In all cases, half of the iron ions are oxidised to iron(III) forming the paramagnetic tetrachloroferrato counterions. Reaction of tBu2btp with Fe(ClO4)2 ⋅ 6H2O led to the octahedral [FeII(tBu2btp‐κ3N,N’,N”)2](ClO4)2 ⋅ 4DCM (4 a ⋅ 4DCM), which shows solvent‐dependent spin crossover behaviour: while 4 a ⋅ 4DCM is blocked in the high spin state, its unsolvated form, 4 a, undergoes spin transition to low spin in two subsequent steps at 206 K, with opening of a 23‐K hysteresis (T1/2↓=194 K, T1/2↑=217 K), and at 136 K (T1/2↓=135 K, T1/2↑=137 K). The magnetic profile changes to an incomplete spin transition when the sample absorbs water molecules yielding 4 a ⋅ 1.5H2O.
Development of a cascaded lattice Boltzmann model for two‐layer shallow water flows
Authors: Di Francesco Silvia , Venturi Sara , Padrone Jessica , Agresta Antonio
Published: March 2024

Many environmental phenomena, such as flows in rivers or in coastal region can be characterised by means of the ‘shallow approach’. A multi‐layer scheme allows to extend it to density layered shallow water flows (e.g., gravity currents). Although a variety of models allowing numerical investigation of single and multi‐layer shallow water flows, based on continuum and particle approaches, have been widely discussed, there are still some computational aspects that need further investigation. Focusing on the Lattice Boltzmann models (LBM), available multi‐layer models generally use the standard linear collision operator (CO). In this work we adopt a multi relaxation time (MRT) cascaded collision operator to develop a two‐layered liquid Lattice‐Boltzmann model (CaLB‐2). Specifically, the model solves the shallow water equations, taking into account two separate sets of particle distribution function (PDF), one for each layer, solved separately. Layers are connected through coupling terms, defined as external forces that model the mutual actions between the two layers. The model is validated through comparisons with experimental and numerical results from test cases available in literature. First results are very promising, highlighting a good correspondence between simulation results and literature benchmarks.
Gray matter volume associations in youth with ADHD features of inattention and hyperactivity/impulsivity
Authors: Reimann Gabrielle E. , Jeong Hee Jung , Durham E. Leighton , Archer Camille , Moore Tyler M. , Berhe Fanual , Dupont Randolph M. , Kaczkurkin Antonia N.
Published: March 2024

Background

Prior research has shown smaller cortical and subcortical gray matter volumes among individuals with attention‐deficit/hyperactivity disorder (ADHD). However, neuroimaging studies often do not differentiate between inattention and hyperactivity/impulsivity, which are distinct core features of ADHD. The present study uses an approach to disentangle overlapping variance to examine the neurostructural heterogeneity of inattention and hyperactivity/impulsivity dimensions.

Methods

We analyzed data from 10,692 9‐ to 10‐year‐old children from the Adolescent Brain Cognitive Development (ABCD) Study. Confirmatory factor analysis was used to derive factors representing inattentive and hyperactive/impulsive traits. We employed structural equation modeling to examine these factors' associations with gray matter volume while controlling for the shared variance between factors.

Results

Greater endorsement of inattentive traits was associated with smaller bilateral caudal anterior cingulate and left parahippocampal volumes. Greater endorsement of hyperactivity/impulsivity traits was associated with smaller bilateral caudate and left parahippocampal volumes. The results were similar when accounting for socioeconomic status, medication, and in‐scanner motion. The magnitude of these findings increased when accounting for overall volume and intracranial volume, supporting a focal effect in our results.

Conclusions

Inattentive and hyperactivity/impulsivity traits show common volume deficits in regions associated with visuospatial processing and memory while at the same time showing dissociable differences, with inattention showing differences in areas associated with attention and emotion regulation and hyperactivity/impulsivity associated with volume differences in motor activity regions. Uncovering such biological underpinnings within the broader disorder of ADHD allows us to refine our understanding of ADHD presentations.
Canonical‐Cell Tilings and their Atomic Decorations
Authors: Fujita Nobuhisa , Mihalkovič Marek , Henley Christopher L.
Published: March 2024

The canonical cell tiling is a geometrical framework that uses four kinds of basic polyhedra, called the canonical cells, to model the packing of atoms and clusters in icosahedral quasicrystals and related periodic approximants. Over the past three decades, it has become increasingly clear that this framework is the most sensible approach to describe related structures, albeit technically much less tractable than the Ammann‐Kramer‐Neri tiling, which is the simplest icosahedral tiling geometry based on the two Ammann rhombohedra. Geometrical arrangements of cells pose a number of combinatorial problems that cannot be handled using simple linear algebra, making it infeasible to determine structures using the standard six‐dimensional scheme. This up‐to‐date review begins with the motivation, definition, and mathematical facts about the canonical cell tiling. Then the reader is taken through the zoo of concrete structures, from smaller periodic approximants to larger ones, along with an overview of the techniques and heuristics used to study them. The recent discovery of a quasiperiodic canonical cell tiling is also briefly illustrated. The latter half of this review surveys the atomistic modeling of real atomic structures in all the three existing structural families based on the decoration concept of the canonical cell tiling.
The Tsai vs. Bergman Cluster Stability in ZnMgSc 1/1 Periodic Approximant Crystal
Authors: Buganski Ireneusz , Strzalka Radoslaw , Wolny Janusz
Published: March 2024

Quasicrystals with icosahedral symmetry can be classified into two main groups: Bergman‐type and Tsai‐type. While these are considered as distinct phases, they share a common feature of being constructed from atomic clusters, either Tsai or Bergman. In this study, we employ Density Functional Theory to perform electronic structure calculations on the Zn84.79Mg0.86Sc14.35 periodic approximant crystal phase. Our investigation involves systematically displacing atoms from Tsai cluster sites to Bergman cluster sites, allowing us to explore modifications in the electronic structure. Our findings reveal that the stability of the phase is influenced by the interaction between Zn‐4p and Sc‐3d orbitals. We observe that the sp‐d hybridization effect may play a more crucial role rather than Hume‐Rothery stabilization, as this observation holds true regardless of the presence or absence of periodic boundary conditions. Notably, the additional atom present in the Tsai structure serves as a significant electron acceptor in low‐energy orbitals. Its absence in Bergman structures results in a composition with fewer atoms possessing high‐energy d orbitals. This discovery provides a rationale for the frequent occurrence of Bergman phases with transition metals or rare earth elements, which occupy less than 10 % of the sites in the structure.
Mitochondrial respiratory supercomplexes of the yeast Saccharomyces cerevisiae
Authors: Eldeeb Mazzen H. , Camacho Lopez Lizeth J. , Fontanesi Flavia
Published: March 2024

The functional and structural relationship among the individual components of the mitochondrial respiratory chain constitutes a central aspect of our understanding of aerobic catabolism. This interplay has been a subject of intense debate for over 50 years. It is well established that individual respiratory enzymes associate into higher‐order structures known as respiratory supercomplexes, which represent the evolutionarily conserved organizing principle of the mitochondrial respiratory chain. In the yeast Saccharomyces cerevisiae, supercomplexes are formed by a complex III homodimer flanked by one or two complex IV monomers, and their high‐resolution structures have been recently elucidated. Despite the wealth of structural information, several proposed supercomplex functions remain speculative and our understanding of their physiological relevance is still limited. Recent advances in the field were made possible by the construction of yeast strains where the association of complex III and IV into supercomplexes is impeded, leading to diminished respiratory capacity and compromised cellular competitive fitness. Here, we discuss the experimental evidence and hypotheses relative to the functional roles of yeast respiratory supercomplexes. Moreover, we review the current models of yeast complex III and IV assembly in the context of supercomplex formation and highlight the data scattered throughout the literature suggesting the existence of cross talk between their biogenetic processes.
Exploring epistemic aspects of engineering for K–12 science and engineering education
Authors: Yesilyurt Ezgi , Deniz Hasan , Kaya Erdogan
Published: March 2024

Background

Since the advent of the Next Generation Science Standards (NGSS), there has been an increasing focus on engineering in K–12 education. As educators and researchers have gained a better understanding of the nature of engineering in the decade following the release of the NGSS, there are new opportunities for growth and complexity.

Purpose

This study used an epistemological approach to seek insights from experts in the science and engineering communities about the prominent aspects of engineering for K–12 education.

Design/Method

This mixed‐methods study employed a three‐round Delphi study and a focus group meeting to elicit experts' opinions on the epistemic aspects of engineering that could shed light on the nature of engineering knowledge and practices. Constructivist grounded theory methodology was used to identify preliminary themes concerning the epistemic aspects of engineering and then to develop main themes by combining relevant themes together.

Results

The analysis process yielded 21 preliminary themes that reflect key ideas about the engineering knowledge base, engineering design activities, and values and norms of the engineering community. Additionally, the current study identified eight main themes that captured the broader patterns in the data.

Conclusions

The outcome of this study, including the preliminary themes and main themes concerning the epistemic aspects of engineering, could serve as a conceptual tool for establishing and improving students' conceptions of engineering and as a guide for designing and implementing engineering design activities in K–12 education settings.