bluuebunny/crossref_metadata_2025 huggingface dataset:
Rejuvenating Aged Perovskite Quantum Dots for Efficient Solar Cells
Authors: Chen Jingxuan , Jia Donglin , Zhuang Rongshan , Hua Yong , Zhang Xiaoliang
Published: September 2023

Perovskite quantum dots (PQDs) have emerged as one of the most promising candidates for next‐generation solar cells owing to its remarkable optoelectronic properties and solution processability. However, the optoelectronic properties of PQDs suffer from severe degradation in storage due to the dynamically binding ligands, predominantly affecting photovoltaic applications. Herein, an in situ defect healing treatment (DHT) is reported to effectively rejuvenate aged PQDs. Systematically, experimental studies and theoretical calculations are performed to fundamentally understand the causes leading to the recovered optoelectronic properties of aged PQDs. The results reveal that the I3− anions produced from tetra‐n‐octylammonium iodide and iodine could strongly anchor on the surface matrix defects of aged PQDs, substantially diminishing the nonradiative recombination of photogenerated charge carriers. Meanwhile, an DHT could also renovate the morphology of aged PQDs and thus improve the stacking orientation of PQD solids, substantially ameliorating charge carrier transport within PQD solids. Consequently, by using a DHT, the PQD solar cell (PQDSC) yields a high efficiency of up to 15.88%, which is comparable with the PQDSCs fabricated using fresh PQDs. Meanwhile, the stability of PQDSCs fabricated using the rejuvenated PQDs is also largely improved.
Oxidation Driven Thin‐Film Solid‐State Metal Dealloying Forming Bicontinuous Nanostructures
Authors: Chung Cheng‐Chu , Clark Charles , Zhao Chonghang , Kisslinger Kim , Camino Fernando , Nykypanchuk Dmytro , Zhong Hui , Ghose Sanjit , Li Ruipeng , Nam Chang‐Yong , Chen‐Wiegart Yu‐chen Karen
Published: September 2023

Solid‐state metal dealloying (SSMD) is a promising method for fabricating nanoscale metallic composites and nanoporous metals across a range of materials. Thin‐film SSMD is particularly attractive due to its ability to create fine features via solid‐state interfacial reactions within a thin‐film geometry, which can be integrated into devices for various applications. This work examines a new dealloying couple, namely the Nb–Al alloy with the dealloying agent Sc, as previously predicted in the machine‐learning (ML) models. Prior ML predictions aimed to guide the design of nanoarchitectured materials through dealloying, relying on intuition‐driven discovery within a large parameter space. However, this work reveals that at the nanoscale, the involvement of oxygen in thin film processing may instead drive the dealloying process, resulting in the formation of bicontinuous nanostructures similar to those formed by metal‐agent dealloying. The phase evolution, as well as chemical and morphological changes, are closely analyzed using a combination of X‐ray absorption spectroscopy, diffraction, and scanning transmission electron microscopy to understand the mechanisms behind nanostructure formation. The findings suggest a potential pathway for utilizing oxygen to drive the formation of bicontinuous metal–metal oxide nanocomposites, paving the way for further development of functional nanoporous materials in diverse fields.
Flexible Gas Sensors Based on Carbon Nanotube Hybrid Films: A Review
Authors: Huang Xinguang , Pang Rui , Yang Mengdan , Zhang Shipeng , Guo Fengmei , Xu Jie , Zhang Yingjiu , Cao Anyuan , Shang Yuanyuan
Published: September 2023

Flexible gas sensors, which can detect gas markers from the human body and hazardous gases from the environment, are attracting tremendous attention recently. Carbon nanotube (CNT) films are explored for flexible gas sensors due to its sensing ability at room temperature, strong adsorption for foreign molecules, mechanical robustness, and remarkable flexibility, and providing nanoscale surfaces with large surface area for various functional materials, etc. In this paper, recent advances in flexible gas sensors based on CNT films are reviewed. It discusses various strategies to design the structure of flexible CNT films and improve flexibility/stretchability performance. It generalizes different types of sensitive materials loaded for detected gases and analyzes the sensing mechanism of CNT films, with interface interactions and synergistic effects leading to an improvement in gas sensing. In addition, it discusses the preparation of CNT self‐standing films and the use of flexible substrates in transformation and assembly, in order to enable CNT films with improved flexible properties. CNT films show remarkable response and flexibility to hazard or greenhouse gases, such as ammonia, nitrogen dioxide, hydrogen, nitric oxide, carbon dioxide, and others. Summary and perspectives toward the future development of flexible gas sensors based on CNT films are proposed.
Electrochromism and Electrofluorochromism based on Viologen Derivative with 1,10‐Phenanthroline Moiety for Multicolor Large‐Area and Patterned Display
Authors: Zhuang Yanling , Li Jianming , Zhu Mingye , Li Feiyang , Liu Shujuan , Zhao Qiang
Published: September 2023

Viologens, a typical group of electrochromic materials, show rich color changes under the external electrical stimulus. Recently, some of the viologen derivatives are reported to exhibit good luminescent performance. However, their luminescence colors are difficult to adjust owing to the strong electron‐accepting properties of viologens, which seriously hinders their applications in smart light‐emitting devices. In this work, the color/emission dual‐switchable viologen derivative Phen‐vio is designed and synthesized by introducing fluorophore 1,10‐phenanthroline into 4,4′‐bipyridine, for multicolor large‐area and patterned electrochromic/electrofluorochromic devices. Under voltage driving of −2.3 and −2.8 V, the devices exhibited reversible color and fluorescence color changes from light yellow to dark orange to dark blue, and from yellow to orange to green, respectively. Moreover, the devices displayed a high color contrast ratio of up to 77% at 600 nm. More importantly, the driving voltages of the devices do not vary with the change of the device area, which is huge application potential in smart windows and tags.
Large‐Scaled and Solar‐Reflective Kirigami‐Based Building Envelopes for Shading and Occupants’ Thermal Comfort
Authors: Jung Heesuk , Hou Miaomiao , Kang Byungsoo , Wang Zherui , Choi Hyojeong , Lee Hyeong Won , Lee Yongju , Lee Doh‐Kwon , Lee Phillip , Aviv Dorit , Kim Hyeok , Yang Shu
Published: September 2023

Conventional air conditioning in buildings consumes substantial energy contributing to an increase in greenhouse gas emissions, which aggravates global warming. Kirigami envelopes with reflective surfaces offer a promising option to reduce indoor heat gain. So far none has performed outdoor testing of kirigami envelopes nor numerical simulation to understand how they interact with the environment. To understand the impact of the geometric design of the kirigami shading system on both daylighting and temperature variation in the indoor environment, a series of prototypes and simulations is devised to investigate the real‐time shading behavior in an outdoor environment. Large‐scaled and silver‐coated kirigami‐based envelopes of different cut patterns and stretching ratios are fabricated and placed in front of custom‐designed chambers equipped with six thermo‐sensors. Simulation is performed to investigate the effect of light modulation and hence temperature inside the chamber, which corroborates with the experiments. The indoor daylighting pattern and temperature are significantly influenced by the geometry of the stretched kirigami envelope, and overall, both the indoor temperature and the spatial distribution of illuminance are more uniform compared with that without the kirigami envelope. These results indicate that the installation of kirigami envelopes can improve building energy saving and occupants’ comfort.
Nature‐Inspired Depolymerization of Soda Lignin: Light‐Induced Free Radical Promoted Cleavage of β‐O‐4 Bonds
Authors: Kaya Kerem , Atsay Armagan , Gunduz Hande , Slabon Adam , Yagci Yusuf
Published: September 2023

The development of sustainable valorization methods for lignin is a challenging task because the vast majority of the reported studies involve either harsh conditions or expensive transition metal catalysts. Inspired by the sunlight degradation of lignin compounds, known as lignin yellowing, the use of a commercially available cheap organic photoinitiator, namely, phenacyl bromide (PAB) is reported here, for the efficient cleavage of lignin model compound 2‐phenoxyacetophenone (2‐PAP) and for the depolymerization of soda pulped lignin (SL) under UV‐A irradiation and ambient conditions. Real‐time NMR investigations of the photoreaction between 2‐PAP and PAB shed light on the possible reaction mechanisms involving different radical species, HBr, and molecular oxygen. Interestingly, combined spectral, chromatographic, powder X‐ray diffraction, and thermal studies of the photoreaction between PAB and SL indicate the formation of guaiacyl alcohol as the main product. The unprecedented performance of PAB is attributed to the excess generation of phenacyl radicals, the generation of photolabile brominated species, and HBr playing key roles in the cleavage of β‐O‐4 linkages. This work represents a new edge for sustainable lignin valorization under mild reaction conditions and offers the opportunity for large‐scale production of valuable aromatics using technical lignins as feedstock.
Cyclic Stretch Promotes Cellular Reprogramming Process through Cytoskeletal‐Nuclear Mechano‐Coupling and Epigenetic Modification
Authors: Park Sung‐Min , Lee Jung‐Hwan , Ahn Kwang Sung , Shim Hye Won , Yoon Ji‐Young , Hyun Jeongeun , Lee Jun Hee , Jang Sunyoung , Yoo Kyung Hyun , Jang Yoon‐Kwan , Kim Tae‐Jin , Kim Hyun Kyu , Lee Man Ryul , Jang Jun‐Hyeog , Shim Hosup , Kim Hae‐Won
Published: September 2023

Advancing the technologies for cellular reprogramming with high efficiency has significant impact on regenerative therapy, disease modeling, and drug discovery. Biophysical cues can tune the cell fate, yet the precise role of external physical forces during reprogramming remains elusive. Here the authors show that temporal cyclic‐stretching of fibroblasts significantly enhances the efficiency of induced pluripotent stem cell (iPSC) production. Generated iPSCs are proven to express pluripotency markers and exhibit in vivo functionality. Bulk RNA‐sequencing reveales that cyclic‐stretching enhances biological characteristics required for pluripotency acquisition, including increased cell division and mesenchymal‐epithelial transition. Of note, cyclic‐stretching activates key mechanosensitive molecules (integrins, perinuclear actins, nesprin‐2, and YAP), across the cytoskeletal‐to‐nuclear space. Furthermore, stretch‐mediated cytoskeletal‐nuclear mechano‐coupling leads to altered epigenetic modifications, mainly downregulation in H3K9 methylation, and its global gene occupancy change, as revealed by genome‐wide ChIP‐sequencing and pharmacological inhibition tests. Single cell RNA‐sequencing further identifies subcluster of mechano‐responsive iPSCs and key epigenetic modifier in stretched cells. Collectively, cyclic‐stretching activates iPSC reprogramming through mechanotransduction process and epigenetic changes accompanied by altered occupancy of mechanosensitive genes. This study highlights the strong link between external physical forces with subsequent mechanotransduction process and the epigenetic changes with expression of related genes in cellular reprogramming, holding substantial implications in the field of cell biology, tissue engineering, and regenerative medicine.
Associations of cortical SPP1 and ITGAX with cognition and common neuropathologies in older adults
Authors: Lopes Katia de Paiva , Yu Lei , Shen Xianli , Qiu Yiguo , Tasaki Shinya , Iatrou Artemis , Beeri Michal Schnaider , Seyfried Nicholas T. , Menon Vilas , Wang Yanling , Schneider Julie A. , Cantor Harvey , Bennett David A.
Published: September 2023

INTRODUCTION

The secreted phosphoprotein 1 (SPP1) gene expressed by CD11c+ cells is known to be associated with microglia activation and neuroinflammatory diseases. As most studies rely on mouse models, we investigated these genes and proteins in the cortical brain tissue of older adults and their role in Alzheimer's disease (AD) and related disorders.

METHODS

We leveraged protein measurements, single‐nuclei, and RNASeq data from the Religious Orders Study and Rush Memory and Aging Project (ROSMAP) of over 1200 samples for association analysis.

RESULTS

Expression of SPP1 and its encoded protein osteopontin were associated with faster cognitive decline and greater odds of common neuropathologies. At single‐cell resolution,  integrin subunit alpha X (ITGAX) was highly expressed in microglia, where specific subpopulations were associated with AD and cerebral amyloid angiopathy.

DISCUSSION

The study provides evidence of SPP1 and ITGAX association with cognitive decline and common neuropathologies identifying a microglial subset associated with disease.
Edema Reduction versus Penumbra Salvage: Investigating Treatment Effects of Mechanical Thrombectomy in Ischemic Stroke
Authors: Broocks Gabriel , Kemmling Andre , Kniep Helge , Meyer Lukas , Faizy Tobias D. , Hanning Uta , Rimmele Leander D. , Klapproth Susan , Schön Gerhard , Zeleňák Kamil , Fiehler Jens , McDonough Rosalie
Published: September 2023

Objective

Mechanical thrombectomy (MT) is of benefit to patients with ischemic stroke; however, the effect of recanalization on lesion pathophysiology is not yet well understood. The aim of this study was to quantitatively assess how the effect of vessel recanalization on clinical outcome is mediated by edema reduction versus penumbra salvage.

Methods

Consecutive analysis was made of anterior circulation ischemic stroke patients triaged by multimodal computed tomography (CT) undergoing MT. Edema reduction was defined using the difference of quantitative net water uptake (NWU) determined on baseline and follow‐up CT (∆NWU). Penumbra salvage volume (PSV) was defined as the difference between admission penumbra and net infarct growth volumes to follow‐up. Mediation analyses were performed with vessel recanalization as independent variable (modified Thrombolysis in Cerebral Infarction ≥ 2b) and ∆NWU/PSV as mediator variables. Modified Rankin Scale scores at 90 days served as endpoint.

Results

Of 422 included patients, 321 (76%) achieved successful recanalization. The median ∆NWU was 6.8% (interquartile range [IQR] = 3.9–10.4), and the median PSV was 66ml (IQR = 8–124). ∆NWU, PSV, and recanalization were significantly associated with functional outcome in logistic regression analysis. ∆NWU and PSV partially mediated the relationship between recanalization and outcome. Sixty‐six percent of the relationship between recanalization and functional outcome could be explained by treatment‐induced edema reduction, whereas 22% was mediated by PSV (p < 0.0001).

Interpretation

Compared to penumbra salvage, edema reduction was a stronger mediator of the effect of recanalization on functional outcome. Given the current trials on adjuvant neuroprotectants also targeting ischemic edema formation, combining reperfusion with antiedematous neuroprotectants may have synergistic effects resulting in better outcomes in patients with ischemic stroke. ANN NEUROL 2024;95:137–145
Control of Correlation Using Confinement in Case of Quantum System
Authors: Kumar Kirtee , Prasad Vinod
Published: September 2023

This article investigates the behavior of a Moshinsky atom in a 1D harmonic trap. Focus is given on the theoretical foundations of confinement and its impact on the correlation between particles in the Moshinsky atom. The investigation begins by illustrating the (de)localization of the probability density function using Shannon entropy. The basics of correlation and interpretation of correlation using tools such as mutual information and statistical correlation coefficients and how these can be quantified are discussed. Then the concept of confinement is explored. The impact of interaction strength and confinement on Shannon entropy, statistical correlation coefficients, and mutual information is investigated. How interaction strength and confinement can be used to induce correlations between previously uncorrelated particles, as well as how they can be used to suppress correlations between previously correlated particles is discussed. Their implications for quantum information processing and quantum simulation are discussed. In conclusion, confinement is a powerful tool for controlling correlations in quantum systems, and its impact on correlation can be understood through theoretical models. The importance of experimental studies in this field, which provide insights into the behavior of quantum systems under confinement and pave the way for future applications in quantum technology is also emphasized.
Rapidly Synthesized Single‐Ion Conductive Hydrogel Electrolyte for High‐Performance Quasi‐Solid‐State Zinc‐ion Batteries
Authors: Qiu Tianyu , Wang Tonghui , Tang Wensi , Li Yingqi , Li Yangguang , Lang Xingyou , Jiang Qing , Tan Huaqiao
Published: September 2023

Single‐ion conductive electrolytes can largely eliminate electrode polarization, reduce the proportion of anion migration and inhibit side reactions in batteries. However, they usually suffer from insufficient ion conductivity due to the strong interaction between cations and cationic receptors. Here we report an ultrafast light‐responsive covalent organic frameworks (COF) with sulfonic acid groups modification as the acrylamide polymerization initiator. Benefiting from the reduced electrostatic interaction between Zn2+ and sulfonic acid groups through solvation effects, the as‐prepared COF‐based hydrogel electrolyte (TCOF‐S‐Gel) receives an ion conductivity of up to 27.2 mS/cm and Zn2+ transference number of up to 0.89. In addition, sufficient hydrogen bonds endow the single‐ion conductive TCOF‐S‐Gel electrolyte to have good water retention and superb mechanical properties. The assembled Zn||TCOF‐S‐Gel||MnO2 full zinc‐ion battery exhibits high discharge capacity (248 mAh/g at 1C), excellent rate capability (90 mAh/g at 10C) and superior cycling performance. These enviable results enlist the instantaneously photocured TCOF‐S‐Gel electrolyte to be qualified to large‐scaled flexible high‐performance quasi‐solid‐state zinc‐ion batteries.
Combination of Resonance and Non‐Resonance Chiral Raman Scattering in a Cobalt(III) Complex
Authors: Yang Qin , Bloino Julien , Šestáková Hana , Šebestík Jaroslav , Kessler Jiří , Hudecová Jana , Kapitán Josef , Bouř Petr
Published: September 2023

Resonance Raman optical activity (RROA) spectra with high sensitivity reveal details on molecular structure, chirality, and excited electronic properties. Despite the difficulty of the measurements, the recorded data for the Co(III) complex with S,S‐N,N‐ethylenediaminedisuccinic acid are of exceptional quality and, coupled with the theory, spectacularly document the molecular behavior in resonance. This includes a huge enhancement of the chiral scattering, contribution of the antisymmetric polarizabilities to the signal, and the Herzberg‐Teller effect significantly shaping the spectra. The chiral component is by about one order of magnitude bigger than for an analogous aluminum complex. The band assignment and intensity profile were confirmed by simulations based on density functional and vibronic theories. The resonance was attributed to the S0→S3 transition, with the strongest signal enhancement of Raman and ROA spectral bands below about 800 cm−1. For higher wavenumbers, other excited electronic states contribute to the scattering in a less resonant way. RROA spectroscopy thus appears as a unique tool to study the structure and electronic states of absorbing molecules in analytical chemistry, biology, and material science.
Structures, Bonding Analyses and Reactivity of a Dicationic Digallene and Diindene Mimicking trans‐bent Ditetrylenes
Authors: Barthélemy Antoine , Scherer Harald , Daub Michael , Bugnet Alexis , Krossing Ingo
Published: September 2023

The reaction of bisdicyclohexylphosphinoethane (dcpe) and the subvalent MI sources [MI(PhF)2][pf] (M=Ga+, In+; [pf]−=[Al(ORF)4]−; RF=C(CF3)3) yielded the salts [{M(dcpe)}2][pf]2, containing the first dicationic, trans‐bent digallene and diindene structures reported so far. The non‐classical MI⇆MI double bonds are surprisingly short and display a ditetrylene‐like structure. The bonding situation was extensively analyzed by quantum chemical calculations, QTAIM (Quantum Theory of Atoms in Molecules) and EDA‐NOCV (Energy Decomposition Analysis with the combination of Natural Orbitals for Chemical Valence) analyses and is compared to that in the isoelectronic and isostructural, but neutral digermenes and distannenes. The dissolved [{Ga(dcpe)}2]2+([pf]−)2 readily reacts with 1‐hexene, cyclooctyne, diphenyldisulfide, diphenylphosphine and under mild conditions at room temperature. This reactivity is analyzed and rationalized.
Zincophilic Interfacial Manipulation against Dendrite Growth and Side Reactions for Stable Zn Metal Anodes
Authors: Zeng Yinxiang , Pei Zhihao , Guo Yan , Luan Deyan , Gu Xiaojun , Lou Xiong Wen (David)
Published: September 2023

Constructing multifunctional interphases to suppress the rampant Zn dendrite growth and detrimental side reactions is crucial for Zn anodes. Herein, a phytic acid (PA)‐ZnAl coordination compound is demonstrated as a versatile interphase layer to stabilize Zn anodes. The zincophilic PA‐ZnAl layer can manipulate Zn2+ flux and promote rapid desolvation kinetics, ensuring the uniform Zn deposition with dendrite‐free morphology. Moreover, the robust PA‐ZnAl protective layer can effectively inhibit the hydrogen evolution reaction and formation of byproducts, further contributing to the reversible Zn plating/stripping with high Coulombic efficiency. As a result, the Zn@PA‐ZnAl electrode shows a lower Zn nucleation overpotential and higher Zn2+ transference number compared with bare Zn. The Zn@PA‐ZnAl symmetric cell exhibits a prolonged lifespan of 650 h tested at 5 mA cm−2 and 5 mAh cm−2. Furthermore, the assembled Zn battery full cell based on this Zn@PA‐ZnAl anode also delivers decent cycling stability even under harsh conditions.
Electrocatalytic Synthesis of Pyridine Oximes using in Situ Generated NH2OH from NO species on Nanofiber Membranes Derived from NH2‐MIL‐53(Al)
Authors: Xiang Runan , Wang Shihan , Liao Peisen , Xie Fangyan , Kang Jiawei , Li Suisheng , Xian Jiahui , Guo Linna , Li Guangqin
Published: September 2023

Pyridine oximes produced from aldehyde or ketone with hydroxylamine (NH2OH) have been widely applied in pharmaceutics, enzymatic and sterilization. However, the important raw material NH2OH exhibits corrosive and unstable properties, leading to substantial energy consumption during storage and transportation. Herein, this work presents a novel method for directly synthesizing highly valuable pyridine oximes using in situ generated NH2OH from electrocatalytic NO reduction with well‐design nanofiber membranes (Al‐NFM) derived from NH2‐MIL‐53(Al). Particularly, 2‐pyridinealdoxime, the precursor of antidote pralidoxime (2‐PAM) for nerve agents suffering from scarcity and high cost, was achieved with a Faraday efficiency up to 49.8 % and a yield of 92.1 %, attributing to the high selectivity of NH2OH production on Al‐NFM, further easily reacted with iodomethane to produce 2‐PAM. This study proposes a creative approach, having wide universality for synthesizing pyridine and other oximes with a range of functional groups, which not only facilitates the conversion of exhaust gas (NO) and waste water (NO2−) into valuable chemicals especially NH2OH production and in situ utilization through electrochemistry, but also holds significant potential for synthesis of neuro detoxifying drugs to humanity security.
Anti‐Stokes Luminescence in Multi‐Resonance‐Type Thermally‐Activated Delayed Fluorescence Molecules
Authors: Kohata Shintaro , Nakanotani Hajime , Chitose Youhei , Yasuda Takuma , Tsuchiya Youichi , Adachi Chihaya
Published: September 2023

Photon‐upconversion in organic molecular systems is one of the promising technologies for future energy harvesting systems because these systems can generate excitons that possess higher energy than excitation energy. The photon‐upconversion caused by absorbing ambient heat as additional energy is particularly interesting because it could ideally provide a light‐driving cooling system. However, only a few organic molecular systems have been reported. Here, we report the anti‐Stokes photoluminescence (ASPL) derived from hot‐band absorption in a series of multi‐resonance‐type thermally‐activated delayed fluorescence (MR‐TADF) molecules. The MR‐TADF molecules exhibited an anti‐Stokes shift of approximately 0.1 eV with a high PL quantum yield in the solution state. The anti‐Stokes shift corresponded well to the 1–0 vibration transition from the ground state to the excited singlet state, and we further evaluated a correlation between the activation energy for the ASPL intensity and the TADF process. Our demonstration underlines that MR‐TADF molecules have become a novel class of ASPL materials for various future applications, such as light‐driving cooling systems.
The separation of fine minerals in the synergy between the vertical fluidization section and inclined channels of the reflux classifier
Authors: Zhang Zhiyuan , Fang Jiahao , Jing Longlong , Li Yanfeng
Published: September 2023

In the gravity separation of fine minerals, the misfit phenomenon caused by particle size cannot be completely overcome, which makes it difficult to effectively recover useful minerals of a given density. In this paper, a novel reflux classifier (RC) experimental equipment was designed in which the cross‐sectional area of the inclined channel is smaller than that of the vertical portion. As the rising water entered the inclined channel, its velocity increases, leading to a higher shear rate. A series of particle fractionation experiments were conducted in this paper to examine the effect of synergy between the inclined and vertical sections of the RC on weakening the segregation arising from the particle size range. Sand, glass bead, and magnetite particles were used in separate investigations. An empirical equation for predicting the rising water fluidization flow rates that put the particles in a critical state was developed to describe the broad range of experimental data. The results show that the novel RC system creates a more suitable fluid environment through the synergy of vertical and inclined sections, allowing for the complete separation of sand and magnetite mixtures, as well as the separation of particles with different particle sizes but the same terminal settling velocity at the same flow rate. This indicates a reduced dependence on particle size for separation. The theoretical model can accurately predict the fluidization rate and the particle size composition of the separated product.
Highly transparent antibacterial polystyrene/styrene‐butadiene block copolymer/polyhexamethylene guanidine composite
Authors: Song Yinghui , Zhang Mingfa , Yin Lu , Sun Zhaobo
Published: September 2023

The combination of transparency, antibacterial activity, and flexbility is of great importance for practical applications in industry. However, this remains a huge challenge to date. In this work, a ternary system of polystyrene (PS), styrene‐butadiene block copolymer (SBC), and polyhexamethylene guanidine (PHMG) is reported via a green melt blending method. Because of the excellent compatibility of the components, the elongation at break of the composite increased by 3.0%. The composite shows high optical transparency of 81.8% owing to the similar refractive index of PS, SBC, and PHMG. More importantly, the addition of 0.3 wt% PHMG endows the composite with splendid antibacterial property, which eliminates 99.9% of E. coli and restrains the formation of the biological membrane. The composite is expected to find promising applications in medical industry and electrical apparatus.
Towards safe phosphine oxides photoinitiators with good cytocompatibility for 3D printing of thermoplastics
Authors: Buchon Loïc , Becht Jean‐Michel , Rubatat Laurent , Wang Wei , Wei Hua , Xiao Pu , Lalevee Jacques
Published: September 2023

3D printing is the technology of choice for the rapid production of objects with complex morphologies and controlled physical and chemical properties. 3D printing by photopolymerization is of great interest because of its ability to access very small scales and its high resolution. In the case of recent 3D printers, the preferred wavelength for light irradiation is 405 nm since it is a safe and energy‐economical irradiation. For 3D printing to be effective, it is therefore necessary to develop easily accessible, stable and highly efficient photoinitiating systems at the 405 nm wavelength. Beside, with the increasing use of photoinitiators, it is essential to develop structures with low cytotoxicity. Hence, the development of new photoinitiators is currently of major interest. To this end, the photochemical properties (triplet energy, bond dissociation energy, cleavage reaction enthalpy, and absorption properties) of several molecules have been calculated by molecular modeling and the most promising compounds have been synthesized. In this paper, four phosphine oxides photoinitiators (ADPO‐1, CPO‐2, CPO‐3, and FPO‐1) are synthesized and characterized. Subsequently, their absorption properties are measured and their efficiencies in photopolymerization under LED irradiation at 405 nm are evaluated. It is important to note that these structures have never been reported in 3D printing. Markedly, among the obtained photoinitiators, two of them show better efficiency than the commercially available and widely used phenylbis(2,4,6‐trimethylbenzoyl)phosphine oxide (BAPO) in photopolymerization (i.e., (Rp/[M0]) x100 values are 6.94, 12.95, and 4.93 s−1 for CPO‐2, ADPO‐1, and BAPO; with [M0] the initial acrylate function concentration). Furthermore, one of the synthesized photoinitiators is successfully used in 3D printing of thermoplastics for potential recycling ability. Finally, one of the obtained structures shows a lower cytotoxicity than the benchmark structure diphenyl(2,4,6‐trimethylbenzoyl)phosphine oxide (TPO).
The fossil record of appendicular muscle evolution in Synapsida on the line to mammals: Part II—Hindlimb
Authors: Bishop Peter J. , Pierce Stephanie E.
Published: September 2023

This paper is the second in a two‐part series that charts the evolution of appendicular musculature along the mammalian stem lineage, drawing upon the exceptional fossil record of extinct synapsids. Here, attention is focused on muscles of the hindlimb. Although the hindlimb skeleton did not undergo as marked a transformation on the line to mammals as did the forelimb skeleton, the anatomy of extant tetrapods indicates that major changes to musculature have nonetheless occurred. To better understand these changes, this study surveyed the osteological evidence for muscular attachments in extinct mammalian and nonmammalian synapsids, two extinct amniote outgroups, and a large selection of extant mammals, saurians, and salamanders. Observations were integrated into an explicit phylogenetic framework, comprising 80 character–state complexes covering all muscles crossing the hip, knee, and ankle joints. These were coded for 33 operational taxonomic units spanning >330 Ma of tetrapod evolution, and ancestral state reconstruction was used to evaluate the sequence of muscular evolution along the stem lineage from Amniota to Theria. The evolutionary history of mammalian hindlimb musculature was complex, nonlinear, and protracted, with several instances of convergence and pulses of anatomical transformation that continued well into the crown group. Numerous traits typically regarded as characteristically “mammalian” have much greater antiquity than previously recognized, and for some traits, most synapsids are probably more reflective of the ancestral amniote condition than are extant saurians. More broadly, this study highlights the utility of the fossil record in interpreting the evolutionary appearance of distinctive anatomies.
Mechanochemical activation of NHC–CS2 adducts for the generation of N‐heterocyclic carbenes
Authors: Park Subin , Kim Youngsuk
Published: September 2023

Stable N‐heterocyclic carbenes (NHCs) have garnered significant attention in synthetic chemistry due to their versatile applications. In this study, we explored a novel mechanochemical method for the generation of free carbenes, which could be a good complement to traditional approaches that require strong bases or reductants. Ball milling of NHC–CS2 adducts at room temperature successfully resulted in the quantitative formation of free carbenes that can be subsequently trapped by sulfur or selenium. Importantly, heating NHC–CS2 adducts in solution phase did not lead to the successful generation of free carbenes, in agreement with the high activation energy required for NHC–CS2 dissociation. These findings underscore the potential of ball milling as a robust and versatile approach for generating NHCs from stable NHC‐small molecule adducts, and opens new avenues for developing mechanochemical strategies for generating valuable NHC‐derived compounds.
Proactive boundary‐spanning search, organizational resilience, and radical green innovation
Authors: Xue Chun , Wang Juanru
Published: September 2023

Radical green innovation has emerged as an effective strategy for firms to achieve sustainable development in the volatility, uncertainty, complexity, and ambiguity (VUCA) environment. Although the importance of external knowledge acquisition has been recognized, the mechanism of how proactive boundary‐spanning search affects radical green innovation is still blurred. Drawing on the resource‐based view and dynamic capabilities theory, this research discusses the impact of two types of proactive boundary‐spanning search on radical green innovation and considers the mediating role of organizational resilience and the moderating role of big data analytics capability. Based on data collected from 294 manufacturing firms in China, the results show that both value‐chain‐based proactive search and industry–university‐based proactive search positively influence radical green innovation. Furthermore, organizational resilience fully mediates the relationship between value‐chain‐based proactive search and radical green innovation, and partially mediates the relationship between industry–university‐based proactive search and radical green innovation. Moreover, we demonstrate that big data analytics capability moderates the relationship between industry–university‐based proactive search and radical green innovation. This research clarifies not only the mechanism of proactive boundary‐spanning search driving radical green innovation by highlighting the mediating role of organizational resilience and the moderating role of big data analytics capability, but also provides theoretical and managerial implications for manufacturing firms and other stakeholders to carry out radical green innovation.
Exploring the delivery of community‐based trauma support by volunteer counsellors in a South African context
Authors: Henning‐Pugh Mariette , Frith Hannah , Troops Mon Ami Trauma
Published: September 2023

South Africa experiences high levels of violence and trauma in a context where formal mental healthcare is not widely accessible. Lay (non‐professional) trauma counselling services, staffed by volunteers, often fill this gap in provision. Extant research highlights the risk of secondary traumatic stress and burnout for volunteers, and although volunteering is often a collective activity, research typically focuses on the individual volunteer's characteristics, motivations and attitudes. Drawing on a case study with one organisation, this study explores lay counsellors' experiences of providing voluntary emotional support in a context of high trauma and low resources. Semi‐structured interviews with volunteers (n = 12) explored the nature of the work, reasons for volunteering and perceptions of the organisation. Thematic analysis generated two overarching themes, each with three subthemes: ‘We serve our community’ (sub‐themes: ‘Giving back to our community’, ‘Need outstrips resources’ and ‘Being there is powerful’) and ‘We are family’ (sub‐themes: ‘Being there for each other’, ‘Working through the work’ and ‘Being put in a safety net’). Findings illustrate how organisations with few resources can mitigate the psychological risks of trauma‐focused work by fostering strong bonds, collective identity and an ethos of care.
Near‐infrared spectroscopy enables quality selection in wheat breeding
Authors: Walker Cassandra K. , Panozzo Joe F.
Published: September 2023

Background and Objectives

Near‐infrared spectroscopy (NIRS) and small‐scale testing are used to evaluate wheat germplasm is a cost‐effective strategy to reduce thousands of wheat lines to hundreds and then to tens of lines. Identification of high‐quality germplasm among thousands of lines is dependent on the accuracy of the tests that are used and how well these data correlate with the large‐scale tests that are used to confirm the end‐use quality before commercial release of a new wheat variety. In this study, NIR‐based testing was investigated to determine the effectiveness of this high‐throughput, nondestructive technology.

Findings

To demonstrate the effectiveness of NIRS and small‐scale testing as a selection strategy, interpretive population statistics evaluating three consecutive generations (F4, F5, and F6) from a wheat breeding program were compared. The F4 (early stage) generation (2019) was predicted for milling yield with a proportion of 13.9% of lines above 74% (w/w) milling yield. From those lines that progressed to F5 (mid‐generation in 2020), the proportion increased to 26.2% of lines above 74% (w/w) milling yield. Selected lines from F5 were progressed to F6 (advanced generation in 2021), where 62.4% of lines were above 74% (w/w) milling yield.

Conclusions

Each time the set progressed through the selection strategy, the portion of lines above 74% (w/w) milling yield increased.

Significance and Novelty

This study demonstrates the value and efficiency of high‐throughput selection strategies using nondestructive NIRS at the F4 (early‐stage generation) stage and small‐scale testing at the F5 stage of a wheat breeding program.
Pt Nanoparticles on Beta zeolites for Catalytic Toluene Oxidation: Effect of the Hydroxyl Groups of Beta Zeolite**
Authors: Zou Run , Chansai Sarayute , Xu Shaojun , An Bing , Zainal Shima , Zhou Yangtao , Xin Ruojia , Gao Pan , Hou Guangjin , D'Agostino Carmine , Holmes Stuart M. , Hardacre Christopher , Jiao Yilai , Fan Xiaolei
Published: September 2023

Stabilisation of metal species using hydroxyl‐rich dealuminated zeolites is a promising method for catalysis. However, insights into the interactions between the hydroxyl groups in zeolite and noble metals and their effects on catalysis are not yet fully understood. Herein, comparative studies were conducted using Pt catalysts supported on hydroxyl‐rich dealuminated Beta (deAl‐Beta) and the pristine proton‐form Beta (H‐Beta) for catalytic oxidation of toluene. The findings suggest that during impregnation the Pt precursor (i. e., Pt(NH3)4(NO3)2) interacted with different sites on deAl‐Beta and H‐Beta, leading to the formation of supported Pt nanoparticles with different physicochemical properties. In detail, for H‐Beta, the Pt precursor interacted with Al‐OH and isolated external Si‐OH sites, yielding Pt NPs with a higher Pt0 proportion of ~71 % compared to ~57 % Pt0 on deAl‐Beta. Comparatively, abundant hydroxyl groups on deAl‐Beta such as silanol nest and isolated internal Si‐OH stabilised highly active Pt‐O species. The resulting Pt/deAl‐Beta exhibited improved activity and anti‐coking ability than Pt/H‐Beta in catalytic toluene oxidation. For example, the temperature for 50 % toluene conversion was 193 °C for Pt/deAl‐Beta vs. 232 °C for Pt/H‐Beta, and the coke deposition was 1.7 % vs. 6.7 % (after the 24‐h longevity test), respectively. According to the toluene‐temperature programmed desorption (toluene‐TPD), 1H nuclear magnetic resonance (1H NMR) relaxation and in situ diffuse reflection Fourier transform spectroscopy (in situ DRIFTS) characterisation, the enhanced performance of Pt/deAl‐Beta could be ascribed to (i) the active Pt‐O sites stabilised by hydroxyl groups, which interact with toluene easily for conversion, and (ii) the acid‐free feature of the deAl‐Beta support, which avoids the formation of coke precursors (such as benzoate species) on the catalyst surface. Findings of the work can serve as the design guidelines for making effective supported metal catalysts using zeolitic carriers.
Stability of Bipolar Plate Materials for Proton‐Exchange Membrane Water Electrolyzers: Dissolution of Titanium and Stainless Steel in DI Water and Highly Diluted Acid
Authors: Fiedler Lena , Ma Tien‐Ching , Fritsch Birk , Risse Jan H. , Lechner Michael , Dworschak Dominik , Merklein Marion , Mayrhofer Karl J. J. , Hutzler Andreas
Published: September 2023

The widespread use of proton exchange membrane water electrolyzers (PEMWE) is hindered by their high cost, of which a colossal factor is caused by the bipolar plates (BPP). In this paper, we investigate the stability of two BPP materials on‐line with an optimized scanning flow cell setup coupled to an inductively coupled plasma mass spectrometer (SFC‐ICP‐MS), as well as scanning electron microscopy (SEM). The stability of currently used titanium and a cheaper alternative, stainless steel (SS) 316L, were characterized in deionized (DI) water and 0.5 mM H2SO4 to mimic the conditions at the BPP under operation. We show that the dissolution of Ti is negligible, whereas SS 316L degrades notably. Here, besides pH, the applied potentials play a crucial role. Nonetheless, even for the highest measured dissolution rate of SS 316L, the contamination in a full cell is estimated to remain below 1 ppm. This work illustrates the capabilities of on‐line high‐throughput stability tests for BPP materials and could therefore contribute towards optimization of cost‐effective PEMWE.
A Methoxylation‐Promoted CPET Reaction
Authors: Mukherjee Souvik , Maji Kuntal , Saha Pinaki , Ghosh Prasanta
Published: September 2023

The manuscript discloses a methoxylation reaction to an aromatic carbonyl function that carries out a CPET reaction oxidizing a transition metal ion. Spontaneous methoxylation of a redox non‐innocent fragment coordinated to a high spin cobalt(II) ion, promoted concerted proton electron transfer (CPET) reaction oxidizing cobalt(II) to cobalt(III) in air and subsequent demethoxylation induced reduction of cobalt(III) to cobalt(II) producing H2O2 are authenticated. The cobalt(III)/cobalt(II) electron transfer (ET) potential of the designed complex in CH2Cl2 is −0.27 V vs Fc+/Fc redox couple. However, in presence of MeOH the reduction potential decreases to −1.02 V due to CPET involving MeOH proton. In CH2Cl2/CHCl3 spontaneous demethoxylation occurs giving back the original complex and reactive methoxyl radical that reacts with O2 producing H2O2. Overall one molecule of MeOH produces one molecule of H2O2. To analyze the involvement of the proton, the rate constants of the CPET reactions in CH2Cl2‐MeOH (2 : 1) and CH2Cl2‐CD3OD (2 : 1) and the demethoxylation reaction in CHCl3 at 330 K were determined by time drive UV‐Vis spectroscopy.
Group I Alkoxides and Amylates as Highly Efficient Silicon–Nitrogen Heterodehydrocoupling Precatalysts for the Synthesis of Aminosilanes
Authors: Reuter Matthew B. , Javier‐Jiménez Diego R. , Bushey Claire E. , Waterman Rory
Published: September 2023

Group I alkoxides are highly active precatalysts in the heterodehydrocoupling of silanes and amines to afford aminosilane products. The broadly soluble and commercially available KOtAmyl was utilized as the benchmark precatalyst for this transformation. Challenging substrates such as anilines were found to readily couple primary, secondary, and tertiary silanes in high conversions (>90 %) after only 2 h at 40 °C. Traditionally challenging silanes such as Ph3SiH were also easily coupled to simple primary and secondary amines under mild conditions, with reactivity that rivals many rare earth and transition‐metal catalysts for this transformation. Preliminary evidence suggests the formation of hypercoordinated intermediates, but radicals were detected under catalytic conditions, indicating a mechanism that is rare for Si−N bond formation.
Carbon Monoxide as C1 Building Block in Fine Chemical Synthesis†
Authors: Carrilho Rui M. B. , Calvete Mário J. F. , Mikle Gábor , Kollár László , Pereira Mariette M.
Published: September 2023

Comprehensive Summary

Carbon monoxide (CO) has become one of the most relevant and versatile renewable C1 building blocks for chemical synthesis, especially in the fine chemicals industry, due to the development of efficient and selective catalysts for its activation. In this review, we present a comprehensive critical analysis of the last 10 years literature on the use of CO as a renewable feedstock for fine chemicals production. The review is organized by type of catalytic reaction, namely alkene and alkyne carbonylation, hydroformylation, carbonylation of aryl halides, carbonylative cross‐coupling and C—H carbonylation. Notable examples of the synthesis of relevant building blocks and/or known pharmaceuticals are highlighted. Emphasis is placed on examples of utilizing CO as the C1 building block in one or more catalytic steps. The catalyst used and the reaction conditions are consistently presented throughout all of the examples.
Bioequivalence of Reference and Biosimilar Preparations of Premixed Biphasic Insulin Aspart: A Comparative Clamp Study
Authors: Dorotenko Artem , Makarenko Igor , Karonova Tatiana , Protsenko Ekaterina , Gefen Maria , Galstyan Gagik , Antonova Elizaveta , Shitov Leonid , Dzhurko Yurij , Drai Roman
Published: September 2023

Biphasic insulin aspart 30 is a premixed formulation containing a soluble fraction of insulin aspart (30%) and a protamine‐crystallized fraction (70%) that was developed to combine the rapid‐acting and prolonged advantages of commercially available insulins. The aim of this bioequivalence study was to compare the pharmacokinetics (PKs) of GP‐bi‐asp and Novo‐bi‐asp, and evaluate the pharmacodynamic (PD) properties as well as the safety of these drugs in the hyperinsulinemic euglycemic clamp (HEC) procedure. This was a phase 1, randomized, double‐blind, 2‐sequence, 2‐period crossover study. Thirty‐four male volunteers who met the inclusion criteria underwent the HEC procedure following a single subcutaneous injection of 0.4 IU/kg of either GP‐bi‐asp or Novo‐bi‐asp in the abdomen. After the treatment, the subjects’ plasma glucose levels were monitored for 24 hours and the glucose infusion rate (GIR) was adjusted to maintain the target blood glucose level. The PD parameters were calculated using GIR values. Insulin aspart concentrations were measured in blood plasma using validated ELISA assays to evaluate the PK parameters of the investigated drugs. The 90% confidence intervals for the geometric mean ratios of PK (Cins and AUCins–T) parameters of Gp‐bi‐asp and Novo‐bi‐asp were close to 100% and within the 80%‐125% limits for establishing bioequivalence. The safety profiles of both drugs were also comparable.