bluuebunny/crossref_metadata_2025 huggingface dataset:
C−H‐Funktionalisierung von Tryptophan‐haltigen Peptiden mit Thianthreniumsalzen im späten Synthesestadium: Konjugation und Ligation
Authors: Kaplaneris Nikolaos , Puet Alejandro , Kallert Felix , Pöhlmann Julia , Ackermann Lutz
Published: December 2022

Die bioorthogonale Diversifizierung strukturell komplexer Peptide im späten Stadium der Synthese besitzt ein großes Potenzial für die Entdeckung von neuen Arzneimitteln und die molekulare Bildgebung. Wir berichten über eine Palladium‐katalysierte C−H‐Arylierung von Tryptophan‐haltigen Peptiden mit leicht zugänglichen und modularen Arylthianthrenium‐Salzen. Unter äußerst milden Reaktionsbedingungen konnte die Diversifizierung im späten Stadium der Synthese von strukturell komplexen Peptiden erreicht werden. Die Abstimmbarkeit und einfache Herstellung von Arylthianthrenium‐Salzen ermöglichte die zweckmäßige Verknüpfung von Tryptophan‐haltigen Peptiden mit Arzneimittel‐, Naturstoff‐ und Peptidgerüsten, durch das Bilden sterisch anspruchsvoller Biaryl‐Bindungen. Die Robustheit des Palladiumkatalyseregimes spiegelte sich in der vollständigen Toleranz gegenüber einer Vielzahl empfindlicher und koordinierender funktioneller Gruppen wieder. Somit ermöglichte die Vielseitigkeit unserer Methode den effizienten Zugang zu stark substituierten, markierten, konjugierten und ligierten linearen und zyklischen Peptiden.
Ein neuer Thiolat‐gebundener Dimangan‐Cluster als strukturelles und funktionales Modell der Class Ib Ribonukleotidreduktasen
Authors: Battistella Beatrice , Lohmiller Thomas , Cula Beatrice , Hildebrandt Peter , Kuhlmann Uwe , Dau Holger , Mebs Stefan , Ray Kallol
Published: December 2022

In Class Ib Ribonukleotidreduktasen (RNRs) aktiviert ein Dimangan(II)‐Cluster Superoxid (O2⋅−) anstelle von molekularem Sauerstoff (O2), um eine hochvalente MnIII‐O2‐MnIV‐Spezies zu bilden, die für die Oxidation von Tyrosin zum Tyrosyl‐Radikal verantwortlich ist. Im vorliegenden biomimetischen Ansatz wird ein Thiolat‐gebundener Dimangan‐Komplex [MnII2(BPMT)(OAc)2](ClO)4 (BPMT=(2,6‐Bis{[bis(2‐pyridylmethyl)amino]methyl}‐4‐methylthiophenolat) (1) synthetisiert und dessen Reaktion mit O2⋅− zur Bildung des [(BPMT)MnO2Mn]2+‐Komplexes 2 gezeigt. Resonanz‐Raman‐Untersuchungen zeigen das Vorliegen einer O‐O‐Bindung in 2, während die ESR‐Analyse ein Signal bei g=2 mit 16 Linien für St=
aufzeigt, das typischerweise mit einem MnIIIMnIV‐Kern assoziiert wird, wie es auch in Class Ib RNR detektiert wurde. Anders als zuvor publizierte Mn‐O2‐Mn‐Komplexe, die durch O2⋅−‐Aktivierung an Mn2‐Zentren gebildet wurden, ist 2 ein geeignetes elektrophiles Oxidationsmittel für Aldehyd‐Deformylierungsreaktionen und Phenol‐Oxidationsreaktionen, sodass es eines der besten strukturellen und funktionalen Modelle der Class Ib RNRs darstellt.
Engineering a Highly Regioselective Fungal Peroxygenase for the Synthesis of Hydroxy Fatty Acids
Authors: Gomez de Santos Patricia , González‐Benjumea Alejandro , Fernandez‐Garcia Angela , Aranda Carmen , Wu Yinqi , But Andrada , Molina‐Espeja Patricia , Maté Diana M. , Gonzalez‐Perez David , Zhang Wuyuan , Kiebist Jan , Scheibner Katrin , Hofrichter Martin , Świderek Katarzyna , Moliner Vicent , Sanz‐Aparicio Julia , Hollmann Frank , Gutiérrez Ana , Alcalde Miguel
Published: December 2022

The hydroxylation of fatty acids is an appealing reaction in synthetic chemistry, although the lack of selective catalysts hampers its industrial implementation. In this study, we have engineered a highly regioselective fungal peroxygenase for the ω‐1 hydroxylation of fatty acids with quenched stepwise over‐oxidation. One single mutation near the Phe catalytic tripod narrowed the heme cavity, promoting a dramatic shift toward subterminal hydroxylation with a drop in the over‐oxidation activity. While crystallographic soaking experiments and molecular dynamic simulations shed light on this unique oxidation pattern, the selective biocatalyst was produced by Pichia pastoris at 0.4 g L−1 in a fed‐batch bioreactor and used in the preparative synthesis of 1.4 g of (ω‐1)‐hydroxytetradecanoic acid with 95 % regioselectivity and 83 % ee for the S enantiomer.
Alkynyl‐Protected Chiral Bimetallic Ag22Cu7 Superatom with Multiple Chirality Origins
Authors: Deng Guocheng , Lee Kangjae , Deng Hongwen , Malola Sami , Bootharaju Megalamane S. , Häkkinen Hannu , Zheng Nanfeng , Hyeon Taeghwan
Published: December 2022

Understanding the origin of chirality in the nanostructured materials is essential for chiroptical and catalytic applications. Here we report a chiral AgCu superatomic cluster, [Ag22Cu7(C≡CR)16(PPh3)5Cl6](PPh4), Ag22Cu7, protected by an achiral alkynyl ligand (HC≡CR: 3,5‐bis(trifluoromethyl)phenylacetylene). Its crystal structure comprises a rare interpenetrating biicosahedral Ag17Cu2 core, which is stabilized by four different types of motifs: one Cu(C≡CR)2, four −C≡CR, two chlorides and one helical Ag5Cu4(C≡CR)10(PPh3)5Cl4. Structural analysis reveals that Ag22Cu7 exhibits multiple chirality origins, including the metal core, the metal‐ligand interface and the ligand layer. Furthermore, the circular dichroism spectra of R/S‐Ag22Cu7 are obtained by employing appropriate chiral molecules as optical enrichment agents. DFT calculations show that Ag22Cu7 is an eight‐electron superatom, confirm that the cluster is chirally active, and help to analyze the origins of the circular dichroism.
Diethylzinc‐Mediated Cross‐Coupling Reactions between Dibromoketones and Monobromo Carbonyl Compounds
Authors: Takeshima Aika , Kano Taichi
Published: December 2022

A novel route to synthesize 1,4‐dicarbonyl compounds is described. α,α‐Dibromoketones generate zinc enolates through a diethylzinc‐mediated halogen‐metal exchange and react with α‐bromocarbonyl compounds to furnish 1,4‐dicarbonyl compounds via a second generation of zinc enolates. This cross‐coupling reaction is enabled by the chemoselective formation of zinc enolates from α,α‐dibromoketones in the presence of α‐bromocarbonyl compounds. Chiral 1,4‐dicarbonyl compounds can be obtained via the enantioselective bromination of aldehydes using a chiral secondary amine catalyst and a subsequent cross‐coupling reaction between the resulting chiral α‐bromoaldehydes and α,α‐dibromoacetophenones.
Rational Design of Ferroelectric 2D Perovskite for Improving the Efficiency of Flexible Perovskite Solar Cells Over 23 %
Authors: Han Bin , Wang Yaohua , Liu Chang , Sun Kexuan , Yang Mengjin , Xie Lisha , Yang Shuncheng , Meng Yuanyuan , Lin Shuyuan , Xu Peng , Li Jun , Qiu Qingqing , Ge Ziyi
Published: December 2022

Despite the great progress of flexible perovskite solar cells (f‐PSCs), it still faces several challenges during the homogeneous fabrication of high‐quality perovskite thin films, and overcoming the insufficient exciton dissociation. To the ends, we rationally design the ferroelectric two‐dimensional (2D) perovskite based on pyridine heterocyclic ring as the organic interlayer. We uncover that incorporation of the ferroelectric 2D material into 3D perovskite induces an increased built‐in electric field (BEF), which enhances the exciton dissociation efficiency in the device. Moreover, the 2D seeds could assist the 3D crystallization by forming more homogeneous and highly‐oriented perovskite crystals. As a result, an impressive power conversion efficiency (PCE) over 23 % has been achieved by the f‐PSCs with outstanding ambient stability. Moreover, the piezo/ferroelectric 2D perovskite intrigues a decreased hole transport barriers at the ITO/perovskite interface under tensile stress, which opens new possibilities for developing highly‐efficient f‐PSCs.
High‐Precision Mapping of Membrane Proteins on Synaptic Vesicles using Spectrally Encoded Super‐Resolution Imaging
Authors: Jiang Yifei , Zhang Jicheng , Jung Seung‐Ryoung , Chen Haobin , Xu Shihan , Chiu Daniel T.
Published: December 2022

The spatial resolution of single‐molecule localization microscopy is limited by the photon number of a single switching event because of the difficulty of correlating switching events dispersed in time. Here we overcome this limitation by developing a new class of photoswitching semiconducting polymer dots (Pdots) with structured and highly dispersed single‐particle spectra. We imaged the Pdots at the first and the second vibronic emission peaks and used the ratio of peak intensities as a spectral coding. By correlating switching events using the spectral coding and performing 4–9 frame binning, we achieved a 2–3 fold experimental resolution improvement versus conventional superresolution imaging. We applied this method to count and map SV2 and proton ATPase proteins on synaptic vesicles (SVs). The results reveal that these proteins are trafficked and organized with high precision, showing unprecedented level of detail about the composition and structure of SVs.
Site‐ and Stereoselective C(sp3)−H Borylation of Strained (Hetero)Cycloalkanols Enabled by Iridium Catalysis
Authors: Gao Qian , Xu Senmiao
Published: December 2022

Transition metal‐catalyzed site‐ and stereoselective C−H activation of strained (hetero)cycloalkanes remains a formidable challenge. We herein report a carbamate‐directed iridium‐catalyzed asymmetric β−C(sp3)−H borylation of cyclopropanol derivatives. A variety of densely functionalized cyclopropanols were obtained in good enantioselectivities via desymmetrization and kinetic resolution. In addition, site‐selective C(sp3)−H borylation of methine groups furnished α‐borylated (hetero)cycloalkanols in moderate to good yields. The synthetic utility of the method was further shown in a gram‐scale synthesis and diverse downstream transformations of borylated products.
Machine Learning Informs RNA‐Binding Chemical Space**
Authors: Yazdani Kamyar , Jordan Deondre , Yang Mo , Fullenkamp Christopher R. , Calabrese David R. , Boer Robert , Hilimire Thomas , Allen Timothy E. H. , Khan Rabia T. , Schneekloth John S.
Published: December 2022

Small molecule targeting of RNA has emerged as a new frontier in medicinal chemistry, but compared to the protein targeting literature our understanding of chemical matter that binds to RNA is limited. In this study, we reportedRepositoryOfBInders toNucleic acids (ROBIN), a new library of nucleic acid binders identified by small molecule microarray (SMM) screening. The complete results of 36 individual nucleic acid SMM screens against a library of 24 572 small molecules were reported (including a total of 1 627 072 interactions assayed). A set of 2 003 RNA‐binding small molecules was identified, representing the largest fully public, experimentally derived library of its kind to date. Machine learning was used to develop highly predictive and interpretable models to characterize RNA‐binding molecules. This work demonstrates that machine learning algorithms applied to experimentally derived sets of RNA binders are a powerful method to inform RNA‐targeted chemical space.
Oxidation‐Reduction Molecular Junction Covalent Organic Frameworks for Full Reaction Photosynthesis of H2O2
Authors: Chang Jia‐Nan , Li Qi , Shi Jing‐Wen , Zhang Mi , Zhang Lei , Li Shan , Chen Yifa , Li Shun‐Li , Lan Ya‐Qian
Published: December 2022

The full reaction photosynthesis of H2O2 that can combine water‐oxidation and oxygen‐reduction without sacrificial agents is highly demanded to maximize the light‐utilization and overcome the complex reaction‐process of anthraquinone‐oxidation. Here, a kind of oxidation‐reduction molecular junction covalent‐organic‐framework (TTF‐BT‐COF) has been synthesized through the covalent‐coupling of tetrathiafulvalene (photo‐oxidation site) and benzothiazole (photo‐reduction site), which presents visible‐light‐adsorption region, effective electron‐hole separation‐efficiency and photo‐redox sites that enables full reaction generation of H2O2. Specifically, a record‐high yield (TTF‐BT‐COF, ≈276 000 μM h−1 g−1) for H2O2 photosynthesis without sacrificial agents has been achieved among porous crystalline photocatalysts. This is the first work that can design oxidation‐reduction molecular junction COFs for full reaction photosynthesis of H2O2, which might extend the scope of COFs in H2O2 production.
Electron beam assisted recycling of polyurethane (PU) sponge: Turning it into a superabsorbent for wastewater treatment
Authors: Jha Atanu , Shaik Khader Abdul , Bhardwaj Yatender Kumar , Pant Harish Jagat , Chowdhury Subhendu Ray
Published: December 2022

Polyurethane (PU) sponge is being used on a large scale now‐a‐days, but that generates environmental pollution as it is not bio‐degradable. Moreover, the PU recycling existing techniques face several problems, which are being addressed sincerely throughout the world. Here, we report an easy, scalable, environment‐friendly, economic, and high throughput technique for converting scrap PU sponge into a superabsorbent for wastewater treatment. This is a new strategy for recycling scrap PU foam. This conversion follows the modification of surface energy of the PU sponge and generation of tiny‐scale roughness by a single‐step electron beam (EB) radiation‐assisted covalent attachment of dodecyl methacrylate (DMA) onto the waste PU sponge. The effect of degree of modification on the surface wettability is studied. Important process parameters namely, total dose, DMA concentration, solvent composition, and so forth are systematically varied and optimized to achieve the required extent of modification (~30 wt%). This desired degree of modification is achieved at 30 kGy total dose and in 15 vol% DMA concentration and 15 vol% water content in the reaction mixture. Grafting yield is measured gravimetrically and successful grafting is further confirmed by Fourier‐transform infrared spectroscopy, surface wettability, and surface morphology. The recycled PU shows superhydrophobicity with very high water contact angle (152°). Now, the recycled sponge can remove major liquid components of wastewater, namely, toxic organic solvents, oily liquids, nonpolar solvent soluble dyes from water media with high absorption capacity (25–30 g/g) successfully.
Anion exchange membranes based on poly (styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene) grafted poly (2,6‐dimethyl‐1,4‐phenylene oxide)
Authors: Liu Rui , Nie Yiwen , Chen Junjie , Shen Chunhui , Gao Shanjun
Published: December 2022

Poly (styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene) (SEBS) has been widely studied in the field of anion exchange membranes (AEMs) due to its superior flexibility and chemical stability, but the poor dimensional stability of functionalized SEBS restricts its further application. Thus, we adopt an effective strategy to reinforce AEMs based on SEBS via grafting poly (2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) using Williamson ether synthesis reaction. With the addition of PPO, grafted membranes exhibit outstanding comprehensive properties, such as mechanical strength, chemical stability, especially dimensional stability. SEBS‐PPO‐QA‐1 grafted membrane with the highest content of PPO showed the best tensile strength (20.54 MPa), and restrained swelling behavior (swelling ratio of 4.81% at 25°C). Moreover, the conductivity retention of SEBS‐PPO‐QA‐1 grafted membrane is up to 92.71% at 80°C after 10 days alkaline treatment. The ion exchange capacity of SEBS‐PPO‐QA‐3 grafted membrane is 1.719 mmol/g, and the ionic conductivity of SEBS‐PPO‐QA‐3 grafted membrane reach 58.27 mS/cm at 80°C and 25.53 mS/cm at 20°C. Therefore, the SEBS‐PPO‐QA‐X grafted membranes, which combine the advantages of PPO and SEBS, are promising in AEM application.
Building Better Lithium‐Sulfur Batteries—A Reassessment of the Working Mechanism
Authors: Tan Jian , Li Xuanyang , Shen Jianfeng
Published: December 2022

Lithium‐sulfur (Li−S) batteries have captured global attention and in‐depth research interest. Nevertheless, its massive commercialization has been bothered by the “shuttle effect” caused by the soluble Li polysulfides (LiPSs) and unremitted growth of Li dendrites originated from unstable solid electrolyte interphase (SEI) film. Over the few decades have witnessed the remarkable progress of Li−S batteries, while several controversial views on the working mechanism have emerged in recent three years, which are challenging for previous related research. In this perspective, we give a brief review on the latest studies and reassess the working mechanism of Li−S batteries. With this regard, we start with a simple introduction to emphasize the significance of developing Li metal batteries. Then, we specifically elucidate the formation process and composition of SEI film. Next, we detailly discuss LiPSs cation as the dominant species in Li−S battery. Subsequently we review the case that contend no LiPSs intermediates formation in Li−S battery using γ‐S as the cathode. Afterwards, we conduct a discussion between dry SEI film vs. wet SEI film on the surface of Li metal anode, followed by the strategies to design rational electrolytes for engineering stable Li metal anodes. Finally, we propose personal insights and perspectives on the development direction of Li−S batteries. We hope this timely perspective will be of great interest to the numerous scientific researchers focusing on Li−S batteries.
Unraveling the Influence of Li+‐cation and TFSI−‐anion in Poly(ionic liquid) Binders for Lithium‐Metal Batteries
Authors: Del Olmo Rafael , Guzmán‐González Gregorio , Santos‐Mendoza Ilda O. , Mecerreyes David , Forsyth Maria , Casado Nerea
Published: December 2022

Ion transport in composite electrodes plays a key role in the electrochemical performance of lithium‐metal batteries (LMBs), particularly at high current densities, and hence, some works have suggested the use of ionic conducting polymers as binders. Herein, in order to assess the importance of the type of ion conduction in binders, two poly(ionic liquid) polymers were analyzed as binders in LiFePO4 (LFP) cathodes: poly(lithium 1‐[3‐(methacryloyloxy)propylsulfonyl]‐1‐(trifluoromethane sulfonyl) imide) (PMTFSI−Li), and poly(diallyldimethylammonium bis(trifluoromethane sulfonyl)imide) (PDADMA−TFSI). Their functionalities allow modulating the individual transport of their counter‐ions, Li+ and TFSI−, respectively; in comparison with conventional PVDF binder. Thus, LFP−C‐Binder cathodes, namely C−PVDF, C−PDADMA−TFSI and C−PMTFSI−Li, were evaluated in LMBs. C−PMTFSI−Li exhibited the best performance reaching the theoretical specific capacity (170.3±0.8 mAh g−1) at C/10, an outstanding capacity at 10 C (100.6±0.5 mAh g−1), and long lifespan (>500 cycles at 1 C). C−PDADMA−TFSI showed good long‐term cycling and high performance at high C‐rate, while C−PVDF ended up fading before reaching 500 cycles. Surprisingly, it was observed that the presence of ionic binders into the cathode formulation influenced on Li0 metal deposition morphology, leading to a more homogeneous plating (specially PMTFSI−Li) in comparison with PVDF; and therefore, exhibiting a mitigation of mossy lithium growth.
Techno‐economic analysis of biochemical conversion of biomass to biofuels and platform chemicals
Authors: Hakeem Ibrahim Gbolahan , Sharma Anita , Sharma Tanima , Sharma Abhishek , Joshi Jyeshtharaj B. , Shah Kalpit , Ball Andrew S. , Surapaneni Aravind
Published: December 2022

Biomass is the most versatile feedstock for renewable energy and chemical production. Biochemical techniques such as fermentation and biomethanation have been developed extensively for converting biomass into bioethanol, biogas, and high‐value platform chemicals. However, the techno‐economic feasibility of the various biochemical techniques for the production of a range of biofuels and chemicals has not been fully consolidated in a review. This paper reviews the techno‐economic studies of biochemical conversion of biomass in a comparative fashion between feedstocks, treatment methods, and product types. The review starts with an overview of various biomass treatment approaches and the need for pre‐treatment for processing second‐generation feedstocks. This is followed by a review of the main biochemical conversion processes, offering insights into process stages, product yields and quality, as well as commercialization prospects and challenges. The various techno‐economic aspects of biomass conversion via biochemical techniques, such as conversion efficiency, production capacity, minimum selling price, capital cost, unit production cost, and profitability metrics, are critically reviewed. It was found that bioethanol and biogas are the most commercially viable products from the biochemical processing of biomass. The production of other biofuels and chemicals such as biobutanol, biohydrogen, furfural, volatile fatty acids, succinate, levulinic acid, and sugar alcohols via biochemical techniques is still largely limited by low conversion, frail microbial strains, cost of enzymes, and separation, and refining challenges. Overcoming these technical bottlenecks, and addressing the issues of feedstock price and supply security, are crucial for enhancing the overall techno‐economic attractiveness of biochemical processes for fuels and chemical production from biomass resources. © 2023 Society of Industrial Chemistry and John Wiley & Sons Ltd.
Techno‐economic modeling and assessment of cultivated meat: Impact of production bioreactor scale
Authors: Negulescu Patrick G. , Risner Derrick , Spang Edward S. , Sumner Daniel , Block David , Nandi Somen , McDonald Karen A.
Published: December 2022

Increases in global meat demands cannot be sustainably met with current methods of livestock farming, which has a substantial impact on greenhouse gas emissions, land use, water consumption, and farm animal welfare. Cultivated meat is a rapidly advancing technology that produces meat products by proliferating and differentiating animal stem cells in large bioreactors, avoiding conventional live‐animal farming. While many companies are working in this area, there is a lack of existing infrastructure and experience at commercial scale, resulting in many technical bottlenecks such as scale‐up of cell culture and media availability and costs. In this study, we evaluate theoretical cultivated beef production facilities with the goal of envisioning an industry with multiple facilities to produce in total 100,000,000 kg of cultured beef per year or ~0.14% of the annual global beef production. Using the computer‐aided process design software, SuperPro Designer®, facilities are modeled to create a comprehensive analysis to highlight improvements that can lower the cost of such a production system and allow cultivated meat products to be competitive. Three facility scenarios are presented with different sized production reactors; ~42,000 L stirred tank bioreactor (STR) with a base case cost of goods sold (COGS) of $35/kg, ~211,000 L STR with a COGS of $25/kg, and ~262,000 L airlift reactor (ALR) with a COGS of $17/kg. This study outlines how advances in scaled up bioreactors, alternative bioreactor designs, and decreased media costs are necessary for commercialization of cultured meat products.
A randomised controlled trial of a cognitive behaviourally informed intervention for changing violent sexual attitudes among adult sexual offenders in prison
Authors: Ede Moses Onyemaechi , Okeke Chinedu Ifedi , Onah Sebastian O.
Published: December 2022

Background

Predatory sexual acts by adults cause concern worldwide. Patterns of distorted thinking and weakened self‐control are among the leading explanations. Amidst growing concerns about sexual offences in Nigeria, it might be that more psychologically informed interventions in prison could reduce the risks of further harm compared with the standard prison regime.

Aims

To test the effectiveness of a cognitive behaviourally informed intervention (CBII) in reducing violent sexual attitudes among men in prison in Nigeria for a sexual offence.

Methods

In a randomised controlled trial, men in two prisons who responded to in‐prison advertising about the trial were screened for nature of offence and willingness to participate. Those nearing their sentence end or in other psychological therapy were excluded. Sample size was confirmed by power calculation. The Compulsive Sexual Behaviour Inventory (CSBI‐22) and the Hypersexual Behaviour Inventory (HBI) were administered before, immediately after and 3 months after completion of a 12‐session (18 h) Cognitive Behavioural Informed Intervention or equivalent periods of ‘treatment as usual’ (TAU) alone. The CBII was designed to change sexual attitudes, and delivered by trained cognitive therapists to the men, as a group, in one of the prisons while the controls received only TAU in the other.

Results

Before the intervention, the 39 men in each group had similar psychosocial histories and sexual attitude scores. Following CBII, the intervention group showed a significant reduction in scale scores that was sustained, whereas the TAU group showed no significant change in scores. An ANCOVA analysis confirmed between‐group differences immediately after the intervention and 3 months later.

Conclusions

This randomised controlled trial adds to existing knowledge in the field because prior studies have been from high income countries, where interventions are generally delivered in more privacy and at greater length. Given that our study had to be limited to change in sexual attitudes as the main outcome, future research must focus on the extent to which such change maps on to changes in interpersonal behaviour among such men. If these findings can be extended in this way and replicated, this could pave the way for more cost‐efficient interventions in higher income countries too.
Preliminary Evaluation of the Heating and Cooling Capability of an Insulating Glass Unit
Authors: Möckel Maximilian , Weller Bernhard , Schmidt Thomas , Buning Markus
Published: December 2022

In order to achieve maximum transparency of the buildings, architects plan large facades and large window areas. These glass surfaces have the disadvantage that they form a cold surface in winter and the sun heats the room in summer. It is desirable to use the potential of the huge surfaces of the glass for controlled heating and cooling. To be able to use an insulating glass unit as a heater, the temperature must be distributed uniformly over the glass. Existing solutions rely on heating wires between the panes of a laminated glass, but these are visible for the user. To create an invisible system, the cavity of the insulating glass can be used. The idea is to fill the cavity with helium instead of argon or krypton. Due to the good thermal conductivity of helium, temperatures in the cavity can be distributed over the whole glass. Content of this paper is the basics research, experimental research of the gas tightness with helium in the cavity and the first functional tests for heating and cooling with helium. The results give a first look at the heating and cooling capability of and insulating glass unit and include the basics for further researches on this topic. These are the first results of a current research project of the Institute of Building Construction at the TU Dresden.
Innovative recycling approaches to enable new material loops for AAC
Authors: Thome Volker , Shamshafshejani Taban
Published: December 2022

This paper shows different approaches to save mineral resources or energy for the production of autoclaved aerated concrete (AAC) using secondary materials. The goal is to implement new recycling routes in the building industry and to establish new material loops. It could be shown, that AAC can act as a sink for fine fractions from building rubble consisting of waste concrete and calcium silicate masonry units (CSU) by replacing the primary quartz sand. By choosing secondary raw materials like rice husk ash with a higher solubility than quartz, it is even possible to achieve AAC with the desired properties at lower autoclaving temperatures. After the end of life, AAC can be treated with the patented approach “ENSUBA,” a wet‐chemical washing procedure, which enables the complete removal of sulfate ions, which usually cause problems in the recycling of AAC. After this treatment waste AAC can easily be brought back to the material cycle and for example be used as a raw material for cement production. Most importantly, this ENSUBA approach can be combined sensibly with a carbon capture technique like the chilled ammonia process. This process captures CO2 from the cement production in an ammonia solution, leading to the precipitation of ammonium carbonate, which is needed for the ENSUBA process.
Belite cement clinker from autoclaved aerated concrete waste – A contribution towards CO2‐reduced circular building materials
Authors: Stemmermann Peter , Ullrich Angela , Beuchle Günter , Garbev Krassimir , Schweike Uwe
Published: December 2022

The processing of belite cement clinker in a rotary kiln at about 1000oC is a new recycling option for autoclaved aerated concrete (AAC) waste that otherwise must be landfilled. The clinker produced can partially substitute ordinary portland cement (OPC) in AAC production. Waste quantities and landfill costs are minimized, while at the same time CO2 emissions and the primary resource consumption of AAC production are reduced. The technology is currently under development. New analytical possibilities and modeling have made it possible to optimize the process conditions to such an extent that the use of belite cement clinker in aerated concrete production has already been technically tested. Particularly large effects on CO2 emissions can be achieved through the electrical heating of the rotary kiln and the coupled sequestration of the released CO2 in other secondary products such as recycled aggregate for concrete production from waste concrete. Comparable concepts for the AAC cycle are currently being worked on together with the industry partner Xella. Although decentralized plant concepts would be useful in order to minimize transportation, small plants are currently not economical according to initial estimates. In the long term, emission‐free product cycles are aimed at.
Transition‐Metal‐Free Synthesis of Polyfluoro‐Polyarylmethanes via Direct Cross‐Coupling of Polyfluoroarenes and Benzyl Chlorides
Authors: Zhou Yu , Hu Dandan , Zhang Yuting , Cen Qiyou , Dong Zhi‐Bing , Zhang Jun‐Qi , Ren Hongjun
Published: December 2022

The transition‐metal‐free direct cross‐coupling between polyfluoroarenes and benzyl chlorides is reported. In this strategy, a variety of polyfluoro di‐, tri‐ and tetra‐arylmethanes was efficiently prepared with good to excellent yields in the presence of Mg turnings via a one‐pot procedure. Significantly, this method provides a general approach for the synthesis of polyfluorinated polyarylmethanes.
A Facile Cation‐Exchange Strategy for ZnS‐SnS‐Sb2S3@C Submicron Box as Advanced Anode for Li‐Ion Batteries
Authors: Chen Miao‐Ling , Chen Yi‐Zhao , Wang Ling‐Zhi , Cao Jing‐Ru , Huang Xing‐Wen , Li Yue‐Zhu , Wang Rui‐Bin , Liu Yi‐Dong , Hu Jun‐Qi , Liao Song‐Yi , Min Yong‐Gang
Published: December 2022

In this work, a hierarchical ZnS‐SnS‐Sb2S3@C (ZTAS@C) submicron box has been successfully prepared via a facile cation‐exchange strategy and is used as advanced anode for Li‐ion batteries. The composition and morphology of the as‐prepared samples are measured by XRD, SEM and TEM, respectively. In addition, the as‐synthesized hollow ZTAS@C architecture delivers a rate capability of 1001, 862, 765, 621, and 419 mAh g−1 at 0.2, 0.5, 1.0, 2.0, and 4.0 A g−1, respectively, and maintains reversible specific capacity of 581 mAh g−1 after 100 cycles at 1.0 A g−1 with the high CE value around almost 100%. Since 1 mol Sb2S3 could hold 4.8 times more Li+ ions than ZnS, the as‐synthesized ZTAS@C delivers 2∼3 times more specific capacity than the un‐treated ZnS‐SnS@C sample without cation‐exchange during electrochemical testing. Moreover, the cycled ZTAS@C could maintain a relatively complete microscopic morphology of the submicron box with a lower electrode expansion rate of ∼131%. Owing to synergistic effects between ZnS‐SnS‐Sb2S3, such as stable structure from ZnS, faster ionic conductivity from SnS and higher capacity from Sb2S3 (theoretically 947 mAh/g), ZTAS@C anode showed excellent electrochemical enhancements as using for LIBs anode. Therefore, the cation exchange strategy should be a facile way to improve the rate performance and cycle stability of multi‐metals sulfide composites.
Pharmacokinetic Interaction of Chiglitazar with CYP3A4 Inducer or Inhibitor: An Open‐Label, Sequential Crossover, Self‐Control, 3‐Period Study in Healthy Chinese Volunteers
Authors: Yuan Fei , Li Jing , Li Xuening , Li Hui , Chen Weili , Yang Mengjie , Chen Hanjing , Sheng Lei , Liu Chao , Wu Yujia , Xu Hongrong
Published: December 2022

Chiglitazar, a pan agonist of non‐thiazolidinedione peroxisome proliferator‐activated receptor, has the potential to regulate blood sugar, improve lipid metabolism, and reduce cardiovascular complications. This study aimed to examine the effect of cytochrome P450 (CYP) 3A4 inhibitors/inducers on the in vivo metabolism of chiglitazar and provide a reference for the clinical combination use of chiglitazar. A single‐center, open‐label, sequential crossover, and self‐control study was carried out in 24 healthy subjects to determine the pharmacokinetics of chiglitazar dosed with and without CYP3A4 inhibitors and inducers. The findings showed that the CYP3A4 inhibitor itraconazole had no apparent pharmacokinetic drug interaction with chiglitazar, whereas rifampicin did. When combined with rifampicin after continuous dosing, chiglitazar exposure was not theoretically reduced but increased compared to a single dose of chiglitazar. The possible explanation may be the transporters of bile salt export pump, but this needs to be confirmed. The safety of chiglitazar in single or combination doses was well tolerated. The findings of this study provide a basis for clinical combinations of chiglitazar with CYP3A4 inhibitors or inducers.
Cross‐domain sentiment classification using decoding‐enhanced bidirectional encoder representations from transformers with disentangled attention
Authors: Singh Rahul Kumar , Sachan Manoj Kumar , Patel Ram Bahadur
Published: December 2022

Cross‐domain sentiment classification is a significant task of sentiment analysis that objectives to predict the opinion orientation of text documents in the target domain by using the source domain's learned classifier. Most of the existing approaches of domain‐adaptation in sentiment classification focus on sharing low‐dimensional features across the domain using domain independent and specific features to mitigate the gap between domains. Earlier cross‐domain sentiment classification approaches mainly focused on document level and sentence level, they cannot consider the full impact of aspect words, position of the words, and long‐term dependencies. To address this concern, we propose a model for cross‐domain sentiment classification, which is based on decoding‐enhanced BERT with disentangled attention (DeBERTa). DeBERTa is a pretrained language model based on transformer architecture. In this article, we perform sentence and aspect embedding to mine wordpiece information from text document. DeBERTa language‐model utilize disentangled attention mechanism and an enhanced mask decoder to understand the expression features. Disentangled attention mechanism is used to encode each word into two vectors (i.e., content and position vector). In order to predict the masked tokens during model pretraining, an enhanced mask decoder is employed, which incorporates absolute positions in the decoding layer. Finally, experiments are conducted on the benchmark dataset that demonstrates the superiority of fine‐tuned DeBERTa model for cross‐domain sentiment classification tasks.
Diversity achieving full‐duplex DF relaying with joint relay‐antenna selection under Nakagami‐m fading environment
Authors: Shirzadian Gilan Mahsa , Maham Behrouz
Published: December 2022

One of the main imperfections degrading the performance of full‐duplex (FD) relaying systems is the outage floor. In this work, a power scaling method is proposed, which overcomes this effect even when there does not exist a direct channel between source and destination nodes. The system is composed of
decode‐and‐forward (DF) FD relays over the Nakagami‐m fading environment. To promote system performance, joint antenna and relay selection methods are employed in the FD relaying systems. Each FD relay is equipped with multiple antennas for receiving and the other for transmitting the information. The transmitting and receiving antennas are chosen based on the instantaneous channel variations, and one relay is selected to improve the signal‐to‐interference and noise ratio (SINR) of the FD relaying system. The performance of the proposed design is investigated. Moreover, the closed‐form equations of the ergodic capacity and outage probability are attained. The analytical results are confirmed by different simulations. Results indicate that the proposed design achieves an additional spatial diversity gain because of using the antenna selection at the relay nodes. Moreover, by power scaling (PS) method, the system performance is effectively improved compared to the conventional FD relaying structures.
Langerhans cell histiocytosis: A diagnostic challenge on thyroid fine needle aspiration cytology
Authors: Agnihotri Mona , Boral Sayan , Kothari Kanchan
Published: December 2022

Thyroid gland involvement by Langerhans cell histiocytosis (LCH) is extremely rare. A 28‐year‐old woman with a history of polyuria, polydipsia and amenorrhoea presented with a diffuse thyroid swelling of 2 months duration. Clinical diagnosis was diabetes insipidus. Endocrine profile was normal. Fine needle aspiration cytology (FNAC) from thyroid revealed numerous large histiocytes with prominent nuclear grooves against an inflammatory background rich in eosinophils. A diagnosis of LCH was made and immunocytochemistry with CD1a confirmed the same. Subsequent skin biopsy also showed LCH. FNAC diagnosis of LCH in thyroid is challenging. The diagnostic pitfalls range from thyroiditis due to the presence of inflammatory cells in the background to papillary thyroid carcinoma due to grooved nuclei. Additional material should be collected at FNAC for ancillary studies to confirm the diagnosis.
Assay validation for vilanterol and its metabolites in human urine with application for doping control analysis
Authors: Panchal Tina , Baldwin Sandra , Østergaard Martin , Hansen Erik Soeren Halvard , Backer Vibeke , Hostrup Morten , Daley‐Yates Peter
Published: December 2022

A bioanalytical method for detecting the ultra‐long‐acting beta2‐agonist (U‐LABA) inhaled vilanterol and its metabolites, GSK932009 and GW630200, in urine was developed to potentially monitor permitted therapeutic versus prohibited supratherapeutic use in sport. The World Anti‐Doping Agency (WADA) has established urinary concentration thresholds for the beta2‐agonists salbutamol and formoterol. Therapeutic use of vilanterol (25 μg once daily) was recently permitted by WADA; however, there is no established decision limit for adverse analytical findings due to insufficient urine concentration data. In this study, we validated an assay to detect vilanterol in urine collected from four healthy male and female athletes 0–72 h who received inhaled corticosteroid fluticasone furoate/U‐LABA vilanterol (800/100 μg) combination, four times the normal therapeutic dose. After administration, subjects performed 1 h of bike ergometer exercise. The experiment was conducted again after repeat dosing for 1 week. Our method utilised liquid chromatography with tandem mass spectrometry and was validated over urine concentrations of 5–5000 (vilanterol) and 50–50,000 pg/ml (GSK932009 and GW630200). Plasma samples were analysed for vilanterol, using a previously validated assay. The peak concentration values for urine vilanterol, GSK932009 and GW630200 were 9.5, 10.4 and 0.17 ng/ml, for single dosing, and 18.6, 19.5 and 0.20 ng/ml, for repeat dosing. Urine samples from four volunteers using the final validated method are reported, demonstrating this assay has sensitivity to detect vilanterol or GSK932009 in urine for ≥72 h post single or repeat dosing with 800/100 μg fluticasone furoate/vilanterol, whereas GW630200 was quantifiable ≤4 h post dose.
Inorganic Chemistry in Hong Kong
Authors: Kam‐Wing Lo Kenneth
Published: December 2022

Inorganic chemistry research has developed impressively in Hong Kong, attaining worldwide recognition. This Guest Editorial introduces the research showcased in the Institute Feature “Universities in Hong Kong”, which is conducted in seven universities: City University of Hong Kong (CityU), The Chinese University of Hong Kong (CUHK), The Education University of Hong Kong (EdUHK), Hong Kong Baptist University (HKBU), The University of Hong Kong (HKU), The Hong Kong University of Science and Technology (HKUST), and The Hong Kong Polytechnic University (PolyU).
Oropharyngeal dysphagia and cachexia: Intertwined in head and neck cancer
Authors: Willemsen Anna C. H. , Pilz Walmari , Hoeben Ann , Hoebers Frank J. P. , Schols Annemie M. W. J. , Baijens Laura W. J.
Published: December 2022

Background

This study aims to investigate the relationship between cancer cachexia and oropharyngeal dysphagia (OD) in patients with head and neck cancer (HNC) prior to chemoradiotherapy or bioradiotherapy (CRT/BRT).

Methods

A prospective cohort study with patients with HNC undergoing CRT/BRT (2018–2021) was conducted. Body composition and skeletal muscle function were evaluated using bioelectrical impedance analysis, handgrip strength, and the short physical performance battery (SPPB). The M. D. Anderson Dysphagia Inventory (MDADI), Eating Assessment Tool (EAT)‐10 questionnaire, and patient characteristics were collected. A standardized videofluoroscopic swallowing study was offered to patients.

Results

Sixty‐six patients were included. Twenty‐six patients scored EAT‐10 ≥ 3 and seventeen were cachectic. ACE‐27 score >1, cachexia, abnormal SPPB‐derived repeated chair‐stand test, lower MDADI scores, and higher overall stage grouping showed potential predictive value (p ≤ 0.10) for EAT‐10 ≥ 3. Using multivariable regression analysis, only cachexia remained a significant predictor of EAT‐10 ≥ 3 (HR 9.000 [95%CI 2.483–32.619], p = 0.001).

Conclusion

Cachexia independently predicted the presence of patient‐reported OD.
Augmentation of BMP Signaling in Cranial Neural Crest Cells Leads to Premature Cranial Sutures Fusion through Endochondral Ossification in Mice
Authors: Ueharu Hiroki , Pan Haichun , Liu Xia , Ishii Mamoru , Pongetti Jessica , Kulkarni Anshul K. , Adegbenro Folasade E. , Wurn Jaden , Maxson Robert E. , Sun Hongchen , Komatsu Yoshihiro , Zhang Honghao , Yang Jingwen , Mishina Yuji
Published: December 2022

Craniosynostosis is a congenital anomaly characterized by the premature fusion of cranial sutures. Sutures are a critical connective tissue that regulates bone growth; their aberrant fusion results in abnormal shapes of the head and face. The molecular and cellular mechanisms have been investigated for a long time, but knowledge gaps remain between genetic mutations and mechanisms of pathogenesis for craniosynostosis. We previously demonstrated that the augmentation of bone morphogenetic protein (BMP) signaling through constitutively active BMP type 1A receptor (caBmpr1a) in neural crest cells (NCCs) caused the development of premature fusion of the anterior frontal suture, leading to craniosynostosis in mice. In this study, we demonstrated that ectopic cartilage forms in sutures prior to premature fusion in caBmpr1a mice. The ectopic cartilage is subsequently replaced by bone nodules leading to premature fusion with similar but unique fusion patterns between two neural crest‐specific transgenic Cre mouse lines, P0‐Cre and Wnt1‐Cre mice, which coincides with patterns of premature fusion in each line. Histologic and molecular analyses suggest that endochondral ossification in the affected sutures. Both in vitro and in vivo observations suggest a greater chondrogenic capacity and reduced osteogenic capability of neural crest progenitor cells in mutant lines. These results suggest that the augmentation of BMP signaling alters the cell fate of cranial NCCs toward a chondrogenic lineage to prompt endochondral ossification to prematurely fuse cranial sutures. By comparing P0‐Cre;caBmpr1a and Wnt1‐Cre;caBmpr1a mice at the stage of neural crest formation, we found more cell death of cranial NCCs in P0‐Cre;caBmpr1a than Wnt1‐Cre;caBmpr1a mice at the developing facial primordia. These findings may provide a platform for understanding why mutations of broadly expressed genes result in the premature fusion of limited sutures. © 2022 The Authors. JBMR Plus published by Wiley Periodicals LLC on behalf of American Society for Bone and Mineral Research.
Collaborative construction of artificial intelligence curriculum in primary schools
Authors: Dai Yun , Liu Ang , Qin Jianjun , Guo Yanmei , Jong Morris Siu‐Yung , Chai Ching‐Sing , Lin Ziyan
Published: December 2022

Background

The recent discussion of introducing artificial intelligence (AI) knowledge to K–12 students, like many engineering and technology education topics, has attracted a wide range of stakeholders and resources for school curriculum development. While teachers often have to directly interact with external stakeholders out of the public schooling system, few studies have scrutinized their negotiation process, especially teachers' responses to external influences, in such complex environments.

Purpose

Guided by an integrated theoretical framework of social constructionism, this research examined the process of how a teacher‐initiated AI curriculum was constructed with external influences. The research focused on teachers' perspectives and responses in mediating external influences into local schools and classrooms.

Methods

A 3‐year ethnographic study was conducted in relation to an AI curriculum project among 23 Computer Science (CS) teachers from primary schools. Data collected from ethnographic observation, teacher interviews, and artifacts, were analyzed using open coding and triangulation rooted in the ethnographic, interpretivist approach.

Results

Three sets of external influences were found salient for teachers' curriculum decisions, including the orientation of state‐level educational policies, AI faculty at a partner university, and students' media and technology environments. The teachers' situational logics and strategic actions were reconstructed with thick descriptions to uncover how they navigated and negotiated the external influences to fulfill local challenges and expectations in classrooms and schools.

Conclusions

The ethnographic study uncovered the dynamic and multifaceted negotiation involved in the collaborative curriculum development, and offers insights to inform policymaking, teacher education, and student support in engineering education.