bluuebunny/crossref_metadata_2025 huggingface dataset:
Epitaxial Growth of Lead‐Free Double Perovskite Shell for CsPbX3/Cs2SnX6 (X = Cl, Br, and I) Core/Shell Perovskite Nanocrystals with Enhanced Photoelectric Properties and Stability
Authors: Lin Hanjie , Li Shuya , Zhang Yuchen , Chu Chun , MacSwain Walker , Meulenberg Robert W. , Qiao Quinn , Zhao Dong , Zheng Weiwei
Published: November 2023

All‐inorganic lead halide perovskite nanocrystals (NCs) have great optoelectronic properties with promising applications in light‐emitting diodes (LEDs), lasers, photodetectors, solar cells, and photocatalysis. However, the intrinsic toxicity of Pb and instability of the NCs impede their broad applications. Shell‐coating is an effective method for enhanced environmental stability while reducing toxicity by choosing non‐toxic shell materials such as metal oxides, polymers, silica, etc. However, multiple perovskite NCs can be encapsulated within the shell material and a uniform epitaxial‐type shell growth of well‐isolated NCs is still challenging. In this work, lead‐free vacancy‐ordered double perovskite Cs2SnX6 (X = Cl, Br, and I) shells are epitaxially grown on the surface of CsPbX3 NCs by a hot‐injection method. The effectiveness of the non‐toxic double perovskite shell protection is demonstrated by the enhanced environmental and phase stability against UV illumination and water. In addition, the photoluminescence quantum yields (PL QYs) increase for the CsPbCl3 and CsPbBr3 NCs after shelling because of the type I band alignment of the core/shell materials, while enhanced charge transport properties obtained from CsPbI3/Cs2SnI6 core/shell NCs are due to the efficient charge separation in the type II core/shell band alignment.
A2‐A1‐D‐A1‐A2‐Type Nonfullerene Acceptors
Authors: Tang Ailing , Cong Peiqing , Dai Tingting , Wang Zongtao , Zhou Erjun
Published: November 2023

The A2‐A1‐D‐A1‐A2‐type molecules consist of one electron‐donating (D) core flanked by two electron‐accepting units (A1 and A2) and have emerged as an essential branch of nonfullerene acceptors (NFAs). These molecules generally possess higher molecular energy levels and wider optical bandgaps compared with those of the classic A‐D‐A‐ and A‐DA'D‐A‐type NFAs, owing to the attenuated intramolecular charge transfer effect. These characteristics make them compelling choices for the fabrication of high‐voltage organic photovoltaics (OPVs), ternary OPVs, and indoor OPVs. Herein, the recent progress in the A2‐A1‐D‐A1‐A2‐type NFAs are reviewed, including the molecular engineering, structure‐property relationships, voltage loss (Vloss), device stability, and photovoltaic performance of binary, ternary, and indoor OPVs. Finally, the challenges and provided prospects are discussed for the further development of this type of NFAs.
Large Room‐Temperature Magnetoresistance in a High‐Spin Donor–Acceptor Conjugated Polymer
Authors: Tahir Hamas , Eedugurala Naresh , Hsu Sheng‐Ning , Mahalingavelar Paramasivam , Savoie Brett M. , Boudouris Bryan W. , Azoulay Jason D.
Published: November 2023

Open‐shell conjugated polymers (CPs) offer new opportunities for the development of emerging technologies that utilize the spin degree of freedom. Their light‐element composition, weak spin‐orbit coupling, synthetic modularity, high chemical stability, and solution‐processability offer attributes that are unavailable from other semiconducting materials. However, developing an understanding of how electronic structure correlates with emerging transport phenomena remains central to their application. Here, the first connections between molecular, electronic, and solid‐state transport in a high‐spin donor–acceptor CP, poly(4‐(4‐(3,5‐didodecylbenzylidene)‐4H‐cyclopenta[2,1‐b:3,4‐b’]dithiophen‐2‐yl)‐6,7‐dimethyl‐[1,2,5]‐thiadiazolo[3,4‐g]quinoxaline), are provided. At low temperatures (T < 180 K), a giant negative magnetoresistance (MR) is achieved in a thin‐film device with a value of −98% at 10 K, which surpasses the performance of all other organic materials. The thermal depopulation of the high‐spin manifold and negative MR decrease as temperature increases and at T > 180 K, the MR becomes positive with a relatively large MR of 13.5% at room temperature. Variable temperature electron paramagnetic resonance spectroscopy and magnetic susceptibility measurements demonstrate that modulation of both the sign and magnitude of the MR correlates with the electronic and spin structure of the CP. These results indicate that donor–acceptor CPs with open‐shell and high‐spin ground states offer new opportunities for emerging spin‐based applications.
Photocatalytic H2O2 Generation Reaction with a Benchmark Rate at Air‐Liquid‐Solid Joint Interfaces
Authors: Yan Shiwei , Li Yong , Yang Xinyue , Jia Xiaohua , Xu Jingsan , Song Haojie
Published: November 2023

The rapid charge recombination, low selectivity for two‐electron oxygen reduction reaction (ORR), and limited O2 diffusion rate hinder the practical applications of photocatalytic H2O2 generation. Herein, a triphase photocatalytic system in which the H2O2 generation occurs at the air‐liquid‐solid joint interfaces is developed, using polymeric carbon nitride (PCN). The introduction of pyrrole units and cyano group into PCN can promote the activation of oxygen molecules and facilitate the spatial separation of HOMO and LUMO orbits, hence improving the charge carrier separation efficiency and enhancing the formation of H2O2. Importantly, the gas‐liquid‐solid triphase interface system allows for the rapid transport of oxygen from the air to the reaction interface, overcoming the low solubility and slow diffusion of oxygen in the water in conventional liquid reaction systems. The triphase system shows a benchmark H2O2 generation rate over PCN‐based materials in pure water (2063.21 µmol g−1 h−1), which is an approximate tenfold enhancement as compared to powder photocatalyst (215.44 µmol g−1 h−1). Simulation and electrochemical tests reveal that the rapid oxygen diffusion rate of triphase interface can promote charge separation and provide more O2 to generate H2O2. This work provides a promising strategy for constructing an efficient and sustainable H2O2 production system.
Elucidating the Bulk Morphology of Cellulose‐Based Conducting Aerogels with X‐Ray Microtomography
Authors: Oikonomou Vasileios K. , Dreier Till , Sandéhn Alexandra , Mohammadi Mohsen , Christensen Jakob Lønborg , Tybrandt Klas , Dahl Anders Bjorholm , Dahl Vedrana Andersen , Bech Martin , Stavrinidou Eleni
Published: November 2023

Conducting cellulose composites are promising sustainable functional materials that have found application in energy devices, sensing and water purification. Herein, conducting aerogels are fabricated based on nanofibrillated cellulose and poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate, using the ice templating technique, and their bulk morphology is characterized with X‐ray microtomography. The freezing method (−20 °C in a freezer vs liquid nitrogen) does not impact the mean porosity of the aerogels but the liquid‐N2 aerogels have smaller pores. The integration of carbon fibers as addressing electrodes prior to freezing results in increased mean porosity and pore size in the liquid‐N2 aerogels signifying that the carbon fibers alter the morphology of the aerogels when the freezing is fast. Spatially resolved porosity and pore size distributions also reveal that the liquid‐N2 aerogels are more inhomogeneous. Independent of the freezing method, the aerogels have similar electrochemical properties. For aerogels without carbon fibers, freezer‐aerogels have higher compression modulus and are less stable under cycling compression fatigue test. This can be explained by higher porosity with larger pores in the center of liquid‐N2 aerogels and thinner pore walls. This work demonstrates that micro‐CT is a powerful tool for characterizing the morphology of aerogels in a non‐destructive and spatially resolved manner.
Electrodeposition in Perovskite Solar Cells: A Critical Review, New Insights, and Promising Paths to Future Industrial Applications
Authors: Al‐Katrib Mirella , Perrin Lara , Flandin Lionel , Planes Emilie
Published: November 2023

The active layer quality significantly impacts perovskite solar cell performances. In competition with the common spin, the electrodeposition (ED) method has emerged as a cost‐effective, scalable, and environmentally friendly alternative for perovskite deposition. This article combines an up‐to‐date critical review with experimental results for the development of perovskite photovoltaics. The first review section offers a critical understanding of the current state of the art for the processing of perovskite using an ED step. With the comparison of various methods described in the literature, the pros and cons of the technique are reviewed to assess its applicability at the industrial scale. The second part presents experimental findings from the authors, resulting from a 5‐year experience in this area. Various important and specific topics are covered including the optimization of the ED parameters, the influence of the substrate, the material's selection, the architecture, and the impact on active surface properties. The comparison of the performance data from the literature and the new set of experimental data allows to pace the way for the future development and the integration of stable, affordable, and large‐scale photovoltaics cells.
Flexible a‐IGZO TFT‐Based Circuit for Active Addressing in Neural Stimulation Electrode Arrays
Authors: Rodriguez‐Lopez Ovidio , Rocha‐Flores Pedro E. , Maeng Jimin , Cogan Stuart F. , Pancrazio Joseph J. , Tamil Lakshman , Voit Walter E. , Gutierrez‐Heredia Gerardo
Published: November 2023

Neural interfaces have undergone significant advancements in recent decades, aiming for flexible, compact, and high‐density electrode arrays with a large number of channels. However, the scalability of these devices is often hindered by the number of wires needed to separately connect each electrode to external electronics. To address this limitation, thin‐film transistor (TFT)‐based electronic circuits offer a promising solution by enabling active addressing of stimulation electrodes and potentially increasing the channel count with fewer interconnections. This paper presents the integration of a circuit comprising two amorphous indium–gallium–zinc‐oxide (a‐IGZO) TFTs and a titanium nitride (TiN) electrode on a flexible polymer platform. This circuit precisely controls the electrode's On/Off states and the delivery of current for nerve stimulation. Characterization studies involving frequency and electrochemical analysis demonstrate the TFT‐based circuit's capability to operate at high frequencies, deliver biphasic stimulation pulses to the electrode, and store sufficient charge for effective neural stimulation. Moreover, the a‐IGZO TFTs exhibit remarkable stability during repeated gate voltage sweeps with minimal changes in electrical performance. This circuit has the potential to be extended to active‐matrix devices that enable electrode arrays with a high number of channels and enhanced spatial resolution, which is crucial for selective neural stimulation.
Enantioselective Assembly of α, β‐Diamine Acid Derivatives via Three‐Component Reaction of α‐H Diazoacetates with Sulfonamides and Imines
Authors: Sha Hongkai , Xie Xiongda , Zhang Dan , Hu Wenhao , Kang Zhenghui
Published: November 2023

An asymmetric three‐component reaction of α‐H diazoacetate with sulfonamide and imine has been developed under the co‐catalyzation of Rh2(OAc)4 and a chiral phosphoric acid (CPA), which proceed through Mannich‐type interception of transient ammonium ylide. The reaction offers a convenient access to α, β‐diamine acid derivatives with two adjacent chiral centers in 59%‐74% yields with 91%‐99% ee and 92:8 to>95:5 dr. Moreover, the generated products could be easily converted to free chiral diamines and other useful chiral motifs.
Thienoacene‐Based Conjugated Porous Polymer/TiO2 Hybrids as Photocatalysts in Artificial Photosynthesis
Authors: López‐Calixto Carmen G. , Gomez‐Mendoza Miguel , Barawi Mariam , Collado Laura , Liras Marta , de la Peña O´Shea Víctor A.
Published: November 2023

Herein, the design and synthesis of a couple of CPPs based on thienoacene units (named as IEP‐14 and IEP‐15, stand for IMDEA Energy Polymer numbers 14 and 15) are described, which show high BET surface areas, good photo(thermal) stabilities, and appropriate electronic alignment with TiO2 to prepare hybrids (named as IEP‐x@T‐10, X = 14 and 15, being 10 wt% of polymer loading). It is shown that the simultaneous UV–vis irradiation of both materials leads to better H2 production (ca. 925 and 827 µmol g−1 h−1 by IEP‐15@T‐10 and IEP‐14@T‐10, 12 and 11‐fold higher production than bare TiO2) than the solely irradiation at visible of the CPPs (ca. 124 and 90 µmol g−1 h−1 by IEP‐15@T‐10 and IEP‐14@T‐10 when TiO2 is photocatalytically inactive). The reason is attributed to the charge‐transfer mechanisms that occur between the counterparts of the hybrid material: in the first case it consists in a Z‐scheme charge transfer mechanism, while in the second one is a sensitization charge transfer mechanism. Both mechanisms are elucidated by advanced techniques. Furthermore, in a gas phase CO2 photoreduction test, IEP‐15@T‐10 shows sixfold higher CH4 evolution than TiO2, which result in a selectivity shift from CO to CH4 (i.e., >26% greater selectivity than bare TiO2).
The Mechanism of Fluorine Doping for the Enhanced Lithium Storage Behavior in Cation‐Disordered Cathode Oxide
Authors: Jiao Sichen , Sun Yujian , Wang Junyang , Shi Dekai , Li Yapei , Jiang Xiangkang , Wang Fangwei , Zhang Yuanpeng , Liu Jue , Wang Xuelong , Yu Xiqian , Li Hong , Chen Liquan , Huang Xuejie
Published: November 2023

Li‐rich cation‐disordered rock‐salt (DRX) materials have emerged as promising candidates for high‐capacity oxide cathodes. Their fluorinated variants have shown improved cycling stability with effectively suppressed oxygen loss. However, a comprehensive understanding of how fluorination impacts the multiscale structure and lithium transportation in DRX remains elusive in experiments. Herein, the neutron total scattering technique in conjunction with the advanced reverse Monte Carlo (RMC) fitting method is employed to characterize the intricate structure of Li1.16Ti0.37Ni0.37Nb0.1O2 (LTNNO) and the fluorinated Li1.2Ti0.35Ni0.35Nb0.1O1.8F0.2 (LTNNOF). Through rigorous statistical analysis, the multiscale structural evolution upon fluorination is quantified from atomic (≤5 Å) to long‐range scale (≈100 Å). The local Li‐rich environments around F induce a modest 2.4% increment in the number of fast Li 0TM (transition metal) channels. Crucially, at a broader scale, the proportion of 0TM channels participating in percolation increases significantly from 2.9% in LTNNO to 8.7% in LTNNOF. Fluorination improves the capacity release mainly through merging isolated fast Li channels into the percolation network. This work experimentally unravels the multiscale mechanism of fluorination‐induced performance improvement in DRX materials and highlights the necessity of adopting an advanced RMC fitting method to obtain a full view of the complex structural features in developing high‐capacity DRX cathodes.
High dynamic separation performance of metal–organic frameworks forD2/H2: Independent or competitive adsorption?
Authors: Li Yu , Situ Yizhen , Guan Kexin , Guan Yafang , Huang Xiaoshan , Cai Chengzhi , Li Shuhua , Liu Zili , Liang Hong , Wu Yufang , Yang Qingyuan , Qiao Zhiwei
Published: November 2023

Most traditional D2/H2separation techniques are energy‐intensive with low efficiency. Metal–organic frameworks (MOFs) provide a promising solution for D2/H2separation due to their excellent chemical and structural characteristics. Here, machine learning‐assisted high‐throughput computational screening was employed to identify the high‐performance MOFs for the dynamic D2/H2separation. Extensive data analysis reveals that there were two adsorption behaviors in the optimal MOFs, independent adsorption and competitive adsorption, and the independent adsorption was favorable for the preferential adsorption of D2. To quantify these two adsorption behaviors, we introduced and defined overlap degree (OD) and independence degree (ID), and developed a software for the rapid assessment of OD/ID. After batch simulation of the breakthrough curves of 2000 optimal MOFs, ~80% MOFs exhibited independent occupancy, confirming its contribution to good dynamic separation capabilities. This work provides a new idea for designing MOFs with independent adsorption behavior to improve the dynamic separation performance of hydrogen isotopes.
A Proposal for a Low‐Frequency Axion Search in the 1–2 μ$\umu$ eV Range and Below with the BabyIAXO Magnet
Authors: Ahyoune Saiyd , Álvarez Melcón Alejandro , Arguedas Cuendis Sergio , Calatroni Sergio , Cogollos Cristian , Devlin Jack , Díaz‐Morcillo Alejandro , Díez‐Ibáñez David , Döbrich Babette , Galindo Javier , Gallego Juan Daniel , García‐Barceló Jose María , Gimeno Benito , Golm Jessica , Gu Yikun , Herwig Louis , Garcia Irastorza Igor , Lozano‐Guerrero Antonio Jose , Malbrunot Chloé , Miralda‐Escudé Jordi , Monzó‐Cabrera Juan , Navarro Pablo , Navarro‐Madrid Jose Ramón , Redondo Javier , Reina‐Valero José , Schmieden Kristof , Schneemann Tim , Siodlaczek Marc , Ulmer Stefan , Wuensch Walter
Published: November 2023

In the near future BabyIAXO will be the most powerful axion helioscope, relying on a custom‐made magnet of two bores of 70 cm diameter and 10 m long, with a total available magnetic volume of more than 7 m3. In this document, it proposes and describe the implementation of low‐frequency axion haloscope setups suitable for operation inside the BabyIAXO magnet. The RADES proposal has a potential sensitivity to the axion‐photon coupling down to values corresponding to the KSVZ model, in the (currently unexplored) mass range between 1 and 2 eV, after a total effective exposure of 440 days. This mass range is covered by the use of four differently dimensioned 5‐meter‐long cavities, equipped with a tuning mechanism based on inner turning plates. A setup like the one proposed will also allow an exploration of the same mass range for hidden photons coupled to photons. An additional complementary apparatus is proposed using LC circuits and exploring the low energy range ( eV). The setup includes a cryostat and cooling system to cool down the BabyIAXO bore down to about 5 K, as well as an appropriate low‐noise signal amplification and detection chain.
Understanding the Synergy between Fe and Mo Sites in the Nitrate Reduction Reaction on a Bio‐Inspired Bimetallic MXene Electrocatalyst
Authors: Abbott Daniel F. , Xu Yuan‐Zi , Kuznetsov Denis A. , Kumar Priyank , Müller Christoph R. , Fedorov Alexey , Mougel Victor
Published: November 2023

Mo‐ and Fe‐containing enzymes catalyze the reduction of nitrate and nitrite ions in nature. Inspired by this activity, we study here the nitrate reduction reaction (NO3RR) catalyzed by an Fe‐substituted two‐dimensional molybdenum carbide of the MXene family, viz., Mo2CTx : Fe (Tx are oxo, hydroxy and fluoro surface termination groups). Mo2CTx : Fe contains isolated Fe sites in Mo positions of the host MXene (Mo2CTx) and features a Faradaic efficiency (FE) and an NH3 yield rate of 41 % and 3.2 μmol h−1 mg−1, respectively, for the reduction of NO3− to NH4+ in acidic media and 70 % and 12.9 μmol h−1 mg−1 in neutral media. Regardless of the media, Mo2CTx : Fe outperforms monometallic Mo2CTx owing to a more facile reductive defunctionalization of Tx groups, as evidenced by in situ X‐ray absorption spectroscopy (Mo K‐edge). After surface reduction, a Tx vacancy site binds a nitrate ion that subsequently fills the vacancy site with O* via oxygen transfer. Density function theory calculations provide further evidence that Fe sites promote the formation of surface O vacancies, which are identified as active sites and that function in NO3RR in close analogy to the prevailing mechanism of the natural Mo‐based nitrate reductase enzymes.
Alicyclic‐Amine‐Derived Imine‐BF3 Complexes: Easy‐to‐Make Building Blocks for the Synthesis of Valuable α‐Functionalized Azacycles
Authors: Dutta Subhradeep , Kim Jae Hyun , Bhatt Kamal , Rickertsen Dillon R. L. , Abboud Khalil A. , Ghiviriga Ion , Seidel Daniel
Published: November 2023

A new strategy to access α‐functionalized alicyclic amines via their corresponding imine‐BF3 complexes is reported. Isolable imine‐BF3 complexes, readily prepared via dehydrohalogenation of N‐bromoamines in a base‐promoted/18‐crown‐6 catalyzed process followed by addition of boron trifluoride etherate, undergo reactions with a wide range of organometallic nucleophiles to afford α‐functionalized azacycles. Organozinc and organomagnesium nucleophiles add at ambient temperatures, obviating the need for cryogenic conditions. In situ preparation of imine‐BF3 complexes provides access to α‐functionalized morpholines and piperazines directly from their parent amines in a single operation. α‐Functionalized morpholines can be elaborated further, for instance by installing a second substituent in the α′‐position.
The Art of Communicating Risk and Benefit to Promote Shared Decision‐Making, Informed by Behavioral Economic Principles
Authors: Curtis Jeffrey R. , Fraenkel Liana
Published: November 2023

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Comparing biofilm reactors inoculated with Shewanella for decolorization of Reactive Black 5 using different carrier materials
Authors: Zheng Yumin , Song Haihong , Chen Qianfei , Hou Yayi , Zhang Xinxin , Han Songlei
Published: November 2023

This study assessed the performance of biofilm reactors inoculated with azo dye degrading Shewanella for the decolorization of Reactive Black 5 (RB5), using three different carrier materials, namely almond shell biochar, moving bed biofilm reactor (MBBR), and polypropylene carrier (PPC). The reactors were fed with low‐nutrient artificial wastewater containing RB5, and all three carriers showed good RB5 decolorization performance, with varying efficiencies. Liquid Chromatography‐Mass Spectrometry analysis revealed distinct RB5 degradation pathways associated with each carrier, influenced by carrier materials and microbial communities. The MBBR carrier exhibited good stability due to its rough surface and microbial aggregates. Sequencing results highlighted differences in the microbial community structures among the carriers. Shewanella predominated the functional bacteria in the MBBR and PPC carriers, while the biochar carrier fostered highly efficient degrading microbial communities. The physicochemical properties of carrier materials significantly influenced the microbial community and RB5 degradation efficiency. These findings provide valuable insights for optimizing biofilm reactors for dye‐containing wastewater treatment.
Porous ZnP matrix for long‐lifespan and dendrite‐free Zn metal anodes
Authors: Lei Xinyue , Ma Zhipeng , Bai Lei , Wang Lei , Ding Yali , Song Shenglu , Song Ailing , Dong Haifeng , Tian Hao , Tian Huajun , Meng Xiangtong , Liu Hao , Sun Bing , Shao Guangjie , Wang Guoxiu
Published: November 2023

The reversibility of Zn plating/stripping during cycling is adversely affected by dendritic growth, electrochemical corrosion, surface passivation, and hydrogen generation on the Zn anodes for rechargeable aqueous zinc ion batteries (ZIBs). Herein, through an ordinary anodic etching process, a uniform porous ZnP matrix protective layer was created on the Zn foil (Zn@ZnP). The large and accessible specific surface area of the prepared Zn@ZnP can facilitate contact with the electrolyte, accelerating the migration and enhancing the desolvation of Zn2+, effectively enhancing the Zn deposition kinetics. According to studies from scanning electron microscopy (SEM) and multiscale optical microscopy, the Zn@ZnP electrode effectively inhibits the growth of dendrites with excellent Zn plating/stripping reversibility. In consequence, the symmetric cell with the Zn@ZnP electrodes displays a long‐term cycle life of over 1260 h at 10  mA  cm−2. The full cell, consisting of Zn@ZnP anodes and MnO2‐based cathode, demonstrated a high discharge capacity of 145 mAh g−1 after cycling 500 times at the current density of 1000 mA  g−1. A scalable method for designing a homogeneous anode protection layer enables dendrite‐free zinc metal anodes, paving the way for interface modification of other metal anodes.
Active involvement of patients, radiation oncologists, and surgeons in a multidisciplinary team approach: Guiding local therapy in recurrent, metastatic rectal cancer
Authors: Choi Seo Hee , Yang Gowoon , Koom Woong Sub , Yang Seung Yoon , Kim Seung‐Seob , Lim Joon Seok , Kim Han Sang , Shin Sang Joon , Chang Jee Suk
Published: November 2023

Background

Despite the extensive implementation of an organized multidisciplinary team (MDT) approach in cancer treatment, there is little evidence regarding the optimal format of MDT. We aimed to investigate the impact of patient participation in MDT care on the actual application rate of metastasis‐directed local therapy.

Methods

We identified all 1211 patients with locally advanced rectal cancer treated with neoadjuvant radiochemotherapy at a single institution from 2006 to 2018. Practice patterns, tumor burden and OMD state were analyzed in recurrent, metastatic cases.

Results

With a median follow‐up of 60.7 months, 281 patients developed metastases, and 96 (34.2%), 92 (32.7%), and 93 (33.1%) patients had 1, 2–5, and >5 lesions, respectively. In our study, 27.1% were managed in the MDT clinic that mandated the participation of at least four to five board‐certified multidisciplinary experts and patients in decision‐making processes, while the rest were managed through diverse MDT approaches such as conferences, tumor board meetings, and discussions conducted via phone calls or email. Management in MDT clinic was significantly associated with more use of radiotherapy (p = 0.003) and more sessions of local therapy (p < 0.001). At the time of MDT clinic, the number of lesions was 1, 2–5, and >5 in 9 (13.6%), 35 (53.1%), and 19 (28.8%) patients, respectively. The most common states were repeat OMD (28.8%) and de novo OMD (27.3%), followed by oligoprogression (15%) and induced OMD (10.6%).

Conclusion

Our findings suggest that active involvement of patients and radiation oncologists, and surgeons in MDT care has boosted the probability of using local therapies for various types of OMD throughout the course of the disease.
Chemoenzymatic Synthesis of a New Germacrene Derivative Named Germacrene F
Authors: Struwe Henry , Droste Jörn , Dhar Dipendu , Davari Mehdi D. , Kirschning Andreas
Published: November 2023

The new farnesyl pyrophosphate (FPP) derivative with a shifted olefinic double bond from C6‐C7 to C7‐C8 is accepted and converted by the sesquiterpene cyclases protoilludene synthase (Omp7) as well as viridiflorene synthase (Tps32). In both cases, a so far unknown germacrene derivative was found to be formed, which we name “germacrene F”. Both cases are examples in which a modification around the central olefinic double bond in FPP leads to a change in the mode of initial cyclization (from 1→11 to 1→10). For Omp7 a rationale for this behaviour was found by carrying out molecular docking studies. Temperature‐dependent NMR experiments, accompanied by NOE studies, show that germacrene F adopts a preferred mirror‐symmetric conformation with both methyl groups oriented in the same directions in the cyclodecane ring.
MOF‐Templated Hierarchical Porous Hollow Core‐Shell Framework Cobalt Oxide for Enhancing Hydrogen Generation from Borohydride‐Based Hydrolysis
Authors: Tran Dinh Trinh , Van Tap Huu , Tsai Yu‐chih , Lin Kun‐Yi Andrew , Duong Tuan Dinh
Published: November 2023

Designing and fabricating a competent cobalt‐based catalyst for sodium borohydride (NaBH4) hydrolysis is of great importance. The present work reports the synthesis of hierarchical porous hollow core‐shell framework cobalt oxide (HCSCO) via etching and calcination processes, which is then employed for catalyzing NaBH4 hydrolysis. The surface morphology and the hollow core‐shell framework of HCSCO were revealed by scanning electron microscope (SEM) and transmission electron microscope (TEM) analyses; the crystalline structure and the formation of Co3O4 in HCSCO were determined by X‐ray diffraction (XRD) and Raman spectroscopy; the surface area and porosity of HCSCO were verified by N2 adsorption‐desorption isotherm; and X‐ray photoelectron spectroscopy (XPS) was utilized to examine the chemical states of HCSCO. The as‐prepared HCSCO showed prominent catalytic hydrolysis of NaBH4 to generate H2 with a H2 generation rate of 441 ml min−1 gcatalyst−1 and a low activation energy (Ea) of 34.8 kJ mol−1. This Ea value of HCSCO is substantially lower than that of other catalysts, including noble metal catalysts or composites reported in the literature. Besides, HCSCO could remain its superb activity (~100 % H2 generation efficiency) over multiple hydrolysis cycles without significant changes of morphology and microstructure. The catalytic hydrolysis mechanism for H2 generation from NaBH4 using HCSCO is also proposed. This work provides a valuable strategy for the synthesis and fabrication of state‐of‐art catalysts for H2 generation from the hydrolysis of NaBH4.
Benefit‐to‐radiation‐risk of low‐dose computed tomography lung cancer screening
Authors: Hendrick R. Edward , Smith Robert A.
Published: November 2023

Background

The US National Lung Screening Trial (NLST) and Dutch‐Belgian NELSON randomized controlled trials have shown significant mortality reductions from low‐dose computed tomography (CT) lung cancer screening (LCS). NLST, ITALUNG, and COSMOS trials have provided detailed dosimetry data for LCS.

Methods

LCS trial mortality benefit results, organ dose and effective dose data, and Biological Effects of Ionizing Radiation, Report VII (BEIR VII) organ dose‐to‐cancer‐mortality risk data are used to estimate benefit‐to‐radiation‐risk ratios of the NLST, ITALUNG, and COSMOS trials. Data from those trials also are used to estimate benefit‐to‐radiation‐risk ratios for longer‐term LCS corresponding to scenarios recommended by United States Preventive Services Task Force and the American Cancer Society.

Results

Including only screening doses, NLST benefit‐to‐radiation‐risk ratios are 12:1 for males, 19:1 for females, and 16:1 overall. Including both screening and estimated follow‐up doses, benefit‐to‐radiation‐risk ratios for NLST are 9:1 for males, 13:1 for females, and 12:1 overall. For the ITALUNG trial, the benefit‐to‐radiation‐risk ratio is 58–63:1. For the COSMOS trial, assuming sex‐specific mortality benefits like those of the NELSON trial, the benefit‐to‐radiation‐risk ratio is 23:1. Assuming a conservative 20% mortality benefit, annual screening in people 50–79 years old with a 20+ pack‐year history of smoking has benefit‐to‐radiation‐risk ratios of 23:1 (with follow‐up doses adding 40% to screening doses) to 29:1 (with follow‐up adding 10%) based on COSMOS dose data.

Conclusions

Based on linear, no threshold BEIR VII dose‐risk estimates, benefit‐to‐radiation‐risk ratios for LCS are highly favorable. Results emphasize the importance of using modern CT technologies, maintaining low diagnostic follow‐up rates, and minimizing both screening and diagnostic follow‐up doses.

Plain Language Summary

The benefits of lung cancer screening significantly outweigh estimates of future harms associated with exposure to radiation during screening and diagnostic follow‐up examinations.

Our findings emphasize the importance of lung cancer screening practices using state‐of‐the‐art computed tomography scanners and specialized low‐dose lung screening and diagnostic follow‐up techniques.
Assessing the impact of increasing lung screening eligibility by relaxing the maximum years‐since‐quit threshold: A simulation modeling study
Authors: Meza Rafael , Cao Pianpian , de Nijs Koen , Jeon Jihyoun , Smith Robert A. , ten Haaf Kevin , de Koning Harry
Published: November 2023

Background

In 2021, the US Preventive Services Task Force expanded its lung screening recommendation to include persons aged 50–80 years who had ever smoked and had at least 20 pack‐years of exposure and less than 15 years since quitting (YSQ). However, studies have suggested that screening persons who formerly smoked with longer YSQ could be beneficial.

Methods

The authors used two validated lung cancer models to assess the benefits and harms of screening using various YSQ thresholds (10, 15, 20, 25, 30, and no YSQ) and the age at which screening was stopped. The impact of enforcing the YSQ criterion only at entry, but not at exit, also was evaluated. Outcomes included the number of screens, the percentage ever screened, screening benefits (lung cancer deaths averted, life‐years gained), and harms (false‐positive tests, overdiagnosed cases, radiation‐induced lung cancer deaths). Sensitivity analyses were conducted to evaluate the effect of restricting screening to those who had at least 5 years of life expectancy.

Results

As the YSQ criterion was relaxed, the number of screens and the benefits and harms of screening increased. Raising the age at which to stop screening age resulted in additional benefits but with more overdiagnosis, as expected, because screening among those older than 80 years increased. Limiting screening to those who had at least 5 years of life expectancy would maintain most of the benefits while considerably reducing the harms.

Conclusions

Expanding screening to persons who formerly smoked and have greater than 15 YSQ would result in considerable increases in deaths averted and life‐years gained. Although additional harms would occur, these could be moderated by ensuring that screening is restricted to only those with reasonable life expectancy.
MOSFET only low power sub‐bandgap voltage reference by subtraction of slope compensated proportional‐to‐absolute‐temperature voltage references
Authors: Thomas Abraham Nithin , K.J. Dhanaraj
Published: November 2023

Voltage references are typically designed by combining a complimentary to absolute temperature (CTAT) and proportional to absolute temperature (PTAT) voltage references. However, in contrast to conventional voltage references, the proposed circuit generates a voltage reference by subtracting two PTAT voltages, resulting in an extremely low process‐dependent voltage reference. A novel subtractor is also proposed for subtracting PTAT voltages, which is used to generate the reference voltage. The temperature coefficient of the proposed voltage reference is further improved using a novel PTAT slope compensation technique. The proposed voltage reference is a MOS‐only ultra‐low power circuit that works with sub‐bandgap supply voltage. Simulation results using UMC 0.18 m technology MOSFETs show that the proposed circuit has a line sensitivity of 0.5%/V, a temperature coefficient of 21.37 ppm/° C, a power consumption of 15.6 nW, and an output voltage variation of only 0.22% due to process variations.
Participatory development of a home‐based depression care model with lived experience older Nigerians and their caregivers: A theory of change
Authors: Ojagbemi Akin , Daley Stephanie , Feeney Yvonne , Elugbadebo Olufisayo , Kola Lola , Gureje Oye
Published: November 2023

Objectives

There is a huge treatment gap for late‐life depression in sub‐Saharan Africa. Building on prior work to scale‐up mental healthcare with the aid of the WHO Mental Health Gap Action Programme Intervention Guide electronic version (emhGAP‐IG), this study aims to involve older people in the iterative development of innovations to overcome challenges in the detection and clinical management of late‐life depression by frontline non‐specialist primary healthcare workers (PHCW) in Nigeria.

Methods

There were 43 participants in the study. We conducted formative qualitative research using 15 in‐depth key informant interviews with persons who were 60 years or older and had a recent experience of depression. We also conducted two focus group discussions comprising 13 of their caregivers. Through a full day stakeholders workshop comprising 15 participants, we drew on the results of our qualitative explorations to identify the pathway to impact of an intervention package (emhGAP‐Age) appropriate for the specific needs of persons with late‐life depression in Nigeria.

Results

A Theory of Change (ToC) map was produced. It highlights the expected long‐term outcomes of emhGAP‐Age to include the potential for improvement of the mental health and wellbeing of older people living in Nigeria and the generation of interest among governmental agencies concerned with policy and planning for mental healthcare. Key resources that serve as preconditions were identified to consist of the availability of PHCW who are skilled in the identification and treatment of depression and have interest in and commitment to providing care to older people. Required community resources include support from immediate family, neighbours, and informal groups. Interventions that are appropriate for depression in old age need to incorporate these community resources and address not only the symptoms of the condition but also comorbid physical health problems.

Conclusions

A participatory ToC process led to the identification of the key components of an age‐appropriate version of the emhGAP‐IG for delivering care to older persons with depression by PHCW in Nigeria.
Tile drainage as a driver of streamflow flashiness in agricultural areas of the Midwest, USA
Authors: Adelsperger Seth R. , Ficklin Darren L. , Robeson Scott M.
Published: November 2023

The Midwest of the USA is a highly productive agricultural region, in part due to the installation of perforated subsurface pipes, known as tile drains that remove excess water from wet soils. Tile drains rapidly move water to nearby streams, influencing how quickly streamflow rises and falls (i.e., streamflow “flashiness”). Currently, there are no comprehensive studies that compare the extent to which tile drainage influences flashiness across large and diverse agricultural regions. We address this knowledge gap by examining growing‐season (April–October) flashiness using the Richards‐Baker Index (RBI) in 139 watersheds located throughout the Midwest. Using a spatial tile‐drainage dataset, watersheds were split into low, medium, and high tile‐drainage classes. We found no significant differences between the flashiness of these three classes using a one‐way Kruskal–Wallis test. When watersheds were separated into infiltration groups to help control for different soil types, the high tile‐drainage class RBI was significantly higher than the low tile‐drainage class RBI in the high infiltration group. To further understand the causes of flashiness, additional environmental variables and their relationship to flashiness were examined using multivariate regression. In the low infiltration group, tile drainage significantly reduced flashiness, with watershed area and average depth to water table being the largest influences on flashiness. Tile drainage produced a larger reduction in flashiness in the high infiltration watersheds, with the largest influences being percent clay in the watershed and watershed area. These results indicate that the influence of tile drainage on flashiness emerges only after other watershed variables are accounted for. Given that tile drainage may increase in the future as precipitation patterns and extremes change, flashiness will likely continue to be modified. These results lead to an improved understanding of flood‐generating and nutrient transport mechanisms that are relevant to stakeholders across a wide range of sectors.
Peritumoral SPARC expression induced by exosomes from nasopharyngeal carcinoma infected Epstein‐Barr virus: A poor prognostic marker
Authors: Dochi Hirotomo , Kondo Satoru , Komura Shigetaka , Moriyama‐Kita Makiko , Komori Takeshi , Nanbo Asuka , Sakaguchi Miako , Fukuyo Masaki , Hamabe‐Horiike Toshihide , Tanaka Mariko , Mizokami Harue , Kano Makoto , Kitagawa Yuki , Kobayashi Eiji , Hirai Nobuyuki , Ueno Takayoshi , Nakanishi Yosuke , Endo Kazuhira , Sugimoto Hisashi , Hanayama Rikinari , Kaneda Atsushi , Yoshizaki Tomokazu
Published: November 2023

Epstein‐Barr virus (EBV)‐associated nasopharyngeal carcinoma (NPC) cells have high metastatic potential. Recent research has revealed that the interaction of between tumor cells and the surrounding stroma plays an important role in tumor invasion and metastasis. In this study, we showed the prognostic value of expression of SPARC, an extracellular matrix protein with multiple cellular functions, in normal adjacent tissues (NAT) surrounding NPC. In the immunohistochemical analysis of 51 NPC biopsy specimens, SPARC expression levels were significantly elevated in the NAT of EBER (EBV‐encoded small RNA)‐positive NPC compared to that in the NAT of EBER‐negative NPC. Moreover, increased SPARC expression in NAT was associated with a worsening of overall survival. The enrichment analysis of RNA‐seq of publicly available NPC and NAT surrounding NPC data showed that high SPARC expression in NPC was associated with epithelial mesenchymal transition promotion, and there was a dynamic change in the gene expression profile associated with interference of cellular proliferation in NAT, including SPARC expression. Furthermore, EBV‐positive NPC cells induce SPARC expression in normal nasopharyngeal cells via exosomes. Induction of SPARC in cancer‐surrounding NAT cells reduced intercellular adhesion in normal nasopharyngeal structures and promoted cell competition between cancer cells and normal epithelial cells. These results suggest that epithelial cells loosen their own binding with the extracellular matrix as well as stromal cells, facilitating the invasion of tumor cells into the adjacent stroma by activating cell competition. Our findings reveal a new mechanism by which EBV creates a pro‐metastatic microenvironment by upregulating SPARC expression in NPC.
Long‐Term Dialysis Programs: New Selection Criteria, New Problems
Authors: Perkoff Gerald
Published: November 2023

The following transcript is adapted from a case conference held in the Barnes and Wohl Hospitals, St. Louis, Missouri. The participants are members of the Departments of Internal Medicine and Pathology of the Washington University School of Medicine. Dr. Renée Fox, professor and chairman of the Department of Sociology at the University of Pennsylvania and co‐author of the book The Courage to Fail, was a guest at the conference.
Browning of white adipose tissue may be an appropriate adaptive response to critical illness
Authors: McClave Stephen A. , Martindale Robert G.
Published: November 2023

Both the baseline amount of brown adipose tissue (BAT) and the capacity to stimulate browning of white adipose tissue (WAT) may provide a protective effect to the patient in a critical care setting. Critical illness is associated with reduced mitochondrial volume and function resulting in the increased production of reactive oxygen species, greater demand for adenosine triphosphate, a switch to uncoupled fat metabolism, and hibernation of the organelle, which all contribute to multiple organ failure. Increasing insulin resistance, decreasing fatty acid oxidation, and dependence on carbohydrate metabolism result. Browning of WAT may oppose many of these adverse effects. The presence of BAT and the changes associated with browning may help dissipate oxidative stress, increase consumption and utilization of metabolites, and reduce pro‐inflammatory actions. The number of mitochondria increases, and there is greater infiltration of macrophages into adipose tissue. A shift occurs in macrophage expression from the M1 to M2 phenotype, an effect which further dampens inflammation, increases insulin sensitivity, and improves tissue healing and remodeling. Any benefit from these responses may be lost in the disease states of chronic hypermetabolism (such as burns or cancer cachexia) in which the persistence of these physiologic effects may become detrimental, contributing to excessive weight loss, adipose wasting, and loss of lean body mass. This paper discusses the plasticity of adipose tissue and whether shifts in its physiology provide clinical advantages in the intensive care unit.
Suppression of subgingival bacteria by antimicrobial photodynamic therapy using transgingival irradiation: A randomized clinical trial
Authors: Hayashi Jun‐ichiro , Ono Kohta , Iwamura Yuki , Sasaki Yasuyuki , Ohno Tasuku , Goto Ryoma , Nishida Eisaku , Yamamoto Genta , Kikuchi Takeshi , Higuchi Naoya , Mitani Akio , Fukuda Mitsuo
Published: November 2023

Background

Antimicrobial photodynamic therapy (aPDT) is an effective method for eradicating bacteria in periodontal therapy. Standard aPDT requires the insertion of a laser tip into a periodontal pocket, in which the direction of irradiation is limited. Therefore, we devised an aPDT method that uses a transgingival near‐infrared wavelength and indocyanine green‐encapsulated and chitosan‐coated nanoparticles as a photosensitizer.

Methods

Forty patients undergoing supportive periodontal therapy, who had a single root tooth with a pocket of 5 mm or deeper, were used as subjects. In the test group, aPDT was performed by laser irradiation from outside the gingiva using photosensitizer nanoparticles. In the control group, pseudo aPDT without photosensitizer was performed by transgingival irradiation. Subgingival plaque was sampled from inside the pocket before, immediately after, and 1 week after treatment, and evaluated by colony counting and real‐time polymerase chain reaction.

Results

There were no significant differences in age, sex, periodontal pocket depth, and bleeding on probing between the test and control groups. Compared with the colony count before treatment, the count in the test group was significantly reduced immediately after treatment. The number of patients with colony reduction to ≤50% and ≤10% was significantly higher in the test group than in the control group. None of the participants reported pain, although one participant reported discomfort.

Conclusion

As a bacterial control method for residual pockets in patients undergoing supportive periodontal therapy, transgingival aPDT is a promising treatment strategy that is not generally accompanied by pain or discomfort.
Oropharyngeal free flap reconstruction: Transoral robotic surgery versus open approach
Authors: Virós Porcuna David , Viña Soria Constanza , Vila Poyatos Jordi , Palau Viarnès Mar , Malagon López Paloma , Gonzàlez Lluch Carlota , Higueras Suñe Carmen , Pollán Guisasola Carlos M. , Carrasco López Cristian
Published: November 2023

Objective

Transoral robotic surgery (TORS) has evolved since its 2009 US Food and Drug Administration approval for use in local stage T1–T2 oropharyngeal carcinoma. The ability to resect increasingly larger and more complex lesions has led to the need to introduce reconstructive techniques through this route, avoiding the classic transmandibular or pull‐through approach. Few studies have compared the safety, efficacy, and advantages of TORS versus classic open approaches in oropharyngeal salvage surgery with reconstruction using microanastomosed flaps. Here we retrospectively compare our center's experience with the open approach and TORS and describe the technical variations used.

Methods

Between 2013 and 2021, 30 stage III–IV oropharyngeal cancer patients underwent salvage surgery with reconstruction in our center. From 2013 to 2017, 15 patients underwent surgery with the classic open approach, and from 2018 to 2021, an additional 15 patients underwent TORS. We have compared surgical outcomes, post‐surgical results, and survival in the two groups.

Results

Patient characteristics were similar in the two groups. TORS was associated with shorter surgical time (p < .001), fewer complications (p = .01), shorter hospital stay (p < .001), and lower feeding tube requirements (p = .003). No significant differences were observed between the two groups in the free margin rate or survival.

Conclusion

Oropharyngeal salvage surgery with TORS with free flap reconstruction reduced associated morbidity compared to the open approach in a patient cohort with poor prognosis.

Level of Evidence

4.