bluuebunny/crossref_metadata_2025 huggingface dataset:
Machine Learning Enhanced High‐Throughput Fabrication and Optimization of Quasi‐2D Ruddlesden–Popper Perovskite Solar Cells
Authors: Meftahi Nastaran , Surmiak Maciej Adam , Fürer Sebastian O. , Rietwyk Kevin James , Lu Jianfeng , Raga Sonia Ruiz , Evans Caria , Michalska Monika , Deng Hao , McMeekin David P. , Alan Tuncay , Vak Doojin , Chesman Anthony S.R. , Christofferson Andrew J. , Winkler David A. , Bach Udo , Russo Salvy P.
Published: July 2023

Organic–inorganic perovskite solar cells (PSCs) are promising candidates for next‐generation, inexpensive solar panels due to their commercially competitive cost and high power conversion efficiencies. However, PSCs suffer from poor stability. A new and vast subset of PSCs, quasi‐two‐dimensional Ruddlesden–Popper PSCs (quasi‐2D RP PSCs), has improved photostability and superior resilience to environmental conditions compared to three‐dimensional metal‐halide PSCs. To accelerate the search for new quasi‐2D RP PSCs, this work reports a combinatorial, machine learning (ML) enhanced high‐throughput perovskite film fabrication and optimization study. This work designs a bespoke experimental strategy and produces perovskite films with a range of different compositions using only spin‐coating free, reproducible robotic fabrication processes. The performance and characterization data of these solar cells are used to train a ML model that allow materials parameters to be optimized and direct the design of improved materials. The new, ML‐optimized, drop‐cast quasi‐2D RP perovskite films yield solar cells with power conversion efficiencies of up to 16.9%.
High‐Throughput Computing Guided Low/High Index Optical Coupling Layer for Record‐Performance Semitransparent Organic Solar Cells
Authors: Xu Tao , Deng Baozhong , Zhao Yanglin , Wang Zihan , Lévêque Gaëtan , Lambert Yannick , Grandidier Bruno , Wang Shenghao , Zhu Furong
Published: July 2023

Semitransparent organic solar cells (ST‐OSCs) can be made in different colors, allowing light to pass through, and yet absorb enough visible and near‐infrared (NIR) light to generate electricity. However, it remains a challenge to achieve high performing ST‐OSCs over the two competing indexes of power conversion efficiency (PCE) and average visible transmittance (AVT). This work reports an effort to develop record‐performance ST‐OSCs using a low/high index optical coupling layer (OCL) and a 2D photonic‐structured antireflective (AR) coating. High‐throughput optical screening is used to improve the understanding of OCL structure−performance relationships and the predicting of NIR absorption enhancement for ST‐OSCs. The concurrent use of a low/high index Na3AlF6 (170 nm)/ZnS (110 nm) OCL, identified among about 200 thousand simulated device configurations and a 900 nm pitch‐sized 2D photonic‐structured AR coating, fabricated using nanoimprint lithography, enables the record‐performance ternary PM6:BTP‐eC9:L8‐BO‐based ST‐OSCs, achieving simultaneously a record‐high PCE of 15.2%, a high AVT of 32%, an impressive light utilization efficiency of 4.86%, and a favorable color‐rendering index of 82. The results of the ST‐OSCs demonstrated in this work provide an attractive option for a plethora of applications in self‐powered greenhouses and building‐integrated photovoltaic systems.
A Rapid Bioinspired N‐Acyliminium Ion Strategy for the ABC Core of the Stemona Alkaloids
Authors: Chavan Subhash P. , Kalbhor Dinesh B. , Gonnade Rajesh G.
Published: July 2023

A concise and highly diastereoselective bioinspired key cationic cyclization strategy for the asymmetric synthesis of the tricyclic core of the (−)‐stemoamide, together with 8,9‐bis‐epi‐stemoamide has been described. The key N‐acyliminium ion precursors were accessed from L‐tartaric acid and L‐malic acid respectively. The use of ethyl acetoacetate derived bifunctional allylidenetriphenylphosphorane reagent in the early stage of the synthetic strategy is advantageous for the rapid construction of highly functionalized key pyrrolo[1,2‐α]azepine frameworks.
Mechanochemical Synthesis of Aryl Fluorides by Using Ball Milling and a Piezoelectric Material as the Redox Catalyst
Authors: Wang Xiaohong , Zhang Xuemei , Xue Li , Wang Qingqing , You Fengzhi , Dai Lunzhi , Wu Jiagang , Kramer Søren , Lian Zhong
Published: July 2023

Aryl fluorides are important structural motifs in many pharmaceuticals. Although the Balz–Schiemann reaction provides an entry to aryl fluorides from aryldiazonium tetrafluoroborates, it suffers from drawbacks such as long reaction time, high temperature, toxic solvent, toxic gas release, and low functional group tolerance. Here, we describe a general method for the synthesis of aryl fluorides from aryldiazonium tetrafluoroborates using a piezoelectric material as redox catalyst under ball milling conditions in the presence of Selectfluor. This approach effectively addresses the aforementioned limitations. Furthermore, the piezoelectric material can be recycled multiple times. Mechanistic investigations indicate that this fluorination reaction may proceed via a radical pathway, and Selectfluor plays a dual role as both a source of fluorine and a terminal reductant.
Solvent‐Free Chemical Recycling of Polymethacrylates made by ATRP and RAFT polymerization: High‐Yielding Depolymerization at Low Temperatures
Authors: Whitfield Richard , Jones Glen R. , Truong Nghia. P. , Manring Lewis E. , Anastasaki Athina
Published: July 2023

Although controlled radical polymerization is an excellent tool to make precision polymeric materials, reversal of the process to retrieve the starting monomer is far less explored despite the significance of chemical recycling. Here, we investigate the bulk depolymerization of RAFT and ATRP‐synthesized polymers under identical conditions. RAFT‐synthesized polymers undergo a relatively low‐temperature solvent‐free depolymerization back to monomer thanks to the partial in situ transformation of the RAFT end‐group to macromonomer. Instead, ATRP‐synthesized polymers can only depolymerize at significantly higher temperatures (>350 °C) through random backbone scission. To aid a more complete depolymerization at even lower temperatures, we performed a facile and quantitative end‐group modification strategy in which both ATRP and RAFT end‐groups were successfully converted to macromonomers. The macromonomers triggered a lower temperature bulk depolymerization with an onset at 150 °C yielding up to 90 % of monomer regeneration. The versatility of the methodology was demonstrated by a scalable depolymerization (≈10 g of starting polymer) retrieving 84 % of the starting monomer intact which could be subsequently used for further polymerization. This work presents a new low‐energy approach for depolymerizing controlled radical polymers and creates many future opportunities as high‐yielding, solvent‐free and scalable depolymerization methods are sought.
Efficient Synthesis of Hydrolytically Degradable Block Copolymer Nanoparticles via Reverse Sequence Polymerization‐Induced Self‐Assembly in Aqueous Media
Authors: Farmer Matthew A. H. , Musa Osama M. , Armes Steven P.
Published: July 2023

Hydrolytically degradable block copolymer nanoparticles are prepared via reverse sequence polymerization‐induced self‐assembly (PISA) in aqueous media. This efficient protocol involves the reversible addition‐fragmentation chain transfer (RAFT) polymerization of N,N′‐dimethylacrylamide (DMAC) using a monofunctional or bifunctional trithiocarbonate‐capped poly(ϵ‐caprolactone) (PCL) precursor. DMAC monomer is employed as a co‐solvent to solubilize the hydrophobic PCL chains. At an intermediate DMAC conversion of 20–60 %, the reaction mixture is diluted with water to 10–25 % w/w solids. The growing amphiphilic block copolymer chains undergo nucleation to form sterically‐stabilized PCL‐core nanoparticles with PDMAC coronas. 1H NMR studies confirm more than 99 % DMAC conversion while gel permeation chromatography (GPC) studies indicate well‐controlled RAFT polymerizations (Mw/Mn≤1.30). Transmission electron microscopy (TEM) and dynamic light scattering (DLS) indicate spheres of 20–120 nm diameter. As expected, hydrolytic degradation occurs within days at 37 °C in either acidic or alkaline solution. Degradation is also observed in phosphate‐buffered saline (PBS) (pH 7.4) at 37 °C. However, no degradation is detected over a three‐month period when these nanoparticles are stored at 20 °C in deionized water (pH 6.7). Finally, PDMAC30‐PCL16‐PDMAC30 nanoparticles are briefly evaluated as a dispersant for an agrochemical formulation based on a broad‐spectrum fungicide (azoxystrobin).
Photoredox‐Catalyzed Decarboxylative Bromination, Chlorination and Thiocyanation Using Inorganic Salts
Authors: Wu Jingjing , Shu Chao , Li Zhihang , Noble Adam , Aggarwal Varinder K.
Published: July 2023

Decarboxylative halogenation reactions of alkyl carboxylic acids are highly valuable reactions for the synthesis of structurally diverse alkyl halides. However, many reported protocols rely on stoichiometric strong oxidants or highly electrophilic halogenating agents. Herein, we describe visible‐light photoredox‐catalyzed decarboxylative halogenation reactions of N‐hydroxyphthalimide‐activated carboxylic acids that avoid stoichiometric oxidants and use inexpensive inorganic halide salts as the halogenating agents. Bromination with lithium bromide proceeds under simple, transition‐metal‐free conditions using an organic photoredox catalyst and no other additives, whereas dual photoredox‐copper catalysis is required for chlorination with lithium chloride. The mild conditions display excellent functional‐group tolerance, which is demonstrated through the transformation of a diverse range of structurally complex carboxylic acid containing natural products into the corresponding alkyl bromides and chlorides. In addition, we show the generality of the dual photoredox‐copper‐catalyzed decarboxylative functionalization with inorganic salts by extension to thiocyanation with potassium thiocyanide, which was applied to the synthesis of complex alkyl thiocyanates.
Solvation Modulation Enhances Anion‐Derived Solid Electrolyte Interphase for Deep Cycling of Aqueous Zinc Metal Batteries
Authors: Wang Dongdong , Lv Dan , Peng Huili , Wang Cheng , Liu Hongxia , Yang Jian , Qian Yitai
Published: July 2023

Stable Zn anodes with a high utilization efficiency pose a challenge due to notorious dendrite growth and severe side reactions. Therefore, electrolyte additives are developed to address these issues. However, the additives are always consumed by the electrochemical reactions over cycling, affecting the cycling stability. Here, hexamethylphosphoric triamide (HMPA) is reported as an electrolyte additive for achieving stable cycling of Zn anodes. HMPA reshapes the solvation structures and promotes anion decomposition, leading to the in situ formation of inorganic‐rich solid‐electrolyte‐interphase. More interestingly, this anion decomposition does not involve HMPA, preserving its long‐term impact on the electrolyte. Thus, the symmetric cells with HMPA in the electrolyte survive ≈500 h at 10 mA cm−2 for 10 mAh cm−2 or ≈200 h at 40 mA cm−2 for 10 mAh cm−2 with a Zn utilization rate of 85.6 %. The full cells of Zn||V2O5 exhibit a record‐high cumulative capacity even under a lean electrolyte condition (E/C ratio=12 μL mAh−1), a limited Zn supply (N/P ratio=1.8) and a high areal capacity (6.6 mAh cm−2).
Managing Excess Lead Iodide with Functionalized Oxo‐Graphene Nanosheets for Stable Perovskite Solar Cells
Authors: Li Guixiang , Hu Yalei , Li Meng , Tang Ying , Zhang Zuhong , Musiienko Artem , Cao Qing , Akhundova Fatima , Li Jinzhao , Prashanthan Karunanantharajah , Yang Fengjiu , Janasik Patryk , Appiah Augustine N. S. , Trofimov Sergei , Livakas Nikolaos , Zuo Shengnan , Wu Luyan , Wang Luyao , Yang Yuqian , Agyei‐Tuffour Benjamin , MacQueen Rowan W. , Naydenov Boris , Unold Thomas , Unger Eva , Aktas Ece , Eigler Siegfried , Abate Antonio
Published: July 2023

Stability issues could prevent lead halide perovskite solar cells (PSCs) from commercialization despite it having a comparable power conversion efficiency (PCE) to silicon solar cells. Overcoming drawbacks affecting their long‐term stability is gaining incremental importance. Excess lead iodide (PbI2) causes perovskite degradation, although it aids in crystal growth and defect passivation. Herein, we synthesized functionalized oxo‐graphene nanosheets (Dec‐oxoG NSs) to effectively manage the excess PbI2. Dec‐oxoG NSs provide anchoring sites to bind the excess PbI2 and passivate perovskite grain boundaries, thereby reducing charge recombination loss and significantly boosting the extraction of free electrons. The inclusion of Dec‐oxoG NSs leads to a PCE of 23.7 % in inverted (p‐i‐n) PSCs. The devices retain 93.8 % of their initial efficiency after 1,000 hours of tracking at maximum power points under continuous one‐sun illumination and exhibit high stability under thermal and ambient conditions.
Alignment and Dynamic Inversion of Planar Chirality in Pillar[n]arenes
Authors: Kato Kenichi , Fa Shixin , Ogoshi Tomoki
Published: July 2023

Pillar[n]arenes are symmetrical macrocyclic compounds composed of benzene panels with para‐methylene linkages. Each panel usually exhibits planar chirality and prefers chirality‐aligned states. Because of this feature, pillar[n]arenes are attractive scaffolds for chiroptical materials that are easy to prepare and optically resolve and show intense circular dichroism (CD) signals. In addition, rotation of the panels endows the chirality of pillar[n]arenes with a dynamic nature. The chirality in tubular oligomers and supramolecular assemblies sometimes show time‐ and procedure‐dependent alignment phenomena. Furthermore, the CD signals of some pillar[n]arenes respond to the addition of chiral guests when their dynamic chirality is coupled with host–guest properties. By using diastereomeric pillar[n]arenes with additional chiral structures, the response can also be caused by achiral guests and changes of the environment, providing molecular sensors.
Diboriranide σ‐Complexes of d‐ and p‐Block Metals
Authors: Grewelinger Philipp , Wiesmeier Tim , Präsang Carsten , Morgenstern Bernd , Scheschkewitz David
Published: July 2023

Diboriranides are the smallest conceivable monoanionic aromatic cycles, yet only limited examples have been reported and their reactivity and complexation behavior remain completely unexplored. We report a straightforward synthesis of the first peraryl diboriranide c‐(DurB)2CPh− as its lithium salt in three steps via the corresponding non‐classical diborirane from a readily available 1,2‐dichlorodiborane(4) (Dur=2,3,5,6‐tetramethylphenyl). With the preparation and complete characterization of representative complexes with tin, copper, gold and zinc, we demonstrate the strong preference of the diboriranide for σ‐type coordination modes towards main group and transition metal centers under unperturbed retention of the three‐membered B2C‐ring's 2e− π‐system.
ECHO autism adult healthcare: Training community clinicians to provide quality care for autistic adults
Authors: Malow Beth A. , Mazurek Micah , Stobbe Gary , Agrawal Mavara M. , Loftin Rachel , Caudel David , Hess Amy , Westphal Alexander , Smith Joshua , Shouse Janet , Cheak‐Zamora Nancy , Sohl Kristin
Published: July 2023

Autistic adults experience significant unmet healthcare needs, with opportunities for improvement in both the systems and the practitioners who serve this population. Primary care physicians/practitioners (PCPs) are a natural choice to provide comprehensive care to autistic adults but often lack experience in serving this population. This pilot study developed and tested an Extension for Community Healthcare Outcomes (ECHO) Autism model adapted from our previous work, focused specifically on training PCPs in best‐practice care for autistic adults. The project was informed directly by the perspectives and preferences of autistic adults, caregivers, and PCPs. Two consecutive cohorts of PCPs participated in ECHO Autism Adult Healthcare sessions. Each cohort met 1 h twice a month for 6 months, with 37 PCPs (n = 20 in Cohort 1, and n = 17 in Cohort 2) participating. Based on findings from the first cohort, adjustments were made to refine the session preparation, curriculum, conduct of the ECHO, resources, and evaluation. After participation in the ECHO Autism program, PCP self‐efficacy and satisfaction improved, while the number of perceived barriers did not change. Knowledge did not improve significantly in Cohort 1, but after adjustments to the training model, participants in Cohort 2 showed significant knowledge gains. While attention to systems of care is critical to addressing barriers in healthcare in the autistic population, the ECHO Autism Adult Healthcare model is feasible and holds promise for improving PCP satisfaction and self‐efficacy in working with autistic adults.
Facile Preparation of Higher Conductivity Porous Polyimide‐based Separators by Phase Inversion and its Overcharge‐sensitive Modification for Lithium‐ion Batteries
Authors: Feng Xiangming , Wang Mengzhen , Zheng Jinyun , Ge Junmin , Yang Mingrui , Chen Weihua
Published: July 2023

Separator plays multiple roles in the performance and safety of lithium‐ion batteries owing to the lower conductivity of the organic electrolyte and the hyperactive electrode materials. However, the commercial polyolefin separator suffers from the poor thermal stability, weak electrolyte‐wettability, low porosity as well as the demanding and costly manufacturing. Herein, we demonstrate the facial synthesis of a sponge‐like, isotropic, polyimide‐based separator by phase inversion, which possessed the higher electrolyte‐saturating conductivity (1.74 mS cm−1) and ion transference number (0.81) besides its excellent wettability and thermal stability. Meanwhile, the bearable stress was further promoted by 60 % with the 30 wt % epoxy‐strengthening tactic and the high porosity (67 %) and conductivity (1.47 mS cm−1) still preserved. Additionally, an overcharge‐sensitive PI separator was further developed by combining the conductive copolymer of coumarin‐triphenylamine by virtue of the eminent processability of PI, which demonstrated the outstanding voltage‐restraining capability for LiFePO4‐based cell during overcharge. Therefore, polyimide‐based separator could be a quite promising candidate due to its facile manufacturing, preferable performance and versatile functionalizing.
Tuina therapy promotes behavioral improvement and brain plasticity in rats with peripheral nerve injury and repair
Authors: Ma Shu‐Jie , Zhang Jun‐Peng , Hua Xu‐Yun , Wu Jia‐Jia , Zheng Mou‐Xiong , Xu Jian‐Guang
Published: July 2023

Introduction

Tuina is currently one of the popular complementary and alternative methods of rehabilitation therapy. Tuina can improve patients' pain and mobility function. However, the underlying physiological mechanism remains largely unknown, which might limit its further popularization in clinical practice. The aim of this study is to explore the short‐term and long‐term changes in brain functional activity following Tuina intervention for peripheral nerve injury repair.

Methods

A total of 16 rats were equally divided into the intervention group and the control group. Rats in the intervention group received Tuina therapy applying on the gastrocnemius muscle of the right side for 4 months following sciatic nerve transection and immediate repair, while the control group received nerve transection and repair only. The block‐design functional magnetic resonance imaging scan was applied in both groups at 1 and 4 months after the surgery. During the scan, both the injured and intact hindpaw was electrically stimulated according to a “boxcar” paradigm.

Results

When stimulating the intact hindpaw, the intervention group exhibited significantly lower activation in the somatosensory area, limbic/paralimbic areas, pain‐regulation areas, and basal ganglia compared to the control group, with only the prefrontal area showing higher activation. After 4 months of sciatic nerve injury, the control group exhibited decreased motor cortex activity compared to the activity observed at 1 month, and the intervention group demonstrated stronger bilateral motor cortex activity compared to the control group.

Conclusion

Tuina therapy on the gastrocnemius muscle of rats with sciatic nerve injury can effectively alleviate pain and maintain the motor function of the affected limb. In addition, Tuina therapy reduced the activation level of pain‐related brain regions and inhibited the decreased activity of the motor cortex caused by nerve injury, reflecting the impact of peripheral stimulation on brain plasticity.
Chemo‐Enzymatic Fluorescence Labeling Of Genomic DNA For Simultaneous Detection Of Global 5‐Methylcytosine And 5‐Hydroxymethylcytosine**
Authors: Avraham Sigal , Schütz Leonie , Käver Larissa , Dankers Andreas , Margalit Sapir , Michaeli Yael , Zirkin Shahar , Torchinsky Dmitry , Gilat Noa , Bahr Omer , Nifker Gil , Koren‐Michowitz Maya , Weinhold Elmar , Ebenstein Yuval
Published: July 2023

5‐Methylcytosine and 5‐hydroxymethylcytosine are epigenetic modifications involved in gene regulation and cancer. We present a new, simple, and high‐throughput platform for multi‐color epigenetic analysis. The novelty of our approach is the ability to multiplex methylation and de‐methylation signals in the same assay. We utilize an engineered methyltransferase enzyme that recognizes and labels all unmodified CpG sites with a fluorescent cofactor. In combination with the already established labeling of the de‐methylation mark 5‐hydroxymethylcytosine via enzymatic glycosylation, we obtained a robust platform for simultaneous epigenetic analysis of these marks. We assessed the global epigenetic levels in multiple samples of colorectal cancer and observed a 3.5‐fold reduction in 5hmC levels but no change in DNA methylation levels between sick and healthy individuals. We also measured epigenetic modifications in chronic lymphocytic leukemia and observed a decrease in both modification levels (5‐hydroxymethylcytosine: whole blood 30 %; peripheral blood mononuclear cells (PBMCs) 40 %. 5‐methylcytosine: whole blood 53 %; PBMCs 48 %). Our findings propose using a simple blood test as a viable method for analysis, simplifying sample handling in diagnostics. Importantly, our results highlight the assay‘s potential for epigenetic evaluation of clinical samples, benefiting research and patient management.
STAR procedure becomes SAFER: First‐in‐man case series of a new antegrade dissection re‐entry technique
Authors: Carlino Mauro , Uretsky Barry F. , Azzalini Lorenzo , Nascimbene Angelo , Brilakis Emmanouil S. , Colombo Antonio , Nakamura Sunao , Godino Cosmo , Avran Alexandre , Rinfret Stéphane , Faurie Benjamin
Published: July 2023

Introduction

Antegrade dissection and re‐entry (ADR) is an integral part of the hybrid algorithm, which has allowed for improved outcomes in chronic total occlusion (CTO) coronary intervention (PCI).

Methods

A new ADR method, Subintimal Antegrade FEnestration and Re‐entry (SAFER), is described. The results of a first‐in‐man series are presented.

Results

SAFER was performed on seven consecutive patients with angiographic and clinical success in all patients.

Conclusions

This first‐in‐man study has shown that the SAFER technique is feasible and effective with the possibility of improving the antegrade PCI CTO success rate.
SALL4 as an indicator for the diagnosis of hepatoid carcinoma of the ovary: A case report and literature review
Authors: Li Jiana , Wu Xiaohua
Published: July 2023

Key Clinical Message

Primary HCO is a rare, aggressive ovarian malignant tumor, morphologically resembling HCC. SALL4 can be adopted to differentiate HCO from HCC. The serum AFP and CA125 rather than HE4 can be employed as possible biomarkers to track treatment and monitor recurrence.

We report a case of a postmenopausal woman presenting with lower abdominal pain and vaginal bleeding. She went through a maximal debulking surgery, and the pathological biopsy revealed hepatoid carcinoma of the ovary (HCO). Immunohistochemical assay demonstrates SALL4 as an indicator to differentiate HCO from hepatocellular carcinoma (HCC).
Hybrid surgery of arteriovenous malformation and aneurysm of the sole
Authors: Nazari Iraj , Mousavi Seyyed Masoud , Zargar Mohammad Amin , Alavi Seyed Mohammad Amin
Published: July 2023

Key Clinical Message

The study describes the successful treatment of a rare type of arteriovenous malformation (AVM) in the sole using hybrid surgery, which consists of open resection and embolization. Moreover, the possibility of utilizing ultrasound during examination in addition to angiography for the diagnosing of AVM of the sole is proposed.
Report of two cases of Schaaf‐Yang syndrome: Same genotype and different phenotype
Authors: Rodriguez Ana Maria , Schain Katherine , Jayakar Parul , Wright Meredith S. , Chowdhury Shimul , Salyakina Daria
Published: July 2023

Key Clinical Message

We report two, genotypically identical but phenotypically distinct cases of Schaaf‐Yang syndrome and propose the early use of Genome Sequencing in patients with nonspecific presentations to facilitate the early diagnosis of children with rare genetic diseases and improve overall health care outcomes.
Chiroptical Recognition of Carboxylates with Charge‐Neutral Double‐Stranded Zinc(II) Helicates
Authors: Kalarikkal Malavika G. , Drechsler Christoph , Tusha Gers , Schäfer Lars V. , Van Craen David
Published: July 2023

Chirality analysis of small molecules for the determination of their enantiopurity is nowadays ruled by streamlined chromatographic methods which utilize chiral stationary phases. Chiroptical probes which rely on host–guest interactions are so far overshadowed by the latter but have the benefit of depending only on common spectroscopic techniques such as CD spectroscopy to distinguish enantiomers and to quantify their ratio. Interest into this receptor‐based approach is constantly rising because non‐invasive high‐throughput screenings with a minimal waste production can be performed. In this study we investigate the possibility to utilize metal‐based containers in form of charge‐neutral helicates able to recognize anions for this purpose. Key building block of the helicates are triazole units which show rotational freedom and give rise to either a meso‐structure or a racemic mixture of the right‐ and left‐handed complex. A chiroptical response of the probe is observed upon recognition of chiral mono‐ or dicarboxylates and chirality analysis of tartrate is conducted by CD spectroscopy.
Iso‐Pentadienyl Carbonate as a Five Carbon Synthon in Manganese(I)‐Catalyzed Selective Linear 1,3‐Dienylation
Authors: Singh Shubham , Parammal Athira , Kumar Manoj , X Joe Sam , Subramanian Parthasarathi
Published: July 2023

Selective linear 1,3‐dienylations are essential transformations, and numerous synthetic efforts have been documented. However, a general method enabling access to electron‐rich, ‐poor, and biologically relevant dienyl molecules is in high demand. Hence, we report a straightforward method of manganese(I)‐catalyzed C−H dienylation of arenes by using iso‐pentadienyl carbonate as a five carbon synthon. This is a highly unprecedented report for selective linear 1,3‐dienylation using manganese C−H activation catalysis. Our method facilitates the synthesis of varieties of dienes, including those suitable for normal or inverse electron demand Diels‐Alder reactions, dienyl glycoconjugates, and unnatural amino acids. Extensive mechanistic studies, including isolation of C−H activated organo‐manganese complex and isotopic analyses, have supported the proposed mechanism of this dienylation. The synthetic applicability of this method eased to deliver a 6/6/5‐fused tricyclic nagilactone scaffold.
Electrolysis of Direct Seawater: Challenges, Strategies, and Future Prospects†
Authors: Hu Lin , Tan Xiao , Yang Xuhao , Zhang Kan
Published: July 2023

Comprehensive Summary

The use of renewable sources such as solar, ocean, geothermal, and wind energy to drive water electrolysis reactions to obtain green and clean hydrogen fuels is one of the important paths to achieve sustainable energy development. At present, most water electrolysis technologies need to conduct corresponding pre‐processing, such as diluting water sources and purifying dehydration, which will greatly increase operating costs. The development of direct seawater electrolytic process can effectively solve the above problems. Here, we review the latest progress of the electrode materials and catalysts of the direct electrolysis process of seawater, and discuss how to design high activity and high‐selective electrode materials for water electrolysis with familiar impurities (such as chloride, metal ions and biological organisms) existing in the future.
Joint modelling of quantile regression for longitudinal data with information observation times and a terminal event
Authors: Pang Weicai , Liu Yutao , Zhao Xingqiu , Zhou Yong
Published: July 2023

Longitudinal data arise frequently in biomedical follow‐up observation studies. Conditional mean regression and conditional quantile regression are two popular approaches to model longitudinal data. Many results are derived under the case where the response variables are independent of the observation times. In this article, we propose a quantile regression model for the analysis of longitudinal data, where the longitudinal responses are allowed to not only depend on the past observation history but also associate with a terminal event (e.g., death). Non‐smoothing estimating equation approaches are developed to estimate parameters, and the consistency and asymptotic normality of the proposed estimators are established. The asymptotic variance is estimated by a resampling method. A majorize‐minimize algorithm is proposed to compute the proposed estimators. Simulation studies show that the proposed estimators perform well, and an HIV‐RNA dataset is used to illustrate the proposed method.
The incidence of subclinical atherosclerosis in subjects with low and moderate cardiovascular risk
Authors: Li Yan , Zhang Yinghua , Xiao Keling , Si Jin , Zhang Haoyu , Sun Lijie , Miao Zupei , Zhao Ting , Sun Jinghao , Sun Xipeng , Liu Zhi , Gao Jing , Zhao Jing , Chu Xi , Li Jing
Published: July 2023

Background

The cardiovascular risk models and subclinical atherosclerotic indicators are both recommended for cardiovascular risk stratification. The accordance between the incidence of subclinical atherosclerosis and subjects with low and moderate cardiovascular risk is unclear.

Hypothesis

Subjects with low and moderate cardiovascular risk have a lower incidence of subclinical atherosclerosis compared with subjects with high risk.

Methods

Brachial‐ankle pulse wave velocity (BaPWV) and brachial flow‐mediated dilation (BFMD) were measured in 421 subjects without a history of atherosclerotic cardiovascular disease (ASCVD) from October 2016 to January 2020. All subjects were classified into low, moderate, and high risk based on Framingham and China‐par risk models respectively.

Results

Mean age was 57.05 ± 9.35 years and 248 (58.9%) were male. In subjects with low, moderate, and high risk assessed by Framingham and China‐par risk models, the percentage of abnormal BaPWV ( > 1400 cm/s) was 42.9%, 70.1%, 85.7%, and 40.4%, 71.4%, 89.7%, respectively. Meanwhile, the percentage of abnormal BFMD ( ≤ 7%) was 43.8%, 68.5%, 77.3%, and 44.9%,72.1%, and 76.6%. According to Framingham‐based high‐risk categories, positive predictive value (PPV), negative predictive value (NPV), sensitivity and specificity for BaPWV abnormality were 85.7%, 39.4%, 36.1%, and 87.5%, respectively. For BFMD abnormality, the values were 77.3%, 40.1%, 34.1%, and 81.8%, respectively. According to China‐par high‐risk categories, the values for BaPWV abnormality were 89.7%, 43.8%, 45.6%, and 89.0%, respectively. For BFMD abnormality, the values were 76.6%, 41.3%, 40.7%, and 77%, respectively. In multivariate analysis, age and blood pressure were the independent predictors for subclinical atherosclerosis in subjects with low‐moderate risk.

Conclusions

More than one‐half of subjects with low and moderate risk already have detectable subclinical atherosclerosis, indicating higher cardiovascular risk beyond the traditional stratification.
Single BRAFV600E mutation is not associated with aggressive biological behavior in adolescent and pediatric papillary thyroid carcinoma
Authors: Zhou Bin , Lu Xiaoyu , Hei Hu , Zhang Songtao , Li Yanqing , Fang Jugao , Qin Jianwu , Ge Hong
Published: July 2023

Background

Papillary thyroid carcinoma is more likely to show aggressive biological behaviors in the majority of pediatric patients than in adult patients. The aim of this study was to investigate the mutation rate of the BRAFV600E gene in adolescents and children with papillary thyroid carcinoma and to analyze the association between BRAFV600E gene mutation and tumor‐aggressive pathological factors.

Methods

A total of 42 pediatric patients with papillary thyroid carcinoma who underwent thyroid surgery from 2017 to 2022 were studied retrospectively. Whether the BRAFV600E gene mutation in papillary thyroid carcinoma was related to aggressive biological behavior was analyzed.

Results

Among the 42 pediatric patients with papillary thyroid carcinoma, the median patient age was 15.71 ± 2.51 years (mean ± SD) and the median tumor diameter was 24.95 ± 12.29 mm (mean ± SD). Among all enrolled patients, the mutation rate of the BRAFV600E gene was 54.76% (23 of 42). There were 33 patients with classic papillary thyroid carcinoma, and 22 (66.67%) with classic subtypes were BRAFV600E positive. The BRAFV600E mutation was associated with lower distant metastasis (p = .013) and less Hashimoto’s thyroiditis (p = .006). There was no significant difference in clinicopathological factors such as sex, age, tumor size, capsular invasion, multifocality, hypothyroidism, recurrence, lymph node metastasis, and extrathyroidal extension.

Conclusions

The BRAFV600E mutation is not uncommon in pediatric papillary thyroid carcinoma but is not significantly associated with aggressive biological behavior. It is not possible to determine whether to adopt more active diagnosis and treatment measures on the basis of the mutation of a single BRAFV600E gene.
Species richness and functional diversity enhance winter annual forage productivity and nutritive value
Authors: Rusch Hannah L. , Dubeux Jose C. B. , Queiroz Luana M. Dantas , Wallau Marcelo O. , Wilson Chris H.
Published: July 2023

Winter annual forages can extend grazing into the cool‐season in the US southeast, however uncertainty regarding potential tradeoffs between winter annual mixtures versus monocultures exists. We examined increasingly species‐rich and functionally diverse winter annual forage mixtures at two Florida locations to evaluate impacts of including more plant species with distinct traits (e.g., different maturities and nitrogen [N] scavenging vs. N2‐fixing capabilities) on forage accumulation (FA), nutritive value, and evenness of forage distribution across the cool‐season compared with a rye (Secale cerealeL.) monoculture. Furthermore, we quantified the N2‐fixing potential of winter annual legumes to measure their contribution to soil fertility and ecosystem N cycling. We found that greater species richness enhanced total cool‐season FA at both sites, ranging from 0.92 to 4.38 Mg DM ha−1in Gainesville and 6.48 to 9.11 Mg DM ha−1in Marianna. In Marianna, where legumes accounted for approximately 25% or more of the biomass accumulated by winter annual forage mixtures, legume inclusion enhanced forage shoot N concentration. Furthermore, >50% of the N in legume tissues derived from the atmosphere, supplying 0.18–2 kg N ha−1in Gainesville and 30–52 kg N ha−1in Marianna. Altogether, our data suggest that species richness enhanced winter annual forage production and legume inclusion improved forage nutritive value although these responses were site‐specific. Thus, our multi‐site study provides information that can guide decision‐making regarding appropriate winter annual forage selections to increase cool‐season forage production in the southeastern United States.
Re‐evaluating the Magnesium‐ion Storage Capability of Vanadium Dioxide, VO2(B): Uncovering the Influence of Water Content on the Previously Overestimated High Capacity
Authors: Setiawan Dedy , Chae Munseok S. , Hong Seung‐Tae
Published: July 2023

Magnesium batteries have emerged as a promising alternative to lithium‐ion batteries due to their theoretical high energy density and abundant magnesium resources. Vanadium dioxide, VO2(B), has been reported as a high‐capacity cathode material for magnesium batteries. However, the electrochemical intercalation mechanism requires further elucidation due to a limited understanding of the structure‐property relationship. In this study, we re‐evaluated the magnesium storage capability of the material, with a particular focus on the influence of water content in nonaqueous electrolytes. The higher discharge capacity of 250 mAh g−1 is achieved exclusively in the wet electrolyte with 650 ppm water content. A significantly lower capacity of 51 mAh g−1 was observed in the dry electrolyte solution containing 40 ppm water content. Through X‐ray structural and elemental analyses, as well as magnesium‐ion diffusion pathway analysis using bond‐valence‐energy‐landscape calculations, the restricted capacity was clarified by examining the reaction mechanism. According to this study, the impressive capacity of magnesium‐ion battery cathodes may be exaggerated due to the involvement of non‐magnesium‐ion insertion unless the electrolytes′ water content is appropriately regulated.
Closed‐Loop Recyclable Poly(imine‐acetal)s with Dual‐Cleavable Bonds for Primary Building Block Recovery
Authors: Saito Keita , Türel Tankut , Eisenreich Fabian , Tomović Željko
Published: July 2023

Chemical recycling offers a promising solution for the end‐of‐life treatment of synthetic polymers. However, the efficient recovery of well‐defined recycled building blocks continues to be a major challenge, especially for crosslinked thermosets. Here, we developed vanillin‐based polymer networks functionalized with dual‐cleavable imine and acetal bonds that facilitate chemical recycling to primary building blocks and their convenient separation at the molecular level. A library of crosslinked poly(imine‐acetal)s was synthesized by combining the in‐bulk synthesized liquid di‐vanillin acetal monomer (DVA) with commercially available liquid di‐ and triamines under solvent‐free conditions. These thermosets showed tailor‐made thermal and mechanical properties along with outstanding chemical recyclability. Under aqueous acidic conditions, poly(imine‐acetal)s selectively and completely disintegrate into small molecules. During the polymer design stage, these compounds were carefully selected to enable facile separation without tedious techniques. As a result, the primary building blocks were isolated in high yields and purity and immediately reused to produce fresh polymers with identical thermomechanical properties. Since our “design for recycling” concept aims at obtaining the primary building blocks rather than monomers after depolymerization, a plethora of possibilities are unlocked to utilize these chemical resources, including closed‐loop recycling as portrayed.
CH selection and compressive sensing‐based data aggregation in WSN using hybrid Golden circle‐inspired optimization
Authors: T P Rani , Srinadh Vemireddi , P Mano Paul , J.P Ananth
Published: July 2023

The arbitrary distribution of sensor nodes and irregularity of the routing path led to unordered data, which is complex to handle in a wireless sensor network (WSN). To increase WSN lifetime, data aggregation models are developed to minimize energy consumption or ease the computational burden of nodes. The compressive sensing (CS) provides a new technique for prolonging the WSN lifetime. A hybrid optimized model is devised for cluster head (CH) selection and CS‐based data aggregation in WSN. The method aids to balance the energy amidst different nodes and elevated the lifetime of the network. The hybrid golden circle inspired optimization (HGCIO) is considered for cluster head (CH) selection, which aids in selecting the CH. The CH selection is done based on fitness functions like distance, energy, link quality, and delay. The routing is implemented with HGCIO to transmit the data projections using the CH to sink and evenly disperse the energy amidst various nodes. After that, compressive sensing is implemented with the Bayesian linear model. The convolutional neural network‐long short term memory (CNN‐LSTM) is employed for the data aggregation process. The proposed HGCIO‐based CNN‐LSTM provided the finest efficiency with a delay of 0.156 s, an energy of 0.353 J, a prediction error of 0.044, and a packet delivery ratio (PDR) of 76.309%.
Diagnostic and therapeutic strategies for colorectal tumor with positive muscle‐retracting sign
Authors: Tanaka Hidenori , Takehara Yudai , Morimoto Shin , Tanino Fumiaki , Yamamoto Noriko , Kamigaichi Yuki , Tsuboi Akiyoshi , Yamashita Ken , Kotachi Takahiro , Arihiro Koji , Oka Shiro
Published: July 2023

Objectives

Endoscopic submucosal dissection (ESD) for colorectal tumors with positive muscle‐retracting (MR) sign often results in incomplete resection or discontinuation owing to the difficulty of submucosal dissection. The present study aimed to evaluate the usefulness of endoscopic ultrasonography (EUS) in diagnosing the MR sign and performing ESD using the pocket‐creation method (PCM).

Methods

Thirty‐six cases of colorectal tumors with positive MR sign during ESD between January 2015 and December 2021 were retrospectively reviewed. Cases were divided into two groups: 1) the conventional method (CM) group, comprising 29 cases, and 2) the PCM group with seven cases, in which preoperative EUS and ESD using PCM were performed. Treatment outcomes were compared between the groups. The diagnostic yield of EUS for the MR sign was evaluated among large sessile tumors >20 mm in which preoperative EUS was performed.

Results

Histologic diagnosis was adenoma or Tis carcinoma in 12 cases (33%), T1 carcinoma in 18 cases (50%), T2 carcinoma in four cases (11%), and unevaluable in two cases (6%). The sensitivity and specificity of the EUS‐MR sign for large sessile tumors were 87.5% and 83.3%, respectively. ESD was achieved in all cases in the PCM group, although it was discontinued in eight cases (28%) in the CM group. There were significant differences between the PCM and CM groups in en bloc resection (100% vs. 48%, p = 0.013) and R0 resection rates (71% vs. 31%, p = 0.049).

Conclusion

The MR sign can be predicted by preoperative EUS, and ESD using PCM allows en bloc resection.
Waterfowl show spatiotemporal trends in influenza A H5 and H7 infections but limited taxonomic variation
Authors: Kent Cody M. , Bevins Sarah N. , Mullinax Jennifer M. , Sullivan Jeffery D. , Prosser Diann J.
Published: July 2023

Influenza A viruses in wild birds pose threats to the poultry industry, wild birds, and human health under certain conditions. Of particular importance are wild waterfowl, which are the primary reservoir of low‐pathogenicity influenza viruses that ultimately cause high‐pathogenicity outbreaks in poultry farms. Despite much work on the drivers of influenza A virus prevalence, the underlying viral subtype dynamics are still mostly unexplored. Nevertheless, understanding these dynamics, particularly for the agriculturally significant H5 and H7 subtypes, is important for mitigating the risk of outbreaks in domestic poultry farms. Here, using an expansive surveillance database, we take a large‐scale look at the spatial, temporal, and taxonomic drivers in the prevalence of these two subtypes among influenza A‐positive wild waterfowl. We document spatiotemporal trends that are consistent with past work, particularly an uptick in H5 viruses in late autumn and H7 viruses in spring. Interestingly, despite large species differences in temporal trends in overall influenza A virus prevalence, we document only modest differences in the relative abundance of these two subtypes and little, if any, temporal differences among species. As such, it appears that differences in species' phenology, physiology, and behaviors that influence overall susceptibility to influenza A viruses play a much lesser role in relative susceptibility to different subtypes. Instead, species are likely to freely pass viruses among each other regardless of subtype. Importantly, despite the similarities among species documented here, individual species still may play important roles in moving viruses across large geographic areas or sustaining local outbreaks through their different migratory behaviors.
Solving the stochastic dynamics of population growth
Authors: Marrec Loïc , Bank Claudia , Bertrand Thibault
Published: July 2023

Population growth is a fundamental process in ecology and evolution. The population size dynamics during growth are often described by deterministic equations derived from kinetic models. Here, we simulate several population growth models and compare the size averaged over many stochastic realizations with the deterministic predictions. We show that these deterministic equations are generically bad predictors of the average stochastic population dynamics. Specifically, deterministic predictions overestimate the simulated population sizes, especially those of populations starting with a small number of individuals. Describing population growth as a stochastic birth process, we prove that the discrepancy between deterministic predictions and simulated data is due to unclosed‐moment dynamics. In other words, the deterministic approach does not consider the variability of birth times, which is particularly important with small population sizes. We show that some moment‐closure approximations describe the growth dynamics better than the deterministic prediction. However, they do not reduce the error satisfactorily and only apply to some population growth models. We explicitly solve the stochastic growth dynamics, and our solution applies to any population growth model. We show that our solution exactly quantifies the dynamics of a community composed of different strains and correctly predicts the fixation probability of a strain in a serial dilution experiment. Our work sets the foundations for a more faithful modeling of community and population dynamics. It will allow the development of new tools for a more accurate analysis of experimental and empirical results, including the inference of important growth parameters.