bluuebunny/crossref_metadata_2025_split 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

AbstractOrganic–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

AbstractSemitransparent 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

AbstractA 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

AbstractAryl 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

AbstractAlthough 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

AbstractHydrolytically 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

AbstractDecarboxylative 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

AbstractStable 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

AbstractStability 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

AbstractPillar[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

AbstractDiboriranides 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

AbstractAutistic 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

AbstractSeparator 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

AbstractIntroductionTuina 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.MethodsA 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.ResultsWhen 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.ConclusionTuina 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

Abstract5‐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

AbstractIntroductionAntegrade 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).MethodsA new ADR method, Subintimal Antegrade FEnestration and Re‐entry (SAFER), is described. The results of a first‐in‐man series are presented.ResultsSAFER was performed on seven consecutive patients with angiographic and clinical success in all patients.ConclusionsThis 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.