bluuebunny/crossref_metadata_2025 huggingface dataset:
Vivências trans e disputas identitárias:
Authors: Melo Késia Maria Maximiano de
Published: June 2023

O presente artigo é fruto de reflexões em torno da chave das disputas identitárias, no âmbito das vivências de pessoas que dissidem de genero e sexualidade. Para tal, parto de uma pesquisa que teve como objetivo central a compreensão do modo pelo qual as pessoas trans têm se apropriado de espaços online de interação a fim de fomentar debates políticos, e tecer redes de solidariedade e sociabilidade. Assim, parto da investigação da proliferação desses espaços, tomando como ponto de partida um grupo de uma plataforma online, (mas não permanecendo apenas nela), visto não somente o quantitativo de membros no grupo, mas, principalmente, as temáticas frequentemente discutidas e a participação ativa de um elevado número de participantes nas discussões. Utilizei-me da etnografia multissituada como aporte teórico-metodológico, especialmente no que diz respeito ao entrecruzamento entre as interações on e offline, tendo em vista que o acesso a novas possibilidades tecnológicas e a novos espaços de discussão, associada a transformações sociais e políticas tendem a modificar a forma com que as pessoas trans experienciam os sentidos atribuídos ao ser e se tornar pessoa trans.
Automated treatment planning for proton pencil beam scanning using deep learning dose prediction and dose‐mimicking optimization
Authors: Maes Dominic , Holmstrom Mats , Helander Rasmus , Saini Jatinder , Fang Christine , Bowen Stephen R.
Published: June 2023

Purpose

The purpose of this study is to investigate the use of a deep learning architecture for automated treatment planning for proton pencil beam scanning (PBS).

Methods

A 3‐dimensional (3D) U‐Net model has been implemented in a commercial treatment planning system (TPS) that uses contoured regions of interest (ROI) binary masks as model inputs with a predicted dose distribution as the model output. Predicted dose distributions were converted to deliverable PBS treatment plans using a voxel‐wise robust dose mimicking optimization algorithm. This model was leveraged to generate machine learning (ML) optimized plans for patients receiving proton PBS irradiation of the chest wall. Model training was carried out on a retrospective set of 48 previously‐treated chest wall patient treatment plans. Model evaluation was carried out by generating ML‐optimized plans on a hold‐out set of 12 contoured chest wall patient CT datasets from previously treated patients. Clinical goal criteria and gamma analysis were used to compare dose distributions of the ML‐optimized plans against the clinically approved plans across the test patients.

Results

Statistical analysis of mean clinical goal criteria indicates that compared to the clinical plans, the ML optimization workflow generated robust plans with similar dose to the heart, lungs, and esophagus while achieving superior dosimetric coverage to the PTV chest wall (clinical mean V95 = 97.6% vs. ML mean V95 = 99.1%, p < 0.001) across the 12 test patients.

Conclusions

ML‐based automated treatment plan optimization using the 3D U‐Net model can generate treatment plans of similar clinical quality compared to human‐driven optimization.
Dosimetry impact of distinct gating strategies in cine MR image‐guided breath‐hold pancreatic cancer radiotherapy
Authors: Dong Yuyan , Hu Panpan , Li Xiaoyang , Liu Wei , Yan Bing , Yang Fei , Ford John Chetley , Portelance Lorraine , Yang Yidong
Published: June 2023

Purpose

To investigate the dosimetry effects of different gating strategies in cine magnetic resonance imaging (MRI)‐guided breath‐hold pancreatic cancer radiotherapy.

Methods

Two cine MRI‐based gating strategies were investigated： a tumor contour‐based gating strategy at a gating threshold of 0–5% and a tumor displacement‐based gating strategy at a gating threshold of 3–5 mm. The cine MRI videos were obtained from 17 pancreatic cancer patients who received MRI‐guided radiation therapy. We calculated the tumor displacement in each cine MR frame that satisfied the gating threshold and obtained the proportion of frames with different displacements. We generated IMRT and VMAT plans using a 33 Gy prescription, and motion plans were generated by adding up all isocenter‐shift plans corresponding to different tumor displacements. The dose parameters of GTV, PTV, and organs at risk (OAR) were compared between the original and motion plans.

Results

In both gating strategies, the difference was significant in PTV coverage but not in GTV coverage between the original and motion plans. OAR dose parameters deteriorate with increasing gating threshold. The beam duty cycle increased from 19.5±14.3% (median 18.0%) to 60.8±15.6% (61.1%) for gating thresholds from 0% to 5% in tumor contour‐based gating and from 51.7±11.5% (49.7%) to 67.3±12.4% (67.1%) for gating thresholds from 3 to 5 mm in tumor displacement‐based gating.

Conclusion

In tumor contour‐based gating strategy, the dose delivery accuracy deteriorates while the dose delivery efficiency improves with increasing gating thresholds. To ensure treatment efficiency, the gating threshold might be no less than 3%. A threshold up to 5% may be acceptable in terms of the GTV coverage. The displacement‐based gating strategy may serve as a potential alternative to the tumor contour based gating strategy, in which the gating threshold of approximately 4 mm might be a good choice for reasonably balancing the dose delivery accuracy and efficiency.
Retinal hypoplasia and degeneration result in vision loss in Friedreich ataxia
Authors: Rodden Layne N. , McIntyre Kellie , Keita Medina , Wells Mckenzie , Park Courtney , Profeta Victoria , Waldman Amy , Rummey Christian , Balcer Laura J. , Lynch David R.
Published: June 2023

Objective

Friedreich ataxia (FRDA) is an inherited condition caused by a GAA triplet repeat (GAA‐TR) expansion in the FXN gene. Clinical features of FRDA include ataxia, cardiomyopathy, and in some, vision loss. In this study, we characterize features of vision loss in a large cohort of adults and children with FRDA.

Methods

Using optical coherence tomography (OCT), we measured peripapillary retinal nerve fiber layer (RNFL) thickness in 198 people with FRDA, and 77 controls. Sloan letter charts were used to determine visual acuity. RNFL thickness and visual acuity were compared to measures of disease severity obtained from the Friedreich Ataxia Clinical Outcomes Measures Study (FACOMS).

Results

The majority of patients, including children, had pathologically thin RNFLs (mean = 73 ± 13 μm in FRDA; 98 ± 9 μm in controls) and low‐contrast vision deficits early in the disease course. Variability in RNFL thickness in FRDA (range: 36 to 107 μm) was best predicted by disease burden (GAA‐TR length X disease duration). Significant deficits in high‐contrast visual acuity were apparent in patients with an RNFL thickness of ≤68 μm. RNFL thickness decreased at a rate of −1.2 ± 1.4 μm/year and reached 68 μm at a disease burden of approximately 12,000 GAA years, equivalent to disease duration of 17 years for participants with 700 GAAs.

Interpretation

These data suggest that both hypoplasia and subsequent degeneration of the RNFL may be responsible for the optic nerve dysfunction in FRDA and support the development of a vision‐directed treatment for selected patients early in the disease to prevent RNFL loss from reaching the critical threshold.
Study suggests benefits of checklist to screen for SUD in primary care
Authors: Enos Gary
Published: June 2023

A substance use symptom checklist that is now routinely used at Kaiser Permanente primary care clinics in Washington state is effective in determining the severity of a disorder and does not appear to discriminate based on patient demographic characteristics, a newly published study has found. The results suggest the feasibility of tools that can be used in primary care settings to guide accurate diagnostic and treatment decisions for patients with substance use disorders (SUDs).
NIDA and NIH invite research into drug‐checking tools
Authors: Knopf Alison
Published: June 2023

More drug‐detecting tools and other ways to prevent overdose deaths are urgently needed, according to a Commentary in the June 12 issue of The New England Journal of Medicine. Nora Volkow, M.D., director of the National Institute on Drug Abuse (NIDA), and Lawrence A. Tabak, D.D.S., Ph.D., acting director of the National Institutes of Health, call for addressing the current gaps in the research, development, and implementation of fentanyl test strips and other rapid drug‐detecting tools that could help prevent overdose deaths. Barriers to these tools exist at the state and local levels.
Deep Learning in Mechanical Metamaterials: From Prediction and Generation to Inverse Design
Authors: Zheng Xiaoyang , Zhang Xubo , Chen Ta‐Te , Watanabe Ikumu
Published: June 2023

Mechanical metamaterials are meticulously designed structures with exceptional mechanical properties determined by their microstructures and constituent materials. Tailoring their material and geometric distribution unlocks the potential to achieve unprecedented bulk properties and functions. However, current mechanical metamaterial design considerably relies on experienced designers' inspiration through trial and error, while investigating their mechanical properties and responses entails time‐consuming mechanical testing or computationally expensive simulations. Nevertheless, recent advancements in deep learning have revolutionized the design process of mechanical metamaterials, enabling property prediction and geometry generation without prior knowledge. Furthermore, deep generative models can transform conventional forward design into inverse design. Many recent studies on the implementation of deep learning in mechanical metamaterials are highly specialized, and their pros and cons may not be immediately evident. This critical review provides a comprehensive overview of the capabilities of deep learning in property prediction, geometry generation, and inverse design of mechanical metamaterials. Additionally, this review highlights the potential of leveraging deep learning to create universally applicable datasets, intelligently designed metamaterials, and material intelligence. This article is expected to be valuable not only to researchers working on mechanical metamaterials but also those in the field of materials informatics.
Exotic Electronic Properties of 2D Nanosheets Isolated from Liquid Phase Exfoliated Phyllosilicate Minerals
Authors: Wei Cencen , Roy Abhijit , Tripathi Manoj , Aljarid Adel K.A. , Salvage Jonathan P. , Roe S. Mark , Arenal Raul , Boland Conor S.
Published: June 2023

Spectrally inactive, electrically insulating, and chemically inert are adjectives broadly used to describe phyllosilicate minerals like mica and chlorite. Here, the above is disproved by demonstrating aqueous suspensions of liquid exfoliated nanosheets from five bulk mica types and chlorite schist. Nanosheet quality is confirmed via transmission electron and X‐ray photoelectron spectroscopies, as well as electron diffraction. Through Raman spectroscopy, a previously unreported size‐ and layer‐dependent spectral fingerprint is observed. When analyzing the high‐yield suspensions (≈1 mg mL−1) through UV–vis spectroscopy, all phyllosilicates present bandgap (Eg) narrowing from ≈7 eV in the bulk to ≈4 eV for monolayers. Unusually, the bandgap is inversely proportional to the areal size (A) of the nanosheets, measured via atomic force microscopy. Due to an unrecorded quantum confinement effect, nanosheet electronic properties scale toward semiconducting behavior (bandgap ≈3 eV) as nanosheet area increases. Furthermore, modeling X‐ray diffraction spectra shows that the root cause of the initial bandgap narrowing is lattice relaxation. Finally, with their broad range of isomorphically substituted ions, phyllosilicate nanosheets show remarkable catalytic properties for hydrogen production.
Improving Photovoltaic Performance and Stability of Perovskite Solar Cells via Molecular Bridge Strategy
Authors: Yang Yinrun , Wei Tingting , Shai Xuxia , Song Qinghe , Zeng Chunhua , He Dongmei , Zhang Hong , Chen Jiangzhao
Published: June 2023

Although perovskite solar cells (PSCs) are regarded as one of the most promising photovoltaic technologies, the interfacial defects and energy barrier are the main bottlenecks for further improving their photovoltaic performance and stability. Herein, an effective, facile “molecular bridge” strategy to improve the photovoltaic performance and stability of PSCs simultaneously is reported. This strategy is realized by introducing a self‐assembly molecule, namely, 5‐fluoro‐pyridine carboxylic acid (5‐FPA), to modify the SnO2/perovskite buried interface. The functional groups (F and CO) of 5‐FPA form strong chemical interactions with perovskite and SnO2 layers, which improve interfacial carrier extraction and perovskite film quality with better crystallization and less strain. As a result, photovoltaic performance is substantially improved with power conversion efficiencies exceeding 23%, accompanied by enhanced stability under thermal and ambient conditions. This study opens a new avenue to improve the performance and stability of perovskite photovoltaics through the “molecular bridge” strategy.
Encryption‐Decryption Strategy of High Security Constructed via Encoded Fluorescence Sensing and Linear Discriminant Analysis Technique
Authors: Ji Haiwei , Chen Huanhuan , Mao Tianzhi , Zhao Lingfeng , Zhang Ke , Yang Majun , Zhou Xiaobo , Wang Qi , Wu Li , Qin Yuling
Published: June 2023

Innovative fluorescence materials combining the special reagent stimuli response have considerable potential to provide a convenient and highly secure communication strategy for encoding messages. With the unique decryption method, encrypted information that is previously unidentifiable can now be accurately parsed without the risk of interception or decipherment. Herein, white‐emitting light semiconducting polymer dots for advanced secret communication are developed, along with a machine learning‐based encryption‐decryption strategy. The encrypted data are readily hidden by the fluorescent polymer‐stimulus system, which can be identified by fluorescence imaging equipment and only be decrypted via the special linear discriminant analysis route pre‐transferred to the recipient. The results presented here suggest that chemical‐stimulated fluorescence information storage and the unique decoding strategy can be developed as prospective methods for advanced data communication and security protection.
Pathways to Next‐Generation Fire‐Safe Alkali‐Ion Batteries
Authors: Zhang Yubai , Feng Jiabing , Qin Jiadong , Zhong Yu Lin , Zhang Shanqing , Wang Hao , Bell John , Guo Zaiping , Song Pingan
Published: June 2023

High energy and power density alkali‐ion (i.e., Li+, Na+, and K+) batteries (AIBs), especially lithium‐ion batteries (LIBs), are being ubiquitously used for both large‐ and small‐scale energy storage, and powering electric vehicles and electronics. However, the increasing LIB‐triggered fires due to thermal runaways have continued to cause significant injuries and casualties as well as enormous economic losses. For this reason, to date, great efforts have been made to create reliable fire‐safe AIBs through advanced materials design, thermal management, and fire safety characterization. In this review, the recent progress is highlighted in the battery design for better thermal stability and electrochemical performance, and state‐of‐the‐art fire safety evaluation methods. The key challenges are also presented associated with the existing materials design, thermal management, and fire safety evaluation of AIBs. Future research opportunities are also proposed for the creation of next‐generation fire‐safe batteries to ensure their reliability in practical applications.
Total Synthesis and Structural Plasticity of Kratom Pseudoindoxyl Metabolites**
Authors: Angyal Péter , Hegedüs Kristóf , Mészáros Bence Balázs , Daru János , Dudás Ádám , Galambos Anna Rita , Essmat Nariman , Al‐Khrasani Mahmoud , Varga Szilárd , Soós Tibor
Published: June 2023

Mitragynine pseudoindoxyl, a kratom metabolite, has attracted increasing attention due to its favorable side effect profile as compared to conventional opioids. Herein, we describe the first enantioselective and scalable total synthesis of this natural product and its epimeric congener, speciogynine pseudoindoxyl. The characteristic spiro‐5‐5‐6‐tricyclic system of these alkaloids was formed through a protecting‐group‐free cascade relay process in which oxidized tryptamine and secologanin analogues were used. Furthermore, we discovered that mitragynine pseudoindoxyl acts not as a single molecular entity but as a dynamic ensemble of stereoisomers in protic environments; thus, it exhibits structural plasticity in biological systems. Accordingly, these synthetic, structural, and biological studies provide a basis for the planned design of mitragynine pseudoindoxyl analogues, which can guide the development of next‐generation analgesics.
Non‐activated Esters as Reactive Handles in Direct Post‐Polymerization Modification
Authors: Van Guyse Joachim F. R. , Bernhard Yann , Podevyn Annelore , Hoogenboom Richard
Published: June 2023

Non‐activated esters are prominently featured functional groups in polymer science, as ester functional monomers display great structural diversity and excellent compatibility with a wide range of polymerization mechanisms. Yet, their direct use as a reactive handle in post‐polymerization modification has been typically avoided due to their low reactivity, which impairs the quantitative conversion typically desired in post‐polymerization modification reactions. While activated ester approaches are a well‐established alternative, the modification of non‐activated esters remains a synthetic and economically valuable opportunity. In this review, we discuss past and recent efforts in the utilization of non‐activated ester groups as a reactive handle to facilitate transesterification and aminolysis/amidation reactions, and the potential of the developed methodologies in the context of macromolecular engineering.
New Anderson‐Based Polyoxometalate Covalent Organic Frameworks as Electrodes for Energy Storage Boosted Through Keto‐Enol Tautomerization
Authors: Pakulski Dawid , Gorczyński Adam , Brykczyńska Daria , Montes‐García Verónica , Czepa Włodzimierz , Janica Iwona , Bielejewski Michał , Kubicki Maciej , Patroniak Violetta , Samorì Paolo , Ciesielski Artur
Published: June 2023

The unique electrochemical properties of polyoxometalates (POMs) render them ideal components for the fabrication of next‐generation high‐performance energy storage systems. However, their practical applications have been hindered by their high solubility in common electrolytes. This problem can be overcome by the effective hybridization of POMs with other materials. Here we present the design and synthesis of two novel polyoxometalate‐covalent organic frameworks (POCOF) via one‐pot solvothermal strategy between an amino‐functionalized Anderson‐type POM and a trialdehyde‐based building unit. We show that structural and functional complexity can be enriched by adding hydroxyl groups in the 2,4,6 position to the benzene‐1,3,5‐tricarbaldehyde allowing to exploit for the first time in POCOFs the keto‐enol tautomerization as additional feature to impart greater chemical stability to the COFs and enhanced properties leading to large specific surface area (347 m2/g) and superior electrochemical performance of the POCOF‐1 electrodes, when compared with POCOF‐2 electrodes that possess only imine‐type linkage and with pristine POM electrodes. Specifically, POCOF‐1 electrodes display remarkable specific, areal, and volumetric capacitance (125 F/g, 248 mF/cm2 and 41.9 mF/cm3, respectively) at a current density of 0.5 A/g, a maximum energy density (56.2 Wh/kg), a maximum power density (3.7 kW/kg) and an outstanding cyclability (90 % capacitance retention after 5000 cycles).
Desolvation‐Induced Highly Symmetrical Terbium(III) Single‐Molecule Magnet Exhibiting Luminescent Self‐Monitoring of Temperature
Authors: Wang Junhao , Zakrzewski Jakub J. , Zychowicz Mikolaj , Xin Yue , Tokoro Hiroko , Chorazy Szymon , Ohkoshi Shin‐ichi
Published: June 2023

A conjunction of Single‐Molecule Magnet (SMM) behavior and luminescence thermometry is an emerging research line aiming at contactless read‐out of temperature in future SMM‐based devices. The shared working range between slow magnetic relaxation and the thermometric response is typically narrow or absent. We report TbIII‐based emissive SMMs formed in a cyanido‐bridged framework whose properties are governed by the reversible structural transformation from [TbIII(H2O)2][CoIII(CN)6] ⋅ 2.7H2O (1) to its dehydrated phase, TbIII[CoIII(CN)6] (2). The 8‐coordinated complexes in 1 show the moderate SMM effect but it is enhanced for trigonal‐prismatic TbIII complexes in 2, showing the SMM features up to 42 K. They are governed by the combination of QTM, Raman, and Orbach relaxation with the energy barrier of 594(18) cm−1 (854(26) K), one of the highest among the TbIII‐based molecular nanomagnets. Both systems exhibit emission related to the f–f electronic transitions, with the temperature variations resulting in the optical thermometry below 100 K. The dehydration leads to a wide temperature overlap between the SMM behavior and thermometry, from 6 K to 42 K. These functionalities are further enriched after the magnetic dilution. The role of post‐synthetic formation of high‐symmetry TbIII complexes in achieving the SMM effect and hot‐bands‐based optical thermometry is discussed.
Biomimetic Design of a Robustly Stabilized Folded State Enabling Seed‐Initiated Supramolecular Polymerization under Microfluidic Mixing**
Authors: Ogi Soichiro , Takamatsu Aiko , Matsumoto Kentaro , Hasegawa Shintaro , Yamaguchi Shigehiro
Published: June 2023

We have investigated the folding and assembly behavior of a cystine‐based dimeric diamide bearing pyrene units and solubilizing alkyl chains. In low‐polarity solvents, it forms a 14‐membered ring through double intramolecular hydrogen bonds between two diamide units. The spectroscopic studies revealed that the folded state is thermodynamically unstable and eventually transforms into more energetically stable helical supramolecular polymers that show an enhanced chiral excitonic coupling between the transition dipoles of the pyrene units. Importantly, compared to an alanine‐based monomeric diamide, the dimeric diamide exhibits a superior kinetic stability in the metastable folded state, as well as an increased thermodynamic stability in the aggregated state. Accordingly, the initiation of supramolecular polymerization can be regulated using a seeding method even under microfluidic mixing conditions. Furthermore, taking advantage of a self‐sorting behavior observed in a mixture of l‐cysteine‐ and d‐cysteine‐based dimeric diamides, a two‐step supramolecular polymerization was achieved by stepwise addition of the corresponding seeds.
Crystalline Nanoparticles of Water‐Soluble Covalent Basket Cages (CBCs) for Encapsulation of Anticancer Drugs
Authors: Liyana Gunawardana Vageesha W. , Ward Carson , Wang Han , Holbrook Joseph H. , Sekera Emily R. , Cui Honggang , Hummon Amanda B. , Badjić Jovica D.
Published: June 2023

We herein describe the preparation, assembly, recognition characteristics, and biocompatibility of novel covalent basket cage CBC‐11, composed of four molecular baskets linked to four trivalent aromatic amines through amide groups. The cage is tetrahedral in shape and similar in size to small proteins (Mw=8637 g/mol) with a spacious nonpolar interior for accommodating multiple guests. While 24 carboxylates at the outer surface of CBC‐11 render it soluble in aqueous phosphate buffer (PBS) at pH=7.0, the amphiphilic nature prompts its assembly into nanoparticles (d=250 nm, DLS). Cryo‐TEM examination of nanoparticles revealed their crystalline nature with wafer‐like shapes and hexagonally arranged cages. Nanoparticulate CBC‐11 traps anticancer drugs irinotecan and doxorubicin, with each cage binding up to four drug molecules in a non‐cooperative manner. The inclusion complexation resulted in nanoparticles growing in size and precipitating. In media containing mammalian cells (HCT 116, human colon carcinoma), the IC50 value of CBC‐11 was above 100 μM. While this work presents the first example of a large covalent organic cage operating in water at the physiological pH and forming crystalline nanoparticles, it also demonstrates its biocompatibility and potential to act as a polyvalent binder of drugs for their sequestration or delivery.
Alleviating Side Reactions on Zn Anodes for Aqueous Batteries by a Cell Membrane Derived Phosphorylcholine Zwitterionic Protective Layer
Authors: Meng Zhen , Jiao Yucong , Wu Peiyi
Published: June 2023

Aqueous zinc (Zn) ion batteries are attractive for next generation batteries with high safety, yet their applications are still hindered by the uncontrollable dendrite formation and side reactions on Zn anode. Here, a polyzwitterion protective layer (PZIL) was engineered by polymerizing 2‐methacryloyloxyethyl phosphorylcholine (MPC) in carboxymethyl chitosan (CMCS), which renders the following merits: the choline groups of MPC can preferentially adsorb onto Zn metal to avoid side reactions; the charged phosphate groups chelate with Zn2+ to regulate the solvation structure, further improving side reaction inhibition; the Hofmeister effect between ZnSO4 and CMCS can enhance the interfacial contact during electrochemical characterization. Consequently, the symmetrical Zn battery with PZIL can keep stable for more than 1000 hours under the ultra‐high current density of 40 mA cm−2. The PZIL confers the Zn/MnO2 full battery and Zn/active carbon (AC) capacitor with stable cycling performance under high current density.
Harmonious Heterointerfaces Formed on 2D‐Pt Nanodendrites by Facet‐Respective Stepwise Metal Deposition for Enhanced Hydrogen Evolution Reaction
Authors: Gu Byeong Su , Dutta Soumen , Hong Yu‐Rim , Ngome Okello Odongo Francis , Im Hyeonae , Ahn Seungil , Choi Si‐Young , Woo Han Jeong , Ryu Sunmin , Lee In Su
Published: June 2023

The performance of nanocrystal (NC) catalysts could be maximized by introducing rationally designed heterointerfaces formed by the facet‐ and spatio‐specific modification with other materials of desired size and thickness. However, such heterointerfaces are limited in scope and synthetically challenging. Herein, we applied a wet chemistry method to tunably deposit Pd and Ni on the available surfaces of porous 2D−Pt nanodendrites (NDs). Using 2D silica nanoreactors to house the 2D‐PtND, an 0.5‐nm‐thick epitaxial Pd or Ni layer (e‐Pd or e‐Ni) was exclusively formed on the flat {110} surface of 2D−Pt, while a non‐epitaxial Pd or Ni layer (n‐Pd or n‐Ni) was typically deposited at the {111/100} edge in absence of nanoreactor. Notably, these differently located Pd/Pt and Ni/Pt heterointerfaces experienced distinct electronic effect to influence unequally in electrocatalytic synergy for hydrogen evolution reaction (HER). For instance, an enhanced H2 generation on the Pt{110} facet with 2D‐2D interfaced e‐Pd deposition and faster water dissociation on the edge‐located n‐Ni overpowered their facet‐located counterparts in respective HER catalysis. Therefore, a feasible assembling of the valuable heterointerfaces in the optimal 2D n‐Ni/e‐Pd/Pt catalyst overcame the sluggish alkaline HER kinetics, with a catalytic activity 7.9 times higher than that of commercial Pt/C.
Influence of Molecular Separation on Through‐Space Intervalence Transient Charge Transfer in Metal–Organic Frameworks with Cofacially arranged Redox Pairs
Authors: Nath Akashdeep , Kumar Vikas , Shukla Ayushi , Ghosh Hirendra Nath , Mandal Sukhendu
Published: June 2023

We demonstrate direct evidence of photoinduced through‐space intervalence charge transfer (IVCT) between two cofacially arranged redox‐active pairs in metal–organic frameworks and their dynamic variation with their molecular separation. Two homologous MOFs [Co2(NDC)2(DPTTZ)2]. DPTTZ. DMF, 1 and [Co2(BDC)2(DPTTZ)2]. DMF, 2 (where NDC=naphthalene dicarboxylate, BDC=benzene dicarboxylate, DPTTZ=N, N′‐di(4‐pyridyl)thiazolo‐[5,4‐d]thiazole, DMF=N, N′‐dimethyl formamide) are considered for this, whose intra‐dimer distance of redox‐active DPTTZ ligands differs ca. 1 Å from one system to another. Spectroelectrochemical study detects the formation of IVCT band at the NIR region between cofacially oriented DPTTZ molecules in both MOFs. Transient spectroscopy shows faster charge separation as well as charge recombination when intra‐dimer distance is lesser (in MOF 2) due to stronger electronic coupling. We quantify the extent of IVCT by charge transfer integral calculation; and also by optical pump terahertz probe spectroscopy, where MOF 2 shows three times higher carrier mobility due to lesser inter‐DPTTZ distance than MOF 1. These findings reveal a more localized aspect of through‐space IVCT between cofacially organized redox‐active pair in a three‐dimensional framework.
Production of sugars from mixed hardwoods for use in the synthesis of sugar fatty acid esters catalyzed by immobilized‐stabilized derivatives of Candida antarctica lipase B
Authors: Gonçalves Maria Carolina Pereira , Cansian Ana Bárbara Moulin , Tardioli Paulo Waldir , Saville Bradley A.
Published: June 2023

The synthesis of sugar fatty acid esters (SFAEs) from lignocellulosic biomass and oleic acid (C18:1) was catalyzed by immobilized‐stabilized derivatives of Candida antarctica lipase B in a methyl ethyl ketone medium. After steam‐explosion pretreatment of mixed hardwoods and enzymatic hydrolysis at 15%wt solids, xylose and glucose were purified/concentrated to a mass ratio of ~3 to 1. These lignocellulosic sugars were superior to commercial sugars as the carbohydrate source for the esterification reaction in terms of sugar conversions. The highest conversions were obtained using 1.5% w/v of Novozyme 435 (N435, uncoated) as the biocatalyst for the synthesis of SFAEs. Coating the N435 with polyethyleneimine (PEI) prevented enzyme leakage into the reaction medium and produced 35% and 50% higher xylose and glucose conversions to SFAEs, respectively, at the same enzyme loading. After six 24 h reuse cycles with the PEI‐coated N435, xylose conversion decreased by 44%, while a 65% reduction in xylose conversion was observed with the uncoated lipase. Mass spectrometry analysis confirmed the production of xylose and glucose mono‐ and di‐esters. Our purified product presented an emulsion capacity (EC) close to that of a commercial sugar ester and the ECs of the xylose oleate, laurate, and palmitate synthesized in previous studies. © 2023 The Authors. Biofuels, Bioproducts and Biorefining published by Society of Industrial Chemistry and John Wiley & Sons Ltd.
Three‐dimensional spheroid formation of adipose‐derived stem cells improves the survival of fat transplantation by enhance their therapeutic effect
Authors: He Yucang , Zhang Zikai , Li Zihao , Lin Ming , Ding Siqi , Wu Hanwen , Yang Fangfang , Cai Zhongming , Li Tian , Wang Jingping , Ke Chen , Pan Shengsheng , Li Liqun
Published: June 2023

Adipose‐derived stem cells (ADSCs) have important applications in basic research, especially in fat transplantation. Some studies have found that three‐dimensional (3D) spheroids formed by mesenchymal stem cells have enhanced therapeutic potential. However, the fundamental basics of this effect are still being discussed. ADSCs were harvested from subcutaneous adipose tissues and 3D spheroids were formed by the automatic aggregation of ADSCs in a non‐adhesive 6‐well plate. Oxygen glucose deprivation (OGD) was used to simulate the transplantation microenvironment. We found that 3D culture of ADSCs triggered cell autophagy. After inhibiting autophagy by Chloroquine, the rates of apoptosis were increased. When the 3D ADSC‐spheroids were re‐planked, the number of senescent ADSCs decreased, and the proliferation ability was promoted. In addition, there were more cytokines secreted by 3D ADSC‐spheroids including VEGF, IGF‐1, and TGF‐β. After adding the conditioned medium with human umbilical vein endothelial cells (HUVECs), 3D ADSC‐spheroids were more likely to promote migration, and tube formation, stimulating the formation of new blood vessels. Fat grafting experiments in nude mice also showed that 3D ADSC‐spheroids enhanced survival and neovascularization of fat grafts. These results suggested that 3D spheroids culturing of ADSCs can increase the therapeutic potential in fat transplantation.
A protocol for tactile function assessment using JVP domes: Feasibility study and preliminary results
Authors: Wang Yung‐Jung , Sung Chung‐Tung , Huang Jian‐Jia , Pei Yu‐Cheng , Chang Bao‐Luen
Published: June 2023

Background

Touch is a crucial sense for perceiving the spatial characteristics of objects. The JVP dome was developed to evaluate tactile spatial acuity using a grating orientation task. There were few studies depicting sequences and details for the entire task, including practice, training, and testing sessions. Therefore, we proposed and elaborated a protocol for the grating orientation task using the staircase method, which required fewer testing trials compared with the method of constant stimuli.

Methods

Twenty‐three healthy participants were enrolled in this experiment. The JVP domes with 11 different groove widths were used. Tactile discrimination thresholds were estimated using a two‐down‐one‐up staircase method. The experiment comprised practice, training, and testing sessions, conducted by trained examiners who performed grating stimulation on participants’ index fingerpads.

Results

All participants passed the required accuracy in the practice and training sessions. Eight transition points were obtained in the testing session for each participant. The tactile discrimination thresholds were determined from the last six transition points. We obtained the mean tactile discrimination threshold as 1.8 ± 0.75 mm (n = 23). The results demonstrated that the proposed protocol was successfully applied to assess tactile discrimination thresholds.

Conclusions

The present study investigated the protocol of grating orientation tasks requiring a small number of testing trials with the assurance of the task quality. The feasibility study and preliminary results indicated the potentiality of this protocol for future clinical application.
Attitudes moralization and outgroup dehumanization in the dynamic between pro‐ vs. anti‐vaccines against COVID‐19
Authors: Ballone Chiara , Pacilli Maria Giuseppina , Teresi Manuel , Palumbo Riccardo , Pagliaro Stefano
Published: June 2023

Attitudes towards socially sensitive topics tend to be polarized and moralized. Literature showed that in the political arena people tend to consider their group different from the outgroup in moral terms, and how this perceived distance is capable of producing discrimination against the outgroup. In light of this evidence, the aim of this study (N = 234) was to examine the dynamics between Pro‐vaxers and No‐vaxers in relation to the SARS‐COV‐2 vaccine. Participants evaluated the strength of their attitude towards the COVID‐19 vaccine, and the extent to which this attitude was moralized. They reported the perceived moral distance between the ingroup and the outgroup and completed a scale of outgroup animalistic dehumanization. Results showed a positive association between the strength of the attitude towards the vaccine and its moralization. The tendency to moralize the attitude was positively associated with the perception of moral distance between ingroup and outgroup, and this positively associated with the outgroup dehumanization. A sequential mediation model showed an indirect effect that links attitude strength to dehumanization through attitude moralization and the perception of moral distance between groups. Results are discussed in the light of recent theories on the moralization of attitudes and its importance in institutional communication. Please refer to the Supplementary Material section to find this article's Community and Social Impact Statement.
Photoinduced Ring‐Opening and Phototoxicity of an Indolin‐3‐one Derivative
Authors: Doloczki Susanne , Kern Christoph , Holmberg Karl O. , Swartling Fredrik J. , Streuff Jan , Dyrager Christine
Published: June 2023

The study of a fluorescent indolin‐3‐one derivative is reported that, as opposed to its previously described congeners, selectively undergoes photoactivated ring‐opening in apolar solvents. The excited state involved in this photoisomerization was partially deactivated by the formation of singlet oxygen. Cell studies revealed lipid droplet accumulation and efficient light‐induced cytotoxicity.
Polymer Nanoantidotes
Authors: Yang Jiazhen , Li Hongjie , Zou Haoyang , Ding Jianxun
Published: June 2023

Intoxication is one of the most common causes of accidental death globally. Although some antidotes capable of neutralizing the toxicity of certain xenobiotics have become well established, the current reality is that clinicians primarily rely on nonspecific extracorporeal techniques to remove toxins. Nano‐intervention strategies in which nanoantidotes neutralize toxicity in situ via physical interaction, chemical bonding, or biomimetic clearance have begun to show clinical potential. However, most nanoantidotes remain in the proof‐of‐concept stage, and the difficulty of constructing clinical relevance models and the unclear pharmacokinetics of nanoantidotes hinder their translation to clinic. This Concept reviews the detoxification mechanisms of polymer nanoantidotes and predicts the opportunities and challenges associated with their clinical application.
Recent Developments on Photochemical Synthesis of 1,n‐Dicarbonyls
Authors: Mondal Subhashis , Chatterjee Nirbhik , Maity Soumitra
Published: June 2023

1,n‐dicarbonyls are one of the most fascinating chemical feedstocks finding abundant usage in the field of pharmaceuticals. Besides, they are utilized in a plethora of synthesis in general synthetic organic chemistry. A number of ‘conventional’ methods are available for their synthesis, such as the Stetter reaction, Baker‐Venkatraman rearrangement, oxidation of vicinal diols, and oxidation of deoxybenzoins, synonymous with unfriendly reagents and conditions. In the last 15 years or so, photocatalysis has taken the world of synthetic organic chemistry by a remarkable renaissance. It is fair to say now that everybody loves the light and photoredox chemistry has opened a new gateway to organic chemists towards milder, more simpler alternatives to the previously available methods, allowing access to many sensitive reactions and products. In this review, we present the readers with the photochemical synthesis of a variety of 1,n‐dicarbonyls. Diverse photocatalytic pathways to these fascinating molecules have been discussed, placing special emphasis on the mechanisms, giving the reader an opportunity to find all these significant developments in one place.
Surface Chemistry and Specific Surface Area Rule the Efficiency of Gold Nanoparticle Sensitizers in Proton Therapy
Authors: Johny Jacob , van Halteren Charlotte E. R. , Cakir Fatih‐Can , Zwiehoff Sandra , Behrends Carina , Bäumer Christian , Timmermann Beate , Rauschenbach Laurèl , Tippelt Stephan , Scheffler Björn , Schramm Alexander , Rehbock Christoph , Barcikowski Stephan
Published: June 2023

Gold nanoparticles (AuNPs) are currently the most studied radiosensitizers in proton therapy (PT) applicable for the treatment of solid tumors, where they amplify production of reactive oxygen species (ROS). However, it is underexplored how this amplification is correlated with the AuNPs’ surface chemistry. To clarify this issue, we fabricated ligand‐free AuNPs of different mean diameters by laser ablation in liquids (LAL) and laser fragmentation in liquids (LFL) and irradiated them with clinically relevant proton fields by using water phantoms. ROS generation was monitored by the fluorescent dye 7‐OH‐coumarin. Our findings reveal an enhancement of ROS production driven by I) increased total particle surface area, II) utilization of ligand‐free AuNPs avoiding sodium citrate as a radical quencher ligands, and III) a higher density of structural defects generated by LFL synthesis, indicated by surface charge density. Based on these findings it may be concluded that the surface chemistry is a major and underexplored contributor to ROS generation and sensitizing effects of AuNPs in PT. We further highlight the applicability of AuNPs in vitro in human medulloblastoma cells.
Selective Photodynamic Activity of Tetrakis(4‐aminophenyl)porphyrins with and without Acetyl Protecting Groups on Cancer and Normal Cells
Authors: Okuno Masafumi , Yamana Keita , Kawamura Shogo , Nishimura Kotaro , Hino Shodai , Kawasaki Riku , Ikeda Atsushi
Published: June 2023

Tetrakis(4‐aminophenyl)porphyrin (1) and tetrakis(4‐acetamidophenyl)porphyrin (2) were dissolved in water with the incorporation of a polysaccharide (λ‐carrageenan (CGN)) as a water‐solubilizing agent. Although the photodynamic activity of the CGN‐2 complex was considerably lower than that of the CGN‐1 complex, the selectivity index (SI; IC50 in a normal cell/IC50 in a cancer cell) of the CGN‐2 complex was considerably higher than that of the CGN‐1 complex. This is because the photodynamic activity of the CGN‐2 complex was significantly affected by the intracellular uptakes by the normal and cancer cells. During in vivo experiments, the CGN‐2 complex inhibited tumor growth under light irradiation with high blood retention compared with the CGN‐1 complex and Photofrin, which exhibited lower blood retention. This study showed that the photodynamic activity and SI are influenced by substituent groups of arene in the meso‐positions of porphyrin analogs.
In Situ Formation of CoP/Co3O4 Heterojunction for Efficient Overall Water Splitting
Authors: Tian Guoliang , Liu Xiaolei , Song Shuhong , Zhang Qianqian , Wang Zeyan , Liu Yuanyuan , Zheng Zhaoke , Cheng Hefeng , Dai Ying , Huang Baibiao , Wang Peng
Published: June 2023

Electrochemical water splitting is an environmentally friendly and effective energy storage method. However, it is still a huge challenge to prepare non‐noble metal based electrocatalysts that possess high activity and long‐term durability to realize efficient water splitting. Here, we present a novel method of low‐temperature phosphating for preparing CoP/Co3O4 heterojunction nanowires catalyst on titanium mesh (TM) substrate that can be used for oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and overall water splitting. CoP/Co3O4@TM heterojunction showed an excellent catalytic performance and long‐term durability in 1.0 M KOH electrolyte. The overpotential of CoP/Co3O4@TM heterojunction was only 257 mV at 20 mA cm−2 during the OER process, and it could work stably more than 40 h at 1.52 V versus reversible hydrogen electrode (vs. RHE). During the HER process, the overpotential of CoP/Co3O4@TM heterojunction was only 98 mV at −10 mA cm−2. More importantly, when used as anodic and cathodic electrocatalyst, they achieved 10 mA cm−2 at 1.59 V. The Faradaic efficiencies of OER and HER were 98.4 % and 99.4 %, respectively, outperforming Ru/Ir‐based noble metal electrocatalysts and other non‐noble metal electrocatalysts for overall water splitting.
Factors Controlling Complex Morphologies of Isomorphous Metal‐Organic Frameworks**
Authors: Singh Vivek , Feldman Yishay , Leitus Gregory , Brumfeld Vlad , Shimon Linda J. W. , Lahav Michal , van der Boom Milko E.
Published: June 2023

We demonstrate here how nitrate salts of bivalent copper, nickel, cobalt, and manganese, along with an achiral organic ligand, assemble into various structures such as symmetrical double‐decker flowers, smooth elongated hexagonal bipyramids, and hexagonal prisms. Large morphological changes occur in these structures because of different metal cations, although they maintain isomorphous hexagonal crystallographic structures. Metal cations with stronger coordination to ligands (Cu and Ni) tend to form uniform crystals with unusual shapes, whereas weaker coordinating metal cations (Mn and Co) produce crystals with more regular hexagonal morphologies. The unusual flower‐like crystals formed with copper nitrate have two pairs of six symmetrical petals with hexagonal convex centers. The texture of the petals indicates dendritic growth. Two different types of morphologies were formed by using different copper nitrate‐to‐ligand ratios. An excess of the metal salt results in uniform and hexagonal crystals having a narrow size distribution, whereas the use of an excess of ligand results in double‐decker morphologies. Mechanistically, an intermediate structure was observed with slightly concave facets and a domed center. Such structures most likely play a key role in the formation of double‐decker crystals that can be formed by fusion processes. The coordination chemistry results in isostructural chiral frameworks consisting of two types of continuous helical channels. Four pyridine units from four separate ligands are coordinated to the metal center in a plane having a chiral (propeller‐type) arrangement. The individual double‐decker flower crystals are homochiral and a batch consists of crystals having both handedness.
Impact of Catalyst Deuteration on the Reactivity of Chiral Phase‐Transfer Organocatalysts
Authors: Murayama Sei , Li Zhurong , Liang Huatai , Liu Yan , Naka Hiroshi , Maruoka Keiji
Published: June 2023

Site‐specifically deuterated organocatalysts were prepared and found to show improved reactivity over the non‐deuterated analogs. Two privileged C2‐symmetric chiral binaphthyl‐modified tetraalkylammonium salts were selected for this study. The stability of these phase‐transfer catalysts was generally improved by site‐specific deuteration, though the degree of improvement was structure dependent. In particular, a large secondary kinetic isotope effect was observed for the tetradeuterated phase‐transfer catalyst. The performance of these deuterated catalysts in the asymmetric catalytic alkylation of amino acid derivatives was better than that of non‐deuterated analogs at low catalyst loadings. The results suggest that catalyst deuteration is a promising strategy for enhancing the stability and performance of organocatalysts.
Can we still measure circular dichroism with circular dichroism spectrometers: The dangers of anisotropic artifacts
Authors: Ugras Thomas J. , Yao Yuan , Robinson Richard D.
Published: June 2023

Chiral materials with strong linear anisotropies are difficult to accurately characterize with circular dichroism (CD) because of artifactual contributions to their spectra from linear dichroism (LD) and birefringence (LB). Historically, researchers have used a second‐order Taylor series expansion on the Mueller matrix to model the LDLB interaction effects on the spectra in conventional materials, but this approach may no longer be sufficient to account for the artifactual CD signals in emergent materials. In this work, we present an expression to model the measured CD using a third‐order expansion, which introduces “pairwise interference” terms that, unlike the LDLB terms, cannot be averaged out of the signal. We find that the third‐order pairwise interference terms can make noticeable contributions to the simulated CD spectra. Using numerical simulations of the measured CD across a broad range of linear and chiral anisotropy parameters, the LDLB interactions are most prominent in samples that have strong linear anisotropies (LD, LB) but negligible chiral anisotropies, where the measured CD strays from the chirality‐induced CD by factors greater than 103. Additionally, the pairwise interactions are most significant in systems with moderate‐to‐strong chiral and linear anisotropies, where the measured CD is inflated twofold, a figure that grows as linear anisotropies approach their maximum. In summary, media with moderate‐to‐strong linear anisotropy are in great danger of having their CD altered by these effects in subtle manners. This work highlights the significance of considering distortions in CD measurements through higher‐order pairwise interference effects in highly anisotropic nanomaterials.