bluuebunny/crossref_metadata_2025_split huggingface dataset:
Polyelectrolyte Hydrogel‐Functionalized Photothermal Sponge Enables Simultaneously Continuous Solar Desalination and Electricity Generation Without Salt Accumulation
Authors: Li Lin , Xue Chaorui , Chang Qing , Ren Xiaohu , Li Ning , Yang Jinlong , Hu Shengliang , Xu Haolan 
Published: March 2024

AbstractTechnologies that can simultaneously generate electricity and desalinate seawater are highly attractive and required to meet the increasing global demand for power and clean water. Here, a bifunctional solar evaporator that features continuous electric generation in seawater without salt accumulation is developed by rational design of polyelectrolyte hydrogel‐functionalized photothermal sponge. This evaporator not only exhibits an unprecedentedly high water evaporation rate of 3.53 kg m−2 h−1along with 98.6% solar energy conversion efficiency but can also uninterruptedly deliver a voltage output of 0.972 V and a current density of 172.38 µA cm−2 in high‐concentration brine over a prolonged period under one sun irradiation. Many common electronic devices can be driven by simply connecting evaporator units in series or in parallel without any other auxiliaries. Different from the previously proposed power generation mechanism, this study reveals that the water‐enabled proton concentration fields in intermediate water region can also induce an additional ion electric field in free water region containing solute, to further enhance electricity output. Given the low‐cost materials, simple self‐regeneration design, scalable fabrication processes, and stable performance, this work offers a promising strategy for addressing the shortages of clean water and sustainable electricity.
Synthesis of 2‐Amino‐3‐arylindoles and their Fused Analogues via Intramolecular C‐Arylation
Authors: Žáková Kateřina , Králová Petra , Soural Miroslav 
Published: March 2024

Abstract2‐Aminobenzyl cyanide was reacted with nitrobenzenesulfonyl chlorides and alkylated under Mitsunobu or Fukuyama conditions. The resulting intermediates were exposed to basic conditions, which triggered a Truce‐Smiles rearrangement, leading to intramolecular C‐arylation. This reaction was followed by spontaneous cycloaddition, which yielded 2‐aminoindole derivatives. The developed synthetic route represents a metal‐free approach for accessing 1‐substituted 2‐amino‐3‐arylindoles. Furthermore, pyrimido[1,2‐a]indoles and 7,8dihydrobenzo[6,7][1,3]diazepino[4,5‐b]indoles were synthesized through the use of functionalized alcohols.
Humic Acids: A Material from Renewable Sources with the Potential for Making Supercapacitors
Authors: Vitale Paula , Bavio Marcela Alejandra 
Published: March 2024

AbstractThis paper examines the electrochemical performance of humic acids extracted from natural water and fertile soil, like electrode materials for supercapacitors, as proposed and evaluated. Humic acids come from the decomposition of organic matter in the humus formation process, therefore they are considered renewable resources. The humic acids are characterized by Fourier transform infrared spectroscopy, UV–vis spectroscopy, optical microscopy, and scanning electron microscopy with energy‐dispersive X‐ray spectroscopy. Electrochemical techniques are used to evaluate the behavior of humic acids like electrode materials for supercapacitors. Cyclic voltamperometry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy are performed in H2SO4 0.5 mol L−1. The highest capacitance, energy, and power values are found with humic acids from the soil. Thus, the specific capacitance of 87.15 F g−1 at 0.040 A g−1, maximum power of 32680 W kg−1, and energy of 60.52 W h kg−1 are obtained. The humic acids from soil have good cycling stability and high energy efficiency, placing them as promising materials in energy storage.
GrafeoPlad Palladium: Insight on Structure and Activity of a New Catalyst Series of Broad Scope
Authors: Formenti Matteo , Casaletto Maria Pia , Barone Giampaolo , Pagliaro Mario , Della Pina Cristina , Butera Valeria , Ciriminna Rosaria 
Published: March 2024

AbstractGrafeoPlad‐Pd, a new metal‐organic alloy comprised of Pd nanoparticles doped with 3D‐entrapped graphene oxide, has promising applicative potential in sustainable synthetic organic chemistry. Besides hydrogenation, the metal nanopowder comprising the material is also active and relatively stable in cross‐coupling reactions carried out consecutively. X‐ray photoelectron spectroscopy (XPS) surface investigation and density functional theory (DFT) calculations are applied to gain new insight into the structure and potential new catalytic activity of this new class of molecularly doped metals.
Redox Engineering of Fe‐Rich Disordered Rock‐Salt Li‐Ion Cathode Materials
Authors: Fong Richie , Mubarak Nauman , Park Sang‐Wook , Lazaris Gregory , Liu Yiwei , Malik Rahul , Seo Dong‐Hwa , Lee Jinhyuk 
Published: March 2024

AbstractThe pursuit of high‐performance and cost‐effective Li‐ion batteries emphasizes the need for cathode materials composed of abundant elements, such as Fe. Disordered rock‐salt (DRX) cathode materials, known for their high compositional flexibility, offer a unique opportunity in this regard. However, Fe‐rich DRX (Fe‐DRX) cathodes, potentially the most cost‐effective among all DRXs, have seen limited research interest due to their comparatively restrained performance. This limitation stems from the inaccessibility of the Fe3+/Fe4+ redox in the DRX structure, prompting the need for redox engineering to enable Fe‐DRXs with readily utilizable redox mechanisms. In this work, utilizing both experiments and theoretical study, reversible Fe2+/Fe3+ redox in an Fe2+‐based DRX cathode is demonstrated. This design minimizes the reliance on O redox, resulting in a high capacity (≈290 mAh g−1) and energy density (≈700 Wh kg−1), as opposed to an Fe3+‐based DRX operating on the limited Fe3+/Fe4+ redox and extensive O redox upon cycling. Overall, the study introduces a novel approach to redox engineering to develop low‐cost, high‐performing Fe‐rich cathode materials.
Ramadan fasting in the third trimester of pregnancy and postpartum colostrum cortisol concentrations in Morocco
Authors: Guilfoyle Meagan M. 
Published: March 2024

AbstractBreast milk cortisol concentration varies among and within lactating women, but the causes and consequences of variation are not yet fully understood. This study investigated whether maternal fasting from food and water for over 16 h per day during the third trimester of pregnancy was associated with increased concentrations of cortisol in colostrum during the month of Ramadan in a Moroccan sample. Participants were women who gave birth at the public maternity hospital in Rabat, Morocco throughout the month of and month following Ramadan. Participants completed interviews (N = 92), underwent anthropometric assessment (N = 73), and colostrum samples (N = 63) were collected approximately 48–72 h postpartum. Cortisol analysis was completed on a subset of colostrum samples (N = 43). Women were categorized as fasting every day of Ramadan before giving birth (N = 52/92, 57%), fasting some days (N = 29/92, 32%), and not fasting (N = 11/92, 11%). For women who fasted, average fasting duration was 19.5 days (range: 1–29 days), and average time between the last day of fasting and birth was 8.8 days (range: 0–43 days). The number of days of fasting was positively associated with cortisol concentrations in colostrum (p < .009) in a multivariate analysis controlling for maternal anthropometry, hypertension and/or diabetes, and reasons for opting out of fasting. Each day of fasting was associated with a 4.05% increase in colostrum cortisol. Results are consistent with the hypothesis that maternal fasting during the third trimester of pregnancy increases breast milk cortisol and thus alters the hormonal milieu to which the infant is exposed.
Delineating cognitive resilience using fractal regulation: Cross‐sectional and longitudinal evidence from the Rush Memory and Aging Project
Authors: Li Peng , Gao Chenlu , Yu Lei , Gao Lei , Cai Ruixue , Bennett David A. , Schneider Julie A. , Buchman Aron S. , Hu Kun 
Published: March 2024

AbstractINTRODUCTIONDegradation of fractal patterns in actigraphy independently predicts dementia risk. Such observations motivated the study to understand the role of fractal regulation in the context of neuropathologies.METHODSWe examined associations of fractal regulation with neuropathologies and longitudinal cognitive changes in 533 older participants who were followed annually with actigraphy and cognitive assessments until death with brain autopsy performed. Two measures for fractal patterns were extracted from actigraphy, namely, α1 (representing the fractal regulation at time scales of <90 min) and α2 (for time scales 2 to 10 h).RESULTSWe found that larger α1 was associated with lower burdens of Lewy body disease or cerebrovascular disease pathologies; both α1 and α2 were associated with cognitive decline. They explained an additional significant portion of the variance in the rate of cognitive decline above and beyond neuropathologies.DISCUSSIONFractal patterns may be used as a biomarker for cognitive resilience against dementia‐related neuropathologies.
Wrist‐worn actigraphy in agitated late‐stage dementia patients: A feasibility study on digital inclusion
Authors: Guu Ta‐Wei , Brem Anna‐Katharine , Albertyn Christopher P. , Kandangwa Pooja , Aarsland Dag , ffytche Dominic 
Published: March 2024

AbstractBACKGROUNDWrist‐worn actigraphy can be an objective tool to assess sleep and other behavioral and psychological symptoms in dementia (BPSD). We investigated the feasibility of using wearable actigraphy in agitated late‐stage dementia patients.METHODSAgitated, late‐stage Alzheimer's dementia care home residents in Greater London area (n = 29; 14 females, mean age ± SD: 80.8 ± 8.2; 93.1% White) were recruited to wear an actigraphy watch for 4 weeks. Wearing time was extracted to evaluate compliance, and factors influencing compliance were explored.RESULTSA high watch‐acceptance (96.6%) and compliance rate (88.0%) was noted. Non‐compliance was not associated with age or BPSD symptomatology. However, participants with “better” cognitive function (R = 0.42, p = 0.022) and during nightshift (F1.240, 33.475 = 8.075, p = 0.005) were less compliant. Female participants were also marginally less compliant (F1, 26 = 3.790, p = 0.062).DISCUSSIONSWrist‐worn actigraphy appears acceptable and feasible in late‐stage agitated dementia patients. Accommodating the needs of both the patients and their carers may further improve compliance.
Stereodivergent, Kinetically Controlled Isomerization of Terminal Alkenes via Nickel Catalysis
Authors: Rubel Camille Z. , Ravn Anne K. , Ho Hang Chi , Yang Shenghua , Li Zi‐Qi , Engle Keary M. , Vantourout Julien C. 
Published: March 2024

AbstractBecause internal alkenes are more challenging synthetic targets than terminal alkenes, metal‐catalyzed olefin mono‐transposition (i.e., positional isomerization) approaches have emerged to afford valuable E‐ or Z‐ internal alkenes from their complementary terminal alkene feedstocks. However, the applicability of these methods has been hampered by lack of generality, commercial availability of precatalysts, and scalability. Here, we report a nickel‐catalyzed platform for the stereodivergent E/Z‐selective synthesis of internal alkenes at room temperature. Commercial reagents enable this one‐carbon transposition of terminal alkenes to valuable E‐ or Z‐internal alkenes via a Ni−H‐mediated insertion/elimination mechanism. Though the mechanistic regime is the same in both systems, the underlying pathways that lead to each of the active catalysts are distinct, with the Z‐selective catalyst forming from comproportionation of an oxidative addition complex followed by oxidative addition with substrate and the E‐selective catalyst forming from protonation of the metal by the trialkylphosphonium salt additive. In each case, ligand sterics and denticity control stereochemistry and prevent over‐isomerization.
Light‐Regulated Nucleation for Growing Highly Uniform Single‐Crystalline Microrods
Authors: Sun Lishan , Gong Yanjun , Che Yanxue , Ji Hongwei , Liu Bing , Che Yanke , Zhao Jincai 
Published: March 2024

AbstractWe report a light‐irradiation method to control the synchronous nucleation of a donor‐acceptor (D‐A) fluorophore for growing highly uniform single‐crystalline microrods, which is in sharp contrast to the prevailing methods of restricting spontaneous nucleation and additionally adding seeds. The D‐A fluorophore was observed to undergo photoinduced electron transfer to CrCl3, leading to the generation of HCl and the subsequent protonation of the D‐A fluorophore. By intensifying photoirradiation or prolonging its duration, the concentration of protonated D‐A fluorophores can be rapidly increased to a high supersaturation level. This results in the formation of a controlled number of nuclei in a synchronous manner, which in turn kickstart the epitaxial growth of protonated D‐A fluorophores towards uniform single‐crystalline microrods of controlled sizes. The light‐regulated synchronous nucleation and uniform growth of microrods are a unique phenomenon that can only be achieved by specific Lewis acids, making it a novel probing method for sensitively detecting strong Lewis acids such as chromium chloride.
Reticular Modulation of Piezofluorochromic Behaviors in Organic Molecular Cages by Replacing Non‐Luminous Components
Authors: Li Yang , Wang Kai , Feng Rui , Wang Jingtian , Xi Xiao‐Juan , Lang Feifan , Li Quanwen , Li Wei , Zou Bo , Pang Jiandong , Bu Xian‐He 
Published: March 2024

AbstractOrganic piezochromic materials that manifest pressure‐stimuli‐responses are important in various fields such as data storage and anticounterfeiting. The manipulation of piezofluorochromic behaviors for these materials is promising but remains a great challenge. Herein, a non‐luminous components regulated strategy is developed and organic molecular cages (OMCs), a burgeoning class of crystalline organic materials with structural dynamics, are first explored for the design of piezofluorochromic materials with tunable luminescence. A series of OMCs based on aggregation‐induced emission (AIE) chromophores, termed Cage 1–3, are synthesized and their piezofluorochromic behaviors are investigated by diamond anvil cell technique. Due to the sufficient voids between its flexible chromophores offered by the OMC structure, Cage 1 exhibits thermofluorochromic and piezofluorochromic properties. Moreover, the piezofluorochromic performance of this OMC could be further promoted by replacing its non‐luminous components with improved flexibilities, and a remarkable luminescence peak shift by 150 nm together with a response sensitivity of 13.8 nm GPa−1 was achieved upon hydrostatic compression. The cage structure plays a vital role in facilitating efficient and reversible piezofluorochromic behaviors. This study has shed light on the rational design and exploitation of OMCs as an exceptional platform to accomplish customizable piezofluorochromic behaviors and enlarge their potential applications in pressure‐based luminescence.
Dual Enhancement of Phosphorescence and Circularly Polarized Luminescence through Entropically Driven Self‐Assembly of a Platinum(II) Complex
Authors: Wang Yanqing , Li Na , Chu Liangwen , Hao Zelin , Chen Junyu , Huang Jiang , Yan Junlin , Bian Hongtao , Duan Pengfei , Liu Jing , Fang Yu 
Published: March 2024

AbstractAddressing the dual enhancement of circular polarization (glum) and luminescence quantum yield (QY) in circularly polarized luminescence (CPL) systems poses a significant challenge. In this study, we present an innovative strategy utilizing the entropically driven self‐assembly of amphiphilic phosphorescent platinum(II) complexes (L−Pt) with tetraethylene glycol chains, resulting in unique temperature dependencies. The entropically driven self‐assembly of L−Pt leads to a synergistic improvement in phosphorescence emission efficiency (QY was amplified from 15 % at 25 °C to 53 % at 60 °C) and chirality, both in the ground state and the excited state (glum value has been magnified from 0.04×10−2 to 0.06) with increasing temperature. Notably, we observed reversible modulation of phosphorescence and chirality observed over at least 10 cycles through successive heating and cooling, highlighting the intelligent control of luminescence and chiroptical properties by regulating intermolecular interactions among neighboring L−Pt molecules. Importantly, the QY and glum of the L−Pt assembly in solid state were measured as 69 % and 0.16 respectively, representing relatively high values compared to most self‐assembled CPL systems. This study marks the pioneering demonstration of dual thermo‐enhancement of phosphorescence and CPL and provides valuable insights into the thermal effects on high‐temperature and switchable CPL materials.
Robust Covalent Organic Framework Photocatalysts for H2O2 Production: Linkage Position Matters
Authors: Yang Tao , Zhang De , Kong Aiguo , Zou Yingying , Yuan Ling , Liu Chao , Luo Sijia , Wei Guangfeng , Yu Chengzhong 
Published: March 2024

AbstractCovalent organic frameworks (COFs) are promising photocatalysts for hydrogen peroxide (H2O2) synthesis. However, the nature of organic polymers makes the balance between high activity and stability challenging. We demonstrate that the linkage position matters in the design of robust COF photocatalysts with durable high activity without sacrificial reagents. COFs with ortho‐ and para‐linkages (o‐COFs and p‐COFs) were constructed by 1,3,5‐triformylphloroglucinol with benzene‐, pyridine‐, pyrazine‐orthodiamines and paradiamines. The pyrzaine‐containing o‐COFs with two pyridinic nitrogen atoms exhibited a H2O2 production rate of 4396 μmol g−1 h−1 together with long‐time continuous H2O2 photosynthesis performance in pure water (48 h), superior to the corresponding p‐COFs. A four‐step reaction mechanism is proposed by density function calculations. Moreover, the active sites and origin of stability enhancement for o‐COFs are clarified. This work provides a simple and effective molecular design strategy in the design of robust COF photocatalysts for artificial H2O2 photosynthesis.
Near‐Infrared Light Activated Formulation for the Spatially Controlled Release of CRISPR‐Cas9 Ribonucleoprotein for Brain Gene Editing
Authors: Simões Susana , Lino Miguel , Barrera Angela , Rebelo Catarina , Tomatis Francesca , Vilaça Andreia , Breunig Christopher , Neuner Andrea , Peça João , González Ricardo , Carvalho Alexandra , Stricker Stefan , Ferreira Lino 
Published: March 2024

AbstractThe CRISPR/Cas9 system has emerged as a promising platform for gene editing; however, the lack of an efficient and safe delivery system to introduce it into cells continues to hinder clinical translation. Here, we report a rationally designed gene‐editing nanoparticle (NP) formulation for brain applications: an sgRNA:Cas9 ribonucleoprotein complex is immobilized on the NP surface by oligonucleotides that are complementary to the sgRNA. Irradiation of the formulation with a near‐infrared (NIR) laser generates heat in the NP, leading to the release of the ribonucleoprotein complex. The gene‐editing potential of the formulation was demonstrated in vitro at the single‐cell level. The safety and gene editing of the formulation were also demonstrated in the brains of reporter mice, specifically in the subventricular zone after intracerebral administration and in the olfactory bulb after intranasal administration. The formulation presented here offers a new strategy for the spatially controlled delivery of the CRISPR system to the brain.
Entropy‐Driven Direct Air Electrofixation
Authors: Sun Yuntong , Li Ming , Duan Jingjing , Antonietti Markus , Chen Sheng 
Published: March 2024

AbstractAccording to the principles of chemical thermodynamics, the catalytic activation of small molecules (like N2 in air and CO2 in flue gas) generally exhibits a negative activity dependence on O2 owning to the competitive oxygen reduction reaction (ORR). Nevertheless, some catalysts can show positive activity dependence for N2 electrofixation, an important route to produce ammonia under ambient condition. Here we report that the positive activity dependence on O2 of (Ni0.20Co0.20Fe0.20Mn0.19Mo0.21)3S4 catalyst arises from high‐entropy mechanism. Through experimental and theoretical studies, we demonstrate that under the reaction condition in the mixed N2/O2, the adsorption of O2 on high‐entropy catalyst contributes to activating N2 molecules characteristic of elongated N≡N bond lengths. As comparison to the low‐ and medium‐entropy counterparts, high entropy can play the second role of attenuating competitive ORR by displaying a negative exponential entropy‐ORR activity relationship. Accordingly, benefiting from the O2, the system for direct air electrofixation has demonstrated an ammonia yield rate of 47.70 μg h−1 cm−2, which is even 1.5 times of pure N2 feedstock (31.92 μg h−1 cm−2), overtaking all previous reports for this reaction. We expect the present finding providing an additional dimension to high entropy that leverages systems beyond the constraint of traditional rules.
Photocatalytic Functionalization of Dehydroalanine‐Derived Peptides in Batch and Flow
Authors: Kaplaneris Nikolaos , Akdeniz Merve , Fillols Méritxell , Arrighi Francesca , Raymenants Fabian , Sanil Gana , Gryko Daniel T. , Noël Timothy 
Published: March 2024

AbstractUnnatural amino acids, and their synthesis by the late‐stage functionalization (LSF) of peptides, play a crucial role in areas such as drug design and discovery. Historically, the LSF of biomolecules has predominantly utilized traditional synthetic methodologies that exploit nucleophilic residues, such as cysteine, lysine or tyrosine. Herein, we present a photocatalytic hydroarylation process targeting the electrophilic residue dehydroalanine (Dha). This residue possesses an α,β‐unsaturated moiety and can be combined with various arylthianthrenium salts, both in batch and flow reactors. Notably, the flow setup proved instrumental for efficient scale‐up, paving the way for the synthesis of unnatural amino acids and peptides in substantial quantities. Our photocatalytic approach, being inherently mild, permits the diversification of peptides even when they contain sensitive functional groups. The readily available arylthianthrenium salts facilitate the seamless integration of Dha‐containing peptides with a wide range of arenes, drug blueprints, and natural products, culminating in the creation of unconventional phenylalanine derivatives. The synergistic effect of the high functional group tolerance and the modular characteristic of the aryl electrophile enables efficient peptide conjugation and ligation in both batch and flow conditions.
K2CO3 on porous supports for moisture‐swing CO2 capture from ambient air
Authors: Zheng Shiqiang , Cheng Xinyue , Zhou Wenjia , Wang Tong , Zhu Liangliang , Xiao Hang , Chen Xi 
Published: March 2024

AbstractDirect air capture (DAC) of CO2 is an important technology to mitigate mobile carbon emissions, reduce atmospheric CO2 concentration, and cope with climate change. Moisture‐swing adsorption is regarded as one of the most promising technologies in DAC due to its low energy consumption and ease of operation. In this work, a cheap and easily available moisture‐swing adsorbent of potassium carbonate loaded on porous supports (i.e., activated carbon, magnesium oxide, and zeolite) was prepared for CO2 capture from ambient air. The composite adsorbent of potassium carbonate on activated carbon showed the best performance with a DAC capacity of 0.562 mmol/g at 25°C and 5% relative humidity. The effects of temperature, relative humidity, and CO2 concentration on the adsorption performance were investigated systematically, as well as the cyclic DAC performance. In 50 adsorption–desorption cycles, the adsorption capacity of the composite adsorbent decreased by ~40% due to potassium carbonate leaching loss during water evaporation but can be fully recovered simply by re‐impregnating with potassium carbonate again.