bluuebunny/crossref_metadata_2025_split huggingface dataset:
Heterogeneous Nanosized Metal (Metallic Compound)@Metal‐Organic Framework Composites: Recent Advances in the Preparation and Applications
Authors: Cui Yang , Zhao Yujie , Wu Jie , Hou Hongwei 
Published: May 2023

AbstractMetal‐organic framework (MOF) composites based on MOFs‐wrapped metals or metallic compounds (denoted as M/MC@MOFs) are an important class of materials that integrate M/MCs and MOFs. MOFs can fix and confine M/MCs to regulate their size, prevent uncontrollable aggregation, and enhance the exposure and ordered arrangement of active sites. In turn, M/MCs support the MOFs to enhance their stability and realize more targeted properties. In this review, the features and application scope of different M/MC@MOF synthesis methods are explored, considering the influential factors and regulation modes of the M/MC–MOFs integration. Additionally, the performances of the M/MC@MOF composites are comprehensively discussed, and the underlying mechanisms are clarified. The performance of M/MC@MOFs is dependent on the orderly synergy between the MOFs and M/MCs. MOFs can sieve and transfer specific molecules to the M/MC surface, whereas the robust interface provides new charge/energy‐transfer pathways, which enhance the activity and selectivity of the composites for diverse molecules. Furthermore, the challenges facing this field are analyzed, and the recommendations for advancing the development of M/MC@MOF composites are presented.
Natural Targeting Potent ROS‐Eliminating Tungsten‐Based Polyoxometalate Nanodots for Efficient Treatment of Pulmonary Hypertension
Authors: Liu Hong , Wang Shuya , Chen Qiaohui , Ge Xiaoyue , Ning Huang , Guo Yanzi , Wang Di , Ai Kelong , Hu Changping 
Published: May 2023

AbstractPulmonary hypertension (PH) is a disease of pulmonary artery stenosis and blockage caused by abnormal pulmonary artery smooth muscle cells (PASMCs), with high morbidity and mortality. High levels of reactive oxygen species (ROS) in pulmonary arteries play a crucial role in inducing phenotypic switch and abnormal proliferation of PASMCs. However, antioxidants are rarely approved for the treatment of PH because of a lack of targeting and low bioavailability. In this study, the presence of an enhanced permeability and retention effect (EPR)‐like effect in the pulmonary arteries of PH is revealed by tissue transmission electron microscopy (TEM). Subsequently, for the first time, tungsten‐based polyoxometalate nanodots (WNDs) are developed with potent elimination of multiple ROS for efficient treatment of PH thanks to the high proportion of reduced W5+. WNDs are effectively enriched in the pulmonary artery by intravenous injection because of the EPR‐like effect of PH, and significantly prevent the abnormal proliferation of PASMCs, greatly improve the remodeling of pulmonary arteries, and ultimately improve right heart function. In conclusion, this work provides a novel and effective solution to the dilemma of targeting ROS for the treatment of PH.
Lipid Nanoparticle (LNP) Enables mRNA Delivery for Cancer Therapy
Authors: Zong Yan , Lin Yi , Wei Tuo , Cheng Qiang 
Published: May 2023

AbstractMessenger RNA (mRNA) has received great attention in the prevention and treatment of various diseases due to the success of coronavirus disease 2019 (COVID‐19) mRNA vaccines (Comirnaty and Spikevax). To meet the therapeutic purpose, it is required that mRNA must enter the target cells and express sufficient proteins. Therefore, the development of effective delivery systems is necessary and crucial. Lipid nanoparticle (LNP) represents a remarkable vehicle that has indeed accelerated mRNA applications in humans, as several mRNA‐based therapies have already been approved or are in clinical trials. In this review, the focus is on mRNA‐LNP‐mediated anticancer therapy. It summarizes the main development strategies of mRNA‐LNP formulations, discusses representative therapeutic approaches in cancer, and points out current challenges and possible future directions of this research field. It is hoped that these delivered messages can help further improve the application of mRNA‐LNP technology in cancer therapy.
Designer Adhesives for Tough and Durable Interfaces in High‐Performance Ti‐Carbon PEKK Hybrid Joints
Authors: Kafkopoulos Georgios , Marinosci Vanessa M. , Duvigneau Joost , Grouve Wouter J. B. , Wijskamp Sebastiaan , de Rooij Matthijn B. , Vancso G. Julius , Akkerman Remko 
Published: May 2023

AbstractAdvanced high‐performance structural applications require the right materials in the right place and suitable interface engineering. However, poor adhesion in harsh environmental conditions frequently challenge material interfaces. An example is the moisture sensitivity of titanium‐poly ether ketone ketone (PEKK) interfaces. Here, this work offers a high‐performance composite adhesive system, which combines strong adhesion and high interfacial toughness, particularly when used in metal‐polymer bonding. This system includes aminopropyl triethoxy silane (APTES)–polydopamine (SiPDA) layers, which can be formed on the titanium surface before the joining process with carbon fiber‐reinforced PEKK (C/PEKK). Adhesion between PEKK and titanium is evaluated before and after hot/wet conditioning using mandrel peel tests. This work discovers that applying thin SiPDA layers not only results in a remarkable rise in the interfacial fracture toughness but also provides durable bond stability after hot/wet conditioning. These findings indicate that polydopamine‐based coatings show great potential to achieve stable interfaces for the next generation of high‐performance metal‐polymer hybrid materials.
Suppression of Oxygen Vacancies in Rutile Ruo2 via In Situ Exsolution for Enhanced Water Electrocatalysis
Authors: Zhang Yudi , Wang Yan , Sun Wen , Ma Dandan , Ma Jinfu , Rao Jiancun , Xu Qiunan , Huo Juntao , Liu Jian , Li Guowei 
Published: May 2023

AbstractElemental vacancies are proposed as an effective approach to tuning the electronic structure of catalysts that are critical for energy conversion. However, for reactions such as the sluggish oxygen evolution reaction, the excess of oxygen vacancies (VO) is inevitable and detrimental to catalysts’ electrochemical stability and activities, e.g., in the most active RuO2. While significant work is carried out to hinder the formation of VO, the development of a fast and efficient strategy is limited. Herein, a protection SrO layer produced successfully at the surface of RuO2 with the in situ exsolution method with perovskite SrRuO3 as the precatalyst, which could significantly hinder the generation of VO. Benefited from the suppression of VO, the surface‐modified RuO2 requires a low overpotential of 290 mV at 100 mA cm−2, accompanied by remarkably high electrochemical stability (100 h) and Faraday efficiency (≈100%). Theoretical investigation reveals that the formation energy of VO in RuO2 is almost doubled in the exsolved RuO2 phase as a result of the weakened RuO bond covalency. This work not only provides insight into the structural evolution of perovskite oxide catalysts but also demonstrates the feasibility of controlling vacancy formation via in situ exsolution.
Optical Gain Switching by Thermo‐Responsive Light‐Emitting Nanofibers through Moisture Sorption Swelling
Authors: Archimi Matteo , Schoolaert Ella , Becelaere Jana , Hoogenboom Richard , Camposeo Andrea , De Clerck Karen , Pisignano Dario 
Published: May 2023

AbstractThe development of intelligent photonic systems made of stimuli‐responsive materials, i.e., with features tunable and switchable by environmental signals, is gaining increasing attention. Here, the study reports on switchable optical gain based on complex arrays of nanofibers made of thermo‐responsive poly(2‐n‐propyl‐2‐oxazoline), incorporating a blue‐emitting chromophore. The fluorescent component endows the nanofibers with optical gain in addition to the moisture absorption capability of the polymer. Light amplification is found with temperature‐ and humidity‐dependent excitation threshold. The threshold value is halved close to the polymer cloud point temperature, enabling reversible switching of the emission intensity upon temperature change. Waveguiding analysis by back‐focal plane imaging on individual fibers allows the switching mechanisms to be rationalized, in terms of moisture sorption swelling‐induced morphological changes. These responsive light‐emitting nanofibers may find application in a novel class of lasers with dynamically‐controlled properties, environmentally‐switchable optoelectronics, and smart sensors.
Composition‐Dependent High‐Performance Phototransistors Based on Solution Processed CH3NH3PbI3/ZnO Heterostructures
Authors: Haque Farjana , Hasan Md Mehedi , Bestelink Eva , Sporea Radu A. , Mativenga Mallory 
Published: May 2023

AbstractRecently, hybrid organic−inorganic perovskites have emerged as promising photo‐sensing materials for next‐generation solution‐processed phototransistors, achieving high responsivity, detectivity, and fast response. Here, a phototransistor that can detect visible light using a low‐cost, solution processed methylammonium lead iodide/zinc oxide (CH3NH3PbI3/ZnO) heterostructure is reported. While typical ZnO thin‐film transistors (TFTs) do not show any photocurrent under visible light illumination, CH3NH3PbI3 (MAPbI3) coated ZnO TFTs exhibit substantial photocurrent. Additionally, the optical, morphological, and structural characteristics of the light‐absorbing layers are further controlled by altering the precursor ratio of methylammonium iodide and lead (II) iodide (MAI:PbI2), which in turn affects the photosensitivity. Stoichiometric composition (MAI:PbI2 = 1:1) of MAPbI3 demonstrates optimal characteristics with a responsivity of 234 A/W and a high detectivity of 3.74 × 1013 Jones under white light illumination. The high photo‐responsivity and detectivity result from the combination of the suitable optoelectronic properties of the stoichiometric MAPbI3 film and its smooth interface with the ZnO channel.
Mn2+ as an “Optical Energy Shutter” to Regulate Red‐to‐NIR Luminescence in Rare Earth Doped Layered Quadruple Perovskites
Authors: Yang Wei , Dang Peipei , Zhang Guodong , Lian Hongzhou , Cheng Ziyong , Li Guogang , Lin Jun 
Published: May 2023

AbstractMetal halide perovskites (MHPs) have shown great application prospects in the field of optoelectronics owing to their superior optical and optoelectronic properties. Bandgap engineering and impurity doping are effective ways to achieve regulation of luminous properties in the visible light region. However, realizing efficient deep red and wide‐range tunable near‐infrared (NIR) emission remains a challenge. Here, a series of rare earth (RE3+) ions (RE = Nd, Dy, Ho, Er, Tm, Yb) doped Cs4Cd1−xMnxSb2Cl12 (0 ≤ x ≤ 1) quadruple perovskites are designed. An efficient tunable luminescence from red to NIR light is achieved based on the energy transfer (ET) from Mn2+ to RE3+ by building the Mn2+ energy bridge, which covers the NIR‐I (650–900 nm) and NIR‐II (900–1700 nm) regions. Moreover, the ET efficiency is availably influenced by the doping concentration of Mn2+. Interestingly, the energy bridge from Mn2+ to RE3+ is cut off because of the increased bandgap when Bi3+ is introduced into the RE3+‐doped Cs4Cd0.4Mn0.6Sb2−yBiyCl12 (0 ≤ y ≤ 2) lattice. Through bandgap engineering, the ET from Mn2+ to RE3+ resembles an “optical energy shutter” which quenches the NIR emission of RE3+ owing to the mismatched energy level but enhances the emission of Mn2+.
Na3SiS3F: A Wide Bandgap Fluorothiosilicate with Unique [SiS3F] Unit and High Laser‐Induced Damage Threshold
Authors: Zhou Jiazheng , Wang Linan , Chu Yu , Wang Hongshan , Pan Shilie , Li Junjie 
Published: May 2023

AbstractThe exploration of antilaser damage wide bandgap infrared (IR) nonlinear optical (NLO) materials is urgent but challenging. Herein, by introducing the idea of fluorination into chalcogenides, a wide bandgap IR NLO material Na3SiS3F with unprecedented [SiS3F] tetrahedra is designed and synthesized. Na3SiS3F shows a wide bandgap of 4.75 eV (the largest one in the reported quaternary metal chalcogenides), resulting in a high laser damage induced threshold of ≈5 × AgGaS2(AGS). Meanwhile, the compound has a moderate NLO response (≈0.3 ×AGS) with phase‐matching behavior, large birefringence (0.15@1064 nm), and wide IR transparent region. The introduction of fluorine breaks the structural symmetry and broadens the highest occupied molecular orbital‐lowest unoccupied molecular orbital (HOMO‐LUMO) gap, polarizability anisotropy, and hyperpolarizability of the Si–S tetrahedral unit. The results indicate that Na3SiS3F is a promising IR NLO material for the high‐power laser application and open an avenue for the design of new wide bandgap IR NLO materials based on NLO‐active [SiSxF4−x] (x = 1, 2, 3) mixed anionic tetrahedral group.
Ultrafast Jahn‐Teller Photoswitching in Cobalt Single‐Ion Magnets
Authors: Canton Sophie E. , Biednov Mykola , Pápai Mátyás , Lima Frederico A. , Choi Tae‐Kyu , Otte Florian , Jiang Yifeng , Frankenberger Paul , Knoll Martin , Zalden Peter , Gawelda Wojciech , Rahaman Ahibur , Møller Klaus B. , Milne Christopher , Gosztola David J. , Zheng Kaibo , Retegan Marius , Khakhulin Dmitry 
Published: May 2023

AbstractSingle‐ion magnets (SIMs) constitute the ultimate size limit in the quest for miniaturizing magnetic materials. Several bottlenecks currently hindering breakthroughs in quantum information and communication technologies could be alleviated by new generations of SIMs displaying multifunctionality. Here, ultrafast optical absorption spectroscopy and X‐ray emission spectroscopy are employed to track the photoinduced spin‐state switching of the prototypical complex [Co(terpy)2]2+ (terpy = 2,2′:6′,2″‐terpyridine) in solution phase. The combined measurements and their analysis supported by density functional theory (DFT), time‐dependent‐DFT (TD‐DFT) and multireference quantum chemistry calculations reveal that the complex undergoes a spin‐state transition from a tetragonally elongated doublet state to a tetragonally compressed quartet state on the femtosecond timescale, i.e., it sustains ultrafast Jahn‐Teller (JT) photoswitching between two different spin multiplicities. Adding new Co‐based complexes as possible contenders in the search for JT photoswitching SIMs will greatly widen the possibilities for implementing magnetic multifunctionality and eventually controlling ultrafast magnetization with optical photons.
A Curcumin‐Modified Coordination Polymers with ROS Scavenging and Macrophage Phenotype Regulating Properties for Efficient Ulcerative Colitis Treatment
Authors: Yao Hang , Wang Feifei , Chong Hui , Wang Jingjing , Bai Yang , Du Meng , Yuan Xiaohui , Yang Xiaofei , Wu Ming , Li Yuping , Pang Huan 
Published: May 2023

AbstractOverexpression of classically activated macrophages (M1) subtypes and assessed reactive oxygen species (ROS) levels are often observed in patients with ulcerative colitis. At present, the treatment system of these two problems has yet to be established. Here, the chemotherapy drug curcumin (CCM) is decorated with Prussian blue analogs in a straightforward and cost‐saving manner. Modified CCM can be released in inflammatory tissue (acidic environment), eventually causing M1 macrophages to transform into M2 macrophages and inhibiting pro‐inflammatory factors. Co(III) and Fe(II) have abundant valence variations, and the lower REDOX potential in CCM‐CoFe PBA enables ROS clearance through multi‐nanomase activity. In addition, CCM‐CoFe PBA effectively alleviated the symptoms of UC mice induced by DSS and inhibited the progression of the disease. Therefore, the present material may be used as a new therapeutic agent for UC.
Unidirectional Moisture Delivery via a Janus Photothermal Interface for Indoor Dehumidification: A Smart Roof
Authors: Shi Wenbo , Bai Haoyu , Cao Moyuan , Wang Xinsheng , Ning Yuzhen , Li Zhe , Liu Kesong , Jiang Lei 
Published: May 2023

AbstractRational control of the humidity in specific environments plays an important role in green building, equipment protection, etc. A smart apparatus that can actively expel inner moisture and largely prevent outer liquid penetration can be highly desirable. Through the integration of the Janus interface with unidirectional liquid manipulation and the solar evaporating layer, here, a Janus solar dehumidifying interface (JSDI) is designed for the switchable moisture management of an indoor environment. By covering with the JSDI roof, the continuous elimination of inner water is achieved via outward condensate delivery and solar evaporation on sunny days. On rainy days, JSDI with a hydrophobic lower surface can largely hamper inward liquid leakage and then spontaneously drain the accumulated water via a siphoning structure. The real‐world water evaporation rate via the JSDI is ≈0.38 kg m−2 h−1 on an autumn day, showing a promising function of in situ moisture expelling. In addition, the JSDI is made of natural materials that are easy to scale up with a cost of four dollars per square meter. It is envisioned that the JSDI may meet the wide requirements of indoor dehumidification and update the understanding of the integration of Janus interfaces and solar steam generation.
A High Utilization and Environmentally Sustainable All‐Organic Aqueous Zinc‐Ion Battery Enabled by a Molecular Architecture Design
Authors: Yang Jin , Hua Haiming , Yang Huiya , Lai Pengbin , Zhang Minghao , Lv Zeheng , Wen Zhipeng , Li Cheng Chao , Zhao Jinbao , Yang Yang 
Published: May 2023

AbstractDespite their safe and cost‐effective merits, the cycling durability of aqueous zinc–organic batteries is hindered by cathode dissolution and low coulombic efficiency of Zn metal anodes. Herein, a Zn metal‐free all‐organic zinc‐ion battery (ZIB) is proposed by using quinoxalino[2,3‐i]diquinoxalino[2′,3′:6,7]quinoxalino[2,3‐a:2,3‐c] phenazine (QDPA) cathode coupled with a 1,4,5,8‐Naphthalenetetracarboxylic diimide (NPI) anode, rendering excellent electrochemical reversibility with high utilization. Based on the molecular architecture strategy, a QDPA cathode with an enlarged aromatic ring system is designed and synthesized, which not only effectively inhibits structural collapse during cycling but also enhances the working voltage without lowering the active group ratio. Moreover, theoretical calculations and experimental results confirm the rapid H+ storage mechanism in the CN active sites of QDPA, affording ultra‐fast electrochemical kinetics. Thus, it delivers a negligible capacity decay of 0.002% up to 13 000 cycles at 20 A g−1. Moreover, the QDPA//NPI all‐organic aqueous ZIB with a high energy density of 43.1 Wh kg−1 is demonstrated to be easily disassembled and recycled by the incineration treatment after battery failure, ensuring outstanding environmental sustainability.
Tailoring Interfacial Chemistry of Defective Carbon‐Supported Ru Catalyst Toward Efficient and CO‐Tolerant Alkaline Hydrogen Oxidation Reaction
Authors: Yang Zhilong , Lai Wenchuan , He Bingling , Wang Jian , Yu Feifan , Liu Qinghua , Liu Maochang , Zhang Shiguo , Ding Wei , Lin Zhiqun , Huang Hongwen 
Published: May 2023

AbstractThe ability to create highly active and CO‐tolerant platinum‐free catalysts toward alkaline hydrogen oxidation reaction (HOR) represents a significant endeavor to enable commercialization of alkaline fuel cells. This, however, remains a grand challenge. Herein, a robust defective‐carbon‐supported Ru catalyst (denoted as Ru@C) is crafted to achieve efficient and CO‐tolerant HOR in alkaline media via delicately tailoring interfacial chemistry of catalyst. Notably, the degree of defects in the carbon support is the key to tune the interface chemistry. An integrated experimental and density functional theory calculations study demonstrates that the favorable interfacial chemical interaction between Ru and carbon support controlled by the covalently bonded Ru─O─C redistributes the d electrons of Ru and downshiftsits d‐band center, which in turn weakens the hydrogen adsorption and suppresses the Ru 4d→CO 2π* back donation. Consequently, the optimized Ru@C catalyst renders a 6.6‐fold enhancement in mass activity (@25 mV) for alkaline HOR over the conventional Ru/C counterpart, which also outperforms the state‐of‐the‐art catalysts. Intriguingly, the catalyst can tolerate 20 000 ppm CO, far exceeding that of commercial Pt/C and PtRu/C catalysts. This work elucidates the correlation between precisely tailored interfacial chemistry and HOR performance, and is expected to further enlighten the design of advanced catalysts.
Toward More Efficient Organic Solar Cells: A Detailed Study of Loss Pathway and Its Impact on Overall Device Performance in Low‐Offset Organic Solar Cells
Authors: Sun Bowen , Tokmoldin Nurlan , Alqahtani Obaid , Patterson Acacia , De Castro Catherine S. P. , Riley Drew B. , Pranav Manasi , Armin Ardalan , Laquai Frédéric , Collins Brian A. , Neher Dieter , Shoaee Safa 
Published: May 2023

AbstractLow‐offset organic solar cell systems have attracted great interest since nonfullerene acceptors came into the picture. While numerous studies have focused on the charge generation process in these low‐offset systems, only a few studies have focused on the details of each loss channel in the charge generation process and their impact on the overall device performance. Here, several nonfullerene acceptors are blended with the same polymer donor to form a series of low‐offset organic solar cell systems where significant variation in device performance is observed. Through detailed analyses of loss pathways, it is found that: i) the donor:acceptor interfaces of PM6:Y6 and PM6:TPT10 are close to the optimum energetic condition, ii) energetics at the donor:acceptor interface are the most important factor to the overall device performance, iii) exciton dissociation yield can be field‐dependent owing to the sufficiently small energetic offset at the donor:acceptor interface, and iv) the change in substituents in the terminal group of Y‐series acceptors in this work mainly affects energetics at the donor:acceptor interface instead of the interface density in the active layer. In general, this work presents a path toward more efficient organic solar cells.
Expanding the genetic spectrum of ALKU syndrome: Compound heterozygosity for two deleterious variants in SMG8 gene
Authors: Fernandes André Aires , Grangeia Ana , Dias Leonor , Guimarães Joana 
Published: May 2023

AbstractAlzahrani–Kuwahara syndrome (ALKUS) is a neurodevelopmental disorder that includes microcephaly, facial dysmorphism, and variable congenital and eye malformations. We present the first case of ALKUS described in the European population caused by two variants in compound heterozygosity of the gene SMG8. We present a patient with two variants in compound heterozygosity in the SMG8 gene identified by in trio whole exome sequencing based in next generation sequencing (xGEN® Exome Research Panel, Nextseq550 platform). International case reporting (CARE) criteria were followed. Patient written consent was obtained through legal responsible persons. We describe a 27‐year‐old male, the second child of a healthy and non‐consanguineous couple, whose genetic analysis showed two variants in compound heterozygosity, c.1159C > T (p.Arg387*) and c.2407del (p.Arg803Glyfs*10), in the SMG8 gene, both classified as likely pathogenic. As described by Fatema Alzahrani et al. in a series of eight patients, our patient had global developmental delay with impaired intellectual development, facial dysmorphism, and limb disproportion. Additionally, our patient had lower limb spastic paraparesis, marked osteotendinous hyperreflexia with extensor plantar response bilaterally and paretic gait. Our patient resembles the phenotype described by Fatema Alzahrani et al., however, he is the first patient with two SMG8 deleterious variants in compound heterozygosity, and the first to exhibit pyramidal signs and gait disorder as part of the phenotype.