bluuebunny/crossref_metadata_2025_split huggingface dataset:
Tunable Nonlinear Optical Properties Based on Metal–Organic Framework Single Crystals
Authors: Yuan Hongye , Xu Xueli , Qiao Zhiwei , Kottilil Dileep , Shi Dongchen , Fan Weidong , Yuan Yi Di , Yu Xin , Babusenan Anu , Zhang Mingming , Ji Wei 
Published: January 2024

AbstractSolid‐state hybrid materials with designability in topology and tunable photo‐responsiveness hold great promise for multitudinous applications from optoelectronics to information storage/communication. However, the judicious design and synthesis of metal–organic frameworks (MOFs) with intrinsically custom‐made nonlinear optical (NLO) properties including multiple photon absorption and harmonic generation effects suitable for miniaturized devices remain highly challenging. Herein, the design and synthesis of a novel pillared framework named after Zn‐TCPE‐DPNI MOF coordinated by zinc ions (Zn2+), aggregation induced emission (AIE) featured [1,1′‐biphenyl]‐4‐carboxylic acid (H4TCPE), and N,N′‐di(4‐pyridyl)‐1,4,5,8‐naphthalenetetracarboxydiimide (DPNI) are reported. The highly ordered Zn‐TCPE‐DPNI MOF single crystal exhibits tunable NLO responses by switching incident excitation wavelengths of a femtosecond laser from 900 to 1500 nm. The noticeable transformation from two‐ or three‐photon excited photoluminescence (2PL or 3PL) to the concurrent occurrence of 3PL and third harmonic generation (THG), and eventually to the mere emergence of THG with a high effective susceptibility χ(3) (3ω) of 2.9 × 10−12 esu is observed. This study paves a novel avenue for the design and synthesis of photoluminescent MOF crystals with tunable NLO responses toward the fabrication of multifunctional NLO devices targeted for optoelectronics and information communication.
Tricolor Upconversion Phosphors of LiYO2:RE3+/Yb3+ (RE = Tm, Ho, Eu) for Metamerism Anti‐Counterfeiting and 3D Volumetric Display
Authors: Zhao Shanshan , Yu Dechao , Li Benchun , Kanwal Saima , Shen Tiantian , Wu Jincheng , Zhuang Songlin , Zhang Dawei 
Published: January 2024

AbstractThe development of blue/green/red tricolor upconversion (UC) phosphors under invisible light irradiation has attracted significant interest in emerging applications such as anti‐counterfeiting, three‐dimensional (3D) optical data storage, and solid‐state 3D displays. In this study, a series of LiYO2:RE3+,Yb3+ (RE = Tm, Ho, Eu) phosphors are successfully prepared via first precipitation process followed by calcination, and completely optimized for efficient tricolor UC luminescence with 980 nm laser excitation. Mechanisms involving two‐ or three‐photon absorption processes and low‐phonon‐energy‐suppressed multi‐phonon relaxation have been proposed for Ho3+(Eu3+)/Yb3+ and Tm3+/Yb3+ codoping, respectively. In addition, the RE3+ (Yb3+) concentration‐induced phase transition of the LiYO2 host is discussed for interesting possibilities in spectral regulation. Based on the broad color gamut achieved by the tricolor UC phosphor mixture, homochromatic and polychromatic metamerisms are experimentally fabricated via screen printing for high‐level anti‐counterfeiting and information security. Moreover, for a proof‐of‐concept demonstration, prototypes of 3D optical data storage and volumetric displays are constructed by embedding tricolor UC mixtures and their 3D printed patterns in polydimethylsiloxane. It is believed that the continuous exploration of tricolor UC under invisible light excitation for metamerism anti‐counterfeiting and 3D displays can promote the development of high‐level information security and advanced volumetric display technologies.
A Universal Strategy for Tuning Afterglow Color In Situ Via Radiative Energy Transfer
Authors: Chen Junru , Xie Zongliang , Shan Yi , Wang Tongtong , Liu Bin 
Published: January 2024

AbstractColorful afterglow materials have promising applications in optoelectronic displays. To effectively fine‐tune the afterglow color, an assembly structure that includes UV lamp, persistent room temperature phosphorescence (pRTP) layer, and fluorescent layer (from the bottom to the top) with superimposition of pRTP and fluorescence, is designed. The fluorescence component is emitted from a PMMA film doped with asymmetric 4‐(7‐methoxy‐5,6‐dinitrobenzo[c][1,2,5,]thiadiazol‐4‐yl)‐N,N‐diphenylaniline (TPA‐TD), which has a broad absorption that covers the entire visible region, facilitating effective radiative energy transfer between various pRTP materials and TPA‐TD. Due to its aggregation‐induced‐emission nature, the fluorescence intensity of TPA‐TD enhances with increased doping concentration in PMMA films. Meanwhile, the transmission of TPA‐TD film reduces as the doping concentration increases, which results in a reduction of pRTP intensity through the TPA‐TD film. Therefore, the afterglow color can be fine‐tuned in situ by regulating the ratio of pRTP and fluorescence.
High‐Performance UV Photodetector via Energy Band Engineering and LSPR‐Enhanced Pyro‐Phototronic Effect in Au Decorated 2D‐PbI2/1D‐ZnO Heterojunction
Authors: Zheng Xuemei , Dong Mengji , Li Qi , Liu Yanli , Di Xuan , Lu Xianmao , Meng Jianping , Li Zhou 
Published: January 2024

AbstractUltraviolet (UV) photodetectors have attracted extensive attention in various applications, including aerospace, optical communication, and fire warning. However, the intrinsic coupling of high responsivity and fast response as well as imperfect interface transmission impede the further improvement of UV photodetector. Here, a high‐performance Au‐decorated PbI2/ZnO pn junction UV photodetector with a one‐dimensional (1D) and two‐dimensional (2D) interspersed structure is presented. The pyro‐phototronic effect and energy band engineering effect from the localized pn junction generated by the layered p‐type PbI2 nanosheets along the c‐axis of ZnO are coupled to modulate the separation and transport of photogenerated carriers. Furthermore, the localized surface plasmon resonance of Au nanoparticles produces transient thermal power to raise temperature fast to enhance pyroelectric current. The self‐powered Au@PbI2/ZnO photodetector displays a high responsivity of 0.21 A W−1, excellent detectivity of 7.9 × 1012 Jones, and fast response/recovery time of 25/31 ms, under the illumination of 325 nm light with the power density of 0.08 µW cm−2. This work offers an effective strategy for designing high‐performance next‐generation optoelectronic devices.
Recent Advances in the Use of 2‐Aminobenzyl Alcohols in the Synthesis of Quinolines, Quinazolines and Other N‐Heterocycles
Authors: Doraghi Fatemeh , Gilaninezhad Farzad , Karimian Somaye , Mahdavian Amir Mohammad , Larijani Bagher , Mahdavi Mohammad 
Published: January 2024

AbstractN‐Heterocyclic compounds, in particular, quinolines and quinazolines are frequently used in medicinal chemistry. Therefore, the direct and clean synthesis of these valuable scaffolds has been a great interest for many years. 2‐Aminobenzyl alcohols as an alternative reactant instead of unstable and expensive 2‐aminobenzaldehydes can be used in the construction of N‐fused heterocycles including quinolines, quinazolines, oxazines, thiazines, selenazines, imidazoles, diazepines, etc. In this review article, we have discussed recent developments in the use of 2‐aminobenzyl alcohols in the synthesis of diverse heterocycles.
Aryl Ketone‐Catalyzed Light‐Driven Radical Oxy‐Functionalization of Non‐Acidic C(sp3)−H Bonds Enabled by Triple Role of TEMPO
Authors: Kamijo Shin , Azami Masaya , Kamijo Kaori , Umeno Hina , Ishii Ryo , Murafuji Toshihiro 
Published: January 2024

AbstractA light‐driven radical oxy‐functionalization of non‐acidic aliphatic and benzylic C(sp3)−H bonds was achieved with 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) in a single‐step by employing an aryl ketone as a sole catalyst. The transformation was initiated by homolysis of a C(sp3)−H bond in the starting substance by the photo‐excited aryl ketone. The derived carbon radical was then promptly trapped by TEMPO leading to the formation of the TEMPO‐adduct. The derived TEMPO‐adduct is synthetically versatile as an alcohol equivalent since it can be readily converted to the corresponding ketone by oxidation and to the corresponding alcohol by reduction. The key to realizing the present catalytic reaction relies on the distinctive triple role of TEMPO, which acts as the precursor of the oxygen functionality, the oxidant to regenerate the aryl ketone, and the protective group for the derived TEMPO‐adduct from over‐oxidation.
Acid‐Cooperative Transition Metal‐Catalysed Oxygen‐Atom‐Transfer: Ruthenium‐Catalysed C−H Oxygenation
Authors: Doiuchi Daiki , Shimoda Nanako , Okazaki Koushi , Uchida Tatsuya 
Published: January 2024

AbstractThe prospect of developing methods to control the reactivity of metal(oxo) holds appeal for both synthetic and bioinorganic chemistry. In this study, we observed that carboxylic acids enhance reactivity in C−H oxidation by forming hydrogen bonds with the oxo ligand, thereby increasing the basicity and electrophilicity of the oxo intermediate. Additionally, we discovered that H‐dicarboxylate ligands, such as oxalate, malonate, and maleate, significantly improve the catalyst turnover frequency (up to 760/h) in unactivated C(sp3)−H oxidation. Furthermore, the addition of maleic acid was also found to activate Fe and Mn(pdp)‐catalysed C−H oxygenation. Notably, Ru(bpga)(H‐maleate)2 3‐catalyzed C−H functionalization exhibited a broad functional group tolerance, including bromine, hydroxyl, benzoate, nitro, nitryl, sulfonate, imide, sulfonylamide, and carbamate, yielding up to 98% in a site‐ and chemoselective manner with only 0.1–2.0 mmol% loading.
Protein Kinase STK24 Promotes Tumor Immune Evasion via the AKT‐PD‐L1 Axis
Authors: Wang Ning , Jiang Yu , Li Mengjie , Wang Haofei , Pan Jie , Tang Yang , Xie Shaofang , Xu Yunyang , Li Xu , Zhou Xuefei , Xu Pinglong , Lin Wenlong , Wang Xiaojian 
Published: January 2024

AbstractImmunotherapy targeting PD‐L1 is still ineffective for a wide variety of tumors with high unpredictability. Deploying combined immunotherapy with alternative targeting is practical to overcome this therapeutic resistance. Here, the deficiency of serine‐threonine kinase STK24 is observed in tumor cells causing substantial attenuation of tumor growth in murine syngeneic models, a process relying on cytotoxic CD8+ T and NK cells. Mechanistically, STK24 in tumor cells associates with and directly phosphorylates AKT at Thr21, which promotes AKT activation and subsequent PD‐L1 induction. Deletion or inhibition of STK24, by contrast, blocks IFN‐γ‐mediated PD‐L1 expression. Various murine models indicate that in vivo silencing of STK24 can significantly enhance the efficacy of the anti‐PD‐1 blockade strategy. Elevated STK24 levels are observed in patient specimens in multiple tumor types and inversely correlated with intratumoral infiltration of cytotoxic CD8+ T cells and with patient survival. The study collectively identifies STK24 as a critical modulator of antitumor immunity, which engages in AKT and PD‐L1/PD‐1 signaling and is a promising target for combined immunotherapy.
Tailoring Magnetic Anisotropy in Ultrathin Cobalt by Surface Carbon Chemistry
Authors: Brondin Carlo Alberto , Ghosh Sukanya , Debnath Saikat , Genuzio Francesca , Genoni Pietro , Jugovac Matteo , Bonetti Stefano , Binggeli Nadia , Stojić Nataša , Locatelli Andrea , Menteş Tevfik Onur 
Published: January 2024

AbstractThe ability to manipulate magnetic anisotropy is essential for magnetic sensing and storage tools. Surface carbon species offer cost‐effective alternatives to metal‐oxide and noble metal capping layers, inducing perpendicular magnetic anisotropy in ultrathin ferromagnetic films. Here, the different mechanisms by which the magnetism in a few‐layer‐thick Co thin film is modified upon adsorption of carbon monoxide (CO), dispersed carbon, and graphene are elucidated. Using X‐ray microscopy with chemical and magnetic sensitivity, the in‐plane to out‐of‐plane spin reorientation transition in cobalt is monitored during the accumulation of surface carbon up to the formation of graphene. Complementary magneto‐optical measurements show weak perpendicular magnetic anisotropy (PMA) at room temperature for dispersed carbon on Co, while graphene‐covered cobalt exhibits a significant out‐of‐plane coercive field. Density‐functional theory (DFT) calculations show that going from CO/Co to C/Co and to graphene/Co, the magnetocrystalline and magnetostatic anisotropies combined promote out‐of‐plane magnetization. Anisotropy energies weakly depend on carbidic species coverage. Instead, the evolution of the carbon chemical state from carbidic to graphitic is accompanied by an exponential increase in the characteristic domain size, controlled by the magnetic anisotropy energy. Beyond providing a basic understanding of the carbon‐ferromagnet interfaces, this study presents a sustainable approach to tailor magnetic anisotropy in ultrathin ferromagnetic films.
Graphene Acetic Acid‐Based Hybrid Supercapacitor and Liquid‐Gated Transistor
Authors: Hensel Rafael C. , Di Vizio Biagio , Montes‐García Verónica , Yang Jijin , Ilie Georgian G. , Sedona Francesco , Sambi Mauro , Samorì Paolo , Cester Andrea , Agnoli Stefano , Casalini Stefano 
Published: January 2024

AbstractSupercapacitors and transistors are two key devices for future electronics that must combine portability, high performance, easy scalability, etc. Graphene‐related materials (GRMs) are frequently chosen as active materials for these applications given their unique physical properties that are tunable via chemical functionalization. Up to date, among GRMs, only reduced graphene oxide (rGO) showed sufficient versatility and processability in mild media, rendering it suitable for integration in these two types of devices. Here, a sound alternative to rGO is provided, namely graphene acetic acid (GAA), whose physico‐chemical features offer specific advantages. In particular, the use of a GAA‐based cathode in a zinc hybrid supercapacitor (Zn‐HSC) delivers state‐of‐the‐art gravimetric capacitance of ≈400 F g−1at a current density of 0.05 A g−1. Conversely, GAA‐based LGT, supported onto Si/SiO2, shows an ambipolar behavior in 0.1 mNaCl, featuring a clear p‐doping quantified by Dirac voltage higher than 100 mV. Such a device is successfully implemented in paper fluidics, thereby demonstrating the feasibility of real‐time monitoring.
Compositional Transformation and Impurity‐Mediated Optical Transitions in Co‐Evaporated Cu2AgBiI6 Thin Films for Photovoltaic Applications
Authors: Putland Benjamin W. J. , Righetto Marcello , Jin Heon , Fischer Markus , Ramadan Alexandra J. , Zaininger Karl‐Augustin , Herz Laura M. , Sansom Harry C. , Snaith Henry J. 
Published: January 2024

AbstractQuaternary copper‐silver‐bismuth‐iodide compounds represent a promising new class of wide‐bandgap (2 eV) semiconductors for photovoltaic and photodetector applications. In this study, vapor phase co‐evaporation is utilized to fabricate Cu2AgBiI6 thin films and photovoltaic devices. The findings show that the properties of vapor‐deposited films are highly dependent upon processing temperature, exhibiting increased pinhole density and transforming into a mixture of quaternary, binary, and metallic phases depending on the post‐deposition annealing temperature. This change in phase is accompanied by an enhancement in photoluminescence (PL) intensity and charge‐carrier lifetime, along with the emergence of an additional absorption peak at high energy (≈3 eV). Generally, increased PL is a desirable property for a solar absorber material, but this change in PL is ascribed to the formation of CuI impurity domains, whose defect‐mediated optical transition dominates the emission properties of the thin film. Via optical pump terahertz probe spectroscopy, it is revealed that CuI impurities hinder charge‐carrier transport in Cu2AgBiI6 thin films. It is also revealed that the predominant performance limitation in Cu2AgBiI6 materials is the short electron‐diffusion length. Overall, the findings pave the way for potential solutions to critical issues in copper‐silver‐bismuth‐iodide materials and indicate strategies to develop environmentally compatible wide‐bandgap semiconductors.
Defective ZnO Nanoplates Supported AuPd Nanoparticles for Efficient Photocatalytic Methane Oxidation to Oxygenates
Authors: Chen Fan , Zhou Huanyu , Liu Dandan , Qin Xin , Jing Yangchi , Chen Lingying , Shi Rui , Liu Yana , Zhang Jiguang , Zhu Yunfeng , Wang Jun 
Published: January 2024

AbstractDirect photocatalytic methane oxidation into value‐added oxygenates under mild conditions enables the sustainable chemical production but suffers from the lack of active photocatalysts and the overoxidation issue. Herein, defective ZnO nanoplates supported AuPd nanoparticles for efficient methane oxidation with O2 as the oxidant at room temperature are reported. A maximum liquid oxygenates productivity of 152.2 mm g−1 h−1 and a selectivity of 86.7%, more than half of which is CH3OH, are achieved over the optimized AuPd/ZnO photocatalyst, resulting in a 16.5% apparent quantum efficiency at 380 nm. The superior photocatalytic performance is benefited from the synergistic effect between defective ZnO substrate and AuPd cocatalyst, wherein the former facilitates CH4 adsorption, and the latter promotes light absorption, charge separation, as well as O2 activation into the reactive oxygen species. This work provides new guidance for regulating the activity and selectivity of the photocatalyst toward methane oxidation.
Trends in sustainability claims and labels for newly introduced food products across selected European countries
Authors: Nes Kjersti , Antonioli Federico , Ciaian Pavel 
Published: January 2024

AbstractThe European Union (EU) farm‐to‐fork strategy aims to empower consumers to make sustainable food choices, among others, through harmonizing voluntary green claims and labels and potentially introducing a common sustainable claims and labels framework for food products. The literature on the current use of sustainability claims and labels (SCLs) in the EU market is scarce. This paper analyzes the trend developments of SCLs in product launches by food companies across different product groups and countries. The analyses are based on Mintel Global New Product Database on newly introduced products with SCLs, covering 24 food product categories and 19 European countries over the 2005–2021 period. The results show that, on aggregate, across all covered countries and products, the share of product launches with SCLs increased by 2.83% annually from 2005 to 2021. This trend varies greatly among countries, product categories and SCL types. Further, the results show that products covering environmental only SCLs make the highest contribution to the overall sustainability trend (68.2%), followed by products with a combination of both environmental and social SCLs (27.5%), whereas only social SCLs have a minor representation (4.2%). [EconLit Citations: Q18, Q01].
Effects of Deuterium Isotopes on Pt(II) Complexes and Their Impact on Organic NIR Emitters
Authors: Wang Sheng‐Fu , Zhou Dong‐Ying , Kuo Kai‐Hua , Wang Chih‐Hsing , Hung Chieh‐Ming , Yan Jie , Liao Liang‐Sheng , Hung Wen‐Yi , Chi Yun , Chou Pi‐Tai 
Published: January 2024

AbstractInsight into effect of deuterium isotopes on organic near‐IR (NIR) emitters was explored by the use of self‐assembled Pt(II) complexes H‐3‐f and HPh‐3‐f, and their deuterated analogues D‐3‐f and DPh‐3‐f, respectively (Scheme 2). In vacuum deposited thin film, albeit having nearly identical emission spectral feature maximized at ~810 nm, H‐3‐f and D‐3‐f exhibit remarkable difference in photoluminescence quantum yield (PLQY) of 29 % and 50 %, respectively. Distinction in PLQY is also observed for HPh‐3‐f (800 nm, 50 %) and DPh‐3‐f (798 nm, 67 %). We then elucidated the theoretical differences in the impact on near‐infrared (NIR) luminescence between Pt(II) complexes and organic small molecules upon deuteration. The results establish a general guideline for the deuteration on NIR emission efficiency. From a perspective of practical application, NIR OLEDs based on D‐3‐f and DPh‐3‐f emitters attain EQEmax of 15.5 % (radiance 31,287 mW Sr−1 m−2) and 16.6 % (radiance of 32,279 mW Sr−1 m−2) at 764 nm and 796 nm, respectively, both of which set new records for NIR OLEDs of >750 nm.
π‐Extended Diaza[7]helicenes with Dual Negatively Curved Heptagons: Extensive Synthesis and Spontaneous Resolution into Strippable Homochiral Lamellae with Helical Symmetry
Authors: Gan Fuwei , Zhang Guoli , Liang Juncong , Shen Chengshuo , Qiu Huibin 
Published: January 2024

AbstractWe report a unique category of π‐extended diaza[7]helicenes with double negative curvatures. This is achieved by two‐fold regioselective heptagonal cyclization of the oligoarylene‐carbazole precursors through either intramolecular C−H arylation or Scholl reaction. The fusion of two heptagonal rings in the helical skeleton dramatically increases the intramolecular strain and forces the two terminal carbazole moieties to stack in a compressed fashion. The presence of the deformable negatively curved heptagonal rings endows the resulting diaza[7]helicenes with dynamic chiral skeletons, aggregation‐induced emission feature and relatively low racemization barrier of ca. 25.6 kcal mol−1. Further π‐extension on the carbazole moieties subsequently leads to a more sophisticated C2‐symmetric homochiral triple helicene. Notably, these π‐extended diaza[7]helicenes show structure‐dependent stacking upon crystallization, switching from heterochiral packing to intra‐layer homochiral stacking. Interestingly, the C2‐symmetric triple helicene molecules spontaneously resolve into a homochiral lamellar structure with 31 helix symmetry. Upon ultrasonication in a nonsolvent, the crystals can be readily exfoliated into large‐area ultrathin nanosheets with height of ca. 4.4 nm corresponding to two layers of stacked triple helicene molecules and relatively thicker nanosheets constituted by even‐numbered molecular lamellae. Moreover, regular hexagonal thin platelets with size larger than 30 μm can be readily fabricated by flash aggregation.
Template‐Directed Synthesis of Strained meso‐meso‐Linked Porphyrin Nanorings
Authors: Van Raden Jeff M. , Deng Jie‐Ren , Gotfredsen Henrik , Hergenhahn Janko , Clarke Michael , Edmondson Matthew , Hart Jack , O'Shea James N. , Duarte Fernanda , Saywell Alex , Anderson Harry L. 
Published: January 2024

AbstractStrained macrocycles display interesting properties, such as conformational rigidity, often resulting in enhanced π‐conjugation or enhanced affinity for non‐covalent guest binding, yet they can be difficult to synthesize. Here we use computational modeling to design a template to direct the formation of an 18‐porphyrin nanoring with direct meso‐meso bonds between the porphyrin units. Coupling of a linear 18‐porphyrin oligomer in the presence of this template gives the target nanoring, together with an unexpected 36‐porphyrin ring by‐product. Scanning tunneling microscopy (STM) revealed the elliptical conformations and flexibility of these nanorings on a Au(111) surface.