bluuebunny/crossref_metadata_2025_split huggingface dataset:
Giant Second‐Order Nonlinearity and Anisotropy of Large‐Sized Few‐Layer SnS with Ferroelectric Stacking
Authors: Moqbel Redhwan , Nanae Ryo , Kitamura Satsuki , Lee Ming‐Hao , Lan Yann‐Wen , Lee Chi‐Cheng , Nagashio Kosuke , Lin Kung‐Hsuan 
Published: April 2024

AbstractThe giant second‐order nonlinearity of SnS with ferroelectric stacking is reported. Based on theoretical calculations, the susceptibility of second harmonic generation (SHG) from SnS with ferroelectric stacking is up to 1354 pm V−1, which is three orders of magnitude higher than the values of traditional nonlinear crystals such as BBO and KTP. The SHG from ferroelectric SnS few layers is experimentally measured and its intensity is found to be 131 times larger than that of a MoS2 monolayer under the same experimental conditions, with a photon energy of 1.55 eV. The SHG susceptibility is determined to be on the order of 100 pm V−1. Numerous SnS flakes are systematically investigated using polarization‐resolved SHG. Micrometer‐sized flakes with a single domain are found, and their SHG anisotropic patterns fit well with the theoretical calculations derived from first‐principles methods. The variation in SHG anisotropic patterns, attributed to SHG interference from multiple domains, is investigated both theoretically and experimentally. Additionally, the impact of stacking disorder on the SHG anisotropic pattern is explored. It is demonstrated that polarization‐resolved SHG microscopy is a valuable tool for identifying domains in SnS flakes and examining stacking disorder.
Directed Chiral Self‐Assembly of Purely Organic Phosphors for Room‐Temperature Circularly Polarized Phosphorescence
Authors: Heo Jung‐Moo , Kim John , Hasan Md Ikramul , Woo Hochul , Lahann Joerg , Kim Jinsang 
Published: April 2024

AbstractCircularly polarized phosphorescence (CPP) is increasingly recognized in materials science for its unique applications in optoelectronic devices, chiral recognition, and bioimaging. This study underscores a novel directed chiral self‐assembly strategy of purely organic phosphors into supramolecular nanostructures to achieve bright room‐temperature circularly polarized phosphorescence (RT‐CPP). RT‐CPP molecules are built on an aromatic carbonyl structure having also Br to mix (n,π*) and (π,π*) characters and to enable the heavy atom effect. Side chains are rationally designed to have strong hydrogen bonding, van der Waals interactions, and a chiral center for directed chiral self‐assembly into supramolecular nanostructures. The tightly packed resulting supramolecular nanostructures also impower efficient suppression of molecular motions, thereby minimizing non‐radiative decay and facilitating bright CPP emission at room temperature. The developed self‐assembled supramolecular structures exhibit RT‐CPP with the dissymmetry factor (glum) of ≈10−3, a high phosphorescence quantum yield of 4.1%, and a rapid triplet decay time of 180 microseconds. The presented molecular design principle enabling RT‐CPP from purely organic phosphors may pave the way for novel photonic materials.
A Mild Metal‐Free Approach for the Direct Synthesis of Carbamoyl Azides from Carboxylic Acid Redox Active Esters
Authors: Qiu Yan‐Hua , Zhu Yuping , Rao Ming‐Hua , Huang Chang‐Qi , Huang Zi‐Ying , Chen Zhengwang , Zhu Jinbin , Yu Daohong 
Published: April 2024

AbstractCarbamoyl azide is a pivotal compound used in the transformation into urea and amines, as well as in nitrene insertion reactions. In this study, we present a pioneering method for synthesizing carbamoyl azide directly from acid redox active esters without the use of metals or oxidants. This approach demonstrates tolerance for various functional groups, enhancing its applicability. Furthermore, this technique facilitates late‐stage modifications of natural products and pharmaceuticals, thereby accelerating the development and identification of novel drug candidates.
Copper‐Catalyzed Alkenylation and Alkenyloxylation with‐Alkenyl(phenyl)iodonium Salts
Authors: Song Zhao‐Xin , Yang Meng‐Wei , Wu Teng‐Teng , Xu Yun‐He 
Published: April 2024

AbstractA Cu‐catalyzed vinylation method for alkenyl ethers has been developed. In this strategy, both chain and cyclic alkenyl ether substrates were applicable, and the target products were obtained in up to 95% yields and with the E/Z selectivities of >98:2. Furthermore, we have successfully applied this method to directly vinylate the C‐2 position of protected glucals, offering a valuable tool for their functionalization. Moreover, through the utilization of alkenyl alcohols as substrates, we accomplished a 1,2‐alkenyloxylation of alkenyl double bond, enabling the synthesis of functionalized cyclic ether compounds with five or six‐membered rings.
Catalytic Asymmetric Cascade Dearomatization of Indoles via a Photoinduced Pd‐Catalyzed 1,2‐Bisfunctionalization of Butadienes
Authors: Zhan Xiaohang , Nie Zhiwen , Li Na , Zhou Ao , Lv Haotian , Liang Mingrong , Wu Keqin , Cheng Gui‐Juan , Yin Qin 
Published: April 2024

AbstractPhotoinduced Pd‐catalyzed bisfunctionalization of butadienes with a readily available organic halide and a nucleophile represents an emerging and attractive method to assemble versatile alkenes bearing various functional groups at the allylic position. However, enantiocontrol and/or diastereocontrol in the C−C or C−X bond‐formation step have not been solved due to the open‐shell process. Herein, we present a cascade asymmetric dearomatization reaction of indoles via photoexcited Pd‐catalyzed 1,2‐biscarbonfunctionalization of 1,3‐butadienes, wherein asymmetric control on both the nucleophile and electrophile part is achieved for the first time in photoinduced bisfunctionalization of butadienes. This method delivers structurally novel chiral spiroindolenines bearing two contiguous stereogenic centers with high diastereomeric ratios (up to >20 : 1 dr) and good to excellent enantiomeric ratios (up to 97 : 3 er). Experimental and computational studies of the mechanism have confirmed a radical pathway involving excited‐state palladium catalysis. The alignment and non‐covalent interactions between the substrate and the catalyst were found to be essential for stereocontrol.
Controlled Biocatalytic Synthesis of a Metal Nanoparticle‐Enzyme Hybrid: Demonstration for Catalytic H2‐driven NADH Recycling
Authors: Browne Lucy B. F. , Sudmeier Tim , Landis Maya A. , Allen Christopher S. , Vincent Kylie A. 
Published: April 2024

AbstractHere we demonstrate the preparation of enzyme‐metal biohybrids of NAD+ reductase with biocatalytically‐synthesised small gold nanoparticles (NPs, <10 nm) and core‐shell gold‐platinum NPs for tandem catalysis. Despite the variety of methods available for NP synthesis, there remains a need for more sustainable strategies which also give precise control over the shape and size of the metal NPs for applications in catalysis, biomedical devices, and electronics. We demonstrate facile biosynthesis of spherical, highly uniform, gold NPs under mild conditions using an isolated enzyme moiety, an NAD+ reductase, to reduce metal salts while oxidising a nicotinamide‐containing cofactor. By subsequently introducing platinum salts, we show that core‐shell Au@Pt NPs can then be formed. Catalytic function of these enzyme‐Au@Pt NP hybrids was demonstrated for H2‐driven NADH recycling to support enantioselective ketone reduction by an NADH‐dependent alcohol dehydrogenase.
Bionic lotus‐leaf‐structured fluorine‐free polyurethane by combining electrospinning and electro‐spraying for waterproof and breathable textiles
Authors: Zheng Haimin , Li Fang , Chen Dandan , Nie Gaowei , Yu Bo , Chen Xiaoxiao , Guo Hao , Luo Zhouai , Cheng Zhikang , He Jianxin 
Published: April 2024

AbstractDeveloping environmentally friendly and high‐performing viable waterproof and breathable membranes (WBMs) is critical but significantly challenging. Herein, we combine electrospinning and electro‐spraying methods. First, elastic thermoplastic polyurethane (TPU) is used as the polymer, and poly(methylhydrosiloxane) (PMHS) with low surface energy is introduced to prepare TPU/PMHS fiber‐based membranes by electrospinning. Electro‐spraying is performed using a dilute solution of TPU/PMHS/SiO2, with fluorine‐free hydrophobic SiO2 nanoparticles introduced to facilitate the construction of a rough lotus‐leaf‐like surface structure, ultimately obtaining TPU/PMHS/SiO2 WBMs with bead‐on‐string fiber binary structures and a strong water repellency. The results indicate that the TPU/PMHS/SiO2 WBMs comprise a three‐dimensional porous structure formed by randomly arranged fibers and a lotus biomimetic structure consisting of bead‐like fibers, providing the membrane with excellent mechanical properties and waterproof breathability, including a tensile strength of 15.8 MPa, static water pressure of 33 kPa, water vapor transmission rate of 5169 g m−2 d−1, and contact angle of 142°. Additionally, the fiber membrane exhibits an excellent strain recovery after 1000 cycles of cyclic stretching under 100% strain, verifying the excellent elastic properties of the TPU/PMHS/SiO2 WBMs. This simple preparation process and unique composite structure can facilitate the design and preparation of environmentally friendly, waterproof, and breathable materials.
Fluorescent Labeling of a Target Protein with an Alkyl Diazirine Photocrosslinker Bearing a Cinnamate Moiety
Authors: Nakashima Taikai , Iwanabe Takumi , Tanimoto Hiroki , Tomohiro Takenori 
Published: April 2024

AbstractA novel fluorogenic alkyl diazirine photocrosslinker bearing an o‐hydroxycinnamate moiety has been developed for identification of the targets of bioactive molecules. The o‐hydroxycinnamate moiety can be converted to the corresponding 7‐hydroxycoumarin derivative, which should be created on the interacting site within the photocaptured target protein. The label yield and fluorescence intensity have been immensely improved in comparison with our previous aromatic crosslinkers to facilitate target identification in small quantities.
Cluster analysis of teachers report for identifying symptoms of autism spectrum and/or attention deficit hyperactivity in school population: EPINED study
Authors: Kaur Sharanpreet , Morales‐Hidalgo Paula , Voltas Núria , Canals‐Sans Josefa 
Published: April 2024

AbstractAn early detection of Neurodevelopmental Disorders (NDDs) is crucial for their prognosis; however, the clinical heterogeneity of some disorders, such as autism spectrum disorder (ASD) or attention‐deficit hyperactivity disorder (ADHD) is an obstacle to accurate diagnoses in children. In order to facilitate the screening process, the current study aimed to identify symptom‐based clusters among a community‐based sample of preschool and school‐aged children, using behavioral characteristics reported by teachers. A total of 6894 children were assessed on four key variables: social communication differences, restricted behavior patterns, restless‐impulsiveness, and emotional lability (pre‐schoolers) or inattention and hyperactivity‐impulsivity (school‐aged). From these behavioral profiles, four clusters were identified for each age group. A cluster of ASD + ADHD and others including children with no pathology was clearly identified, whereas two other clusters were characterized by subthreshold ASD and/or ADHD symptoms. In the school‐age children, the presence of ADHD was consistently observed with ASD patterns. In pre‐schoolers, teachers were more proficient at identifying children who received a diagnosis for either ASD and/or ADHD from an early stage. Considering the significance of early detection and intervention of NDDs, teachers' insights are important. Therefore, promptly identifying subthreshold symptoms in children can help to minimize consequences in social and academic functioning.
Artificial intelligence and psychotherapy: A counterpoint
Authors: Richards Derek 
Published: April 2024

AbstractPsychotherapy practice is a human endeavour. Research on the specific and non‐specific factors of treatment has helped crystallise its relevance and clinical impact. The challenges currently faced by the field revolve around ensuring access to evidence‐based treatments and enhancing their effectiveness. Digitally delivered formats of empirically supported treatments increase access while supporting the relevance of the treatment‐specific ingredients and the necessity for human guidance. Excitement surrounds the potential integration of novel artificial intelligence (AI) machine learning methods to advance psychotherapy effectiveness. The abundance of data in digitally delivered formats positions them well to harness the capabilities of AI. Recent work provides proof of concept in areas including detection and diagnosis, predicting outcomes, treatment adherence, remission and relapse. A potential risk emerges when applying machine learning methods, in which an overreliance on AI inferences may overshadow the human aspect of psychotherapy. The contrast is simple: we may over‐invest in the rationality and relevance of our AI inferences, blindly obeying the algorithmic counsel that may lead to unintended consequences, such as oversimplifying human complexity. This would amount to changing psychotherapy from a human‐centric to a techno‐centric endeavour, something we should steadily avoid. This perspective highlights the importance of balancing enthusiasm for AI advancements with a cautious approach. The discussion outlines the risks associated with overdependence on AI and provides reasons to avoid a scenario in which psychotherapy loses its human essence. In conclusion, the perspective suggests avenues for future research to prevent such a transformation and maintain the human‐centric nature of psychotherapy.
Contiguous diastematomyelia with tethered cord, intradural extramedullary dermoid tumor, and lipomyelomeningocele: A unique case of spinal dysraphism
Authors: Ghimire Sagun , Shrestha Shikher , Shrestha Dinuj , Ranabhat Kajan , Bhattarai Suman , Maharjan Ananta , Bhandari Kritick , Chaudhary Prabin 
Published: April 2024

Key Clinical MessageDiastematomyelia, tethered cord, intradural extramedullary dermoid tumor and lipomyelomeningocele such disease entities themselves are rare in their own form and concurrent presentation of all those pathological states in a single individual can be considered one of the rarest forms of spinal dysraphism globally. Moreover for prompt management with optimal prognosis needs refined neurosurgical intervention guided by intraoperative neuromonitoring so as to bring about the best quality of life in the patient.
Complete idiopathic resorption of distobuccal root of a maxillary first molar: A case report
Authors: Li Tianqi , Meng Xiangbo , Zhou Sunxin , Li Shuaichen , Luo Qiang , Zhang Tong 
Published: April 2024

Key Clinical MessageThis case report provides a rare case of idiopathic root resorption in maxillary first molar and suggests the importance of CBCT in the diagnosis and treatment outcome of complex endodontic diseases. Endodontic surgery is an effective method for treating teeth with persistent apical periodontitis.AbstractIdiopathic root resorption is an unexplained root resorption when the patient experiences root resorption without any local or systemic factors. Early diagnosis and appropriate treatment are crucial for long‐term outcomes.
Plasma cell myeloma in a 9‐year‐old male: Case report and literature review
Authors: Ronald Kato , Jacinta Ambaru , Umaru Ssebagala 
Published: April 2024

Key Clinical MessagePlasma cell myeloma is a rare entity in the pediatric population. The peak incidence is in the seventh decade, with less than 2% of cases occurring in patients under the age of 40. It is worth noting that any destructive bony lesion in a child should be investigated.AbstractPlasma cell myeloma (multiple myeloma) is the most common form of plasma cell neoplasm. It is a rare entity in young patients. The peak incidence is in the seventh decade, with less than 2% of cases occurring in patients under the age of 40. A male patient aged 9 years old with a progressive pain in lower back for about 1 month, aggravated by bending, associated with inability to stand upright, no any history of trauma. He complained about left pin‐point chest pain, no any history of febrile illness. MRI showed a mass lesion of the L3 vertebra; CT scan revealed osteolytic lesions in the left T12, S2‐sacral region, and left calvarium. Histology report of L3 lesion revealed cells with an eccentric nucleus, prominent Golgi apparatus and Flow cytometry revealed cells stained positive for CD 138 and CD56 and negative for CD45 expression. In situ hybridization identified k‐light chain band restriction. Bone marrow evaluation was normal. A small serum monoclonal immunoglobin A spike of k‐light chain type was noted. Other tests like complete blood count, lactate dehydrogenase levels, renal functional tests, and B2‐microglobulin were normal. A diagnosis of plasma cell myeloma was made and the patient was started on emergent radiation to L3 lesion due to progressive neurological symptoms followed systemic therapy which resulted int reduction of L3 lesion. Plasma cell myeloma is extremely rare form of liquid tumor in the pediatric population, and it is important for any destructive bony lesion in a child to have appropriate work up.
Classical versus Collective Interactions in Asymmetric Trigonal Bipyramidal Alkaline Metal–Boron Halide Complexes
Authors: Badri Zahra , Foroutan‐Nejad Cina 
Published: April 2024

AbstractCollective interactions are a novel type of chemical bond formed between metals and electron‐rich substituents around an electron‐poor central atom. So far only a limited number of candidates for having collective interactions are reported. In this work, we extend the newly introduced concept of collective bonding to a series of neutral boron complexes with the general formula M2BX3 (M=Li, Na, and K; X=F, Cl, and Br). Our state‐of‐the‐art ab initio computations suggest that these complexes form trigonal bipyramidal structures with a D3h to C3v distortion along the C3 axis of symmetry. The BX3 unit in the complexes distorts from planar to pyramidal akin to a sp3 hybridized atom. Interestingly, the interaction of the metals with the pyramidal side of BX3, where the lone pair in a hypothetical [BX3]2− should be located, is weaker than the interactions of metals with the inverted side, i. e., the middle of three halogen atoms. The origin of this stronger interaction can be explained by the formation of collective interactions between metals and halogen atoms as we explored via energy decomposition within the context of the theory of interacting quantum atoms, IQA.
Determining Structures of Layer‐by‐Layer Spin‐Coated Zinc Dicarboxylate‐Based Metal‐Organic Thin Films
Authors: Fischer Jan C. , Steentjes Robbin , Chen Dong‐Hui , Richards Bryce S. , Zojer Egbert , Wöll Christof , Howard Ian A. 
Published: April 2024

AbstractThin films of crystalline solids with substantial free volume built from organic chromophores and metal secondary building units (SBUs) are promising for engineering new optoelectronic properties through control of interchromophore coupling. Zn‐based SBUs are especially relevant in this case because they avoid quenching the chromophore's luminescence. We find that layer‐by‐layer spin‐coating using Zn acetate dihydrate and benzene‐1,4‐dicarboxylic acid (H2BDC) and biphenyl‐4,4’‐dicarboxylic acid (H2BPDC) linkers readily produces crystalline thin films. However, analysis of the grazing‐incidence wide‐angle X‐ray scattering (GIWAXS) data reveals the structures of these films vary significantly with the linker, and with the metal‐to‐linker molar ratio used for fabrication. Under equimolar conditions, H2BPDC creates a type of structure like that proposed for SURMOF‐2, whereas H2BDC generates a different metal‐hydroxide‐organic framework. Large excess of Zn2+ ions causes the growth of layered zinc hydroxides, irrespective of the linker used. Density functional theory (DFT) calculations provide structural models with minimum total energy that are consistent with the experimentally observed diffractograms. In the broader sense, this work illustrates the importance in this field of careful structure determination, e. g., by utilizing GIWAXS and DFT simulations to determine the structure of the obtained crystalline metal‐organic thin films, such that properties can be rationally engineered and explained.
Thermoelectric Performance of Hybrid Inorganic/Organic Composites Based on PEDOT:PSS/Tin(II) Oxide
Authors: Vázquez‐López Antonio , Maestre David , Cremades Ana 
Published: April 2024

AbstractPEDOT:PSS(poly(3,4‐ethylenedioxylthiophene):poly(styrenesulfonate))‐based composites often exhibit remarkable characteristics regarding high electrical conductivity and great processability, being a suitable candidate for thermoelectric (TE) applications. To increase its performance, PEDOT:PSS is commonly blended with scarce and toxic inorganic compounds based on Se, Te or Bi. In this work we propose the use of one p‐type metal oxide semiconductor (MOs): tin(II) oxide (SnO), motivated by its abundance and low toxicity. Hybrid PEDOT:PSS/SnO composites were obtained by firstly blending Ethylene glycol (EG) with PEDOT:PSS and then by adding p‐type SnO, previously synthesized by a chemical route. The mixture was deposited via spin‐coating onto glass substrates. The Power Factor (PF) of the composites increased by a factor of 300 with the combined EG/SnO composition.
Identifying Exchangeable Protons in a 1D NMR Spectrum by Spatially Selective Exchange‐Editing
Authors: Rotzinger Markus , Schuster Nathalie , Zangger Klaus 
Published: April 2024

AbstractThe front cover artwork is provided by Markus Rotzinger at the University of Graz, Austria. The front cover picture illustrates the way the 1D exchange‐editing NMR method makes exchanging protons visible by sign alteration. The depicted spectrum of D‐glucose shows all exchanging signals inverted, thus allowing a fast qualitative determination, potentially in a single scan. Read the full text of the Research Article at 10.1002/cphc.202300713.
Enhancement of VoWiFi cell capacity using A‐MPDU frame aggregation technique in WiFi 6 considering VBR traffic
Authors: Chinmay Ayes , Kumar Pati Hemanta 
Published: April 2024

SummaryThe rapid growth in wireless communication technology and the proliferation of multimedia applications, specifically Voice over Wireless Fidelity (VoWiFi), necessitate the exploration of innovative techniques for improving network performance and quality‐of‐service (QoS). This research paper presents an innovative approach to enhance VoWiFi cell capacity using aggregate medium access control protocol data unit (A‐MPDU) frame aggregation for variable bit rate (VBR) traffic. In this research article, we investigated the effect that the retransmission of voice packets has on the cell capacity of a wireless local area network (WLAN) standard that provides VoWiFi service while taking into account the A‐MPDU approach. When taking into consideration the constant bit rate (CBR) and VBR traffics, we compared the results obtained using WiFi 6 (i.e., IEEE 802.11ax) with older WLAN standards such as IEEE 802.11b/g/n/ac.
Copper‐Promoted Oxidative Amidation of Imines: A Facile Route to Amides
Authors: Cao Zhonghua , Sheng Da , Zhang Zhiyang , Ren Haitao , Liu Yong , Wu Songhai , Zhang Jiaxiang , Han Xu 
Published: April 2024

AbstractHerein, an environmentally friendly and efficient amidation method of imines by Oxone and CuO has been developed. This facile method shows excellent selectivity without affecting other functional groups such as phenyls, halogens, cyans, esters or heterocycles. This method features a broad substrate scope, mild conditions and high yields (≤90 %), and the yield in the gram scale experiment also reaches up to 81 %. Flonicamid, moclobemide and bupivacaine are also successfully synthesized to demonstrate its potential utilities.