bluuebunny/crossref_metadata_2025 huggingface dataset:
A Selenium‐Containing Polymer Donor Enables 16.9% Efficiency in Non‐Fused Electron Acceptor‐Based Organic Photovoltaic Cells
Authors: Xiao Yang , Yao Huifeng , Wang Jingwen , Zhang Tao , Chen Zhihao , Qiao Jiawei , Yang Ni , Yu Yue , Ren Junzhen , Li Zi , Hao Xiaotao , Hou Jianhui
Published: May 2024

Organic photovoltaic cells (OPVs) based on non‐fused electron acceptors (nfEAs) have exhibited substantial progress in enhancing the power conversion efficiency (PCE). However, controlling the morphology of the donor/acceptor blend remains a significant challenge, making the regulation of film formation kinetics crucial. Here, by designing a new selenium‐containing polymer donor PQSe‐TCl, the pre‐aggregation behavior is modulated and finely tune the resultant morphologies. Compared with its thiophene analogue PBQx‐TCl, PQSe‐TCl exhibits a larger π–π stacking distance and weaker pre‐aggregation performance, leading to a longer film‐formation duration in the fabrication process. Consequently, the PQSe‐TCl:A4T‐16‐based device records an outstanding PCE of 16.9%, which is the highest value for fully nfEA‐based OPVs. This study highlights the importance of regulating the film‐formation kinetics for obtaining high‐efficiency nfEA‐based OPVs.
Surface to Bulk Synergetic Modulation of Nickel‐Rich LiNi0.83Co0.06Mn0.11O2 via a Three‐in‐One Approach for Long‐Cycle Lithium‐Ion Batteries
Authors: Zhang Shuping , Wu Jianyang , Jiang Ning , Sun Hao , Yang Huanfang , Shen Lanyao , Zhou Mingyue , Liu Wen , Zhou Henghui , Zhao Hailei
Published: May 2024

Nickel‐rich cathode materials have gained popularity in the development of lithium‐ion batteries (LIBs) due to their high energy density, which exceeds 250 Wh kg−1. However, the instability of bulk and surface structures has significantly limited their industrial application. In this study, a three‐in‐one approach to synergistically modulate the structure of LiNi0.83Co0.06Mn0.11O2 (NCM83) from surface to bulk by a phytic acid (PA) coating is proposed. This surface treatment leads to the spontaneous formation of an amorphous lithium phosphates coating layer on the outermost surface, a reconstructed NiO layer at the subsurface, and a gradient P doping in the NCM83 bulk. The resulting hierarchical and multifunctional structure provides a facilitated surface Li‐ion conduction, a NiO‐stabilized subsurface with strong resistance toward side reactions between the electrode and electrolyte, a fast Li ion bulk diffusion endowed by the enlarged LiO6 slab due to the P doping, and an enhanced H2−H3 phase transition reversibility. As a result, the PA‐NCM83 sample exhibits excellent capacity retention with 72.4% after 300 cycles at 1 C within 2.8–4.45 V, and 69.8% after 200 cycles at an elevated temperature of 45 °C. This approach provides a facile and efficient method to stabilize Ni‐rich cathode materials for next‐generation high‐energy LIBs.
Unswitched memory B cell deficiency in children with sickle cell disease and response to pneumococcal polysaccharide vaccine
Authors: Tubman Venée N. , Maysonet Daniel , Estrada Norma , Halder Tripti , Ramos Lindsey , Bhamidipati Sameera , Carisey Alexandre F. , Minard Charles G. , Allen Carl E.
Published: May 2024

Early mortality in sickle cell disease (SCD) is attributed to increased infections due to loss of splenic function. Marginal zone B cells are important for initial opsonization of pathogens and can be absent in spleen histopathology in SCD. The frequency of unswitched memory B cells (UMBC), the circulating correlate of marginal zone B cells, reflects the immunologic function of the spleen. We hypothesized that asplenia in SCD is associated with alterations in the peripheral blood lymphocyte population and explored whether UMBC deficiency was associated with a clinical phenotype. We analyzed B cell subsets and clinical history for 238 children with SCD and 63 controls. The median proportion of UMBCs was lower in children with SCD compared with controls (4.7% vs. 6.6%, p < .001). Naïve B cells were higher in SCD compared with controls (80.6 vs. 76.3%, respectively, p = .02). UMBC frequency declined by 3.4% per year increase in age in SCD (95% CI: 2%, 4.7%, p < .001), but not in controls. A majority of children in all cohorts had an IgM concentration in the normal range for age and there were no differences between groups (p = .13). Subjects developed titers adequate for long‐term protection to fewer serotypes in the polysaccharide vaccine than controls (14.7 vs. 19.4, p < .001). In this cohort, bacteremia was rare and specific clinical complications were not associated with UMBC proportion. In summary, UMBC deficiency occurs in SCD and is associated with age. Future studies should investigate B cell subsets prospectively and identify the mechanism of B cell loss in the spleen.
Giant ab‐Plane Birefringence in Quasi‐1D Fibrous Red Phosphorus
Authors: Chen Wujia , Zhang Bowen , Tao Kezheng , Li Qiang , Sun Jia‐Lin , Yan Qingfeng
Published: May 2024

Quasi‐one‐dimensional (quasi‐1D) van der Waals crystal fibrous red phosphorus (RP) exhibits pronounced in‐plane optical anisotropy, positioning it as a potential candidate for polarization‐related micro‐nano devices. Unfortunately, a comprehensive investigation into the complex refractive index of fibrous RP and the structure–activity relationship connecting the distinctive quasi‐1D structure with optical anisotropy is currently deficient. Herein, we have collectively determined the complex refractive index of the fibrous RP flakes within the ab‐plane through Kramers–Kronig (KK) analysis and theoretical calculation. Notably, the maximum birefringence of fibrous RP reaches 0.642@475 nm with an absolute extinction coefficient of only 0.08, superior to the reported traditional optical crystals and the emerging low‐dimensional materials as well. The remarkable birefringence can be attributed to the synergistic influence of the large electronic dipole polarizability, anisotropic electron density distribution and the distortion of stereochemically active lone pair (SCALP). This work demonstrates the potential of fibrous RP for polarization‐sensitive devices, illuminating possibilities to exploit novel giant birefringent crystals based on the structure–activity relationship.
Tuning Ion Mobility in Lithium Argyrodite Solid Electrolytes via Entropy Engineering
Authors: Lin Jing , Schaller Mareen , Indris Sylvio , Baran Volodymyr , Gautam Ajay , Janek Jürgen , Kondrakov Aleksandr , Brezesinski Torsten , Strauss Florian
Published: May 2024

The development of improved solid electrolytes (SEs) plays a crucial role in the advancement of bulk‐type solid‐state battery (SSB) technologies. In recent years, multicomponent or high‐entropy SEs are gaining increased attention for their advantageous charge‐transport and (electro)chemical properties. However, a comprehensive understanding of how configurational entropy affects ionic conductivity is largely lacking. Herein we investigate a series of multication‐substituted lithium argyrodites with the general formula Li6+x[M1aM2bM3cM4d]S5I, with M being P, Si, Ge, and Sb. Structure‐property relationships related to ion mobility are probed using a combination of diffraction techniques, solid‐state nuclear magnetic resonance spectroscopy, and charge‐transport measurements. We present, to the best of our knowledge, the first experimental evidence of a direct correlation between occupational disorder in the cationic host lattice and lithium transport. By controlling the configurational entropy through compositional design, high bulk ionic conductivities up to 18 mS cm−1 at room temperature are achieved for optimized lithium argyrodites. Our results indicate the possibility of improving ionic conductivity in ceramic ion conductors via entropy engineering, overcoming compositional limitations for the design of advanced electrolytes and opening up new avenues in the field.
Sono‐Triggered Cascade Lactate Depletion by Semiconducting Polymer Nanoreactors for Cuproptosis‐Immunotherapy of Pancreatic Cancer
Authors: Yu Ningyue , Zhou Jianhui , Ding Mengbin , Li Meng , Peng Shaojun , Li Jingchao
Published: May 2024

The high level of lactate in tumor microenvironment not only promotes tumor development and metastasis, but also induces immune escape, which often leads to failures of various tumor therapy strategies. We here report a sono‐triggered cascade lactate depletion strategy by using semiconducting polymer nanoreactors (SPNLCu) for cancer cuproptosis‐immunotherapy. The SPNLCu mainly contain a semiconducting polymer as sonosensitizer, lactate oxidase (LOx) conjugated via a reactive oxygen species (ROS)‐cleavable linker and chelated Cu2+. Upon ultrasound (US) irradiation, the semiconducting polymer generates singlet oxygen (1O2) to cut ROS‐cleavable linker to allow the release of LOx that catalyzes lactate depletion to produce hydrogen peroxide (H2O2). The Cu2+ will be reduced to Cu+ in tumor microenvironment, which reacts with the produced H2O2 to obtain hydroxyl radical (⋅OH) that further improves LOx release via destroying ROS‐cleavable linkers. As such, sono‐triggered cascade release of LOx achieves effective lactate depletion, thus relieving immunosuppressive roles of lactate. Moreover, the toxic Cu+ induces cuproptosis to cause immunogenic cell death (ICD) for activating antitumor immunological effect. SPNLCu are used to treat both subcutaneous and deep‐tissue orthotopic pancreatic cancer with observably enhanced efficacy in restricting the tumor growths. This study thus provides a precise and effective lactate depletion tactic for cancer therapy.
Regulating Spin Density using TEMPOL Molecules for Enhanced CO2‐to‐Ethylene Conversion by HKUST‐1 Framework Derived Electrocatalysts
Authors: Yin Baipeng , Wang Can , Xie Shijie , Gu Jianmin , Sheng Hua , Wang De‐Xian , Yao Jiannian , Zhang Chuang
Published: May 2024

The selectivity of multicarbon products in the CO2 reduction reaction (CO2RR) depends on the spin alignment of neighboring active sites, which requires a spin catalyst that facilitates electron transfer with antiparallel spins for enhanced C−C coupling. Here, we design a radical‐contained spin catalyst (TEMPOL@HKUST‐1) to enhance CO2‐to‐ethylene conversion, in which spin‐disordered (SDO) and spin‐ordered (SO) phases co‐exist to construct an asymmetric spin configuration of neighboring active sites. The replacement of axially coordinated H2O molecules with TEMPOL radicals introduces spin‐spin interactions among the Cu(II) centers to form localized SO phases within the original H2O‐mediated SDO phases. Therefore, TEMPOL@HKUST‐1 derived catalyst exhibited an approximately two‐fold enhancement in ethylene selectivity during the CO2RR at −1.8 V versus Ag/AgCl compared to pristine HKUST‐1. In situ ATR‐SEIRAS spectra indicate that the spin configuration at asymmetric SO/SDO sites significantly reduces the kinetic barrier for *CO intermediate dimerization toward the ethylene product. The performance of the spin catalyst is further improved by spin alignment under a magnetic field, resulting in a maximum ethylene selectivity of more than 50 %. The exploration of the spin‐polarized kinetics of the CO2RR provides a promising path for the development of novel spin electrocatalysts with superior performance.
Revealing Hydrogen Bond Effect in Rechargeable Aqueous Zinc‐Organic Batteries
Authors: Guo Jun , Du Jia‐Yi , Liu Wan‐Qiang , Huang Gang , Zhang Xin‐Bo
Published: May 2024

The surrounding hydrogen bond (H‐bond) interaction around the active sites plays indispensable functions in enabling the organic electrode materials (OEMs) to fulfill their roles as ion reservoirs in aqueous zinc‐organic batteries (ZOBs). Despite important, there are still no works could fully shed its real effects light on. Herein, quinone‐based small molecules with a H‐bond evolution model has been rationally selected to disclose the regulation and equilibration of H‐bond interaction between OEMs, and OEM and the electrolyte. It has been found that only a suitable H‐bond interaction could make the OEMs fully liberate their potential performance. Accordingly, the 2,5‐diaminocyclohexa‐2,5‐diene‐1,4‐dione (DABQ) with elaborately designed H‐bond structure exhibits a capacity of 193.3 mAh g−1 at a record‐high mass loading of 66.2 mg cm−2 and 100 % capacity retention after 1500 cycles at 5 A g−1. In addition, the DABQ//Zn battery also possesses air‐rechargeable ability by utilizing the chemistry redox of proton. Our results put forward a specific pathway to precise utilization of H‐bond to liberate the performance of OEMs.
BINOL‐Based Chiral Macrocycles and Cages
Authors: Yu Yabing , Hu Yaning , Ning Chengbing , Shi Wudi , Yang Ao , Zhao Yibo , Cao Zhong‐Yan , Xu Youzhi , Du Pingwu
Published: May 2024

Chirality, a fundamental principle in chemistry, biology, and medicine, is prevalent in nature and in organisms. Chiral molecules, such as DNA, RNA, and proteins, are crucial in biomolecular synthesis, as well as in the development of functional materials. Among these, 1,1′‐binaphthyl‐2,2′‐diol (BINOL) stands out for its stable chiral configuration, versatile functionality, and commercial availability. BINOL is widely employed in asymmetric catalysis and chiral materials. This review mainly focuses on recent research over the past five years concerning the use of BINOL derivatives for constructing chiral macrocycles and cages. Their contributions to chiral luminescence, enantiomeric separation, transmembrane transport, and asymmetric catalysis were examined.
Selective Photoreforming of Waste Plastics into Diesel Olefins via Single Reactive Oxygen Species
Authors: Yue Shuai , Zhao Zhiyong , Zhang Tao , Li Fei , Liu Kewang , Zhan Sihui
Published: May 2024

The accumulation of plastic waste poses a pressing environmental challenge. Catalytic conversion stands out as an ideal approach for plastics upcycling, particularly through solar‐driven plastics photoreforming. However, due to the common effects of multiple reactive oxygen species (ROS), selectively generating high‐value chemicals becomes challenging. In this study, we developed a universal strategy to achieve >85 % selective production of diesel olefins (C15–C28) from polyolefin waste plastics via single ROS. Using tetrakis (4‐carboxyphenyl) porphyrin supramolecular (TCPP) with different central metals as an example to regulate single ROS generation, results show Ni‐TCPP facilitates triplet exciton production, yielding 1O2, while Zn‐TCPP generates ⋅O2− due to its strong built‐in electric field (IEF). 1O2 directly dechlorinates polyvinyl chloride (PVC) due to the electro‐negativity of chlorine atoms and the low dissociation energy of C−Cl bonds, while ⋅O2− promotes direct dehydrogenation of polyethylene (PE) due to the electro‐positivity of hydrogen atoms and the high dissociation energy of C−H bonds. This method is universally applicable to various single ROS systems. Installation experiments further affirm the application potential, achieving the highest diesel olefin production of 76.1 μmol h−1. Such a universally adaptive approach holds promise for addressing the global plastic pollution problem.
One‐pot construction of polydopamine‐based superhydrophobic coating with enhanced chemical stability and anti‐fouling performance
Authors: Xia Gongwei , Xu Xiao , Chen Jianfang , Jiang Ruitao , Zheng Hao
Published: May 2024

A facile strategy to construct superhydrophobic coatings was carried out by one‐pot process using novel nano zero‐valent iron and hydrogen peroxide as trigger in ethanol and Tris buffer mixed system containing dopamine and 1H,1H,2H,2H‐perfluorodecanethiol (PFDT) for the first time. The polydopamine (PDA) modified by PFDT composite coating can be deposited onto various substrates including glass slides, polyurethane sheets, polytetrafluoroethylene wafers, 304 stainless steel sheets, and polyurethane sponges, revealing excellent hydrophobicity with the water contact angles from 157.1° to 162.2° and the sliding angle lower than 1°. The flourier transformed infrared spectroscopy and x‐ray photoelectron spectroscopy information of the composite coating demonstrated the successful covalent interaction between catechol group in PDA and thiol group of PFDT via Michael addition reaction. As‐prepared PFDT/PDA composite coatings exhibited enhanced chemical stability in highly acidic solutions for 6 days, alkaline aqueous solutions for 5 days, salty solutions (3.5 wt%) for 28 days, and polar organic solvents for 24 h, respectively, as well as resistance to algae adhesion. The excellent corrosion resistance and chemical stability of the composite coating and their simple, time saving and inexpensive construction process are expected to be widely applied in various areas, including marine anti‐corrosion, anti‐fouling, and oil–water separation.
Role of small nucleolar RNAs in alternative splicing of the doublesex gene in the silkworm, Bombyx mori
Authors: Qian Yu‐Xin , Guo Shi‐Gang , Zhao Xu‐Hui , Li Zhong‐Wei , Qiu Reng , Kan Yun‐Chao , Li Dan‐Dan
Published: May 2024

More and more evidence shows that small noncoding RNAs (ncRNAs) play diverse roles in development, stress response and other cellular processes, but functional study of intermediate‐size ncRNAs is still rare. Here, the expression profile of 16 intermediate‐size ncRNAs in ovary and testis of silkworm Bombyx mori were analyzed. Twelve ncRNAs, including 5 small nucleolar RNAs (snoRNAs) and 7 unclassified ncRNAs, accumulated more in the testis than in the ovary of silkworm, especially Bm‐163, Bm‐51 and Bm‐68. Four ncRNAs (including three orphan snoRNAs and one unclassified ncRNA) had higher expression level in the ovary than in the testis, especially Bm‐86. Overexpression of the testis‐enriched snoRNA Bm‐68 in the female led to the accumulation of male‐specific isoform of doublesex (BmdsxM) and increased the expression ratio of BmdsxM: BmdsxF. While overexpression of ovary‐enriched snoRNA Bm‐86 in the male decreased the expression ratio of BmdsxM: BmdsxF, indicating the roles of the two snoRNAs played in the alternative splicing of Bmdsx of silkworm, which will provide new clues for the functional study of snoRNAs in insects.
Sneaked references: Fabricated reference metadata distort citation counts
Authors: Besançon Lonni , Cabanac Guillaume , Labbé Cyril , Magazinov Alexander
Published: May 2024

We report evidence of an undocumented method to manipulate citation counts involving “sneaked” references. Sneaked references are registered as metadata for published scientific articles in which they do not appear. This manipulation exploits trusted relationships between various actors: publishers, the Crossref metadata registration agency, digital libraries, and bibliometric platforms. By collecting metadata from various sources, we show that extra undue references are actually sneaked in at Digital Object Identifier (DOI) registration time, resulting in artificially inflated citation counts. As a case study, focusing on three journals from a given publisher, we identified at least 9% sneaked references () mainly benefiting two authors. Despite not being present in the published articles, these sneaked references exist in metadata registries and inappropriately propagate to bibliometric dashboards. Furthermore, we discovered “lost” references: the studied bibliometric platform failed to index at least 56% () of the references present in the HTML version of the publications. This research led to an investigation by Crossref (confirming our findings) and to subsequent corrective actions. The extent of the distortion—due to sneaked and lost references—in the global literature remains unknown and requires further investigations. Bibliometric platforms producing citation counts should identify, quantify, and correct these flaws to provide accurate data to their patrons and prevent further citation gaming.
Correlation Between Li‐Fe Anti‐Site and Memory Effect of LiFePO4 in Li‐Ion Batteries
Authors: Lu Xingguang , Ren Yuanyuan , Chen Daming , Guo Xiaolong , Li De , Chen Yong
Published: May 2024

In Li‐ion batteries, the origin of memory effect in Al‐doped Li4Ti5O12 has been revealed as the reversible Al‐ion switching between 8a and 16c sites in the spinel structure, but it is still not clear about that for olivine LiFePO4, which is one of the most important cathode materials. In this work, a series of Na‐doped and Ti‐doped LiFePO4 are prepared in a high‐temperature solid‐state method, electrochemically investigated in Li‐ion batteries and characterized by X‐Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR) and Magic‐Angle‐Spinning Nuclear Magnetic Resonance (MAS NMR). Compared with non‐doped LiFePO4, the Ti doping can simultaneously suppress the memory effect and the Li−Fe anti‐site, while they are simultaneously enhanced by the Na doping. Meanwhile, the Ti doping improves the electrochemical performance of LiFePO4, opposite to the Na doping. Accordingly, a schematic diagram of phase transition is proposed to interpret the memory effect of LiFePO4, in which the memory effect is attributed to the defect of Li−Fe anti‐site.
Novel Pyrazole‐Chalcone Hybrids: Synthesis and Computational Insights Against Breast Cancer
Authors: Dabhade Pratap S. , Dabhade Manjushri P. , Rathod Lala S. , Dhawale Sachin A. , More Shweta A. , Chaudhari Somdatta Y. , Mokale Santosh N.
Published: May 2024

More women die of breast cancer than of any other malignancy. The resistance and toxicity of traditional hormone therapy created an urgent need for potential molecules for treating breast cancer effectively. Novel biphenyl‐substituted pyrazole chalcones linked to a pyrrolidine ring were designed by using a hybridization approach. The hybrids were assessed against MCF‐7 and MDA‐MB‐231 cells by NRU assay. Among them, 8 k, 8 d, 8 m, 8 h, and 8 f showed significantly potent IC50 values: 0.17, 5.48, 8.13, 20.51, and 23.61 μM) respectively, on MCF‐7 cells compared to the positive control Raloxifene and Tamoxifen. Furthermore, most active compound 8 k [3‐(3‐(4‐fluorophenyl)‐1‐phenyl‐1H‐pyrazol‐4‐yl)‐1‐(2‐(2‐(pyrrolidin‐1‐yl)‐ethoxy)‐phenyl)‐chalcone] showed cell death induced through apoptosis, cell cycle arrest at the G2/M phase, and demonstrated decrease of ER‐α protein in western blotting study. Docking studies of 8 k and 8 d established adequate interactions with estrogen receptor‐α as required for SERM binding. The active hybrids exhibited good pharmacokinetic properties for oral bioavailability and drug‐likeness. Whereas, RMSD, RMSF, and Rg values from Molecular dynamics studies stipulated stability of the complex formed between compound 8 k and receptor. All of these findings strongly indicate the antiproliferative potential of pyrazole‐chalcone hybrids for the treatment of breast cancer.
Capsaicin reverses cisplatin resistance in tongue squamous cell carcinoma by inhibiting the Warburg effect and facilitating mitochondrial‐dependent apoptosis via the AMPK/AKT/mTOR axis
Authors: Liu Xiayang , Li Zhuang , Zhao Qiwei , Zhou Xinyue , Wang Yu , Zhao Gang , Guo Xiaohong
Published: May 2024

Cisplatin is commonly used for the chemotherapy of tongue squamous cell carcinoma (TSCC); however, adverse side effects and drug resistance impact its therapeutic efficacy. Capsaicin is an active ingredient in chili peppers that exerts antitumor effects, whether it exerts antitumor effects on cisplatin‐resistant cells remains unknown. Therefore, in this study, we investigated the effect of capsaicin on cisplatin resistance in TSCC cells and explored the underlying mechanisms. A cisplatin‐resistant TSCC cell line was established by treated with increasing cisplatin concentrations. Combined treatment with cisplatin and capsaicin decreased the glucose consumption and lactate dehydrogenase activity and increased the adenosine triphosphate production both in vitro and in vivo, suggesting the inhibition of the Warburg effect. Moreover, this combined treatment induced cell apoptosis and significantly upregulated the levels of proapoptotic proteins, such as Bax, cleaved caspase‐3, ‐7, and ‐9, and apoptosis‐inducing factor. In contrast, levels of the antiapoptotic protein, Bcl‐2, were downregulated. Additionally, LKB1 and AMPK activities were stimulated, whereas those of AKT and mTOR were suppressed. Notably, AMPK knockdown abolished the inhibitory effects of capsaicin and cisplatin on the AKT/mTOR signaling pathway and Warburg effect. Overall, combined treatment with capsaicin and cisplatin reversed cisplatin resistance by inhibiting the Warburg effect and facilitating mitochondrial‐dependent apoptosis via the AMPK/AKT/mTOR axis. Our findings suggest combination therapy with capsaicin and cisplatin as a potentially novel strategy and highlight capsaicin as a promising adjuvant drug for TSCC treatment.
Homogeneous Iron Catalyzed C−H Amination
Authors: Possenti Dario , Olivo Giorgio
Published: May 2024

Iron‐catalyzed C−H amination is emerging as an attractive and sustainable method to install amine functionalities into organic compounds. Amination of C(sp3)−H bonds is usually mediated by an iron‐nitrene intermediate via a Hydrogen Atom Abstraction/Radical Recombination mechanism reminiscent of biomimetic C−H oxidation. Accordingly, this transformation can be catalyzed by engineered iron enzymes, heme and nonheme iron complexes as well as iron salts, although it is often limited to intramolecular reactions and/or activated positions. Aromatic C(sp2)−H amination is mediated by addition of electrophilic iron nitrenes or protonated N‐radical intermediates (produced with Fe catalysts) to aromatic systems. Again, high selectivity is obtained via (pseudo) intramolecular reactions. From a mechanistic perspective, several iron nitrene intermediates have been isolated and characterized over the years in different ligand scaffolds and iron oxidation states. Structure‐activity correlations have been drawn only in few cases and point to a key role of the spin density on the nitrene ligand and of the iron oxidation state. This review describes the state of the art for homogeneous iron catalyzed C(sp3)−H and C(sp2)−H amination focusing on the last 5 years (2019–2023) from a mechanism‐driven catalyst design perspective.
An Alternative Cascade for the Selective Methylation of Catechols and Tetrahydroisoquinolines by O‐Methyltransferases
Authors: Salinger Matthew T. , Castellano Garrido Daniel , Lamming Eleanor D. , Ward John M. , Moody Thomas S. , Jeffries Jack W. E. , Hailes Helen C.
Published: May 2024

Methyltransferases are gaining traction as a method to achieve greener and regioselective methylations of a wide array of substrates. In this work, a halide methyltransferase biomethylation cascade was successfully adapted with the incorporation of a methionine adenosyltransferase to generate the S‐adenosyl‐L‐methionine (SAM) methylation cofactor in situ from less costly ATP and L‐methionine, instead of directly adding SAM to start the cascade. Furthermore, this cascade was applied to achieve novel catechol and tetrahydroisoquinoline methylations with the O‐methyltransferases RnCOMT, MxSafC and NpN4OMT with high conversions and regioselectivities. In addition, the cascade was successfully trialled with the less toxic methyl group donor, methyl tosylate.
Catalysed Aryl Amine Syntheses via Azides: From Azidation of Aryl Halides to Azide Reduction and Direct Amination
Authors: Roemer Max
Published: May 2024

This review summarises and discusses aryl amine and azide syntheses from aryl halides employing azides. The majority of the reported reactions proceed with copper catalysis or mediation. Often, an aryl azide is formed in the first step, which is then reduced in situ to an aryl amine in a second step. The occurrence of the second step, the reduction, depends on the chosen reaction conditions and the substrates. The formation of only aryl azides through Cu‐mediated C−N bond formations is discussed, followed by mediated and catalytic aryl azide reduction employing different catalytic systems, and azidation with in situ azide reduction to amines, viz. azidation‐amination strategies. The azidation‐amination allows for the synthesis of complex heterocycles in multi‐step one‐pot procedures, of which several are summarised here. Examples of the application of azidation‐amination for synthesising important aryl amines employed in or as biologically active compounds, catalysis and materials science are also summarised. Finally, conducted control reactions have been collected and discussed in combination with mechanistic proposals. This literature survey allows us to pinpoint design criteria for the azide reduction to valuable amines, which includes the choice of reaction conditions such as solvent system and additives, involved metal and promising substrates.
Grain Boundary Defect Engineering in Rutile Iridium Oxide Boosts Efficient and Stable Acidic Water Oxidation
Authors: Zhang Ning , Fan Yingqi , Wang Depeng , Yang Hong , Yu Yang , Liu Jianwei , Zeng Jianrong , Bao Di , Zhong Haixia , Zhang Xinbo
Published: May 2024

Proton exchange membrane water electrolysis (PEMWE) is considered a promising technology for coupling with renewable energy sources to achieve clean hydrogen production. However, constrained by the sluggish kinetics of the anodic oxygen evolution reaction (OER) and the acidic abominable environment render the grand challenges in developing the active and stable OER electrocatalyst, leading to low efficiency of PEMWE. Herein, we develop the rutile‐type IrO2 nanoparticles with abundant grain boundaries and the continuous nanostructure through the joule heating and sacrificial template method. The optimal candidate (350‐IrO2) demonstrates remarkable electrocatalytic activity and stability during the OER, presenting a promising advancement for efficient PEMWE. DFT calculations verified that grain boundaries can modulate the electronic structure of Ir sites and optimize the adsorption of oxygen intermediates, resulting in the accelerated kinetics. 350‐IrO2 affords a rapid OER process with 20 times higher mass activity (0.61 A mgIr−1) than the commercial IrO2 at 1.50 V vs. RHE. Benefiting from the reduced overpotential and the preservation of the stable rutile structure, 350‐IrO2 exhibits the stability of 200 h test at 10 mA cm−2 with only trace decay of 11.8 mV. Moreover, the assembled PEMWE with anode 350‐IrO2 catalyst outputs the current density up to 2 A cm−2 with only 1.84 V applied voltage, long‐term operation for 100 h without obvious performance degradation at 1 A cm−2.
Spectroscopy and Photochemistry of [Al, N, C, O, H]: Connectivity to Aluminium‐Bearing Species in the Universe
Authors: Wang Lina , Jiang Xin , Sun Beibei , Trabelsi Tarek , Francisco Joseph S. , Zeng Xiaoqing , Zhou Mingfei
Published: May 2024

Aluminium is one of the most abundant metals in the universe and impacts the evolution of various astrophysical environments. Currently detected Al‐bearing molecules represent only a small fraction of the aluminium budget, suggesting that aluminium may reside in other species. AlO and AlOH molecules are abundant in the oxygen‐rich supergiant stars such as VY Canis Majoris, a stellar molecular factory with 60+ molecules including the prebiotic NC‐bearing species. Additional Al‐bearing molecules with N, C, O, and H may form in O‐rich environments with radiation‐accelerated chemistry. Here, we present spectroscopic identification of novel aluminium‐bearing molecules composed of [Al, N, C, O, H] and [Al, N, C, O] from the reactions of Al atoms and HNCO in solid argon matrix, which are potential Al‐bearing molecules in space. Photoinduced transformations among six [Al, N, C, O, H] isomers and three [Al, N, C, O] isomers, along with their dissociation reactions forming the known interstellar species, have been disclosed. These results provide new insight into the chemical network of astronomically detected Al‐bearing species in space.
Tetrazole‐Functionalized Organoboranes Exhibiting Dynamic Intramolecular N→B‐Coordination and Cyanide‐Selective Anion Binding
Authors: Schepper Jonas , Orthaber Andreas , Pammer Frank
Published: May 2024

Starting from two different cyano‐functionalized organoboranes, we demonstrate that 1,3‐dipolar [3+2] azide‐nitrile cycloaddition can serve to generate libraries of alkyl‐tetrazole‐functionalized compounds capable of intramolecular N→B‐Lewis adduct formation. Due to the relatively low basicity of tetrazoles, structures can be generated that exhibit weak and labile N→B‐coordination. The reaction furnishes 1‐ and 2‐alkylated regio‐isomers that exhibit different effective Lewis‐acidities at the boron centers, and vary in their optical absorption and fluorescence properties. Indeed, we identified derivatives capable of selectively binding cyanide over fluoride, as confirmed by 11B NMR. This finding demonstrates the potentialities of this synthetic strategy to systematically fine‐tune the properties of lead structures that are of interest as chemical sensors.
Towards sustainable, direct printed, organic transistors with biocompatible copolymer gate dielectrics
Authors: Massey Roslyn , Song Xiaoyu , Ashoori Shiva , Guan Jingwen , Prakash Ravi
Published: May 2024

We have investigated the potential of three dielectric materials to meet the future demands of green dielectrics: Polycaprolactone (PCL) thermoplastic, polyvinyl alcohol (PVA)‐carrageenan (CAR) crosslinked biopolymer, and boron nitride nanotubes (BNNTs) as a nano additive in PVA. Metal–insulator–metal (MIM) capacitors and organic thin film transistors (OTFT) were built with bilayer dielectric stacks of PVA‐CAR, PVA‐PCL, and PVA‐BNNT materials to examine their electrical properties. The PVA‐CAR layer uses a cyclic freeze thaw process to crosslink PVA and CAR for superior mechanical and electrical properties to either material alone. The PVA‐CAR MIM capacitors showed a dielectric constant of 23, which was found to be consistent with the extracted OTFT gate dielectric characteristics. Of the OTFT devices tested, PVA‐CAR OTFT showed highest device currents at low applied biases and produced an ON/OFF ratio of 104–105, both values were highest amongst the tested gate dielectrics. This material is therefore extremely promising for green electronics. The PVA‐PCL OTFT had very low leakage current and beneficial hydrophilic properties with comparable electrical properties to the commonly used organic material polytetrafluoroethylene. PVA‐BNNT MIM capacitors showed a low dielectric constant of 0.7, and the high resistivity makes this a promising material for shielding or substrates in high frequency applications. All three materials have the potential to fulfil different niches in a sustainable electronics future.
Association of transportation noise with cardiovascular diseases
Authors: Shah Badar ud Din , Raj Rohan , Kaur Parvinder , Karim Ali , Bansari Raveena Bai , Mehmoodi Amin , Malik Jahanzeb
Published: May 2024

This comprehensive article delves into the intricate and multifaceted issue of noise pollution, shedding light on its diverse sources, profound health implications, and the economic burden it imposes on societies. Noise pollution is an increasingly prevalent environmental challenge, impacting millions of people worldwide, often without their full awareness of its adverse effects. Drawing from a wealth of scientific research, the article underscores the well‐established links between noise pollution and a spectrum of health issues, including cardiovascular diseases, sleep disturbances, and psychological stress. While exploring the sources and consequences of noise pollution, the article highlights the urgent need for a holistic and collaborative approach to mitigate its impact. This entails a combination of regulatory measures, technological innovations, urban planning strategies, and public education campaigns. It is increasingly evident that the detrimental effects of noise pollution extend beyond physical health, encompassing mental and social well‐being. The article also addresses the synergistic relationship between noise pollution and other environmental stressors, emphasizing the importance of considering noise in conjunction with factors like air pollution and access to green spaces. It examines the potential of green spaces to mitigate the effects of noise pollution and enhance overall health.
Roles of myosin 1e and the actin cytoskeleton in kidney functions and familial kidney disease
Authors: Liu Pei‐Ju , Sayeeda Kazi , Zhuang Cindy , Krendel Mira
Published: May 2024

Mammalian kidneys are responsible for removing metabolic waste and maintaining fluid and electrolyte homeostasis via selective filtration. One of the proteins closely linked to selective renal filtration is myosin 1e (Myo1e), an actin‐dependent molecular motor found in the specialized kidney epithelial cells involved in the assembly and maintenance of the renal filter. Point mutations in the gene encoding Myo1e, MYO1E, have been linked to familial kidney disease, and Myo1e knockout in mice leads to the disruption of selective filtration. In this review, we discuss the role of the actin cytoskeleton in renal filtration, the known and hypothesized functions of Myo1e, and the possible explanations for the impact of MYO1E mutations on renal function.
Statin use and risks of breast cancer recurrence and mortality
Authors: Guo Hanbing , Malone Kathleen E. , Heckbert Susan R. , Li Christopher I.
Published: May 2024

Background

Preclinical evidence suggests improved breast cancer survival associated with statin use, but findings from observational studies are conflicting and remain inconclusive. The objective of this study was to assess the association between statin use after cancer diagnosis and cancer outcomes among breast cancer patients.

Methods

In this retrospective cohort study, 38,858 women aged ≥66 years who were diagnosed with localized and regional stage breast cancer from 2008 through 2017 were identified from the linked Surveillance, Epidemiology, and End Results Medicare database. Statin use was ascertained from Medicare Part D pharmacy claims data. Multivariable Cox proportional hazards models were used to estimate hazard ratios (HRs) and 95% confidence intervals (CIs) for the association between post‐diagnosis statin use and risks of breast cancer recurrence and breast cancer–specific mortality.

Results

Over a median follow‐up of 2.9 years for recurrence and 3.7 years for mortality, 1446 women experienced a recurrence, and 2215 died from breast cancer. The mean duration of post‐diagnosis statin use was 2.2 years. Statin use post‐diagnosis was not associated with recurrence risk (HR, 1.05; 95% CI, 0.91–1.21), but was associated with a reduced risk of cancer‐specific mortality (HR, 0.85; 95% CI, 0.75–0.96). The reduction was more pronounced in women with hormone receptor–positive/human epidermal growth factor receptor 2–negative breast cancer (HR, 0.71; 95% CI, 0.57–0.88).

Conclusions

These findings suggest that post‐diagnosis statin use is associated with improved cancer‐specific survival in women with breast cancer and should be confirmed in randomized trials of statin therapy in breast cancer patients.
The Calogero–Moser derivative nonlinear Schrödinger equation
Authors: Gérard Patrick , Lenzmann Enno
Published: May 2024

We study the Calogero–Moser derivative nonlinear Schrödinger NLS equation
posed on the Hardy–Sobolev space with suitable . By using a Lax pair structure for this ‐critical equation, we prove global well‐posedness for and initial data with sub‐critical or critical ‐mass . Moreover, we prove uniqueness of ground states and also classify all traveling solitary waves. Finally, we study in detail the class of multi‐soliton solutions and we prove that they exhibit energy cascades in the following strong sense such that as for every .
Understanding the Mechanochemistry of Mechano‐Radicals in Self‐Growth Materials by Single‐Molecule Force Spectroscopy
Authors: Liu Jing , Yang Jiahui , Xue Bin , Cao Yi , Cheng Wei , Li Yiran
Published: May 2024

Recent research on mechano‐radicals has provided valuable insights into self‐growth and adaptive responsive materials. Typically, mechanophores must remain inert in the absence of force but respond quickly to external tension before other linkages within the polymer network. Azo compounds exhibit promising combinations of mechanical stability and force‐triggered reactivity, making them widely used as mechano‐radicals in force‐responsive materials. However, the activation conditions and behavior of azo compounds have yet to be quantitatively explored. In this study, we investigated the mechanical strength of three azo compounds using single‐molecule force spectroscopy. Our results revealed that these compounds exhibit rupture forces ranging from ~500 to 1000 pN, at a loading rate of 3×104 pN s−1. Importantly, these mechanophores demonstrate distinct kinetic properties. Their unique mechanical attributes enable azo bond scission and free radical generation before causing major polymer backbone damage of entire material during polymer network deformation. This fundamental understanding of mechanophores holds significant promise for the development of self‐growth materials and their related applications.
Characterizing the Behavior of Water Interacting with a Nano‐Pore Material: A Structural Investigation in Native Environment Using Magnetic Resonance Approaches
Authors: Ye Kai , Chin Sze Yuet , Xi Nicole Lin , Sharma Bhargy , Lu Yunpeng , Xue Kai
Published: May 2024

The study of fluid absorption, particularly that of water, into nanoporous materials has garnered increasing attention in the last decades across a broad range of disciplines. However, most investigation approaches to probe such behaviors are limited by characterization conditions and may lead to misinterpretations. In this study, a combined MRI and MAS NMR method was used to study a nanoporous silica glass to acquire information about its structural framework and interactions with confined water in a native humid environment. Specifically, MRI was used for a quantitative analysis of water extent. While MAS NMR techniques provided structural information of silicate materials, including interactive surface area and framework packing. Analysis of water spin‐spin relaxation times (T2) suggested differences in water confinement within the characterized framework. Subsequent unsuccessful delivery of paramagnetic molecule into the pores enabled a quantitative assessment of the dimensions that “bottleneck” the pores. Finally, pore sizes were derived from the paramagnetic molecular size, density function theory (DFT) simulation and characterizations on standard samples. Our result matches with Brunauer‐Emmett‐Teller (BET) analysis that the pore size is less than 1.3 nm. The use of a paramagnetic probe for pore size determination introduces a new approach of characterization in the liquid phase, offering an alternative to the conventional BET analysis that uses gas molecule as probes.
The Chemical Bond at the Bottom of the Periodic Table: The Case of the Heavy Astatine and the Super‐Heavy Tennessine
Authors: Gamboni Giulia , Belpassi Leonardo , Belanzoni Paola
Published: May 2024

In this work, we study the chemical bond in molecules containing heavy and super‐heavy elements according to the current state‐of‐the‐art bonding models. An Energy Decomposition Analysis in combination with Natural Orbital for Chemical Valence (EDA‐NOCV) within the relativistic four‐component Dirac‐Kohn‐Sham (DKS) framework is employed, which allows to successfully include the spin‐orbit coupling (SOC) effects on the chemical bond description. Simple halogen‐bonded adducts ClX⋯L (X=At, Ts; L=NH3, Br−, H2O, CO) of astatine and tennessine have been selected to assess a trend on descending along a group, while modulating the ClX⋯L bond features through the different electronic nature of the ligand L. Interesting effects caused by SOC have been revealed: i) a huge increase of the ClTs dipole moment (which is almost twice as that of ClAt), ii) a lowering of the ClX⋯L bonding energy arising from different contributions to the ClX…L interaction energy strongly depending on the nature of L, iii) a quenching of one of the π back‐donation components to the bond. In the ClTs(CO) adduct, the back‐donation from ClTs to CO becomes the most important component. The analysis of the electronic structure of the ClX dimers allows for a clear interpretation of the SOC effects in these systems.
The Effects of Patient Preference on Clinical Outcome, Satisfaction and Adherence Within the Treatment of Anxiety and Depression: A Meta‐Analysis
Authors: Eigenhuis Eline , van Buuren Vanessa E. M. , Boeschoten Rosa E. , Muntingh Anna D. T. , Batelaan Neeltje M. , van Oppen Patricia
Published: May 2024

Background

Taking patient preference into consideration has received increased attention in the last decades. We conducted a meta‐analysis to estimate the effects of patient preference on clinical outcome, satisfaction and adherence regarding treatment of depression and anxiety.

Methods

Pubmed, Embase, PsycINFO and Scopus were searched for (cluster) randomized controlled trials. Twenty‐six randomized controlled clinical trials were included, comprising 3670 participants, examining the effect of patient preference regarding treatment of anxiety and depression on clinical outcome, satisfaction and/or adherence.

Results

No effect of patient preference was found on clinical outcome [d = 0.06, 95% CI = (−0.03, 0.15), p = 0.16, n = 23 studies]. A small effect of patient preference was found on treatment satisfaction [d = 0.33, 95% CI = (0.08, 0.59), p = 0.01, n = 6 studies] and on treatment adherence [OR = 1.55, 95% CI = (1.28, 1.87), p < 0.001, n = 22 studies].

Limitations

Patient preference is a heterogeneous concept, future studies should strive to equalize operationalization of preference. Subgroup analyses within this study should be interpreted with caution because the amount of studies per analysed subgroup was generally low. Most studies included in this meta‐analysis focused on patients with depression. The small number of studies (n = 6) on satisfaction, prevents us from drawing firm conclusions.

Conclusions

While this meta‐analysis did not find a positive effect of considering patient preference on clinical outcome, it was associated with slightly better treatment satisfaction and adherence. Accommodating preference of patients with anxiety and depression can improve treatment.

Trial Registration

PROSPERO: CRD42020172556
Assessment of Voice Content for Voice Hearers: Psychometric Evaluation of the Perth Voice Content Questionnaire
Authors: Salt Erica , Skeffington Petra , Reddyhough Caitlin , Paulik Georgie
Published: May 2024

The experience of hearing voices is common to an estimated 7% of the general population, with the presence of negative content being the best predictor of whether individuals will require clinical support. Whilst largely neglected in the literature to date, there are calls to consider the significance of voice content for reducing voice‐related distress. However, no quantitative and comprehensive measure of voice content with suitability for research and clinical use exists. This pilot study aimed to demonstrate preliminary psychometric properties of a newly developed measure, the Perth Voice Content Questionnaire (PVCQ), designed to measure the intensity and themes of positively and negatively valenced voice content, primarily of the dominant voice. The PVCQ and measures of voice severity and related beliefs were completed by 47 voice‐hearing participants. The measure was found to be internally consistent, loaded onto two distinct factors of positive and negative content, and these factors were associated with voice‐related distress and negative beliefs about voices and positive beliefs about voices, respectively, indicating good validity. The PVCQ offers the first self‐report measure of voice content, with preliminary psychometric properties indicating its suitability for clinical and research use.