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Fluorination is a useful approach for tailoring the physicochemical properties of nanocarbon materials. However, owing to the violent reactivity of fluorination, achieving edge-perfluorination of nanographene while maintaining its original π-conjugated structure is challenging. Instead of using traditional fluorination, here, we employed a bottom-up strategy involving fluorine preinstallation and synthesized decafluorinated and perfluorinated warped nanographenes ( DFWNG and PFWNG , respectively) through a 10-fold Suzuki-Miyaura coupling followed by a harsh Scholl reaction, whereby precisely edge-perfluorinated nanographene with an intact π-conjugated structure was achieved for the first time. X-ray crystallography confirmed the intact π-conjugated structure and more twisted saddle-shaped geometry of PFWNG compared to that of DFWNG . Dynamic study revealed that the 26-ring carbon framework of PFWNG is less flexible than that of DFWNG and the pristine WNG , enabling chirality resolution of PFWNG and facilitating the achievement of CD spectra at -10 °C. The edge-perfluorination of PFWNG resulted in improved solubility, lower lowest unoccupied molecular orbital, and a surface electrostatic potentials/dipole moment direction opposite those of the pristine WNG . Likely owing to its intact π-conjugated structure, PFWNG exhibits comparable electron mobility with well-known PC 61 BM. Furthermore, perfluorination improves thermal stability and hydrophobicity, making PFWNG suitable for use as a thermostable/hydrophobic n -type semiconductor material. In the future, this fluorination strategy can be used to synthesize other perfluorinated nanocarbon materials, such as perfluorinated graphene nanoribbons and porous nanocarbon.

Herein, corannulene-based quintuple [6]helicenes (Q[6]H-1 and Q[6]H-2) and [7]helicene (Q[7]H) were synthesized via penta-fold Heck and Mallory reaction. Notably, Q[7]H represents the highest reported helicene based on corannulene. X-ray crystallography reveals that Q[6]H-2 adopts a propeller-shaped conformation with a well-preserved corannulene core, while Q[6]H-1 and Q[7]H exhibit quasi-propeller-shaped conformations. Upon heating, conformer Q[6]H-1 undergoes conversion to the thermodynamically more stable conformer Q[6]H-2, whereas conformer Q[7]H remains unchanged due to larger steric congestion. Racemization of the enantiomer of Q[6]H-1 and conformational conversion were observed simultaneously at elevated temperature, with DFT studies indicating a racemization barrier of 32.06 kcal ⋅ mol -1 . In contrast, the racemization barrier for Q[6]H-2 was calculated to be 45.46 kcal ⋅ mol -1 , indicating exceptional chiral stability. Surprisingly, the bowl inversions of Q[6]H-1 and Q[6]H-2 conformers are somewhat inhibited by the helical blades, whereas this was not observed for other possible conformers of Q[6]H. These results first demonstrated that subtle conformational variations can lead to significant changes in chiral stability and bowl inversions of multiple helicenes. Due to the well-preserved corannulene core, propeller-shaped conformation and electron complementarity, Q[6]H-2 can recognize fullerenes in both solution and solid state, which is a rare instance of co-crystallization assembly between multiple helicenes and fullerenes., (© 2024 Wiley-VCH GmbH.)

Coinage-metal clusters with excellent luminescence properties have attracted considerable interest due to their intriguing structures and potential applications. However, achieving strong near-infrared (NIR) luminescence in these clusters is highly challenging. Here, we have successfully synthesized the first Ln III /Cu I bimetallic clusters, formulated as [LnCu 54 O 6 Cl 3 (2-MeO-PhC≡C) 36 ] (ClO 4 ) 6 (Ln = Yb for YbCu 54 , Er for ErCu 54 , and Gd for GdCu 54 ). Single crystal X-ray diffraction showed that the LnCu 54 clusters have a three-layered core-shell structure, consisting of (LnO 6 )@Cu 18 Cl 3 @Cu 36 units protected by 36 2-MeO-PhC≡C - ligands. Notably, the YbCu 54 cluster exhibits significant NIR-II luminescence at 986 nm with the solid quantum efficiency of 33.3%, the highest among Cu clusters with NIR-II emission. This work not only reports the first category of Ln III /Cu I clusters but also presents a method to enhance NIR luminescence in coinage-metal clusters through the incorporation of Ln III ions.

The exploration of artificial metal-peptide assemblies (MPAs) is one of the most exciting fields because of their great potential for simulating the dynamics and functionality of natural proteins. However, unfavorable enthalpy changes make forming discrete complexes with large and adaptable cavities from flexible peptide ligands challenging. Here, we present a strategy integrating metal-cluster building blocks and peptides to create chiral metal-peptide assemblies and get a family of enantiopure [R-/S-Ni 3 L 2 ] n (n = 2, 3, 6) MPAs, including the R-/S-Ni 6 L 4 capsule, the S-Ni 9 L 6 trigonal prism, and the R-/S-Ni 18 L 12 octahedron cage. X-ray crystallography shows MPA formation reactions are highly solvent-condition-dependent, resulting in significant changes in ligand conformation and discrete cavity sizes. Moreover, we demonstrate that a structure transformation from Ni 18 L 12 to Ni 9 L 6 in the presence of benzopyrone molecules depends on the peptide conformational selection in crystallization. This work reveals that a metal-cluster building block approach enables facile bottom-up construction of artificial metal-peptide assemblies., (© 2024. The Author(s).)

Hole transport materials (HTMs) are essential for improving the stability and efficiency of perovskite solar cells (PSCs). In this study, we have designed and synthesized a novel organic small molecule HTM, cor-(DPA) 5 , characterized by a bowl-shaped core with symmetric five diphenylamine groups. Compared to already-known HTMs, the bowl-shaped and relatively compact structure of cor-(DPA) 5 facilitates intermolecular π-π interactions, promotes film formations, and enhances charge transport. Consequently, the cor-[DPA(2)] 5 HTM exhibits high charge mobility, exceptional hydrophobicity, and a significantly elevated glass transition temperature. Superior to previously reported HTMs such as spiro-OMeTAD and cor-OMePTPA, our newly synthesized cor-(DPA) 5 HTM is free from any ionic dopants. As a result, the dopant-free cor-[DPA(2)] 5 -based PSC demonstrates an impressive efficiency of 24.01 %, and exhibits outstanding operational stability. It retains 96 % after continuous exposure to 1 sun irradiation for 800 hours under MPP (maximum power point) tracking in ambient air. These findings present a structurally compact novel HTM and exemplify a new approach to the molecular design of HTM for the development of stable and effective PSCs., (© 2024 Wiley-VCH GmbH.)

A novel cooperative pseudo[3]rotaxane system was successfully constructed by the inclusion complexation of two identical amine naphthotubes with a bis-pyridinium/isoquinolinium guest. Single crystal structure analysis revealed that weak C sp 3 -H⋯O hydrogen bonds between the two hosts are responsible for the positive cooperativity during the formation of pseudo[3]rotaxanes. Moreover, intermolecular charge-transfer interactions between the electron-rich host and the electron-poor guests were observed. The pseudo[3]rotaxanes showed pH-controllable association/dissociation processes with naked-eye color changes in solution.

By combining the rigidity of inorganic components with the flexibility of organic components, molecule-based ferroelectrics emerge as promising candidates for flexible, self-powered piezoelectric sensors. While it is well known that the performance of piezoelectric sensor devices depends not only on the materials' piezoelectric properties but also on the device architecture, research into enhancing molecule-based piezoelectric sensor performance through microstructure optimization has never been investigated. Here, we report the synthesis of a molecule-based ferroelectric, [(2-bromoethyl) trimethylammonium][GaBr 4 ] ([(CH 3 ) 3 NCH 2 CH 2 Br][GaBr 4 ]) (1), which exhibits a piezoelectric coefficient ( d 33 ) of up to 331 pC N -1 . Our investigation reveals that the power density of a composite piezoelectric sensor device made from 1@S-PDMS(800#) (with microstructures) is twelve times that of 1-Flat-PDMS (without microstructures), due to a synergistic combination of piezoelectric and triboelectric effects. Interestingly, this flexible piezoelectric sensor can effectively detect human physiological signals, such as finger bending, breathing, and speech recognition, without the need for an external power supply., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The development of high-performance organic photovoltaic materials is of crucial importance for the commercialization of organic solar cells (OSCs). Herein, two structurally simple donor-π-conjugated linker-acceptor (D-π-A)-configured small-molecule donors with methyl-substituted triphenylamine as D unit, 1,1-dicyanomethylene-3-indanone as A unit, and thiophene or furan as π-conjugated linker, named DTICPT and DTICPF, are developed. DTICPT and DTICPF are facilely prepared via a two-step synthetic process with simple procedures. DTICPF with a furan π-conjugated linker exhibits stronger and broader optical absorption, deeper highest occupied molecular orbital (HOMO) energy levels, and better charge transport, compared to its thiophene analog DTICPT. As a result, vacuum-deposited OSCs based on DTICPF: C 70 show an impressive power conversion efficiency (PCE) of 9.36% (certified 9.15%) with short-circuit current density (J sc ) up to 17.49 mA cm -2 (certified 17.56 mA cm -2 ), which is the highest J sc reported so far for vacuum-deposited OSCs. Besides, devices based on DTICPT: C 70 and DTICPF: C 70 exhibit excellent long-term stability under different aging conditions. This work offers important insights into the rational design of D-π-A configured small-molecule donors for high efficient and stable vacuum-deposited OSCs., (© 2024 Wiley‐VCH GmbH.)

Zinc finger protein 180 (ZNF180) is a multifunctional protein that interacts with nucleic acids and regulates various cellular processes; however, the function of ZNF180 in colorectal cancer (CRC) remains unclear. The present study investigated the role and function of ZNF180 in CRC, and aimed to reveal the underlying molecular mechanism. The results revealed that ZNF180 was downregulated in CRC tissues and was associated with a good prognosis in patients with CRC. Additionally, the expression of ZNF180 was downregulated by methylation in CRC. In vivo and in vitro experiments revealed that ZNF180 overexpression was functionally associated with the inhibition of cell proliferation and the induction of apoptosis. Mechanistically, chromatin immunoprecipitation‑PCR and luciferase assays demonstrated that ZNF180 markedly regulated the transcriptional activity of methyltransferase 14, N6‑adenosine‑methyltransferase non‑catalytic subunit (METTL14) by directly binding to and activating its promoter region. Simultaneous overexpression of ZNF180 and knockdown of METTL14 indicated that the reduction of METTL14 could suppress the effects of ZNF180 on the induction of apoptosis. Clinically, the present study observed a significant positive correlation between ZNF180 and METTL14 expression levels, and low expression of ZNF180 and METTL14 predicted a poor prognosis in CRC. Overall, these findings revealed a novel mechanism by which the ZNF180/METTL14 axis may modulate apoptosis and cell proliferation in CRC. This evidence suggests that this axis may serve as a prognostic biomarker and therapeutic target in patients with CRC.

The magneto-optical response of chiral materials holds significant potential for applications in physics, chemistry, and biology. However, exploration of the near-infrared (NIR) magneto-optical response remains limited. Herein, we report the synthesis and strong NIR-II magneto-optical activity of three pairs of chiral 3 d- 4 f clusters of R/S -Ln 15 Cu 54 (Ln = Sm, Gd, and Dy). Structural analysis reveals that R/S -Ln 15 Cu 54 features a triangular prism cage with C 3 symmetry. Interestingly, magnetic circular dichroism (MCD) spectra exhibit remarkable magneto-optical response in the NIR-II region, driven by the f-f transition. The maximum g -factor of R/S -Sm 15 Cu 54 reaches 5.5 × 10 -3 T -1 around 1300-1450 nm, surpassing values associated with Dy III and Cu II ions. This remarkable NIR-II magneto-optical activity may be attributed to strong magnetic-dipole-allowed f-f transitions and helix chirality of the structure. This work not only presents the largest Ln-Cu clusters to date but also demonstrate the key role of magnetic-dipole-allowed transitions on magneto-optical activity.

Open hollow dodecahedral cage clusters have long been a coveted target in synthetic chemistry, yet their creation poses immense challenges. Here we report two open hollow dodecahedral lanthanide-aluminum (Ln-Al) heterometallic cage clusters, namely, [Ln 210 Al 140 (μ 2 -OH) 210 (μ 3 -OH) 540 (OAc) 180 (H 2 O) 156 ](ClO 4 ) 120 ·(MeCN) x ·(H 2 O) y , (Ln = Dy and x = 27, y = 300 for 1 ; Ln = Y and x = 28, y = 420 for 2 ). Remarkably, the 350 metal atoms in 1 and 2 display a Keplerate-type four-shell structure of truncated icosidodecahedron@dodecahedron@dodecahedron@icosidodecahedron. The diameter of the cationic cluster in 1 is approximately 5.0 nm, with an inner cavity diameter of about 2.8 nm and a window diameter of roughly 0.66 nm. The cluster in 1 boasts an accessible inner void volume of up to 15,000 Å 3 . Notably, these cage clusters maintain stability in water, and the truncated icosidodecahedrons in 1 and 2 are the first of their kind synthesized to date. Given that the open hollow dodecahedral Ln-Al cage cluster has never been reported before, this work represents a member in the family of hollow open dodecahedral cages.

Background: Data on disparities in outcomes and risk factors in Asian patients with advanced chronic kidney disease admitted for heart failure are scare., Methods: This was a retrospective cohort study that utilized data from the National Inpatient Sample between January 2016 and December 2019. Patients who had a primary diagnosis of acute decompensated heart failure and a concomitant diagnosis of advanced CKD were included. The primary outcome of interest was in-hospital mortality. Secondary outcomes include hospital cost, length of stay, and other clinical outcomes. Weighted multivariable logistic regression was used to adjust for comorbidities., Results: There were 251,578 cases of ADHF with advanced CKD, out of which 2.6 % were from individuals of Asian ethnicity. Asian patients exhibited a higher burden of comorbidities in comparison to other UREM patients, but a lower burden than White patients. Regardless of differences in comorbidity burden, Asian patients exhibited a higher likelihood of experiencing severe consequences. After adjusting for comorbidies, White (OR:1.11; 95 % CI 1.03-1.20;0.009) patients had higher odds of mortality than Asian patients. However, Blacks (OR: 0.58; 95 % CI 0.53 to 0.63; p < 0.001) and Hispanics (OR: 0.69; 95 % CI 0.62 to 0.78; p < 0.001) had lower odds of mortality., Conclusion: This first population-based studies shows that Asian patients with advanced CKD admitted for ADHF have greater comorbidity burden and poorer outcomes Black and Hispanic patients. This data underscores the importance of comprehensive approaches in phenotyping, and ethnic specific interventions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Atomically precise metal clusters serve as a unique model for unraveling the intricate mechanism of the catalytic reaction and exploring the complex relationship between structure and activity. Herein, three series of water-soluble heterometallic clusters LnCu 6 , abbreviated as LnCu 6 -AC (Ln = La, Nd, Gd, Er, Yb; HAC = acetic acid), LnCu 6 -IM (Ln = La and Nd; IM = Imidazole), and LnCu 6 -IDA (Ln = Nd; H 2 IDA = Iminodiacetic acid) are presented, each featuring a uniform metallic core stabilized by distinct protected ligands. Crystal structure analysis reveals a triangular prism topology formed by six Cu 2+ ions around one Ln 3+ ion in LnCu 6 , with variations in Cu···Cu distances attributed to different ligands. Electrocatalytic oxygen evolution reaction (OER) shows that these different LnCu 6 clusters exhibit different OER activities with remarkable turnover frequency of 135 s -1 for NdCu 6 -AC, 79 s -1 for NdCu 6 -IM and 32 s -1 for NdCu 6 -IDA. Structural analysis and Density Functional Theory (DFT) calculations underscore the correlation between shorter Cu···Cu distances and improves OER catalytic activity, emphasizing the pivotal role of active-site distance in regulating electrocatalytic OER activities. These results provide valuable insights into the OER mechanism and contribute to the design of efficient homogeneous OER electrocatalysts., (© 2024 Wiley‐VCH GmbH.)

Adiabatic demagnetization refrigeration (ADR) is a promising cooling technology with high efficiency and exceptional stability in achieving ultralow temperatures, playing an indispensable role at the forefront of fundamental and applied science. However, a significant challenge for ADR is that existing magnetic refrigerants struggle to concurrently achieve low magnetic ordering temperatures ( T 0 ) and substantial magnetic entropy changes (-Δ S m ) at ultralow temperatures. In this work, we propose the combination of Gd 3+ and Yb 3+ to effectively regulate both -Δ S m and T 0 in ultralow temperatures. Notably, the -Δ S m values for Gd 0.1 Yb 0.9 F 3 ( 1 ) and Gd 0.3 Yb 0.7 F 3 ( 2 ) in the 0.4-1.0 K range exceed those of all previously reported magnetic refrigerants within this temperature interval, positioning them as the most efficient magnetic refrigerants for the third stage to date. Although the -Δ S m values for Gd 0.5 Yb 0.5 F 3 ( 3 ) in 1-4 K are less than those of the leading magnetic refrigerant Gd(OH)F 2 , the -Δ S m values for Gd 0.7 Yb 0.3 F 3 ( 4 ) in 1-4 K at 2 T surpass those of all magnetic refrigerants previously documented within the same temperature range, making it the superior magnetic refrigerant for the fourth stage identified thus far.

Keggin-Fe 13 clusters are considered foundational building blocks or prenucleation precursors of ferrihydrite. Understanding the factors that influence the rotational configuration of these clusters, and their transformations in water, is vital for comprehending the formation mechanism of ferrihydrite. Here, we report syntheses and crystal structures of four lanthanide-iron-oxo clusters, namely, [Dy 6 Fe 13 (Gly) 12 (μ 2 -OH) 6 (μ 3 -OH) 18 (μ 4 -O) 4 (H 2 O) 17 ]·13ClO 4 ·19H 2 O ( 1 ), [Dy 6 Fe 13 (Gly) 12 (μ 3 -OH) 24 (μ 4 -O) 4 (H 2 O) 18 ]·13ClO 4 ·14H 2 O ( 2 ), [Pr 8 Fe 34 (Gly) 24 (μ 3 -OH) 28 (μ 3 -O) 30 (μ 4 -O) 4 (H 2 O) 30 ]·6ClO 4 ·20H 2 O ( 3 ), and [Pr 6 Fe 13 (Gly) 12 (μ 3 -OH) 24 (μ 4 -O) 4 (H 2 O) 18 ]·13ClO 4 ·22H 2 O ( 4 , Gly = glycine). Single-crystal analyses reveal that 1 has a β-Keggin-Fe 13 cluster, marking the first documented instance of such a cluster to date. Conversely, both 2 and 4 contain an α-Keggin-Fe 13 cluster, while 3 is characterized by four hexavacant ε-Keggin-Fe 13 clusters. Magnetic property investigations of 1 and 2 show that 2 exhibits ferromagnetic interactions, while 1 exhibits antiferromagnetic interactions. An exploration of the synthetic conditions for 1 and 2 indicates that a higher pH promotes the formation of α-Keggin-Fe 13 clusters, while a lower pH favors β-Keggin-Fe 13 clusters. A detailed analysis of the transition from 3 to 4 emphasizes that lacunary Keggin-Fe 13 clusters can morph into Keggin-Fe 13 clusters with a decrease in pH, accompanied by a significant change in their rotational configuration.

Adiabatic demagnetization refrigeration is known to be the only cryogenic refrigeration technology that can achieve ultralow temperatures (≪1 K) at gravity-free conditions. The key indexes to evaluate the performance of magnetic refrigerants are their magnetic entropy changes (-Δ S m ) and magnetic ordering temperature ( T 0 ). Although, based on the factors affecting the -Δ S m of magnetic refrigerants, one has been able to judge if a magnetic refrigerant has a large -Δ S m , how to accurately predict their T 0 remains a huge challenge due to the fact that the T 0 of magnetic refrigerants is related to not only magnetic exchange but also single-ion anisotropy and magnetic dipole interaction. Here, we, taking GdCO 3 F ( 1 ), Gd(HCOO)F 2 , Gd 2 (SO 4 ) 3 ·8H 2 O, GdF 3 , Gd(HCOO) 3 and Gd(OH) 3 as examples, demonstrate that the T 0 of magnetic refrigerants with very weak magnetic interactions and small anisotropy can be accurately predicted by integrating mean-field approximation with quantum Monte Carlo simulations, providing an effective method for predicting the T 0 of ultralow-temperature magnetic refrigerants. Thus, the present work lays a solid foundation for the rational design and preparation of ultralow-temperature magnetic refrigerants in the future.

Here we report on the strong magneto-chiral dichroism (MChD) detected through visible and near-infrared light absorption up to 5.0 T on {Er 5 Ni 6 } metal clusters obtained by reaction of enantiopure chiral ligands and Ni II and Er III precursors. Single-crystal diffraction analysis reveals that these compounds are 3 d- 4 f heterometallic clusters, showing helical chirality. MChD spectroscopy reveals a high g MChD dissymmetry factor of ca. 0.24 T -1 ( T = 4.0 K, B = 1.0 T) for the 4 I 13/2 ← 4 I 15/2 magnetic-dipole allowed electronic transition of the Er III centers. This record value is 1 or 2 orders of magnitude higher than that of the d-d electronic transitions of the Ni II ions and the others f-f electric-dipole induced transitions of the Er III centers. These findings clearly show the key role that magnetic-dipole allowed transitions have in the rational design of chiral lanthanide systems showing strong MChD.

Objective: To explore the distribution of allergen-specific IgE (sIgE) for children with atopic dermatitis in Tianjin City and provide the evidences of clinical diagnosis and treatment. Methods: A retrospective cross-sectional study was conducted to analyze the children who were suspected of atopic dermatitis and tested for serum sIgE in the Tianjin Children's Hospital from March 2021 to February 2023. Using first detection results only, a total of 1 841 serum samples were tested for twenty common allergens. The method was the enzyme-linked immune capture assay. The allergen epidemiological characteristics were statistically analyzed by Chi square test based on the children's characteristics and factors such as different sexes, ages and seasons by the mass data. Results: Among the 1 841 cases, the results showed that 1 247 (67.73%) were sensitized to at least 1 allergen-sIgE, comprising to 49.86% (918/1 841) to food allergen-sIgE and 47.96% (883/1 841) to aeroallergen-sIgE. The top three food allergens-sIgE were egg 32.10% (591/1 841), milk 25.91% (477/1 841) and wheat flour 14.61% (269/1 841); the top three positive rates of aeroallergens-sIgE were house dust 24.33% (448/1 841), alternaria 20.59% (379/1 841) and dermatophagoides farinae 14.83% (273/1 841). The positive rates of food allergens-sIgE were the highest in the 1-3 years old group (64.11%, 434/677) ( χ 2 =122.854, P <0.001), while the positive rates of aeroallergens-sIgE were higher in the 11-14 years old group (71.26%, 62/87) ( χ 2 =134.968, P <0.001). No seasonal difference was revealed in the overall positive rate of food allergen-sIgE and aeroallergen-sIgE ( χ 2 =4.047, P =0.256; χ 2 =7.549, P =0.056). The positive rates of soybean-sIgE and milk-sIgE were the highest in summer ( χ 2 =11.329, P =0.010; χ 2 =28.720 , P <0.001), whereas alternaria-sIgE and mugwort-sIgE were the highest in summer and autumn, respectively ( χ 2 =8.462, P =0.037; χ 2 =10.641 , P =0.014). Among the 1 841 cases, 32.21% were sensitized to three or more allergens-sIgE. The sIgE concentration levels of egg, milk and house dust were mainly level 1 to 2, and the proportions of level 3 and above were all under 15%; although the positive rates of crab, shrimp, and peanut were low, the proportions of grade 3 and above were all beyond 30%. Children sensitized to alternaria, dermatophagoides farinae, mugwort, and cat dander had higher sIgE concentration levels, which were 68.07%, 49.45%, 56.57% and 47.83% respectively. Conclusions: This study can reflect the epidemic characteristics of allergen-sIgE in children with atopic dermatitis in Tianjin region to a certain extent. Allergen-sIgE positivity in patients differed by age, and there were seasonal differences and grade distribution differences in the positive rates of some allergens-sIgE. It is necessary to reasonably avoid the high-risk allergens according to the epidemiological characteristics and clinical symptoms, which provide valuable information for the prevention, diagnosis and treatment of atopic dermatitis.

The interactions between ether naphthotube and a series of dication guests in organic solution were investigated. It was found that ether naphthotube formed stable host-guest complexes selectively with these guests in a 1 : 1 stoichiometric ratio with association constants ranging from 10 2 to 10 6  M -1 , which were confirmed by 1 H-NMR spectra and ITC experiments. The host-guest interactions are driven by enthalpy change as the entropic factors are unfavorable. Positive correlations between ΔH and ΔS have been observed in the host-guest complexes. Furthermore, the para-substitution of the guests can significantly affect the binding affinities through a combination of field/inductive and resonance effects by following a linear free energy relationship. Based on the host-guest complexes composed of ether naphthotube and organic cations, two interlocked [2]rotaxanes were prepared by cationization reaction and Huisgen cycloaddition between the cations and the stopper components. The ether naphthotube-based host-guest complexes are useful for creating sophisticated interlocked molecules., (© 2024 Wiley-VCH GmbH.)

Selective recognition and enrichment of fullerenes ( e.g. , C 60 and C 70 ) remains challenging due to the same diameter and geometrical similarity. Herein, we report a hexagonal anthracene-based nanotube (1) through a one-pot Suzuki-Miyaura cross-coupling reaction. With anthracene-based side walls and pyridine linkers, 1 features a nano-scale tubular cavity measuring 1.2 nm in diameter and 0.9 nm in depth, along with pH-responsive properties. Interestingly, the electron-rich 1 shows high binding affinity ( K a ≈ 10 6 M -1 ) and selectivity ( K s ≈ 140) to C 70 over C 60 in toluene, resulting from their different contribution of π-π interactions with the host. The protonation of 1 simultaneously alters the electronic properties within the nanotube, resulting in the release of the fullerene guests. Lastly, the selective recognition and pH stimuli-responsive properties of the nanotube have been utilized to enrich C 70 from its low-content mixtures of fullerenes in chloroform., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

A series of chiral heterometallic Ln-Co clusters, denoted as Co 2 Ln and Co 3 Ln 2 (Ln = Dy and Er), were synthesized by reacting the chiral chelating ligand ( R / S )-2-(1-hydroxyethyl)pyridine (Hmpm), CoAc 2 ·4H 2 O, and Ln(NO 3 ) 3 ·6H 2 O. Co 2 Ln and Co 3 Ln 2 exhibit perfect mirror images in circular dichroism within the 320-700 nm range. Notably, the Co 2 Er and Co 3 Er 2 clusters display pronounced magnetic circular dichroism (MCD) responses of the hypersensitive f-f transitions 4 I 15/2 - 4 G 11/2 at 375 nm and 4 I 15/2 - 2 H 11/2 at 520 nm of Er III ions. This study highlights the strong magneto-optical activity associated with hypersensitive f-f transitions in chiral 3d-4f magnetic clusters.

Objective: To explore clinical effect of different intervertebral fusion devices (cage) in treating postoperative recurrent lumbar disc herniation (LDH)., Methods: One hundred and forty-two LDH patients with recurrence after simple intervertebral disc nucleus pulpoideectomy from January 2019 to January 2021 were retrospectively analyzed. All patients were treated with combined underchannel fixation and interbody fusion and divided into a single anatomical group,two-anatomical group and a single banana group according to types and numbers of implanted cage. There were 51 patients in a single anatomical group,included 29 males and 22 females,aged from 39 to 65 years old with an average of (53.74±5.68) years old;body mass index (BMI) ranged from 18.62 to 28.13 kg·m -2 with an average of (22.08±2.15) kg·m -2 ;the interval between operation and recurrence ranged from 0.5 to 4.0 years with an average of (2.7±0.8) years;5 patients with L 3,4 ,35 patients with L 4,5 and 11 patients with L 5 S 1 ;a single anatomical cage was implanted. There were 46 patients in two-anatomical group,included 25 males and 21 females,aged from 37 to 66 years old with an average of (54.52±6.02) years old;BMI ranged from 18.25 to 28.44 kg·m -2 with an average of (21.74±1.83) kg·m -2 ;the interval between operation and recurrence ranged from 0.5 to 5.0 years with an average of (2.7±0.9) years;4 patients with L 3,4 ,32 patients with L 4,5 and 10 patients with L 5 S 1 ;two-anatomical cages were implanted. There were 45 patients in a single banana group,included 22 males and 23 females,aged from 38 to 65 years old with an average of (54.49±6.45) years old;BMI ranged from 18.85 to 28.20 kg·m -2 with an average of (21.63±1.59) kg·m -2 ;the interval between operation and recurrence ranged from 0.5 to 5.0 years with an average of (2.6±1.0) years;3 patients with L 3,4 ,36 patients with L 4,5 and 16 patients with L 5 S 1 ;a single banana cage was implanted. Operation time,intraoperative blood loss,incision length,postoperative incision drainage volume,hospital stay and complications among 3 groups were observed and compared. The height of intervertebral space before and after operation,curvature of lordosis and the postoperative intervertebral fusion were compared. Visual analogue scale (VAS) and Oswestry disability index (ODI) were used to evaluate degree of lumbar pain and lumbar function before operation,1 and 6 months after operation,respectively., Results: All patients among 3 groups were followed up at least 6 months,and no cases were fell out. There were no significant difference in operation time,intraoperative blood loss,incision length,postoperative incision drainage volume and hospital stay among 3 groups ( P >0.05). At 6 months after operation,the height of intervertebral space in two-anatomical group and a single group were [(11.08±1.78) mm,(10.95±1.62) mm],curvature of lordosis were [(12.05±1.86) °,(11.63±1.57) °],which were higher than those in a single dissection group (10.14±1.54) mm,(10.92±1.45) °,and the difference were statistically significant ( P <0.05). The interbody fusion rate between two-anatomical and a banana group (95.65%,95.56%) were higher than that in a single anatomical group (78.43%) at 6 months after operation ( P <0.05). VAS and ODI of lumbar among 3 groups were decreased at 1 and 6 months after operation ( P <0.05). There was no significant difference in complications among 3 groups ( P >0.05)., Conclusion: The three fusion devices could achieve significant results in treating postoperative recurrence of LDH,but the implantation of two-anatomical cage and a single banana cage are more helpful to maintain the height of intervertebral space and lordosis curvature of patients with postoperative recurrence of LDH,and obtain good intervertebral fusion results.

Nasopharyngeal carcinoma (NPC) originates in the epithelial cells of the nasopharynx and is a common malignant tumor in southern China and Southeast Asia. Metastasis of NPC remains the main cause of death for NPC patients even though the tumor is sensitive to radiotherapy and chemotherapy. Here, we found that the transmembrane protein tetraspanin1 (TSPAN1) potently inhibited the in vitro migration and invasion, as well as, the in vivo metastasis of NPC cells via interacting with the IKBB protein. In addition, TSPAN1 was essential in preventing the overactivation of the NF-kB pathway in TSPAN1 overexpressing NPC cells. Furthermore, reduced TSPAN1 expression was associated with NPC metastasis and the poor prognosis of NPC patients. These results uncovered the suppressive role of TSPAN1 against NF-kB signaling in NPC cells for preventing NPC metastasis. Its therapeutic value warrants further investigation., (© 2023. The Author(s), under exclusive licence to Springer Nature America, Inc.)

Five decanuclear lanthanide-iron clusters, formulated as [Ln 2 Fe 8 (hmp) 10 (μ 2 -OH) 4 (μ 3 -OH) 2 (μ 4 -O) 4 (H 2 O) 6 ]·6ClO 4 · x H 2 O ( x ≈ 8, Ln = Y for 1; x ≈ 6, Ln = Dy for 2; x ≈ 6, Ln = Ho for 3; x ≈ 7, Ln = Tb for 4; x ≈ 7, Ln = Gd for 5, Hhmp = 2-(hydroxymethyl)pyridine), have been synthesized and structurally characterized. Single-crystal structural analysis reveals that the cluster consists of six face-sharing defective cubane units. Dynamic magnetic investigations indicated that cluster 2 exhibits single-molecule magnet behavior under a zero dc field eliciting an effective energy barrier of U eff = 17.76 K and a pre-exponential factor of τ 0 = 7.93 × 10 -8 s. Investigation of the performance of a series of Fe III -Dy III SMMs indicates that the relatively low energy barrier in 2 is associated with the weak ferromagnetic coupling between Fe III and Dy III ions, while the strength of ferromagnetic interaction in these clusters is mainly related to the bond distances between Dy III and O atoms coordinated to Fe III ions. Clusters 3 and 4 exhibit similar dual relaxation pathways under their respective optimal external applied dc field, where the direct relaxation process occurs in the low-frequency area, which impedes the extraction of the U eff , while the secondary relaxation process appears at a higher frequency, which is probably a connection with intermolecularly driven relaxation. Our findings offer a magneto-structural correlation model for further investigating the single-molecule magnet behavior in lanthanide-iron systems.

The water oxidation half reaction in water splitting for hydrogen production is extremely rate-limiting. This study reports the synthesis of two heterometallic clusters (Gd 6 Cu 24 -IM and Gd 6 Cu 24 -AC) for application as efficient water oxidation catalysts. Interestingly, the maximum turnover frequency of Gd 6 Cu 24 -IM in an NaAc solution of a weak acid (pH 6) was 319 s -1 . The trimetallic catalytic site, H 2 O-Gd III Cu II 2 -H 2 O, underwent two consecutive two-electron two-proton coupled transfer processes to form high-valent Gd III -O-O-Cu III 2 intermediates. Furthermore, the O-O bond was formed via intramolecular interactions between the Cu III and Gd III centers. The results of this study revealed that synergistic catalytic water oxidation between polymetallic sites can be an effective strategy for regulating O-O bond formation., Competing Interests: The authors declare no competing financial interest., (This journal is © The Royal Society of Chemistry.)

Objective: This study aimed to analyze the clinical characteristics of patients with diabetic foot ulcers combined with peripheral arterial disease (PAD) and the risk factors., Patients and Methods: A retrospective study was conducted on 120 patients with diabetic foot ulcers in the Second Affiliated Hospital of Dalian Medical University from October 2018 to February 2021. The patients were divided into uncombined with the PAD group (42 cases) and combined with the PAD group (78 cases). The baseline information and clinical indicators were measured from two groups. Univariate and binary logistic regression was used to analyze the risk factors of PAD in patients with diabetic foot ulcers., Results: The proportion of patients with age ≥ 60 years, Wagner grade 4-5 and smoking history in the combined group was higher than that in the uncombined group (p < 0.05). The diastolic blood pressure (DBP) of the combined group was lower than that of the uncombined group, while the C-reactive protein (CRP), neutrophil-to-lymphocyte ratio (NLR) and glycated hemoglobin (HbA1c) levels of the combined group were higher than those of the uncombined group (p < 0.05). Binary logistic regression analysis showed that age ≥ 60 years, high Wagner grade, smoking, elevated CRP, NLR and HbA1c levels were risk factors for patients with diabetic foot ulcer combined with PAD (OR > 1, p < 0.05). An elevated DBP level was the protective factor for PAD in patients with diabetic foot ulcer (OR < 1, p < 0.05)., Conclusions: Patients with diabetic foot ulcer combined with PAD have the clinical characteristics of poor blood pressure control, long course of disease, and low ABI value. Age ≥ 60 years, high Wagner grade, smoking history, elevated CRP, NLR and HbA1c levels are the risk factors of PAD in patients with diabetic foot ulcer. Increased DBP is protective for PAD in patients with diabetic foot ulcer.

Precise binding towards structurally similar substrates is a common feature of biomolecular recognition. However, achieving such selectivity-especially in distinguishing subtle differences in substrates-with synthetic hosts can be quite challenging. Herein, we report a novel design strategy involving the combination of different rigid skeletons to adjust the distance between recognition sites within the cavity, which allows for the highly selective recognition of hydrogen-bonding complementary substrates, such as 4-chromanone. X-ray single-crystal structures and density functional theory calculations confirmed that the distance of endo-functionalized groups within the rigid cavity is crucial for achieving high binding selectivity through hydrogen bonding. The thermodynamic data and molecular dynamics simulations revealed a significant influence of the hydrophobic cavity on the binding affinity. The new receptor possesses both high selectivity and high affinity, which provide valuable insights for the design of customized receptors., (© 2023 Wiley-VCH GmbH.)

Ratiometric luminescent thermometers with excellent performance often require the luminescent materials to possess high thermal stability and relative sensitivity ( S r ). However, such luminescent materials are very rare, especially in physiological (298-323 K) and high-temperature (>373 K) regions. Here we report the synthesis and luminescent property of [Tb 0.995 Eu 0.005 (pfbz) 2 (phen)Cl] ( 3 ), which not only exhibits high S r in physiological temperature but also has a S r up to 7.47% K -1 at 440 K, the largest S r at 440 K in known lanthanide-based coordination compound luminescent materials.

Distant metastasis is the primary reason for treatment failure in patients with nasopharyngeal carcinoma (NPC). In this study, we investigated the effect of ulinastatin (UTI) on NPC metastasis and its underlying mechanism. Highly-metastatic NPC cell lines S18 and 58F were treated with UTI and the effect on cell proliferation, migration, and invasion were determined by MTS and Transwell assays. S18 cells with luciferase-expressing (S18-1C3) were injected into the left hind footpad of nude mice to establish a model of spontaneous metastasis from the footpad to popliteal lymph node (LN). The luciferase messenger RNA (mRNA) was measured by quantitative polymerase chain reaction (qPCR), and the metastasis inhibition rate was calculated. Key molecular members of the UTI-related uPA, uPAR, and JAT/STAT3 signaling pathways were detected by qPCR and immunoblotting. UTI suppressed the migration and infiltration of S18 and 5-8F cells and suppressed the metastasis of S18 cells in vivo without affecting cell proliferation. uPAR expression decreased from 24 to 48 h after UTI treatment. The antimetastatic effect of UTI is partly due to the suppression of uPA and uPAR. UTI partially suppresses NPC metastasis by downregulating the expression of uPA and uPAR., (© 2023 Wiley Periodicals LLC.)

Inorganic molecular cages are emerging multifunctional molecular-based platforms with the unique merits of rigid skeletons and inherited properties from constituent metal ions. However, the sensitive coordination bonds and vast synthetic space have limited their systematic exploration. Herein, two giant cage-like clusters featuring the organic ligand-directed inorganic skeletons of Ni 4 [La 74 Ni 104 (IDA) 96 (OH) 184 (C 2 O 4 ) 12 (H 2 O) 76 ]·(NO 3 ) 38 ·(H 2 O) 120 ( La 74 Ni 104 , 5 × 5 × 3 - C 2 O 4 ) and [La 84 Ni 132 (IDA) 108 (OH) 168 (C 2 O 4 ) 24 (NO 3 ) 12 (H 2 O) 116 ]·(NO 3 ) 72 ·(H 2 O) 296 ( La 84 Ni 132 , 5 × 5 × 5 - C 2 O 4 ) were discovered by a high-throughput synthetic search. With the assistance of machine learning analysis of the experimental data, phase diagrams of the two clusters in a four-parameter synthetic space were depicted. The effect of alkali, oxalate, and other parameters on the formation of clusters and the mechanism regulating the size of two n × m × l clusters were elucidated. This work uses high-throughput synthesis and machine learning methods to improve the efficiency of 3d-4f cluster discovery and finds the highest-nuclearity 3d-4f cluster to date by regulating the size of the n × m × l inorganic cages through oxalate ions, which pushes the synthetic methodology study on elusive inorganic giant cages in a significantly systematic way.

The selective fluorination of C-H bonds at room temperature using heterogeneous visible-light catalysts is both interesting and challenging. Herein, we present the heterogeneous sandwich-type structure uranyl-polyoxotungstate cluster Na 17 {Na@[(SbW 9 O 33 ) 2 (UO 2 ) 6 (PO 3 OH) 6 ]}·46H 2 O (denoted as U 6 P 6 ) to regulate the selective fluorination of the C-H bond under visible light and room temperature. This is the first report in which uranyl participates in the fluorination reaction in the form of an insoluble substance. U 6 P 6 is capable of the effective selective fluorination of cycloalkanes and the recyclability of the photocatalyst due to the synergistic effect of multiple uranyl (UO 2 ) 2+ and the insolubility of organic reagents of polyoxotungstate. In situ electron paramagnetic resonance spectroscopy captured the generation of cycloalkane radicals during the photoreaction, confirming the mechanism of direct hydrogen atom transfer.

Single crystals with chiral shapes aroused the interest of chemists due to their fascinating polarization rotation properties. Although the formation of large-scale spiral structures is considered to be a potential factor in chiral crystals, the precise mechanism behind their formation remains elusive. Herein, we present a rare phenomenon involving the multitransfer and expression of chirality at micro-, meso-, and macroscopic levels, starting from chiral carbon atoms and extending to the double-helical secondary structure, ultimately resulting in the chiral geometry of crystals. The assembly of the chiral double helices is facilitated by the dual characteristics of amide groups derived from amino acids, which serve as both hydrogen bond donors and receptors, similar to the assembly pattern observed in DNA. Crystal face analysis and theoretical morphology reveal two critical factors for the mechanism of the chiral crystal: inherent intrinsically symmetrical distribution of crystal faces and their acquired growth. Importantly, the magnetic circular dichroism (MCD) study reveals the strong magneto-optical response of the hypersensitive f - f transition in the UV-vis-NIR region, which is much stronger than previously observed signals. Remarkably, an external magnetic field can reverse the CD signal. This research highlights the potential of lanthanide-based chiral helical structures as promising magneto-optical materials.

Developing chiral receptors with an endo-functionalized cavity for chiral recognition is of great significance in the field of molecular recognition. This study presents two pairs of chiral naphthotubes containing a bis-thiourea endo-functionalized cavity. Each chiral naphthotube has two homochiral centers which were fixed adjacent to the thiourea groups, causing the skeleton and thiourea groups to twist enantiomerically through chiral transfer. These chiral naphthotubes are highly effective at enantiomerically recognizing various neutral chiral molecules with an enantioselectivity up to 17.0. Furthermore, the mechanism of the chiral recognition has been revealed to be originated from differences in multiple non-covalent interactions. Various factors, such as the shape of cavities, substituents of guests, flexibility of host and binding modes are demonstrated to contribute to creating differences in the non-covalent interactions. Additionally, the driving force behind enantioselectivity is mainly attributed to enthalpic differences, and enthalpy -entropy compensation has also been observed to influence enantioselectivity., (© 2023. Springer Nature Limited.)

The left-right symmetry breaking of vertebrate embryos requires nodal flow. However, the molecular mechanisms that mediate the asymmetric gene expression regulation under nodal flow remain elusive. Here, we report that heat shock factor 1 (HSF1) is asymmetrically activated in the Kupffer's vesicle of zebrafish embryos in the presence of nodal flow. Deficiency in HSF1 expression caused a significant situs inversus and disrupted gene expression asymmetry of nodal signaling proteins in zebrafish embryos. Further studies demonstrated that HSF1 is a mechanosensitive protein. The mechanical sensation ability of HSF1 is conserved in a variety of mechanical stimuli in different cell types. Moreover, cilia and Ca 2+ -Akt signaling axis are essential for the activation of HSF1 under mechanical stress in vitro and in vivo . Considering the conserved expression of HSF1 in organisms, these findings unveil a fundamental mechanism of gene expression regulation by mechanical clues during embryonic development and other physiological and pathological transformations., Competing Interests: There are no competing interests., (© 2023 The Authors.)

To investigate the common specific immunoglobulin E(sIgE) in children with eczema and urticaria, compare the allergies in children with different diseases, genders and ages, and provide the scientific basis for the prevention, diagnosis and treatment. A retrospective study was conducted to analyze the children who were suspected of eczema and urticaria and tested for serum sIgE in the Tianjin Children's Hospital from December 2019 to August 2021. A total of 8 092 serum samples were tested for ten food allergens and ten inhaled allergens. The method was the enzyme-linked immune capture assay. The allergen epidemiological characteristics were statistically analyzed by Chi square test based on the children's characteristics and factors such as different sexes and ages and by the mass data. The results showed that the positive rate of eczema was 64.42%(5 213/8 092), and the urticaria was 35.58%(2 879/8 092). The positive rate of specific IgE was 66.65%(5 393/8 092), the food allergens was 61.74%(4 996/8 092), and the inhaled allergens was 34.85%(2 820/8 092). The top three positive rates of food allergens were egg 46.65%(3 775/8 092), milk 32.64%(2 641/8 092) and wheat flour 15.08%(1 220/8 092). The top three positive rates of inhaled allergens were house dust 21.40%(1 732/8 092), Alternaria 11.78%(953/8 092) and Dermatophagoides farinae 7.33%(593/8 092). The positivity of food allergens and inhaled allergens was significantly different in different age groups. The positive rates of food allergens in different age groups were 48.92%(947/1 936) in<1 year old, 72.28%(2 680/3 708) in 1-3 years old, 64.58%(919/1 423) in 4-6 years old and 43.90%(450/1 025) in>6 years old. The positive rates of inhaled allergens in different age groups were 17.67%(342/1 936) in<1 year old, 36.35%(1 348/3 708) in 1-3 years old, 46.38%(660/1 423) in 4-6 years old and 45.85%(470/1 025) in>6 years old. The top six positive rates of allergens of eczema were the same with urticaria, which were egg, milk, house dust, wheat flour, Alternaria and Dermatophagoides farinae. The allergens (greater than or equal to grade 4) differed in children with eczema and urticaria. Moreover, there were significant differences in the positive rates of Alternaria, egg, wheat flour, crab and shrimp. In conclusion, this study can reflect the epidemic characteristics of allergens in children with eczema and urticaria to a certain extent. There were significant differences in the positive rates of allergens between different age groups. It is necessary to reasonably avoid the high-risk allergens according to the epidemiological characteristics and clinical symptoms, which provide valuable information for the prevention, diagnosis and treatment of allergic diseases.

Background: The continuously developing pesticide resistance is a great threat to agriculture and human health. Understanding the mechanisms of insecticide resistance is a key step in dealing with the phenomenon. Insect cuticle is recently documented to delay xenobiotic penetration which breaks the previous stereotype that cuticle is useless in insecticide resistance, while the underlying mechanism remains scarce., Results: Here, we find the integument contributes over 40.0% to insecticide resistance via different insecticide delivery strategies in oriental fruit fly. A negative relationship exists between cuticle thickening and insecticide penetration in resistant/susceptible, also in field strains of oriental fruit fly which is a reason for integument-mediated resistance. Our investigations uncover a regulator of insecticide penetration that miR-994 mimic treatment causes cuticle thinning and increases susceptibility to malathion, whereas miR-994 inhibitor results in opposite phenotypes. The target of miR-994 is a most abundant cuticle protein (CPCFC) in resistant/susceptible integument expression profile, which possesses capability of chitin-binding and influences the cuticle thickness-mediated insecticide penetration. Our analyses find an upstream transcriptional regulatory signal of miR-994 cascade, long noncoding RNA (lnc19419), that indirectly upregulates CPCFC in cuticle of the resistant strain by sponging miR-994. Thus, we elucidate the mechanism of cuticular competing endogenous RNAs for regulating insecticide penetration and demonstrate it also exists in field strain of oriental fruit fly., Conclusions: We unveil a regulatory axis of lnc19419 ~ miR-994 ~ CPCFC on the cuticle thickness that leads to insecticide penetration resistance. These findings indicate that competing endogenous RNAs regulate insecticide resistance by modulating the cuticle thickness and provide insight into the resistance mechanism in insects., (© 2023. BioMed Central Ltd., part of Springer Nature.)

Electrically conductive metal-organic frameworks (MOFs) have been extensively studied for their potential uses in energy-related technologies and sensors. However, achieving that goal requires MOFs to be highly stable and maintain their conductivity under practical operating conditions with varying solution environments and temperatures. Herein, we have designed and synthesized a new series of {[Ln 4 (μ 4 -O)(μ 3 -OH) 3 (INA) 3 (GA) 3 ](CF 3 SO 3 )(H 2 O) 6 } n (denoted as Ln 4 -MOFs , Ln = Gd, Tm, and Lu, INA = isonicotinic acid, GA = glycolic acid) single crystals, where electrons are found to transport along the π-π stacked aromatic carbon rings in the crystals. The Ln 4 -MOFs show remarkable stability, with minimal changes in conductivity under varying solution pH (1-12), temperature (373 K), and electric field as high as 800 000 V/m. This stability is achieved through the formation of strong coordination bonds between high-valent Ln(III) ions and rigid carboxylic linkers as well as hydrogen bonds that enhance the robustness of the electron transport path. The demonstrated lanthanide MOFs pave the way for the design of stable and conductive MOFs.

Endohedral metallofullerenes (EMFs) are sub-nano carbon materials with diverse applications, yet their formation mechanism, particularly for metastable isomers, remains ambiguous. The current theoretical methods focus mainly on the most stable isomers, leading to limited predictability of metastable ones due to their low stabilities and yields. Herein, we report the successful isolation and characterization of two metastable EMFs, Sc 2 C 2 @ C 1 (39656)-C 82 and Sc 2 C 2 @ C 1 (51383)-C 84 , which violate the isolated pentagon rule (IPR). These two non-IPR EMFs exhibit a rare case of planar and pennant-like Sc 2 C 2 clusters, which can be considered hybrids of the common butterfly-shaped and linear configurations. More importantly, the theoretical results reveal that despite being metastable, these two non-IPR EMFs survived as the products from their most stable precursors, Sc 2 C 2 @ C 2 v (5)-C 80 and Sc 2 C 2 @ C s (6)-C 82 , via a C 2 insertion during the post-formation annealing stages. We propose a systematic theoretical method for predicting metastable EMFs during the post-formation stages. The unambiguous molecular-level structural evidence, combined with the theoretical calculation results, provides valuable insights into the formation mechanisms of EMFs, shedding light on the potential of post-formation mechanisms as a promising approach for EMF synthesis.

The oriental fruit fly, Bactrocera dorsalis , is a damaging insect pest for many vegetable and fruit crops that has evolved severe chemical insecticide resistance, including organophosphorus, neonicotinoid, pyrethroid, and macrolides. Hence, it is important to elucidate its detoxification mechanism to improve its management and mitigate resource destruction. Glutathione S -transferase (GST) is a critical secondary phase enzyme that plays multiple detoxification functions against xenobiotics. In this study, we identified several BdGSTs by characterizing their potential relationships with five insecticides using inducible and tissue-specific expression pattern analyses. We found that an antenna-abundant BdGSTd8 responded to four different classes of insecticides. Subsequently, our immunohistochemical and immunogold staining analysis further confirmed that BdGSTd8 was primarily located in the antenna. Our investigations also confirmed that BdGSTd8 possesses the capability to enhance cell viability by directly interacting with malathion and chlorpyrifos, which clarified the function of antenna-abundant GST in B. dorsalis . Altogether, these findings enrich our understanding of GST molecular characteristics in B. dorsalis and provide new insights into the detoxification of superfluous xenobiotics in the insect antenna.

Background: Metastasis is one of the main obstacles impeding the survival of nasopharyngeal carcinoma (NPC) patients, with the molecular mechanism underlying NPC metastasis still unclear., Results: In this study, Cystatin A (CSTA) was found downregulated in NPC tissues with metastasis compared with those without metastasis. Shorter overall survival and distant metastasis-free survival were found in NPC patients with lower CSTA expression. Using functional assays, we found that CSTA prevented both the in vitro motility of NPC cells and their ability to metastasize in vivo. Transcriptome sequencing and western blot analysis revealed that CSTA inhibited the phosphorylation of AKT. Moreover, activating AKT using AKT agonist SG79 rescued the motility of CSTA-overexpressing NPC cells, whereas, treatment with AKT inhibitor MK2206 inhibited the motility of CSTA-knockdown NPC cells. Mechanically, immunoprecipitation coupled mass spectrometry found that CSTA interacted with the N6-adenosine-methyltransferase subunit METTL3 and promoted its ubiquitin-proteasome-mediated degradation following the upregulation of NKX3-1 and LHPP, which are negative regulators of AKT. Furthermore, knock-down of NKX3-1 and LHPP enhanced the motility of CSTA-overexpressing NPC cells., Conclusions: The inhibitory effect of CSTA upon NPC metastasis mainly depended on suppressing AKT signaling by the upregulation of NKX3-1 and LHPP expression resulting from the binding between CSTA and METLL3. Our study suggests that the CSTA-METLL3-NKX3-1/LHPP-AKT axis could be of therapeutic value for inhibiting NPC metastasis., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Cu is considered to be an effective electrocatalyst in CO/CO 2 reduction reactions (CORR/CO 2 RR) because of its C-C coupling into C 2+ products, but it still remains a formidable challenge to rationally design Cu-based catalysts for highly selective CO/CO 2 reduction to C 2+ liquid products such as acetate. We here demonstrate that spraying atomically layered Cu atoms onto CeO 2 nanorods (Cu-CeO 2 ) can lead to a catalyst with an enhanced acetate selectivity in CORR. Owing to the existence of oxygen vacancies (O v ) in CeO 2 , the layer of Cu atoms at interface coordinates with Ce atoms in the form of Cu-Ce (O v ), as a result of strong interfacial synergy. The Cu-Ce (O v ) significantly promotes the adsorption and dissociation of H 2 O, which further couples with CO to selectively produce acetate as the dominant liquid product. In the current density range of 50-150 mA cm -2 , the Faradaic efficiencies (FEs) of acetate are over 50% with a maximum value of 62.4%. In particular, the turnover frequency of Cu-CeO 2 reaches 1477 h -1 , surpassing that of Cu nanoparticle-decorated CeO 2 nanorods, bare CeO 2 nanorods, as well as other existing Cu-based catalysts. This work advances the rational design of high-performance catalysts for CORR to highly value-added products, which may attract great interests in diverse fields including materials science, chemistry, and catalysis.

Two Keggin Fe 13 -oxo clusters, [Pr 12 Fe 33 (NO 3 ) 6 (L-van) 4 (D-van) 5 (TEOA) 12 (μ 3 -OH) 12 (μ 4 -OH) 12 (μ 4 -O) 28 (H 2 O) 4 ]·(ClO 4 ) 3 ·(NO 3 )·10H 2 O ( 1 ) and [Dy 12 Fe 33 (NO 3 ) 2 (L-van) 3 (D-van) 3 (TEOA) 12 (μ 3 -OH) 18 (μ 4 -OH) 6 (μ 4 -O) 28 (H 2 O) 9 ]·(ClO 4 ) 5 ·(NO 3 ) 6 ·15H 2 O ( 2 ), where L-van = l-valine, D-van = d-valine, and TEOA = triethanolamine, were prepared by using Ln 3+ as a stabilizer. Cluster 1 crystallizes in a chiral space group of C 2, while cluster 2 crystallizes in a centrosymmetric space group of Pnma . Dynamic magnetic measurements of 2 under a zero direct-current field reveal that 2 exhibits single-molecule-magnet characteristics with an energy barrier of 18.79 K. Significantly, the formation of the chiral cluster 1 is closely related to the larger radius of the Pr 3+ ion.

The designed synthesis of chiral luminescent molecules with excellent circularly polarized luminescence (CPL) performance and high quantum yield (QY) levels has attracted great interest but remains very challenging. Herein, we report three pairs of chiral europium-titanium-oxo clusters featuring both modest CPL characteristics and high QY levels (up to 79%), which can be regulated by switching between different ligand substituents.

Hybrid organic-inorganic halide perovskites (HOIPs) have received continued interest for their structure diversity and potential application in optoelectronic, solar cells, nonlinear optics (NLO), and ferroelectrics. Structural symmetry breaking induced by water molecules in single-crystal-to-single-crystal (SCSC) transformations is beneficial to develop ferroelectrics or second-harmonic generation (SHG) materials. Along this line, a water-containing two-dimensional (2D) double perovskite, (C 6 H 16 N 2 ) 2 AgBiBr 8 ·H 2 O ( 1 ), was prepared. Acentric 1 suffered a twice SCSC transformation when subjected to dehydration and rehydration, where the new centric (C 6 H 16 N 2 ) 2 AgBiBr 8 ( 2 ) and acentric (C 6 H 16 N 2 ) 2 AgBiBr 8 ·0.5H 2 O ( 3 ) were generated. In contrast to the irreversible transformation from 1 to 2 (symmetry: P 2 1 → Pmna ), it is prominent that the reversible conversion of centric 2 to acentric 3 (symmetry: Pmna ↔ P 2 1 2 1 2). The result validated the effect of guest water on inducing structural transformation and symmetry breaking of 2D perovskites, inspiring further explorations on water-involved 2D materials.

Lanthanide-iron clusters usually display interesting structures and outstanding magnetic properties. However, due to the high reactivity (acidity) of the Fe 3+ -H 2 O bond and the inability to form a terminal oxo ligand, the preparation of high-nuclearity Ln-Fe clusters is a great challenge. Herein, a series of lanthanide-iron-oxo clusters with the formulas [Y 6 Fe(HL) 10 (NO 3 ) 2 (EG) 2 (μ 3 -OH) 8 (H 2 O) 4 ]·ClO 4 ·N-H 2 BDEA·2H 2 O ( Y 6 Fe , 1 , H 2 L = 3-hydroxypivalic acid, EG = ethylene glycol, N-H 2 BDEA = 2,2'-(butylimino)diethanol), [Ln 8 Fe 3 (H 2 TEOA) 2 (HTEOA) 2 (HL) 10 (μ 3 -OH) 9 (μ 2 -OH)(μ 4 -O) 2 (H 2 O) 4 ]·(NO 3 ) 3 · x H 2 O (Ln = Y, x = 13 for 2 , Y 8 Fe 3 ; Ln = Dy, x = 10 for 3 , Dy 8 Fe 3 ; H 3 TEOA = triethanolamine), and [Ln 12 Fe 14 (HL) 16 (μ 3 -OH) 20 (μ 2 -OH) 12 (μ 4 -O) 12 (H 2 O) 12 ]·(NO 3 ) 6 · x H 2 O (Ln = Y, x = 40 for 4 , Y 12 Fe 14 ; Ln = Dy, x = 30 for 5 , Dy 12 Fe 14 ) were obtained by adjusting the pH with different aminopolyols as organic alkalis. Structural analysis showed that a cubane-like unit was the main structural unit in compounds 1 - 5 . Compound 1 was formed by two {Y 3 Fe(μ 3 -OH) 4 } units with the common vertices, and compounds 2 and 3 were formed by two {Y 3 Fe(μ 3 -OH) 3 (μ 4 -O)} units with the common vertices bridging a quadrilateral unit {Ln 2 Fe 2 (μ 3 -OH) 3 (μ 2 -OH)}. The basic structural units of cubane-like {Ln 2 Fe 2 (μ 3 -OH)(μ 4 -O) 3 }, triangular {LnFe 2 (μ 3 -OH) 2 (μ 4 -O)}, and neutral iron-hydroxyl {Fe(μ 3 -OH)(μ 2 -OH) 2 } were found in compounds 4 and 5 . The universality of building blocks for the assembly has been demonstrated in high-nuclearity lanthanide-iron-oxo clusters. Meanwhile, the structural regulation of the lanthanide-iron-oxo clusters 1 - 5 was realized by adjusting the pH with different organic alkalis, which provided the reference for the effective synthesis of high-nuclearity lanthanide-iron-oxo clusters. Magnetic studies showed that 3 and 5 displayed a slow magnetic relaxation behavior.

A [2]rotaxane-based molecular shuttle with an acid-responsive asymmetric macrocycle on a symmetric dumbbell axle is reported. Upon adding TFA, the macrocycle, namely the amine naphthotube, is protonated and translocates from the di(quaternary ammonium) station to the triazole stations because of electrostatic repulsion and weakened binding. The shuttling kinetics are slow due to the steric hindrance caused by the ethyl group on the quaternary ammonium center and can be followed by 1 H NMR spectroscopy. Interestingly, it was found that the shuttling kinetics depends on the concentration of TFA. A kinetic intermediate was detected and can even be captured in the presence of a high concentration of TFA. Extensive control experiments revealed that the shuttling kinetics and the capture of the kinetic intermediate are related to the different protonation states of the rotaxanes., (© 2022 Wiley-VCH GmbH.)

Based on the Venturi self-pumping effect, real-time sniffing with mass spectrometry (R-sniffing MS) is developed as a tool for direct and real-time mass spectrometric analysis of both gaseous and solid samples. It is capable of dual-mode operation in either gaseous or solid phase, with the corresponding techniques termed as R g -sniffing MS and R s -sniffing MS, respectively. In its gaseous mode, R g -sniffing MS is capable of analyzing a gaseous mixture with response time (0.8-2.1 s rise time and 7.3-9.6 s fall time), spatial resolution (<80 μm), three-dimensional diffusion imaging, and aroma distribution imaging of red pepper. In its solid mode, an appropriate solvent droplet desorbs the sample from a solid surface, followed by the aspiration of the mixture using the Venturi self-pumping effect into the mass spectrometer, wherein it is ionized by a standard ion source. Compared with the desorption electrospray ionization (DESI) technique, R s -sniffing MS demonstrated considerably improved limit of detection (LOD) values for arginine (0.07 μg/cm 2 R s -sniffing vs 1.47 μg/cm 2 DESI), thymopentin (0.10 μg/cm 2 vs 2.67 μg/cm 2 ), and bacitracin (0.16 μg/cm 2 vs 2.28 μg/cm 2 ). R s -sniffing is applicable for the detection of C 60 (OCH 3 ) 6 Cl - , an intermediate in the methoxylation reaction involving C 60 Cl 6 (solid) and methanol (liquid). The convenient and highly sensitive R-sniffing MS has a characteristic separation of desorption from the ionization process, in which the matrix atmosphere of desorption can be interfaced by a pipe channel and self-pumped by the Venturi effect with consequent integration using a standard ion source. The R-sniffing MS operates in a voltage-, heat-, and vibration-free environment, wherein the analyte is ionized by a standard ion source. Consequently, a wide range of samples can be analyzed simultaneously by the R-sniffing MS technique, regardless of their physical state.

Hundreds of members have been synthesized and versatile applications have been promised for endofullerenes (EFs) in the past 30 y. However, the formation mechanism of EFs is still a long-standing puzzle to chemists, especially the mechanism of embedding clusters into charged carbon cages. Here, based on synthesis and structures of two representative vanadium-scandium-carbido/carbide EFs, VSc 2 C@ I h (7)-C 80 and VSc 2 C 2 @ I h (7)-C 80 , a reasonable mechanism-C 1 implantation (a carbon atom is implanted into carbon cage)-is proposed to interpret the evolution from VSc 2 C carbido to VSc 2 C 2 carbide cluster. Supported by theoretical calculations together with crystallographic characterization, the single electron on vanadium (V) in VSc 2 C@ I h (7)-C 80 is proved to facilitate the C 1 implantation. While the V=C double bond is identified for VSc 2 C@ I h (7)-C 80 , after C 1 implantation the distance between V and C atoms in VSc 2 C 2 @ I h (7)-C 80 falls into the range of single bond lengths as previously shown in typical V-based organometallic complexes. This work exemplifies in situ self-driven implantation of an outer carbon atom into a charged carbon cage, which is different from previous heterogeneous implantation of nonmetal atoms (Group-V or -VIII atoms) driven by high-energy ion bombardment or high-pressure offline, and the proposed C 1 implantation mechanism represents a heretofore unknown metal-carbon cluster encapsulation mechanism and can be the fundamental basis for EF family genesis.