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Epitaxial strain provides important pathways to control the magnetic and electronic states in transition-metal oxides. However, the large strain is usually accompanied by a strong reduction of the oxygen-vacancy formation energy, which hinders the direct manipulation of their intrinsic properties. Here, using a postdeposition ozone annealing method, we obtain a series of oxygen stoichiometric SrCoO3 thin films with the tensile strain up to 3.0%. We observe a robust ferromagnetic ground state in all strained thin films, while interestingly the tensile strain triggers a distinct metal-to-insulator transition along with the increase of the tensile strain. The persistent ferromagnetic state across the electrical transition therefore suggests that the magnetic state is directly correlated with the localized electrons, rather than the itinerant ones, which then calls for further investigation of the intrinsic mechanism of this magnetic compound beyond the double-exchange mechanism.

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).)

Diabetic cardiomyopathy (DCM) is a complication of diabetes mellitus characterized by heart failure and cardiac remodeling. Previous studies show that tetrahydroberberrubine (THBru) retrogrades cardiac aging by promoting PHB2-mediated mitochondrial autophagy and prevents peritoneal adhesion by suppressing inflammation. In this study we investigated whether THBru exerted protective effect against DCM in db/db mice and potential mechanisms. Eight-week-old male db/db mice were administered THBru (25, 50 mg·kg -1 ·d -1 , i.g.) for 12 weeks. Cardiac function was assessed using echocardiography. We showed that THBru administration significantly improved both cardiac systolic and diastolic function, as well as attenuated cardiac remodeling in db/db mice. In primary neonatal mouse cardiomyocytes (NMCMs), THBru (20, 40 μM) dose-dependently ameliorated high glucose (HG)-induced cell damage, hypertrophy, inflammatory cytokines release, and reactive oxygen species (ROS) production. Using Autodock, surface plasmon resonance (SPR) and DARTS analyses, we revealed that THBru bound to the domain of the receptor for advanced glycosylation end products (RAGE), subsequently leading to inactivation of the PI3K/AKT/NF-κB pathway. Importantly, overexpression of RAGE in NMCMs reversed HG-induced inactivation of the PI3K/AKT/NF-κB pathway and subsequently counteracted the beneficial effects mediated by THBru. We conclude that THBru acts as an inhibitor of RAGE, leading to inactivation of the PI3K/AKT/NF-κB pathway. This action effectively alleviates the inflammatory responses and oxidative stress in cardiomyocytes, ultimately leading to ameliorated DCM., (© 2024. The Author(s), under exclusive licence to Shanghai Institute of Materia Medica, Chinese Academy of Sciences and Chinese Pharmacological Society.)

Deuteration of amine compounds has been widely of concern because of its practical role in organic reaction mechanisms and drug research; however, only limited deuteration label methods are accessible with D 2 O as a deuterium source. Herein, we propose a convenient deuteration protocol, including preparing D 2 by the AlGa activation method, using PtRu nanowires as catalysts, and utilizing the elementary step in the couple reaction involving an imine unit, to realize the rapid preparation of a secondary amine with a diversified deuteration label. The self-coupling between nitriles not only provides a symmetric secondary amine with four α-D atoms but also produces high-valued ND 3 in an atomic-economic way.

Two polyhedral silver-thiolate clusters, [S@Ag 16 (Tab) 10 (MeCN) 8 ](PF 6 ) 14 (Ag 16 ) and [Ag 12 (Tab) 6 (DMF) 12 ](PF 6 ) 12 (Ag 12 ), were synthesized by using electroneutral Tab species as protective ligands (Tab=4-(trimethylammonio)benzenethiolate, DMF=N,N-dimethylformamide, MeCN=acetonitrile). Ag 16 has a decahedral shape composed of eight pentagon {Ag 5 } units and two square {Ag 4 } units. The structure of Ag 12 is a cuboctahedron, a classical Archimedean structure composed of six triangular faces and eight square faces. The former configuration is discovered in silver-thiolate cluster for the first time, possibly benefited from the more flexible coordination between the Tab ligand and Ag + facilitated by the electropositive -N(CH 3 ) 3 + substituent group. Third-order nonlinear optical studies show that both clusters in DMF exhibit reverse saturate absorption response under the irradiation of 532 nm laser., (© 2024 Wiley-VCH GmbH.)

Zwitterionic thiolate ligands have the potential to introduce novel assembly modes and functions for noble metal clusters. However, their utilization in the synthesis of silver clusters remains understudied, particularly for the clusters containing reductive Ag(0) species. In this article, we report the first synthesis of a mixed-valence silver(0/I) cluster protected by zwitterionic Tab as thiolate ligands (Tab = 4-(trimethylammonio)benzenethiolate), denoted as [Ag 22 (Tab) 24 ](PF 6 ) 20 ·16CH 3 OH·6Et 2 O ( Ag 22 ·16CH 3 OH·6Et 2 O), alongside an Ag(I) cluster [Ag 20 (Tab) 12 (PhCOO) 10 (MeCN) 2 (H 2 O)](PF 6 ) 10 ·11MeCN ( Ag 20 ·11MeCN). Ag 22 has a distinct hierarchical supratetrahedral structure with a central {Ag 6 } kernel surrounded by four [Ag 4 (Tab) 6 ] 4+ units. High-resolution electrospray ionization mass spectra demonstrate that Ag 22 has two free electrons, indicating a superatomic core. Ag 20 has a drum-like [Ag 12 (Tab) 6 (PhCOO) 6 (H 2 O)] 6+ inner core capped by two tetrahedral-like [Ag 4 (Tab) 3 (PhCOO) 2 (MeCN)] 2+ units. Ag 20 can be transformed into Ag 22 after its reaction with NaBH 4 in solution. Antibacterial measurements reveal that Ag 22 has a significantly lower minimum inhibitory concentration than that of the Ag 20 cluster. This work not only extends the stabilization of silver(0/I) clusters to neutral thiol ligands but also offers new materials for the development of novel antibacterial materials.

The effect on acetabular management in developmental dysplasia of the hip (DDH) patients aged 7 or older with modified low Dega osteotomy procedure was evaluated. Patients between 7 and 14 years old were managed with modified low Dega osteotomy and open reduction and concomitant procedures to evaluate whether low level osteotomy improved the clinical and radiologic outcomes after treatment. Clinical status was assessed using the modified McKay's criteria; radiologic evaluations were assessed for the modified Severin classification, the mean acetabular index (AI), Sharp angle and center-edge (CE) angle. And occurrence of triradiate cartilage injury and complications was recorded. Forty-two DDH patients (57 hips) between 7 and 14 years old were managed with modified low Dega osteotomy. The results demonstrated the latest follow-up 43 hips (75.4%) were rated excellent and 10 hips (17.5%) rated good according to the modified McKay criteria and 41 hips (71.9%) were rated excellent and 11 hips (19.3%) rated good according to Modified Severin classification, respectively. The mean Hip Score improved from 69.53 ± 7.14 before the operation to 93.17 ± 8.43 at the final follow-up. The mean AI changed from 31.9° to 20.2°, mean Sharp angle decreased from 59.3° to 38.8° and mean CE angle increased from -10.9° to 35.2°, preoperatively and at latest follow-up, respectively. The modified low Dega osteotomy combined with open reduction and concomitant procedures were found to be adequate in improving instant and sustained clinical and radiographic outcomes for the late detected pediatric walking DDH patients., (Copyright © 2024 The Author(s). Published by Wolters Kluwer Health, Inc.)

Although interlocked three-dimensional molecules display unique properties associated with their spatial structures, their synthesis and study of their host-guest properties remain challenging. We report the formation of a novel [2]catenane, [Et 4 N]@[(Tp*WS 3 Cu 3 Cl) 2 ( cis -bpype) 3 ] 2 (OTf) 5 ([Et 4 N][ 1 ](OTf) 5 ), by self-assembly of the cluster node [Tp*WS 3 Cu 3 Cl] + and the organic linker ( Z )-1,2-diphenyl-1,2-bis(4-(pyridin-4-yl)phenyl)ethene ( cis -bpype). Single-crystal X-ray and NMR analyses established that [ 1 ] 4+ is formed by the interpenetration of two cluster-organic cages. Unique cation-in-cation host-guest complexes were observed with this catenane. The crystalline, empty catenane was formed by taking advantage of the electrostatic repulsion-induced weak binding of the host. Encapsulation experiments also reveal that the empty catenane can adaptively encapsulate cations such as [Et 4 N] + and [Pr 4 N] + in the cross cavity but is unable to encapsulate [Bu 4 N] + and [Me 4 N] + , although the size of the latter is compatible with that of the cavity. Theoretical calculations and volume analysis allow to unravel the ingenious role of catenane structures and the interplay between electrostatic repulsion and attractive noncovalent interactions for size-specific recognition behavior in host-guest systems involving species with similar electric charges.

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.

Objective: To investigate the level of nucleic acid oxidation in myocardial tissue of patients aged over 85 with heart failure with preserved ejection fraction (HFpEF) and the correlation with myocardial amyloid deposition. Methods: This was a retrospective case-control study. Data of patients≥85 years old who underwent systematic pathological autopsy in Beijing Hospital from 2003 to 2017 were retrospectively collected. Twenty-six patients were included in the HFpEF group and 13 age-and sex-matched patients who had not been diagnosed with heart failure and died of non-cardiovascular diseases served as the control group. The left ventricular myocardium slices of both groups were semi-quantitatively analyzed using immunohistochemical staining of 8-oxidized guanine riboside (8-oxo-G) and 8-oxidized guanine deoxyriboside (8-oxo-dG) to evaluate the oxidation of RNA and DNA in cardiomyocytes. Using the median of the mean absorbance value of 8-oxo-G immunohistochemical staining as the cut-off value, patients were divided into high-absorbance group and low-absorbance group. Congo red staining was used to compare myocardial amyloid deposition between the two groups. Results: The mean age of patients in HFpEF group was (91.8±3.7) years, 24 (92.3%) were males. The mean age of patients in control group was (91.7±3.7) years old, 11 (84.6%) were males. The median mean optical absorbance value of 8-oxo-G immunohistochemical staining of myocardium was significantly higher in HFpEF patients than in control group (0.313 8 (0.302 2, 0.340 6) vs. 0.289 2 (0.276 7, 0.299 4), Z =-3.245, P= 0.001). The median mean absorbance value of 8-oxo-dG immunohistochemical staining of myocardial tissue was similar between the two groups (0.300 0 (0.290 0, 0.322 5) vs. 0.300 0 (0.290 0, 0.320 0), Z =-0.454, P= 0.661). Proportion of patients with moderate and severe cardiac amyloid deposition was significantly higher in the high-absorbance group than in the low-absorbance group ((85.0%, 17/20) vs. (31.6%, 6/19), P =0.001). Conclusion: The RNA oxidation degree of myocardium in HFpEF patients is higher than that in elderly people without heart failure. Degree of myocardial amyloid deposits is higher in patients with high levels of RNA oxidation.

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.

Introduction: To establish an animal model of delayed intravenous resuscitation following seawater immersion after hemorrhagic shock (HS)., Methods: Adult male SD rats were randomly divided into three groups: group NI (HS with no immersion), group SI (HS with skin immersion), and group VI (HS with visceral immersion). Controlled HS in rats was induced by withdrawing 45% of the calculated total blood volume within 30 min. In SI group, immediately after blood loss, 0.5 cm below the xiphoid process was immersed in artificial seawater, at (23 ± 1) °C, for 30 min. In VI group, the rats were performed by laparotomy and the abdominal organs were immersed in (23 ± 1) °C seawater for 30 min. Two hours after seawater immersion, the extractive blood and lactated Ringer's solution were delivered intravenously. The mean arterial pressure (MAP), lactate, and other biological parameters were investigated in different time points. The survival rate of 24 h after HS was recorded., Results: After seawater immersion following HS, MAP and abdominal viscera blood flow decreased significantly, and the plasma levels of lactate and the organ function parameters were increased than the baseline. The above changes in VI group were more serious than those in SI and NI group, especially in myocardial and small intestine damage. The hypothermia, hypercoagulation, and metabolic acidosis were also observed after seawater immersion; the injury was more severely in VI group than that of SI group. However, the plasma levels of sodium, potassium, chlorine, and calcium in VI group were significantly higher than those before injury and in the other two groups. In the VI group, the level of plasma osmolality in instant, 2 h, and 5 h after immersion was 111%, 109%, and 108% of the SI group, respectively, all P < 0.01. The 24-h survival rate of VI group was 25%, which was significantly lower than that of SI group (50%) and NI group (70%), P < 0.05., Conclusions: The model fully simulated the key damage factors and field treatment conditions, reflected the effects of low temperature and hypertonic damage caused by seawater immersion on the severity and prognosis of naval combat wounds, and provided a practical and reliable animal model for the study of field treatment technology of marine combat shock., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

Although the synthesis of low-dimensional metal sulfides by assembling cluster-based units is expected to promote the development of optical materials and models of enzyme active centers such as dinitrogenase, it is faced with limited assembly methodology. Herein we present a cut-to-link strategy to generate high-nuclearity assemblies, inspired by the formation of a Z-type dimer of the W-S-Cu analogues of P N cluster through in situ release of active linkers. Four new compounds with structures based on the same {Tp*WS 3 Cu 3 } incomplete cubane-like units were obtained using varied combinations of mild reagents. Open-aperture Z -scan measurements demonstrated the highest-nuclearity complex has the largest nonlinear optical absorption coefficient among discrete cluster-based materials reported to date. This approach enables building high-nuclearity metal sulfide clusters through cluster-based building blocks and opens a way to the design and exploration of materials based on well-identified building blocks.

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.

Introduction: A high malignancy rate and poor prognosis are common problems with triple-negative breast cancer (TNBC). There is increasing evidence that glycolysis plays vital roles in tumorigenesis, tumor invasion, immune evasion, chemoresistance, and metastasis. However, a comprehensive analysis of the diagnostic and prognostic significance of glycolysis in TNBC is lacking., Methods: Transcriptomic and clinical data of TNBC patients were obtained from The Cancer Genome Atlas (TCGA) and Molecular Taxonomy of Breast Cancer International Consortium (METABRIC) databases, respectively. Glycolysis-related genes (GRGs) were collected from the Molecular Signatures Database (MSigDB). Differential comparative analysis was performed to obtain the differentially expressed (DE)-GRGs associated with TNBC. Based on the DE-GRGs, a glycolysis-related risk signature was established using Least Absolute Shrinkage and Selector Operation (LASSO) and multivariable Cox regression analyses. The prognostic value, tumor microenvironment, mutation status, and chemotherapy response of different risk groups were analyzed. An independent cohort from the METABRIC database was used for external validation. Furthermore, the expression patterns of five genes derived from the prognostic model were validated by quantitative real-time polymerase chain reaction (RT-qPCR)., Results: The glycolysis-related prognostic signature included five genes (IFNG, ACSS2, IRS2, GFUS, and GAL3ST1) and predicted the prognosis of TNBC patients independent of clinical factors (p < 0.05). Patients were divided into high- and low-risk groups based on the median risk score. Compared to low-risk TNBC patients, high-risk patients had significantly decreased overall survival (HR = 2.718, p < 0.001). Receiver operating characteristic and calibration curves demonstrated that the model had high performance in terms of predicting survival and risk stratification. The results remained consistent after external verification. Additionally, the tumor immune microenvironment significantly differed between the risk groups. Low-risk TNBC patients had a better immunotherapy response than high-risk patients. High-risk TNBC patients with a poor prognosis may benefit from targeted therapy., Conclusions: This study developed a novel glycolysis and prognosis-related (GRP) signature based on GRGs to predict the prognosis of TNBC patients, and may aid clinical decision-making for these patients., (© 2022. The Author(s), under exclusive licence to Springer Healthcare Ltd., part of Springer Nature.)

A series of Schiff base LH (( E )-2-((pyridin-2-ylmethylene)amino)phenol) supported phenoxo bridged symmetric [Dy 2 (L) 2 (hfac) 4 ] (1), [Dy 2 (L) 2 (tfac) 4 ] (2) and asymmetric [Dy 2 (L) 2 (thd) 3 (NO 3 )]·1.5H 2 O (3) binuclear complexes were isolated using differently substituted β-diketonate co-ligands (Hhfac = hexafluoroacetylacetonate, Htfac = trifluoroacetylacetonate, and Hthd = 2,2,6,6-tetramethyl-3,5-heptanedione). In all the three complexes 1-3, the two LH ligands provide phenoxo bridging and N-donor atoms. The {Dy 2 (μ 2 -O) 2 } magnetic core structures with LH ligands are found to be the same in 1-3 while the dissimilar functionalities of the axially coordinated different β-diketonate co-ligands play a crucial role in modulating the magnetic anisotropy of individual Dy III sites and magnetic exchange between them. The experimental static magnetic behaviour suggests the presence of intramolecular antiferromagnetic interactions in all the three complexes 1-3. The strength of the magnetic exchange coupling decreases with increasing magnetic anisotropy of individual Dy III ions from complex 1 to complex 3 and simultaneously their zero-field slow magnetic relaxation behaviors were found to increase with effective energy barriers (Δ E / k B ) of 9.04 K, 24.06 K and 25.65 K, respectively. Furthermore, the DFT and ab initio theoretical calculations performed on the X-ray structures of complexes 1-3 support our experimental findings.

Spin defects like the negatively charged boron vacancy color center (V B - ) in hexagonal boron nitride (hBN) may enable new forms of quantum sensing with near-surface defects in layered van der Waals heterostructures. Here, the effect of strain on V B - color centers in hBN is revealed with correlative cathodoluminescence and photoluminescence microscopies. Strong localized enhancement and redshifting of the V B - luminescence is observed at creases, consistent with density functional theory calculations showing V B - migration toward regions with moderate uniaxial compressive strain. The ability to manipulate spin defects with highly localized strain is critical to the development of practical 2D quantum devices and quantum sensors.

A series of acetylacetone-protected lanthanide-titanium-oxo clusters (LTOCs), formulated as [La 6 Ti(μ 3 -OH) 8 (acac) 12 (CH 3 O) 2 (CH 3 OH) 6 ] ( La 6 Ti ; Hacac = acetylacetone) and [Ln 9 Ti 2 (μ 4 -O)(μ 3 -OH) 14 (acac) 17 (CH 3 O) 2 (CH 3 OH) 3 ] [Ln = Eu ( Eu 9 Ti 2 ) and Tb ( Tb 9 Ti 2 )], were synthesized through the reactions of LnCl 3 ·6H 2 O (Ln = La, Eu, and Tb), Hacac, Ti(O i Pr) 4 , and triethylamine in methanol. Crystal structural analysis shows that La 6 Ti exhibits an hourglass-like structure consisting of two La 3 Ti cubane subunits by sharing one Ti 4+ ion, while Eu 9 Ti 2 can be viewed as a combination of four Eu 3 Ti cubane subunits by sharing three corners and one side. The photoluminescence (PL) measurements show that Tb 9 Ti 2 exhibits excellent PL properties with a high quantum yield (QY) of 34.8%, while Eu 9 Ti 2 only has a QY of 1.4% because of the different photosensitizations of ligands to Eu 3+ and Tb 3+ ions in the photophysical process.

Previous studies have suggested that replacing saturated fat with unsaturated fat is beneficial for cardiometabolic health. However, research that directly compares the effects of polyunsaturated fatty acids (PUFAs) and monounsaturated fatty acids (MUFAs) is rare. The present 3-month, three-arm, randomized, controlled-feeding trial aimed to investigate the effects of n-6 PUFA- and MUFA-rich cooking oils on body weight and cardiometabolic profiles among middle-aged and elderly Chinese women at high cardiovascular risk. Ninety participants were recruited and randomly assigned to groups fed diets using n-6 PUFA-rich soybean oil (SO, n = 30), MUFA-rich olive oil (OO, n = 30), and MUFA-rich camellia seed oil (CSO, n = 30) as cooking oils considering traditional Chinese eating habits for 3 months. Participants were required to eat only the foods provided for lunch and dinner, and avoid intake of edible oils in breakfast. Body weight and cardiovascular profiles were measured at the baseline, middle, and end of the intervention, and group differences in changes of outcomes during intervention were examined by a linear mixed model. We found no significant difference in the changes of body weight among the SO group (mean change, 0.31 kg; 95% CI, -0.88 to 0.27), the OO group (mean change, -0.13 kg; 95% CI, -0.62 to 0.36), and the CSO group (mean change, -0.72 kg; 95% CI, -1.38 to -0.07). For secondary outcomes, the OO group showed a slight increase in HDL cholesterol ( P = 0.03), while the CSO group showed greater reduction in aspartate aminotransferase (AST) ( P = 0.02) when compared with the SO group. These results suggested that MUFA-rich OO and CSO exerted more favorable effects on cardiometabolic profiles among middle-aged and elderly Chinese women at high cardiovascular risk than the n-6 PUFA-rich SO.

The discovered giant clusters are always highly symmetric owing to the spontaneous assembly of one or two basic units. Herein we report the Gd 44 Co 28 crown and Gd 95 Co 60 cage, formulated as [Gd 44 Co 28 (IDA) 20 (OH) 72 (CO 3 ) 12 (OAc) 28 (H 2 O) 64 ]⋅(ClO 4 ) 24 and [Na 4 Gd 95 Co 60 (IDA) 40 (OH) 150 (CO 3 ) 40 (OAc) 58 (H 2 O) 164 ] ⋅ (ClO 4 ) 41 (H 2 IDA=iminodiacetic acid), respectively, by providing a library containing multiple low-nuclearity units. The heart-like units and crown-like tetramer found in both compounds indicate unprecedented assembly levels, leading to an atypical geometry characteristic compared to the giant clusters directly assembled by regular units. These two clusters not only significantly increase the size of Ln-Co clusters but also exhibit the enhanced magnetic entropy change at ultra-low temperatures. This work provided an effective way to fabricate cluster compounds with giant size and geometry complexity simultaneously., (© 2022 Wiley-VCH GmbH.)

The understanding of the hydrolysis mechanism of lanthanide ions is limited by their elusive coordination configuration and undeveloped technology. A potential solution by high-resolution mass spectroscopy studies is hindered by the lack of a stable model under electrospray ionization (ESI) conditions and the complexity of the spectra. Herein, it is demonstrated that diketonate ligands can efficiently stabilize the hydrolyzed intermediate cluster of Ln 3+ under ESI conditions, and an effective mass difference fingerprint of isomorphism (MDFI) method is proposed, which can allow the determination of the nuclearity-number of the species without depth resolution. Thus, the hydrolysis of Ln 3+ into an atomically precise hydroxide cluster is observed at the level of precise formulae. The species evolution upon hydrolysis is along the dominant path of {Eu 3 }-{Eu 4 }-{Eu 9 }-{Eu 10 }-{Eu 11 }-{Eu 15 }-{Eu 16 } and a nondominant path of {Eu 3 }-{Eu 4 }-{Eu 8 -1}-{Eu 8 -2} under the investigated conditions. The crystal of the {Eu 16 } species was obtained via low-temperature crystallization, and single-crystal X-ray diffraction studies show that its structure contains three octahedral {o-Ln 6 } units. The contradiction between multiple {o-Ln 6 } units in the structure and the absence in the formation process indicates that the repetitive subunit observed in the structure does not necessarily correspond to the construction units of high-nuclearity clusters. Photophysical measurements indicate that Eu 16 cluster has a high total emission quantum efficacy of 12.8% in the solid state. This study provides fundamental insights into the formation, evolution, and assembly of small lanthanide hydroxide units upon hydrolysis, which is vital for the goal of directional synthesis of lanthanide hydroxide clusters.

Building blocks with multiple components are promising for the synthesis of complex molecular assemblies, but are rarely available. Herein, we report a modification procedure for a multi-component building block [Ln 3 Ti(HSA) 6 (SA) 4 (H 2 O)] - ({Ln 3 Ti-SA}, H 2 SA=salicylic acid, Ln=Eu/Gd) to form new building blocks {Ln 3 Ti x -MSA} (H 2 MSA=5-methoxysalicylic acid, x=1, 2, 3) by constructing [Ti(MSA) 3 ] 2- units. The obtained {Ln 3 Ti x -MSA} can further assemble into a chiral Ln 22 Ti 14 ring with the formulae [Eu 22 Ti 14 (MSA) 48 (HMSA) 22 (CH 3 COO) 4 (H 2 O) 10 (iPrOH)] and [Gd 22 Ti 14 (MSA) 46 (HMSA) 26 (CH 3 COO) 4 (H 2 O) 8 ]. Parallel experiments without Ti 4+ result in linear Ln chains. Detailed analysis shows that the [Ti(MSA) 4 ] 4- unit makes the originally variable Ln chains become available building blocks and the modified [Ti(MSA) 3 ] 2- further triggers interesting chiral-sorting behavior. Finally, the electronic adsorption and magneto-optic responses of these molecular rings are investigated., (© 2021 Wiley-VCH GmbH.)

Functional and versatile nano- and microassemblies formed by biological molecules are found at all levels of life, from cell organelles to full organisms. Understanding the chemical and physicochemical determinants guiding the formation of these assemblies is crucial not only to understand the biological processes they carry out but also to mimic nature. Among the synthetic peptides forming well-defined nanostructures, the octapeptide Lanreotide has been considered one of the best characterized, in terms of both the atomic structure and its self-assembly process. In the present work, we determined the atomic structure of Lanreotide nanotubes at 2.5-Å resolution by cryoelectron microscopy (cryo-EM). Surprisingly, the asymmetric unit in the nanotube contains eight copies of the peptide, forming two tetramers. There are thus eight different environments for the peptide, and eight different conformations in the nanotube. The structure built from the cryo-EM map is strikingly different from the molecular model, largely based on X-ray fiber diffraction, proposed 20 y ago. Comparison of the nanotube with a crystal structure at 0.83-Å resolution of a Lanreotide derivative highlights the polymorphism for this peptide family. This work shows once again that higher-order assemblies formed by even well-characterized small peptides are very difficult to predict., Competing Interests: The authors declare no competing interest., (Copyright © 2022 the Author(s). Published by PNAS.)

Advances in medical imaging have enabled patient-specific biomechanical modelling of arterial lesions such as atherosclerosis and aneurysm. Geometry acquired from in-vivo imaging is already pressurized and a zero-pressure computational start shape needs to be identified. The backward displacement algorithm was proposed to solve this inverse problem, utilizing fixed-point iterations to gradually approach the start shape. However, classical fixed-point implementations were reported with suboptimal convergence properties under large deformations. In this paper, a dynamic learning rate guided by the deformation gradient tensor was introduced to control the geometry update. The effectiveness of this new algorithm was demonstrated for both idealized and patient-specific models. The proposed algorithm led to faster convergence by accelerating the initial steps and helped to avoid the non-convergence in large-deformation problems., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Two-dimensional hybrid organic-inorganic perovskites (HOIPs) have recently drawn intense attention as potential photovoltaic materials. However, n = 1 two-dimensional (2D) HOIPs face the challenge of low conductivity between the inorganic layers, leading to unsatisfactory device performance. Interestingly, 2D HOIPs employing π-conjugated molecules as organic moieties show energy and charge transfers between organic and inorganic layers, indicating potentially efficient carrier transport for photovoltaic applications. Nevertheless, the development of 2D HOIP-based solar cells especially utilizing polycyclic aromatic alkylammonium as cations is in its infancy. Herein, we investigated the electronic structure and band alignment of a series of n = 1 2D Ruddlesden-Popper (RP) phase HOIPs containing different polycyclic aromatic groups and alkyl chains, based on density functional theory calculations. We find that the polycyclic aromatic group plays an important role in controlling the functionality of 2D HOIPs by directly modifying band-edge states, and the band alignment at the organic-inorganic interface can be designed to promote either exciton trapping or dissociation for light-emitting or photovoltaic applications, respectively.

Background: This study aimed to develop and validate an electronic frailty index (eFI) based on routine electronic health records (EHR) for older adult inpatients and to analyze the correlations between frailty and hospitalized events and costs. Methods: We created an eFI from routine EHR and validated the effectiveness by the consistency of the comprehensive geriatric assessment-frailty index (CGA-FI) with an independent prospective cohort. Then, we analyzed the correlations between frailty and hospitalized events and costs by regressions. Results: During the study period, 49,226 inpatients were included in the analysis, 42,821 (87.0%) of which had enough data to calculate an eFI. A strong correlation between the CGA-FI and eFI was shown in the validation cohort of 685 subjects (Pearson's r = 0.716, P < 0.001). The sensitivity and specificity for an eFI≥0.15, the upper tertile, to identify frailty, defined as a CGA-FI≥0.25, were 64.8 and 88.7%, respectively. After adjusting for age, sex, and operation, an eFI≥0.15 showed an independent association with long hospital stay (odds ratio [OR] = 2.889, P < 0.001) and death in hospital (OR = 19.97, P < 0.001). Moreover, eFI values (per 0.1) were positively associated with total costs (β = 0.453, P < 0.001), examination costs (β = 0.269, P < 0.001), treatment costs (β = 0.414, P < 0.001), nursing costs (β = 0.381, P < 0.001), pharmacy costs (β = 0.524, P < 0.001), and material costs (β = 0.578, P < 0.001) after adjusting aforementioned factors. Conclusions: We successfully developed an effective eFI from routine EHR from a general hospital in China. Frailty is an independent risk factor for long hospital stay and death in hospital. As the degree of frailty increases, the hospitalized costs increase accordingly., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Liang, Xie, Du, Shi, Yang and Wang.)

Ionically bonded organic metal halide hybrids have emerged as versatile multicomponent material systems exhibiting unique and useful properties. The unlimited combinations of organic cations and metal halides lead to the tremendous structural diversity of this class of materials, which could unlock many undiscovered properties of both organic cations and metal halides. Here we report the synthesis and characterization of a series benzoquinolinium (BZQ) metal halides with a general formula (BZQ)Pb 2 X 5 (X = Cl, Br), in which metal halides form a unique two-dimensional (2D) structure. These BZQ metal halides are found to exhibit enhanced photoluminescence and stability as compared to the pristine BZQ halides, due to the scaffolding effects of 2D metal halides. Optical characterizations and theoretical calculations reveal that BZQ + cations are responsible for the emissions in these hybrid materials. Changing the halide from Cl to Br introduces heavy atom effects, resulting in yellow room temperature phosphorescence (RTP) from BZQ + cations.

The emergence of halide double perovskites significantly increases the compositional space for lead-free and air-stable photovoltaic absorbers compared to halide perovskites. Nevertheless, most halide double perovskites exhibit oversized band gaps (>1.9 eV) or dipole-forbidden optical transition, which are unfavorable for efficient single-junction solar cell applications. The current device performance of halide double perovskite is still inferior to that of lead-based halide perovskites, such as CH 3 NH 3 PbI 3 (MAPbI 3 ). Here, by ion type inversion and anion ordering on perovskite lattice sites, two new classes of pnictogen-based quaternary antiperovskites with the formula of X 6 B 2 AA' and X 6 BB'A 2 are designed. Phase stability and tunable band gaps in these quaternary antiperovskites are demonstrated based on first-principles calculations. Further photovoltaic-functionality-directed screening of these materials leads to the discovery of 5 stable compounds (Ca 6 N 2 AsSb, Ca 6 N 2 PSb, Sr 6 N 2 AsSb, Sr 6 N 2 PSb, and Ca 6 NPSb 2 ) with suitable direct band gaps, small carrier effective masses and low exciton binding energies, and dipole-allowed strong optical absorption, which are favorable properties for a photovoltaic absorber material. The calculated theoretical maximum solar cell efficiencies based on these five compounds are all larger than 29%, comparable to or even higher than that of the MAPbI 3 based solar cell. Our work reveals the huge potential of quaternary antiperovskites in the optoelectronic field and provides a new strategy to design lead-free and air-stable perovskite-based photovoltaic absorber materials.

BRCA2 and its interactors are required for meiotic homologous recombination (HR) and fertility. Loss of HSF2BP, a BRCA2 interactor, disrupts HR during spermatogenesis. We test the model postulating that HSF2BP localizes BRCA2 to meiotic HR sites, by solving the crystal structure of the BRCA2 fragment in complex with dimeric armadillo domain (ARM) of HSF2BP and disrupting this interaction in a mouse model. This reveals a repeated 23 amino acid motif in BRCA2, each binding the same conserved surface of one ARM domain. In the complex, two BRCA2 fragments hold together two ARM dimers, through a large interface responsible for the nanomolar affinity - the strongest interaction involving BRCA2 measured so far. Deleting exon 12, encoding the first repeat, from mBrca2 disrupts BRCA2 binding to HSF2BP, but does not phenocopy HSF2BP loss. Thus, results herein suggest that the high-affinity oligomerization-inducing BRCA2-HSF2BP interaction is not required for RAD51 and DMC1 recombinase localization in meiotic HR., (© 2021. The Author(s).)

Recently, ternary copper(I) halides have emerged as alternatives to lead halide perovskites for light emission applications. Despite their high-efficiency photoluminescence (PL) properties, most copper(I) halides are blue emitters with unusually poor tunability of their PL properties. Here, we report the impact of substitution of copper with silver in the high-efficiency blue-emitting Cu(I) halides through hydrothermal synthesis and characterization of (NH 4 ) 2 AgX 3 (X = Br, I). (NH 4 ) 2 AgX 3 are found to exhibit contrasting light emission properties compared to the blue-emitting Cu(I) analogues. Thus, (NH 4 ) 2 AgBr 3 and (NH 4 ) 2 AgI 3 exhibit broadband whitish light emission at room temperature with PL maxima at 394 and 534 nm and full width at half-maximum values of 142 and 114 nm, respectively. Based on our combined experimental and computational results, the broadband emission in (NH 4 ) 2 AgX 3 is attributed to the presence of high-stability self-trapped excitons and defect-bound excitons. (NH 4 ) 2 AgBr 3 and (NH 4 ) 2 AgI 3 both have significantly improved air and moisture stability as compared to the related copper(I) halides, which are prone to degradation via oxidation. Our results suggest that silver halides should be considered alongside their copper analogues for high-efficiency light emission applications., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

In budding yeast, the MutL homolog heterodimer Mlh1-Mlh3 (MutLγ) plays a central role in the formation of meiotic crossovers. It is also involved in the repair of a subset of mismatches besides the main mismatch repair (MMR) endonuclease Mlh1-Pms1 (MutLα). The heterodimer interface and endonuclease sites of MutLγ and MutLα are located in their C-terminal domain (CTD). The molecular basis of MutLγ's dual roles in MMR and meiosis is not known. To better understand the specificity of MutLγ, we characterized the crystal structure of Saccharomyces cerevisiae MutLγ(CTD). Although MutLγ(CTD) presents overall similarities with MutLα(CTD), it harbors some rearrangement of the surface surrounding the active site, which indicates altered substrate preference. The last amino acids of Mlh1 participate in the Mlh3 endonuclease site as previously reported for Pms1. We characterized mlh1 alleles and showed a critical role of this Mlh1 extreme C terminus both in MMR and in meiotic recombination. We showed that the MutLγ(CTD) preferentially binds Holliday junctions, contrary to MutLα(CTD). We characterized Mlh3 positions on the N-terminal domain (NTD) and CTD that could contribute to the positioning of the NTD close to the CTD in the context of the full-length MutLγ. Finally, crystal packing revealed an assembly of MutLγ(CTD) molecules in filament structures. Mutation at the corresponding interfaces reduced crossover formation, suggesting that these superstructures may contribute to the oligomer formation proposed for MutLγ. This study defines clear divergent features between the MutL homologs and identifies, at the molecular level, their specialization toward MMR or meiotic recombination functions., Competing Interests: The authors declare no competing interest.

Barrier-to-autointegration factor (BAF), encoded by the BANF1 gene, is an abundant and ubiquitously expressed metazoan protein that has multiple functions during the cell cycle. Through its ability to cross-bridge two double-stranded DNA (dsDNA), it favours chromosome compaction, participates in post-mitotic nuclear envelope reassembly and is essential for the repair of large nuclear ruptures. BAF forms a ternary complex with the nuclear envelope proteins lamin A/C and emerin, and its interaction with lamin A/C is defective in patients with recessive accelerated aging syndromes. Phosphorylation of BAF by the vaccinia-related kinase 1 (VRK1) is a key regulator of BAF localization and function. Here, we demonstrate that VRK1 successively phosphorylates BAF on Ser4 and Thr3. The crystal structures of BAF before and after phosphorylation are extremely similar. However, in solution, the extensive flexibility of the N-terminal helix α1 and loop α1α2 in BAF is strongly reduced in di-phosphorylated BAF, due to interactions between the phosphorylated residues and the positively charged C-terminal helix α6. These regions are involved in DNA and lamin A/C binding. Consistently, phosphorylation causes a 5000-fold loss of affinity for dsDNA. However, it does not impair binding to lamin A/C Igfold domain and emerin nucleoplasmic region, which leaves open the question of the regulation of these interactions., (© The Author(s) 2021. Published by Oxford University Press on behalf of Nucleic Acids Research.)

Cocrystallization of different metal nanoclusters facilitates the preparation of cluster-based nanomaterials with enhanced properties. Herein, two pairs of enantiomeric 3d-4f cocrystallization structures of clusters R/S -[Mn 10 Ln 6 ] and R/S -[Mn 6 Ln 2 ] (Ln = Dy for 1 R and 1 S , Y for 2 R and 2 S ) have been reported. Compounds R/S -[Mn 10 Ln 6 ][Mn 6 Ln 2 ] exhibit a large optical activity and magneto-optic effect as verified by natural circular dichroism (NCD) and magnetic circular dichroism (MCD). In addition, alternating current (ac) magnetic measurements show that the chiral R/S -[Mn 10 Dy 6 ][Mn 6 Dy 2 ] cocrystallization structure displays slow magnetic relaxation with U eff = 25.1 K.

DNA double-strand breaks (DSBs) are accidental lesions generated by various endogenous or exogenous stresses. DSBs are also genetically programmed events during the V(D)J recombination process, meiosis, or other genome rearrangements, and they are intentionally generated to kill cancer during chemo- and radiotherapy. Most DSBs are processed in mammalian cells by the classical nonhomologous end-joining (c-NHEJ) pathway. Understanding the molecular basis of c-NHEJ has major outcomes in several fields, including radiobiology, cancer therapy, immune disease, and genome editing. The heterodimer Ku70/80 (Ku) is a central actor of the c-NHEJ as it rapidly recognizes broken DNA ends in the cell and protects them from nuclease activity. It subsequently recruits many c-NHEJ effectors, including nucleases, polymerases, and the DNA ligase 4 complex. Beyond its DNA repair function, Ku is also involved in several other DNA metabolism processes. Here, we review the structural and functional data on the DNA and RNA recognition properties of Ku implicated in DNA repair and in telomeres maintenance.

Here we report for the first time soluble lanthanide-transition-metal clusters Ln 36 Co 12 (Ln = Eu, Gd and Dy) as effective homogeneous water oxidation electrocatalysts. The stable 48-metal Ln 36 Co 12 clusters show an effective water oxidation activity under acidic conditions because of the synergistic effect between lanthanide and transition metals in O-O bond formation.

The assembly of gigantic heterometallic metal clusters remains a great challenge for synthetic chemistry. Herein, based on the slow release strategy of lanthanide ions and in situ formation of lacunary polyoxometalates, two giant 3d-4f polyoxometalate inorganic clusters [LaNi 12 W 35 Sb 3 P 3 O 139 (OH) 6 ] 23- (LaNi 12 ) and [La 10 Ni 48 W 140 Sb 16 P 12 O 568 (OH) 24 (H 2 O) 20 ] 86- (La 10 Ni 48 ) are obtained. The nanoscopic inorganic cluster La 10 Ni 48 possesses a super tetrahedron structure, which can be viewed as assembly from four LaNi 12 molecules encapsulating a central [La 6 (SbO 3 ) 4 (H 2 O) 20 ] 6+ octahedron core. This giant aesthetic La 10 Ni 48 tetrahedron containing 214 metal ions is the largest 3d-4f cluster reported thus far in polyoxometalate system. More interestingly, the LaNi 12 and La 10 Ni 48 display high stability in solution and La 10 Ni 48 displays excellent proton conductivity., (© 2020 Wiley-VCH GmbH.)

Low-dimensional hybrid organic-inorganic metal halides have received increased attention because of their outstanding optical and electronic properties. However, the most studied hybrid compounds contain lead and have long-term stability issues, which must be addressed for their use in practical applications. Here, we report a new zero-dimensional hybrid organic-inorganic halide, RInBr 4 , featuring photoemissive trimethyl(4-stilbenyl)methylammonium (R + ) cations and nonemissive InBr 4 - tetrahedral anions. The crystal structure of RInBr 4 is composed of alternating layers of inorganic anions and organic cations along the crystallographic a axis. The resultant hybrid demonstrates bright-blue emission with Commission Internationale de l'Eclairage color coordinates of (0.19, 0.20) and a high photoluminescence quantum yield (PLQY) of 16.36% at room temperature, a 2-fold increase compared to the PLQY of 8.15% measured for the precursor organic salt RBr. On the basis of our optical spectroscopy and computational work, the organic component is responsible for the observed blue emission of the hybrid material. In addition to the enhanced light emission efficiency, the novel hybrid indium bromide demonstrates significantly improved environmental stability. These findings may pave the way for the consideration of hybrid organic In(III) halides for light emission applications.

Background: Magnesium sulfate (MgSO4) is widely used in analgesia for different conditions. Recent randomized controlled trials (RCTs) have evaluated the effects of MgSO4 on renal colic; however, this new evidence has not been synthesized. Thus, we conducted a systematic review and meta-analysis to assess the efficacy and safety of MgSO4 in comparison with control for renal colic., Methods: PubMed, EMBASE, and Scopus databases were searched from inception to February 2020. We included RCTs that evaluated MgSO4 vs control for patients with renal colic. Data were independently extracted by 2 reviewers and synthesized using a random-effects model., Results: Four studies with a total of 373 patients were analyzed. Intravenous MgSO4 15 to 50 mg/kg did not significantly reduce renal colic pain severity at 15 minutes (mean difference [MD] = 0.35, 95% confidence interval [CI] -0.51 to 1.21; 2 RCTs), 30 minutes (MD = 0.19, 95% CI -0.74 to 1.13; 4 RCTs), and 60 minutes (MD = -0.28, 95% CI -0.72 to 0.16; 3 RCTs) in comparison with controls. In patients who failed to respond to initial analgesics, intravenous MgSO4 15 mg/kg or 2 ml of 50% solution provided similar pain relief to ketorolac or morphine at 30 minutes (P = .90) and 60 minutes (P = .57). No significant hemodynamic changes were observed with short-term use of MgSO4 in these studies., Conclusion: MgSO4 provides no superior therapeutic benefits in comparison with control treatments. MgSO4 may be used as a rescue medication in patients not responding to initial analgesics. The short-term use of MgSO4 did not affect hemodynamic values.

Low-dimensional perovskite-related metal halides have emerged as a new class of light-emitting materials with tunable broadband emission from self-trapped excitons (STEs). Although various types of low-dimensional structures have been developed, fundamental understating of the structure-property relationships for this class of materials is still very limited, and further improvement of their optical properties remains greatly important. Here, we report a significant pressure-induced photoluminescence (PL) enhancement in a one-dimensional hybrid metal halide C 4 N 2 H 14 PbBr 4 , and the underlying mechanisms are investigated using in situ experimental characterization and first-principles calculations. Under a gigapascal pressure scale, the PL quantum yields (PLQYs) were quantitatively determined to show a dramatic increase from the initial value of 20% at ambient conditions to over 90% at 2.8 GPa. With in situ characterization of photophysical properties and theoretical analysis, we found that the PLQY enhancement was mainly attributed to the greatly suppressed nonradiative decay. Pressure can effectively tune the energy level of self-trapped states and increase the exciton binding energy, which leads to a larger Stokes shift. The resulting highly localized excitons with stronger binding reduce the probability for carrier scattering, to result in the significantly suppressed nonradiative decay. Our findings clearly show that the characteristics of STEs in low-dimensional metal halides can be well-tuned by external pressure, and enhanced optical properties can be achieved.

The formation mechanism of ferrihydrite is the key to understand its treatment of pollutants in waste water and purification of surface water and groundwater. Although emerging evidence suggests that formation of the ferrihydrite occurs through the aggregation of prenucleation clusters, rather than classical atom-by-atom growth, its formation mechanism remains unclear. Herein, an iron-oxo anionic cluster of [Fe 22 (μ 4 -O) 8 (μ 3 -OH) 20 (μ 2 -OH) 18 (CH 3 COO) 16 (H 2 O) 2 ] 4- viewed as a dimer of bivacant β-Keggin-Fe 13 clusters was for the first time obtained by using lanthanide ions as stabilizers. Upon dissolution in a mixed solution of isopropanol and water, the lacunary β-Keggin-Fe 13 cluster can transform into an α-Keggin-Fe 13 cluster, distinctly demonstrating that the Keggin-Fe 13 cluster rotational isomerization can be realized through the vacant Keggin-Fe 13 cluster., (© 2020 Wiley-VCH GmbH.)

Photosynthesis in nature uses the Mn 4 CaO 5 cluster as the oxygen-evolving center to catalyze the water oxidation efficiently in photosystem II. Herein, we demonstrate bio-inspired heterometallic LnCo 3 (Ln = Nd, Eu and Ce) clusters, which can be viewed as synthetic analogs of the CaMn 4 O 5 cluster. Anchoring LnCo 3 on phosphorus-doped graphitic carbon nitrides (PCN) shows efficient overall water splitting without any sacrificial reagents. The NdCo 3 /PCN-c photocatalyst exhibits excellent water splitting activity and a quantum efficiency of 2.0% at 350 nm. Ultrafast transient absorption spectroscopy revealed the transfer of a photoexcited electron and hole into the PCN and LnCo 3 for hydrogen and oxygen evolution reactions, respectively. A density functional theory (DFT) calculation showed the cooperative water activation on lanthanide and O-O bond formation on transition metal for water oxidation. This work not only prepares a synthetic model of a bio-inspired oxygen-evolving center but also provides an effective strategy to realize light-driven overall water splitting., (© The Author(s) 2020. Published by Oxford University Press on behalf of China Science Publishing & Media Ltd.)

Halide perovskites have undergone remarkable developments as highly efficient optoelectronic materials for a variety of applications. Several studies indicated the critical role of defects on the performance of perovskite devices. However, the parameters of defects and their interplay with free charge carriers remain unclear. In this study, we explored the dynamics of free holes in methylammonium lead tribromide (MAPbBr 3 ) single crystals using the time-of-flight (ToF) current spectroscopy. By combining ToF spectroscopy and Monte Carlo simulation, three energy states were detected in the bandgap of MAPbBr 3 In addition, we found the trapping and detrapping rates of free holes ranging from a few microseconds to hundreds of microseconds. Contrary to previous studies, we revealed a strong detrapping activity of traps. We showed that these traps substantially affect the transport properties of MAPbBr 3 , including mobility and mobility-lifetime product. Our results provide an insight on charge transport properties of perovskite semiconductors., (Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

Two high-nuclearity lanthanide-transition metal clusters with the general formula [Ln 18 Co II Co III 6 (OH) 14 (CO 3 ) 9 (CH 3 CH 2 COO) 6 (dea) 12 (H 2 O) 30 ]·(NO 3 ) 8 ·Cl 4 ·(CH 3 CH 2 OH) 6 ·(H 2 O) 12 ( Ln 18 Co 7 , Ln = Gd ( 1 ) and Dy ( 2 )) have been obtained by reacting CoCl 2 ·6H 2 O, Ln(NO 3 ) 3 ·6H 2 O, and a mixture of ligands consisting of propionate and diethanolamine (H 2 dea). Crystal structural analysis exhibits two three-blade propellers composed of the Co III 3 Ln 9 units connected by one Co II ion and three CO 3 2- ions, which assemble into a double-propeller-like structure ( Ln 18 Co II Co III 6 ). Magnetocaloric effect (MCE) studies indicate that Gd 18 Co 7 exhibits a large entropy change (-Δ S m ) of 36.9 J kg -1 K -1 .

The diagnosis of frailty is usually subjective, which calls for objective biomarkers in clinical medicine. 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodGsn) and 8-oxo-7, 8-dihydroguanosine (8-oxoGsn) in urine are two aging biomarkers that have not been explored deeply in cases of frailty. A total of 508 elderly patients with cardiovascular disease (mean age 75.0 ± 6.5 years, 50.8% males) were enrolled consecutively. Frailty was assessed by the Fried phenotype (robust: 0 score; pre-frail: 1-2 scores; frail: 3-5 scores). The concentrations of 8-oxoGsn and 8-oxodGsn in urine were measured by improved ultra-high-performance liquid chromatography-mass spectrometry (UPLC-MS/MS). Urinary creatinine (Cre) was tested to correct the 8-oxoGsn and 8-oxodGsn levels. According to the Fried phenotype score, the proportions of robust, pre-frail, and frail subjects were 20.5% (104/508), 53.9% (274/508), and 25.6% (130/508), respectively. The urinary 8-oxoGsn/Cre (P < 0.001) differed significantly among these 3 groups, but the urinary 8-oxodGsn/Cre (P = 0.600) showed no marked difference. Univariate and multivariate logistic regression showed that the age (odds ratio [OR] = 1.090, P < 0.001), systolic blood pressure (OR = 0.981, P = 0.008), 8-oxoGsn/Cre (OR = 1.203, P = 0.007), hemoglobin (OR = 0.980, P = 0.007), and sodium (OR = 0.915, P = 0.044) were independently associated with frailty. The sensitivity and specificity to identify frailty were 53.08% and 71.96%, respectively, for 8-oxoGsn/Cre at the optimal cut-off value of 3.879 μmol/mol according to the maximal Youden index. Urinary 8-oxoGsn, as a recognized biomarker of RNA oxidation, is independently associated with frailty in elderly patients with cardiovascular disease. However, the urinary 8-oxodGsn shows no obvious correlation with frailty. To obtain a better diagnostic performance for frailty, more biomarkers from different pathophysiological pathways should be explored in the future., Competing Interests: Declaration of competing interest The authors declare that they have no competing interests., (Copyright © 2020. Published by Elsevier Inc.)

Atomically precise molecular metal-oxo clusters provide ideal models to understand metal oxide surfaces, self-assembly, and form-function relationships. Devising strategies for synthesis and isolation of these molecular forms remains a challenge. Here, the synthesis of four Ln-Fe oxo clusters that feature the ϵ-{Fe 13 } Keggin cluster in their core is reported. The {Fe 13 } metal-oxo cluster motif is the building block of two important iron oxyhydroxyide phases in nature and technology, ferrihydrite (as the δ-isomer) and magnetite (the ϵ-isomer). The reported ϵ-{Fe 13 } Keggin isomer as an isolated molecule provides the opportunity to study the formation of ferrihydrite and magnetite from this building unit. The four currently reported isostructural lanthanide-iron-oxo clusters are fully formulated [Y 12 Fe 33 (TEOA) 12 (Hyp) 6 (μ 3 -OH) 20 (μ 4 -O) 28 (H 2 O) 12 ](ClO 4 ) 23 ⋅50 H 2 O (1, Y 12 Fe 33 ), [Gd 12 Fe 33 (TEOA) 12 (Hyp) 6 (μ 3 -OH) 20 (μ 4 -O) 32 (H 2 O) 12 ](ClO 4 ) 15 ⋅50 H 2 O (2, Gd 12 Fe 33 ) and [Ln 16 Fe 29 (TEOA) 12 (Hyp) 6 (μ 3 -OH) 24 (μ 4 -O) 28 (H 2 O) 16 ](ClO 4 ) 16 (NO 3 ) 3 ⋅n H 2 O (Ln=Y for 3, Y 16 Fe 29 , n=37 and Ln=Gd for 4, Gd 16 Fe 29 n=25; Hyp=trans-4-Hydroxyl-l-proline and TEOA=triethanolamine). The next metal layer surrounding the ϵ-{Fe 13 } core within these clusters exhibits a similar arrangement as the magnetite lattice, and Fe and Ln can occupy the same positions. This provides the opportunity to construct a family of compounds and optimize magnetic exchange in these molecules through composition tuning. Small-angle X-ray scattering (SAXS) and high-resolution electrospray ionization mass spectrometry (HRESI-MS) show that these clusters are stable upon dissolution in both water and organic solvents, as a first step to performing further chemistry towards building magnetic arrays or investigating ferrihydrite and magnetite assembly from pre-nucleation clusters., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Phosphors that emit in the deep-red spectral region are critical for plant cultivation light-emitting diodes. Herein, ultrabroadband deep-red luminescence of Mn 4+ in La 4 Ti 3 O 12 was studied, which showed intense zero phonon line emission. The double-perovskite structural La 4 Ti 3 O 12 simultaneously contains two Ti 4+ sites forming slightly- and highly-distorted TiO 6 octahedra, respectively. The influence of octahedral distortion on the Mn 4+ emission energy in the two distinct Ti 4+ sites was studied both experimentally and theoretically. The spectral measurements indicated that Mn 4+ in La 4 Ti 3 O 12 showed intense zero phonon line emission (ZPL) at deep-red 710-740 nm under excitation of 400 nm charging the O 2- → Mn 4+ charge transfer transition. The splitting of the ZPL of the Mn 4+ 2 E g → 4 A 2g transition as well as the intensity of ZPL relative to the vibronic phonon sideband emissions were found to be greatly influenced by the degree of octahedral distortion. The crystal-field strength and Racah parameters of Mn 4+ in each Ti 4+ site were also estimated. The Mn 4+ 2 E g → 4 A 2g luminescence exhibited severe thermal quenching, which was explained by the low-lying 4 T 2g level and charge-transfer state.

Anti-silencing function 1 (ASF1) is a conserved H3-H4 histone chaperone involved in histone dynamics during replication, transcription, and DNA repair. Overexpressed in proliferating tissues including many tumors, ASF1 has emerged as a promising therapeutic target. Here, we combine structural, computational, and biochemical approaches to design peptides that inhibit the ASF1-histone interaction. Starting from the structure of the human ASF1-histone complex, we developed a rational design strategy combining epitope tethering and optimization of interface contacts to identify a potent peptide inhibitor with a dissociation constant of 3 nM. When introduced into cultured cells, the inhibitors impair cell proliferation, perturb cell-cycle progression, and reduce cell migration and invasion in a manner commensurate with their affinity for ASF1. Finally, we find that direct injection of the most potent ASF1 peptide inhibitor in mouse allografts reduces tumor growth. Our results open new avenues to use ASF1 inhibitors as promising leads for cancer therapy., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Low-dimensional halide perovskites exhibit intriguing excitonic properties and emerge as an important class of self-activated luminescent materials. However, the ability to manipulate and optimize their luminescent properties is limited by the lack of the microscopic understanding of the exciton relaxation and emission and the inconsistency in the theoretical results in the literature. In this work, based on first-principles calculations, we studied excitons in 1D lead halide perovskites, C 4 N 2 H 14 PbBr 4 and C 4 N 2 H 14 PbCl 4 , which are both bright visible-light emitters. We find that, in both compounds, the polaron-pair exciton (EX-PP) is more stable than the onsite exciton (EX-OS) and only the EX-PP emission energy from the calculation is close to the main photoluminescence (PL) peak observed in the experiment. The EX-OS is found to emit UV light in both compounds. Therefore, the EX-PP is responsible for the experimentally observed visible light emission in both C 4 N 2 H 14 PbBr 4 and C 4 N 2 H 14 PbCl 4 . Furthermore, the calculated small energy difference between the EX-PP and EX-OS in C 4 N 2 H 14 PbBr 4 suggests that the metastable EX-OS can be thermally populated at room temperature (RT); the calculated EX-OS emission energy agrees well with the energy of a minor PL peak observed at RT but not at 77 K. The validity our approach in the exciton calculation is supported by the benchmark of the calculated exciton emission energies against the experimental results in 13 0D and 1D metal halides. The discrepancies between this work and a recent theoretical study in the literature are also discussed.