Large Scale Synthesis of a Stable Prefunctionalized Silver Nanocluster.

Due to the stability issue, It is difficult to prepare a silver nanocluster bearing functional sites, especially at a large scale. We report the synthesis and structure of a stable silver nanocluster bearing multiple surface aldehyde groups [Ag21(Ph2PO2)10(p-CHOPhC≡C)6]SbF6, which allows for postsynthesis modification such as surface functionalization through aldimine condensation to give homochiral clusters. Remarkably, the preparation of this cluster can be done in ~90% high yield at gram scale, which facilitates further studies and potential applications. Through DFT calculations and geometric structure analysis, the high stability of this cluster is attributed to the geometric closure and electronic structure. This is the first time that an effective one-pot method has been developed to synthesize functional silver nanoclusters in high yield. The title cluster will be useful in the development of a variety of cluster-based materials.

Integration of Metal Catalysis and Organocatalysis in a Metal Nanocluster with Anchored Proline.

Chiral metal nanoclusters have recently been attracting great attention. It is challenging to realize asymmetric catalysis via atomically precise metal nanoclusters. Herein, we report the synthesis and total structure determination of chiral clusters [Au7Ag8(dppf)3(l-/d-proline)6](BF4)2 (l-/d-Au7Ag8). Superatomic clusters l-/d-Au7Ag8 display intense and mirror-image Cotton effects in their CD spectra. Density functional theory (DFT) calculations were carried out to understand the correlation between electronic structures and the optical activity of the enantiomeric pair. Surprisingly, the incorporation of proline in a metal nanocluster can significantly promote the catalytic efficiency in asymmetric Aldol reactions. The increase of catalytic activity of Au7Ag8 in comparison with organocatalysis by proline is attributed to the cooperative effect of the metal core and prolines, showing the advantages of the integration of metal catalysis and organocatalysis in a metal nanocluster.

Activating α7nAChR helps post-myocardial infarction healing by regulating macrophage polarization via the STAT3 signaling pathway.

BACKGROUND: Monocytes/macrophages play critical roles in inflammation and cardiac remodeling following myocardial infarction (MI). The cholinergic anti-inflammatory pathway (CAP) modulates local and systemic inflammatory responses by activating α7 nicotinic acetylcholine receptors (α7nAChR) in monocytes/macrophages. We investigated the effect of α7nAChR on MI-induced monocyte/macrophage recruitment and polarization and its contribution to cardiac remodeling and dysfunction. METHODS: Adult male Sprague Dawley rats underwent coronary ligation and were intraperitoneally injected with the α7nAChR-selective agonist PNU282987 or the antagonist methyllycaconitine (MLA). RAW264.7 cells were stimulated with lipopolysaccharide (LPS) + interferon-gamma (IFN-γ) and treated with PNU282987, MLA, and S3I-201 (a STAT3 inhibitor). Cardiac function was evaluated by echocardiography. Masson's trichrome and immunofluorescence were used to detect cardiac fibrosis, myocardial capillary density, and M1/M2 macrophages. Western blotting was used to detect protein expression, and the proportion of monocytes was measured using flow cytometry. RESULTS: Activating the CAP with PNU282987 significantly improved cardiac function and reduced cardiac fibrosis and 28-day mortality after MI. On days 3 and 7 post-MI, PNU282987 reduced the percentage of peripheral CD172a + CD43low monocytes and the infiltration of M1 macrophages in the infarcted hearts, whereas it increased the recruitment of peripheral CD172a + CD43high monocytes and M2 macrophages. Conversely, MLA exerted the opposite effects. In vitro, PNU282987 inhibited M1 macrophage polarization and promoted M2 macrophage polarization in LPS + IFN-γ-stimulated RAW264.7 cells. These PNU282987-induced changes in LPS + IFN-γ-stimulated RAW264.7 cells were reversed by administering S3I-201. CONCLUSION: Activating α7nAChR inhibits the early recruitment of pro-inflammatory monocytes/macrophages during MI and improves cardiac function and remodeling. Our findings suggest a promising therapeutic target for regulating monocyte/macrophage phenotypes and promoting healing after MI.

Disc-Like Silver Nanocluster Ag93 Built with Bicapped Hexagonal Prismatic Ag15 and Ino Decahedral Ag13 Units.

The reduction of alkynyl-silver and phosphine-silver precursors with a weak reducing reagent Ph2 SiH2 led to the formation of a novel silver nanocluster [Ag93 (PPh3 )6 (C≡CR)50 ]3+ (R=4-CH3 OC6 H4 ), which is the largest structurally characterized cluster of clusters. This disc-shaped cluster has a Ag69 kernel consisting of a bicapped hexagonal prismatic Ag15 unit wrapped by six Ino decahedra through edge-sharing. This is the first time that Ino decahedra are used as a building block to assemble a cluster of clusters. Moreover, the central silver atom has a coordination number of 14, which is the highest in metal nanoclusters. This work provides a diverse metal packing pattern in metal nanoclusters, which is helpful for understanding metal cluster assembling mechanisms.

Face-Centered Cubic Silver Nanoclusters Consolidated with Tetradentate Formamidinate Ligands.

Growing attention has been paid to nanoclusters with face-centered cubic (fcc) metal kernels, due to its structural similarity to bulk metals. We demonstrate that the use of tetradentate formamidinate ligands facilitate the construction of two fcc silver nanoclusters: [Ag52(5-F-dpf)16Cl4](SbF6)2 (Ag52, 5-F-Hdpf = N,N'-di(5-fluoro-2-pyridinyl)formamidine) and [Ag53(5-Me-dpf)18](NO3)5 (Ag53, 5-Me-Hdpf = N,N'-di(5-methyl-2-pyridinyl)formamidine). Single-crystal X-ray structural analysis revealed that the silver atoms in both clusters are in a layer-by-layer arrangement, which can be viewed as a portion of the fcc packing of silver. The nitrogen donors of amidinate ligands selectively passivate the {111} facets. All silver atoms are involved in the fcc packing, that is, no staple motifs are observed due to the linear arrangement of the four N donors of the dpf ligands. The characteristic optical absorption bands of Ag52 and Ag53 have been studied with a time-dependent density functional theory. This work provides a facile access to assembling atomically precise fcc-type nanoclusters and shows the prospect of amidinates as protecting ligands in synthesizing metal nanoclusters.

Ligand Engineering toward the Trade-Off between Stability and Activity in Cluster Catalysis.

We report the structures, stability and catalysis properties of two Ag21 nanoclusters, namely [Ag21 (H2 BTCA)3 (O2 PPh2 )6 ]SbF6 (1) and [Ag21 (C≡CC6 H3 -3,5-R2 )6 (O2 PPh2 )10 ]SbF6 (2) (H4 BTCA=p-tert-butylthiacalix[4]arene, R=OMe). Both Ag21 structures possess an identical icosahedral kernel that is surrounded by eight peripheral Ag atoms. Single-crystal structural analysis and ESI-MS revealed that 1 is an 8-electron cluster and 2 has four free electrons. Theoretical results show that the P-symmetry orbitals are found as HOMO-1 and HOMO states in 1, and the frontier unoccupied molecular orbitals (LUMO, LUMO+1 and LUMO+2) show D-character, indicating 1 is a superatomic cluster with an electronically closed shell 1S2 1P6 , while 2 has an incomplete shell configuration 1S2 1P2 . These two Ag21 clusters show superior stability under ambient conditions, and 1 is robust even at 90 °C in toluene and under oxidative conditions (30 % H2 O2 ). Significantly, 2 exhibits much higher activity than 1 as catalyst in the reduction of 4-nitrophenol. This work demonstrates that ligands can influence the electronic structures of silver clusters, and further affect their stability and catalytic performance.

Robust Gold Nanocluster Protected with Amidinates for Electrocatalytic CO2 Reduction.

The first all-amidinate-protected gold nanocluster [Au28 (Ph-form)12 ](OTf)2 (Ph-form=N,N'-diphenylformamidinate) (Au28 ) has been synthesized and structurally resolved. Single crystal X-ray diffraction reveals that Au28 has a compact Au4 @Au24 tetrahedral core-shell structure of T symmetry, which is fully protected by 12 bridging formamidinate ligands. This cluster is quite robust as indicated by the fact that it can stay intact in solution at 80 °C for 6 d. It exhibits excellent catalytic performance for the electroreduction of CO2 with 96.5 % Faradaic efficiency (FE) at -0.57 V and a maximum TOF of 1731 h-1 at -0.87 V. Its superior stability is also manifested in the fact that the supported catalyst Au28 /CNTs maintains stable potentials at ca. -0.69 V for 40 h with FE(CO)s>91 %. A superatomic electron configuration of 1S2 1P6 2S2 1D4 has been clarified by DFT computations, and the strong gold-ligand binding and geometric shell closure account for the superior stability of Au28 .

Total Structure Determination of the Largest Alkynyl-Protected fcc Gold Nanocluster Au110 and the Study on Its Ultrafast Excited-State Dynamics.

Great attention has been paid to nanoclusters having face-centered-cubic (fcc) metal kernels, because of the similarity of metal packing to that of bulk gold. So far, there is no precedent example of an all-alkynyl-protected fcc gold nanocluster with more than 100 gold atoms. We report the synthesis and total structure determination of an alkynyl-protected gold nanocluster [NEt3H]2[Au110(p-CF3C6H4C≡C)48] (Au110). It has an fcc Au86 kernel with 24 peripheral Au(C≡CR)2 staples. The Au86 kernel consists of six close packing layers in the pattern of Au6:Au16:Au21:Au21:Au16:Au6. Electronic absorption spectroscopy shows Au110 has a molecular-like discrete electronic structure, and transient absorption experiments reveal its nonmetallic nature.

Nomogram prediction of vessels encapsulating tumor clusters in small hepatocellular carcinoma ≤ 3 cm based on enhanced magnetic resonance imaging.

BACKGROUND: Vessels encapsulating tumor clusters (VETC) represent a recently discovered vascular pattern associated with novel metastasis mechanisms in hepatocellular carcinoma (HCC). However, it seems that no one have focused on predicting VETC status in small HCC (sHCC). This study aimed to develop a new nomogram for predicting VETC positivity using preoperative clinical data and image features in sHCC (≤ 3 cm) patients. AIM: To construct a nomogram that combines preoperative clinical parameters and image features to predict patterns of VETC and evaluate the prognosis of sHCC patients. METHODS: A total of 309 patients with sHCC, who underwent segmental resection and had their VETC status confirmed, were included in the study. These patients were recruited from three different hospitals: Hospital 1 contributed 177 patients for the training set, Hospital 2 provided 78 patients for the test set, and Hospital 3 provided 54 patients for the validation set. Independent predictors of VETC were identified through univariate and multivariate logistic analyses. These independent predictors were then used to construct a VETC prediction model for sHCC. The model's performance was evaluated using the area under the curve (AUC), calibration curve, and clinical decision curve. Additionally, Kaplan-Meier survival analysis was performed to confirm whether the predicted VETC status by the model is associated with early recurrence, just as it is with the actual VETC status and early recurrence. RESULTS: Alpha-fetoprotein_lg10, carbohydrate antigen 199, irregular shape, non-smooth margin, and arterial peritumoral enhancement were identified as independent predictors of VETC. The model incorporating these predictors demonstrated strong predictive performance. The AUC was 0.811 for the training set, 0.800 for the test set, and 0.791 for the validation set. The calibration curve indicated that the predicted probability was consistent with the actual VETC status in all three sets. Furthermore, the decision curve analysis demonstrated the clinical benefits of our model for patients with sHCC. Finally, early recurrence was more likely to occur in the VETC-positive group compared to the VETC-negative group, regardless of whether considering the actual or predicted VETC status. CONCLUSION: Our novel prediction model demonstrates strong performance in predicting VETC positivity in sHCC (≤ 3 cm) patients, and it holds potential for predicting early recurrence. This model equips clinicians with valuable information to make informed clinical treatment decisions.

Near-unity NIR phosphorescent quantum yield from a room-temperature solvated metal nanocluster.

Metal nanoclusters have emerged as promising near-infrared (NIR)-emissive materials, but their room-temperature photoluminescence quantum yield (PLQY), especially in solution, is often low (<10%). We studied the photophysics of Au22(tBuPhC≡C)18 (Au22) and its alloy counterpart Au16Cu6(tBuPhC≡C)18 (Au16Cu6) (where tBu is tert-butyl and Ph is phenyl) and found that copper (Cu) doping suppressed the nonradiative decay (~60-fold less) and promoted intersystem crossing rate (~300-fold higher). The Au16Cu6 nanocluster exhibited >99% PLQY in deaerated solution at room temperature with an emission maximum at 720 nanometers tailing to 950 nanometers and 61% PLQY in the oxygen-saturated solution. The approach to achieve near-unity PLQY could enable the development of highly emissive metal cluster materials.

Electrocardiographic Characteristics of Ventricular Arrhythmias Originating from Different Areas Adjacent to the Mitral Annulus.

BACKGROUND: This study aimed to explore the electrocardiographic (ECG) characteristics of ventricular arrhythmias (VAs) arising from epicardial and endocardial areas adjacent to the mitral annulus (MA). METHODS: This study involved 283 patients with MA-VAs who received radiofrequency catheter ablation at the center. The ECG characteristics of these patients were analyzed retrospectively. RESULTS: The origin of MA-VAs was judged based on the ECG variables. Among all MA-VAs, intrinsicoid deflection time (IDT) > 77 ms or maximum deflection index (MDI) > 0.505 predicted the VAs arising from the epicardium (sensitivity of 70.20% and 73.51%, specificity of 94.70% and 82.58%, positive predictive value (PPV) of 93.81% and 82.84%, and negative predictive value (NPV) of 73.53% and 73.15%). Among all epicardial MA-VAs, the RV1/RV2 ratio > 0.87 predicted the VAs originating from the epicardial anteroseptal wall adjacent to the MA. It had a sensitivity, specificity, PPV, and NPV of 62.86%, 98.06%, 91.67%, and 88.60%, respectively. Among all endocardial MA-VAs, Q(q)R(r) morphology in lead V1 predicted the VAs arising from the endocardial septal wall adjacent to the MA. It had a sensitivity, specificity, PPV, and NPV of 92.98%, 100%, 100%, and 94.94%, respectively. Among all endocardial septal MA-VAs, a predominant positive wave in lead II and a predominant negative wave in lead III predicted the VAs arising from the endocardial midseptal portion adjacent to the MA. It had a sensitivity, specificity, PPV, and NPV of 86.04%, 100%, 100%, and 70.00%, respectively. CONCLUSION: the ECG characteristics of VAs from the different sites adjacent to the MA can enable judging the arrhythmia's origin and designing the ablation plan accordingly.

Cardiac-Specific Overexpression of Caveolin-1 in Rats With Ischemic Cardiomyopathy Improves Arrhythmogenicity and Cardiac Remodelling.

BACKGROUND: Ischemic cardiomyopathy (ICM) is associated with electrical and structural remodelling, leading to arrhythmias. Caveolin-1 (Cav1) is a membrane protein involved in the pathogenesis of ischemic injury. Cav1 deficiency has been associated with arrhythmogenicity. The current study aimed to determine how Cav1 overexpression inhibits arrhythmias and cardiac remodelling in ICM. METHODS: ICM was modelled using left anterior descending (LAD) artery ligation for 4 weeks. Cardiac-specific Cav1 overexpression in ICM on arrhythmias, excitation-contraction coupling, and cardiac remodelling were investigated using the intramyocardial injection of an adeno-associated virus serotype 9 (AAV-9) system, carrying a specific sequence expressing Cav1 (AAVCav1) under the cardiac troponin T (cTnT) promoter. RESULTS: Cav1 overexpression decreased susceptibility to arrhythmias by upregulating gap junction connexin 43 (CX43) and reducing spontaneous irregular proarrhythmogenic Ca2+ waves in ventricular cardiomyocytes. It also alleviated ischemic injury-induced contractility weakness by improving Ca2+ cycling through normalizing Ca2+-handling protein levels and improving Ca2+ homeostasis. Masson stain and immunoblotting revealed that the deposition of excessive fibrosis was attenuated by Cav1 overexpression, inhibiting the transforming growth factor-ß (TGF-ß)/Smad2 signalling pathway. Coimmunoprecipitation assays demonstrated that the interaction between Cav1 and cSrc modulated CX43 expression and Ca2+-handling protein levels. CONCLUSIONS: Cardiac-specific overexpression of Cav1 attenuated ventricular arrhythmia, improved Ca2+ cycling, and attenuated cardiac remodelling. These effects were attributed to modulation of CX43, normalized Ca2+-handling protein levels, improved Ca2+ homeostasis, and attenuated cardiac fibrosis.

Spin Selectivity in Chiral Hybrid Cobalt Halide Films with Ultrasmooth Surface.

Introducing chirality into low-dimensional hybrid organic-inorganic halides (HOIHs) creates brand-new opportunities for HOIHs in spintronics and spin-related optoelectronics owing to chirality-induced spin selectivity (CISS). However, preparing smooth films of low-dimensional HOIHs with small roughness is still a great challenge due to the hybrid and complex crystal structure, which severely inhibits their applications in spintronic devices. Exploring new lead-free chiral HOIHs with both efficient spin selectivity and excellent film quality is urgently desired. Here, cobalt-based chiral metal halide crystals (R/S-NEA)2 CoCl4 constructed by 0D [CoCl4 ] tetrahedrons and 1-(1-naphtyl)ethylamine (NEA) are synthesized. The orderly configuration of NEA molecules stabilized by noncovalent CH···π interaction endows (NEA)2 CoCl4 with good film-forming ability. (NEA)2 CoCl4 films exhibit strong chiroptical activity (gCD  ≈ 0.05) and significant spin-polarized transport (CISS efficiency up to 90%). Furthermore, ultrasmooth films (roughness ∼ 0.3 nm) with enhanced crystallinity can be achieved by incorporating tiny amount tris(8-oxoquinoline)aluminum that has analogous conjugated structure to NEA. The realization of highly efficient spin selectivity and sub-nanometer roughness in lead-free chiral halides can boost the practical process of low-dimensional HOIHs in spintronics and other fields.

Overcoming High Impedance in the Transitional Area of the Distal Great Cardiac Vein during Radiofrequency Catheter Ablation of Ventricular Arrhythmia.

(1) Background: Radiofrequency catheter ablation (RFCA) is an essential treatment for ventricular arrhythmia (VA). However, high impedance in the transitional area of the distal great cardiac vein (TAODGCV) often leads to ablation failure. This study aimed to explore the factors influencing impedance and identify effective ways to reduce impedance. (2) Methods: A total of 156 patients with VA arising from the TAODGCV received RFCA therapy at our center from October 2009 to August 2021 and were retrospectively analyzed. Local impedance variation during RFCA was monitored, recorded, and analyzed. (3) Results: The impedance increased from the proximal to distal portions of the TAODGCV and decreased by increasing the saline flow rate at the same site. To overcome high impedance, we implemented the following strategies: (1) Reset the upper limit impedance to 300 Ω and accelerate the saline flow rate to 60 mL/min (effective in 118 of 144 patients); (2) turn off the upper limit impedance (effective in eleven of 21 patients); (3) use high-flow-rate irrigation devices (effective in five of 15 patients); and (4) increase the upper limit temperature (effective in six of ten patients). (4) Conclusions: In the TAODGCV, local impedance is mainly influenced by the target site location and saline flow rate. We concluded several methods to overcome the high impedance and contribute to a successful ablation.

Increased serum levels of miR-214 in patients with PCa with bone metastasis may serve as a potential biomarker by targeting PTEN.

MicroRNAs (miRNAs/miRs) are identified to serve key functions in the progression of various tumors. miR-214 is aberrantly expressed in various types of cancer. In the present study, the function of miR-214 and its feasibility as a potential non-invasive biomarker for patients with prostate cancer (PCa) in a hyperplasia group and a control group were investigated. First, RNA was isolated from the serum of 75 patients with PCa with bone metastasis, 65 patients with PCa with no bone metastasis and 70 healthy controls. The level of miR-214 expression was significantly upregulated in the serum of the bone metastasis group compared with the healthy control and non-bone metastasis groups. Expression levels of alkaline phosphatase (ALP), bone sialoprotein (BSP), collagen type I pyridine crosslinking peptide (ICTP) were also evaluated. The results indicated that serum levels of BSP, ALP and ICTP were increased in the bone metastasis group compared with that in the non-bone metastasis group, hyperplasia group and the control group (P<0.05). The expression level of miR-214 is positively associated with poorly differentiated tumors in patients with PCa with a Gleason score >7 (P<0.05). Western blot analysis demonstrated that phosphatase and tensin homolog (PTEN) was a target gene of miR-214. Additionally, silencing of PTEN significantly increased the invasive ability of PC3 cells even when miR-214 expression was inhibited. In summary, serum miR-214 expression may serve as a potential novel non-invasive biomarker for PCa screening through targeting PTEN.

Associations of Caspase-3 gene polymorphism with lumbar disc herniation.

To investigate Caspase-3 gene polymorphisms (rs4647693 G/A, rs4647610 A/G, and rs12108497 T/C) and susceptibility to lumbar intervertebral disc herniation (LDH). The genotype frequency distributions of the polymorphisms were detected by polymerase chain reaction-restriction fragment length polymorphism in 107 LDH patients (case group) and 121 healthy individuals (control group). SHEsis software was used to conduct gene linkage disequilibrium and haplotype analysis. Regression analysis was used to analyze possible risk factors for LDH. Statistically significant differences in family history of LDH, amateur sports, leisure activities, bed types, and spine load grade were found between the case and control groups. The distribution of allele and genotype frequencies of rs4647693 G/A, rs4647610 A/G, and rs12108497 T/C polymorphisms of Caspase-3 were significantly different between the case and control groups. Haplotype analysis showed that the G-G-C (rs4647693-rs4647610-rs12108497) haplotype might be a risk factor for LDH, whereas the A-A-T haplotype might be a protective factor (p < 0.05). Binary logistic regression analysis showed that the GA+AA genotype of rs4647693 was negatively associated with the risk of LDH, whereas high spine load grade was positively associated with the risk of LDH. These findings revealed that rs4647693 G/A, rs4647610 A/G, and rs12108497 T/C polymorphisms of Caspase-3 may be associated with susceptibility to LDH and that interaction and modification effects may exist between Caspase-3 polymorphisms.

Review on antibacterial characteristics of bridge engineering biomaterials.

This review summarizes the research on timber construction materials used in bridge construction. It focuses on the application of antiseptic treatments and the use of timber engineering materials in decks and bridges. This review also provides an overview on the future research and prospects of engineered timber materials.

Review on antibacterial biocomposites of structural laminated veneer lumber.

In this review, the characteristics and applications of structural laminated veneer lumber made from planted forest wood is introduced, and its preparation is explained, including various tree species and slab qualities, treatments for multiple effects and reinforced composites. The relevant factors in the bonding technology and pressing processes as well as the mechanical properties, research direction and application prospects of structural laminated veneer lumber made from planted forest wood are discussed.