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How cage transformation interacts with cluster configuration has been elucidated by three designed metallofullerenes, namely Lu3N@Cs(17 490)-C76, Lu3N@C2(22 010)-C78, and Lu3N@D3h(5)-C78, with an easy-to-compare cluster configuration and cage arrangement.

While the strong interaction between the internal unit and the fullerene cage inside metallofullerenes is widely acknowledged, how the cage transformation interacts with the cluster configuration remains elusive. For this purpose, we herein synthesized three metallofullerene molecules with an easy-to-compare cluster configuration and cage arrangement, namely Lu

Four copper(I) alkynyl complexes incorporating phosphate ligands, namely, [Cu16(tBuC≡C)12(PhOPO3)2]n (1; PhOPO3 = phenyl phosphate), [Cu16(tBuC≡C)12(1-NaphOPO3)2]n (2; 1-NaphOPO3 = 1-naphthyl phosphate), [VO4@Cu25(tBuC≡C)19(1-NaphOPO3)](PF6)0.5(F)0.5 (3), and [PO4@Cu25(tBuC≡C)19(1-NaphOPO3)](PF6)0.5(F)0.5 (4), were solvothermally synthesized and well-characterized by IR spectroscopy, powder X-ray diffraction, and single-crystal X-ray diffraction. Single-crystal X-ray analysis revealed that the Cu16 cluster-based coordination chain polymers 1 and 2 are formed by assembly during crystallization, while 3 and 4 contain high-nuclearity copper(I) composite clusters enclosing orthovanadate and phosphate template ions, respectively, that are supported by ROPO32- ligands. Complexes 1-4 exhibit crystallization-induced emission enhancement. Their crystalline state shows strong luminescence, in striking contrast to the weak emission of the amorphous state and solution phase. A detailed investigation of the crystal structure suggests that well-arranged C-H···π and π···π interactions between the ligands are the major factors for this enhanced emission. Clusters 3 and 4 also exhibit photocurrent responses upon visible-light illumination.

A zwitterionic ligand 3-(triethylammonio)propyne (TAP) has been employed to construct nine silver ethynide compounds for the first time. Single-crystal X-ray analyses reveal that compounds 1 and 2 are silver ethynide assemblies based on the Ag3 subunits and clusters 3-8 are small discrete clusters of Ag3, Ag6, Ag8, and Ag12, respectively, ligated by the bulky TAP ligand with different auxiliary ligands. In addition, upon acquiring the tripod-like tBuPO32-, a unprecedented 80 nuclei silver ethynide cluster was isolated and determined to be [(CF3CO2)5@Ag80(TAP)14(tBuPO3)16(CF3CO2)24]19+ by crystallography and thermogravimetric analysis. The C1 symmetry of Ag80 was deconstructed to be two [Ag40(TAP)7(tBuPO3)8(CF3CO2)12]12+ secondary building subunits arranged in a cross way, with five CF3CO2- trapped in the center. These results highlight that the elaborate selection of ethynide ligands is of great importance in the synthesis of novel silver ethynide clusters.

To scientifically measure the water environment carrying capacity of Harbin City and its change trend, based on analysis of the implications of the sustainability of the urban water environment’s carrying capacity, an evaluation index system for the sustainability of the water environment carrying capacity of Harbin City was constructed. Most existing evaluation methods rely on static data to construct correlation functions between research objects and rank criteria, while the dynamic nature of the information is not considered enough. In this paper, we use hierarchical analysis (analytic hierarchy process, AHP) to determine the weights of each index of the system and then apply the projection tracing method (projection pursuit, PP) to optimize the determined weights. Combining the set pair analysis posture evaluation method and bias coefficients method to explore the dynamic balance mechanism between different index factor levels, a sustainability evaluation model for water environment carrying capacity integrating informational evolution is constructed. Finally, the applicability of the optimization model is tested by comparing the confidence criterion judging method. The model realizes quantitative evaluation of the carrying capacity of the urban water environment. It provides a new and effective means for accurate and reasonable determination of the coefficient of variance and the number of links and dynamic analysis of the water environment carrying capacity system and judgment of its sustainable development trend. The results show that the weight for water resource quality is 0.55, which is the subsystem with the greatest overall impact on the carrying capacity of the water environment in Harbin. The evaluation level of the set-to-potential eigenvalue for 2010–2017 is biased positive 2, and the rest of the years are quasi 2. The reduced value of the coefficient of oppositeness corresponding to the years 2010–2017 is more significant. The maximum value of the dynamic evolution of the load-carrying capacity level is nearly −0.35. From the vertical comparison of different levels, it is found that the water environment carrying capacity of Harbin City gradually recovered to the normal loadable level over time. This overall shows an improving trend.

Herein, in this study, we utilized Ag+-ligand interactions for critically regulating the morphology of carbon by the Stober-silica/carbon co-assembly method for the first time. Tetraethyl orthosilicate (TEOS) and resorcinol/formaldehyde (RF) assemble upon dictation by Ag+ and pyridyl-functionalized surfactants, producing porous carbon tubes (RF1) with a high surface area of 696 m2 g-1 and accessible mesopores ∼15 nm in size. Furthermore, when using tetrapropyl orthosilicate (TPOS) with a slower hydrolysis rate than that of TEOS, carbon tubes (RF2) with enhanced uniformity and a surface area as high as 2112 m2 g-1 are generated. Additionally, when using dopamine hydrochloride instead of RF as a carbon precursor, tubular polydopamine (TDA) with lengths of tens of microns is fabricated, which exhibits excellent catalytic activity toward oxygen reduction reactions in alkaline solutions due to its unique structural feature, a high surface area of 1350 m2 g-1, metallic silver remains of 8.3 wt%, and a rich nitrogen content of 3.6 wt%. This work sheds light on the engineering of a micellar soft template and synthesizing novel nanostructures by the extension of the Stober method.

Four silver thiolate clusters, [H3 O][(Ag3 S3 )(BF4 )@Ag27 (tBuS)18 (hfac)6 H2 O]⋅H2 O (1; hfac = hexafluoroacetylacetone), [(Ag3 S3 )(CF3 CO2 )@Ag30 (tBuS)16 (CF3 CO2 )9 (CH3 CN)4 ]⋅CF3 CO2 ⋅4 CH3 CN (2), [(Ag3 S3 )(MoO4 )@Ag30 (tBuS)16 (CF3 CO2 )9 (CH3 CN)4 ]⋅2 CH3 CN (3), and [(Ag3 S3 )(CrO4 )@Ag30 (tBuS)16 (CF3 CO2 )9 (CH3 CN)4 ]⋅4 CH3 CN (4), were isolated. They have similar nestlike structures assembled by an [Ag3 S3 ]3- template together with one of the BF4 - , CF3 CO2 - , MoO4 2- , or CrO4 2- anions. Interestingly, the solid-state emissions of 2-4 are dependent on the templating anions and are tunable from green to orange and then to red by changing the template from CF3 CO2 - to MoO4 2- and to CrO4 2- , and this may be correlated to the charge transfer between these templates to metal atoms. This work helps to understand the templating role of heteroanions and the relationship between structure and properties.

Doxorubicin (DOX) leads to myocardial cell damage and irreversible heart failure, which limits the clinical application of DOX. Naringin has biological functions of inhibiting inflammation, oxidative stress and apoptosis. Our aim was to investigate whether Naringin could prevent DOX-related cardiotoxicity in mice. Naringin was administered by gavage and mice were intraperitoneally injected with doxorubicin (1 mg/kg/day) for 15 days. H&E, Masson, TUNEL and others experiments were examined. NRVMs and H9C2 cells were treated with Naringin and DOX in vitro. Using IF, ELISA and Western Blot to detect the effect of Naringin and ECHS1 on cells. The results showed that Naringin could prevent DOX related cardiac injury, inhibit cardiac oxidative stress, inflammation and apoptosis in vivo and in vitro. Inhibition of ECHS1 could interfere the effect of Naringin on DOX-induced myocardial injury. Naringin may provide a new cardiac protective tool for preventing the cardiotoxicity of anthracycline drugs.

Background MiRNA can be involved in regulating tumor genesis and development by regulating the expression of specific genes and regulating corresponding signaling pathways. In this study, we explored the function and mechanisms of miR-302e in glioma progression. Methods Experimental methods include the following: real-time quantitative PCR, Western Blot Analysis, CCK8 assay and detection of apoptosis. Results MiR-302e was down-regulated in cancer tissues and cell lines, and the expression of miR-302e was negatively correlated with the tumor grade, which indicated poor prognosis in glioma patients. Followed functional analysis showed overexpression of miR-302e inhibited proliferation, migration and invasion but promoted apoptosis of glioma cells, while silencing miR-302e showed the opposite effects. Mechanistic studies have shown that VEGFA was a directed target of miR-302e. Forced expression of VEGFA removed the inhibiting impact of miR-302e on glioma development. In vivo tumorigenesis experiments showed that miR-302e suppressed glioma development by targeting VEGFA. Conclusion Present study emphasized miR-302e suppressed glioma development by targeting VEGFA, which might be a valuable target for glioma treatment.

Aviation bearing bracket is an important part of aircraft and other aviation products. In this paper, based on additive and subtractive hybrid manufacturing technology with high manufacturing flexibility and high machining accuracy, a machining scheme of aviation bearing bracket is designed. First, milling simulation was carried out to obtain the influence law of different cutting parameters on machining deformation, so as to guide the selection of reasonable finish machining parameters in the subsequent process planning. Then, the temperature field distribution of workpiece in the additive manufacturing was simulated, and the influence of different additive manufacturing parameters on the results was analyzed to determine the parameter selection range. Finally, considering the material utilization rate, machining accuracy, machining efficiency and machinability in the machining process of aviation bearing bracket, and proceeding from additive, subtractive and alternating manufacturing methods, the manufacturing process arrangement and process planning for aviation bearing bracket were designed.

Building construction has developed from the use of primitive tools to that of machinery, with a tendency toward automation. Automation of processes and robotics can improve efficiency, accuracy and safety in construction. On the other hand, structural prefabrication for construction is increasingly being adopted worldwide to enhance productivity and to alleviate the environmental impact of conventional construction processes. The combination and application of automation and prefabrication technologies may therefore introduce new developments to the construction industry. This paper provides a comprehensive review of the use of automation technology for structural prefabrication and construction, including recent developments, challenges and future trends. Five stages following the sequence of construction are proposed: design, construction management, robotic manufacturing, autonomous transportation and automatic structural assembly. The paper concludes that the widespread use of automation technology is preferable to structural prefabrication for construction, and that the design for robotic construction introduced through connection innovations may be beneficial as a means of avoiding complex operations and thus improving the efficiency of robotic assembly processes.

Six dierbium carbide endohedral metallofullerenes have been synthesized and chromatographically isolated. Single-crystal X-ray diffractometry unambiguously ascertains their structures as Er2C2@C2v(...

The immunoproteasome contains three catalytic subunits (β1i, β2i and β5i) that are important modulators of immune cell homeostasis. A previous study showed a correlation between β5i and human atherosclerotic plaque instability; however, the causative role of β5i in atherosclerosis and the underlying mechanisms remain unknown. Here we explored this issue in apolipoprotein E (Apoe) knockout (eKO) mice with genetic deletion or pharmacological inhibition of β5i. We found that β5i expression was upregulated in lesional macrophages after an atherogenic diet (ATD). β5i/Apoe double KO (dKO) mice fed on the ATD had a significant decrease in both lesion area and necrotic core area, compared with eKO controls. Moreover, dKO mice had less caspase-3+ apoptotic cell accumulation but enhanced efferocytosis of apoptotic cells and increased expression of Mer receptor tyrosine kinase (MERTK). Consistently, similar phenotypes were observed in eKO mice transplanted with dKO bone marrow or treated with β5i-specific inhibitor PR-957. Mechanistic studies in vitro revealed that β5i deletion reduced IκBα degradation and inhibited NF-κB activation, promoting Mertk transcription and efferocytosis, thereby attenuating apoptotic cell accumulation. In conclusion, we demonstrate that β5i plays an important role in diet-induced atherosclerosis by altering MERTK-mediated efferocytosis. β5i might be a potential pharmaceutical target against atherosclerosis. © 2019 Pathological Society of Great Britain and Ireland. Published by John Wiley & Sons, Ltd.

Metal nanoclusters (NCs) consist of tens to hundreds of metal atoms with a diameter of

Thiols, alkynyls and phosphines are the most widely used organic ligands to attain atomically precise metal nanoclusters, while oxometalates as inorganic ligands have almost been neglected in this field. Here, we used oxometalates (e.g., MoO42− and WO42−) as protecting ligands along with phosphines, such as 1,4-bis(diphenylphosphino)butane (dppb), to design and synthesize a new class of silver nanoclusters including Ag28(dppb)6(MoO4)4, Ag28(dppb)6(WO4)4 and Ag32(dppb)12(MoO4)4(NO3)4. Each cluster consists of a two-shell Ag4@Ag24 core protected by 4 oxometalates. These clusters exhibit similar optical absorption and photoluminescence properties that are not dependent on surface ligands. Furthermore, the electronic structure analysis shows that the clusters are 20-electron “superatoms”. This work demonstrates that oxometalates can play a key role in the formation of silver nanoclusters, and the effect of oxometalates should be considered in the design and synthesis of metal nanoclusters.

Constructing silver(i)-thiolate clusters from simple building blocks usually involves elusive self-assembly processes and remains a long-standing challenge. In this work, we report 6 silver(i)-thiolate clusters protected by pyridines, namely, [Ag3(tBuS)2(Py)(NO3)]n (Py = pyridine) (1), [Ag10(tBuS)6(Py)6(CF3CO2)4]·3Py (2), [Ag12(iPrS)6(Py)8(NO3)6]·2H2O (3), Ag12(iPrS)6(Py)8(CF3CO2)6 (4), Ag12(iPrS)6(4-ap)6(NO3)6 (4-ap = 4-aminopyridine) (5), and [Ag50S13(tBuS)20(Py)12]·4BF4·4Py·4CH3OH·2H2O (6). Single-crystal X-ray crystallography analysis reveals that six clusters are constructed by four types of structural blocks, including the PyAg(tBuS)2 monomer, Py2Ag2(tBuS)2 dimer, Py3Ag3(tBuS)3 trimer and (4-ap)6Ag6(iPrS)6 hexamer. Notably, cluster 6 consists of a rhombic dodecahedron S@Ag14 kernel with 12 interstitial S2- atoms encapsulated by 8 μ4-tBuS- ligands, as well as six unique butterfly-like (Py)2Ag6(tBuS)2 staple motifs composed of a Py2Ag2(tBuS)2 dimer and four silver ions. Moreover, it is found that pyridine ligands have important influence on the construction of silver thiolate clusters and their Ag-SR bond lengths.

Diets rich in polyphenols are known to be beneficial for cardiovascular health. Gallic acid (GA) is a plant-derived triphenolic chemical with multiple cardio-protective properties, such as antiobesity, anti-inflammation, and antioxidation. However, whether GA could protect against atherosclerotic cardiovascular diseases is still not defined. Here, we investigated the effects of low-dose GA administration on diet-induced metabolic disorders and atherosclerosis in the atherosclerosis-prone apolipoprotein E (Apoe) knockout mice fed on a high-fat Western-type diet (WTD) for 8 weeks. Our data showed that GA administration by oral gavage at a daily dosage of 20 mg/kg body weight did not significantly ameliorate WTD-induced hyperlipidemia, hepatosteatosis, adipogenesis, or insulin resistance; furthermore, GA administration did not significantly ameliorate WTD-induced atherosclerosis. In conclusion, our data demonstrate that low-dose GA administration does not elicit significant health effect on diet-induced metabolic disorders or atherosclerosis in the Apoe knockout mice. Whether GA could be beneficial for atherosclerotic cardiovascular diseases therefore needs further exploration.

Variation of the reaction conditions with Cu powder, Cu(NO3)2, and tBuC≡CH as starting materials afforded three new Cu(I) alkynyl complexes, namely, [Cu14(tBuC≡C)10(NO3)4(MeOH)2]·H2O (1), Cu15(tBuC...

Successful isolation and characterization of a series of Er-based dimetallofullerenes present valuable insights into the realm of metal-metal bonding. These species are crystallographically identified as Er2 @Cs (6)-C82 , Er2 @C3v (8)-C82 , Er2 @C1 (12)-C84 , and Er2 @C2v (9)-C86 , in which the structure of the C1 (12)-C84 cage is unambiguously characterized for the first time by single-crystal X-ray diffraction. Interestingly, natural bond orbital analysis demonstrates that the two Er atoms in Er2 @Cs (6)-C82 , Er2 @C3v (8)-C82 , and Er2 @C2v (9)-C86 form a two-electron-two-center Er-Er bond. However, for Er2 @C1 (12)-C84 , with the longest Er⋅⋅⋅Er distance, a one-electron-two-center Er-Er bond may exist. Thus, the difference in the Er⋅⋅⋅Er separation indicates distinct metal bonding natures, suggesting a distance-dependent bonding behavior for the internal dimetallic cluster. Additionally, electrochemical studies suggest that Er2 @C82-86 are good electron donors instead of electron acceptors. Hence, this finding initiates a connection between metal-metal bonding chemistry and fullerene chemistry.

Aims Improvements in cancer treatment have significantly extended the lifespan of patients. However, due to the adverse effects of cancer treatment, cancer survivors are at increased risk of cardiovascular complications. Doxorubicin is a widely used spectrum antitumor drug, but the life-threatening side-effect of cardiotoxicity limits its clinical application. Ammonium chloride (NH4Cl), as a heteropolar compound with pH value regulation, can cause intracellular alkalization and metabolic acidosis thus effecting enzymatic activity and influencing the process of biological system. The underlying effect of NH4CL in DOX-induced cardiomyocyte apoptosis and hypertrophy in mice has never been reported before. Main methods This study we used DOX to induce cardiac remodeling and dysfunction in mice. Myocardial histology was performed using HE staining. Myocardial cell size was measured by wheat germ agglutinin (WGA) staining. Echocardiographic evaluation of cardiac function, qPCR detection of the mRNA expression of cardiac hypertrophy and inflammation markers. Apoptosis was detected by TUNEL method. Transmission electron microscopy (TEM) was used to detect autophagy. Key findings We found that NH4CL effectively improved DOX-induced cardiomyocyte apoptosis and cardiac dysfunction in mice. Our results showed that NH4CL significantly improved DOX-induced contractile dysfunction, inflammation, apoptosis and autophagy in mice. Significance Our results indicate that NH4CL is effective in improving DOX-induced cardiac dysfunction and remodeling. It may therefore be a therapeutic entry point to limit doxorubicin-mediated adverse cardiac reactions.

The prototypical η1-coordinated complexes of endohedral metallofullerenes (EMFs) have never been reported because of their low stability. Herein, we have developed a highly efficient radical-coupli...

Two Er@C82 isomers have been isolated and unambiguously characterized as Er@ C2 v(9)-C82 and Er@ C s(6)-C82, respectively, by single-crystal X-ray diffraction. Er@ C s(6)-C82 is identified as a dimeric structure in the crystalline state, but dimerization does not occur for Er@ C2 v(9)-C82 under identical crystallization conditions, indicating a cage-symmetry-induced dimerization process. Density functional theory calculations reveal that the major unpaired spin resides on a special C atom of Er@ C s(6)-C82, which leads to regioselective dimerization. Calculations also found that the dimeric structure of Er@ C s(6)-C82·Ni(OEP) is much more stable than the two monomers, suggesting a thermodynamically favorable dimerization process. Vis-near-IR spectrometric and electrochemical results demonstrate that the electronic structure of Er@C82 isomers is Er3+@C823-, instead of the theoretically proposed Er2+@C822-.

Direct yttrium–yttrium bonding has been a long-sought puzzle in organometallic chemistry to understand the catalytic processes that involve yttrium. Herein, we report the first crystallographic authentication of direct Y–Y bonding inside the hollow cavity of fullerene cages by forming endohedral metallofullerenes (EMFs). Based on an efficient separation/purification process, which involves Lewis-acid treatment and HPLC separation, we have obtained sufficient amounts of a series of Y2C2n (2n = 82, 88–94) isomers for systematic studies. The unambiguous single-crystal X-ray diffraction (XRD) crystallographic results show that two of them are di-EMFs, namely Y2@Cs(6)-C82 and Y2@C3v(8)-C82, in which the long-sought Y–Y single bond between the two divalent yttrium ions is experimentally confirmed for the first time. In contrast, all the other EMFs with relatively large cages are carbide cluster metallofullerenes (CCMFs), namely, Y2C2@Cs(15)-C86, Y2C2@C1(26)-C88, Y2C2@C2(41)-C90 and Y2C2@C2(61)-C92. Consistently, our computational results prove that these experimentally obtained EMFs are all abundant at the high temperatures for fullerene formation (∼1500–3000 K) due to the strong coordination ability of yttrium ions, which enables the formation of either direct Y–Y bonds (for Y2@Cs(6)-C82 and Y2@C3v(8)-C82) or the inclusion of a C2-unit (in Y2C2@Cs(15)-C86, Y2C2@C1(26)-C88, Y2C2@C2(41)-C90 and Y2C2@C2(61)-C92). Our results suggest that metal atoms such as yttrium tend to adopt a low valence state during the arc-discharge process because of the presence of the highly reductive carbon plasma in the chamber, enabling the formation of an Y2 dimer with direct Y–Y bonding in small cages like C82.

A series of Er-based nitride clusterfullerenes (NCFs), Er3N@C80–88, have been successfully synthesized and isolated. In particular, Er3N@Ih(7)-C80, Er3N@D5h(6)-C80, Er3N@C2v(9)-C82, Er3N@Cs(51365)-C84, and Er3N@D2(35)-C88 have been characterized by single-crystal X-ray diffraction (XRD) for the first time. The planar configuration of the inserted Er3N cluster is identified unambiguously and the Er–N distances increase in accordance with cage expansion to maintain strong metal–cage interactions. Additionally, the electrochemical properties of the Er3N@C80–88 series are studied by means of cyclic voltammetry. It is found that the first reduction potentials are roughly similar for all compounds under study, while the first oxidation potentials are cathodically shifted along with the increase of the cage size in the Er3N@C2n (2n = 80, 84, 86, 88) series, leading to a decrease in the corresponding electrochemical band gaps. Nevertheless, for Er3N@C2v(9)-C82, a good electron donating ability is manifested by its relatively small first oxidation potential, which results from the relatively higher energy level of the highest occupied molecular orbital. The redox behaviors observed in such Er3N-based NCFs may promise their great potential applications in donor–acceptor systems.

The successful isolation and unambiguous crystallographic assignment of a series of lutetium-containing endohedral metallofullerenes (EMFs), Lu2C2n (2n = 76, 78, 80, 84, 86, 88, 90), reveal an unrecognized decisive effect of the cage size on the configuration of the encapsulated clusters. The molecular structures of these compounds are unambiguously assigned as Lu2@Td(2)-C76, Lu2@D3h(5)-C78, Lu2@C2v(5)-C80, Lu2@C2v(7)-C84, Lu2@Cs(8)-C86, Lu2@Cs(15)-C86, Lu2@C1(26)-C88, Lu2C2@C2v(9)-C86, Lu2C2@Cs(32)-C88 and Lu2C2@D2(35)-C88. Specifically, when the cage is relatively small, Lu2@C2n (2n = 76–86) are all dimetallofullerenes (di-EMFs) and a Lu–Lu single bond could be formed between the two lutetium ions inside the cages. However, when the cage expands further, the valence electrons forming the possible Lu–Lu bond donate to a readily inserted C2-unit, resulting in the formation of carbide EMFs, Lu2C2@C2n (2n = 86, 88). Consistently, our theoretical results reveal that all these EMFs are thermodynamically favorable isomers. Thus the comprehensive characterization of the series of Lu2C76–90 isomers and the overall agreement between the experimental and theoretical results reveal for the first time that the exact configuration of the internal metallic cluster is determined by the cage size, taking a solid step towards the controlled synthesis of novel hybrid molecules which may have potential applications as building blocks of single molecule devices.

The Lewis acid–base pairing reaction between strained N-heterocyclic carbene (NHC) and endohedral metallofullerenes (EMFs) is an efficient strategy to obtain stable derivatives in a highly regioselective manner. Herein, we report an in-depth study on the reactions between 3-dimesityl-1H-imidazol-3-ium-2-ide (1) and three different EMFs, namely, Lu3N@Ih(7)-C80, Lu2@C3v(8)-C82, and Lu2@C2v(9)-C82, respectively. Only one monoadduct is obtained for each EMF under certain conditions, demonstrating surprisingly high regioselectivity and exclusive formation of monoadducts. X-ray results of the derivatives of Lu3N@C80 reveal that an epoxide adduct (2a) with a specific [6,6,6]-carbon atom of the C80 cage singly bonded to the normal carbene center (C2) of the NHC is obtained under ambient condition, whereas a pure argon atmosphere gives 2b with an abnormal C5-bonding structure. In contrast, the derivatives of Lu2@C82 (3 and 4) are both normal C2-bonding [5,6,6]-adducts without oxygen addition, even though air is in...

tert-Butylphosphonic acid and rare-earth precursors are employed to construct four trinuclear rare-earth phosphonate clusters, RE3(tBuPO3)2(hfac)5(CH3OH)8]·2CH3OH (RE = Eu, Y, Pr, and Sm; hfac = hexafluoroacetylacetonate), which are composed of three RE3+ ions alternately bridged by two phosphonates. With the introduction of bismuth oxido diketonate, [Bi9O7(hfac)13], three different types of rare-earth/bismuth phosphonate clusters, Bi12RE2 (RE = Pr and Sm), Bi6Eu7, and Bi6Y9, are successfully obtained via variation of the reaction conditions, and they are the first reported examples of bismuth–oxo clusters encapsulated by cyclic rare-earth–oxo or rare-earth/bismuth–oxo phosphonate clusters, respectively. These clusters show obvious absorption in the UV region, and the Eu-containing clusters exhibit bright-red fluorescence.

Two crystalline silver alkynyl assemblies, namely, [Ag6(tBuC≡C)4 L1]n (1), [Ag10(tBuC≡C)6(L2)2]n (2) (H2L1 = 1,8-naphthalene dicarboxylic acid and H2L2 = 1,4-naphthalene dicarboxylic acid) have been obtained by the reaction of polymeric [tBuC≡CAg]n with silver salts and dicarboxylic acids under mild solvothermal conditions. Compounds 1 and 2 are coordination polymers of irregular silver alkynyl clusters. 1 is chains of cube-like silver clusters connected with L1 and tBuC≡C- ligands. In compound 2, the Ag10 clusters surrounded by six tBuC≡C- ligands are linked by silver atoms to 1D chains, which are further extended by L2 ligands to a rare 3D framework. From the topological view, the structure of 2 can be regarded as α-Po topology. The luminescence properties indicated that the two complexes display more than one peak maxima at 298 K using 335 nm excitation.

Background and Purpose: Cancer patients treated with anthracyclines are susceptible to atrial fibrillation (AF) with unknown mechanisms. Due to sudden and unpredictable features of AF, detection or prediction of anthracycline-induced AF at early phase is difficult. Experimental Approach: Breast cancer patients (post-surgery) with an anthracycline-containing regimen were recruited for echocardiography at pre-, and 3 and 6 months post-chemotherapy. Mice were injected with doxorubicin or vehicle and the following parameters were determined: left atrial diameter, electrical transmission, AF inducibility. Meanwhile, oxidative stress, cardiomyocyte size, vacuolization, inflammation and fibrosis were measured in mouse atria. The therapeutic effect of dexrazoxane on doxorubicin-induced changes in the aforementioned parameters were also determined. Key Results: Whilst ventricular parameters and functions were unchanged in cancer patients pre- and post-chemotherapy, strain and strain rate of left atrial reservoir function and conduit function were decreased at 3 months post-chemotherapy vs pre-chemotherapy. Doxorubicin-induced atrial dilatation and susceptibility to AF occurred in mice prior to onset of ventricular dysfunction. Doxorubicin-induced AF was via inducing structural remodeling (i.e. cardiomyocyte death, hypotrophy and vacuolization) and electrical remodeling (i.e. reduction and redistribution of connexin 43) in the atrium, which was effectively prevented by dexrazoxane. Atrial remodeling and AF inducibility were induced after doxorubicin injection, which can be inhibited by dexrazoxane. Conclusions and Implications: Clinically, we tested whether anthracycline-induced early atrial remodeling in patients could be detected by echocardiography. Experimentally, we investigated the mechanisms of doxorubicin-induced atrial remodeling and AF in mice, and the protective effect of the free radical scavenger dexrazoxane.

Six dierbium carbide endohedral metallofullerenes have been synthesized and chromatographically isolated. Single-crystal X-ray diffractometry unambiguously ascertains their structures as Er

The small Sc3 N cluster has only been found in such small cages as C2n (2n=68, 78, 80, 82), whereas the large M3 N (M=Y, Gd, Tb, Tm) clusters choose those larger cages C2n (2n=82-88). Herein, concrete experimental evidence is presented to establish the size effect of the internal metallic cluster on selecting the outer cage of endohedral metallofullerenes (EMFs) by using a medium-sized metal, lutetium, which possesses an ionic radius between Sc and Gd. A series of lutetium-containing EMFs have been obtained and their structures are unambiguously determined as Lu3 N@Ih (7)-C80 , Lu3 N@D5h (6)-C80 , Lu3 N@C2v (9)-C82 , Lu3 N@Cs (51365)-C84 , Lu3 N@D3 (17)-C86 , and Lu3 N@D2 (35)-C88 by single-crystal X-ray diffraction crystallography. It was confirmed that the encaged Lu3 N cluster always adopts a planar geometry in Lu3 N@C80-88 isomers to ensure substantial metal-cage/metal-nitrogen interactions. As a result, the Lu3 N cluster selects the C2v (9)-C82 cage, which also encapsulates Sc3 N, instead of the Cs (39663)-C82 cage which is more suitable for M3 N (M=Y, Gd, Tb, Tm). However, different from Sc3 N, Lu3 N can also template the C84-88 cages which are absent for Sc3 N-containing EMFs, confirming clearly the size effect of the internal cluster on selecting the outer cage.

Reaction of AgC≡CtBu with (EtO)2PS2Na at room temperature leads to the isolation of two new silver(I)-ethynide compounds incorporating the dithiophosphate ligand, namely, {CO3@(Ag3)4(C≡CtBu)4(EtO)2PS2]6}·0.5H2O (1) and {(CO3)2@Ag26(C≡CtBu)16[(EtO)2PS2]4}·2(OH)·4MeOH·6H2O (2). Besides, we obtain another three silver(I)-ethynide clusters S@Ag11(C≡CtBu)2[(EtO)2PS2]7 (3), {S@Ag14(C≡CPh)8[(EtO)2PS2]4(TMEDA)2}·5MeOH (4), and {S@Ag14(C≡CPh)8[(iPrO)2PS2]4(TMEDA)2}·7CH3OH (5), with AgC≡CR (R= tBu, Ph) and (RO)2PS2Na (R= Et, iPr) as the starting materials. Complexes 1–2 are templated by a carbonate anion in situ generated from the fixation of atmospheric CO2 in a basic TMEDA-containing solution, and TMEDA can also lead to the disassembly of dithiophosphate to give a sulfide ion as the template for the generation of 3–5.

tert-Butylphosphonic acid and lanthanide precursors were employed to construct two high-nuclearity hybrid silver(I)-ytterbium(III) phosphonate clusters: compound 1 consists of a Ag16 ethynide cluster fused with a trinuclear hydroxoytterbium phosphonate cluster, whereas compound 2 is composed of two Ag16 ethynide clusters bridged by a hexanuclear oxo/hydroxoytterbium phosphonate cluster. Using transition-metal-substituted lacunary polyoxotungstates in place of the lanthanide reactant, new phosphonate-functionalized silver(I)-copper(II) ethynide clusters [Ag34 Cu6 (3) and Ag37 Cu6 (4)] and silver(I) ethynide clusters [Ag51 (5) and Ag72 (6)] were obtained. The structures of complexes 3-6 feature core-shell arrangements, in which silver(I)-copper(II) or silver(I) ethynide cluster shells stabilized by peripheral phosphonate ligands enclose different kinds of tungstate core templates.

A series of giant metallofullerenes Y2C2n (2n = 92–130) have been successfully obtained through the treatment of the fraction enriched by 1,2-dichlorobenzene with SnCl4. Subsequent chromatographic separation gives a pure sample with a composition of Y2C110. Crystallographic results reveal that this endohedral takes the carbide form, namely Y2C2@C1(1660)-C108, representing as the largest metallofullerene that has been characterized by crystallography to date. Despite the disorder of the metal cluster, the major Y2C2 adopts a previously predicted linear configuration, indicating that the compression of the internal cluster by the cage is almost negligible in this giant cage. Electrochemical studies suggest that Y2C2@C1(1660)-C108 is a good electron donor instead of an electron acceptor.

The tert-butylethynide ligand has been employed to construct an atomically precise all-tert-butylethynide-protected silver superatom nanocluster, Ag51(tBuC[triple bond, length as m-dash]C)32 (hereafter denoted as Ag51). The identity of Ag51 is confirmed by high resolution ESI-MS and elemental analysis. Single crystal X-ray analysis revealed that the structure of Ag51 features a three-shell arrangement, Ag@Ag8/Ag6@Ag36@C24/C8. Ag51 exhibits a strong solvatochromic effect, and the emissions are strongly dependent on the solvent polarity and are tunable from blue to red by changing the solvent from less polar dichloromethane to highly polar methanol.

Specific groups in Asia, including the Chinese, are more susceptible to colorectal cancer (CRC). The best strategy for anticancer drug action is to induce cancer cell apoptosis and autophagy. Bufalin is a potent inducer of apoptosis in some human cancer cell lines, but bufalin has barely been evaluated in colorectal cancer cells as a potent autophagy inducing agent. The aim of this study was to investigate the roles and interactions of bufalin in autophagy and the effects of the drug on human colorectal cancer. We applied bufalin and autophagy inhibitors (CQ and 3-MA) in LoVo cells to investigate their potential anticancer bioactivity under certain concentrations of bufalin to monitor autophagy and cell proliferation in vivo and in vitro. Bufalin induced autophagy of LoVo and inhibited proliferation of LoVo cells. Bufalin inhibited the expression of autophagy-related (ATG) proteins and tumor growth in vivo. Our studies identified that bufalin could potentially be a small molecule inhibitor for cancer therapy.

Background/Aims: Cardiac remodeling is a critical pathogenetic process leading to heart failure. Suppressor of cytokine signaling-3 (SOCS3) is demonstrated as a key negative regulator of the gp130 receptor to inhibit cardiac hypertrophy. However, the role of SOCS3 in deoxycorticosterone-acetate (DOCA)-salt-induced cardiac remodeling remains unclear. Methods: Cardiac-specific SOCS3 knockout (SOCS3cKO) and wild-type (WT) C57BL/6J mice were subjected to uninephrectomy and DOCA-salt for 3 weeks. The effect of SOCS3 on cardiac remodeling and inflammation was evaluated by histological analysis. Gene and protein levels were measured by real-time PCR and immunoblotting analysis. Results: After DOCA-salt treatment, the expression of SOCS3, activation of gp130/JAK/STAT3, cardiac dysfunction and fibrosis in DOCA-salt mice were significantly elevated, which were markedly attenuated by eplerenone, a specific mineralocorticoid receptor (MR) blocker. Moreover, DOCA-salt-induced cardiac dysfunction, hypertrophy, fibrosis and inflammation were aggravated in SOCS3cKO mice, but were significantly reduced in AAV9-SOCS3-injected mice. These effects were mostly associated with activation of gp130/STAT3/AKT/ERK1/2, TGF-β/Smad2/3 and NF-κB signaling pathways. Conclusions: Our data demonstrate that loss of SOCS3 in cardiomyocytes promotes DOCA-salt-induced cardiac remodeling and inflammation, and it may be a novel potential therapeutic target for hypertensive heart disease.

In this study, we dispersed MIL-101(Cr) into melamine sponge (MS) by one-step hydro-thermal method and prepared MS/MIL-101(Cr) composite material (MM101CM). It is applied to atmospheric water harvest. The structure and properties of MM101CM were characterized by field emission scanning electron microscopy (SEM), X-ray diffraction (XRD), in situ attenuated total reflection fourier transform infrared spectroscopy (FT-IR) and comprehensive thermal analyzer (TG). The influence of temperature and humidity on atmospheric water collection performance of MM101CM was studied. The composite has good water stability and thermal stability, and its maximum water adsorption capacity can reach 1232 ​g/kg. This study found a simple and effective composite way for metal organic framework materials with hygroscopic properties, which will be conducive to the large-scale application of this kind of materials for atmospheric water collection.

Successful applications of lipidomics in clinic need study large-scale samples, and the bottlenecks are in throughput and robustness of the lipid analytical method. Here, we report an untargeted lipidomics method by combining high throughput pretreatment in the 96-well plate with ultra-high performance liquid chromatography coupled to quadrupole time-of-flight tandem mass spectrometry. The developed method was validated to have satisfactory analytical characteristics in terms of linearity, repeatability and extraction recovery. It can be used to handle 96 samples simultaneously in 25 min and detect 441 lipids in plasma sample. Storage stability investigation on lipid extracts provided an operable procedure for large-scale sample analysis and demonstrated most lipids were stable in autosampler at 10 °C within 36 h and at -80 °C within 72 h after the pretreatment. To prove the usefulness, the method was employed to investigate abnormal plasma lipidome related to atrial fibrillation. A biomarker panel with the area under the curve (AUC) values of 0.831 and 0.745 was achieved in the discovery and external validation sets, respectively. These results showed that the developed method is applicable for large-scale biological sample handling and lipid analysis of plasma.

In this paper, a new composite aerogel egg yolk/zeolitic imidazolate framework-8/crosslinked polyacrylic acid (EY/ZIF-8/CLPAA) was prepared by in situ polymerization of acrylic acid in composite system of egg yolk and ZIF-8. The structure and performance of the composite aerogel were characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), in-situ attenuated total reflection Fourier transform infrared spectrometer (FT-IR) and comprehensive thermal analyzer (TG). The results show that the composite aerogel has irregular porous structure inside, and ZIF-8 has 12-sided crystal structure. The composite aerogel has good thermal stability and water stability and can effectively remove dyes in wastewater. It has different equilibrium adsorption capacity for different dyes: Malachite Green: 2338 ​mg/g, Crystal Violet: 489 ​mg/g, Methyl Orange: 447 ​mg/g and Rhodamine B: 299 ​mg/g. The adsorbent still maintains a certain activity after five adsorption-desorption cycles. The EY/ZIF-8/CLPAA aerogel adsorbs organic dyes mainly through electrostatic interaction, π-π interaction and hydrogen bonding. The adsorption data conforms to the pseudo-second-order kinetic model and follows the Langmuir adsorption isotherm.