A Nanocluster [Ag307Cl62(SPhtBu)110]: Chloride Intercalation, Specific Electronic State, and Superstability.

The controlling synthesis of novel nanoclusters of noble metals (Au, Ag) and the determination of their atomically precise structures provide opportunities for investigating their specific properties and applications. Here we report a novel silver nanocluster [Ag307Cl62(SPhtBu)110] (Ag307) whose structure is determined by X-ray single crystal diffraction. The structure analysis shows that nanocluster Ag307 contains a Ag167 core, a surface shell of [Ag140Cl2S110], and a Cl60 intermediate layer located between Ag167 and [Ag140Cl2S110]. It is a first example that such many chlorides are intercalated into a Ag nanocluster. Chlorides are released in situ from solvent CHCl3. Nanocluster Ag307 exhibits superstability. Differential pulse voltammetry experiment reveals that Ag307 has continuous charging/discharging behavior with a capacitance value of 1.39 aF, while the Ag307 has a surface plasmonic feature. These characteristics show that Ag307 is of metallic behavior. However, its electron paramagnetic resonance (EPR) spectra display a spin magnetic behavior which could be originated from the unpassivated dangling bonds of surface atoms. The direct capture of EPR signals can be attributed to the Cl- intercalating layer which partly suppresses the electronic interactions between core and surface atoms, resulting in the relatively independent electronic states for core and surface atoms.

A longitudinal study on emotional distress among local government staff seven years after the 2008 Wenchuan earthquake in China.

BACKGROUND: The current study examined the change in local government staff's emotional distress over 7 years after the 2008 Wenchuan earthquake, and the influence of earthquake exposure and professional quality of life (ProQOL) on emotional distress. METHODS: This longitudinal study assessed 250 participants at 1 year after the earthquake; 162 (64.8%) were followed up at 7 years. Emotional distress was assessed with the Self-Reporting Questionnaire (SRQ) at both time points. We assessed ProQOL, including compassion satisfaction, burnout, and secondary traumatic stress, and earthquake exposure at 1 year. Wilcoxon signed-rank tests were performed to test longitudinal changes in emotional distress. Hierarchical multiple regression was conducted to examine the effect of earthquake exposure and ProQOL. RESULTS: The positive screening rate of emotional distress (SRQ ≥ 8) was 37.6 and 15.4% at one and 7 years, respectively. Emotional distress scores declined over time (p < 0.001). Earthquake exposure and ProQOL predicted one-year (ps < 0.05) but not seven-year emotional distress, whereas burnout predicted both one-year (p = 0.018) and seven-year (p = 0.047) emotional distress. CONCLUSIONS: Although emotional distress can recover over time, it persists even 7 years later. Actions to reduce burnout during the early stage of post-disaster rescue have long-term benefits to staff's psychological outcomes.

A Discrete Tetrahedral Indium Cage as an Efficient Heterogeneous Catalyst for the Fixation of CO2 and the Strecker Reaction of Ketones.

A discrete tetrahedral indium cage, {[In12(µ3-OH)4(HCO2)24(tcma)4]} (In12-GL), was synthesized solvothermally by the reaction of indium nitrate with the tripodal tricarboxylic acid ligand N,N,N-tris{(2'-carboxy[1,1'-biphenyl]-4-yl)methyl}methylammonium chloride ([H3tcma]+Cl). This cage consists of four trimeric units [In3(µ3-OH)(µ2-CO2)3(µ2-HCO2)3] and four [tcma]2- ligands, which all perform as 3-connection nodes to bridge each other, resulting in a tetrahedral cage structure. The trimeric unit [In3(µ3-OH)(µ2-CO2)3(µ2-HCO2)3] is observed for the first time in the family of In-based metal-organic structures and can be considered as an evolution of a 6-connected [In3(µ3-O)(µ2-CO2)6] unit. Each In3+ is terminally coordinated by a µ1-HCO2 group. This cage contains potential Lewis acidic/basic active sites endowed by In3+ ions as Lewis acidic sites and the uncoordinated oxygen atoms of µ1-HCO2 moieties as Lewis basic sites and was explored as an effective heterogeneous catalyst in the cycloaddition of CO2 with epoxides and the Strecker reaction for amino nitriles. These catalytic reactions were deduced to happen on the surface of the In12-GL cage.

Effects of T-2 toxin on the muscle proteins of shrimp (Litopenaeus vannamei) - a proteomics study.

BACKGROUND: T-2 toxin (T-2) is a potent mycotoxin and a common contaminant of aquatic animal feed, posing a serious risk to health and aquatic animals. We investigated the effect of T-2 on shrimp muscle proteins using proteomics and conventional biochemical methods. Shrimp were fed a diet containing T-2 at 0-12.2 mg kg-1 for 20 days, and changes to the muscle protein composition, ATPase activities, and the sulfhydryl (SH) content and hydrophobicity of actomyosin (AM) were determined. A proteomics study of the proteins was conducted with sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE), two-dimensional (2D) electrophoresis, and matrix-assisted laser desorption/ionization - time of flight mass spectrometry (MALDI-TOF/TOF MS). RESULTS: Exposure to T-2 markedly affected the muscle protein composition of shrimp in a concentration-responsive manner that displayed a diphasic effect. At a low T-2 concentration (1.2 mg kg-1 ), the levels of three major muscle proteins (myofibrillar, sarcoplasmic, and stroma) increased but at higher concentrations they declined progressively. T-2 exposure also led to a breakdown of muscle proteins as evidenced by increases in alkali-soluble protein and the surface hydrophobicity (SoANS) of AM. Thirty differentially expressed proteins were detected, 12 of which showed a concentration-response relationship with T-2 exposure. Among them, 11 homologous proteins were identified by mass spectrometry (MS), with several being key enzymes in energy metabolism. CONCLUSION: This study demonstrated that T-2 exposure at medium to high concentrations could significantly affect the protein composition and quality of shrimp muscle, and potentially some of its key metabolisms. One of the arginine kinases (spot 27) was particularly responsive to T-2 and could potentially be used as a biomarker protein for T-2 intoxication by shrimp. © 2019 Society of Chemical Industry.

[Segmentation Method of Colour White Blood Cell Image Based on HSI Modified Space Information Fusion].

This paper presents a kind of automatic segmentation method for white blood cell based on HSI corrected space information fusion.Firstly,the original cell image is transformed to HSI colour space conversion.Because the transformation formulas of H component piecewise function was discontinuous,the uniformity of uniform visual cytoplasm area in the original image was lead to become lower in this channel.We then modified formulas,and then fetched information of nucleus,cytoplasm,red blood cells and background region according to distribution characteristics of the H,S and I-channel,using the theory and method of information fusion to build fusion imageⅠand fusion imageⅡ,which only contained cytoplasm and a small amount of interference,and fetched nucleus and cytoplasm respectively.Finally,we marked the nucleus and cytoplasm region and obtained the final result of segmentation.The simulation results showed that the new algorithm of image segmentation for white blood cell had high accuracy,robustness and universality.

One-dimensional Cu(I) and Ag(I) ladder-like coordination polymers supported by 2-ethyl-1-(pyridin-3-ylmethyl)-1H-benzimidazole.

The title complexes, poly[[bis[µ2-2-ethyl-1-(pyridin-3-ylmethyl)-1H-benzimidazole-κ(2)N(1):N(3)]copper(I)] tetrafluoroborate acetonitrile monosolvate], {[Cu(C15H15N3)2]BF4·CH3CN}n, (I), and poly[[bis[µ2-2-ethyl-1-(pyridin-3-ylmethyl)-1H-benzimidazole-κ(2)N(1):N(3)]silver(I)] perchlorate methanol monosolvate], {[Ag(C15H15N3)2]ClO4·CH3OH}n, (II), are isostructural and exhibit one-dimensional ladder-like structures in which each asymmetric unit contains one metal ion (Cu(+) or Ag(+)), two 2-ethyl-1-(pyridin-3-ylmethyl)-1H-benzimidazole (bep) ligands, one counter-anion (tetrafluoroborate or perchlorate) and one interstitial molecule (acetonitrile or methanol). Each metal ion exhibits a distorted tetrahedral coordination geometry consisting of two pyridyl and two benzimidazole N atoms from four distinct ligands. Two metal ions are linked by two bep ligands to form a centrosymmetric 18-membered M2(bep)2 metallacycle, while adjacent M2(bep)2 metallacycles are further interlinked by another two bep ligands resulting in a ladder-like array. In the extended structure, four adjacent ladder-like arrays are connected together through C-H···F, O-H···O and C-H···O hydrogen bonds between bep ligands, solvent molecules and counter-anions into a three-dimensional supramolecular structure.

Confined covalent organic framework anchored Fe sites derived highly uniform electrocatalysts for rechargeable aqueous and solid-state Zn-air batteries.

Exploiting clean, highly efficient energy storage and conversion device like Zn-air battery is of significance for alleviating the energy and environmental crises of this society. Metal organic coordination polymers/frameworks have been regarded as ideal templates to synthesize non-noble metal catalysts for a long time. However, the high density of metal nodes inevitably leads to the heavy aggregation of metal nanoparticles during thermolysis transformation process, which greatly hinders the maximizing of electrochemical performances. Herein, covalent organic framework (COF) has been employed to anchor the quantificational Fe ions (COF-Fe) and then confined into the macropores of g-C3N4 to improve the dispersion of metal active sites and avoid severe aggregation during high temperature pyrolysis. After calcination, the metal nanoparticles highly dispersed Fe-CFN catalysts can be obtained. The optimal Fe-CFN-800 catalysts exhibit excellent ORR and OER performances with the potential difference between ORR and OER of merely 0.723 V. Moreover, experimental way and DFT theoretical calculations are also employed to disclose the reaction mechanism. Finally, the all-solid-state and aqueous Zn-air batteries assembled with the optimized Fe-CFN-800 as cathode present excellent performances with high peak power density, flexible rate performance, strong discharge stability and long-term charge-discharge cycling performance.

Mulberry leaves attenuate D-galactose-induced aging in vivo and in vitro.

ETHNOPHARMACOLOGICAL RELEVANCE: Mulberry leaves contain many bioactive compounds and have been widely used in traditional medicines and functional foods for prevention and treatment of age-related diseases, such as diabetes, cognitive impairment and obesity-mediated liver cancer. Aging has an irreversible negative impact on human health for many years, even decades, before death, which is a social and economic burden on society. AIM OF THE STUDY: The objective of this study was to investigate the antioxidant and anti-aging effects of mulberry leaf extract (MLE) in vivo and in vitro. MATERIALS AND METHODS: The Caenorhabditis elegans (C. elegans) was used as a model organism to observe the effects of different concentrations of MLE (1, 2, 4, 8 mg/mL) on nematodes' healthy lifespan, reproductive capacity, locomotion, stress resistance, and antioxidation. In addition, D-galactose (D-gal) induced liver aging in mice and L-02 cells were established. The antioxidant and anti-aging effects of MLE were evaluated by body weight, organ indexes, malondialdehyde (MDA), total superoxide dismutase (T-SOD), total antioxidant capacity (T-AOC), aspartate and alanine aminotransferases (AST and ALT), reactive oxygen species (ROS), mitochondrial membrane potential (MMP), hematoxylin and eosin (H&E), senescence-associated ß-galactosidase (SA-ß-Gal). Besides, the expressions of AMPK/SIRT1/PGC-1α and Nrf2-Keap1 were detected by Western blotting. RESULTS: MLE could significantly prolonged nematodes' average life span and improved most physiological indicators related to aging of C. elegans. Moreover, Treatment with MLE ameliorated the decreased body weight and organ index (weight of organ/body weight) in model mice, and protected against oxidative stress in mice and liver cells, in a dose-dependent manner, up-regulating T-SOD and T-AOC, while reducing ROS and MDA levels. MLE decreased both liver and cell levels of AST and ALT, and enhanced the mitochondrial membrane potential. MLE activated the AMPK/SIRT1/PGC-1α pathways, participated in mitochondrial biosynthesis and oxidative metabolism and delayed D-gal-induced aging. MLE promoted the accumulation of Nrf2 in the nucleus, indicating that the improved oxidative stress response was mediated by the Nrf2-Keap1 pathway in vivo and in vitro. CONCLUSION: MLE appeared to have great potential for stimulating the oxidative stress response and attenuating the aging process of in vivo and in vitro, and provide a novel health-promoting resource against aging and aging-related diseases.

Synthesis of Cyclopenta[b]indoles via Sc(III)-Catalyzed Annulation of Vinyl Diazoacetates with Indole-Derived Unsaturated Imines.

A Lewis acid Sc(OTf)3-catalyzed annulation reaction of vinyl diazoacetates with in situ formed α,ß-unsaturated imines for the preparation of indole-fused tricyclic rings has been reported. This strategy involves a sequential addition/rebound addition process of vinyl diazoacetates and an in situ dedinitrogenation. This annulation protocol features low-cost catalysts, mild reaction conditions, and facilely prepared substrates.

Genome-wide DNA methylation analysis in families with multiple individuals diagnosed with schizophrenia and intellectual disability.

OBJECTIVES: Schizophrenia (SZ) and intellectual disability (ID) are both included in the continuum of neurodevelopmental disorders (NDDs). DNA methylation is known to be important in the occurrence of NDDs. The family study is conducive to eliminate the effects of relative epigenetic backgrounds, and to screen for differentially methylated positions (DMPs) and regions (DMRs) that are truly associated with NDDs. METHODS: Four monozygotic twin families were recruited, and both twin individuals suffered from NDDs (either SZ, ID, or SZ plus ID). Genome-wide methylation analysis was performed in all samples and each family. DMPs and DMRs between NDD patients and unaffected individuals were identified. Functional and pathway enrichment analyses were performed on the annotated genes. RESULTS: Two significant DMPs annotated to CYP2E1 were found in all samples. In Family One, 1476 DMPs mapped to 880 genes, and 162 DMRs overlapping with 153 unique genes were recognised. Our results suggested that the altered methylation levels of FYN, STAT3, RAC1, and NR4A2 were associated with the development of SZ and ID. Neurodevelopment and the immune system may participate in the occurrence of SZ and ID. CONCLUSIONS: Our findings suggested that DNA methylation participated in the development of NDDs by affecting neurodevelopment and the immune system.

Posttraumatic stress disorder and professional burnout among local government staff seven years after the Wenchuan earthquake in China: A longitudinal study.

Although local government staff are crucial in post-quake reconstruction, their long-term psychological and professional consequences remain unclear. This longitudinal study investigated changes of posttraumatic stress disorder (PTSD) and professional burnout over seven years, and their underlying relationship. The study assessed 250 staff at one year (T1y) after the earthquake, and 162 (64.8 %) were followed up at seven years (T7y). PTSD and professional burnout were assessed with the Short Screening Scale for DSM-IV PTSD and the burnout subscale of Professional Quality of Life Scale (ProQOL), respectively, at both time points. Longitudinal changes in PTSD and burnout were examined and cross-lagged panel analyses were conducted to test the relationship between PTSD and burnout. The rates of positive cases of PTSD screening were 23.2 % at T1y and 11.1 % at T7y. The percentages of moderate burnout were 61.7 % at T1y and 23.5 % at T7y. Scores of PTSD (z = -5.70, p < 0.001) and burnout (t = 10.07, p < 0.001) from T1y to T7y decreased. The cross-lagged analysis indicated that burnout at T1y predicted PTSD at T7y (ß = 0.19, p = 0.025). In conclusion, the Wenchuan earthquake has long-lasting negative effects on local government staff, although they can recover over time. Interventions to reduce professional burnout after disaster may does be beneficial to decrease the risk of PTSD in the long run.

Rare double spin canting antiferromagnetic behaviours in a [Co24] cluster.

A fish-basket-shaped [Co24] cluster, [Co24(µ3-O)4(ampc)4(µ3-OH)4(µ2-OH)4(NO3)5(HCO2)22(H2O)10]·[(HCO2)·2(CH3OH)·x(H2O)], was woven by bridging oxygen atoms from O(2-), OH(-), NO3(-) and HCO2(-) groups, and stabilized terminally by a semi-rigid organic ligand 4',4'-[(dimethylamino)dimethylene]-bis[(1,1'-biphenyl)-2-carboxylate] (ampc(-)). Magnetic analyses indicate that the [Co24] cluster exhibits two types of spin canting orders, spin flop and a small hysteresis with a coercive field of ca. 661 Oe and a remanent magnetization of 0.466 Nß.

Aggregation of the metallocycles {Cu8} and {Cu20} using [Cu(bp)] units (H2bp = bis(2-hydroxybenzyl)amine): structures and magnetic properties.

Two metallocycles, {Cu8(bp)4(OH)4(H2O)4(ClO4)4} (1) and {Cu20(bp)20} (2), were afforded by the reactions of the semi-flexible tridentate ligand bis(2-hydroxybenzyl)amine (H2bp) with Cu(ClO4)2·6H2O and Cu(OAc)2·H2O. Complex 1 has a saddle-shaped cyclic structure and complex 2 has a nanosized wheel-shaped structure. The two compounds consist of [Cu(bp)] units.

Counter-anion role in the formation of two supramolecular complexes: [Ag2(DPP)2](ClO4)2·CH3CN and [Ag2(DPP)2(NO3)2] {DPP is N-[(diphenylphosphanyl)methyl]pyridin-4-amine}.

The title compounds, bis{µ-N-[(diphenylphosphanyl)methyl]pyridin-4-amine-κ(2)N(1):P}disilver bis(perchlorate) acetonitrile monosolvate, [Ag2(C18H17N2P)2](ClO4)2·CH3CN, (1), and bis{µ-N-[(diphenylphosphanyl)methyl]pyridin-4-amine-κ(2)N(1):P}bis[(nitrato-κ(2)O,O)silver], [Ag2(C18H17N2P)2(NO3)2], (2), each contain disilver macrocyclic [Ag2(C18H17N2P)2](2+) cations lying about inversion centres. The cations are constructed by two N-[(diphenylphosphanyl)methyl]pyridin-4-amine (DPP) ligands linking two Ag(+) cations in a head-to-tail fashion. In (1), the unique Ag(+) cation has a near-linear coordination geometry consisting of one pyridine N atom and one P atom from two different DPP ligands. Two ClO4(-) anions doubly bridge two metallomacrocycles through Ag···O and N-H···O weak interactions to form a chain extending in the c direction. The half-occupancy acetonitrile molecule lies with its methyl C atom on a twofold axis and makes a weak N···Ag contact. In (2), there are two independent [Ag(C18H17N2P)](+) cations. The nitrate anions weakly chelate to each Ag(+) cation, leading to each Ag(+) cation having a distorted tetrahedral coordination geometry consisting of one pyridine N atom and one P atom from two different DPP ligands, and two chelating nitrate O atoms. Each dinuclear [Ag2(C18H17N2P)2(NO3)2] molecule acts as a four-node to bridge four adjacent equivalent molecules through N-H···O interactions, forming a two-dimensional sheet parallel to the bc plane. Each sheet contains dinuclear molecules involving just Ag1 or Ag2 and these two types of sheet are stacked in an alternating fashion. The sheets containing Ag1 all lie near x = 1/2, 3/2, 5/2 etc, while those containing Ag2 all lie near x = 0, 1, 2 etc. Thus, the two independent sheets are arranged in an alternating sequence at x = 0, 1/2, 1, 3/2 etc. These two different supramolecular structures result from the different geometric conformations of the templating anions which direct the self-assembly of the cations and anions.

Efficacy of olanzapine monotherapy for treatment of bipolar I depression: a randomized, double-blind, placebo controlled study.

RATIONALE AND OBJECTIVE: Depression symptoms are now recognized to be the predominant cause of disability for bipolar disorder (BD) patients. The treatment strategies for the depressed phase of BD remain more anecdotal than data-based. Olanzapine has been investigated as an alternative to antidepressants and a mood stabilizer for acute bipolar depression. The purpose of this study was to assess the efficacy of olanzapine monotherapy for bipolar I depression. METHOD: Sixty-eight patients with bipolar I depression were randomly assigned to treatment with olanzapine (mean final dose 14.4 mg/day) (n=34) or placebo (n=34) in a double-blind parallel-group study design. Planned assessments included Montgomery-Asberg Depression Rating Scale (MADRS), Young Mania Rating Scale (YMRS), Clinical Global Impressions-Severity of Illness scale (CGI-S), Clinical Global Impressions-Improvement scale (CGI-I), Hamilton Depression scale (HAMD), Hamilton Anxiety scale (HAMA), and Treatment Emergent Symptom Scale (TESS). RESULTS: Of the 68 patients who were randomly assigned, 57 (83.8 %) completed treatments. Improvements in MADRS total score, CGI-S, CGI-I, and HAMD in the olanzapine group were significantly greater relative to those in the placebo group during the 8-week follow-up period (p<0.001, p=0.0017, p=0.007, and p<0.001, respectively). Rates of categorical treatment response and remission in the olanzapine group (50.0 % and 35.3 %, respectively) were significantly higher than those in the placebo group (20.6 %, p=0.011 and 11.8 %, p=0.022, respectively). At the 8-week treatment, the mean weight and the total cholesterol, triglyceride, and low-density lipoprotein cholesterol levels increased significantly in the olanzapine group (p=0.037, p=0.029, p=0.030, and p=0.028, respectively). CONCLUSIONS: Olanzapine is effective in the treatment of bipolar I depression but is associated with significant metabolic side effects.

Metformin for treatment of antipsychotic-induced weight gain: a randomized, placebo-controlled study.

OBJECTIVES: To evaluate the efficacy of metformin for treatment of antipsychotic-induced weight gain. METHODS: Seventy-two patients with first-episode schizophrenia who gained more than 7% of their predrug weight were randomly assigned to receive 1000 mg/d of metformin or placebo in addition to their ongoing treatment for 12 weeks using a double-blind study design. The primary outcome was change in body weight. The secondary outcomes included changes in body mass index, fasting glucose and insulin, and insulin resistance index. RESULTS: Of the 72 patients who were randomly assigned, 66 (91.6%) completed treatments. The body weight, body mass index, fasting insulin and insulin resistance index decreased significantly in the metformin group, but increased in the placebo group during the 12-week follow-up period. Significantly more patients in the metformin group lost their baseline weight by more than 7%, which was the cutoff for clinically meaningful weight loss. Metformin was tolerated well by majority patients. CONCLUSION: Metformin was effective and safe in attenuating antipsychotic-induced weight gain and insulin resistance in first-episode schizophrenia patients. Patients displayed good adherence to metformin.