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.

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 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.

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.

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.

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.