Synthesis, characterization of bridged bis(amidinate) lanthanide amides and their application as catalysts for addition of amines to nitriles for monosubstituted N-arylamidines

A series of lanthanide amide complexes supported by bridged bis(amidinate) ligand L, LLnNHAr(1)(DME) (L = [Me(3)SiNC(Ph)N(CH(2))(3)NC(Ph)NSiMe(3)], Ar(1) = 2,6-(i)Pr(2)C(6)H(3), DME = dimethoxyethane, Ln = Y (1), Pr (2), Nd (3), Gd (4), Yb (5)), [Yb(μ(2)-NHPh)](2)(μ(2)-L)(2) (6) and [LYb](2)(μ(2)-NHAr(2))(2) (7) (Ar(2) = (o-OMe)C(6)H(4)), were synthesized by reaction of LLnCl(THF)(2) with the corresponding lithium amide in good yields and structurally characterized by X-ray crystal structure analyses. All complexes were found to be precatalysts for the catalytic addition of aromatic amines to aromatic nitriles to give monosubstituted N-arylamidines. The catalytic activity was influenced by lanthanide metals and the amido groups with the active sequence of Y (1) < Gd (4) < Nd (3) < Pr (2) ～ Yb (5) for the lanthanide metals and -NHAr(2) < -NHPh < -NHAr(1) for the amido groups. The catalytic addition reaction with complex 5 showed a good scope of aromatic amines. Some key reaction intermediates were isolated and structurally characterized, including the amidinate complexes LLn[NPhCNAr(1)](PhCN) (Ln = Y (8), Ln = Yb (9)), LYb[NAr(2)CNAr(1)](Ar(2)CN) (10), and amide complex 5 prepared by protonation of 9 by Ar(1)NH(2). Reactivity studies of these complexes suggest that the present catalytic formation of monosubstituted N-arylamidines proceeds through nucleophilic addition of an amido species to a nitrile, followed by amine protonolysis of the resultant amidinate species.     

New Benzofuranylpropanoids from the Roots of Codonopsis lanceolata

Three new benzofuranylpropanoids, lanceolunes A–C ( 1 – 3 ), were isolated from the roots of Codonopsis lanceolata. Their structures were determined by means of HR‐ESI‐MS, extensive 1D‐ and 2D‐NMR spectroscopic, and chemical evidence.     

A visual representation for RNA secondary structure and its application

The graphical representation of biological sequences is an important subject in the area of genome studies. We propose a novel visual representation for RNA secondary structures. Some symmetric properties and information on the base distribution and compositions can be intuitively reflected by the projection graphs of the points corresponding to the RNA secondary structures. Then our method is applied to compute the similarity of 12 classical samples and 11 real RNA secondary structures. The results indicate that our method can not only effectively analyze the similarity between RNA secondary structures but also show a high consistency with other literatures. Moreover, our method only needs the geometrical center of the characteristic curve of the RNA secondary structure to compute the similarity matrix, which means a low computational complexity. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Synthesis of Fe3O4@SiO2-Ag magnetic nanocomposite based on small-sized and highly dispersed silver nanoparticles for catalytic reduction of 4-nitrophenol

We demonstrate a single-step facile approach for the synthesis of glycine (amino acid) passivated Fe(3)O(4) magnetic nanoparticles (GMNPs) using soft chemical route. The surface passivation of Fe(3)O(4) nanoparticles with glycine molecules was evident from infrared spectroscopy, thermal and elemental analyses, and light scattering measurements. These nanoparticles show better colloidal stability, good magnetization, excellent self-heating capacity under external AC magnetic field and cytocompatibility with cell lines. Further, the active functional groups (-NH(2)) present on the surface of Fe(3)O(4) nanoparticles can be accessible for routine conjugation of biomolecules/biolabelling through well-developed bioconjugation chemistry. Specifically, a new colloidal glycine passivated biocompatible Fe(3)O(4) nanoparticles with excellent specific absorption rate (SAR) have been fabricated, which can be used as an effective heating source for hyperthermia treatment of cancer (thermal therapy).     

An efficient and facile synthesis of inhibitors for hepatitis C viral and anti-SARS agents: 4-aryl-5-cyano-1,6-dihydro-2-thiouracils

One-pot, multicomponent reaction for the synthesis of 4-aryl-5-cyano-1,6-dihydro-2-thiouracils via three-component from aromatic aldehydes, ethyl 2-cyanoacetate and S-benzylisothiourea hydrochloride (methyl carbamimidothioate sulfate) under methanol is described. These compounds have many drug activities, such as anti-hepatitis C viral, anti-Severe acute respiratory syndrome and anti-HIV-1 integrese activity. The advantages of this procedure include the short reaction time, mild reaction conditions and excellent yields.     

Thermal transformation of δ-MnO2 nanoflowers studied by in-situ TEM

In-situ transmission electron microscopy in combination with a heating stage has been employed to real-time monitor variations of -phase MnO2 nanoflowers in terms of their morphology and crystalline structures upon thermal annealing at elevated temperatures up to ~665℃. High-temperature annealing drives the diffusion of the small δ-MnO2 nanocrystallites within short distances less than 15 nm and the fusion of the adjacent δ-MnO2 nanocrystallites, leading to the formation of larger crystalline domains including highly crystalline nanorods. The annealed nanoflowers remain their overall flower-like morphology while they are converted to δ-MnO2 . The preferred transformation of the δ-MnO2 to the δ-MnO2 can be ascribed to the close lattice spacing of most crystalline lattices between δ-MnO2 and δ-MnO2 , that might lead to a possible epitaxial growth of δ-MnO2 lattices on the δ-MnO2 lattices during the thermal annealing process.     

A magnetic copper(II)-imprinted polymer for the selective enrichment of trace copper(II) ions in environmental water

We have developed a convenient, selective and reliable method for the rapid enrichment of trace quantities of Cu(II) by using a magnetic Cu(II) ion-imprinted polymer. This is followed by their determination by FAAS. The imprints were prepared by using (a) Cu(II) ions as the template, (b) 3-aminopropyltriethoxysilane as both the functional monomer and the crosslinking agent, and (c) Fe₃O₄ as the magnetic component. Enrichment is carried out in a single step, and adsorbed copper ions can be separated from the sample solution by applying a strong magnet. The effects of pH, elution condition, amount of imprint, and of potentially interfering ions were evaluated. Under the optimal conditions, the detection limit and enrichment factor are 0.3?μg L^?1 and 100, respectively, and the recovery is >95?%. The procedure was successfully applied in the enrichment and detection of trace copper ions in environmental water.

ZnNe低激发态的量子化学研究

用相对论赝势ＣＡＳＳＣＦ／ＣＩ方法,对ＺｎＮｅ的基态和低激发态进行了计算,得出了它们的电子结构,势能曲线及光谱常数。计算结果表明,ＺｎＮｅ的基态分子是范德华分子,它的几个低激发态分子中的主要作用力为范德华力,这些态的分子仍为范德华分子。     

A novel water-rich mononuclear copper(II) complex with pyridine-2,4-dicarboxylate: Synthesis and crystal structure

A new monomolecular copper(II) complex, [Cu(Phen)₂(Pda)] · 9H₂O (I) (H₂Pda = pyridine-2,4-dicarboxylate acid, Phen = 1,10-phenanthroline), has been prepared from H₂Pda and Phen at room temperature and characterized by IR, elemental analysis, X-ray powder diffraction, and single-crystal X-ray diffraction. Structure analysis shows that each Cu(II) is coordinated by two Phen ligands and one Pda ligand to complete a octahedron CuN₅O chromophore. In addition, a unique water networks paralleling to (001) composed by the crystallization water through hydrogen bonds play a important role in the stability of crystal structure. The crystal structure is found to be orthorombic with space group Pbcn and cell parameters a = 13.651(4), b = 22.516(7), c = 22.386(7) Å, R ₁ = 0.0735 and wR ₂ = 0. 0.1935.     

Microwave‐Assisted Aqueous Synthesis: A Rapid Approach to Poly‐functionalized Indoline‐Spiro Benzofurodiazepines

New cycloaddition has been established for the synthesis of indoline‐spiro benzofurodiazepine derivatives. Those reactions were conducted by reacting readily available and inexpensive starting materials, such as benzene‐1,2‐diamines, tetronic acid and indoline‐2,3‐diones, in aqueous solution under microwave irradiation. When mono‐substituted benzene‐1,2‐diamines as an amine component was employed, the reaction regioselectively resulted in the poly‐functionalized indoline‐spiro benzofurodiazepine with good yields. The present green synthesis shows attractive characteristics such as the use of water as reaction media, concise one‐pot conditions, short reaction periods, easy work‐up/purification and reduced waste production without the use of any strong acids or metal promoters.