Synthesis,structure and catalytic behavior of yttrium complexes bearing a diaminobis（phenolate） ligand

Yttrium complexes stabilized by a diaminobis（phenolate） ligand were synthesized and their catalytic behavior was explored. Reaction of YCI3 with 1 equiv of LNa2 [L= Me2NCH2CH2N{CH2-（2-O-C6H2-^1Bu2-3,5）}2] gave the yttrium chloride LYCI（THF） （1） in 92% yield. Complex I can be used as starting material to prepare the yttrium amido derivative. Complex 1 reacted with 1 equiv of LiNPh2 in THF to afford the expected yttrium amido complex LYNPh2 （2） in high yield. Both of complexes 1 and 2 have been well detected by elemental analysis, NMR spectra and single-crystal X-ray analysis. It was found that complex 2 can efficiently initiate the ring-opening polymerization of L-lactide and ε-caprolactone, and a controlled manner is observed in the former case.     

Synthesis and characterization of a three-ring bent-core compound

To investigate the vacuum-deposited films of the banana-shaped mesogens, we prepared a three-ring bent-core （that is, banana-shaped） compound m-bis（4-p-octoxysryrenyl）benzene （m-OSB） and used it as a prototype for studying the related film physics. Herein the synthesis and the structural characterization of m-OSB are reported.^13C and ^1H NMR spectra and ^1R spectrum confirm that m-OSB has a symmetric and all-trans conformation. The results of differential scanning calorimetry, polarizing optical microscopy and X-ray diffractometry indicate that no liquid crystalline phase but two crystalline phases are present in this material： phase Ⅰ （T〈66℃） and phase Ⅱ （66~C〈T〈157℃）; an isotropic state is observed at above 157℃. Combining the X-ray diffraction and the electronic diffraction, we assign the room-temperature crystalline phase I to orthorhombie system and P212121 space group with cell parameters of a = 7.43A°. b=6.34A°, c=72.07A°, and α=β=γ=90°. Molecular modeling reveals that the molecules in the unit cell adopt a layered structure with an antiferro-eleetrie alignment. The structure of phase Ⅱ is very similar to that of phase Ⅰ. Nonlinear optical measurement shows that m-OSB is active for the second harmonic generation （SHG）. Such characterization of the bulk material is necessary for the understanding of the growth and microstructures in the films.     

Development of Several New Reactions and Their Application to the Total Synthesis of Biologically Active Natural Products :Synthesis of Linderol A and Determination of Its Absolute Configuration

1Introduction Linderol A (1), a monoterpene-polyketide, was isolated in 1995 from the fresh bark of Lindera umbellata (Lauraceae), and its absolute structure was not determined[1]. It was also reported potent inhibitory activity of 1 on the melanin biosynthesis of the cultured B-16 melanoma cells[1]. See Fig. 1. On the other hand,we reported in 1995 an interesting multi-tandem reaction of coumarin derivatives (2; W = electron withdrawing group) by treatment with CH2 = S(O)Me2 to yield stereoselectively a tricyclic 2-substituted cyclopenta [ b ] benzofuran-3-ol derivative (4) via a cyclopropane intermediate (3) (Scheme 1)[2].     

Triphosgene as an Efficient and Electrophilic Reagent for the One-pot Synthesis of Sulfonylsemicarbazids

1 Results Sulfonylsemicarbazide derivatives are important compounds as blowing agents in cellular rubber and plastics[1]. Different methods for the preparation of these compounds are reported. For example, sulfonylsemicarbazides are prepared by reaction of sulfinic acid salt with azodicarbonamide in water[2] and reaction of sulfonylchloride with semicarbazide[3-4]. In these methods the yields of products are not high[3-4], the solvent such as pyridine is toxic and also the sulfinic acid salt as starting material is not commercially available[2]. Recently, triphosgene [bis(trichloromethyl)carbonate], a crystalline solid which can be easily handled, was reported as a safe stable reagent[5]. It was successfully utilized to the synthesis of large variety of organic compounds[6].     

Synthesis of Novel Low-band-Gap Thiophene-based Oligomers and Copolymers

1 Results In this contribution,the synthesis and characterization of low-band-gap oligothiophenes and copolymers based on fluorene and thiophene units are reported.First,5,5′-dibromo derivative of 1 was synthesised and used as a building block for synthesis of quinquethiophene and septithiophene analogues of 1 and the synthesis of a novel low band-gap polymer - soluble alternating copolymer 3,which was prepared by the Suzuki coupling of 5,5′-dibromo derivative of 1 with bis(propane-1,3-diyl) 9,9-bis(2-ethylhexyl)fluorene-2,7-bisboronate.Further,two soluble random copolymers 4 of 3-(3-methylbutyl)thiophene with 3-[2-(pyren-1-yl)vinyl]thiophene were prepared by Grignard metathesis copolymerization of corresponding dibromo monomers.See Fig.1.     

Unexpected carbon-oxygen bond cleavage of THF promoted by guanidinate titanium complex/lithium diisopropylamide： Synthesis and crystal structure

An unexpected carbon-oxygen bond cleavage of THF （THF = tetrahydrofuran） promoted by guanidinate titanium complex was described. Guanidinate lithium [Pr2 ^1NC（NCy）2]Li （Cy = cyclohexyl） formed in situ reacted with TiCl4（THF）2 in a 2：1 molar ratio to produce the guanidinate titanium chloride [Pr2 ^1NC（NCy）2]2TiCl2 （1） in good yield. The reaction of [Pr2 ^1NC（NCy）2]2TiCl2 with lithium diisopropylamide in THF afforded an unexpected [Pr2 ^1NC（NCy）2]2Ti（OBu^n）2 （2）, which was formed by the cleavage of carbon-oxygen bond of THF. Complexes 1 and 2 were fully characterized by elemental analysis, NMR and IR spectroscopies, and X-ray crystal structure determination for complex 2.     

Synthesis and Structure Determination of Mixed-ligand Cobalt Complex with Dibutylphosp- horic acid and Pyridine

Dialkylphosphoric or dialkyphosphonic acids are important extractants for separa-tion of cobalt and nickel.The extraction mechanism and the composition of the ext-racted species have been studies by several authors(1-3).But so far no X-ray struc-tural determination of these extracted complexes has been reported in the literature. In the present investigation,a new mixed ligand dinuclear cobalt complex withdibutylphosphoric acid and pyridine was prepared.The results of elemental analysisshow that the compound may be represented by Co(DBP)_2·3Py·CHCl_3.The magneticmoment of this comples was determined to be 4.79 Bohr magnetons, correponding tothree unpaired electrons per each cobalt atom.     

Applications of Transition Metals in Organic Synthesis and Polymerization

1 Results Classic oxidants require rigorous control of the experimental conditions added with the problem of lack of selectivity. Catalysis by transition metals with environmentally safe oxidants provides synthetic routes to minimize pollution by giving environmental benign by-products. Fe (Ⅵ) is a powerful and a selective oxidant with Fe(Ⅲ) as a by-product, while hydrogen peroxide is clean with water as the only by-product. Separation of sodium or potassium ferrates requires tedious processes. Association of a ferric salt with a clay support had been reported previously also[1-2],which prompted us to find out a way in which sodium ferrate could be used in solution itself. Presence of copper nano-particles adsorbed on solid support, accelerate the process. Present study[3] describes the oxidation of organic substrates with in-situ prepared Fe(Ⅵ)in combination of montmorillonite K10 and metallic copper nano-particles without following the tedious and lengthy process of separation of Fe(Ⅵ). Apart from it the catalytic activities of three transition metals palladium(Ⅱ), iridium(Ⅲ) and rhodium(Ⅲ) in solution phase and under solvent less conditions were studied in the oxidation of various organic compounds by hydrogen peroxide[4] and cerium(Ⅳ) sulphate. In the oxidation by hydrogen peroxide (with substrate: catalyst ratio 1∶62 500 to 1∶1 961) palladium(Ⅱ) was found to be the most efficient catalyst, while iridium(Ⅲ) (catalyst: substrate ratio 1∶57 to 151) was so much efficient with cerium(Ⅳ) that it oxidizes even cyclohexane and benzene giving rise to 44% and 51.8% yields of carbonyl compounds.     

Synthesis and Properties of Novel Copolymers Based on Fluorene and Thiophene

1 Results In this contribution we present the synthesis and characterization of novel copolymers based on fluorene and thiophene (see Scheme 1).They were synthesized by the Pd-catalyzed Suzuki coupling reaction of 9,9-dihexylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester and 3-substituted (R=3-methylbutyl,hexyl,2-(pyren-1-yl)vinyl) 2,5-dibromothiophenes and characterized by GPC,IR and NMR techniques.UV-vis absorption,photoluminescence (PL) and electrochemical behavior of these polymers were also studied.Though a similar absorption was observed in solutions and thin films of the polymers,the maximum at 400 nm for FIPT and F3HT and at 390 nm FPyT,PL of FPyT thin film differs from those of FIPT and F3HT thin films.They exhibited an intense green PL emission,whereas PL emission of FPyT thin film was orange with a red-shifted maximum compared with FIPT and F3HT indicating pronounced aggregation of FPyT in the solid state.Cyclic voltammetry showed that all the polymers are reversibly oxidized and reduced.A similar electrochemical behavior was observed for FIPT and F3HT whereas a higher electron affinity was estimated for FPyT.     

Synthesis and formation mechanism of micro/nano flower-like MgCO3·5H2O

Micro/nano magnesium carbonate pentahydrate（MgCO3 ·5H2 O） with flower-like morphology was synthesized using magnesite as a substrate and potassium dihydrogen phosphate as an additive. The synthesized samples were characterized by scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetry and differential scanning calorimetry. The influence of pyrolysis time on crystal morphology was explored. The formation mechanism was investigated on the basis of the characterized results and the crystal structure of MgCO3 ·5H2 O. The results showed that the flower-like MgCO3 ·5H2 O was 1.5-3.0 μm in length and 100-500 nm in diameter and was successfully obtained with a pyrolysis time of 30 min. The formation mechanism of flower-like MgCO3 ·5H2 O is suggested to be the selective adsorption of potassium dihydrogen phosphate on the surface. The process of flower-like crystal growth is as follows： amorphous nanoparticles formation, acicular and rod monocrystal formation, flower-like monocrystal formation, and flower-like polymers（MgCO3 ·5H2 O） crystallization. In the MgCO3 ·5H2 O crystal, the magnesium ion presents two different octahedral coordinations corresponding to2 26 Mg（H O）＋and2 2 2 4 23 [Mg（H O）（CO） ]--, and the chemical formula of the crystal is2 2 6 2 4 23 Mg（H O） Mg（H O）（CO）2.     

Synthesis and characterization of carbon-coated cobalt ferrite nanoparticles

Cobalt ferrite nanoparticles (CFNPs) were prepared via a reverse micelle method. The CFNPs were subsequently coated with carbon shells by means of thermal chemical vapor deposition (TCVD). In this process, acetylene gas (C₂H₂) was used as a carbon source and the coating was carried out for 1, 2, or 3 h at 750°C. The Ar/C₂H₂ ratio was 10:1. Heating during the TCVD process resulted in a NP core size that approached 30 nm; the thickness of the shell was less than 10 nm. The composition, structure, and morphology of the fabricated composites were characterized using X-ray diffraction, simultaneous thermal analysis, transmission electron microscopy, high-resolution transmission electron microscopy, and selected-area diffraction. A vibrating sample magnetometer was used to survey the samples’ magnetic properties. The deposited carbon shell substantially affected the growth and magnetic properties of the CFNPs. Micro-Raman spectroscopy was used to study the carbon coating and revealed that the deposited carbon comprised graphite, multiwalled carbon nanotubes, and diamond- like carbon. With an increase in coating time, the intensity ratio between the amorphous and ordered peaks in the Raman spectra decreased, which indicated an increase in crystallite size.     

Synthesis and characterization of Au@Pt nanoparticles

Aucore-Ptshell （Au@Pt） nanoparticles were synthesized at room temperature by reducing K2PtCl6 with hydrogen in the solution containing Au colloids and polyvinylpyrrolidone （PVP）. The particles obtained were characterized with UV-Vis, TEM and XPS techniques. UV-Vis spectra show that the surface plasmon absorption feature of Au colloids is significantly reduced with increasing the amount of reduced Pt. TEM images that the metals are found always appear as spherical nanoparticles and their sizes grow apparently due to the reduction of PtCl6^2- ions, indicating that Pt is deposited from solution onto Au particle surface and forms a Pt-layer with uniform thickness. In the XPS spectra, the signals of Au metal decrease due to the reductive deposition of Pt on the surface of the Au colloids. UV-Vis and XPS data are consistent in showing that when the amount of Pt in the AuPt colloids is increased to reach an overall atomic ratio of Pt/Au=2, the Pt deposits form a shell covering completely the surface of Au particles, demonstrating the core-shell structure of the synthesized AuPt particles.     

Structural diversity and reactivity of d^10 metal- （4-pyridylthio）acetate system

The hydrothermal synthesis and crystal structures of four coordination polymers, namely, 2D [Zn（μ3-ta）（pytaH）]n （1）, 2D [Zn（μ3-pyta）Cl]n （2）, 1D [Cd（μ-pyta）2（H2O）]n （3）, and 3D [Cd（μ3-pyta）（μ-Cl）]n （4） （pyta = （4-pyridylthio）acetate, ta = thioglycolate）, are reported. They are based on （4-pyridylthio）acetate and its derived ligand. The ta^2- ligand present in 1 was generated from an in situ C（sp^2）-S bond cleavage of the pyta ligand. In these compounds, versatile intermolecular interactions, such as close S…S interactions and strong （O-H…O/N/S） or weak （C-H…O/S, C-H…Cl） hydrogen bonding interactions, play an important role in the formation of three-dimensional supramolecular networks in the solid state.     

Preparation of New Chiral Ferroceny Phosphine Ligands and Their Application to Organic Synthesis

1 Results The unique structure of chiral ferrocenes allows one to design a variety of chiral phosphine ligands,which are useful tools for metal catalyzed asymmetric reactions.Although some useful chiral ferrocenyl phosphine ligands have already been reported,it is still an challenging subject tocreate new ferrocenyl phosphine ligands in order to cover asymmetric reactions in which conventional ligands do not effectively work[1].We happned to discover that 1,5-dilithiation of o-TMS blocked ferrocene 1 proceeded unexpectedly to give the 1,5-dilithiated ferrocene 2 which was isolated as 1,5-diiodide 3 by trapping with iodine and subsequent removal of TMS group. The 1,5-diiodide 3 was converted into Taniaphos 4 by sequence of re-dilithiation and trapping with Ph2PCl[2].     

Label-free selective sensing of Pb2＋ lead（II） sensors based on the aggregation of a pyrene fluorescent probe

In the present work, we report a label-free fluo- rescence turn-on approach for the sensitive and selective sensing of Pb2＋. Pyrene with one positive charge was used as the fluorescent probe, and thrombin aptamer （TBA）, which was a G-rich oligonucleotide, was employed to form G-quadruplex with lead（II）. When TBA and Pb2＋ were mixed with lead（II） in an aqueous solution, it was folded into a stable G-quadruplex. Subsequently, a single-stranded nucleic acid-specific nuclease S1 was added. The G-quad- ruplex stabilized by Pb2＋ lead（II） had markedly a significant resistant ability to nuclease S1 digestion. However, in the absence of Pb2＋ lead（II）, no quadruplex or less stable quadruplex was formed and TBA was digested by nuclease S1 in 3 min under the optimized experimental conditions. Finally, pyrene probe was Pb2＋ lead（II）. Electrostatic mixed with oligonucleotide in interactions between oligonu- cleotide （a polyanion） and the probe induced the aggregation of the probe, which in turn produced strong emission of the strong pyrene excimer emission. The intensity of the induced excimer emission was directly proportional to the amount of Pb2＋ added. Our approach shows good selectivity and sen- sitivity for the detection of Pb2＋ with a limit of detection limit as low as 800 nmol/L.     

Synthesis and Application of a Polymeric Crosslinking Agent for Improving Fixation of Vinylsulfone-type Dyes on Cotton by a Pad-drycure Process

A new class of novel polymeric crosslinging agent （NPCA）, which contained silane coupling group and the epoxy groups, was designed and synthesized in our laboratory. NPCA was a non-formaldehyde multifunctional crosslinking polymer. The cotton fabrics dyed with 8.0% （owf） Vinylsulpone-type dyes were treated with 3.0%- 4.0% NPCA, 0.5 mol/L potassium thiocyanate as a catalyst, then padded through two dips and two nips to reach a wet pickup of 80%- 85%, then dried at 80℃ for 2 minutes and cured in oven at 140- 150℃ for 3 minutes. Crocking fastness and fixation （%） were improved with up to 1.0 -1. 5 units, 35%- 50%, respectively. And there was little difference between the color yield of dyed fabrics before and after the treatment at certain conditions. The possible crosslinking mechanism of NPCA was also investigated. It was concluded that NPCA can improve colorfastness of cotton fabric by means of the three-dimensional network, covalent bonding and other molecular forces.     

Stereoselective Total Synthesis of Mycalamides

Mycalamides A （1a） and B （1b） are potent antiviral compounds from a New Zealand sponge of the genus Mycale. Apart from their antitumor property, mycalamide A （1a） exhibits immunosuppressive action by blocking T-cell activation in mice and is significantly more potent than FK-506 and cyclosporine A. Because of their intriguing biological activity, unique structures and scarce supply of these natural products, mycalamides A （1a） and B （1b） have attracted considerable attention as target molecules for total synthesis, and total, formal, or partial syntheses of this family of compounds have been reported.     

Urban structure and the risk of influenza A （H1N1） outbreaks in municipal districts

Changsha was one of the most affected areas during the 2009 A （H 1N 1） influenza pandemic in China. Here, we analyze the spatial-temporal dynamics of the 2009 pan- demic across Changsha municipal districts, evaluate the relationship between case incidence and the local urban spatial structure and predict high-risk areas of influenza A （H1NI）. We obtained epidemiological data on all cases of influenza A （H1NI） reported across municipal districts in Changsha dur- ing period May 2009-December 2010 and data on population density and basic geographic characteristics for 239 primary schools, 97 middle schools, 347 universities, 96 mails and markets, 674 business districts and 121 hospitals. Spatial- temporal K functions, proximity models and logistic regres- sion were used to analyze the spatial distribution pattern of influenza A （H1N1） incidence and the association between influenza A （HINI） cases and spatial risk factors and predict the infection risks. We found that the 2009 influenza A （H 1N 1 ） was driven by a transmission wave from the center of the study area to surrounding areas and reported cases increased significantly after September 2009. We also found that the distribution of influenza A （H 1N1） cases was associ- ated with population density and the presence of nearest public places, especially universities （OR = 10.166）. The final pre- dictive risk map based on the multivariate logistic analysis showed high-risk areas concentrated in the center areas of the study area associated with high population density. Our find- ings support the identification of spatial risk factors and high- risk areas to guide the prioritization of preventive and miti- gation efforts against future influenza pandemics.     

Fabrication and characterization of nanocrystalline Al/Al12（Fe,V）3Si alloys by consolidation of mechanically alloyed powders

The aim of this study was to produce bulk nanocrystalline Al/Al12（Fe,V）3Si alloys by mechanical alloying （MA） and subsequent hot pressing （HP） of elemental powders. A nanostructured Al-based solid solution was formed by MA of elemental powders for 60 h. After HP of the as-milled powders at 550℃ for 20 min, the Al12（Fe,V）3Si phase was precipitated in a nanocrystalline Al matrix. Scanning electron microscopy （SEM） images of the bulk samples represented a homogeneous and uniform microstructure that was superior to those previously obtained by rapid solidification-powder metallurgy （RS-PM）. Nanostructured Al-8.5Fe-1.3V-1.7Si and Al-11.6Fe-1.3V-2.3Si alloys ex-hibited high HV hardness values of～205 and～254, respectively, which are significantly higher than those reported for the RS-PM counter-parts.     

Investigation of the kinetic mechanism of the demanganization reaction between carbon-saturated liquid iron and CaF_2–CaO–SiO_2-based slags

The demanganization reaction kinetics of carbon-saturated liquid iron with an eight-component slag consisting of CaO–SiO_2–MgO–FeO–MnO–Al_2O_3–TiO_2–CaF_2 was investigated at 1553, 1623, and 1673 K in this study. The rate-controlling step(RCS) for the demanganization reaction with regard to the hot metal pretreatment conditions was studied via kinetics analysis based on the fundamental equation of heterogeneous reaction kinetics. From the temperature dependence of the mass transfer coefficient of a transition-metal oxide(Mn O), the apparent activation energy of the demanganization reaction was estimated to be 189.46 k J·mol~(–1) in the current study, which indicated that the mass transfer of Mn O in the molten slag controlled the overall rate of the demanganization reaction. The calculated apparent activation energy was slightly lower than the values reported in the literature for mass transfer in a slag phase. This difference was attributed to an increase in the "specific reaction interface"(SRI) value, either as a result of turbulence at the reaction interface or a decrease of the absolute amount of slag phase during sampling, and to the addition of calcium fluoride to the slag.