Bulk ultrafine binderless (W0.4Al0.6)C prepared by high pressure sintering

Pure (W0.4Al0.6)C powder of about 1 mu m in diameter was sintered by the high pressure sintering (HPS) process without the addition of any binder phase. The microstructure, Vickers micro hardness and density versus the sintering time and temperature are well described. The most suitable sintering condition under pressure of 4.5 GPa is 1873 K for 8 min. Under this sintering condition, the hardness can reach 2295 kg mm(-2) and the relative density can reach 98.6%.

SiO2 nanoparticles as scatterers for random organic laser action in red fluorescent dye 4-(dicyanomethylene)-2-tert-butyl-6(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran doped polystyrene films

Random multimode lasers are achieved in 4-(dicyanomethylene)-2-tert-butyl-6(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) doped polystyrene thin films by introducing silicon dioxide (SiO2) nanoparticles as scatterers. The devices emit a resonance multimode peak at a center wavelength of 640 nm with a mode linewidth less than 0.87 nm. The threshold excitation intensity is as low as 0.25 mJ pulse(-1) cm(-2). It can be seen that the microscopic random resonance cavities can be formed by multiple scattering of SiO2 nanoparticles.

A copper/p-sulfonatocalix[6]arene/phenanthroline supramolecular compound with 1D [Cu-2-calixarene](n) coordination chains

A supramolecular complex [Cu(phen)(2)H2O]{[Cu(phen)(H2O)](2)[C6AS]}center dot 2.5H(2)O (phen = 1,10'-phenanthroline and C6AS = p-sulfonatocalix[6]arene) has been synthesized under hydrothermal condition, and characterized by IR spectroscopy, TG analysis and single crystal X-ray diffraction. In the structure, unprecedented 1D ({[Cu(phen)(H2O)](2)[C(6)AS]}(2-))(n) coordination chains (exactly being belts) are stacked into some 2D layers by the pi center dot center dot center dot pi stacking interactions, which are further interconnected into a 3D extended structure by hydrogen bonding.

Room-temperature synthesis and luminescence properties of Eu3+/Tb3+-doped La(1,3,5-BTC)(H2O)(6)

The facile, rapid, and effective synthesis of coordination polymer La(1,3,5-BTC)(H2O)(6) has been realized via direct precipitation at room temperature. It is found that the crystal structure is of monoclinic, space group Cc. The doped Eu3+ or Tb3+ ions samples have the same phase and exhibit red and green emissions under UV light excitation, respectively.

Metal dependent control of cis-/trans-1,4 regioselectivity in 1,3-butadiene polymerization catalyzed by transition metal complexes supported by 2,6-bis[1-(iminophenyl)ethyl]pyridine

Fe(III), Cr(III), Fe(II), Co(II) and Ni(II) chloride complexes supported by 2,6-bis[1-(iminophenyl)ethyl]pyridine have been synthesized and characterized along with single crystal X-ray diffraction. These complexes, in combination with MAO, have been examined in butadiene polymerization. The catalytic activity and regioselectivity are strongly controlled by metal center and cocatalyst (MAO/Co ratio dependent in the case of Co(II) complex). The activity decreases in the order of Fe(III) > Co(II) > Cr(III) approximate to Ni (II) complexes, in consistent with the space around the metal center. Polybutadiene with different microstructure content, from high trans-1,4 units (88-95% for iron(III) and Cr(III)), medium trans-1,4 and cis-1,4 units (55% and 35%, respectively, for iron(II)) to high cis-1,4 units 79% for Co(II) and 97% for Ni(II) call be easily achieved by varying of the metal center.

Synthesis and Characterizations of Poly(9,10-bisarylethynyl-2,6-anthrylene)s and Poly(9,10-bisalkynyl-2,6-anthrylene)

A poly(9,10-bisalkynyl-2,6-anthrylene) (PI) and five poly(9,10-bisarylethynyl-2,6-anthrylene)s(P2-P6) as soluble conjugated polymers have been synthesized and characterized. All polymers exhibit two-dimensional conjugated characteristics as indicated by absorption spectra comprising multi-bands in the range of 300-600 nm. Compared with P1, polymers P2-P5, which contain phenylethynyl substituents with the longer conjugation than alkynyl groups, exhibit a similar to 60 nm red shift of absorption edge. However, further increasing the conjugation length of the arylethynyl substituents (longer than phenylethynyl) has only a no effect on the conjugation of the polymer chains, while comparing the absorption spectra of P6 with those of P2-P5.

Assembly of Seven Supramolecular Compounds with p-Sulfonatocalix[6]arene

Seven supramolecular compounds comprising p-sulfonatocalix[6]arene and transition metals, {[Cu(Imz)-(phen)(H2O)](4)[C6AS]}center dot 10H(2)O (1), {[Cu(Imz)(2)(phen)](2)[Cu(Imz)(phen)(H2O)(2)](2)[C6AS]}center dot 13.3H(2)O (2), {[M(phen)(2)(H2O)]-[(M(phen)(2)](2)[C6AS]}center dot nH(2)O (3 and 4) (3: M = Co and n = 29.6; 4: M = Zn and n = 29.9), {[Cu(phen)(2)](4)[C6AS]}(2)center dot 13H(2)O (5), [H3O](2)[Co(phen)(3)](2)[C6AS]center dot 10.7H(2)O(6), and [Cu(phen)(2)(H2O)](2){[Cu(phen)(2)](2)[C6AS]}center dot 8H(2)O(7)(phen = 1,10-phenanthroline, C6AS = p-sulfonatocalix[6]arene, Imz = imidazole), have been synthesized by a hydrothermal method and structurally characterized by IR spectroscopy, thermogravimetric-differential thermal analysis (TG-DTA), and single crystal X-ray diffraction.

In Situ Scanning Tunneling Microscopy on the Dynamic Process of the Replacement of Coronene on Au (111) by 6-Mercapto-1-Hexanol

The replacement of coronene monolayer on Au (111) by 6-mercapto-1-hexanol (MHO) was studied by in situ scanning tunneling microscopy (STM) in solutions. It was found that the rate of replacement depends strongly on the concentration of MHO. The replacement finished within a second at a higher concentration of MHO. At a lower concentration, the slow replacement could be followed by in situ STM. The replacement occurred initially near the elbow position of reconstructed Au (111) with the formation of pits in a single or several missing molecules. With the proceeding of replacement, these small pits expanded, and the surrounding coronene molecules were gradually substituted by MHO, which developed into ordered domains within a spatial confined environment. Meanwhile, the reconstruction of Au (111) was lifted. The replacement expanded fast along the reconstruction lines in the domain. For the fast replacement, a (root 3 x root 3) R30 degrees adlattice was observed, while a c(4 x 2) superlattice was observed for the slow replacement.

Why [6,6]- and 1,2-Benzal-3-N-4-O-Cyclic Phenylimidate C-60 Undergo Electrochemically Induced Retro-Addition Reactions while 1,4-Dibenzyl-2,3-Cyclic Phenylimidate C-60 Does Not? C-H center dot center dot center dot X (X = N, O) Intramolecular Interactions in Organofullerenes

The electrochemical properties of a series of structurally related fullerooxazoles, [6,6] cyclic phenylimidate C-60 (1), 1,2-benzal-3-N-4-O-cyclic phenylimidate C-60 (2), and 1,4-dibenzyl-2,3-cyclic phenylimidate C-60 (3), are described, and the spectroscopic characterizations of their anionic species are reported. The results show that compounds I and 2 undergo retro-cycloaddition reactions that lead to the formation of C-60 and C61HPh, respectively, upon two-electron-transfer reduction. However, compound 3 demonstrates much more electrochemical stability as no retro-cycloaddition reaction occurs under similar conditions. Natural bond orbital (NBO) calculations on charge distribution show there is no significant difference among the dianions of 1, 2, and 3, indicating that the electrochemical stability of 3 is unlikely to be caused by the charge distribution difference of the dianions of three compounds. Examination on the crystal structure of compound 3 reveals close contacts of the C-H group with the heteroatoms (N and O) of cyclic phenylimidate, suggesting the existence of C-H center dot center dot center dot X (X = N, O) intramolecular hydrogen bonding among the addends, which is further confirmed by NBO analysis.

Microstructures, mechanical properties and corrosion behavior of high-pressure die-cast Mg-4Al-0.4Mn-xPr (x=1, 2, 4, 6) alloys

Mg-4Al-0.4Mn-xPr (x = 1, 2, 4 and 6 wt.%) magnesium alloys were prepared successfully by the high-pressure die-casting technique. The microstructures, mechanical properties, corrosion behavior as well as strengthening mechanism were investigated. The die-cast alloys were mainly composed of small equiaxed dendrites and the matrix. The fine rigid skin region was related to the high cooling rate and the aggregation of alloying elements, such as Pr. With the Pr content increasing, the alpha-Mg grain sizes were reduced gradually and the amounts of the Al2Pr phase and All, Pr-3 phase which mainly concentrated along the grain boundaries were increased and the relative volume ratio of above two phases was changed. Considering the performance-price ratio, the Pr content added around 4 wt.% was suitable to obtain the optimal mechanical properties which can keep well until 200 degrees C as well as good corrosion resistance. The outstanding mechanical properties were mainly attributed to the rigid casting surface layer, grain refinement, grain boundary strengthening obtained by an amount of precipitates as well as solid solution strengthening.

Investigation of heptakis(2,6-di-O-methyl)-beta-cyclodextrin inclusion complexes with flavonoid glycosides by electrospray ionization mass spectrometry

The non-covalent complexes between three flavonoid glycosides (quercitrin, hyperoside and rutin) and heptakis(2,6-di-O-methyl)-beta-cyclodextrin (DM-beta-CD) were investigated by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS). The 1:1 complexation of each flavonoid glycoside (guest) to the DM-beta-CD (host) was monitored in the negative ion mode by mixing each guest with an up to 30-fold molar excess of the host. The binding constants for all complexes were calculated by a linear equation in the order: DM-beta-CD:quercitrin > DM-beta-CD:rutin > DM-beta-CD:hyperoside. A binding model for the complexes has also been proposed based on the binding constants and tandem mass spectrometric data of these complexes.

Synthesis of Arm-6 polystyrene by atom transfer radical polymerization

A new initiator for atom transfer radical polymerization (ATRP), (Cl-2 HCCOO)(3) -C-6 H-3, (TrDCAP),has been designed and successfully synthesized. ATRP of styrene was carried out by using TrDCAP as hexafunctional initiator and the CuCl/bpy catalyst at 130 degrees C in 30% THF via core-first strategy. The Arm-6 PS-AAP was synthesized by etherealization of Arm-6 PS and 4-(4'-methoxyphenylazomethine) phenol (AAP). The initiator and the architectures of the Arm-6 PS were confirmed by H-1-NMR, FT-IR, UV-Vis and GPC.

Synthesis, structure and photochromic properties of a novel 1,6-hexanediamine trimolybdate supramolecular compound

A novel supramolecular compound 1,6-hexanediamine trimolybdate ((C6H18N2[Mo3O10], denoted as HDAMo) has been synthesized by a hydrothermal method and its structure has been characterized by elemental analyses, Fourier transform infrared (FT-IR) spectra, single-crystal X-ray diffraction (XRD) technique. This single crystal compound consists of protonated 1,6-hexanediamine (HDA) cations and polyoxometalate [Mo3O10](2-) anions. Its crystal structure belongs to monoclinic system (space group P2(1)/n) with a = 7.7508(14), b = 11.467(2), c = 16.167(3) angstrom, beta = 92.689(3)degrees, V = 143 5.3(5) angstrom(3), Z = 4 and D-ealc = 2.619 g cm(-3). The final statistics based on F-2 are GOF = 0.980, R-1 = 0.0261 and wR(2) = 0.0506 for I > 2 sigma(I). XRD analysis revealed that in the crystal structure of HDAMo, novel infinite [Mo3O10](2-) chains parallel to a axis are made up of distorted MoO6 octahedra connected by corners and edges. The protonated HDA cations occupy channels formed by [Mo(3)O3(10)](2-) Chains and exhibit strong hydrogen bond interactions to terminal and bridging oxo groups of the chains. The [Mo3O10](2-) chains linked through protonated HAD cations formed a one-dimensional network. The HDAMo compound shows novel photochromic properties, i.e., its color changes from white to reddish brown gradually under UV irradiation. XRD, FT-IR, ESR spectra and XPS are used to investigate the photochromic behavior of the compound.