Synthesis and Characterization of Tris(trimethylsilyl)siloxide Derivatives of Early Transition Metal Alkoxides That Thermally Convert to Varied Ceramic-Silica Architecture Materials.

In an effort to generate single-source precursors for the production of metal-siloxide (MSiO x) materials, the tris(trimethylsilyl)silanol (H-SST or H-OSi(SiMe3)3 (1) ligand was reacted with a series of group 4 and 5 metal alkoxides. The group 4 products were crystallographically characterized as [Ti(SST)2(OR)2] (OR = OPr i (2), OBu t (3), ONep (4)); [Ti(SST)3(OBu n)] (5); [Zr(SST)2(OBu t)2(py)] (6); [Zr(SST)3(OR)] (OR = OBu t (7), ONep, (8)); [Hf(SST)2(OBu t)2] (9); and [Hf(SST)2(ONep)2(py) n] ( n = 1 (10), n = 2 (10a)) where OPr i = OCH(CH3)2, OBu t = OC(CH3)3, OBu n = O(CH2)3CH3, ONep = OCH2C(CH3)3, py = pyridine. The crystal structures revealed varied SST substitutions for: monomeric Ti species that adopted a tetrahedral ( T-4) geometry; monomeric Zr compounds with coordination that varied from T-4 to trigonal bipyramidal ( TBPY-5); and monomeric Hf complexes isolated in a TBPY-5 geometry. For the group 5 species, the following derivatives were structurally identified as [V(SST)3(py)2] (11), [Nb(SST)3(OEt)2] (12), [Nb(O)(SST)3(py)] (13), 2[H][(Nb(µ-O)2(SST))6(µ6-O)] (14), [Nb8O10(OEt)18(SST)2·1/5Na2O] (15), [Ta(SST)(µ-OEt)(OEt)3]2 (16), and [Ta(SST)3(OEt)2] (17) where OEt = OCH2CH3. The group 5 monomeric complexes were solved in a TBPY-5 arrangement, whereas the Ta of the dinculear 16 was solved in an octahedral coordination environment. Thermal analyses of these precursors revealed a stepwise loss of ligand, which indicated their potential utility for generating the MSiO x materials. The complexes were thermally processed (350-1100 °C, 4 h, ambient atmosphere), but instead of the desired MSiO x, transmission electron microscopy analyses revealed that fractions of the group 4 and group 5 precursors had formed unusual metal oxide silica architectures.

Polysulfone and polyacrylate-based zwitterionic coatings for the prevention and easy removal of marine biofouling.

A series of polysulfone and polyacrylate-based zwitterionic coatings were prepared on epoxy-primed aluminum substrata and characterized for their antifouling (AF) and fouling-release (FR) properties towards marine bacteria, microalgae and barnacles. The zwitterionic polymer coatings provided minimal resistance against bacterial biofilm retention and microalgal cell attachment, but facilitated good removal of attached microbial biomass by exposure to water-jet apparatus generated hydrodynamic shearing forces. Increasing the ion content of the coatings improved the AF properties, but required a stronger adhesive bond to the epoxy-primed aluminum substratum to prevent coating swelling and dissolution. Grafted poly(sulfobetaine) (gpSBMA), the most promising zwitterionic coating identified from microfouling evaluations, enabled the removal of four out of five barnacles reattached to its surface without incurring damage to their baseplates. This significant result indicated that gpSBMA relied predominately on its surface chemistry for its FR properties since it was very thin (~1-2 µm) relative to commercial coating standards (>200 µm).

Stability Evaluation of Candidate Precursors for Chemical Vapor Deposition of Hafnium Diboride (HfB2).

Alternative candidate precursors to [Hf(BH4)4] for low-temperature chemical vapor deposition of hafnium diboride (HfB2) films were identified using density functional theory simulations of molecules with the composition [Hf(BH4)2L2], where L = -OH, -OMe, -O-t-Bu, -NH2, -N=C=O, -N(Me)2, and -N(CH2)5NH2 (1-piperidin-2-amine referred to as Pip2A). Disassociation energies (E D), potential energy surface (PES) scans, ionization potentials, and electron affinities were all calculated to identify the strength of the Hf-L bond and the potential reactivity of the candidate precursor. Ultimately, the low E D (2.07 eV) of the BH4 ligand removal from the Hf atom in [Hf(BH4)4] was partially attributed to an intermediate state where [Hf(BH4)3(H)] and BH3 is formed. Of the candidate precursors investigated, three exhibited a similar mechanism, but only -Pip2A had a PES scan that indicated binding competitive with [Hf(BH4)4], making it a viable candidate for further study.

Synthesizing biofunctionalized nanoparticles to image cell signaling pathways.

This minireview outlines the synthetic efforts, from our research group, to produce nanomaterials for use as imaging agents to study cell signaling pathways. An overview of our approach to the synthesis and biofunctionalization of metal, semiconductor, and ceramic nanomaterials is presented. The probes investigated include coinage metals, Cd-based, Ge(o), naturally occurring fluorescent (NOF) minerals, and Ln-based nanoparticles which were synthesized from novel metal alkoxide, amide, and alkyl precursors. We illustrate the applications of some of these materials as imaging probes to detect signaling pathway components and cellular responses to signals (apoptosis and degranulation) in inflammatory and cancer cells.

Morphological and Phase Controlled Tungsten Based Nanoparticles: Synthesis and Characterization of Scheelites, Wolframites, and Oxides Nanomaterials.

For the first time tungsten based nanoparticles (WNPs) of scheelite (MWO(4); M = Ca, Sr, Ba, Pb), wolframite (MWO(4); M = Mn, Fe, Zn & (Mg(0.60)Mn(0.17)Fe(0.26))WO(4)), and the oxide (WO(3) and W(18)O(49)) were synthesized from solution precipitation (i.e.,trioctylamine or oleic acid) and solvothermal (i.e., benzyl alcohol) routes. The resultant WNPs were prepared directly from tungsten (VI) ethoxide (W(OCH(2)CH(3))(6), 1) and stoichiometeric mixtures of the following precursors: [Ca(N(SiMe(3))(2))(2)](2) (2), Pb(N(SiMe(3))(2))(2) (3), Mn[(mu-Mes)(2)Mn(Mes)](2) (4), [Fe(mu-Mes)(Mes)](2) (5), Fe(CO)(5) (6), H(+)[Ba(2)(mu(3)-ONep)(mu-ONep)(2)(ONep)(ONep)(3)(py)](-) (2) (7), H(+)[Sr(5)(mu(4)-O)(mu(3)-ONep)(4)(mu-ONep)(4)(ONep)(py)(4)](-) (8), and [Zn(Et)(ONep)(py)](2) (9) where Mes = C(6)H(2)(CH(3))(3)-2,4,6, ONep = OCH(2)CMe(3), Et = CH(2)CH(3), and py = pyridine. Through these routes, the WNP morphologies were found to be manipulated by the processing conditions, while precursor selection influenced the final phase observed. For the solution precipitation route, 1 yielded (5 x 100 nm) W(18)O(49) rods while stochiometeric reactions between 1 and (2 - 9) generated homogenous sub 30 nm nano-dots, -diamonds, -rods, and -wires for the MWO(4) systems. For the solvothermal route, 1 was found to produce wires of WO(3) with aspect ratios of 20 while (1 & 2) formed 10 - 60 nm CaWO(4) nanodots. Room temperature photoluminescent (PL) emission properties of select WNPs were also examined with fluorescence spectroscopy (lambda(ex) = 320 nm). Broad PL emissions = 430, 420, 395, 420 nm were noted for 5 x 100 nm W(18)O(49) rods, 5 x 15 nm, CaWO(4) rods, 10 - 30 nm CaWO(4) dots, and 10 nm BaWO(4) diamonds, respectively.