We present (29)Si, (27)Al, and (67)Zn NMR evidence to show that silicate ions in alkaline solution form complexes with zinc(II) (present as zincate, Zn(OH)(3)(-) or Zn(OH)(4)(2-)) and, concomitantly, with aluminate (Al(OH)(4)(-)). Zincate reacts with monomeric silicate at pH 14-15 to form [(HO)O(2)Si-O-Zn(OH)(3)](4-) and with dimeric silicate to produce [HO-SiO(2)-O-SiO(2)-O-Zn(OH)(3)](6-). The exchange of Si between these free and Zn-bound sites is immeasurably fast on the (29)Si NMR time scale. The cyclic silicate trimer reacts relatively slowly and incompletely with zincate to form [(HO)(3)Zn{(SiO(3))(3)}](7-). The concentration of the cyclic trimer becomes further depleted because zincate scavenges the silicate monomer and dimer, with which the cyclic trimer is in equilibrium on the time scale of sample preparation. Identification of these zincate-silicate complexes is supported by quantum chemical theoretical calculations. Aluminate and zincate, when present together, compete roughly equally for a deficiency of silicate to form [(HO)(3)ZnOSiO(2)OH](4-) and [(HO)(3)AlOSiO(2)OH](3-) which exchange (29)Si at a fast but measurable rate.

Specialized gold nanostructures are of interest for the development of alternative treatment methods in medicine. Photothermal therapy combined with gene therapy that supports hyperthermia is proposed as a novel multimodal treatment method for prostate cancer. In this work, photothermal therapy using small (<100 nm) gold nanoparticles and near-infrared (NIR) laser irradiation combined with gene therapy targeting heat shock protein (HSP) 27 was investigated. A series of nanoparticles: nanoshells, nanorods, core-corona nanoparticles and hollow nanoshells, were synthesized and examined to compare their properties and suitability as photothermal agents. In vitro cellular uptake studies of the nanoparticles into prostate cancer cell lines were performed using light scattering microscopy to provide three-dimensional (3D) imaging. Small gold nanoshells (40 nm) displayed the greatest cellular uptake of the nanoparticles studied and were used in photothermal studies. Photothermal treatment of the cancer cell lines with laser irradiation at 800 nm at 4 W on a spot size of 4 mm (FWHM) for 6 or 10 min resulted in an increase in temperature of ~12 °C and decrease in cell viability of up to 70%. However, in vitro studies combining photothermal therapy with gene therapy targeting HSP27 did not result in additional sensitization of the prostate cancer cells to hyperthermia.

A convenient and versatile enantioselective synthesis of biologically important alpha-quaternary amino acid derivatives was based on the sequential double alkylation or arylation of dimethyl malonate, followed by desymmetrization with porcine liver esterase (PLE) and Curtius rearrangement. The PLE-mediated hydrolysis of the prochiral dialkylated malonate diesters produced the corresponding chiral half-esters in high yield and with enantiomeric excesses of 43% to >98%. Curtius rearrangement of the latter products, after trapping of the intermediate isocyanates with benzyl alcohol or amines, afforded the corresponding Cbz-protected amino esters or ureas. The absolute configurations of the major products in five examples were established by conversion to compounds with known specific rotations, or by X-ray crystallography of derivatives obtained with chiral amines of known configuration.