Highly regio- and stereoselective hydrometallation reactions of fluorine-containing internal alkynes: Novel approaches to fluoroalkylated alkenes

Hydroalumination, hydrocupration, and hydroboration reactions of various fluorine-containing alkynes were investigated. The alkyne reacted smoothly with 2.0 equiv. of Red-Al at −78 °C to give the hydroaluminated adduct in a highly regio- and stereoselective manner, which was treated with iodine, the corresponding vinyliodide being produced in moderate yield. Hydrocupration of the alkynes also took place, but the resulting vinylmetal reacted with various electrophiles sluggishly. In sharp contrast, the reaction with dicyclohexylborane proceeded smoothly to afford the cis-addition products preferentially, which were subjected to Suzuki-Miyaura cross-coupling reaction, leading to trisubstituted alkenes in high yields.     

Synthesis of brominated directly fused diporphyrins through gold(III)-mediated oxidation

Highly efficient synthesis of meso,meso-dibromo doubly and triply fused diporphyrins has been achieved through a powerful oxidative coupling mediated by AuCl3-AgOTf combination. In addition, palladium-catalyzed debromination of meso-bromoporphyrins has been developed. This debromination protocol enables employment of bromine as a protecting group for the reactive meso-position of porphyrins.     

Synthesis of nanometer-scale porphyrin wheels of variable size

Starting from 1,3-phenylene linked diporphyrin zinc(II) complex 2ZA, repeated stepwise Ag I-promoted coupling reactions provided linear oligomers from 2nZA up to 128ZA. Of these zigzag shaped porphyrin arrays, the Ag I-promoted intramolecular cyclization reaction of 2 nZA (n=5, 6, 8, 9, 12, and 16) under dilute conditions gave the corresponding cyclic porphyrin wheels C2nZA (n=5, 6, 8, 9, 12, and 16), whereas large arrays 2nZA (n=24, 32, and 48) did not provide cyclic porphyrin products. These large discrete porphyrin arrays and wheels were fully characterized by means of 1H NMR spectroscopy, MALDI-TOF mass spectrometry, UV/Vis absorption spectroscopy, GPC-HPLC analysis, and the scanning tunneling microscopy (STM) technique. The STM images of C12ZA and C18ZA reveal their large circular structures. In the cyclic structures of C2nZA in solution, however, the gradual decrease in fluorescence quantum yields and fluorescence lifetimes are observed, reflecting some conformational heterogeneities. Collectively, the present work provides an important contribution to the construction of fully covalently linked large cyclic arranged porphyrin arrays with ample electronic interactions as a model of light-harvesting antenna.     

Helical silica nanotubes: Nanofabrication architecture,transfer of helix and chirality to silica nanotubes

A series of neutral gelators and cationic amphiphiles derived from 1,2 diphenylethylenediamine (I) and 1,2-cyclohexanediamine (II) was synthesised. Helical silica nanotubes were prepared utilising these organic gelators through sol-gel polycondensation of tetraethoxy silane, (TEOS-silica source). Right- and left-handed helical nanotubes respectively were obtained from a 1: 1 mass mixture of optically active, (1S,2S)-III-(1S,2S)-V neutral gelator and (1S,2S)-IV-(1S,2S)-VI cationic amphiphile and a 1: 1 mass mixture of optically active, (1R,2R)-III-(1R,2R)-V neutral gelator and (1R,2R)-IV-(1R,2R)-VI cationic amphiphile, indicating that the handedness of the helical nanotubes varied with the change in the neutral gelator precursors used. The nanotubes were characterised by SEM images.     

Phosphorescent sensor for biological mobile zinc

A new phosphorescent zinc sensor (ZIrF) was constructed, based on an Ir(III) complex bearing two 2-(2,4-difluorophenyl)pyridine (dfppy) cyclometalating ligands and a neutral 1,10-phenanthroline (phen) ligand. A zinc-specific di(2-picolyl)amine (DPA) receptor was introduced at the 4-position of the phen ligand via a methylene linker. The cationic Ir(III) complex exhibited dual phosphorescence bands in CH(3)CN solutions originating from blue and yellow emission of the dfppy and phen ligands, respectively. Zinc coordination selectively enhanced the latter, affording a phosphorescence ratiometric response. Electrochemical techniques, quantum chemical calculations, and steady-state and femtosecond spectroscopy were employed to establish a photophysical mechanism for this phosphorescence response. The studies revealed that zinc coordination perturbs nonemissive processes of photoinduced electron transfer and intraligand charge-transfer transition occurring between DPA and phen. ZIrF can detect zinc ions in a reversible and selective manner in buffered solution (pH 7.0, 25 mM PIPES) with K(d) = 11 nM and pK(a) = 4.16. Enhanced signal-to-noise ratios were achieved by time-gated acquisition of long-lived phosphorescence signals. The sensor was applied to image biological free zinc ions in live A549 cells by confocal laser scanning microscopy. A fluorescence lifetime imaging microscope detected an increase in photoluminescence lifetime for zinc-treated A549 cells as compared to controls. ZIrF is the first successful phosphorescent sensor that detects zinc ions in biological samples.     

Monitoring protein distributions based on patterns generated by protein adsorption behavior in a microfluidic channel

We report a unique monitoring technique of protein distributions based on distinctive patterns generated by protein adsorption behavior on a solid surface in a microfluidic channel. Bare gold and COOH-modified self-assembled monolayer (SAM) sensing surfaces were pre-adsorbed with one of four different proteins: lysozyme, albumin, transferrin, or IgG. Each surface provides a thermodynamically governed platform for immobilizing proteins and generates analyte-specific response patterns. Each surface has its own thermodynamic energy governing pre-adsorbed protein behaviors, so that sample proteins react with the pre-adsorbed ones to different extents depending on their sizes, isoelectric points (pI), and characteristics of the sensing surfaces. Modified surfaces were mounted and monitored in real time using surface plasmon resonance (SPR). Buffer-prepared sample matrices (α1-antitrypsin, haptoglobin, C-reactive protein (CRP), and IgM) characterized protein response patterns. Each surface generated distinctive patterns based on individual SPR angle shifts. We classified each sample with 95% accuracy using linear discriminant analysis (LDA). Our method also discriminated between different concentrations of CRP in the cocktail sample, detecting concentrations as low as 1 nM with 91.7% accuracy. This technique may be integrated with a microfluidic lab-on-a-chip system and monitor the distribution of a specific group of proteins in human serum.