A Tunable,Fullerene-Based Molecular Amplifier for Vibrational Circular Dichroism

Vibrational circular dichroism (VCD) studies are reported on a chiral compound in which a fullerene C₆₀ moiety is used as an electron acceptor and local VCD amplifier for an alanine-based peptide chain. Four redox states are investigated in this study, of which three are reduced species that possess low-lying electronic states as confirmed by UV/Vis spectroelectrochemistry. VCD measurements in combination with (TD)DFT calculations are used to investigate (i) how the low-lying electronic states of the reduced species modulate the amplification of VCD signals, (ii) how this amplification depends on the distance between oscillator and amplifier, and (iii) how the spatial extent of the amplifier influences amplification. These results pave the way for further development of tailored molecular VCD amplifiers.     

STUDIES OF ADHESION OF METAL PARTICLES TO SILICA PARTICLES BASED ON ZETA POTENTIAL MEASUREMENTS

The zeta-potentials of silica, copper, platinum and gold particles have been measured as a function of pH. The isoelectric points were found to be at pH 3.0, 5.8, 3.0 and 3.5, respectively. In the pH range 3.0 to 5.8 copper and silica particles are oppositely charged and accordingly the coating of silica with copper particles could be demonstrated. In the case of gold and platinum the sign of the charge is such that direct adhesion to silica particles cannot be expected and this was also demonstrated in the case of platinum.     

Wavelength-agile H2O absorption spectrometer for thermometry of general combustion gases

Using a novel Fourier-domain mode-locking (FDML) laser scanning 1330-1380 nm, we have developed a gas thermometer based on absorption spectroscopy that is appropriate for combustion gases at essentially arbitrary conditions. The path-integrated measurements are particularly useful in homogeneous environments, and here we present measurements in a controlled piston engine and a shock tube. Engine measurements demonstrate a RMS temperature precision of ±3% at 1500 K and 200 kHz bandwidth; the precision is improved dramatically by averaging. Initial shock tube measurements place the absolute accuracy of the thermometer within ∼2% to 1000 K. The sensor performs best when significant H₂O vapor is present, but requires only at 300 K, at 1000 K, or at 3000 K for 2% accurate thermometry, assuming a 4 kHz measurement bandwidth (200 kHz scans with 50 averages). The sensor also provides H₂O mole fraction and shows potential for monitoring gas pressure based on the broadening of spectral features. To aid in designing other sensors based on high-temperature, high-pressure H₂O absorption spectroscopy, a database of measured spectra is included.     

Solid-phase Pd-catalysed cross-coupling methods for the construction of π-conjugated peptide nanomaterials

We describe the development of two procedures for the synthesis of peptides that are embedded with a variety of π-conjugated semi-conducting oligomers. These procedures utilise solid-phase variants of classical palladium-catalysed cross-couplings commonly used to prepare π-conjugated oligomers. The resulting peptide–π–electron hybrids are soluble in aqueous media and self-assemble to produce 1D nanostructures, simultaneously forming networks of π-stacked conduits. The procedures have allowed for the inclusion of complex chromophores including mixed aryl units, ethynylene linkers and sexithiophenes where the latter peptide's nanostructures demonstrated substantial conductivity when employed as an active layer in a field-effect transistor.     

Amplification of a cyclic mixed-metalloporphyrin tetramer from a dynamic combinatorial library through orthogonal metal coordination

A cyclic porphyrin tetramer, consisting of two bis-phosphine substituted zinc(II) porphyrin units and two Rh(III)TPP units, is selected and amplified virtually quantitatively from a dynamic combinatorial library using 4,4'-bipy as a scaffold and using orthogonal binding modes.     

Amphipols can support the activity of a membrane enzyme

Amphipathic polymers ("amphipols") were introduced several years ago (Tribet, C.; Audebert, R.; Popot, J.-L. Proc. Natl. Acad. Sci. U.S.A. 1996, 93, 15047-15050) as an alternative method for solubilizing integral membrane proteins in stable, nativelike conformations. However, direct maintenance of full membrane protein functionality in amphipol solutions has not previously been demonstrated in the absence of added lipid or detergent. In this contribution, the first zwitterionic amphipol "PMAL-B-100" is introduced. PMAL-B-100 not only maintains membrane protein structure and solubility, but also supports the full catalytic activity of an integral membrane enzyme, diacylglycerol kinase, in the complete absence of additional lipid or detergent. All of the roles which a lipid bilayer normally plays in maintaining diacylglycerol kinase's structure and in facilitating catalysis are satisfied by the environment and interactions supplied by PMAL-B-100.     

Pseudorapidity distributions of charged particles from Au + Au collisions at the maximum RHIC energy,square root[s(NN)] = 200 GeV

We present charged-particle multiplicities as a function of pseudorapidity and collision centrality for the 197Au+197Au reaction at square root[s(NN)] = 200 GeV. For the 5% most central events we obtain dN(ch)/deta/(eta = 0) = 625+/-55 and N(ch)/(-4.7< or =eta < or =4.7) = 4630 +/- 370, i.e., 14% and 21% increases, respectively, relative to square root[s(NN)] = 130 GeV collisions. Charged-particle production per pair of participant nucleons is found to increase from peripheral to central collisions around midrapidity. These results constrain current models of particle production at the highest RHIC energy.     

Disulfide-strapped porphyrins for monolayer formation on gold

Porphyrins with a disulfide-containing strap have been prepared as an alternative to dithiols for self-assembled monolayer formation on gold surfaces. The strapped porphyrins have the advantage of greater air stability than their dithiol analogues. Cis and trans atropisomers of a strapped porphyrin were isolated. Gold electrodes modified with dithiol and disulfide porphyrins were not identical as evidenced by contact angle or electrochemical measurements.     

Acylhydroperoxide oxidations of the anticancer agent hexamethylmelamine

The clinically effective anticancer agent hexamethylmelamine undergoes an unusual acylhydroperoxide oxidative transformation to give the novel product 2,4-bis(dimethylamino)-6-[(dimethylamino)oxy]-1,3,5-triazine.