The origin of chemo- and enantioselectivity in the hydrogenation of diketones on platinum

In the Pt-catalyzed hydrogenation of 1,1,1-trifluoro-2,4-diketones, addition of trace amounts of cinchonidine, O-methyl-cinchonidine, or (R,R)-pantoyl-naphthylethylamine induces up to 93% ee and enhances the chemoselectivity up to 100% in the hydrogenation of the activated carbonyl group to an OH function. A combined catalytic, NMR and FTIR spectroscopic, and theoretical study revealed that the two phenomena are coupled, offering the unique possibility for understanding the substrate-modifier-metal interactions. The high chemo- and enantioselectivities are attributed to the formation of an ion pair involving the protonated amine function of the chiral modifier and the enolate form of the substrate. DFT calculations including the simulation of the interaction of a protonated amine with the enolate adsorbed on a Pt 31 cluster revealed that only the C-O bond next to the CF3 group of the substrate is in direct contact with Pt and can be hydrogenated. The present study illustrates the fundamental role played by the metal surface and indicates that also the enol form can be the reactive species in the hydrogenation of the activated ketone on chirally modified Pt.     

The impact of the pi-electron conjugation length on the three-photon absorption cross section of fluorene derivatives

The three-photon absorption cross sections of three different fluorene derivatives, with extended pi-electron conjugation lengths was experimentally measured and compared with shorter pi-electron conjugation length analogs. The effect of the conjugation length on the three-photon absorption cross section sigma(3) (') of this family of molecules has been elucidated. It is demonstrated that sigma(3) (') of the asymmetric compound D-pi-pi-pi-A is 6.6 times larger than its shorter configuration D-pi-A, while for the symmetric compounds D-pi-pi-pi-D and A-pi-pi-pi-A a two-fold enhancement was found relative to their shorter conjugation length analogs. Measurements of the three-photon excitation of these compounds in THF solution (10(-3)M) were accomplished with a tunable optical pulse generation pumped by a 25 ps Nd-YAG laser.     

Syntheses and properties of water-soluble Nile Red derivatives

Nile Red (compound A) fluoresces at about 530 nm with good quantum yields in apolar solvents. In more polar ones its fluorescence emission shows a dramatic, and potentially useful, shift to about 640 nm, but its quantum yield is significantly reduced. Further, Nile Red has a very poor solubility in aqueous media. The hypothesis tested in this paper is that Nile Red derivatives that incorporate water-solubilizing groups will tend to fluoresce with good quantum yields in aqueous media, and in the more useful wavelength range around 640 nm. Thus three Nile Red derivatives, 1-3, were prepared. Compound 1 had three hydroxyl groups more than Nile Red, but was surprisingly insoluble in aqueous media. However, the dicarboxylic acid 2 and carboxylic/sulfonic acid derivative 3 showed excellent water solubilities. Spectral data for 2 and 3 showed that they do indeed fluoresce with good quantum yields in the 640 nm region in aqueous media. These properties of compounds 2 and 3 might be useful in the development of fluorescent probes for biotechnology.     

Excimer-based peptide beacons: a convenient experimental approach for monitoring polypeptide-protein and polypeptide-oligonucleotide interactions

While protein-polypeptide and nucleic acid-polypeptide interactions are of significant experimental interest, quantitative methods for the characterization of such interactions are often cumbersome. Here we described a relatively simple means of optically monitoring such interactions using excimer-based peptide beacons (PBs). The design of PBs is based on the observation that, whereas short peptides are almost invariably unfolded and highly dynamic, they become rigid when complexed with macromolecular targets. Using this binding-induced folding to segregate two pyrene moieties and therefore inhibit excimer formation, we have produced PBs directed against both anti-HIV antibodies and the retroviral transactive response (TAR) RNA hairpin. For both polypeptides, target recognition is accompanied by a roughly 2-fold decrease in excimer emission, thus allowing the detection of their respective targets at concentrations of a few nanomolar. Because excimer emission requires the formation of a tight, precisely oriented pyrene dimer, even relatively trivial binding-induced segregation reduces fluorescence significantly. This suggests that the PB approach will be suitable for monitoring a wide range of peptide-macromolecule recognition events. Moreover, the synthesis of excimer-based PBs utilizes commercially available modified pyrenes in a simple and well-established protocol, making the approach well suited for routine laboratory applications.     

Building addressable libraries: The use of a mass spectrometry cleavable linker for monitoring reactions on a microelectrode array

Time-of-flight secondary ion mass spectrometry (TOF SIMS) has been used in conjunction with a mass spectrometry cleavable linker to determine the percent conversion of reactions that were conducted site-selectively on an addressable microelectrode array. When combined with fluorescence techniques for analysis of the reactions, the TOF SIMS experiment provides a means for optimization of both reaction confinement and reaction efficiency on the microelectrode arrays.     

Nativelike structure in designed four alpha-helix bundles driven by buried polar interactions

We show that a single internal polar interaction per helix is sufficient to engender structural specificity in that helix in helical bundle proteins. Furthermore, we use histidine-binding cofactors of different shapes which bind directly into the core, demonstrating that this structural specificity is not the result of a prescribed complimentary, "knobs in holes" core packing. We show that we can switch structural specificity of individual helices on and off by ligating cofactors, singly and in pairs, which bind either one or two histidine ligands. To our knowledge, this is the first demonstration of such extensive manipulation of protein structure by ligand binding, an important result of general interest to those working with self-assembled molecular systems. Finally, as these proteins were designed without the use of computational modeling, we not only demonstrate that designing a uniquely structured cofactor binding protein is not as difficult as is generally believed, we have determined why this is so: hydrophobic core complementarity, which is very difficult to design, is not necessary. Instead, a much simpler design process entails the creation of core polar interactions which themselves can drive conformational specificity.     

Simultaneous forward- and backward-hemisphere elastic-light-scattering patterns of respirable-size aerosols

Two-dimensional angular optical scattering (TAOS) patterns of aerosols are measured simultaneously from the forward hemisphere 15 degrees < theta < 90 degrees as well as the backward hemisphere 90 degrees < theta < 165 degrees (detecting 63% of the 4pi sr of scattered light) by using an ellipsoidal reflector and an intensified CCD detector. TAOS patterns were obtained from polystyrene-latex spheres (individuals and aggregates) and from single Bacillus subtilis spores. These information-rich patterns, measured with a single laser pulse for individual particles on the fly, suggest that forward-TAOS and backward-TAOS measurements may be used for rapid classification of single aerosol particles.     

Dynamic shim updating on the human brain

Dynamic alteration of shim settings during a multi-slice imaging experiment can improve static magnetic-field homogeneity over extended volumes. In this report, a pre-emphasized dynamic shim updating (DSU) system capable of rapidly updating all non-degenerate zeroth through second-order shims is presented and applied to high-field multi-slice imaging studies on the human brain. DSU is utilized in both non-oblique and oblique slicing geometries while updating in-plane and through-slice shims. Image-based magnetic-field maps are used to quantify homogeneity improvements and comparisons are made on a slice-specific basis between static global shimming and increasing orders of shim inclusion utilized DSU. The influence of oblique slicing geometry on DSU-utilized global homogeneity is also quantified computationally. Finally, the effect of DSU on susceptibility artifact reduction in single-shot axial-sliced EPI is analyzed using experimental acquisitions.     

Sample-specific diamagnetic and paramagnetic passive shimming

When homogenizing the static magnetic field over extended in vivo volumes, significant residual inhomogeneity can remain after spherical harmonic shim optimization. This is due to the low spatial orders of shims available on in vivo MR systems and the presence of higher-order inhomogeneity in the vicinity of anatomic air cavities. Mediation of this problem through the development of higher-order spherical harmonic shims is severely impeded by bore space limitations. Sample-specific passive shims are not limited to low-order spatial compensation and offer an alternative means to increased homogenization. Here, we present a novel construction protocol for sample-specific passive shims comprised of both diamagnetic (bismuth) and paramagnetic (zirconium) materials. A prototype shim is constructed and shown to significantly homogenize the mouse brain at 9.4 T. Further homogenization capabilities are simulated through alteration of the shim construction.     

Robust passive range estimation using the waveguide invariant

The waveguide invariant principle is used to estimate the range to a broadband acoustic source in a shallow-water waveguide using a single acoustic receiver towed along a path directly toward the acoustic source. A relationship between the signal processing parameters and the ocean-acoustic environmental parameters is used to increase the effective signal-to-noise ratio without requiring detailed knowledge of the environment. Heuristics are developed to estimate the minimum source bandwidth and minimum horizontal aperture required for range estimation. A range estimation algorithm is tested on experimental and simulated data for source ranges of 500-2200 m and frequencies from 350 to 700 Hz. The algorithm is accurate to within approximately 25% for the cases tested and requires only a minimal amount of a priori environmental knowledge.