Identification of a novel Michael acceptor group for the reversible addition of oxygen- and sulfur-based nucleophiles. Synthesis and reactivity of the 3-alkylidene-3H-indole 1-oxide function of avrainvillamide

The 3-alkylidene-3H-indole 1-oxide functional group found in the naturally occurring alkaloid avrainvillamide has been synthesized by a cross coupling-reductive condensation sequence and found to undergo reversible addition of oxygen- and sulfur-based nucleophiles.     

pH responsive Eu(III)-phenanthroline supramolecular conjugate: novel "off-on-off" luminescent signaling in the physiological pH range

The formation of luminescent supramolecular ternary complexes in water: delayed luminescence sensing of aromatic carboxylates using coordinated unsaturated cationic heptadenatate lanthanide ion complexes.     

Directed denaturation: room temperature and stoichiometric unfolding of cytochrome C by a metalloporphyrin dimer

Using circular dichroism, UV-vis, and trypsin proteolysis, we have shown how a metalloporphyrin dimer induces the unfolding of a protein, cytochrome c, under physiologically relevant conditions and accelerates its rate of proteolytic degradation.     

A rare earth-DOTA-binding antibody: probe properties and binding affinity across the lanthanide series

An antibody that binds rare earth complexes selectively could be used as a docking station for a set of probe molecules, of particular interest for medical imaging and therapy. The rare earths are rich in probe properties, such as the paramagnetism of Gd, the luminescence of Tb and Eu, and the nuclear properties of Lu and Y. We find that antibody 2D12.5, initially developed to bind analogues of Y-DOTA (1,4,7,10-tetraazacyclododecane-N,N',N' ',N' '-tetraacetic acid) for radiotherapy, binds not only Y-DOTA analogues but also analogous DOTA complexes of all of the lanthanides. Surprisingly, chelates of some metals such as Gd3+ bind more tightly than the original Y3+ complex. When the shape of the complex is perturbed by either increasing or decreasing the radius of the lanthanide ion, the thermodynamic stability of the protein-ligand complex changes in a regular fashion. The behavior of DeltaDeltaG as a function of ionic radius fits a parabola, as might be expected for a system that behaves in a thermodynamically elastic way. The broad specificity and high affinity of this antibody for all rare earth-DOTA complexes make it particularly interesting for applications that take advantage of the unique characteristics of lanthanides. For example, UV excitation of the Tb-DOTA-2D12.5 complex leads to energy transfer from aromatic side chains of the antibody to bound Tb-DOTA, enhancing green terbium luminescence >104 relative to unbound Tb-DOTA.     

Methyl/ethyl differentiation in diastereoselective hydride addition to [Tp'W(CO)(PhCCMe)(NH=CMeEt)][BAr'(4)

Hydride addition to either an 80:20 or a 93:7 E/Z isomer ratio of coordinated imine complex 2a occurs with high diastereoselectivity. The high diastereoselectivity regardless of the reagent E/Z ratio is explained by a difference between the relative kinetic acidities of the E and Z isomers of the imine complex. The kinetic acidities of related isopropylimine and 3-pentylimine complexes were used in explaining these results.     

Microlens formation in microgel/gold colloid composite materials via photothermal patterning

We report on the nature of photothermally patterned regions inside self-assembled hydrogel nanoparticle materials containing coassembled colloidal Au. These composite materials are prepared from approximately 226-nm diameter particles composed of the environmentally responsive polymer, poly(N-isopropylacrylamide) (pNIPAm). Upon centrifugation to achieve a proper volume fraction, these close-packed assemblies display a sharp Bragg diffraction peak in the midvisible region of the spectrum and can be reversibly converted into a nondiffracting glassy material as the temperature is raised above the characteristic phase transition temperature of the polymer. The addition of 16-nm colloidal Au prior to centrifugation allows the homogeneous distribution of metal nanoparticles throughout the close-packed material. Localized heating is then possible upon excitation of the Au plasmon absorption with a frequency doubled Nd:YAG laser (lambda = 532 nm). Such localized heating events lead to patterned regions of ordered crystalline phases inside of bulk glassy phases. We illustrate that the nature of the locally patterned area results in the formation of a microlens due to density/refractive index gradient in the patterned crystalline region. The Gaussian power distribution of the incident beam is thought to be a contributing factor in the microlens formation. Microlens formation is shown by observing interference patterns similar to Newton's rings, which change over time as the region is formed. A true hallmark of the lens is also demonstrated by focusing an image through the patterned structure.     

Stereoselective construction of cis-2,6-disubstituted tetrahydropyrans via the reductive etherification of delta-trialkylsilyloxy substituted ketones: total synthesis of (-)-centrolobine

[reaction: see text] The stereoselective intramolecular reductive etherification of delta-trialkylsilyloxy substituted ketones with catalytic bismuth tribromide and triethylsilane provides a convenient method for the construction of cis-2,6-disubstituted tetrahydropyrans. This method was highlighted in the key step of an expeditious total synthesis of the antibiotic, (-)-centrolobine.     

Biomimetic synthesis of biatractylolide and biepiasterolide

[reaction: see text] The biomimetic synthesis of the bisesquiterpenoids biatractylolide 1 and biepiasterolide 2 is reported.     

Fluxional behavior of a cadmium zwitterion complex: proton transport and tautomerism in methylene chloride solution

The synthesis and structure of the tautomeric Cd(II) isoindoline zwitterion coordination compound [Cd(4'-MeLH)(NO(3))(2)].CH(3)OH (4'-MeLH = 1,3-bis[2-(4-methylpyridyl)imino]isoindoline) are reported. In methylene chloride solution, tautomer interconversion occurs as the N-H proton moves between the identical imine nitrogen atoms. We report the kinetics of proton transfer as followed by variable temperature (1)H NMR spectroscopy and demonstrate that methanol of solvation and adventitious water facilitate rapid proton transfer.     

Evaluation of the two-dimensional reversed-phase-reversed-phase separations of low-molecular mass polystyrenes

The resolving power of four reversed-phase-reversed-phase two-dimensional (2D) chromatographic systems was evaluated using information theory (IT) and a geometric approach to factor analysis. The first separation dimension employed a C18 column, while the second separation dimension employed a carbon clad zirconia column. Mobile phases in each dimension were either methanol or acetonitrile. The sample matrix that was employed in this study contained a mixture of 58 components, comprised of stereoisomers and structural isomers of a systematic variation in molecular weight. Each of the components were oligostyrenes, with between two and five configurational repeating units having either n-butyl, sec-butyl or tert-butyl end groups. In the two-dimensional systems employed in this study, between 46 and 49 of the 58 components could be separated, depending on the mobile phase combinations--with apparent resolution that could not possibly be achieved in a single one-dimensional separation. The results from this study indicate that in order to fully evaluate the resolving power of a 2D system multiple methods of analysis that evaluate the separation potential are most appropriate. This becomes increasingly important when the sample contains components that are very closely related and the retention of solutes displays a high degree of solute crowding.