Luminescent Zn and Pd tetranaphthaloporphyrins

Zn and Pd complexes of meso-tetraphenyltetranaphthaloporphyrins (Ph(4)TNP) exhibit strong infrared absorption bands and luminesce in solutions at room temperature. S1 --> S0 fluorescence (lambda(max) = 732 nm, phi = 5.3%) is the predominant emission in the case of ZnPh(4)TNP (1). This emission is in part due to the delayed fluorescence (phi = 1.1%). Phosphorescence (T1 --> S0) of 1 (lambda(max) = 973 nm) is very weak (phi = 0.04%) and occurs with lifetime of about 440 micros in deoxygenated DMF. In the case of PdPh(4)TNP (2), almost no S1 --> S0 fluorescence could be observed, while the main emission detected was T1 --> S0 phosphorescence (lambda(max) = 938 nm). The phosphorescence of 2 occurs with lifetime of about 65 micros and (phi=6.5%) in deoxygenated DMF solution. Metalloporphyrins 1 and 2 are promising near infrared dyes biomedical applications.     

Conductivity of a two-dimensional curved microconstriction

The quantum conductance of a long two-dimensional curved microconstriction has been considered theoretically. It is shown that over-the-barrier-reflection of electrons at points in which the curvature of the surface is changed, results in fine structure of quantum steps of the conductance. The observation of this structure would be a demonstration of the influence of the curvature on the quantum properties of two-dimensional electrons.     

Does Urea Preferentially Interact with Amide Moieties or Nonpolar Sidechains? A Question Answered Through a Judicious Selection of Model Systems

The transfer model suggests that urea unfolds proteins mainly by increasing the solubility of the amide backbone, probably through urea-induced increase in hydrogen bonding. Other studies suggest that urea addition increases the magnitude of solvent-solute van der Waals interactions, which increases the solubility of nonpolar sidechains. More recent analyses hypothesize that urea has a similar effect in increasing the solubility of backbone and sidechain groups. In this work, we compare the effects of urea addition on the solvation of amides and alkyl groups. At first, we study the effects of urea addition upon solvent hydrogen bonding acidity and basicity through the perturbation in the fluorescence spectrum of probes 1-AN and 1-DMAN. Our results demonstrate that the solvent's hydrogen bonding properties are minimally affected by urea addition. Subsequently, we show that urea addition does not perturb the intra-molecular hydrogen bonding in salicylic acid significantly. Finally, we investigate how urea preferentially interacts with amide and alkyl groups moieties in water by comparing the effects of urea addition upon the solubility of acetaminophen and 4-tertbutylphenol. We show that urea affects amide and t-butyl solubility (lowers the transfer free energy of both amide (backbone) and alkyl (sidechain) groups) in a similar fashion. In other words, preferential interaction of urea with both moieties contributes to protein denaturation.     

Hofmeister Effects of Group II Cations as Seen in the Unfolding of Ribonuclease A

This work studies the effects of alkaline-earth cation addition on the unfolding free energy of a model protein, pancreatic Ribonuclease A (RNase A) by differential scanning calorimetry analysis. RNase A was chosen because: a) it does not specifically bind Mg²⁺, Ca²⁺ and Sr²⁺ cations and b) maintains its structural integrity throughout a large pH range. We have measured and compared the effects of NaCl, MgCl₂, CaCl₂ and SrCl₂ addition on the melting point of RNase A. Our results show that even though the addition of group II cations to aqueous solvent reduces the solubility of nonpolar residues (and enhances the hydrophobic effect), their interactions with the amide moieties are strong enough to “salt-them-in” the solvent, thereby causing an overall protein stability reduction. We demonstrate that the amide-cation interactions are a major contributor to the observed “Hofmeister Effects” of group II cations in protein folding. Our analysis suggests that protein folding “Hofmeister Effects” of group II cations, are mostly the aggregate sum of how cation addition simultaneously salts-out hydrophobic moieties by increasing the cavitation free energy, while promoting the salting-in of amide moieties through contact pair formation.     

Probing the active site of trypsin with rose bengal: insights into the photodynamic inactivation of the enzyme

In this work the active site of trypsin has been probed with the dye rose bengal. The dye binds competitively to the enzyme, and it can be used as a probe of the active site of the enzyme. On the basis of the emission wavelength, the binding site of trypsin is relatively polar and is similar to that of acetone in its polarity. The triplet state of rose bengal is quenched by trypsin. This quenching may be caused by the tryptophan and tyrosine residues that are in the near vicinity of the trypsin active site. This quenching can compete with the formation of singlet oxygen from the excited triplet state of rose bengal. We demonstrate that the singlet oxygen involved in the photoinactivation of trypsin is produced by the free rose bengal in solution and the bound dye is incapable of producing singlet oxygen. This explains the lack of correlation between photoinactivation efficiency and sensitizer binding capability previously reported by Wade and Spikes.     

Electrical properties and glass transition temperature of multiwalled carbon nanotube/polyaniline composites

Polyaniline (PANI) was synthesized and doped with 0, 2, 4 and 16 wt.% of pure and functionalized multiwall carbon nanotubes (MWCNTs) by “in-situ” polymerization. Measurement of temperature dependence of electrical resistivity showed a reduction in the resistivity of the composites at all temperatures. The reduction was increased by increasing the wt.% of MWCNTs. This decrease was more for the composites containing functionalized MWCNTs and was more prominent for temperatures below 150 K. The glass transition temperature (T_g) of the pure and doped PANI was measured using electrical resistivity measurements. It was observed that by increasing the amount of functionalized MWCNTs in PANI, its T_g increases. Temperature dependence of resistivity of pressed pure PANI showed that by increasing the pelletization pressure, the bulk electrical resistivity decreased but the T_g increased.     

Gold nanothorns-macroporous silicon hybrid structure: a simple and ultrasensitive platform for SERS

We synthesised a novel gold-on-porous silicon hybrid material that exhibits a highly sensitive and reproducible surface-enhanced Raman spectroscopy (SERS) response. The material was fabricated simply by reducing gold chloride with hydrofluoric acid on the surface of macro-porous silicon (macro-PSi). The material consists of thorn-shaped gold nanocrystals with characteristic shapes and sizes on the surface of macro-PSi.