Plasmon-enhanced two-photon excitation fluorescence of rhodamine 6G and an Eu-diketonate complex by a picosecond diode laser.

Two-photon excited fluorescence (TPEF) of rhodamine 6G (Rh6G) and tris(dibenzoylmethane) mono(5-aminophenanthroline) europium (Eu-TDPA) was measured using a pulsed diode laser head (<45 mW, 975 nm, 90 ps pulse width, 40 MHz). Fluorophores were cast on a glass slide modified with triangular silver nanoprisms. A photon-counting photomultiplier detected the TPEF of Rh6G on a glass substrate (1361 Hz) and on the nanoprisms (6322 Hz). On the other hand, Eu-TDPA did not exhibit TPEF on a glass substrate. TPEF was only observed when the extinction of the nanoprisms on the substrates was larger than 0.1. The nanoprisms enhanced the TPEF of these two fluorophores up to the detectable level using a low-power laser diode.

Behavior of chiral induction from polysilsesquioxanes bearing chiral and ammonium groups to anionic pyrene derivatives.

The behavior of chiral induction from ladder-like polysilsesquioxanes (R60- and S60-PSQs) bearing chiral and ammonium side-chain groups (compositional ratio = ca. 60:40) to the anionic pyrene derivative, 1,3,6,8-pyrenetetrasulfonic acid tetrasodium salt (PTSNa4), was investigated. The circular dichroism (CD) spectra of PTSNa4/(R60- and S60-PSQs) mixtures in methanol exhibited reverse peaks at 230-250, 280-290, and 310-370 nm, which were assigned to PTSNa4 and indicated that the achiral PTSNa4 molecule had chirality induced from the chiral PSQs. In addition, it was found that an eximer of PTSNa4 was formed by hybridization with the chiral PSQs, i.e., the emission peaks not only due to a monomer state at 385 and 408 nm but also due to an eximer at 460-520 nm were observed in the fluorescence spectrum excited at 377 nm. This result suggests that the negatively charged PTSNa4 formed an eximer along the positively charged side-chain ammonium groups of PSQs. To investigate the influence of the structures of the pyrene derivatives on chiral induction behavior, the CD measurements of the mixtures of R60- and S60-PSQs in methanol with different pyrene derivative, 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (pyranine), were also performed. It was found that the intensities of the absorptions for the pyanine solutions were lower than those for PTSNa4 solutions. These results suggest that the point-symmetry of the pyrene derivatives influences the level of chiral induction. Therefore, the point-symmetry of pyrene derivatives is an important factor for determining the behavior of chiral induction from chiral PSQs to these compounds.

Photophysical and photochemical studies of chlorophyll a and cobalt(II)tetraphenylporphyrin in poly(L-glutamate)-decylammonium ion complex.

Spectroscopic studies were carried out on chlorophyll a and cobalt(II)tetraphenylporphyrin solubilized in a poly(L-glutamate) (Poly(Glu))-decylammonium chloride (DeAC) complex system, in the presence of methylviologen (MV2+). The cooperative binding occurred between the anionic Poly(Glu) and the cationic DeAC, leading to the formation of micelle-like hydrophobic clusters of DeAC and also the change in conformation of the Poly(Glu) from the random coil to the alpha-helix. All of the absorption spectra, the fluorescence quantum yields and the fluorescence lifetimes indicated the existence of equilibrium between the aggregated biofunctional molecules in the bulk phase and the monomeric species in the complex phase of the Poly(Glu)-DeAC solution. The fluorescence quenching of the biofunctional molecules by methylviologen indicates that the conformation-dependent electron transfer occurs in the complex phase.

Phosphorylation of ovalbumin by dry-heating in the presence of pyrophosphate: effect on protein structure and some properties.

Ovalbumin (OVA) was phosphorylated by dry-heating in the presence of pyrophosphate at pH 4.0 and 85 degrees C for 1 and 5 days, and the physicochemical and structural properties of phosphorylated OVA were investigated. The phosphorus content of OVA increased to 1.01% by phosphorylation, and the electrophoretic mobility of PP-OVA also increased. Although the solubility of dry-heated OVA decreased, the decrease was slightly depressed by phosphorylation. The circular dichroism spectra showed that the change of the secondary structure in the OVA molecule, as measured by alpha-helix content, was mild by phosphorylation. The exchange reaction between the sulfhydryl and disulfide groups was enhanced and the surface hydrophobicity of OVA increased by phosphorylation. The tryptophan fluorescence intensity of OVA decreased by phosphorylation, suggesting that the conformational change occurred in the OVA molecule by phosphorylation. Although the differential scanning calorimetry thermograms of OVA showed a lowering of the denaturation temperature from 78.3 to 70.1 degrees C by phosphorylation, the stability of OVA against heat-induced insolubility at pH 7.0 was improved. The results indicated molten (partially unfolded) conformations of OVA formed by dry-heating in the presence of pyrophosphate.

In situ green synthesis of biocompatible ginseng capped gold nanoparticles with remarkable stability.

We report herein an unprecedented one-step green synthesis of gold nanoparticles (G-AuNps), using naturally occurring Korean red ginseng root (Panax ginseng C.A. Meyer) without any special reducing/capping agents. The AuNps generated through this ginseng-mediated process did not aggregate suggesting that the phytochemicals present in them serve as excellent coatings on the nanoparticles and thus, provide robust shielding from aggregations. The ginseng-generated AuNps exhibit remarkable in vitro stability in various buffers including: cysteine, histidine, saline, sodium chloride and a host of pH ranges. Furthermore, the phytochemical coatings on the G-AuNps rendered them nontoxic as demonstrated through detailed cytotoxicity assays using WST-8 counting kit, performed on normal cervical cells lines. The present study opens up a new possibility of conveniently synthesizing AuNps using natural products which will be useful in optoelectronic and biomedical applications.

Biscembranes from the soft coral Sarcophyton glaucum.

Four novel biscembranes have been isolated from the soft coral Sarcophyton glaucum, collected at Amami Oshima, two of which showed weak activity against proliferation of human promyelocytic leukemia cells (HL-60). Their absolute structures were determined on the basis of the CD spectra.

Potentiometric and Spectroscopic Characterization of Copolypeptide-Surfactant Complexes Formed by a Cooperative Binding System.

The binding behavior of an anionic surfactant, sodium dodecyl sulfate (SDS), to a series of L-lysine-containing copolypeptides in aqueous solutions was investigated in relation to the conformational change of copolypeptide-surfactant complexes with the use of potentiometric and spectroscopic techniques. The present results of CD spectra and the binding isotherm of SDS by copolypeptides of opposite charges can lead us to conclude that SDS binds cooperatively to the positively charged side groups of a series of copolypeptides used in this work, resulting in the formation of a micelle-like cluster due to an additional hydrophobic interaction among bound SDS ions. Solid-state properties of the stoichiometric copolypeptide-SDS complexes were also examined by using CD and FT-IR spectroscopies; (Lys, Tyr) (1:1) and (4:1) systems adopt a beta-pleated sheet conformation, while (Lys, Trp) (4:1) and (Lys, Phe) (1:1) systems adopt an alpha-helical conformation. Based on the results of FT-IR spectra, in all cases surfactant alkyl chains of SDS in the solid complexes were in an extended conformation. Copyright 2000 Academic Press.