Photodynamic Inactivation of Bacteria in Ionic Environments Using the Photosensitizer SAPYR and the Chelator Citrate†

Many studies show that photodynamic inactivation (PDI) is a powerful tool for the fight against pathogenic, multiresistant bacteria and the closing of hygiene gaps. However, PDI studies have been frequently performed under standardized in vitro conditions comprising artificial laboratory settings. Under real-life conditions, however, PDI encounters substances like ions, proteins, amino acids and fatty acids, potentially hampering the efficacy of PDI to an unpredictable extent. Thus, we investigated PDI with the phenalene-1-one-based photosensitizer SAPYR against Escherichia coli and Staphylococcus aureus in the presence of calcium or magnesium ions, which are ubiquitous in potential fields of PDI applications like in tap water or on tissue surfaces. The addition of citrate should elucidate the potential as a chelator. The results indicate that PDI is clearly affected by such ubiquitous ions depending on its concentration and the type of bacteria. The application of citrate enhanced PDI, especially for Gram-negative bacteria at certain ionic concentrations (e.g. CaCl₂ or MgCl₂: 7.5 to 75 mmol L⁻¹). Citrate also improved PDI efficacy in tap water (especially for Gram-negative bacteria) and synthetic sweat solution (especially for Gram-positive bacteria). In conclusion, the use of chelating agents like citrate may facilitate the application of PDI under real-life conditions.     

Solvent-dependent changes in the triazolinedione-alkene ene reaction mechanism

The influence of the solvent on the triazolinedione-alkene ene reaction mechanism has been investigated. Both inter- and intramolecular kinetic isotope effects with tetramethylethylenes and 2,2,2-(trideuterio)methyl-7-methyl-2,6-octadiene-[D3]-1,1,1 provide, for the first time, strong evidence for changes in the mechanism of the reaction on going from non-protic to polar protic solvents. In non-protic polar or apolar solvents, an aziridinium imide that equilibrates to an insignificant extent with an open intermediate (a dipolar or a polarized biradical) is formed irreversibly in the first, rate-determining step of the reaction, which is followed by fast hydrogen abstraction. On the contrary, in polar protic solvents, hydrogen abstraction is rate limiting, allowing the main dipolar intermediate to equilibrate with its open intermediate(s) as well as with the starting reagents.     

ESR and ENDOR Investigations on Various <Emphasis Type="Italic">Wurster</Emphasis>’s Radical Cations in Solution. Experimental Results,Theoretical <Emphasis Type="Italic">Ab Initio</Emphasis>, and DFT Calculations

Summary. ESR and ENDOR spectra are reported of several symmetrical substituted N,N,N,N-tetraalkyl-p-phenylenediamine radical cations in solution. Different N,N-alkyl substituted para-phenylenediamines, like the ethyl, n-propyl, and iso-propyl derivative are compared with the parent N,N,N,N-tetramethyl-p-phenylenediamine (Wursters Blue Cation). N,N,N,N-Tetrabenzyl-p-phenylenediamine, 1,4-dipyrrolidinylbenzene, and N,N-bis[4-(dimethylamino)phenyl]piperazine are additionally investigated. Experimental and calculated hyperfine coupling constants are compared. Characteristic UV-VIS data and redox potentials in acetonitrile are reported, together with the syntheses of the compounds.     

Automated Hydrogen/Deuterium Exchange Electron Transfer Dissociation High Resolution Mass Spectrometry Measured at Single-Amide Resolution

Hydrogen deuterium exchange mass spectrometry (HDX-MS) is a well established method for the measurement of solution-phase deuterium incorporation into proteins, which can provide insight into protein conformational mobility. However, most HDX measurements are constrained to regions of the protein where pepsin proteolysis allows detection at peptide resolution. Recently, single-amide resolution deuterium incorporation has been achieved by limiting gas-phase scrambling in the mass spectrometer. This was accomplished by employing a combination of soft ionization and desolvation conditions coupled with the radical-driven fragmentation technique electron transfer dissociation (ETD). Here, a hybrid LTQ-Orbitrap XL is systematically evaluated for its utility in providing single-amide deuterium incorporation for differential HDX analysis of a nuclear receptor upon binding small molecule ligands. We are able to show that instrumental parameters can be optimized to minimize scrambling and can be incorporated into an established and fully automated HDX platform making differential single-amide HDX possible for bottom-up analysis of complex systems. We have applied this system to determine differential single amide resolution HDX data for the peroxizome proliferator activated receptor bound with two ligands of interest.     

Deducing the electron-beam diameter in a laser-plasma accelerator using x-ray betatron radiation

We investigate the properties of a laser-plasma electron accelerator as a bright source of keV x-ray radiation. During the interaction, the electrons undergo betatron oscillations and from the carefully measured x-ray spectrum the oscillation amplitude of the electrons can be deduced which decreases with increasing electron energies. From the oscillation amplitude and the independently measured x-ray source size of (1.8±0.3) μm we are able to estimate the electron bunch diameter to be (1.6±0.3) μm.     

A Subnanosecond Time-Resolved Fluorescence Lifetime Spectrometer Applying Laser Diodes

Summary.  Since the first application of laser diodes (LD) for the determination of fluorescence lifetimes in our group in 1995, great technical improvements have been made to increase the time resolution of the apparatus. Using the phase fluorometric method, measurements down to 100 ps are now possible. Values can be measured in steps of 10 ps with good reproducibility using a high-frequency signal generator and a GHz digital storage oscilloscope. No additional optical equipment is necessary for this new method. Following an easy calibration procedure, results are available within one minute without any adjustments. The components of the new apparatus including light source, sample chamber for standard fluorescence cuvettes, and detection unit are situated in a 12 × 13 × 9 cm setup. The apparatus was tested with different fluorophores, and the results correlate very well with known values in the range of 0.1 to 1000 ns. Received February 16, 2000. Accepted March 13, 2000     

Characteristics of membrane-electrode assemblies of hydrogen-air fuel cells with PtCoCr/C catalyst

A cathodic catalyst, which can replace monoplatinum commercial catalyst, is developed and investigated. New catalyst combines a smaller consumption of platinum with a higher mass activity and corrosion resistance. A method of fabrication of ternary (PtCoCr/C) catalyst is improved in order to obtain the catalytic system containing 45–50 wt % platinum. This is necessary to form thinner active layers of cathodes of membrane-electrode assemblies of hydrogen-air fuel cells. The activity of the synthesized PtCoCr/C catalyst is by 1.2–1.5 times higher than that of the monoplatinum catalyst containing 60–70 wt % Pt. According to the accelerated-test data, the corrosion resistance of PtCoCr/C catalyst is also higher than that of Pt/C system.     

Electronic effects in the regioselectivity of the singlet oxygen and 4-methyl-1,2,4-triazoline-3,5-dione ene reactions with isobutenylarenes

The regioselectivity of the ene pathway in the photooxidation of several 1-aryl-2-methylpropenes, as probed by stereoselective deuterium-labeling, depends on the electronic nature of the para phenyl-substituents. The reaction of the same array of alkenylarenes with 4-methyl-1,2,4-triazoline-3,5-dione (MTAD) gives ene products with an impressive >97% allylic hydrogen abstraction from the more substituted side of the alkene.     

A Floquet Operator with Purely Point Spectrum and Energy Instability

An example of Floquet operator with purely point spectrum and energy instability is presented. In the unperturbed energy eigenbasis its eigenfunctions are exponentially localized. CRdeO was partially supported by CNPq (Brazil). MSS was supported by CAPES (Brazil). Submitted: September 21, 2006. Accepted: December 12, 2006.