Dose and timing of the first light fraction in two-fold illumination schemes for topical ALA-mediated photodynamic therapy of hairless mouse skin

A fractionated illumination scheme in which a cumulative fluence of 100 J cm(-2) is delivered in two equal light fractions separated by a dark interval of 2 h has been shown to considerably increase the efficacy of 5-aminolevulinic acid (ALA)-photodynamic therapy (PDT). The efficacy of such a scheme is further increased if the fluence of the first light fraction is reduced to 5 J cm(-2). We have investigated the relationship between the PDT response and the kinetics of protoporphyrin IX (PpIX) fluorescence in the SKH1 HR hairless mouse for first fraction fluences below 5 J cm(-2) delivered 4 h after the application of ALA and 10 J cm(-2) delivered 2 h after the application of ALA. Illumination is performed using 514 nm at a fluence rate of 50 mW cm(-2). Reducing the fluence of the first fraction to 2.5 J cm(-2) does not result in significantly different visual skin damage. The PDT response, however, is significantly reduced if the fluence is lowered to 1 J cm(-2), but this illumination scheme (1 + 99 J cm(-2)) remains significantly more effective than a single illumination of 100 J cm(-2). A first light fraction of 10 J cm(-2) can be delivered 2 h earlier, 2 h after the application of ALA, without significant reduction in the PDT response compared with 5 + 95 J cm(-2) delivered 4 and 6 h after the application of ALA. The kinetics of PpIX fluorescence are consistent with those reported previously by us and do not explain the significant increase in PDT response with a two-fold illumination scheme. Histological sections of the illuminated volume showed a trend toward increasing extent and depth of necrosis for the two-fold illumination scheme in which the first light fraction is 5 J cm(-2), compared with a single illumination scheme.     

Molecular orbital calculations on transition metal clusters

Transition metal clusters have been subject of experimental and theoretical interest due to their catalytic activity, as well as their unusual physical properties. Semi-empirical extended Hückel molecular orbital calculations are presented for a series of small metal clusters with nuclearity ranging from 3 to 6. Naked and carbonylated clusters of Fe, Ru, and Os are studied. The charge transfer between ligands shell and metal core is found to be a function of nuclearity, CO coordination and the chemical species forming the bare cluster. The observed magnetic properties of these systems are discussed in terms of their electronic structure and CO-metal charge transfer.     

Nuclear magnetic resonance studies of sulfur inversion in bis(cyclopentadienyl)-molybdenum and -tungsten complexes with dithioethers

The metallocene thioether derivatives [Cp₂M(MeSCH₂CH₂SMe)][PF₆]₂ (1, M = MO; 2, M = W), [Cp₂Mo(SCH₂CH₂SMe)][PF₆] (3) and [Cp₂M(SCH₂CH₂S)] (4, M = Mo; 5, M = W) exhibit temperature-dependent fluxional behavior in solution, owing to the pyramidal sulfur inversion process. The activation energies for this process were determined from proton band-shape analysis in the cases of 1 (54.9 ± 2 kJ mol⁻¹), 2 (51.2 ± 4.6 kJ mol⁻¹) and 3 (30.0 ± 3.1 kJ mol⁻¹). Extended Hückel calculations on related model complexes suggest that local inversion at the sulfur atoms, rather that an inversion of the complete S---C---C---S chain, is responsible for the observed fluxional behaviour.     

NMR characterization of new 10-membered-ring macrolactones and dihydrobenzophenazine-5-one, oxidized derivatives of benzo[a]phenazines

Peroxidation of the phenazine of beta-lapachone using m-ClC6H4CO3H-CH2Cl2 furnished a macrolactone with a rigid 10-membered ring, and the corresponding N-oxide, along with a dihydrobenzophenazine-5-one. All of the new compounds were fully characterized by spectroscopic methods, with the unambiguous assignment of the hydrogens and carbon NMR signals for the N-oxide, with the aid of 2-D NMR, mainly COSY, HMQC, HSQC and HMBC. For the other two compounds some signals could not be assigned owing to their own intrinsic features.     

Vibrational molecular quantum computing: basis set independence and theoretical realization of the Deutsch-Jozsa algorithm

The phase of quantum gates is one key issue for the implementation of quantum algorithms. In this paper we first investigate the phase evolution of global molecular quantum gates, which are realized by optimally shaped femtosecond laser pulses. The specific laser fields are calculated using the multitarget optimal control algorithm, our modification of the optimal control theory relevant for application in quantum computing. As qubit system we use vibrational modes of polyatomic molecules, here the two IR-active modes of acetylene. Exemplarily, we present our results for a Pi gate, which shows a strong dependence on the phase, leading to a significant decrease in quantum yield. To correct for this unwanted behavior we include pressure on the quantum phase in our multitarget approach. In addition the accuracy of these phase corrected global quantum gates is enhanced. Furthermore we could show that in our molecular approach phase corrected quantum gates and basis set independence are directly linked. Basis set independence is also another property highly required for the performance of quantum algorithms. By realizing the Deutsch-Jozsa algorithm in our two qubit molecular model system, we demonstrate the good performance of our phase corrected and basis set independent quantum gates.     

On-line high-performance liquid chromatography/mass spectrometric characterization of native oligosaccharides from glycoproteins

An on-line high-performance liquid chromatography/mass spectrometry (HPLC/MS) method is described for the rapid characterization of any type of oligosaccharide released from glycoproteins. The procedure can be applied without further manipulation to fractions collected from a high-performance anion-exchange chromatography-pulse amperometric detection (HPAEC-PAD) system commonly used for glycosylation mapping of glycoproteins, or to a pool of oligosaccharides directly released from glycoproteins. The system consists of a porous graphitized high-performance chromatography column (Hypercarb) coupled to a quadrupole time-of-flight (TOF) mass spectrometer. Oligosaccharides are eluted from the column with a gradient of ammonium acetate/acetonitrile and directly identified following in-source fragmentation. Some applications of the method are presented, as well as information about the spectra and fragmentation behavior observed for N- and O-linked oligosaccharides released from some recombinant glycoproteins. Low femtomole limits of detection are achieved using proper miniaturization.     

Reaction of platinum complexes with (+)-α-pinene and (+)-limonene. Synthesis, molecular structure, and catalytic activity of dichloro(η4-[p-mentha-1,8{9}-diene])platinum(II)

The transformations of platinum(II) and platinum(IV) complexes with inner-and outer-sphere ligands by the action of (+)-α-pinene and (+)-limonene were studied. Reduction of the metal complex is the main process whose rate increases in the following outer-sphere ligand series: (Me₂SO)₂H⁺ < Et₃NH⁺ < K^? < H⁺. The reaction of K₂PtCl₄ with α-pinene gave cis-terpine monohydrate and dichloro-η⁴-[p-mentha-1,8(9)-diene]platinum(II), and their structure was proved by X-ray analysis. The complex belongs to monoclinic crystal system, the Pt-Cl and Pt-C bonds therein have different lengths, the ClPtCl angle is 85.88°, and the C=C bond plane is orthogonal to the square coordination core. Dichloro-η⁴-[p-mentha-1,8(9)-diene]-platinum(II) was tested as catalyst in the hydrosilylation of acetophenone with diphenylsilane.     

Determination of pirimicarb and endosulfan in commercial pesticide formulations by Fourier transform infrared spectrometry

A routine method based on Fourier transform infrared spectrometry was developed for the simultaneous determination of pirimicarb and endosulfan in commercially available pesticide formulations. The method is based on peak area absorbance measurements between 1362 and 1352 cm(-1), corrected with a baseline fixed at 1338 cm(-1), for pirimicarb and peak area absorbance measurements between 919 and 909 cm(-1) with a baseline fixed at 931 cm(-1) for endosulfan; chloroform solutions for analysis were obtained by direct dilution of emulsifiable concentrates or by solvent extraction from solid samples. Various extraction conditions and appropriate band selection were investigated, and interference studies were performed. Under the experimental conditions selected, limits of detection of 13 microg/g for pirimicarb and 150 microg/g for endosulfan were obtained that correspond to 0.13 and 1.6% (w/w), respectively, in commercial samples. Results from analyses of commercial samples by the developed method compared well with those obtained by a liquid chromatography reference method.     

Flow injection determination of bismuth in urine by successive retention of Bi(III) and tetrahydroborate(III) on an anion-exchange resin and hydride generation atomic absorption spectrometry

Bismuth as BiCl₄⁻ and BH₄⁻ ware successively retained in a column (150 mm × 4 mm, length × i.d.) packed with Amberlite IRA-410 (strong anion-exchange resin). This was followed by passage of an injected slug of hydrochloric acid resulting in bismuthine generation (BiH₃). BiH₃ was stripped from the eluent solution by the addition of a nitrogen flow and the bulk phases were separated in a gas–liquid separator. Finally, bismutine was atomized in a quartz tube for the subsequent detection of bismuth by atomic absorption spectrometry. Different halide complexes of bismuth (namely, BiBr₄⁻, BiI₄⁻ and BiCl₄⁻) were tested for its pre-concentration, being the chloride complexes which produced the best results. Therefore, a concentration of 0.3 mol l⁻¹ of HCl was added to the samples and calibration solutions. A linear response was obtained between the detection limit (3σ) of 0.225 and 80 μg l⁻¹. The R.S.D.% (n = 10) for a solution containing 50 μg l⁻¹ of Bi was 0.85%. The tolerance of the system to interferences was evaluated by investigating the effect of the following ions: Cu²⁺, Co²⁺, Ni²⁺, Fe³⁺, Cd²⁺, Pb²⁺, Hg²⁺, Zn²⁺, and Mg²⁺. The most severe depression was caused by Hg²⁺, which at 60 mg l⁻¹ caused a 5% depression on the signal. For the other cations, concentrations between 1000 and 10,000 mg l⁻¹ could be tolerated. The system was applied to the determination of Bi in urine of patients under therapy with bismuth subcitrate. The recovery of spikes of 5 and 50 μg l⁻¹ of Bi added to the samples prior to digestion with HNO₃ and H₂O₂ was in satisfactory ranges from 95.0 to 101.0%. The concentrations of bismuth found in six selected samples using this procedure were in good agreement with those obtained by an alternative technique (ETAAS). Finally, the concentration of Bi determined in urine before and after 3 days of treatment were 1.94 ± 1.26 and 9.02 ± 5.82 μg l⁻¹, respectively.