Direct relativistic MP2: properties of ground state CuF, AgF and AuF

A computer program for the calculation of the MP2 energy correction for a Kramers-restricted Dirac-Hartree-Fock four component wave-function is presented. In the spirit of the integral-driven direct SCF scheme the algorithm has been developed as direct MP2, calculating integrals as they are needed and avoiding the integral storage bottle-neck of conventional MP2. Relativistic MP2 is applied to ground state (¹Σ⁺) CuF, AgF and AuF. Received: 15 December 1996 / Accepted: 2 April 1997     

Transfer of protoporphyrin IX between cells

Human adenocarcinoma cells of the line WiDr and human leukemia T cells of the line Jurkat were incubated with 5-aminolevulinic acid and found to produce protoporphyrin IX (PpIX). They were able to transfer a fraction of the sensitizer to neighboring control cells. The transfer took place through direct membrane contact. Light exposures, inactivating about 20% of the sensitized cells, did not result in any acceleration of the transfer of PpIX. This is in contrast to what has been reported for PpIX in erythrocytes from patients with erythropoietic protoporphyria. In these cells light exposure transfers PpIX from the binding sites on hemoglobin to the plasma membrane and further to neighboring cells. The lack of light-induced transfer in the WiDr and Jurkat cells may be related to the binding sites of PpIX, supposedly membrane lipids and proteins embedded therein. Light exposure slightly increased the rate of loss of PpIX from WiDr cells.     

DISTRIBUTION OF 5-AMINOLEVULINIC ACID-INDUCED PORPHYRINS IN NODULOULCERATIVE BASAL CELL CARCINOMA

Abstract— Microscopic fluorescence photometry incorporating a light-sensitive thermo-electrically cooled charge-coupled device (CCD) camera was employed to investigate the fluorescence distribution of 5-aminolevulinic acid (ALA)-induced porphyrins in 22 patients with a total number of 52 noduloul-cerative basal cell carcinomas (BCC) after topical ALA application with or without dimethylsulfoxide (DMSO)/ethylenediaminetetraacetic acid (EDTA) or after intravenous administration of ALA. Both localization patterns and amounts of ALA-induced porphyrins in the BCC were studied. The ALA-induced porphyrins were localized only in the superficial layers of the noduloulcerative BCC lesions after topical application of 20% ALA alone for 3 h. However, both the penetration of ALA into deep lesions and the production of the ALA-induced porphyrin fluorescence were increased after topical administration of 20% ALA and 20% DMSO/4% EDTA for 3 h. Prior treatment with 99% DMSO for 15 min further enhanced the ALA penetration into the BCC lesions after topical application of the ALA/DMSO/EDTA mixture and produced more ALA-induced porphyrins by a factor of about three compared with those treated with ALA alone. The penetration of ALA into the deep BCC lesions could also be increased by prolonging the time of topical application of 20% ALA/4% EDTA to 29–48 h (without DMSO). Intravenous injection of ALA led to a more homogeneous distribution of the ALA-derived porphyrins in the whole noduloulcerative BCC lesions.     

A Facile Formal Synthesis of Volicitin

A short and concise synthesis of volicitin is presented. The synthesis is based on repeated chemoselective copper salt cross coupling reactions of alkynes and propargylic halides.     

Single-strand breaks in the DNA of human cells exposed to visible light from phototherapy lamps in the presence and absence of bilirubin

Clinical evidence indicates that phototherapy of hyperbilirubinaemia in newborn infants is a safe and efficient form of therapy. The short-term side effects are not serious and seem to be well controlled. There are few long-term follow-up studies of phototherapy-treated infants. Therefore one cannot completely exclude the possibility that side effects can be found in future studies. With this background we undertook the present study of possible genotoxic effects of phototherapy. Human cells of the established glioblastoma cell line TMG-1 were used. The cells were exposed to visible light in the presence of different concentrations of bilirubin or in the absence of bilirubin. DNA was unwound in alkaline solution and the induction of strand breaks was assayed by a method taking advantage of the fluorescence from the dye Hoechst 33258. Blue light induced single-strand breaks in the DNA of cells in culture in the absence of bilirubin. During irradiation of bilirubin solutions with blue and green phototherapy light, long-lived toxic photoproducts were formed under in vitro conditions. At high and clinically relevant bilirubin concentrations, the effects of blue and green light were relatively similar. At low concentrations, there was a smaller effect of green light as expected from the absorption spectrum of bilirubin. It remains to be seen whether the genotoxic effect observed in the present studies can occur in vivo.     

Stereoselective Synthesis,Configurational Assignment and Biological Evaluations of the Lipid Mediator RvD2n-3 DPA

Herein we report the first total synthesis of RvD2_{n-3 DPA}, an endogenously formed mediator biosynthesized from the omega-3 fatty acid n-3 docosapentaenoic acid. The key steps are the Midland Alpine borane reduction, Sonogashira cross-coupling reactions, and a Z-selective alkyne reduction protocol, yielding RvD2_{n-3 DPA} methyl ester in 13 % yield over 12 steps (longest linear sequence). The physical property data (UV chromophore, chromatography and MS/MS fragmentation) of the synthetic lipid mediator matched those obtained from biologically produced material. Moreover, synthetic RvD2_{n-3 DPA} also carried the potent biological activities of enhancing macrophage uptake of Staphylococcus aureus and zymosan A bioparticles.     

Eigenfunction analysis of stochastic backscatter for characterization of acoustic aberration in medical ultrasound imaging

Presented here is a characterization of aberration in medical ultrasound imaging. The characterization is optimal in the sense of maximizing the expected energy in a modified beamformer output of the received acoustic backscatter. Aberration correction based on this characterization takes the form of an aberration correction filter. The situation considered is frequently found in applications when imaging organs through a body wall: aberration is introduced in a layer close to the transducer, and acoustic backscatter from a scattering region behind the body wall is measured at the transducer surface. The scattering region consists of scatterers randomly distributed with very short correlation length compared to the acoustic wavelength of the transmit pulse. The scatterer distribution is therefore assumed to be delta correlated. This paper shows how maximizing the expected energy in a modified beamformer output signal naturally leads to eigenfunctions of a Fredholm integral operator, where the associated kernel function is a spatial correlation function of the received stochastic signal. Aberration characterization and aberration correction are presented for simulated data constructed to mimic aberration introduced by the abdominal wall. The results compare well with what is obtainable using data from a simulated point source.     

Aluminium in tea—concentrations, speciation and bioavailability

Tea (Camellia sinensis) is one of a few plants accumulating aluminium (Al), making tea a major source of dietary Al intake. This paper reviews published studies on the concentrations, speciation and bioavailability of Al in tea. With very few exceptions, the total concentration of Al in tea infusions is in the range 1-6 mg l⁻¹. Probably more than 90% of this Al is bound to organic matter, but the nature of the organic species is unclear. Three studies using size exclusion chromatography provide evidence for Al species in the molecular mass (MM) range 4000-8500 Da, probably polyphenolic complexes. Two ultrafiltration studies indicate the presence of Al species with MMs above 10,000. The relative amount of the different organic Al species in tea infusions is unclear, and even the identity of any of these has not been demonstrated with certainty. A possible exception is Al trioxalate, which may be an important species based on evidence from two ²⁷Al-NMR studies. It seems fairly well established that drinking tea leads to measurable, but moderate increases in urinary Al excretion. However, the Al present in tea does not seem to be much more bioavailable than that from other dietary sources. Even so, it cannot be dismissed that tea infusions may contain particularly bioavailable and neurotoxic compounds such as Al maltolate, but this is at present speculative.     

Synthetic efforts towards the protoilludenes. A formal synthesis of Δ-protoilludene

An improved route to 5,8,8-trimethylbicyclo[4.3.0]-4-nonen-3-one, a key intermediate for the synthesis of the protoilludane skeleton and in particular Δ⁷-protoilludene, is reported. Attempts on an alternative synthesis of Δ⁶-protoilludene based on a phenylsulfonyl allene cycloaddition reaction is also presented.