In vivo effects of porphyrins on bacterial DNA.

The DNA damage in intact Staphylococcus aureus and E. coli cells induced by photosensitized deuteroporphyrin or hemin is described. Treatment of S. aureus cultures with hemin or photosensitized deuteroporphyrin (Dp) caused time-dependent changes in the plasmidial DNA profiles. The major observation was the disappearance of the plasmid supercoiled fraction. The chromosomal DNA was also affected by hemin and by photosensitized Dp, since its degradation products were detected after exposing the bacterial cells to the porphyrin drugs. Photosensitization of E. coli cells, pretreated with Dp and polymyxin B nonapeptide (PMBNP), also resulted in plasmidial damage. No such damage occurred when E. coli cultures were treated with hemin and PMBNP. The above results can be tightly correlated with the antimicrobial action of porphyrins. Their damage to the bacterial DNA seems to reflect one of the in vivo effects of these porphyrins.     

Stereochemistry of retro-diel-salder fragmentation in gas-phase ions formed by chemical ionization

Retro Diels Alder fragmentation is highly stereospecific in the diones 1 under chemical ionization conditions, both with methane and isobutane as the reagent gases. Only the cis-isomers yield abundant protonated diene and quinone ions. The isotope effect indicates preferential protonation on a CO oxygen, and a subsequent H-migration prior to the formation of the protonated diene cations in the cis isomers.     

Direct detection of low-concentration NO in physiological solutions by a new GaAs-based sensor

Nitric oxide (NO) acts as a signal molecule in the nervous system, as a defense against infections, as a regulator of blood pressure, and as a gate keeper of blood flow to different organs. In vivo, it is thought to have a lifetime of a few seconds. Therefore, its direct detection at low concentrations is difficult. We report on a new type of hybrid, organic-semiconductor, electronic sensor that makes detection of nitric oxide in physiological solution possible. The mode of action of the device is described to explain how its electrical resistivity changes as a result of NO binding to a layer of native hemin molecules. These molecules are self-assembled on a GaAs surface to which they are attached through a carboxylate binding group. The new sensor provides a fast and simple method for directly detecting NO at concentrations down to 1 microM in physiological aqueous (pH=7.4) solution at room temperature.     

Mixed magnesium and nickel nitrate hexahydrates: an unexpected restructuring

Single crystals of the congruently melting equimolar mixture of magnesium nitrate hexahydrate and nickel nitrate hexahydrate have been grown. The compound crystallizes in a structure foreign to both components, namely in the monoclinic cobalt nitrate hexahydrate structure. The cations are located at random on the cation sub-lattice of the latter crystalline structure.     

Extreme Sub-radiance: Can Quantum Effects Generate Dramatically Longer Atomic Lifetimes?

The prolongation of lifetimes for an excited atom due to the presence of nearby atoms in the ground state is shown to follow simply from unitarity of the time evolution. We also discuss possible approaches to the detection and the overcoming of various technical obstacles.     

Band-gaps in electrostatically controlled dielectric laminates subjected to incremental shear motions

The thickness vibrations of a finitely deformed infinite periodic laminate made out of two layers of dielectric elastomers is studied. The laminate is pre-stretched by inducing a bias electric field perpendicular to the layers. Incremental time-harmonic fields superimposed on the initial finite deformation are considered next. Utilizing the Bloch-Floquet theorem along with the transfer matrix method we determine the dispersion relation which relates the incremental fields frequency and the phase velocity.Ranges of frequencies at which waves cannot propagate are identified whenever the Bloch-parameter is complex. These band-gaps depend on the phases properties, their volume fraction, and most importantly on the electric bias field. Our analysis reveals how these band-gaps can be shifted and their width can be modified by changing the bias electric field. This implies that by controlling the electrostatic bias field desired frequencies can be filtered out. Representative examples of laminates with different combinations of commercially available dielectric elastomers are examined.     

A duality theorem on a pair of simultaneous functional equations

Given P and Q convex compact sets in R^kandR^s, respectively, and u a continuous real valued function on P × Q, we consider the following pair of dual problems: Problem I—Minimize ? so that ?: $\text{P × Q → R}\text{and}\text{? ?}\text{Cav}{}_{\mathrm{p}}\text{Vex}{}_{\mathrm{q}}\text{×}\text{max}\text{(u, ?)}$. Problem II—Maximize g so that g: P × Q → R and g ? Vex_q × Cav_pmin(u, g). Here Cav_p is the operation of concavification of a function with respect to the variable p?P (for each fixed q?Q). Similarly, Vex_q is the operation of convexification with respect to q?Q. Maximum and minimum are taken here in the partial ordering of pointwise comparison: $\text{? ? g}\text{means}\text{?(p, q) ? g(p, q) ?(p, q) ? P × Q}$. It is proved here that both problems have the same solution which is also the unique simultaneous solution of the following pair of functional equations: (i) $\text{? =}\text{Vex}{}_{\mathrm{q}}\text{max}\text{(u, ?)}$. (ii) $\text{? =}\text{Cav}{}_{\mathrm{p}}\text{min}\text{(u, ?)}$. The problem arises in game theory, but the proof here is purely analytical and makes no use of game-theoretical concepts.     

Overcrowded naphthologs of mono-bridged tetraarylethylenes: analogs of bistricyclic aromatic enes

The naphthalogous mono-bridged tetraarylethylenes 9,9′-di-(1-naphthylmethylene)-9H-fluorene (5) and 9,9′-di-(1-naphthylmethylene)-9H-xanthene (6), analogs of bifluorenylidene (1) and bixanthenylidene (2), have been synthesized and their molecular and crystal structures have been determined. Ene 5 has been prepared by two alternative synthetic routes. The molecular structures of 5 and 6 show that each of these enes has very small twist around the central double bond, but the two naphthalene rings in both 5 and 6 are highly twisted. According to the NMR study, 5 and 6 in solution adopt conformations which are similar to those found by X-ray crystal structure analysis. The notable upfield shifts of H¹ and H⁸ (6.11 and 6.83 ppm, respectively) and H² and H⁷ (6.70 and 6.44 ppm, respectively) in 5 and 6 are due to the shielding caused by the nearly orthogonally twisted naphthalene rings. The B3LYP/6-31G(d) calculations of 5, 6, and their 2-naphthyl and phenyl analogs have been performed. In the 1-naphthyl series, the more efficient conjugation between the naphthyl substituents and the central C=C and the overcrowding due to the peri-hydrogen atoms lead to higher twists of the naphthyl groups and to lower twists of the central C=C. In the 2-naphthyl series, the opposite effects are noted. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

Photosensitizer–Antibiotic Conjugates: A Novel Class of Antibacterial Molecules

Bacterial resistance to a variety of antibiotics has led to intensive research into the effect of photosensitizers as a cytotoxic agent against bacterial cells. In this study, we synthesized the following conjugates with or without a linker: rose bengal-penicillanic acid (RBPA), rose bengal-linker-penicillanic acid (RBLPA) and rose bengal-linker-kanamycin (RBLKAN). The antibacterial activity of these conjugates was examined on Staphylococcus aureus and Escherichia coli. Exposure of the cultures to 100 J cm⁻² showed that the minimum inhibitory concentration (MIC) of RBPA, RBLPA and RBLKAN on S. aureus was 0.195, 0.156 and 0.004 μm, respectively. The MIC of RBPA, RBLPA and RBLKAN on E. coli was 1.56, 2.5 and 0.156 μm, respectively. In dark control experiments, the MIC of these conjugates was not detected until a concentration that was 16-fold that of the MIC found in the light experiments. RBPA and RBLPA as well as RBLKAN are bactericidal for both bacterial cells. Total eradication of S. aureus and E. coli was observed with RBLKAN (0.078 and 20 μm 16 J cm⁻², respectively). Under these conditions, scanning electron microscopic analysis showed significant damage to these bacteria. However, the photosensitizer and antibiotics individually were not effective.