Peculiar relics from Primordial Black Holes in the inflationary paradigm

Depending on various assumptions on the energy scale of inflation and assuming a primordial power spectrum of a step‐like structure, we explore new possibilities for Primordial Black Holes (PBH) and Planck relics to contribute substantially to Cold Dark Matter in the Universe. A recently proposed possibility to produce Planck relics in four‐dimensional string gravity is considered in this framework. Possible experimental detection of PBHs through gravitational waves is also explored. We stress that inflation with a low energy scale, and also possibly when Planck relics are produced, leads unavoidably to relics originating from PBHs that are not effectively classical during their formation, rendering the usual formalism inadequate for them.     

Mössbauer and infrared spectroscopic studies of novel mixed valence states in cobaltous ferrocyanides and ferricyanides

Novel mixed valence states have been obtained by the treatment of cobaltous ferrocyanides (Co⁺²Fe^II) and ferricyanides (Co⁺²Fe^III) in an ozone flow. The CN stretching bands occur at 2085 cm^–1 for Co⁺²Fe^II and at 2160 cm^–1 for Co⁺²Fe^III. After the ozonization process of Co⁺²Fe^II, an intense band approximately at 2125 cm^–1 is detected. This intermediate band must correspond to a mixed valence state of the type: Fe^II–CN–Co²⁺–NC–Fe^III Mössbauer spectra recorded in situ during the ozonization of Co⁺²Fe^II show the presence of two components: a doublet with isomer shift and quadrupole splitting values close to the cobalti ferricyanide and a very broad line for the mixed valence state. From the Mössbauer and infrared spectra of the aged samples of the Co⁺²Fe^II after ozonization, a relaxation process to the initial state of the samples is observed but the mixed valence state is stable.     

FeCp]+-induced hexafunctionalization of hexamethylbenzene with dendrons for the direct synthesis of redox-active iron-centered metallodendrimers

Phenol tri- and nonaallyl dendrons (3 and 7, respectively) were functionalized at the focal position to give the new triallyl dendrons 4 and 6 and the nonaallyl dendrons 11 and 13 that contain a iodoalkyl or a bromobenzyl termini. All these dendrons were used for the [FeCp]+-induced hexafunctionalization of hexamethylbenzene in [FeCp(eta6-C6Me6)][PF6] (1) under mild conditions in the presence of KOH. These reactions directly yielded the 18-allyl and 54-allyl dendrimers 9, 10, and 14 with a [FeCp(eta6-arene)]+ unit located at the dendrimer core. Cyclic voltammetry studies were recorded in THF and DMF with these metallodendrimers and compared with those of analogous dendrimers or complexes of smaller size that contain a [FeCp(eta6-arene)]+ unit at the core. The decreased rate of heterogeneous electron transfer when the dendritic size increases first disclosed by Diederich and Gross is confirmed. The variation of the redox potential of the Fe(II/I) redox system with increasing dendritic size is negligible even in a solvent of high dielectric constant such as DMF. This trend is attributed to fact that the involved "redox" orbital is buried on the metal center, well protected by the shell of alkyl chains (electron-reservoir nature), unlike in ferrocene. The chemical irreversibility increases in THF as the dendrimer size increases, due to more facile ligand substitution with THF at the 19-electron level when the chain bulk increases.     

PHOTODYNAMIC DAMAGE TO EGG LECITHIN LIPOSOMES*

Abstract— Egg lecithin liposomes were lysed by singlet oxygen (¹O*₂) generated by red light irradiation of oxygenated methylene blue (MB⁺) and by superoxide (O^?₂) generated by blue-green irradiation of oxygenated riboflavin (RF) in the presence of ethylenediaminetetraacetic acid (EDTA) or reduced nicotinamide adenine dinucleotide (NADH). The MB⁺/O₂ sensitized process is more efficient in alkaline solutions, attributed to the stabilization of the triplet state di-cation. The small increase of the lysis efficiency from pH4 to pH9 for the RF/EDTA/O₂ system suggests that HO^?₂ may be more damaging than O^?₂. Estimates based on large-target reaction kinetics indicate that ¹O*₂ is about 200 times more effective than superoxide for inducing liposome lysis. Similar experiments with saturated 1 -α-phosphatidylcholine dipalmitoyl liposomes showed no photosensitized lysis for either system.     

TRIPLET EXCITED STATES OF 4'',5''-PHOTOMONOADDUCTS OF 3- CARBETHOXYPSORALEN and 8-METHOXYPSORALEN WITH DNA NUCLEOSIDES

Abstract— Triplet absorption spectra, triplet extinction coefficient and intersystem crossing for 4',5'-monocycloadducts of 3-carbethoxypsoralen (3-CPs) with thymidine (dThd) and uridine (dUrd) in ethanol have been investigated in order to elucidate whether their triplet state properties could be the limitating step for a further photoreaction of 3-CPs monoadducts with DNA nucleosides. The comparison between the triplet characteristics of 4',5'-monoadducts of 3-CPs and those of 8-methoxypsoralen (8-MOP) shows that the quantum yield is much higher in the case of 3-CPs than for 8-MOP. The monofunctionality of 3-CPs cannot therefore be ascribed to the triplet excited states properties of its monoadducts. It is likely that steric hindrance introduced by the bulky carbethoxy group remains a reasonable explanation.