Ultradian rhythms of activity in a wild subterranean rodent.

Many animals adapt their activity patterns to the best environmental conditions using daily rhythms. African mole-rats are among the mammals that have become models for studying how these rhythms can be entrained by light or temperature in experimental laboratory studies. However, it is unclear whether they exhibit similar circadian rhythms in their natural lightless, subterranean environment.

Laser fluorescence of dentin caries covered with a novel nano-filled sealant.

The aim of the present study was to assess the possibility to measure caries-induced laser fluorescence underneath a novel nano-filled fissure sealant. Sixty freshly extracted human teeth with occlusal dentine carious lesions were horizontally divided, exposing the respective lesion. Teeth were randomly assigned to three groups: (I) white fissure sealant with filler particles (Fissurit F, Voco), (II) clear fissure sealant without filler particles (Fissurit, Voco) and (III) novel experimental fissure sealant with nano-filler particles (Voco).

Heat generation caused by ablation of restorative materials with an ultrashort pulse laser (USPL) system.

Heat generation during the removal of dental restorative materials may lead to a temperature increase and cause painful sensations or damage dental tissues. The aim of this study was to assess heat generation in dental restoration materials following laser ablation using an ultrashort pulse laser (USPL) system. A total of 225 specimens of phosphate cement (PC), ceramic (CE), and composite (C) were used, evaluating a thickness of 1 to 5 mm each.

Free electron transfer--relations between molecule dynamics and reaction kinetics.

Electron transfer in non-polar media (alkanes, alkyl chlorides) exhibits some essential peculiarities. For instance the reaction of hetero-substituted aromatics with parent solvent radical cations results in the parallel formation of metastable donor radical cations and fragmentation products, in comparable amounts. The fragmentation products originate from a dissociative donor radical cation which decays extremely rapidly, i.

Implantation of artificial penile nodules--a review of literature.

Introduction: The implantation of penile nodules under the foreskin is unusual in Western society. This practice is known in Slavic and Asian cultures and occasionally appears in the western world. We review the historical and medical evidence found in world literature to this date.

Free electron transfer with bifunctional donors: p-aminotritylsilanes.

This work provides an in-depth look at the bimolecular free-electron transfer (FET) from bisubstituted (amine and -CR(2)SiMe(3) groups) aromatic molecules to the solvent radical cations of n-BuCl. Because of the low rotational barriers, the substrates obtain all possible arrangements in solution. The electron jump is an unhindered process that does not require a defined encounter complex.

Ionization of amino-, thio- and hydroxy-naphtalenes via free (unhindered) electron transfer.

The electron transfer from various monosubstituted naphthyl derivatives (naphtols, NpOH; naphtylamines, NpNH2; and thionaphtols, NpSH) to parent n-BuCl radical cations was studied by means of pulse radiolysis. The experiments reveal the synchronous and direct formation of two types of transients: the metastable solute radical cation (NpXH(*+), X = heteroatom) and the corresponding heteroatom-containing radical (NpX(*)) in comparable amounts. This is explained in terms of the free (unhindered) electron transfer in nonpolar solvents, which is a bimolecular process reflecting femtosecond time scale events of intramolecular dynamic motions accompanied by significant changes of the electron distribution within the donor molecule.

Kinetic and energetic analysis of the free electron transfer.

In this paper, the bimolecular free (unhindered) electron transfer (FET) from various trityl-containing compounds to the solvent radical cations of n-BuCl is described. In good agreement with the previously studied cases, the FET involving trityl-derived compounds results in the formation of two different types of the radical cation, which undergo the subsequent fragmentation via two alternative reaction channels. This unusual effect is caused by the intramolecular rotational motion in the ground-state molecules around the arrow-marked bond Ar-//-X-CPh 3 (Ar = aromatic moiety; X = S, O, NH, CH 2), since such oscillations are directly connected with the electron distribution within the molecule.

Ionization of aromatic sulfides in nonpolar media: free vs reaction-controlled electron transfer.

The primary products of the bimolecular free electron transfer (FET) from aromatic sulfides (PhSCH2Ph, PhSCHPh2, PhSCPh3) to n-butyl chloride radical cations are two radical cation conformers: a dissociative and a metastable one. In analogy with formerly studied donor systems, this result seems to reflect femtosecond oscillations in the ground state of the sulfides such as torsion motions around the Ar-S bond. This motion is accompanied by a marked electron fluctuation within the HOMO (or the n) orbitals.

Evaluation of selective calculus removal by a fluorescence feedback-controlled Er:YAG laser in vitro.

Objectives: To evaluate the removal of subgingival calculus and dental hard tissues depending on the threshold level of a fluorescence feedback-controlled Er:YAG laser.

Material And Methods: Twenty teeth with calculus on the root surface were treated with an Er:YAG laser. Laser settings were 140 mJ and 10 Hz.

Femtodynamics reflected in nanoseconds: bimolecular free electron transfer in nonpolar media.

The (free) electron transfer (FET) from electron donor molecules to parent solvent radical cations of alkanes and alkyl chlorides exhibits mechanistic peculiarities that are conditioned by the low polarity of these solvents. Because of the negligible solvation of ions in such systems and the almost complete lack of an activation barrier, the electron jump takes place at the very first encounter of the reactants and, as such, in extremely short times of View Article and Find Full Text PDF

Thiyl radical interaction with pyrimidine C5-C6 double bond.

Addition and elimination interaction of thiyl radicals with the C5-C6 double bond in pyrimidines was studied by the pulse radiolysis technique in aqueous solution with the use of different monitoring systems. For this purpose, p-thiocresol, cysteamine hydrochloride, and mercaptoethanol were used. The rate constants of addition and elimination of thiyl radicals were determined by applying the modified version of ACUCHEM (computer program for modeling complex reaction systems).

Ionization of cyclic aromatic amines by free electron transfer: products are governed by molecule flexibility.

The bimolecular electron transfer from secondary aromatic amines to parent radical cations of nonpolar solvents such as alkanes and alkyl chlorides results in the synchronous formation of amine radical cations as well as aminyl radicals, in comparable amounts. If as for cyclic aromatic amines (c-Ar(2)NH) the intramolecular bending motion around the amine group is restricted in varying degrees (acridane, phenothiazine) or completely prevented (carbazole), then this picture is modified. In the free electron transfer, the completely rigid carbazole yields exclusively amine radical cations.

Quantitative description of the deactivation channels of the first excited singlet state of 2- and 4-thiosalicylic acids.

On the bases of picosecond and nanosecond laser flash photolysis with detection by emission and absorption spectroscopy, a quantitative description is given of all of the deactivation channels of the first excited singlet state of 2- and 4-thiosalicyclic acids (TS) such as fluorescence, intersystem crossing (ISC), chemical dissociation into radicals, and radiationless internal conversion (IC). For this purpose, the investigated compounds were studied in solvents of increasing polarity: 1-chlorobutane, acetonitrile, ethanol, and water. As an exception for thiols, and in contrast to recent findings on thiophenol and its methyl- and methoxy-substituted derivatives, the photoinduced first excited triplet state of the thiosalicyclic acids was directly observed by its T1-T(n) absorption spectra and characterized by sensitization experiments.

Ionization of aniline and its N-methyl and N-phenyl substituted derivatives by (free) electron transfer to n-butyl chloride parent radical cations.

The electron transfer from aniline and its N-methyl as well as N-phenyl substituted derivatives (N-methylaniline, N,N-dimethylaniline, diphenylamine, triphenylamine) to parent solvent radical cations was studied by electron pulse radiolysis in n-butyl chloride solution. The ionization results in the case of aniline (ArNH2) and the secondary aromatic amines (Ar2NH, Ar(Me)NH) in the synchronous and direct formation of amine radical cations, as well as aminyl radicals, in comparable amounts. Subsequently, ArNH2*+ deprotonates in a delayed reaction with the present nucleophile Cl-, and forms further ArNH*.

Repair reactions of pyrimidine-derived radicals by aliphatic thiols.

Pyrimidinyl radicals of various structures (Pyr*) were generated in aqueous and alcohol-containing solutions by means of pulse radiolysis to determine the rate constants of their repair reactions by different thiols (RSH = cysteamine, 2-mercaptoethanol, cysteine, and penicillamine): Pyr* + RSH --> PyrH + RS*. C5-OH and C6-OH adduct radicals of the pyrimidines react with thiols with k9 = (1.2-10.

Deactivation of the first excited singlet state of thiophenols.

On the bases of picosecond and nanosecond laser flash photolysis with detection by emission and absorption spectroscopy, a quantitative description is given of all deactivation channels of the first excited singlet state of thiophenols ArSH(S(1)) such as fluorescence, intersystem crossing (ISC), chemical dissociation into radicals, and radiation-less internal conversion (IC). For this purpose, the photolysis of thiophenol and its methyl-, methoxy-, and chloro-substituted derivatives was studied in solvents of increasing polarity: 1-chlorobutane, ethanol, and acetonitrile. The fluorescence lifetime of the thiophenols was found to range from some hundreds of picoseconds up to a few nanoseconds, correlating with fluorescence quantum yields between 0.

Free electron transfer from xanthenyl- and fluorenylsilanes (Me3 or Ph3) to parent solvent radical cations: effects of molecule dynamics.

Parent radical cations of nonpolar solvents (alkanes and alkyl chlorides) ionize 9-(trimethylsilyl)xanthenes and 9-(trimethylsilyl)fluorenes in a diffusion-controlled electron transfer. The actual electron jump as the deciding part of the process does not require a defined encounter complex, and therefore the reactants are not subjected to any geometry optimization. Considering the molecule dynamics of the donors, bending motions of the silyl group are concerted with fluctuations of the highest occupied molecular orbital electrons.

Thiyl radicals in biosystems: effects on lipid structures and metabolisms.

Thiyl radicals are intermediates of enzyme- and radical-driven biochemical processes, and their potential as reactive species in the biological environment has been somehow underestimated. From organic chemistry, however, it is known that thiyl radicals isomerize the double bonds of unsaturated fatty acids to a mixture with very dominating trans isomers. Recently, this reaction has been particularly studied for biosystems, focusing on the effect of thiyl radicals on the natural all-cis double bonds of unsaturated phospholipids, which undergo a conversion to the unnatural trans form.

Trans lipid formation induced by thiols in human monocytic leukemia cells.

Trans lipids in humans originate exogenously from the ingestion of isomerized fats. An endogenous path comprising a thiyl radical-catalyzed cis-trans isomerization of cis-unsaturated phospholipids was proposed. However, whether an isomerization process might be feasible in eukaryotic cells remained to be established.

Radiation-induced free-radical transformation of phospholipids: MALDI-TOF MS study.

Under the action of free-radical reaction initiators on membrane phospholipids, complex processes are taking place in both hydrophobic and hydrophilic parts of the phospholipids. Realization of these processes results in a mixture consisting of the initial lipids and their peroxidation and fragmentation products. Identification of compounds in such mixtures requires analytical methods of high sensitivity, reproducibility and accuracy to be applied.

Radiation-induced fragmentation of cardiolipin in a model membrane.

Purpose: To obtain evidence for the possibility of free-radical fragmentation of cardiolipin under the action of ionizing radiation as measured by its aqueous dispersion from liposomes.

Materials And Methods: Liposomes of tetramyristoylcardiolipin (TMCL) were exposed to gamma-rays from 60Co or 137Cs sources at doses between 1 and 24kGy. Fragmentation products were identified using thin-layer chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS).

Formation of phosphatidic acid, ceramide, and diglyceride on radiolysis of lipids: identification by MALDI-TOF mass spectrometry.

By use of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, phosphatidic acid was found to be the main product of gamma radiolysis of cardiolipin, phosphatidylinositol, and phosphatidylglycerol. It has been shown that gamma irradiation of such glycolipids as cerebroside and galactosyl diglyceride leads to formation of ceramide and diglyceride, respectively. These findings, combined with those obtained earlier, allowed an assumption to be made that, owing to radiation-induced free radical fragmentation of lipids in their polar moiety, formation of signaling molecules can occur.

Highly conjugated p-quinonoid pi-extended tetrathiafulvalene derivatives: a class of highly distorted electron donors.

A new class of pi-extended TTF-type electron donors (11 a-c) has been synthesized by Wittig-Horner olefination of bianthrone (9) with 1,3-dithiole phosphonate esters (10 a-c). In cyclic voltammetry experiments, donors 11 a-c reveal a single, electrochemically irreversible oxidation-yielding the corresponding dicationic products-at relatively low oxidation potentials (approximately 0.7-0.