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Transient Species (transient + species)
Selected AbstractsLaser Flash Photolysis of Disulfonyldiazomethanes: Partitioning between Hetero-Wolff Rearrangement and Intramolecular Carbene Oxidation by a Sulfonyl GroupEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 11 2003Götz Bucher Abstract Laser flash photolysis of bis(phenylsulfonyl)diazomethane (1a) and ditosyldiazomethane (1b) leads to the formation of sulfonylsulfenes 8a/8b (,max = 310 nm). Non-first-order kinetics and non-linear Stern,Volmer behavior suggest the formation of another transient species also absorbing at , = 310 nm. Based on the results of DFT calculations, these species are tentatively identified as dithiocarbonate S,S,S, -trioxides 12a/b, which are formed from the oxathiirene S -oxides 9a/b. The latter compounds bear the characteristics of masked carbenes (, estimated as 700 ps) and are quenched by methanol and cyclooctene. Singlet disulfonylcarbenes 2a/b are not predicted to be minima, since all attempts at optimizing the geometry of 2a led to 9a instead. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Ecological effects of perturbation by drought in flowing watersFRESHWATER BIOLOGY, Issue 7 2003P. S. Lake SUMMARY 1Knowledge of the ecology of droughts in flowing waters is scattered and fragmentary, with much of the available information being gathered opportunistically. Studies on intermittent and arid-zone streams have provided most of the information. 2Drought in streams may be viewed as a disturbance in which water inflow, river flow and water availability fall to extremely low levels for extended periods of time. As an ecological perturbation, there is the disturbance of drought and the responses of the biota to the drought. 3Droughts can either be periodic, seasonal or supra-seasonal events. The types of disturbance for seasonal droughts are presses and for supra-seasonal droughts, ramps. 4In droughts, hydrological connectivity is disrupted. Such disruption range from flow reduction to complete loss of surface water and connectivity. The longitudinal patterns along streams as to where flow ceases and drying up occurs differs between streams. Three patterns are outlined: ,downstream drying', ,headwater drying' and ,mid-reach drying'. 5There are both direct and indirect effects of drought on stream ecosystems. Marked direct effects include loss of water, loss of habitat for aquatic organisms and loss of stream connectivity. Indirect effects include the deterioration of water quality, alteration of food resources, and changes in the strength and structure of interspecific interactions. 6Droughts have marked effects on the densities and size- or age-structure of populations, on community composition and diversity, and on ecosystem processes. 7Organisms can resist the effects of drought by the use of refugia. Survival in refugia may strongly influence the capacity of the biota to recover from droughts once they break. 8Recovery by biota varies markedly between seasonal and supra-seasonal droughts. Faunal recovery from seasonal droughts follows predictable sequences, whilst recovery from supra-seasonal droughts varies from one case to another and may be marked by dense populations of transient species and the depletion of biota that normally occur in the streams. 9The restoration of streams must include the provision of drought refugia and the inclusion of drought in the long-term flow regime. [source] Rare species in communities of tropical insect herbivores: pondering the mystery of singletonsOIKOS, Issue 3 2000Vojtech Novotný The host specificity, taxonomic composition and feeding guild of rare species were studied in communities of herbivorous insects in New Guinea. Leaf-chewing and sap-sucking insects (Orthoptera, Phasmatodea, Coleoptera, Lepidoptera and Hemiptera-Auchenorrhyncha) were sampled from 30 species of trees and shrubs (15 spp. of Ficus, Moraceae, six spp. of Macaranga and nine species of other Euphorbiaceae) in a lowland rain forest. Feeding trials were performed with all leaf-chewers in order to exclude transient species. Overall, the sampling produced 80,062 individuals of 1050 species. The species accumulation curve did not attain an asymptote, despite 950 person-days of sampling. Rare species, defined as those found as single individuals, remained numerous even in large samples and after the exclusion of transient, non-feeding species. There was no difference among plant species in the proportion of rare species in their herbivore communities, which was, on average, 45%. Likewise, various herbivore guilds and taxa had all very similar proportions of rare and common species. There was also no difference between rare and common species in their host specificity. Both highly specialised species and generalists, feeding on numerous plants, contributed to the singleton records on particular plant species. Predominantly, a species was rare on a particular host whilst more common on other, often related, host species, or relatively rare on numerous other host plants, so that its aggregate population was high. Both cases are an example of the "mass effect", since it is probable that such rare species were dependent on a constant influx of immigrants from the other host plants. These other plants were found particularly often among congeneric plants, less so among confamilial plants from different genera and least frequently among plants from different families. There were also 278 very rare species, found as one individual on a single plant species only. Their host specificity could not be assessed; they might have been either very rare specialists, or species feeding also on other plants, those that were not studied. The former possibility is unlikely since monophagous species, collected as singletons at the present sampling effort, would have existed at an extremely low population density, less than 1 individual per 10 ha of the forest. [source] Primary Photoprocesses in a Fluoroquinolone Antibiotic Sarafloxacin,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 4 2009Fernando Lorenzo The photophysical properties of the fluoroquinolone antibiotic sarafloxacin (SFX) were investigated in aqueous media. SFX in water, at pH 7.4, shows intense absorption with peaks at 272, 322 and 335 nm, (, = 36800 and 17000 dm3 mol,1 cm,1, respectively). Both the absorption and emission properties of SFX are pH-dependent; pKa values for the protonation equilibria of both the ground (5.8 and 9.1) and excited singlet states (5.7 and 9.0) of SFX were determined spectroscopically. SFX fluoresces weakly, the quantum yield for fluorescence emission being maximum (0.07) at pH 8. Laser flash photolysis and pulse radiolysis studies have been carried out in order to characterize the transient species of SFX in aqueous solution. Triplet,triplet absorption has a maximum at 610 nm with a molar absorption coefficient of 17,000 ± 1000 dm3 mol,1 cm,1. The quantum yield of triplet formation has been determined to be 0.35 ± 0.05. In the presence of oxygen, the triplet reacts to form excited singlet oxygen with quantum yield of 0.10. The initial triplet (3A*) was found to react with phosphate buffer to form triplet 3B* with lower energy and longer lifetime and having an absorption band centered at 700 nm. SFX triplet was also found to oxidize tryptophan to its radical with concomitant formation of the anion radical of SFX. Hence the photosensitivity of SFX could be initiated by the oxygen radicals and/or by SFX radicals acting as haptens. [source] Primary Photophysical Properties of Moxifloxacin, A Fluoroquinolone AntibioticPHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 5 2008Fernando Lorenzo The photophysical properties of the fluoroquinolone antibiotic moxifloxacin (MOX) were investigated in aqueous media. MOX in water, at pH 7.4, shows two intense absorption bands at 287 and 338 nm (, = 44 000 and 17 000 dm3 mol,1 cm,1, respectively). The absorption and emission properties of MOX are pH-dependent, pKa values for the protonation equilibria of both the ground (6.1 and 9.6) and excited singlet states (6.8 and 9.1) of MOX were determined spectroscopically. MOX fluoresces weakly, the quantum yield for fluorescence emission being maximum (0.07) at pH 8. Phosphorescence from the excited triplet state in frozen ethanol solution has a quantum yield of 0.046. Laser flash photolysis and pulse radiolysis studies have been carried out to characterize the transient species of MOX in aqueous solution. On laser excitation, MOX undergoes monophotonic photoionization with a quantum yield of 0.14. This leads to the formation of a long-lived cation radical whose absorption is maximum at 470 nm (,470 = 3400 dm3 mol,1 cm,1). The photoionization process releases hydrated electron which rapidly reacts (k = 2.8 × 1010 dm3 mol,1 s,1) with ground state MOX, yielding a long-lived anion radical with maximum absorption at 390 nm (,390 = 2400 dm3 mol,1 cm,1). The cation radical of MOX is able to oxidize protein components tryptophan and tyrosine. The bimolecular rate constants for these reactions are 2.3 × 108 dm3 mol,1 s,1 and 1.3 × 108 dm3 mol,1 s,1, respectively. Singlet oxygen sensitized by the MOX triplet state was also detected only in oxygen-saturated D2O solutions, with a quantum yield of 0.075. [source] Coupling of Protonation Switches During Rhodopsin Activation,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 2 2007Reiner Vogel Recent studies of the activation mechanism of rhodopsin involving Fourier-transform infrared spectroscopy and a combination of chromophore modifications and site-directed mutagenesis reveal an allosteric coupling between two protonation switches. In particular, the ring and the 9-methyl group of the all- trans retinal chromophore serve to couple two proton-dependent activation steps: proton uptake by a cytoplasmic network between transmembrane (TM) helices 3 and 6 around the conserved ERY (Glu-Arg-Tyr) motif and disruption of a salt bridge between the retinal protonated Schiff base (PSB) and a protein counterion in the TM core of the receptor. Retinal analogs lacking the ring or 9-methyl group are only partial agonists,the conformational equilibrium between inactive Meta I and active Meta II photoproduct states is shifted to Meta I. An artificial pigment was engineered, in which the ring of retinal was removed and the PSB salt bridge was weakened by fluorination of C14 of the retinal polyene. These modifications abolished allosteric coupling of the proton switches and resulted in a stabilized Meta I state with a deprotonated Schiff base (Meta ISB). This state had a partial Meta II-like conformation due to disruption of the PSB salt bridge, but still lacked the cytoplasmic proton uptake reaction characteristic of the final transition to Meta II. As activation of native rhodopsin is known to involve deprotonation of the retinal Schiff base prior to formation of Meta II, this Meta ISB state may serve as a model for the structural characterization of a key transient species in the activation pathway of a prototypical G protein-coupled receptor. [source] Environmental Effects on the Photochemistry of A2-E, a Component of Human Retinal Lipofuscin,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 3 2001Laura Ragauskaite ABSTRACT Several retinal dystrophies are associated with the accumulation of lipofuscin, a pigment mixture, in the retinal pigment epithelium (RPE). One of the major fluorophores of this mixture has been identified as the bis-retinoid pyridinium compound, A2-E. Because this compound absorbs incident radiation that is transmitted by the anterior segment of the human eye, photophysical and photochemical studies were performed to determine if A2-E could photosensitize potentially damaging reactions. Steady-state fluorescence measurements indicate that the fluorescence emission maximum and quantum yield are very sensitive to the chemical environment and a correlation between these two parameters and the solvent dielectric constant is observed. Time-resolved absorption experiments of A2-E in pure organic solvents showed no formation of transient species on the timescale of our experiments. However, when these measurements were repeated for A2-E in Triton X-100 micelles, a short-lived (,, 14 ,s), weak absorption was observed. This species is quenched by oxygen (k= 2 × 109M,1 s,1) and by the addition of the antioxidants, cysteine and N,N,N,,N, -tetramethylphenylenediamine. Quenching of this species by 2,3,5-trimethylhydroquinone results in the formation of the 2,3,5-trimethylsemiquinone free radical and an increase in yield of the A2-E,derived species. Sensitization of the A2-E triplet excited state indicates that the species observed in micelles upon direct excitation is not consistent with the triplet excited state. Based on these data we tentatively assign this absorption to a free radical. In the RPE these initial processes can ultimately lead to damage to the tissue through the formation of peroxides and other oxidized species. [source] A Time-Resolved Spectroscopic Study of the Bichromophoric Phototrigger 3,,5,-Dimethoxybenzoin Diethyl Phosphate: Interaction Between the Two Chromophores Determines the Reaction PathwayCHEMISTRY - A EUROPEAN JOURNAL, Issue 17 2010Chensheng Ma Dr. Abstract 3,,5,-Dimethoxybenzoin (DMB) is a bichromophoric system that has widespread application as a highly efficient photoremovable protecting group (PRPG) for the release of diverse functional groups. The photodeprotection of DMB phototriggers is remarkably clean, and is accompanied by the formation of a biologically benign cyclization product, 3,,5,-dimethoxybenzofuran (DMBF). The underlying mechanism of the DMB deprotection and cyclization has, however, until now remained unclear. Femtosecond transient absorption (fs-TA) spectroscopy and nanosecond time-resolved resonance Raman (ns-TR3) spectroscopy were employed to detect the transient species directly, and examine the dynamic transformations involved in the primary photoreactions for DMB diethyl phosphate (DMBDP) in acetonitrile (CH3CN). To assess the electronic character and the role played by the individual sub-chromophore, that is, the benzoyl, and the di- meta -methoxybenzylic moieties, for the DMBDP deprotection, comparative fs-TA measurements were also carried out for the reference compounds diethyl phosphate acetophenone (DPAP), and 3,,5,-dimethoxybenzylic diethyl phosphate (DMBnDP) in the same solvent. Comparison of the fs-TA spectra reveals that the photoexcited DMBDP exhibits distinctly different spectral character and dynamic evolution from those of the reference compounds. This fact, combined with the related steady-state spectral and density functional theoretical results, strongly suggests the presence in DMBDP of a significant interaction between the two sub-chromophores, and that this interaction plays a governing role in determining the nature of the photoexcitation and the reaction channel of the subsequent photophysical and photochemical transformations. The ns-TR3 results and their correlation with the fs-TA spectra and dynamics provide evidence for a novel concerted deprotection,cyclization mechanism for DMBDP in CH3CN. By monitoring the direct generation of the transient DMBF product, the cyclization time constant was determined unequivocally to be ,1,ns. This indicates that there is little relevance for the long-lived intermediates (>10,ns) in giving the DMBF product, and excludes the stepwise mechanism proposed in the literature as the major pathway for the DMB cyclization reaction. This work provides important new insights into the origin of the 3,,5,-dimethoxy substitution effect for the DMB photodeprotection. It also helps to clarify the many different views presented in previous mechanistic studies of the DMB PRPGs. In addition to this, our fs-TA results on the reference compound DMBnDP in CH3CN provide the first direct observation (to the best of our knowledge) showing the predominance of a prompt (,2,ps) heterolytic bond cleavage after photoexcitation of meta -methoxybenzylic compounds. This provides insight into the long-term controversies about the photoinitiated dissociation mode of related substituted benzylic compounds. [source] ,-Carbonyl Substituent Effect on the Lifetimes of Triplet 1,4-Biradicals from Norrish-Type-II ReactionsCHEMISTRY - A EUROPEAN JOURNAL, Issue 17 2006Xichen Cai Dr. Abstract Triplet 1,4-biradicals were generated by Norrish-Type-II hydrogen transfer from ,-heteroatom-substituted ,-branched butyrophenones 1,6 and detected by laser flash absorption measurements. For three oxy-substituted compounds 2,4 (R,=OH, OCOMe, OCOOEt) comparable lifetimes were determined in acetonitrile (roughly 1.5 ,s). In benzene, divergent trends were observed: for the hydroxy compound 2 a lower lifetime of 790 ns was determined, whereas for 3 and 4 the lifetimes increased to 4.9 ,s. Photolyses of the ,-amino-substituted compounds 1 and 6 resulted in transient species with significant lower lifetimes (for 1 160 ns in benzene and 450 ns in acetonitrile; for 6 <100 ns in both solvents). The mesyloxy substrate 5 undergoes rapid CO bond cleavage upon photolysis and no transient triplet species were detected. Computational (UB3,LYP/6,31G* and natural don orbital (NBO) analyses) results supported the assumption of a negative hyperconjugative interaction strongly stabilizing ,-oxy-substituted over ,-amino-substituted radicals. [source] Photophysical and Phototoxic Properties of the Antibacterial Fluoroquinolones Levofloxacin and MoxifloxacinCHEMISTRY & BIODIVERSITY, Issue 5 2004Giampietro Viola Two antibacterial fluoroquinolones, levofloxacin and moxifloxacin, were investigated to evaluate their photophysical properties and to explore the mechanism of their phototoxicity. Photophysical experiments were carried out in aqueous solution by stationary and time-resolved fluorimetry, and by laser flash photolysis, to obtain information on the various decay pathways of the excited states of the drugs and on transient species formed upon irradiation. The results obtained show that levofloxacin is able to photosensitize red blood cell lysis in an oxygen-independent way and induce a high decrease in cell viability after UVA irradiation, although to a lesser degree than the racemic mixture ofloxacin. Moxifloxacin, which is an 8-MeO-substituted fluoroquinolone, is less phototoxic than the other compounds. Cellular phototoxicity was inhibited by the addition of superoxide dismutase, catalase, and free radical and hydroxyl radical scavengers (BHA, GSH, mannitol, and DMTU), indicating the involvement of superoxide anion and/or a radical mechanism in their cytotoxicity. A good correlation was observed between lipid peroxidation, protein photodamage, and cellular phototoxicity, indicating that test compounds exert their toxic effects mainly in the cellular membrane. Experiments carried out on pBR322 DNA show that these derivatives do not significantly photocleave DNA directly, but single-strand breaks were evidenced after treatment of photosensitized DNA by two base-excision-repair enzymes, and Endo III. [source] | |||||||||||||