UV tolerance in the two-spotted spider mite, Tetranychus urticae

The two-spotted spider mite, Tetranychus urticae was exposed to UV-C (250 nm), UV-B (300 nm), and UV-A (350 nm). In non-diapausing females, the median effective doses for 50% mortality plus escape incidence (ED₅₀) were 21 (UV-C) and 104 kJ m⁻² (UV-B); those for 50% oviposition rate in continuous darkness-treated mites were 6.2 (UV-C) and 41 kJ m⁻² (UV-B). No significant effects of UV-A on mortality and oviposition rate were observed. The ED₅₀ values for UV-B were similar to the natural UV-B observed for 2-5 days in summer when T. urticae inhabits the undersides of leaves. Therefore, T. urticae possibly uses leaves as a filter to avoid the deleterious effects of UV-B. In diapausing females, low mortality was observed even at high doses of UV radiation, but more than half escaped even at low doses. The orange body color of diapausing females results from accumulation of carotenoids, a scavenger for UV-induced reactive oxygen species; this may explain the low mortality of diapausing females. Diapausing females may overcome the deleterious effects of UV-B during winter in the absence of leaves by emigrating to UV-free environments and by accumulating carotenoids.     

In assessing biological UV-B effects,natural fluctuations of solar radiation should be taken into account

Daily and weekly fluctuations of PAR, UV-A, and UV-B have been continuously monitored for 5 months in Ancient Korinthos, Greece (37°58 N, 23°0 E) using a calibrated instrument based on 3 sharp band sensors. Daily dose ranged between 521–12 006 kJ m^-2 for PAR; 52–1, 239 kJ m^-2 for UV-A; and 0.66–22.5 kJ m² for UV-B. Weekly dose ranged between 16 778-81 788 kJ m^-2 for PAR; 1 406–8 517 kJ m^-2 for UV-A; and 18–151 kJ m^-2 for UV-B. UV-B/PAR and UV-A/PAR ratio distribution, however, does not follow closely PAR fluctuations. Generally, the UV-B/PAR and UV-A/PAR ratios were high in bright light conditions (2.1×10^-3, 118×10^-3) and low in darker weeks (0.9×10^-3, 63×10^-3. The UV-B/UV-A ratio exhibits smaller fluctuations with season (20x1×10^-3, 12×10^-3). Attention is drawn to the effects of sudden changes in ambient radiation and to the ratios of UV-B, UV-A, and PAR.     

Photoproduction of dissolved inorganic carbon in temperate and tropical lakes – dependence on wavelength band and dissolved organic carbon concentration

We have evaluated photoeffects of UV-B, UV-A and PAR radiation on dissolved organic matter (DOM). Photochemical production of dissolved inorganic carbon (DIC) was measured in sterile lake water from Sweden and Brazil after 6 hours of sun exposure. Tubes were exposed to four solar radiation regimes: Full-radiation, Full-radiation minus UV-B, Full-radiation minus UV-B and UV-A (PAR) and darkness.In both areas, lakes with most DOC (varying between 3 and 40 mg C l^-1) were highly humic, resulting in high UV-B attenuation coefficients (K_d = 5–466 m^-1). Under Full-radiation, photooxidative DIC-production varied from 0.09 to 1.7 mg C l^-1per 6 h, without UV-B from 0.07 to 1.4 mg C l^-1 and with PAR only from 0.02 to 0.7 mg C l^-1. UV-B radiation explains a minor part (17%) of the photoooxidative DIC-production, while UV-A and PAR have larger effects (39% and 44%, respectively). Photooxidation was proportional to DOC-content and DIC-production was positively related to decrease in DOC and to loss of absorbance at 250 nm. There was no significant difference in DOC and radiation normalized DIC-production between Swedish and Brazilian lakes. The UV-B dose during incubations was approximately 3 times higher in Brazil compared to Sweden, while UV-A and PAR doses were similar. We conclude that DOC from tropical and temperate freshwaters do not seem to differ with respect to sensitivity to photooxidation.     

Dynamic response of UV-absorbing compounds, quantum yield and the xanthophyll cycle to diel changes in UV-B and photosynthetic radiations in an aquatic liverwort

We studied the diel responses of the liverwort Jungermannia exsertifolia subsp. cordifolia to radiation changes under laboratory conditions. The samples were exposed to three radiation regimes: P (only PAR), PA (PAR + UV-A), and PAB (PAR + UV-A + UV-B). The day was divided in four periods: darkness, a first low-PAR period, the high-PAR plus UV period, and a second low-PAR period. After 15 days of culture, we measured photosynthetic pigments, chlorophyll fluorescence and UV-absorbing compounds in the four periods of the day on two consecutive days. With respect to UV-absorbing compounds, we analyzed their global amount (as the bulk UV absorbance of methanolic extracts) and the concentration of seven hydroxycinnamic acid derivatives, both in the soluble (mainly vacuolar) and insoluble (cell wall-bound) fractions of the plant extracts. PAB samples increased the bulk UV absorbance of the soluble and insoluble fractions, and the concentrations of p-coumaroylmalic acid in the soluble fraction and p-coumaric acid in the cell wall. Most of these variables showed significant diel changes and responded within a few hours to radiation changes (more strongly to UV-B), increasing at the end of the period of high-PAR plus UV. F_v/F_m, Φ_PSII, NPQ and the components of the xanthophyll cycle showed significant and quick diel changes in response to high PAR, UV-A and UV-B radiation, indicating dynamic photoinhibition and protection of PSII from excess radiation through the xanthophyll cycle. Thus, the liverwort showed a dynamic protection and acclimation capacity to the irradiance level and spectral characteristics of the radiation received.     

Temporal dynamics of ROS biogenesis under simulated solar radiation in the cyanobacterium Anabaena variabilis PCC 7937

We studied the temporal generation of reactive oxygen species (ROS) in the cyanobacterium Anabaena variabilis PCC 7937 under simulated solar radiation using WG 280, WG 295, WG 305, WG 320, WG 335, WG 345, and GG 400 nm cut-off filters to find out the minimum exposure time and most effective region of the solar spectrum inducing highest level of ROS. There was no significant generation of ROS in all treatments in comparison to the samples kept in the dark during the first 8 h of exposure; however, after 12 h of exposure, ROS were significantly generated in samples covered with 305, 295, or 280 nm cut-off filters. In contrast with ROS, the fragmentation of filaments was predominantly seen in 280 nm cut-off filter covered samples after 12 h of exposure. After 24 h of exposure, ROS levels were significantly higher in all samples than in the dark; however, the ROS signals were more pronounced in 320, 305, 295, or 280 nm cut-off filter covered samples. In contrast, the length of filaments was reduced in 305, 295, or 280 nm cut-off filter covered samples after 24 h of exposure. Thus, fragmentation of the filament was induced by all wavelengths of the UV-B region contrary to the UV-A region where only shorter wavelengths were able to induce the fragmentation. In contrast, ROS were generated by all wavelengths of the solar spectrum after 24 h of exposure; however, shorter wavelengths of both the UV-A and the UV-B regions were more effective in generating ROS in comparison to their higher wavelengths and photosynthetic active radiation (PAR). Moreover, lower wavelengths of UV-B were more efficient than the lower wavelengths of the UV-A radiation. Findings from this study suggest that certain threshold levels of ROS are required to induce the fragmentation of filaments.     

The role of ammonium in photoprotection against high irradiance in the red alga Grateloupia lanceola

Combined and/or interactive effects of inorganic nitrogen (as ammonium) and irradiance on the accumulation of nitrogenous compounds, like UV-absorbing mycosporine-like amino acids (MAAs), chlorophyll a and phycobiliproteins, were examined in the red alga Grateloupia lanceola (J. Agardh) J. Agardh in a high irradiance laboratory exposure and a subsequent recovery period under low light. Also, photosynthetic activity as in vivo chlorophyll fluorescence of photosystem II, i.e. optimum quantum yield (F_v/F_m), electron transport rate (ETR) and quantum efficiency, were examined. Photosynthetic activity, phycobiliproteins and internal nitrogen content declined during the 3-day PAR (photosynthetically active radiation; 600 μmol s⁻¹ m⁻²) and PAR + UVR (ultraviolet radiation; UVB 280–315 nm 0.8 W m⁻², UVA 315–400 nm 16 W m⁻²) exposure. Ammonium supplied in the culture medium (0, 100 and 300 μM NH₄Cl) modified the responses of the alga to high irradiance exposures in a concentration dependent manner, mainly with respect to recovery, as the highest recovery during a 10-day low light period was produced under elevated concentration of ammonium (300 μM). The recovery of photosynthetic activity and phycobiliproteins was enhanced in the algae previously incubated under PAR + UVR as compared to exposure to only PAR, suggesting a beneficial effect of UVR on recovery or photoprotective processes under enriched nitrogen conditions. However, the content of MAAs did not follow the same pattern and thus it could not be concluded as the cause of observed enhanced recovery.     

Effects of temperature, pH, and UV radiation on alkaline phosphatase activity in the terrestrial cyanobacterium Nostoc flagelliforme

Cyanobacteria produce phosphatases in response to phosphorus deficiency as some other autotrophs. However, little has been documented on the effects of key climate change factors, such as temperature rise and solar UV radiation (280–400 nm), on cyanobacterial alkaline phosphatase activity. Here, we found that the terrestrial cyanobacterium Nostoc flagelliforme showed higher activity of the enzyme with increasing temperature and pH levels, exhibiting maximal values at 45 °C and pH?11, respectively. However, when exposed to solar radiation in the presence of UV-A (320–400 nm) and UV-B (280–320 nm), significant reduction of the enzyme activity was observed at a photosynthetically active radiation (PAR) level of 300 W?m^?2 (1,450 μmol photons m^?2 s^?1), which is equivalent or lower than the noontime level of solar PAR at the organism's habitats. UV-A and UV-A + UV-B induced about 21 and 39 % inhibition of the enzyme activity in the 3-h exposures. The decrease in the activity of phosphatase can be attributed to the UV radiation-induced inactivation of the enzyme and indirectly to the UV radiation-induced production of reactive oxygen species.     

Low light acclimated submerged freshwater plants show a pronounced sensitivity to increasing irradiances

The high light sensitivity of three submerged aquatic freshwater plant species, Egeria densa, Elodea nuttallii and Myriophyllum heterophyllum, which have been cultivated at a photosynthetically active radiation (PAR, 400-700 nm) of 70 μmol photons m⁻² s⁻¹, was studied by means of chlorophyll fluorescence and pigment analyses. Exposure of plants to 100, 300, 600 and 1000 μmol photons m⁻² s⁻¹ PAR for up to 360 min induced a strong reduction of the F_v/F_m ratio, indicating a pronounced inactivation of PSII even at the lowest PAR applied. These changes were accompanied by a reduction of the chlorophyll content to about 60-70% of control values at the highest PAR. Rapidly inducible photoprotective mechanisms were not affected, as derived from the rapid generation of pH-dependent energy dissipation under these conditions. At PAR higher than 100 μmol photons m⁻² s⁻¹, however, the primary quinone acceptor of photosystem II, Q_A, was reduced to about 80% and the effective quantum yield of photosystem II, Φ_PSII, dropped to values of about 10%, indicating a high reduction state of the photosynthetic electron transport chain. These data support the notion that the three aquatic macrophytes have a very low capacity for the acclimation to higher light intensities.     

Perception of solar UV radiation by plants: photoreceptors and mechanisms

About 95% of the ultraviolet (UV) photons reaching the Earth’s surface are UV-A (315–400 nm) photons. Plant responses to UV-A radiation have been less frequently studied than those to UV-B (280–315 nm) radiation. Most previous studies on UV-A radiation have used an unrealistic balance between UV-A, UV-B, and photosynthetically active radiation (PAR). Consequently, results from these studies are difficult to interpret from an ecological perspective, leaving an important gap in our understanding of the perception of solar UV radiation by plants. Previously, it was assumed UV-A/blue photoreceptors, cryptochromes and phototropins mediated photomorphogenic responses to UV-A radiation and “UV-B photoreceptor” UV RESISTANCE LOCUS 8 (UVR8) to UV-B radiation. However, our understanding of how UV-A radiation is perceived by plants has recently improved. Experiments using a realistic balance between UV-B, UV-A, and PAR have demonstrated that UVR8 can play a major role in the perception of both UV-B and short-wavelength UV-A (UV-A_sw, 315 to ∼350 nm) radiation. These experiments also showed that UVR8 and cryptochromes jointly regulate gene expression through interactions that alter the relative sensitivity to UV-B, UV-A, and blue wavelengths. Negative feedback loops on the action of these photoreceptors can arise from gene expression, signaling crosstalk, and absorption of UV photons by phenolic metabolites. These interactions explain why exposure to blue light modulates photomorphogenic responses to UV-B and UV-A_sw radiation. Future studies will need to distinguish between short and long wavelengths of UV-A radiation and to consider UVR8’s role as a UV-B/UV-A_sw photoreceptor in sunlight.

In sunlight, UVR8 mediates the perception of both UV-B and short-wavelength UV-A radiation with its sensitivity moderated by blue light perceived through cryptochromes.     

Responses of a rice-field cyanobacterium Anabaena siamensis TISTR-8012 upon exposure to PAR and UV radiation

The effects of PAR and UV radiation and subsequent responses of certain antioxidant enzymatic and non-enzymatic defense systems were studied in a rice field cyanobacterium Anabaena siamensis TISTR 8012. UV radiation resulted in a decline in growth accompanied by a decrease in chlorophyll a and photosynthetic efficiency. Exposure of cells to UV radiation significantly affected the differentiation of vegetative cells into heterocysts or akinetes. UV-B radiation caused the fragmentation of the cyanobacterial filaments conceivably due to the observed oxidative stress. A significant increase of reactive oxygen species in vivo and DNA strand breaks were observed in UV-B exposed cells followed by those under UV-A and PAR radiation, respectively. The UV-induced oxidative damage was alleviated due to an induction of antioxidant enzymatic/non-enzymatic defense systems. In response to UV irradiation, the studied cyanobacterium exhibited a significant increase in antioxidative enzyme activities of superoxide dismutase, catalase and peroxidase. Moreover, the cyanobacterium also synthesized some UV-absorbing/screening substances. HPLC coupled with a PDA detector revealed the presence of three compounds with UV-absorption maxima at 326, 331 and 345 nm. The induction of the biosynthesis of these UV-absorbing compounds was found under both PAR and UV radiation, thus suggesting their possible function as an active photoprotectant.     

Row orientation effect on UV-B,UV-A and PAR solar irradiation components in vineyards at Tuscany,Italy

Besides playing an essential role in plant photosynthesis, solar radiation is also involved in many other important biological processes. In particular, it has been demonstrated that ultraviolet (UV) solar radiation plays a relevant role in grapevines (Vitis vinifera) in the production of certain important chemical compounds directly responsible for yield and wine quality. Moreover, the exposure to UV-B radiation (280–320 nm) can affect plant–disease interaction by influencing the behaviour of both pathogen and host. The main objective of this research was to characterise the solar radiative regime of a vineyard, in terms of photosynthetically active radiation (PAR) and UV components. In this analysis, solar spectral UV irradiance components, broadband UV (280–400 nm), spectral UV-B and UV-A (320–400 nm), the biological effective UVBE, as well as the PAR (400–700 nm) component, were all considered. The diurnal patterns of these quantities and the UV-B/PAR and UV-B/UV-A ratios were analysed to investigate the effect of row orientation of the vineyard in combination with solar azimuth and elevation angles. The distribution of PAR and UV irradiance at various heights of the vertical sides of the rows was also studied. The results showed that the highest portion of plants received higher levels of daily radiation, especially the UV-B component. Row orientation of the vines had a pronounced effect on the global PAR received by the two sides of the rows and, to a lesser extent, UV-A and UV-B. When only the diffused component was considered, this geometrical effect was greatly attenuated. UV-B/PAR and UV-A/PAR ratios were also affected, with potential consequences on physiological processes. Because of the high diffusive capacity of the UV-B radiation, the UV-B/PAR ratio was significantly lower on the plant portions exposed to full sunlight than on those in the shade.     

Complexation of curium(III) by adenosine 5′-triphosphate (ATP): A time-resolved laser-induced fluorescence spectroscopy (TRLFS) study

The complex formation of curium(III) with adenosine 5′-triphosphate (ATP) was determined by time-resolved laser-induced fluorescence spectroscopy (TRLFS). The interaction between soluble species of curium(III) with ATP was studied at trace Cm(III) concentrations (3 × 10⁻⁷ M). The concentrations of ATP were varied between 6.0 × 10⁻⁷ and 1.5 × 10⁻⁴ M in the pH range of 1.5-7.0 using 0.154 M NaCl as background electrolyte.Three Cm-ATP species, M_pH_qL_r, could be identified from the fluorescence emission spectra: (i) CmH₂ATP⁺ with a peak maximum at 598.6 nm, (ii) CmHATP with a peak maximum at 600.3 nm, and (iii) CmATP⁻ with a peak maximum at 601.0 nm. The formation constants of these complexes were calculated from TRLFS measurements to be log β₁₂₁ = 16.86 ± 0.09, log β₁₁₁ = 13.23 ± 0.10, and log β₁₀₁ = 8.19 ± 0.16. The hydrated Cm-ATP species showed fluorescence lifetimes between 88 and 96 μs; whereas the CmATP⁻ complex has a significantly longer fluorescence lifetime of 187 ± 7 μs.     

Horizontal distribution pattern of the syllid fauna (Annelida: Polychaeta) in the fringing reef lagoon of Anse Forbans (Seychelles, Mahé) and redescription of the abundant Streptosyllis aequiseta

Variability in the effect of solar ultraviolet radiation (UV-B) on primary productivity of natural phytoplankton assemblages was examined in coastal water off Manazuru Harbor, Sagami Bay, central Japan for two full years during the period from September 1996 to September 1998. Solar UV-B, UV-A, and PAR were determined in air and water. Surface water was exposed to UV-B+UV-A+PAR and UV-A+PAR with Mylar film and primary productivity under those two light regimes was determined with ¹³C method. Size distribution of chlorophyll a concentration was also examined. When the occurrence of >10 m size fraction was lower than 80% in a warm season, the UV-B effect was significant. Whenever red tide species occurred, they did not respond to UV-B radiation. Although winter population was also dominated by >10 m size fraction, a ratio of UV-B to UV-A+PAR was already so low that the UV-B effect was insignificant. The occurrence of >10 m size fraction, which might be enhanced by a supply of nitrate and consequently could be related to high supply of dissolved organic matter, seemed to play a significant role in controlling the effect of UV-B on primary productivity in the coastal water. Reduction rate of primary productivity ranged from <10% from November to April to 41% at maximum from May to October with annual reduction rate of 10% in the present study.     

Hybrid organic-inorganic assemblies built up from saturated heteropolyoxoanions and copper coordination polymers with mixed 4,4′-bipyridine and 2,2′-bipyridine ligands

Three new organic-inorganic hybrid compounds [Cu^I(2,2′-bipy)(4,4′-bipy)_0.5]₂[Cu^I(2,2′-bipy)(4,4′-Hbipy)][Cu^I(4,4′-bipy)]₂[P₂W₁₈O₆₂] · 3H₂O (1), [Cu^I(2,2′-bipy)(4,4′-bipy)_0.5]₂[Cu^I(4,4′-bipy)]₂[PW₁₂O₄₀] · 0.25H₂O (2), and[Cu^I(4,4′-bipy)]₃[PMo₁₂O₄₀] · en · 3H₂O (3) (2,2′- bipy = 2,2′-bipyridine, 4,4′-bipy = 4,4′-bipyridine), have been hydrothermally synthesized. Compound 1 represents the first 1D ladderlike structure formed by Dawson-type polyoxoanion [P₂W₁₈O₆₂]⁶⁻ and coordination polymer with mixed 4,4′-bipy and 2,2′-bipy ligands. The novel structure of 2 is composed of 1D hybrid zigzag chains linked by chains into a 3D framework. In compound 3, the [PMo₁₂O₄₀]³⁻ clusters are hung on chains to form a new 1D chain.     

Ultraviolet-B-induced DNA damage and photorepair in the cyanobacterium Anabaena variabilis PCC 7937

The impact of simulated solar radiation on DNA and the mitigation of DNA-damaging effects by photoreactivation was studied in a cyanobacterium Anabaena variabilis PCC 7937. Cultures were irradiated under 295, 320 and 395 nm cut-off filters as well as seven other filters such as WG 280, WG 295, WG 305, WG 320, WG 335, WG 345 and GG 400. Growth of the test organism was found to be affected mostly under UV-B radiation as compared to PAR and PAR + UV-A radiations. Amplification of 16s rDNA and RAPD profile was significantly affected following exposure of genomic DNA to UV-B radiation. The formation of T<>T CPDs was recorded only in the cultures irradiated with UV-B radiation (i.e., under 295 nm as well as under WG 280, WG 295 and WG 305 nm cut-off filters), but maximum yield was found under 280 nm cut-off filter. Furthermore, the considerable induction of thymine dimers was observed with increasing UV-irradiation times. Fluorometric analysis of DNA unwinding (FADU) assay for UV-induced DNA strand breaks exhibited the maximum loss in the percentage of dsDNA under UV-B radiation followed by UV-A and PAR in comparison to the light control samples. We observed that T<>T CPD repair is light-dependent, since these lesions were more efficiently removed upon exposure to visible light than in the darkness. Blue radiation was found to be the most effective in photoreactivation than any other wavebands of light. Furthermore, the rate of photoreactivation was measured under varying temperatures (10, 20 and 30 °C); the repair rate was found to be the maximum at 20 °C under white fluorescent light. Our results indicate that photoreactivation play an important role in survival of the organism under natural conditions in spite of being exposed to the UV-B component present in the solar drops.     

Inhibition of photosynthesis by solar radiation in Dunaliella salina: relative efficiencies of UV-B, UV-A and PAR

Inhibition of photosynthesis after exposure to solar radiation was investigated in the marine green alga Dunaliella salina by monitoring photosynthetic optimal quantum yield F_v/F_m and efficiency of oxygen production. Samples were exposed to solar radiation in Ancient Korinth, Greece (37°58′ N, 23°0′ E) in August 1994. Within 30 min, F_v/F_m and efficiency of oxygen production decreased with similar kinetics with increasing exposure time. The inhibition, however, diminished when ultraviolet radiation was progressively excluded by means of colour filter glasses. Samples exposed for 3 h showed complete or partial recovery of photosynthesis, with almost the same rate under all irradition conditions. The fit of the experimental data with an analytical model describing inhibition of photosynthesis as a function of a linear combination of the photon fluence in the UV-B, UV-A and PAR allows one to estimate the relative mean effectiveness for inhibition by the three spectral ranges [about 2 × 10^?4, 4 × 10^?6 and 2 × 10^?7 (μmol photons m^?2)^?1 for UV-B, UV-A and PAR, respectively].     

Effects of UV-B on motility and photoorientation in the cyanobacterium,Phormidium uncinatum

UV-B irradiation has a detrimental effect on the survival of populations of the filamentous cyanobacterium, Phormidium uncinatum, at levels slightly higher than those currently measured at the surface of the earth. The organisms are not damaged or killed by UV-B radiation at 300 nm of 200 Wm^-2 for up to 20 h; but slightly increased levels of UV-B irradiation (2 h of 200 Wm^-2 at 300 nm) drastically impair motility, phototactic orientation and photophobic responses. These photosynthetic organisms require a narrow light intensity range for growth so that any decrease in their ability to actively search for and move into areas of favorable light conditions is bound to affect the survival of a population. The fluorescence yield of both phycobilins and chlorophyll is not altered even after 20 h of UV-B irradiation (200 Wm^-2 at 270 nm) indicating that UV-B at that dose does not affect the photosynthetic apparatus. The organisms are killed either by too bright intensities which bleach the photosynthetic pigments or by the lack of energy when they are unable to avoid moving into dark areas.     

The action of a range of supplementary ultraviolet (UV) wavelengths on photosynthesis in Brassica napus L. in the natural environment: effects on PS II,CO2 assimilation and level of chloroplast proteins

The effects of different wavebands of UV radiation on photosynthesis and the expression and abundance of photosynthetic proteins in oilseed rape (Brassica napus L. cv. Rebel) were investigated. Plants were grown outdoors under natural radiation (52° N, 0° E) supplemented with six wavebands of UV radiation (0.4 Wm⁻²) between 313 nm and 356 nm. A control treatment was centred at 343 nm. Exposure to supplementary UV-A radiation (320–400 nm) had no significant effects, however UV-B radiation, centred at 313 nm, caused a marked reduction in photosynthesis. This decrease was related to a reduction in the initial carboxylation velocity of Rubisco which was further correlated with a large reduction in the expression and abundance of both large and small subunits of Rubisco. These results indicate a molecular mechanism behind UV-B induced reductions in photosynthesis per unit area in plants grown under field conditions. This revised version was published online in June 2006 with corrections to the Cover Date.     

On the elusive, non-emissive yet reactive, upper excited states of [(4,4′-bpy)Re(CO)3(dppz)]PF6 (dppz = dipyridil[3,2-a:2′3′-c]phenazine)

Gradual solvation of [(4,4′-bpy)Re^I(CO)₃(dppz)]⁺ (dppz = dipyridil[3,2-a:2′3′-c]phenazine) by water molecules causes a quenching of the emission in accordance with Perrin’s model of spheres. The calculated radius of the sphere, r = 2.6 ± 0.2 ?, is therefore very close to the distance from the Re center to the oxygen atom of the CO ligands, i.e., l = 2.73 ?. In addition, excited state reactions with TEA produce [(4,4′-bpy⁻)Re^I(CO)₃(dppz)] and [(4,4′-bpy)Re^I(CO)₃(dppz⁻)]. This experimental observation is inconsistent with the formation of the products in the lowest lying and emissive dppz-centered ³ππ* excited state. Jablonski schemes based on the participation of excited states other than the lowest ³ππ* excited state are proposed.     

Enzymatic characteristics of two novel Myxococcus xanthus enzymes, PdeA and PdeB, displaying 3′,5′- and 2′,3′-cAMP phosphodiesterase, and phosphatase activities

Myxococcus xanthus PdeA and PdeB, enzymes homologous to class III 3′,5′-cyclic nucleotide phosphodiesterases, hydrolyzed 3′,5′- and 2′,3′-cyclic AMP (cAMP) to adenosine, and also demonstrated phosphatase activity toward nucleoside 5′-tri-, 5′-di-, 5′- and 3′-monophosphates with highest activities for nucleoside 5′-monophosphates. The substrate specificities of PdeA and PdeB show no similarity to that of any known cNMP phosphodiesterase, nucleotidase, or phosphatase. The enzyme activities of PdeA and PdeB were stimulated by 50 μM Mn²⁺ or Co²⁺. The K_m values of PdeA and PdeB for 3′,5′-cAMP, 2′,3′-cAMP, 5′-ATP, and 5′-AMP were in the low micromolar range (1.4-12.5  μM).