Quantification of thermal ring flexibilities of aromatic and heteroaromatic compounds

The consequences of thermal fluctuations occurring at room temperatures on the aromatic character of a broad group of compounds were analyzed in three distinct ways. First of all, the ring deformations were modeled along normal coordinates coming from quantum thermo-chemistry computations. The amplitudes of vibrations were estimated according to absorbed energies at room temperature. Alternatively, in-plane and out-of-plane ring deformations were modeled via scanning procedure with partial relaxation of the molecular geometry. The influence of ring deformations on π–electron delocalization was expressed in terms of HOMA values. Besides, the ring deformability was defined as the averaged change of bond angles or dihedral angles constituting the ring that was associated with 1.5 kcal mol-1 increase of the system energy. The molecules structures adopted during vibrations at room temperature can lead to significant heterogeneity of structural index of aromaticity. The broad span of HOMA values was obtained for analyzed five- or six-membered aromatic and heteroaromatic rings. However, the averaged values obtained for such fluctuations almost perfectly match HOMA values of molecule in the ground state. It has been demonstrated that the ring deformability imposed by bond angle changes is much smaller than for dihedral angles with the same rise of system energy. Interestingly in the case of out-of-plane vibrations modeled by scanning procedure there is observed linear correlation between ring deformability and HOMA values. Proposed method for inclusion of thermal vibrations in the framework of π–electron delocalization provides natural shift of the way of thinking about aromaticity from a static quantity to a dynamic and heterogeneous one due to inclusion of a more realistic object of analysis – thermally deformed structures. From this perspective the thermal fluctuations are supposed to be non-negligible contributions to aromaticity phenomenon

Sublittoral seaweed communities on natural and artificial substrata in a high-latitude coral community in South Africa

Coral mortality may result in macroalgal proliferation or a phase shift into an alga dominated state. Subtidal, high-latitude western Indian Ocean coral communities at Sodwana Bay on the KwaZulu-Natal coast, South Africa, have experienced some mortality because of warm water anomalies, storms and other causes, but the response of the macroalgae is unknown. We investigated the abundance and diversity of benthic algae on different hard natural substrata (dead digitate, brain and plate corals and beach rock) on Two-Mile Reef, Sodwana Bay. We also compared algal communities colonising ceramic, marble and pretreated ceramic tiles placed on the reef for six months. We identified 95 algae (14 Chlorophyta, 11 Phaeophyceae, 69 Rhodophyta and one cyanobacterium). Assemblages on natural and artificial substrata were dominated by the brown alga Lobophora variegata (Lamouroux) Womersley ex Oliveira and non-geniculate corallines (Rhodophyta, Corallinaceae). Cluster and ordination analyses revealed that the algae showed no affinity for particular substrata, whether natural or artificial. Algal cover was occasionally higher on rougher tiles and crustose corallines were significantly more abundant on marble than ceramic tiles. Two-Mile Reef had 23.1% dead and 48.4% live scleractinian coral cover, where dead corals were colonised indiscriminately by many small algal species, but there was no evidence of algal proliferation. The results provide a baseline for monitoring this high-latitude reef system.DHE

PET/MR imaging of bone lesions - implications for PET quantification from imperfect attenuation correction

PURPOSE: Accurate attenuation correction (AC) is essential for quantitative analysis of PET tracer distribution. In MR, the lack of cortical bone signal makes bone segmentation difficult and may require implementation of special sequences. The purpose of this study was to evaluate the need for accurate bone segmentation in MR-based AC for whole-body PET/MR imaging. METHODS: In 22 patients undergoing sequential PET/CT and 3-T MR imaging, modified CT AC maps were produced by replacing pixels with values of >100 HU, representing mostly bone structures, by pixels with a constant value of 36 HU corresponding to soft tissue, thereby simulating current MR-derived AC maps. A total of 141 FDG-positive osseous lesions and 50 soft-tissue lesions adjacent to bones were evaluated. The mean standardized uptake value (SUVmean) was measured in each lesion in PET images reconstructed once using the standard AC maps and once using the modified AC maps. Subsequently, the errors in lesion tracer uptake for the modified PET images were calculated using the standard PET image as a reference. RESULTS: Substitution of bone by soft tissue values in AC maps resulted in an underestimation of tracer uptake in osseous and soft tissue lesions adjacent to bones of 11.2 ± 5.4 % (range 1.5-30.8 %) and 3.2 ± 1.7 % (range 0.2-4 %), respectively. Analysis of the spine and pelvic osseous lesions revealed a substantial dependence of the error on lesion composition. For predominantly sclerotic spine lesions, the mean underestimation was 15.9 ± 3.4 % (range 9.9-23.5 %) and for osteolytic spine lesions, 7.2 ± 1.7 % (range 4.9-9.3 %), respectively. CONCLUSION: CT data simulating treating bone as soft tissue as is currently done in MR maps for PET AC leads to a substantial underestimation of tracer uptake in bone lesions and depends on lesion composition, the largest error being seen in sclerotic lesions. Therefore, depiction of cortical bone and other calcified areas in MR AC maps is necessary for accurate quantification of tracer uptake values in PET/MR imaging

The artisanal fishery for East Coast rock lobsters Panulirus homarus along the Wild Coast, South Africa

East coast rock lobsters Panulirus homarus are collected by the indigenous people of the Wild Coast, in the Eastern Cape, South Africa, and are sold to coastal hotels and holidaymakers. The South African government has proposed a small-scale commercial fishery based on P. homarus to improve socio-economic conditions in that region. Catch data and information on fishery operations were collected for the artisanal fishery from Coffee Bay, Presley Bay, Port St Johns and Mbotyi, as well as from a commercial buying station near the Mdumbi Estuary, between March 2003 and October 2005. The catch per unit effort of rock lobster poling varied from 13.5 ± 7.7 fisher–1 outing–1 at Port St Johns to 5.9 ± 3.1 fisher–1 outing–1 at Coffee Bay, but the number of fishers or fishing frequency could not be verified. About two-thirds of the lobsters caught (69%) were smaller than the minimum legal size. Hotels and the buying station complied with size limits, but cottages and campers often bought undersized lobsters. Smaller lobsters (females) are caught by poling than by diving. Geographical variations in poling effort and lobster mean sizes could be indicators of heavy fishing pressure on shallow, inshore reefs. The implications of commercialising the fishery and its associated management are discussed. Keywords: artisanal fishery; catch-and-effort survey; fishery management; Panulirus homarus; Wild CoastAfrican Journal of Marine Science 2008, 30(3): 497–50