On the halogenation of N(1),N(2)-di-t-Boc-5-hydroxy-piperazic acid esters and the conformational preferences of their 5-halo-piperazic acid products. The importance of A1,3 rotameric-strain in determining N(2)-acyl piperazic acid ring conformation

In this Letter, an unambiguous synthetic strategy is reported for the preparation of enantiomerically purecis-5-halo-piperazic acid derivatives in single diastereoisomer form. Contrary to the recent report by Shin and co-workers (Chem. Lett. 2001, 1172), in which it is claimed that the Ph₃P and N-chlorosuccinimide (NCS)-mediated chlorination of (3R,5S)-trans-N(1),N(2)-di-t-Boc-5-hydroxy-piperazic acid derivative 1proceeds with retention of configuration at C(5) to give 2, we now show that this and related Ph₃P-mediated halogenations all occur with S_N2 inversion at the alcohol center, as is customary for such reactions. Specifically, we demonstrate that the (3R,5S)-trans-5-Cl-piperazic acid derivative 2 claimed by Shin and co-workers (Chem. Lett. 2001, 1172) is in actual fact the chlorinated (3S,5R)-enantiomer 6, which must have been prepared from the cis-(3S,5S)-alcohol 3, a molecule whose synthesis is not formally described in the Shin paper. We further show here that the cis-(3R,5R)-5-Cl-Piz 13 claimed by Shin and co-workers inChem. Lett. 2001, 1172, is also (3S,5R)-trans-5-Cl-Piz 6. Authentic 13 has now been synthesized by us, for the very first time, here. Since Lindsley and Kennedy have recently utilized the now invalid Shin and co-workers’ retentive Ph₃P/NCS chlorination procedure on 1 in their synthetic approach to piperazimycin A (Tetrahedron Lett. 2010, 51, 2493), it follows that their claimed 5-Cl-Piz-containing dipeptide 25 probably has the alternate structure 26, where the 5-Cl-Piz residue has a 3,5-cis-configuration. The aforementioned stereochemical misassignments appear to have come from a mix-up of starting materials by Shin and co-workers (Chem. Lett. 2001, 1172), and an under-appreciation of the various steric and conformational effects that operate in N(2)-acylated piperazic acid systems, most especially rotameric A^1,3-strain. The latter has now been unambiguously delineated and defined here under the banner of the A^1,3-rotamer effect.

Confronto tra diverse localizzazioni di un impianto eolico contemperando produttività ed impatto visivo

This paper proposes a series of variations in designing the location of a wind farm on Monti della Tolfa. These project solutions aim at mitigating the visual impact caused by the wind aerogenerators. Besides the usual location of the wind aerogenerators on the skyline, these alternatives within the project design relate to the placement of wind turbines in the middle and at the bottom of the hillside. Other possible mitigation forms relate to the dimensions and the colour of the wind towers. This study proposes both a non-monetary and monetary analysis of the visual impact related to each project proposal. The final aim of the paper is to analyze economic and financial costs-benefits for each alternative to find out the economic optimal solution.

Home-range size in juveniles of the temperate reef fish, the common triplefin (Forsterygion lapillum)

An organism’s home range dictates the spatial scale on which important processes occur (e.g. competition and predation) and directly affects the relationship between individual fitness and local habitat quality. Many reef fish species have very restricted home ranges after settlement and, here, we quantify home-range size in juveniles of a widespread and abundant reef fish in New Zealand, the common triplefin (Forsterygion lapillum). We conducted visual observations on 49 juveniles (mean size = 35-mm total length) within the Wellington harbour, New Zealand. Home ranges were extremely small, 0.053 m2 ± 0.029 (mean ± s.d.) and were unaffected by adult density, body size or substrate composition. A regression tree indicated that home-range size sharply decreased ~4.5 juveniles m–2 and a linear mixed model confirmed that home-range sizes in high-density areas (>4.5 juveniles m–2) were significantly smaller (34%) than those in low-density areas (after accounting for a significant effect of fish movement on our home-range estimates). Our results suggest that conspecific density may have negative and non-linear effects on home-range size, which could shape the spatial distribution of juveniles within a population, as well as influence individual fitness across local density gradients.

Smartphone and GPS technology for freeroaming dog population surveillance -a methodological study (Studio metodologico sull’applicazione di smartphone e tecnologia GPS alla sorveglianza delle popolazioni di cani vaganti)

Free-roaming dogs (FRD) represent a potential threat to the quality of life in cities from an ecological, social and public health point of view. One of the most urgent concerns is the role of uncontrolled dogs as reservoirs of infectious diseases transmittable to humans and, above all, rabies. An estimate of the FRD population size and characteristics in a given area is the first step for any relevant intervention programme. Direct count methods are still prominent because of their non-invasive approach, information technologies can support such methods facilitating data collection and allowing for a more efficient data handling. This paper presents a new framework for data collection using a topological algorithm implemented as ArcScript in ESRI® ArcGIS software, which allows for a random selection of the sampling areas. It also supplies a mobile phone application for Android® operating system devices which integrates Global Positioning System (GPS) and Google Maps™. The potential of such a framework was tested in 2 Italian regions. Coupling technological and innovative solutions associated with common counting methods facilitate data collection and transcription. It also paves the way to future applications, which could support dog population management systems.

Christian Gottlob Neefe and the Early Reception of Le nozze di Figaro and Don Giovanni

A brief account of Christian Gottlob Neefe's engagement with Mozart's Le nozze di Figaro and Don Giovanni as exemplified in his correspondence.

Long-term changes in oxygen depletion in a small temperate lake: effects of climate change and eutrophication

1. We analysed 41 years of data (1968–2008) from Blelham Tarn, U.K., to determine the consequences of eutrophication and climate warming on hypolimnetic dissolved oxygen (DO).
2. The establishment of thermal stratification was strongly related to the onset of DO depletion in the lower hypolimnion. As a result of a progressively earlier onset of stratification and later overturn, the duration of stratification increased by 38 ± 8 days over the 41 years.
3. The observed rate of volumetric hypolimnetic oxygen depletion (VHODobs) ranged from 0.131 to 0.252 g O2 m−3 per day and decreased significantly over the study period, despite the increase in the mean chlorophyll a (Chl a) concentration in the growing season. The vertical transport of DO represented from 0 to 30% of VHODobs, while adjustments for interannual differences in hypolimnetic temperature were less important, ranging from −11 to 9% of VHODobs.
4. The mean wind speed during May made the strongest significant contribution to the variation in VHODobs. VHODobs adjusted for the vertical transport of DO and hypolimnetic temperature differences, VHODadj, was significantly related to the upper mixed layer Chl a concentration during spring.
5. Hypolimnetic anoxia (HA) ranged from 27 to 168 days per year and increased significantly over time, which undoubtedly had negative ecological consequences for the lake.
6. In similar small temperate lakes, the negative effects of eutrophication on hypolimnetic DO are likely to be exacerbated by changes in lake thermal structure brought about by a warming climate, which may undermine management efforts to alleviate the effects of anthropogenic eutrophication.

The role of the seed bank in recovery of temperate heath and blanket bog following wildfires

Questions - Are the germinable seed banks of upland heath and blanket bog reduced following wildfires? Are some species at particular risk? Do the impacts of wildfires on seed banks differ between heathlands and blanket bog?

Location - Northern Ireland, United Kingdom.

Methods - Vegetation surveys and seed bank sampling were conducted in 2012 at burned and unburned areas within six upland sites where large wildfires had occurred during spring 2011. Differences in seedling abundance, species richness and Jaccard similarity indices between burned and unburned areas were compared using GLMMs. Differences in the community composition were examined using pRDA.

Results - In total, 24 of the 51 species in the vegetation were detected in the germinable seed bank. Species richness and the abundance of seedlings other than Calluna vulgaris were lower in areas where wildfires had occurred. Species composition of both germinable seed banks and vegetation differed between burned and unburned areas within sites; with negative associations between burned areas and some key indicator species including Drosera rotundifolia, Eriophorum vaginatum, Empetrum nigrum, Narthecium ossifragum and Trichophorum germanicum. We did not find any evidence of significant interactions between burning and habitat, suggesting that wildfires had similar impacts on each species regardless of the habitat in which they occurred.

Conclusions - This study differs from other UK studies in that it examines impacts of wildfires at sites that have not been previously intensively managed by burning. In particular, we highlight potential impacts on N. ossifragum and D. rotundifolia, which are key components of the upland flora and, to our knowledge, were not present in previous UK studies.

Híbridos orgânicos-inorgânicos para aplicações de baixo custo em óptica integrada

O objectivo desta tese é a utilização de materiais híbridos orgânicos-inorgânicos, designados por di-ureiasis modificados pela adição de tetra-propóxido de zircónio (Zr(i-OPr)4) estabilizado com ácido metacrílico (CH2=C(CH3)COOH), obtidos pela via sol-gel, para aplicações em dispositivos ópticos integrados de baixo custo. A estrutura local dos di-ureiasis com diferentes concentrações de propóxido de zircónio (20 a 80 % mol) foi estudada por difracção de raios-X, espalhamento de raios X a baixos ângulos, microscopia de força atómica, ressonância magnética nuclear dos núcleos dos átomos de 29Si e 13C, espectroscopia no infravermelho por transformada de Fourier, espectroscopia de Raman por transformada de Fourier e termogravimetria. A influência dos parâmetros de síntese, concentração de tetra propóxido de zircónio e rácio tetra propóxido de zircónio: ácido metacrilico na estrutura e propriedades das amostras em monólito e filmes finos (depositados pela técnica de deposição por rotação do substrato) foram avaliadas, permitindo obter amostras transparentes, fotopolimerizáveis e estáveis termicamente até aos 100 ºC. Foram determinadas as propriedades dos guias planares em substratos de vidro borosilicato e silício oxidado (1dice de refracção (1,4774-1,5149 a 1550 nm), espessura (6-10 μm), perdas por propagação (~1,5 dB/cm) e rugosidade (~5,0 nm). Posteriormente o processo de escrita laser directa permitiu a gravação de dispositivos para óptica integrada de que são exemplos: guias de onda em canal com diâmetros modais de 2,5 μm (monomodo) e de 15-20 μm (multimodo) e contraste de valor do índice de refracção de 2x10-3; divisores de potência óptica com geometria em Y com rácios de divisão de ~50:50; filtros ópticos baseados em redes de Bragg com valores de rejeição do sinal óptico de 10 dB (monólitos) e 24 dB (filmes finos); cavidades ópticas do tipo Fabry-Perot com valores de rejeição de ~5 dB e gama espectral livre de 16,5 e 35,5 GHz. A actuação termo-óptica de uma estrutura do tipo Mach-Zhender simétrica conduziu a uma atenuação do sinal óptico de 7,5 dB.

Ontogeny of behavioural abilities in temperate reef fish larvae

Tese de dout., Ciências do Mar, Faculdade de Ciências e Tecnologia, Universidade do Algarve, 2010

Study of sewage sludge aimed at agricultural soil amendment by thermogravimetric analysis and fourier-transform infrared spectroscopy

Thermal degradation and gaseous products evolving from the pyrolysis of sewage sludge, aimed at agricultural soil amendment, were investigated using Thermogravimetric Analysis in conjunction with Fourier Transform Infrared Analysis (TG-FTIR). The materials were studied in temperatures ranging from 30 to 800 ºC. Furthermore infrared spectra of sewage sludge samples were performed as a complementary technique. In parallel the sewage sludge was spiked with ibuprofen in order to test whether the mentioned techniques are able to detect the drug. Thermal analysis showed the range of 200-400ºC as the most characteristic for weight loss, corresponding with the organic matter volatilization, while the range of 500-800ºC was also characteristic and due to the volatilization of carbonates. On the other hand, ibuprofen-spiking tests identified at temperature range (150-250ºC) where the compound totally volatilizes, therefore, in this work, the detection of ibuprofen by TGA was established for concentrations higher than 0.5 g/kg sludge, concentration 102 times higher than the concentrations measured by other authors in regular sewage sludge (Martín, et al., 2010). A correlation has been found between the ibuprofen concentrations in the sludge and the intensity of the absorption bands, both for FT-IR spectra at the maximum emission temperature for ibuprofen (232ºC) as for the FT-IR spectra of the non-pyrolyzed samples.