Novel 2,6-bis(4-methoxyphenyl)-1-methylpiperidin-4-one oxime esters: synthesis and a new insight into their antioxidant and antimicrobial potential

A simple and efficient protocol for the synthesis of novel 2,6-bis(4-methoxyphenyl)-1-methylpiperidin-4-one oxime esters 4(a-q) is described. Initially, p-anisaldehyde 1 was condensed (Mannich reaction) with acetone and ammonium acetate trihydrate afforded 2,6-bis(4-methoxyphenyl)piperidin-4-one 2. Then, methylation followed by oximation with hydroxylamine hydrochloride (NH(2)OHa (TM) HCl) furnished a key scaffold 4. Further, to explore the enhanced biological properties of the piperidin-4-one core i.e. the key scaffold 4 was conjugated with substituted benzoyl chlorides in the presence of anhydrous K2CO3 as base to obtain novel 2,6-bis(4-methoxyphenyl)-1-methylpiperidin-4-one oxime esters 4(a-q) in excellent yields. The newly synthesized compounds were characterized by elemental analysis, IR, H-1 NMR, C-13 NMR and mass spectroscopic techniques, and screened for their in vitro antioxidant and antimicrobial activities. Most of the compounds exerted positive efficacy towards the biological assays performed. Among the synthesized analogues, compounds 4l and 4m exhibited promising antioxidant activity and on the other hand compounds 4b and 4d manifested persuasive antibacterial activity, whereas compound 4b displayed stupendous antifungal activity against A. flavus strain.

Drivers and effects of Karenia mikimotoi blooms in the western English Channel

Naturally occurring red tides and harmful algal blooms (HABs) are of increasing importance in the coastal environment and can have dramatic effects on coastal benthic and epipelagic communities worldwide. Such blooms are often unpredictable, irregular or of short duration, and thus determining the underlying driving factors is problematic. The dinoflagellate Karenia mikimotoi is an HAB, commonly found in the western English Channel and thought to be responsible for occasional mass finfish and benthic mortalities. We analysed a 19-year coastal time series of phytoplankton biomass to examine the seasonality and interannual variability of K. mikimotoi in the western English Channel and determine both the primary environmental drivers of these blooms as well as the effects on phytoplankton productivity and oxygen conditions. We observed high variability in timing and magnitude of K. mikimotoi blooms, with abundances reaching >1000 cells mL�1 at 10 m depth, inducing up to a 12-fold increase in the phytoplankton carbon content of the water column. No long-term trends in the timing or magnitude of K. mikimotoi abundance were evident from the data. Key driving factors were identified as persistent summertime rainfall and the resultant input of low-salinity high-nutrient river water. The largest bloom in 2009 was associated with highest annual primary production and led to considerable oxygen depletion at depth, most likely as a result of enhanced biological breakdown of bloom material; however, this oxygen depletion may not affect zooplankton. Our data suggests that K. mikimotoi blooms are not only a key and consistent feature of western English Channel productivity, but importantly can potentially be predicted from knowledge of rainfall or river discharge.

Improved stability, insulin-releasing activity and antidiabetic potential of two novel N-terminal analogues of gastric inhibitory polypeptide: N-acetyl-GIP and pGlu-GIP

Aims/hypothesis: This study examined the plasma stability, biological activity and antidiabetic potential of two novel N-terminally modified analogues of gastric inhibitory polypeptide (GIP).

Methods: Degradation studies were carried out on GIP, N-acetyl-GIP (Ac-GIP) and N-pyroglutamyl-GIP (pGlu-GIP) in vitro following incubation with either dipeptidylpeptidase IV or human plasma. Cyclic adenosine 3'5' monophosphate (cAMP) production was assessed in Chinese hamster lung fibroblast cells transfected with the human GIP receptor. Insulin-releasing ability was assessed in vitro in BRIN-BD11 cells and in obese diabetic (ob/ob) mice.

Results: GIP was rapidly degraded by dipeptidylpeptidase IV and plasma (t1/2 2.3 and 6.2 h, respectively) whereas Ac-GIP and pGlu-GIP remained intact even after 24 h. Both Ac-GIP and pGlu-GIP were extremely potent (p<0.001) at stimulating cAMP production (EC50 values 1.9 and 2.7 nmol/l, respectively), almost a tenfold increase compared to native GIP (18.2 nmol/l). Both Ac-GIP and pGlu-GIP (10–13–10–8 mmol/l) were more potent at stimulating insulin release compared to the native GIP (p<0.001), with 1.3-fold and 1.2-fold increases observed at 10–8 mol/l, respectively. Administration of GIP analogues (25 nmol/kg body weight, i.p.) together with glucose (18 mmol/kg) in (ob/ob) mice lowered (p<0.001) individual glucose values at 60 min together with the areas under the curve for glucose compared to native GIP. This antihyperglycaemic effect was coupled to a raised (p<0.001) and more prolonged insulin response after administration of Ac-GIP and pGlu-GIP (AUC, 644±54 and 576±51 ng·ml–1·min, respectively) compared with native GIP (AUC, 257±29 ng·ml–1·min).

Conclusion/interpretation: Ac-GIP and pGlu-GIP, show resistance to plasma dipeptidylpeptidase IV degradation, resulting in enhanced biological activity and improved antidiabetic potential in vivo, raising the possibility of their use in therapy of Type II (non-insulin-dependent) diabetes mellitus.

Synthèse formelle de l’hormaomycine et de la bélactosine A par utilisation d’une réaction de cyclopropanation intramoléculaire catalysée par un complexe de rhodium (II)

Ce mémoire présente trois approches différentes vers la synthèse du 3–(trans–2–nitrocyclopropyl)alanine, un intermédiaire synthétique de la hormaomycine. Cette molécule naturelle démontre d’intéressantes activités biologiques et pharmacologiques. Il est intéressant de souligner que ce dérivé donne facilement accès au 3–(trans–2–aminocyclopropyl)alanine, unité centrale de la bélactosine A. Ce composé naturel possédant lui aussi d’intéressantes propriétés biologiques, plusieurs études relationnelles structures-activités menant à des dérivés plus actifs de cette molécule ont été entreprises, démontrant l’intérêt toujours présent de synthétiser de façon efficace et optimale ces dérivés cyclopropaniques. Une méthodologie développée au sein de notre groupe de recherche et basée sur une réaction de cyclopropanation intramoléculaire diastéréosélective sera mise à profit afin d’élaborer une nouvelle voie de synthèse aussi élégante qu’efficace à la construction du 3–(trans–2–nitrocyclopropyl) alanine. En utilisant un carbène de rhodium généré soit par la dégradation d’un dérivé diazoïque, soit par la formation d’un réactif de type ylure d’iodonium, une réaction de cyclopropanation diastéréosélective permettra la formation de deux autres centres contigus et ce, sans même utiliser d’auxiliaire ou de catalyseur énantioenrichis. Ensuite, un réarrangement intramoléculaire précédant deux réactions synchronisées d’ouverture de cycle et de décarboxylation permettront l’obtention du composé d’intérêt avec un rendement global convenable et en relativement peu d’étapes. De cette manière, la synthèse formelle de la bélactosine A et de l’hormaomycine a été effectuée. Cette synthèse se démarque des autres par l’utilisation d’une seule transformation catalytique énantiosélective.

Diversity in Structural and Spectural Characteristics of Some Transition Metal Complexes Derived From Aldehyde Based Thiosemicarbazone Ligands

The study deals with the diversity in structural and spectural characteristics of some transition metal complexes derived from aldehyde based thiosemicarbazone ligands thiosemicarbazones are a family of compounds with beneficial biological activity viz., anticancer,antitumour, antifungal, antibacterial, antimalarial, antifilarial, antiviral and anti-HIV activities. Many thiosemicarbazone ligands and their complexes have been prepared and screened for their antimicrobial activity against various types of fungi and bacteria. The results prove that the compounds exhibit antimicrobial properties and it is important to note that in some cases metal chelates show more inhibitory effects than the parent ligands. The increased lipophilicity of these complexes seems to be responsible for their enhanced biological potency. Adverse biological activities of thiosemicarbazones have been widely studied in rats and in other species. The parameters measured show that copper complexes caused considerable oxidative stress and zinc zinc complexes behaved as antioxidants. It has applications on analytical field also. Some thiosemicarbazones produce highly colored complexes with metal ions. This thesis aims to synthesis some novel thiosemicarbazone ligands and their transition metal complexes together with their physico-chemical characterization.

Mesozooplankton of the Arabian Sea and the Bay of Bengal with special reference to planktonic ostracods

The Arabian Sea and the Bay of Bengal are both highly dynamic ecosystems, due to the seasonally reversing monsoon winds, but the processes affecting the mesozooplankton community remain poorly understood. These are important basins exhibiting enhanced biological production as a result of upwelling, winter cooling and other episodic events such as eddies and gyres. Zooplankters are primarily the prey for almost all fish larvae. Seasonal changes in the biogeochemical processes can strongly affect zooplankton density and distribution, which in turn, strongly affect the larval growth, and consequently, the pelagic fish recruitment. It is clear that plankton biomass and biogeochemical fluxes are not in steady state. Acoustic data on mesozooplankton abundance suggests that they also exist in the mesopelagic zone. Earlier studies were confined only to the upper 200 m and hence the structure of mesozooplankton community in the deeper layers was not well known. Copepods are the dominant mesoplankton group, and therefore the majority of the studies were focused on them. The planktonic ostracods are the second major crustacean group and at times, their swarms can outnumber all other planktonic groups. The understanding of the community structure of the ostracods is essential to establish their role in the marine food web. Mesozooplankton is responsible for the vertical flux of organic matter produced by phytoplankton and is assumed to be equivalent to new production (Eppley & Peterson, 1979). Since the fate of newly produced organic matter depends upon their consumers, the zooplankton biomass must be estimated in size fractions or taxonomic components to understand the vertical flux of organic carbon. It is thus important to update our knowledge on different groups of zooplankton on the basis of seasonal and temporal distribution. The distribution in space and time is essential for modeling the carbon cycling that structure the marine ecosystems

Immobilization of nitrifying bacterial consortia on wood particles for bioaugmenting nitrification in shrimp culture systems

Shrimp grow out systems under zero water exchange mode demand constant remediation of total ammonia nitrogen (TAN) andNO2 −–Nto protect the crop. To address this issue, aninexpensive and user-friendly technology using immobilized nitrifying bacterial consortia (NBC) as bioaugmentors has been developed and proposed for adoption in shrimp culture systems. Indigenous NBC stored at 4 °C were activated at room temperature (28 °C) and cultured in a 2 L bench top fermentor. The consortia, after enumeration by epifluorescence microscopy,were immobilized on delignifiedwood particles of a soft wood tree Ailantus altissima (300–1500 μm) having a surface area of 1.87m2 g−1. Selection of wood particle as substratumwas based on adsorption of NBC on to the particles, biofilm formation, and their subsequent nitrification potential. The immobilization could be achievedwithin 72 h with an initial cell density of 1×105 cells mL−1. On experimenting with the lowest dosage of 0.2 g (wet weight) immobilized NBC in 20 L seawater, a TAN removal rate of 2.4 mg L−1 within three days was observed. An NBC immobilization device could be developed for on site generation of the bioaugmentor preparation as per requirement. The product of immobilization never exhibited lag phase when transferred to fresh medium. The extent of nitrification in a simulated systemwas two times the rate observed in the control systems suggesting the efficacy in real life situations. The products of nitrification in all experiments were undetectable due to denitrifying potency, whichmade the NBC an ideal option for biological nitrogen removal. The immobilized NBC thus generated has been named TANOX (Total Ammonia Nitrogen Oxidizer)

Development of a decision support system for the integrated control of membrane bioreactors

The work presented in this PhD thesis includes various partial studies aimed at developing a decision support system for membrane bioreactor integrated control. The decision support systems (DSS) have as a main goal to facilitate the operation of complex processes due to the multiple variables that are processed. For this reason, the research used has focused on aspects related to nutrient removal, and on the development of indicators or sensors capable of facilitating, automating and controlling the filtration process in an integrated way with the biological processes that taking place. Work has also been done on the design, development, implementation and validation of tools based on the knowledge made available by the automatic control and the supervision of the MBRs

Primary succession in man-made wetlands: biodiversity, structure and dynamics of macrofaunal assemblages

Man-made wetlands are often created to compensate for the loss or degradation of natural wetlands, but little is known about the processes taking place in these artificial environments, especially at the community level. Throughout this thesis, we have assessed the phenomena of primary succession over different time (short-, mid- and long-term) and spatial scales (local, regional, interregional levels), applying different approaches (taxonomic and functional) and subject groups (invertebrates and amphibians). Our main findings regarding time scales show a 3-phase successional pattern in Mediterranean man-made wetlands’ communities, where at the short term (1 year) colonization processes dominate; at mid term perspectives (2 to 7 years) succession signs begin to be conspicuous, and later on (≥ 10 years) parameters such as species richness reach an asymptote. At that moment, some biological strategies dominate, and biodiversity surrogates indicate that communities are indistinct between man-made and natural wetlands. Regarding spatial effects, we corroborated that both local and regional factors affect the establishing communities. Particularly, the low hydrological stability of the Mediterranean region has enhanced biological traits favoring resilience and resistance to disturbances when comparing Mediterranean and cold temperate aquatic communities. Even within the Mediterranean region, low levels of hydrological stability have significant effects on the successional dynamics. In these cases, local communities are highly nested within regional natural ones, and so are not able to make net contributions to regional richness. We also showed the influence of the regional pool of recruiters over local communities, both in the case of invertebrates and amphibians. Especially for the latter group, man-made Mediterranean temporary ponds (MTPs) can play an important role in their conservation.

Control basat en lògica difusa per sistemes de fangs activats. Disseny, implementació i validació en EDAR reals

En aquesta tesi es presenten dues propostes de Sistemes de Control basats en Lògica Difusa (SCLD), des del seu disseny fins a la seva implementació i validació en dues instal·lacions: l'EDAR Granollers i l'EDAR Taradell. El capítol 1 explica els conceptes bàsics per comprendre el desenvolupament dels dos SCLD i el resum d'una revisió d'articles que relacionen la lògica difusa amb aigües residuals. A continuació, s'estableixen els objectius. En el capítol 3 es presenten els materials i mètodes. Els capítols 4 i 5 exposen el treball realitzat per arribar a la implementació dels dos SCLD. Ambdós capítols presenten la mateixa estructura: presentació, definició dels objectius del SCLD, descripció de l'EDAR on s'implementa el SCLD, desenvolupament d'índexs d'avaluació, explicació del disseny del SCLD i la seva avaluació mitjançant estudis de simulació, implementació i validació del SCLD a l'EDAR i, finalment discussió del treball realitzat. En el capítol 6 s'enumeren les conclusions obtingudes.

Desarrollo del proceso anammox para el tratamiento de lixiviados: puesta en marcha y aplicación

La eliminación biológica de nitrógeno amoniacal se ha llevado a cabo, habitualmente, a través del proceso convencional de nitrificación-desnitrificación. Sin embargo, los lixiviados generados en los depósitos controlados de residuos sólidos urbanos contienen elevadas cantidades de amonio y bajas concentraciones de materia orgánica biodegradable, así como una elevada salinidad. En este caso, para reducir el elevado coste económico que supone aplicar los procesos convencionales en este tipo de efluentes es conveniente desarrollar sistemas alternativos. Uno de estos nuevos procesos biológicos se basa en el proceso anammox (acrónimo en inglés de anaerobic ammonium oxidation) previa nitritación parcial de amonio a nitrito. El proceso anammox es un proceso autotrófico que realiza la conversión de amonio y nitrito a nitrógeno gas bajo condiciones anaerobias. El menor consumo de oxígeno durante el proceso de nitritación parcial y la no necesidad de adicionar materia orgánica para desnitrificar representan un importante ahorro económico respecto a los tratamientos convencionales

Diffusion of the synthetic pyrethroid permethrin into bed-sediments

Bed-sediments are a sink for many micro-organic contaminants in aquatic environments. The impact of toxic contaminants on benthic fauna often depends on their spatial distribution, and the fate of the parent compounds and their metabolites. The distribution of a synthetic pyrethroid, permethrin, a compound known to be toxic to aquatic invertebrates, was studied using river bed-sediments in lotic flume channels. trans/cis-Permethrin diagnostic ratios were used to quantify the photoisomerization of the trans isomer in water. Rates were affected by the presence of sediment particles and colloids when compared to distilled water alone. Two experiments in dark/light conditions with replicate channels were undertaken using natural sediment, previously contaminated with permethrin, to examine the effect of the growth of an algal biofilm at the sediment-water interface on diffusive fluxes of permethrin into the sediment. After 42 days, the bulk water was removed, allowing a fine sectioning of the sediment bed (i.e., every mm down to 5 mm and then 5-10 mm, then every 10 mm down to 50 mm). Permethrin was detected in all cases down to a depth of 5-10 mm, in agreement with estimates by the Millington and Quirk model, and measurements of concentrations in pore water produced a distribution coefficient (K-d) for each section, High K-d's were observed for the top layers, mainly as a result of high organic matter and specific surface area. Concentrations in the algal biofilm measured at the end of the experiment under light conditions, and increases in concentration in the top 1 mm of the sediment, demonstrated that algal/bacterial biofilm material was responsible for high K-d's at the sediment surface, and for the retardation of permethrin diffusion. This specific partition of permethrin to fine sediment particles and algae may enhance its threat to benthic invertebrates. In addition,the analysis of trans/cis-permethrin isomer ratios in sediment showed greater losses of trans-permethrin in the experiment under light conditions, which may have also resulted from enhanced biological activity at the sediment surface.

On site flotation for recovering polluted aquatic systems: is it a feasible solution for a Brazilian urban river?

Pinheiros River (Brazil) plays a pivotal role in supplying water to Billings Reservoir, which presents multiple uses (human drinking, energy generation, irrigation, navigation, fishing and leisure) An intense monitoring program was performed during the years 2007 and 2008 to find out whether on site flotation is a feasible solution or not for improving the water quality of this urban river, attenuating the pollutants load caused by the water pumping to the reservoir (approximately 10 m(3)s(-1)) The monitoring of 18 variables (13,429 laboratorial analysis during the period of 490 days), suggested that despite the convenience of the on site approach for water treatment, especially for rivers located in fully urbanized areas, the flotation system is not enough itself to recover Pinheiros River water quality, given the several constraints that apply Total phosphorus removal was high in percentage terms (about 90%), although the remaining concentrations were not so low (mean of 0 05 mg L(-1)) The removal efficiency of some variables was insufficient, leading to high final mean concentrations of metals [e g aluminium (0 29 mg L(-1)), chromium (0 02 mg L(-1)) and iron (1 1 mg L(-1))] as well as nitrogen-ammonia (25 8 mg L(-1)) and total suspended solids (18 mg L(-1)) in the treated water

Avaliação do processo de compostagem de resíduos sólidos urbanos

A crescente produção de resíduos sólidos urbanos e a escassez de áreas para uma destinação final tecnicamente adequada, via implantação de aterros sanitários, faz com que tome importância a técnica de tratamento de resíduos sólidos orgânicos através das compostagem/vermicompostagem. Nesta pesquisa, foi realizada a avaliação destes processos, tendo sido observadas principalmente a influência da aeração e da umidade no desempenho destas técnicas de tratamento, em leiras de pequenos e grandes volumes. Nos experimentos, com leiras de pequenos volumes, realizados no IPH (Instituto de Pesquisas Hidráulicas) da UFRGS, utilizou-se resíduos sólidos de poda (resíduos verdes, com alta concentração de carbono) codispostos (misturados em peso) com resíduos vegetais da CEASA (Companhia Estadual de Abastecimento Sociedade Anônima) e lodos provenientes de estações de tratamento de esgotos sanitários. Nos experimentos, com leiras de grandes volumes, realizados na UTC – Unidade de Triagem e Compostagem de Porto Alegre, utilizou-se resíduos orgânicos domiciliares codispostos com os mesmos resíduos utilizados nos primeiros experimentos. Paralelamente aos experimentos de compostagem, avaliou-se os lixiviados produzidos nos sistemas. Na compostagem de grandes volumes, também foi observado o desempenho de banhados construídos de fluxo subsuperficial para o tratamento desses efluentes líquidos. com teores de resíduos verdes menores que 35 %, o que se justifica pela maior concentração de resíduos de característica facilmente biodegradável e de maior palatabilidade para os vermes. Em todos os experimentos de compostagem, verificou-se que o controle efetivo do processo pode ser realizado através da avaliação sistemática das temperatura e umidade das leiras. Evidenciou-se também que para regiões de clima similar ao de Porto Alegre, com elevadas precipitações principalmente no inverno, é necessário adotar dimensões adequadas ao sistema de compostagem “windrow” para áreas descobertas. Comprovou-se também a necessidade de manutenção da umidade na faixa entre 50% e 70 %, inclusive com reposição desta, mesmo na situação de inverno. A avaliação dos lixiviados da compostagem demonstrou que, com os substratos utilizados nos experimentos, as concentrações de DBO5, DQO e de outras variáveis são elevadas ao início do processo de decomposição, devido à solubilização dos compostos orgânicos e inorgânicos presentes na matéria orgânica. Os lixiviados da compostagem possuem baixas concentrações de condutividade, DBO5, NH4 +, entre outros, quando comparados aos lixiviados de aterros sanitários. tratamento destes efluentes. Os resultados obtidos nos banhados construídos para baixas cargas hidráulicas (1cm/d) e concentrações de DBO5 do afluente abaixo de 150 mg/L apontaram uma eficiência média de remoção de 52,02%. No que se refere a nitrogênio (todas as formas), fósforo, metais, potencial redox e sólidos totais, as eficiências foram variáveis, com melhores resultados para nitrogênio amoniacal e fósforo. A compostagem pode ser considerada uma alternativa viável de tratamento de resíduos orgânicos, utilizando-se o processo “windrow” com revolvimento mecânico, mesmo em pátios descobertos em climas subtropicais. Neste caso, sugere-se que os lixiviados gerados nos primeiros dias de compostagem (30 dias aproximandamente) sejam recirculados e o excedente tratado em ETE. Pode-se, também, utilizar o sistema de banhados construídos como complementação, principalmente para a remoção de nitrogênio e fósforo.

Eficiência de uma ETE em escala real composta por reator UASB seguido de lodo ativado

In the state of Rio Grande do Norte (RN), Brazil, there are about 80 sewage treatment systems being the predominant technology waste stabilization ponds. The Baldo s WWTP , due to its location and low availability of area, was designed as a hybrid conventional system (UASB reactor followed by activated sludge with biodiscs) at a tertiary level, being the most advanced WWTP in the State and also with the larger treatment capacity (1620 m3/h) .The paper presents the results of its performance based on samples collections from May to December 2012. Composite samples of the effluent of the grit chamber, UASB reactors, anoxic chambers, aeration tanks and treated effluent were collected weekly, every 4 hours for 24 hours. The results showed that the WWTP effluent presented adequate ranges of temperatures, pH and DO, however removal efficiencies of BOD and TSS were below the predicted by design. The UASB reactors also showed removals of BOD and TSS less than expected, due to the accumulation of sludge in the reactors, which eventually, was washed out in the effluent. The nitrification process was not satisfactory mainly due to problems in the oxygen distribution in the aeration tanks. The removal of ammonia and TKN were high, probably by the assimilation process