Synthesis and biological activity of sulfur compounds showing structural analogy with combretastatin A-4

We extended our previous exploration of sulfur bridges as bioisosteric replacements for atoms forming the bridge between the aromatic rings of combretastatin A-4. Employing coupling reactions between 5-iodo-1,2,3-trimethoxybenzene and substituted thiols, followed by oxidation to sulfones with m-CPBA, different locations for attaching the sulfur atom to ring A through the synthesis of nine compounds were examined. Antitubulin activity was performed with electrophoretically homogenous bovine brain tubulin, and activity occurred with the 1,2,3-trimethoxy-4-[(4-methoxyphenyl)thio]benzene (12), while the other compounds were inactive. The compounds were also tested for leishmanicidal activity using promastigote forms of Leishmania braziliensis (MHOM/BR175/M2904), and the greatest activity was observed with 1,2,3-trimethoxy-4-(phenylthio)benzene (10) and 1,2,3-trimethoxy-4-[(4-methoxyphenyl) sulfinyl]benzene (15).

Synthesis, characterization, and biological activity of a new class of dialkylphosphorylhydrazone derivatives of isatin

Sixteen dialkylphosphorylhydrazones were synthesized by condensation of phosphorylhydrazines with substituted isatins. Products were characterized by FTIR, ¹H-NMR, 13C-NMR, and 31P-NMR. Fungicidal activities of these compounds against Rhizoctonia solani and Fusarium oxysporum were also evaluated. Some compounds inhibited the growth of Rhizoctonia solani and Fusarium oxysporum by 43% and 51%, respectively. These compounds exhibited no effects on germination of lettuce seeds (Lactuca sativa L).

SYNTHESIS AND BIOLOGICAL EVALUATION OF SPIRO[INDOLINE-3,4’-PYRANO[2,3-C:6,5-C’]DIPYRAZOL]- 2-ONES IN THE PRESENCE OF SBA-Pr-SO3H AS A NANOCATALYST

Sulfonic acid functionalized SBA-15 nanoporous material (SBA-Pr-SO3H) with a large pore size of 6 nm, a high surface area, high selectivity, and excellent chemical and thermal stability was applied as an efficient heterogeneous nanoporous acid catalyst in the reaction of isatin with pyrazolones under mild reaction conditions. A novel class of symmetrical spiro[indoline-3,4'-pyrano[2,3-c:6,5-c']dipyrazol]-2-one derivatives was successfully obtained in high yields. Comparison of these results with those reported in the literature shows that the current method is efficient, and results in better reaction times and yields of the desired products. Other advantages of this new method are its operational simplicity, easy work-up procedure, and the use of SBA-Pr-SO3H as a reusable and environmentally benign nanoreactor, such that the reaction proceeds easily in its nanopores. We also tested the antimicrobial activity of the prepared compounds using the disc diffusion method, and some of the synthesized compounds exhibited the best results against B. subtilis and S. aureus.

SYNTHESIS AND BIOLOGICAL ACTIVITY OF NEW SERIES OF ORGANOTIN(IV) ESTERS WITH N,N-DIACETYLGLYCINE

A bioactive N,N-diacetylglycine (NNDAG) and new organotin(IV) complexes (OTCs) (1-7) were synthesized. Spectroscopic techniques were employed to characterize NNDAG and OTCs. FTIR was employed to verify N,N protection of glycine by acetyl groups. The disappearance of υ(OH) at 3000-2600 cm-1 showed de-protonation of free ligand. The Δυ 150<200 cm-1 of OTCs 4-7 verified bidentate coordination with tetrahedral geometry. The Δυ of OTCs1 and 3 was <200 cm-1 exhibitingtrans -octahedral geometry while OTC 2 dimer was assigned a unique sinusoidal view. The 1H NMR spectra of OTCs verified their synthesis by de-protonation of NNDAG and no chemical shift was found downfield for carboxylic acid proton. The 13C, 119Sn NMR and Mass spectrometric data also supported FTIR and 1H NMR descriptions. The OTCs 4, 5, 6 and7 (500 ppm) proved twice as active against Escherichia coli as the standard antibiotic enoxacin (1000 ppm). The promising property of the OTCs (4, 5, 6 and7) is clearly due to their tetrahedral. The OTCs 4and 5 exhibited excellent activity against M. minimum and good activity against T. castaneum.LD50 of all the compounds were determined and OTCs4, 5 and 7 were found to be active.

Biological and molecular characterization of an isolate of Tobacco streak virus obtained from soybeans in Brazil

A virus was isolated from soybean (Glycine max) plants with symptoms of dwarfing and bud blight in Wenceslau Braz County, Paraná, Brazil. The host range and properties resembled those of Tobacco streak virus (TSV). The purified virus showed three peaks in a frozen sucrose gradient. Antiserum was produced and the virus was serologically related to TSV. Electron microscopy detected 28 nm spherical particles. Coat protein (CP) had a Mr of 29.880 Da. A fragment of 1028 nt was amplified, cloned and sequenced. One open reading frame with 717 nt was identified and associated to the CP. The CP gene shared 83% identity with the sequence of TSV CP from white clover (Trifolium repens) (GenBank CAA25133). This is the first report of the biological and molecular characterization of TSV isolated from soybeans. It is proposed that this isolate be considered a strain of TSV named TSV-BR.

The oxygenation in biological wastewater treatment of pulp and paper industry

The UPM-Kymmene Oyj Pietarsaari pulp and paper Mill biological wastewater treatment plant was built in the 1980's and the plant has been in use ever since. During the past years there have been problems with deviations. The wastewater treatment plant needs update, especially the aeration basin, where the old surface aerators cannot produce enough mixing and indroduce oxygen enough to the wastewater. In this thesis how extra aeration with oxygen affects the wastewater treatment plant effluent was studied. In the literature part the main focus is in aeration devices, which can be used in biological wastewater treatment. The target is to compare different kind of aerators, which are suitable for pulp and paper wastewater treatment. Studies show, that EDI-aerators are commonly used and also most suitable. In the experimental part, the focus is on the Pietarsaari Mills wastewater treatment plant and oxygen aeration during autumn 2008. This thesis presents the results of the trial run. Studies show, that extra oxygen devices can produce lot a of mixing and the oxygenation capacity was more than what the micro-organisms needed. The effect on sludge quality could not been seen during the trial runs.

Biheterocyclic ligands: synthesis, characterization and coordinating properties of bis(4-amino-5-mercapto-1,2,4-triazol-3-yl) alkanes with transition metal ions and their thermokinetic and biological studies

The Co(II), Ni(II) and Cu(II) metal ions complexes of Bis(4-amino-5-mercapto-1,2,4-triazol-3-yl) alkanes (BATs) have been prepared and characterized by elemental analysis, conductivity measurements infrared, magnetic susceptibility, the electronic spectral data and thermal studies. Based on spectral and magnetic results, the ligands are tetradentate coordinating through the N and S-atoms of BATs; six-coordinated octahedral or distorted octahedral and some times four-coordinated square planar were proposed for these complexes. Activation energies computed for the thermal decomposition steps were compared. The ligands and their metal complexes were tested in vitro for their biological effects. Their activities against two gram-positive, two gram-negative bacteria and two fungal species were found to vary from moderate to very strong.

Photo-Fenton process for treating biological laboratory wastewater containing formaldehyde

Laboratories consume great amounts of hazardous chemicals substances and consequently generate wastewater containing them, for example formaldehyde. This substance is widely utilized to preserve biological samples generating many liters of this residue every year. The present work proposes the use of the photo-Fenton process to treat formaldehyde wastewater using sunlight irradiation. Some aspects were investigated such as the iron source, sample and hydrogen peroxide concentration and also the use of stirred systems. The use of ferrioxalate (0.5 mmol L-1) improved the efficiency of the process in relation to the use of iron nitrate, while at least 1.0 mol L-1 H2O2 is necessary to treat the sample of the 500 mg C L-1. Under these conditions, every formaldehyde detectable was degradeted and 89% of the dissolved organic carbon was removed in two hours of exposure to sunlight. These results are satisfaction considerate for São Paulo State Environmental Agency.

Hybrid warfare – just a twist of compound warfare? : views on warfare from the United States Armed Forces perspective

The wars the Western armies are involved with today are different from those that were fought in the end of 20th century. To explain this change, the Western military thinkers have come up with various different types of definitions of warfare over the last 30 years, each describing the tendencies involved in the conflicts of the time. The changing nature of conflicts surfaced a new term – hybrid warfare. The term was to describe and explain the multi-modality and complexity of modern day conflict. This thesis seeks the answer for the question: what is the development of thought behind hybrid warfare? In this thesis the Vietnam War (1965-1975) is used as an example of compound warfare focusing on the American involvement in the war. The Second Lebanon War (2006) serves as an example of hybrid warfare. Both case studies include an irregular opposing force, namely National Liberation Front in Vietnam War and Hezbollah in the Second Lebanon War. These two case studies are compared with the term full spectrum operations introduced in the current U.S. Department of Army Field Manual No. 3-0 Operations to see the differences and similarities of each term. The perspective of this thesis is the American point of view. This thesis concludes that hybrid warfare, compound warfare and full spectrum operations are very similar. The first two terms are included in the last one. Although hybrid warfare is not officially defined, it will most likely remain to be used in the discussion in the future, since hybrid wars and hybrid threats are officially accepted terms.

Application of response surface methodology to study the biological removal of nitrogen from effluent of cattle slaughterhouse in a sequencing batch reactor

The aim of this study was to evaluate the efficiency of a sequencing batch reactor (SBR) on biological removal of nitrogen from cattle slaughterhouse wastewater by nitrification/denitrification processes. The effects of initial concentration of ammoniacal nitrogen were investigated at 100; 150 and 200 mg L-1 and air flow rate at 0.125; 0.375 and 0.625 L min¹ Lreactor-1 on the nitrogen compounds removal, by a Central Composite Rotational Design (CCRD) configuration. There were variations from 9.2 to 94.9%, 4.0 to 19.6% and 20.8 to 92.0% in the conversion of ammoniacal nitrogen to nitrate and nitrite concentration and removal of total nitrogen, respectively. The increase of air flow rate and decrease of the initial concentration of ammoniacal nitrogen resulted in higher efficiencies of total nitrogen removal, as well as the conversion of ammoniacal nitrogen to nitrate. During the pre-established intervals of this study, the removal and conversion efficiencies of nitrogen compounds above 85% were achieved in air flow rate variations from 0.375 to 0.725 L min-1 Lreactor-1 and initial concentration of ammoniacal nitrogen from 80 to 200 mg L-1. On denitrification process, we obtained efficiencies from 91.5 to 96.9% on the removal of nitrite/nitrate and from 78.3 to 87.9% on the removal of organic matter.

Effect of cycle time and airflow in biological nitrogen removal from poultry slaughterhouse wastewater using sequencing batch reactor

This study aimed to evaluate the influence of airflow (0.25, 0.50 and 0.75 L.L-1.min-1) and cycle time (10.45 h, 14.25 h and 17.35 h) on a sequencing batch reactor (SBR) performance in promoting nitrification and denitrification of poultry slaughterhouse wastewater. The operational stages included feeding, aerobic and anoxic reactions, sedimentation and discharge. SBR was operated in a laboratory scale with a working volume of 4 L, keeping 25% of biomass retained inside the reactor as inoculum for the next batch. In the anoxic stage, C: N ratio was maintained between 5 and 6 by adding cassava starch wastewater. A factorial design (22) with five repetitions was designed at the central point to evaluate the influence of cycle time and airflow on total inorganic nitrogen removal (N-NH4++N-NO2-+N-NO3-) and in the whole process (nitrification and denitrification). The highest total inorganic nitrogen removal (93.3%) was observed for airflow of 0.25 L.L-1.min‑1 and a cycle time of 14.25 h. At the end of the experiment, the sludge inside the reactor was characterized by fluorescent in situ hybridization (FISH), indicating the presence of ammonia and nitrite oxidizing bacteria.

Winning time in land warfare : a reading of the classical strategists prior to the age of mechanization

We live in an age where rationalization and demands of efficiency taint every aspect of our lives both as individuals and as a society. Even warfare cannot escape the increased speed of human interaction. Time is a resource to be managed. It has to be optimized, saved and won in military affairs as well. The purpose of this research paper is to analyze the dogmatic texts of military thought to search for answers what the classics of strategy saw in the interrelations of temporality and warfare and if their thoughts remain meaningful in the contemporary conjunction. Since the way a society functions is reflected in the way it conducts its wars, there naturally are differences between an agrarian, industrial and information society. Theorists of different eras emphasize things specific to their times, but warfare, like any human interaction, is always bounded by temporality. Not only is the pace of warfare dependent on the progress of the society, but time permeates warfare in all its aspects. This research paper focuses on two specific topics that arose from the texts themselves; how should time be managed and manipulated in warfare and how to economize and “win” it from the enemy. A method where lengthy quotations are used to illustrate the main point of the strategists has been chosen for this research paper. While Clausewitz is the most prominent source of quotations, thoughts from ancient India and China are represented as well to prove that the combination of right force in the right place at the right time is still the way of the victorious. Tactics change in the course of time but the principles of strategy remain unaltered and are only adapted to suit new situations. While ancient and pre-modern societies had their focus on finding auspicious moments for battle in the flow of kronos-time based on divinities, portents and auguries, we can trace elements of manipulation of time in warfare from the earliest surviving texts. While time as a fourth dimension of the battlespace emerged only in the modern era, all through the history of military thought it has had a profound meaning. In the past time could be squandered, today it always has to be won. This paper asks the question “why”.

Disturbance and ecosystem functioning : the role of changes in benthic biological traits

Rapid changes in biodiversity are occurring globally, as a consequence of anthropogenic disturbance. This has raised concerns, since biodiversity is known to significantly contribute to ecosystem functions and services. Marine benthic communities participate in numerous functions provided by soft-sedimentary ecosystems. Eutrophication-induced oxygen deficiency is a growing threat against infaunal communities, both in open sea areas and in coastal zones. There is thus a need to understand how such disturbance affects benthic communities, and what is lost in terms of ecosystem functioning if benthic communities are harmed. In this thesis, the status of benthic biodiversity was assessed for the open Baltic Sea, a system severely affected by broad-scale hypoxia. Long-term monitoring data made it possible to establish quantitative biodiversity baselines against which change could be compared. The findings show that benthic biodiversity is currently severely impaired in large areas of the open Baltic Sea, from the Bornholm Basin to the Gulf of Finland. The observed reduction in biodiversity indicates that benthic communities are structurally and functionally impoverished in several of the sub-basins due to the hypoxic stress. A more detailed examination of disturbance impacts (through field studies and -experiments) on benthic communities in coastal areas showed that changes in benthic community structure and function took place well before species were lost from the system. The degradation of benthic community structure and function was directed by the type of disturbance, and its specific temporal and spatial characteristics. The observed shifts in benthic trait composition were primarily the result of reductions in species’ abundances, or of changes in demographic characteristics, such as the loss of large, adult bivalves. Reduction in community functions was expressed as declines in the benthic bioturbation potential and in secondary biomass production. The benthic communities and their degradation accounted for a substantial proportion of the changes observed in ecosystem multifunctionality. Individual ecosystem functions (i.e. measures of sediment ecosystem metabolism, elemental cycling, biomass production, organic matter transformation and physical structuring) were observed to differ in their response to increasing hypoxic disturbance. Interestingly, the results suggested that an impairment of ecosystem functioning could be detected at an earlier stage if multiple functions were considered. Importantly, the findings indicate that even small-scale hypoxic disturbance can reduce the buffering capacity of sedimentary ecosystem, and increase the susceptibility of the system towards further stress. Although the results of the individual papers are context-dependent, their combined outcome implies that healthy benthic communities are important for sustaining overall ecosystem functioning as well as ecosystem resilience in the Baltic Sea.