Physicochemical and structural characterization of mesoporous aluminosilicates synthesized from leached saponite with additional aluminum incorporation

A thorough investigation was performed on the physical (mechanical, thermal, and hydrothermal stability) and chemical (ion exchange capacity and silanol number) characteristics of aluminosilicate FSMs, synthesized via a new successful short-time synthesis route using leached saponite and a low concentration of CTAB. Moreover, the influence of an additional Al incorporation, utilizing different aluminum sources, on the structure of the FSM derived from saponite is studied. A mesoporous aluminosilicate with a low Si/Al ratio of 12.8 is synthesized, and still has a very large surface area of 1130 m(2)/g and pore volume of 0.92 cm(3)/g. The aluminum-containing samples all have a high cation exchange capacity of around 1 mmol/9 while they still have a silanol number of about 0.9 OH/nm(2); both characteristics being interesting for high-yield postsynthesis modification reactions. Finally, a study is performed on the transformation of the aluminosilicates into their Bronsted acid form via the exchange with ammonium ions and a consecutive heat treatment.

Nitrifying microbial community analysis of nitrite accumulating biofilm reactor by fluorescence in situ hybridization

Biological nitrogen removal via nitrite pathway in wastewater treatment is very important especially in the cost of aeration and as an electron donor for denitrification. Wastewater nitrification and nitrite accumulations were carried out in a biofilm reactor. The biofilm reactor showed almost complete nitrification and most of the oxidized ammonium was present as nitrite at the ammonium load of 1.2 kg N/m3/d. Nitrite accumulation was achieved by the selective inhibition of nitrite oxidizers by free ammonia and oxygen limitation. Nitrite oxidation activity was recovered as soon as the inhibition factor was removed. Fluorescence in situ hybridization studies of the nitrite accumulating biofilm system have shown that genus Nitrosomonas which is specifically hybridized with probe NSM 156 was the dominant nitrifying bacteria while Nitrospira was less abundant than those of normal nitrification systems. Further FISH analysis showed that the combinations of Nitrosomonas and Nitrospira cells were identified as important populations of nitrifying bacteria in an autotrophic nitrifying biofilm system.

Nitrification of high strength ammonia wastewtaer treatment - process selection is the major factor.

Biological nitrogen removal via the nitrite pathway in wastewater treatment is very important in Saving the cost of aeration and as an electron donor for denitrification. Wastewater nitrification and nitrite accumulation were carried out in a biofilm airlift reactor with autotrophic nitrifying biofilm. The biofilm reactor showed almost complete nitrification and most of the oxidized ammonium was present as nitrite at the ammonium load of 1.5 to 3.5 kg N/m3.d. Nitrite accumulation was stably achieved by the selective inhibition of nitrite oxidizers with free ammonia and dissolved oxygen limitation. Stable 100% conversion to nitrite could also be achieved even under the absence of free ammonia inhibition on nitrite oxidizers. Batch ammonium oxidation and nitrite oxidation with nitrite accumulating nitrifying biofilm showed that nitrite Oxidation was completely inhibited when free ammonia is higher than 0.2 mg N/L. However, nitrite oxidation activity was recovered as soon as the free ammonia concentration was below the threshold level when dissolved oxygen concentration was not the limiting factor. Fluorescence in situ hybridization analysis of cryosectioned nitrite accumulating nitrifying biofilm showed that the β-subclass of Proteobacteria, where ammonia oxidizers belong, was distributed outside the biofilm whereas the α-subclass of Proteobacteria, where nitrite oxidizers belong, was found mainly in the inner part of the biofilm. It is likely that dissolved oxygen deficiency or limitation in the inner part of the nitrifying biofilm, where nitrite oxidizers exist, is responsible for the complete shut down of the nitrite oxidizers activity under the absence of free ammonia inhibition.

Influence of the N/K ratio on the production and quality of cucumber in hydroponic system

The objective of this work was to evaluate the quality of fruits and the nutritional status of cucumber CV. Aodai cultivated in nutrient solutions with different N:K ratios. The hydroponic cultivation was initially performed, during the vegetative growth, in nutrient solution with 1:2.0 mmol L-1 N:K, and, later, during fruit setting, in four different nutrient solutions with N:K (w/w) at the ratios 1:1.4, 1:1.7, 1:2.0 and 1:2.5. An additional treatment with a nutrient solution containing the ratio 1:2.2 (w/w) N:K during the vegetative growth and N:K 1:1.4 (w/w) during fruit setting, both with 10% ammonium (NH4+) was included. The treatments were arranged in a randomized design with six replicates. Irrigation was carried out with deionized water until seed germination, and then with nutrient solution until 30 days after germination, when plants were transplanted. Plants in the hydroponic growing beds were irrigated with the solutions for vegetative growth, and, after 21 days, the solutions were replaced by solutions for fruit setting. At 45 and 60 days after transplanting, the fresh weight, length, diameter, volume and firmness of the fruit were evaluated, and, at 45 days after transplanting, the macronutrient concentrations in the leaves were determined. The use of different N:K ratios during fruit setting influenced the cucumber production. The ratio of 1.0:1.7 N: K (w/w), with 10% of N in the form of ammonia, is recommended for the whole cycle.

Herbicidas alternativos para o controle de Conyza sumatrensis (Retz.) E. H. Walker resistentes aos inibidores da ALS e EPSPs

RESUMO A buva (Conyza sumatrensis), uma das principais plantas daninhas já identificadas no sul do Brasil, vem apresentando controle insatisfatório, em resposta à aplicação dos herbicidas chlorimuron-ethyl e glyphosate. Por esta razão, o objetivo deste estudo foi avaliar herbicidas alternativos, visando ao controle de biótipos de C. sumatrensis, com resistência de nível baixo ao herbicida chlorimuron-ethyl e resistentes ao herbicida glyphosate. O experimento foi realizado em casa de vegetação, entre abril e agosto de 2012, no município de Passo Fundo, RS. O delineamento experimental foi o inteiramente casualizado, com quatro repetições, sendo avaliados 15 tratamentos com herbicidas, além de uma testemunha sem aplicação. As variáveis consideradas foram controle percentual, aos 14, 21 e 28 dias após a aplicação dos tratamentos (DAT) e a matéria seca da parte aérea, aos 28 DAT. Como resultados, observou-se que os biótipos foram 100% controlados, aos 28 DAT, pelos tratamentos alternativos de paraquat + diuron; ammonium glufosinate; glyphosate + 2,4-D; glyphosate + ammonium glufosinate; 2,4-D; tembotrione e tembotrione + atrazine. O biótipo 17 evidenciou menor sensibilidade aos herbicidas inibidores da ALS e os biótipos 05, 17 e 20 não foram controlados pelo herbicida glyphosate.

Productivity of irrigated beans due to sources of stabilized nitrogen fertilizer and controlled release

ABSTRACT New nitrogen fertilizers are available in the market actually, however, does not have results on the efficiency of the Cerrado conditions. With that objective of this study was to evaluate the effect of urea including stabilized and controlled release urea on yield of irrigated common beans (Phaseolus vulgaris L) in no-tillage system. The experiment was conducted in the winter crop, at Embrapa Arroz e Feijão, in Santo Antônio de Goiás, State of Goiás, Brazil. The experimental design was randomized blocks, with five replicates. Treatments consisted of five N sources (urea, urea + NBPT, urea + polymer, ammonium sulphate, and ammonium nitrate) and a control (without N) being applied 20 kg ha-1 of N at sowing and 80 kg ha-1 onf N in topdressing. We evaluated the chlorophyll content in leaves of common beans, the leaf N content and dry mass weight (MSPA) in the flowering of common beans, the number of pods per plant, number of grains per pod, mass of 100 grains, grain yield and final stand of the common beans. The sources of nitrogen fertilizer did not influence, leaf N content, the mass of MSPA and the relative chlorophyll index of common beans. The use of polymerized urea and urea with urease inhibitor, did not produce increases in the number of grains per pod, number of pods per plant, mass of 100 grains and common beans yield compared to traditional sources of N, urea, ammonium sulfate and ammonium nitrate.

Development of a biosensor for urea assay based on amidase inhibition, using an ion-selective electrode

A biosensor for urea has been developed based on the observation that urea is a powerful active-site inhibitor of amidase, which catalyzes the hydrolysis of amides such as acetamide to produce ammonia and the corresponding organic acid. Cell-free extract from Pseudomonas aeruginosa was the source of amidase (acylamide hydrolase, EC 3.5.1.4) which was immobilized on a polyethersulfone membrane in the presence of glutaraldehyde; anion-selective electrode for ammonium ions was used for biosensor development. Analysis of variance was used for optimization of the biosensorresponse and showed that 30 mu L of cell-free extract containing 7.47 mg protein mL(-1), 2 mu L of glutaraldehyde (5%, v/v) and 10 mu L of gelatin (15%, w/v) exhibited the highest response. Optimization of other parameters showed that pH 7.2 and 30 min incubation time were optimum for incubation ofmembranes in urea. The biosensor exhibited a linear response in the range of 4.0-10.0 mu M urea, a detection limit of 2.0 mu M for urea, a response timeof 20 s, a sensitivity of 58.245 % per mu M urea and a storage stability of over 4 months. It was successfully used for quantification of urea in samples such as wine and milk; recovery experiments were carried out which revealed an average substrate recovery of 94.9%. The urea analogs hydroxyurea, methylurea and thiourea inhibited amidase activity by about 90%, 10% and 0%, respectively, compared with urea inhibition.

Membrane selectivity versus sensor response in hydrogenated amorphous silicon CHEMFETs using a semi-empirical model

Toxic amides, such as acrylamide, are potentially harmful to Human health, so there is great interest in the fabrication of compact and economical devices to measure their concentration in food products and effluents. The CHEmically Modified Field Effect Transistor (CHEMFET) based onamorphous silicon technology is a candidate for this type of application due to its low fabrication cost. In this article we have used a semi-empirical modelof the device to predict its performance in a solution of interfering ions. The actual semiconductor unit of the sensor was fabricated by the PECVD technique in the top gate configuration. The CHEMFET simulation was performed based on the experimental current voltage curves of the semiconductor unit and on an empirical model of the polymeric membrane. Results presented here are useful for selection and design of CHEMFET membranes and provide an idea of the limitations of the amorphous CHEMFET device. In addition to the economical advantage, the small size of this prototype means it is appropriate for in situ operation and integration in a sensor array.

Nanofiltration for the treatment of coke plant ammoniacal wastewaters

This work addresses the treatment by nanofiltration (NF) of solutions containing NaCN and NH(4)Cl at various pH values. The NF experiments are carried out in a Lab-Unit equipped with NF-270 membranes for model solutions that are surrogates of industrial ammoniacal wastewaters generated in the coke-making processes. The applied pressure is 30 bar. The main objective is the separation of the compounds NaCN and NH(4)Cl and the optimization of this separation as a function of the pH. Membrane performance is highly dependent on solution composition and characteristics, namely on the pH. In fact, the rejection coefficients for the binary model solution containing sodium cyanide are always higher than the rejections coefficients for the ammonium chloride model solution. For ternary solutions (cyanide/ammonium/water) it was observed that for pH values lower than 9 the rejection coefficients to ammonium are well above the ones observed for the cyanides, but for pH values higher than 9.5 there is a drastic decrease in the ammonium rejection coefficients with the increase of the pH. These results take into account the changes that occur in solution, namely, the solute species that are predominant, with the increase of the pH. The fluxes of the model solutions decreased with increased pH. (C) 2010 Elsevier B.V. All rights reserved.

New ionic liquids and salts derived from β-Lactam antibiotics

In recent years ionic liquids (ILs) have been increasing the popularity and the number of applications. Ionic liquids were used mainly as solvent in organic synthesis, but in recent years they are also used in analytical chemistry, separation chemistry and material science. Additional to significant developments in their chemical properties and applications, ionic liquids are now bringing unexpected opportunities at the interface of chemistry with the life sciences. Ionic liquids (ILs) are currently defined as salts that are composed solely of cations and anions which melt below 100ºC. Our goal in this work is to explore the dual activity of the ionic liquids, due to the presence of two different ions, an anion with bacterial activity as β-lactam antibiotics and different kinds of cations. In this work the anions of ILs and salts were derived from three different antibiotics: ampicillin, penicillin and amoxicillin. The cations were derived from substituted ammonium, phosphonium pyridinium and methylimidazolium salts, such as: tetraethyl ammonium, trihexiltetradecilphosphonium, cetylpyridinium, choline (an essential nutrient), 1-ethyl-3-methylimidazolium, and 1-ethanol-3-methyl imidazolium structures. Commercial ammonium and phosponium halogen salts were first transformed into hydroxides on ionic exchange column (Amberlite IRA-400) in methanol. The prepared hydroxides were then neutralized with β-lactam antibiotics. After crystallization we obtained pure ILs and salts containing β-lactam antibiotics. This work presents a novel method for preparation of new salts of antibiotics with low melting point and their chemistry and microbiological characterization.

Synthesis, characterization and antiproliferative activity on cancer cell lines of new ionic liquids from ampicillin

Ionic Liquids (ILs) are ionic compounds that possess melting temperature below 100ºC and they have been a topic of great interest since the mid-1990s due to their unique properties. The range of IL uses has been broadened, due to a significant increase in the variety of physical, chemical and biological ILs properties. They are now used as Active Pharmaceutical Ingredients (APIs) and recent interests are focused on their application as innovative solutions in new medical treatment and delivery options.1 In this work, our principal objective was the synthesis and investigation of physicochemical and medical properties of ionic liquids (ILs) and organic salts from ampicillin. This approach is of huge interest in pharmaceutical industry as cation and anion composition of ILs and organic salts can greatly alter their desired properties, namely the melting temperature and even synergistic effects can be obtained.2,3 For the synthesis of these compounds we used a recently developed method proposed by Ohno et al.4 for the preparation of quaternary ammonium and phosphonium hydroxides, that were neutralized by ampicillin. After purification we obtained pure ILs and salts in good yields. These ILs shows good antimicrobial and antifungal activities. As it is well known that some ionic liquids containing phosphonium and ammonium cation also shows anti-cancer activity1,5 we also decided to study these compounds against some cancer cell lines.

Preparation and characterization of beta-lactam antibiotic as Ionic liquids and salts

With the increase of bacterial resistance a large number of therapeutic strategies have been used to fight different kind of infections. In recent years ionic liquids (ILs) have been increasing the popularity and the number of applications. First ionic liquids were used mainly as solvent in organic synthesis, but now they are used in analytical chemistry, separation chemistry and material science among others. Additional to significant developments in their chemical properties and applications, ionic liquids are now bringing unexpected opportunities at the interface of chemistry with the life sciences Ionic liquids (ILs) are currently defined as salts that are composed solely of cations and anions which melt below 100ºC. Our goal in this work is to explore the dual activity of the ionic liquids, due to the presence of two different ions, an ion with bacterial activity as a beta-lactam antibiotic and different kinds of cations. In this work the anions of ILs and salts were derived from three different antibiotics: ampicillin, penicillin and amoxicillin. The cations were derived from substituted ammonium, phosphonium pyridinium and methylimidazolium salts, such as: tetraethyl ammonium, trihexiltetradecilphosphonium, cetylpyridinium, choline (an essential nutrient), 1-ethyl-3-methylimidazolium, and 1-ethanol-3-methyl imidazolium structures. Commercial ammonium and phosponium halogen salts were first transformed into hydroxides. on ionic exchange column (Amberlite IRA-400) in methanol. The prepared hydroxides were then neutralized with beta-lactam antibiotics. After crystallization we obtained pure ILs and salts containing beta-lactam antibiotics. This work presents a novel method for preparation of new salts of antibiotics with low melting point and their characterization.

Hexanuclear and undecanuclear iron(III) carboxylates as catalyst precursors for cyclohexane oxidation

Two multinuclear complexes [Fe-6(mu(3)-O)(2)(mu(4)-O-2)L-10(OAc)(2)(H2O)(2)]center dot 2.625Et(2)O center dot 2.375H(2)O (1) and [(Fe11Cl)-Cl-III-(mu(4)-O)(3)(mu(3)-O)(5)L-16(dmf)(2.5)(H2O)(0.5)]center dot Et2O center dot 1.25dmf center dot 3.8H(2)O (2), where HL = 3,4,5-trimethoxybenzoic acid and dmf = dimethylformamide, have been prepared from trinuclear iron(III) carboxylates via their structural rearrangement in dimethylformamide or diethyl ether-dimethylformamide 9:1, respectively, and slow vapor diffusion of diethyl ether into the reaction mixture. Both compounds have been characterized by X-ray diffraction, optical, Mossbauer spectroscopy, and magnetic measurements. Complex 1 possesses a hexanuclear ferric peroxido-dioxido {Fe-6(O-2)(O)(2)}(12+) core unit, which adopts a recliner conformation, while complex 2 contains an unprecedented {Fe11O8Cl}(16+) core, in which 9 ferric ions are six-coordinate and the remaining two are five-coordinate. Another structural feature of note of the undecanuclear core is the presence of a deformed cubane entity {Fe-4(mu(3)-O)(mu(4)-O)(3)}(4+). Both complexes act as catalyst precursors for the oxidation of cyclohexane to cyclohexanol and cyclohexanone with aqueous H2O2, in the presence of pyrazinecarboxylic acid. Remarkable TONs and TOFs (the latter mainly for 1) with concomitant quite good yields have been achieved under mild conditions. Moreover, 1 exhibits remarkably high activity in an exceptionally short reaction time (45 min), being unprecedented for any metal catalyzed alkane oxidation by H2O2. The catalytic reactions proceed via Fenton type chemistry.

Evaluation of solubility and partition properties of ampicillin-based ionic liquids

In order to overcome the problems associated with low water solubility, and consequently low bioavailability of active pharmaceutical ingredients (APIs), herein we explore a modular ionic liquid synthetic strategy for improved APIs. Ionic liquids containing l-ampicillin as active pharmaceutical ingredient anion were prepared using the methodology developed in our previous work, using organic cations selected from substituted ammonium, phosphonium, pyridinium and methylimidazolium salts, with the intent of enhancing the solubility and bioavailability of l-ampicillin forms. In order to evaluate important properties of the synthesized API-ILs, the water solubility at 25 °C and 37 °C (body temperature) as well as octanol–water partition coefficients (Kow's) and HDPC micelles partition at 25 °C were measured. Critical micelle concentrations (CMC's) in water at 25 °C and 37 °C of the pharmaceutical ionic liquids bearing cations with surfactant properties were also determined from ionic conductivity measurements.

Metal deposition using Ionic liquids

There is an interest to create zinc/tin alloys to replace cadmium as a corrosion protective coating material. Existing aqueous electroplating systems for these alloys are commercially available but have several limitations. Dangerous and highly toxic complexing agents are uses e.g. cyanides. To overcome these problems, ionic liquids could provide a solution to obtain an alloy containing 20 to 30% of zinc. Ionic liquids (IL’s) often have wider electrochemical windows which allow the deposition of e.g. refractive metals that can not be deposited from aqueous solutions. In IL’s it is often not necessary to add complexing agents. The Zn/Sn alloy deposition from IL’s is therefore a promising application for the plating industry. Nevertheless, there are some issues with this alternative for aqueous systems. The degradation of the organic components, the control of the concentration of two metals and the risk of a two phase deposition instead of an alloy had to be overcome first. It is the main purpose of this thesis to obtain a Zn/Sn alloy with 20% zinc using IL’s as an electrolyte. First a separate study was performed on both the zinc and the tin deposition. Afterwards, an attempt to deposit a Zn/Sn alloy was made. An introduction to a study about the electrodeposition of refractive metals concludes this work. It initiated the research for oxygen-free IL’s to deposit molybdenum or tungsten. Several parameters (temperature, metal source and concentration, organic complexing agents,…) were optimized for both the zinc, tin and zinc/tin deposition. Experiments were performed both in a parallel plate cell and a Hull cell, so as to investigate the effect of current density as well. Ethaline200 was selected as electrolyte. As substrate, brass and iron were selected, while as anode a plate of the metal to deposit was chosen, tin for the alloy. The best efficiencies were always obtained on brass; however the iron substrate resulted in the best depositions. A concentration of 0.27M ZnCl2, 0.07M SnCl2 with 0.015M of K3-HEDTA as complexant resulted in a deposition containing the desired alloy with the amount of 20% zinc and 80% tin with good appearance. Refractory metals as molybdenum and tungsten cannot be electrodeposited from aqueous solutions without forming a co-deposition with Ni, Co or Fe. Here, IL’s could again provide a solution. A first requirement is the dissolution of a metal source. MoO3 could be suitable, however there are doubts about using oxides. Oxygen-free IL’s were sought for. A first attempt was the combination of ZnCl2 with chlormequat (CCC), which gave liquids below 150°C in molar ratios of 2 : 1 and 3 : 1. Unfortuna tely, MoO3 didn’t dissolve in these IL’s. Another route to design oxygen-free IL’s was the synthesis of quaternary ammonium salts. None of the methods used, proved viable as reaction time was long and resulted in very low yields. Therefore, no sufficient quantities were obtained to perform the possible electrochemical behavior of refractive metals.