Solubilization of decane into gemini surfactant with a modified Jeffamine backbone: Design of hierarchical porous silica

Herein, we have investigated the solubilization of decane into a novel nonionic gemini surfactant, myristoyl-end capped Jeffamine, synthesized from a polyoxyalkyleneamine (ED900). Starting from this system, porous silica materials have been prepared. Performing the hydrothermal treatment at low temperature, a slight increase of the mesopore diameter is observed in the presence of decane. Increasing the temperature of the hydrothermal treatment, no swelling effect of decane is detected. By contrast, the pore diameter decreases but better mesopore homogeneity and a larger wall thickness are obtained. At high decane concentration the new myristoyl-end capped Jeffamine/decane/water system forms oil-in-water emulsions, which are used as template for the formation of hierarchical porous silica materials.

Coexistence of Two Kinds of Fluorinated Hydrogenated Micelles as Building Blocks for the Design of Bimodal Mesoporous Silica with Two Ordered Mesopore Networks

A simple and effective route has been developed for the synthesis of bimodal (3.6 and 9.4 nm) mesoporous silica materials that have two ordered interconnected pore networks. Mesostructures have been prepared through the self assembly mechanism by using a mixture of polyoxyethylene fluoroalkyl ether and triblock copolymer as building block. The investigation of the RF8(EO)9/P123/water phase diagram evidences that in the considered surfactant range of concentrations, the system is micellar (L1). DLS measurements indicate that this micellar phase is composed of two types of micelles, the size of the first one at around 7.6 nm corresponds unambiguously to the pure fluorinated micelles. The second type of micelles at higher diameter consists of fluorinated micelles which have accommodated a weak fraction of P123 molecules. Thus, in this study the bimodal mesoporous silica are really templated by two kinds of micelles.

Design and production of protein nanostructures for biomolecular detection

Particulate nanostructures are increasingly used for analytical purposes. Such particles are often generated by chemical synthesis from non-renewable raw materials. Generation of uniform nanoscale particles is challenging and particle surfaces must be modified to make the particles biocompatible and water-soluble. Usually nanoparticles are functionalized with binding molecules (e.g., antibodies or their fragments) and a label substance (if needed). Overall, producing nanoparticles for use in bioaffinity assays is a multistep process requiring several manufacturing and purification steps. This study describes a biological method of generating functionalized protein-based nanoparticles with specific binding activity on the particle surface and label activity inside the particles. Traditional chemical bioconjugation of the particle and specific binding molecules is replaced with genetic fusion of the binding molecule gene and particle backbone gene. The entity of the particle shell and binding moieties are synthesized from generic raw materials by bacteria, and fermentation is combined with a simple purification method based on inclusion bodies. The label activity is introduced during the purification. The process results in particles that are ready-to-use as reagents in bioaffinity. Apoferritin was used as particle body and the system was demonstrated using three different binding moieties: a small protein, a peptide and a single chain Fv antibody fragment that represents a complex protein including disulfide bridge.If needed, Eu3+ was used as label substance. The results showed that production system resulted in pure protein preparations, and the particles were of homogeneous size when visualized with transmission electron microscopy. Passively introduced label was stably associated with the particles, and binding molecules genetically fused to the particle specifically bound target molecules. Functionality of the particles in bioaffinity assays were successfully demonstrated with two types of assays; as labels and in particle-enhanced agglutination assay. This biological production procedure features many advantages that make the process especially suited for applications that have frequent and recurring requirements for homogeneous functional particles. The production process of ready, functional and watersoluble particles follows principles of “green chemistry”, is upscalable, fast and cost-effective.

Nanoparticle-coated organic-inorganic microparticles: experimental design and gastrointestinal tolerance evaluation

The influences of the spray-drying parameters and the type of nanoparticles (nanocapsules or nanospheres) on the characteristics of nanoparticle-coated diclofenac-loaded microparticles were investigated by using a factorial design 3². Gastrointestinal tolerance following oral administration in rats was evaluated. Formulations were selected considering the best yields, the best encapsulation efficiencies and the lowest water contents, presenting surfaces completely coated by nanostructures and a decrease in the surface areas in relation to the uncoated core. In vitro drug release demonstrated the influence of the nanoparticle-coating on the dissolution profiles of diclofenac. Nanocapsule-coated microparticles presented a protective effect on the gastrointestinal mucosa.

Analytical procedures for determining Pb and Sr isotopic compositions in water samples by ID-TIMS

Few articles deal with lead and strontium isotopic analysis of water samples. The aim of this study was to define the chemical procedures for Pb and Sr isotopic analyses of groundwater samples from an urban sedimentary aquifer. Thirty lead and fourteen strontium isotopic analyses were performed to test different analytical procedures. Pb and Sr isotopic ratios as well as Sr concentration did not vary using different chemical procedures. However, the Pb concentrations were very dependent on the different procedures. Therefore, the choice of the best analytical procedure was based on the Pb results, which indicated a higher reproducibility from samples that had been filtered and acidified before the evaporation, had their residues totally dissolved, and were purified by ion chromatography using the Biorad® column. Our results showed no changes in Pb ratios with the storage time.

Espacios olvidados, lugares diferenciados: transformación social del espacio urbano en Bogotá (1850- 1880) = Forgotten Spaces, distinct places: Social transformation of urban space in Bogotá (1850-1880)

The purpose of this article is linked to some forms of recovery of social and urban spaces fallen into oblivion that are evident in the social transformation of urban space in Bogotá between 1850 and 1880.The following paper presents the preliminary results of the research entitled practices and social uses of water in Bogotá (1850-1888). The text links in first discussions about the understanding of the city as a drawing in space, moving to describe, the growth of the city, integrating its historical, social and cultural structuring

Application of cloud point preconcentration and flame atomic absorption spectrometry for the determination of cadmium and zinc ions in urine, blood serum and water samples

A simple, sensitive and selective cloud point extraction procedure is described for the preconcentration and atomic absorption spectrometric determination of Zn2+ and Cd2+ ions in water and biological samples, after complexation with 3,3',3",3'"-tetraindolyl (terephthaloyl) dimethane (TTDM) in basic medium, using Triton X-114 as nonionic surfactant. Detection limits of 3.0 and 2.0 µg L-1 and quantification limits 10.0 and 7.0 µg L-1were obtained for Zn2+ and Cd2+ ions, respectively. Relative standard deviation was 2.9 and 3.3, and enrichment factors 23.9 and 25.6, for Zn2+ and Cd2+ ions, respectively. The method enabled determination of low levels of Zn2+ and Cd2+ ions in urine, blood serum and water samples.

Química Sem Fronteiras: o desafio da energia

Coal, natural gas and petroleum-based liquid fuels are still the most widely used energy sources in modern society. The current scenario contrasts with the foreseen shortage of petroleum that was spread out in the beginning of the XXI century, when the concept of "energy security" emerged as an urgent agenda to ensure a good balance between energy supply and demand. Much beyond protecting refineries and oil ducts from terrorist attacks, these issues soon developed to a portfolio of measures related to process sustainability, involving at least three fundamental dimensions: (a) the need for technological breakthroughs to improve energy production worldwide; (b) the improvement of energy efficiency in all sectors of modern society; and (c) the increase of the social perception that education is a key-word towards a better use of our energy resources. Together with these technological, economic or social issues, "energy security" is also strongly influenced by environmental issues involving greenhouse gas emissions, loss of biodiversity in environmentally sensitive areas, pollution and poor solid waste management. For these and other reasons, the implementation of more sustainable practices in our currently available industrial facilities and the search for alternative energy sources that could partly replace the fossil fuels became a major priority throughout the world. Regarding fossil fuels, the main technological bottlenecks are related to the exploitation of less accessible petroleum resources such as those in the pre-salt layer, ranging from the proper characterization of these deep-water oil reservoirs, the development of lighter and more efficient equipment for both exploration and exploitation, the optimization of the drilling techniques, the achievement of further improvements in production yields and the establishment of specialized training programs for the technical staff. The production of natural gas from shale is also emerging in several countries but its production in large scale has several problems ranging from the unavoidable environmental impact of shale mining as well as to the bad consequences of its large scale exploitation in the past. The large scale use of coal has similar environmental problems, which are aggravated by difficulties in its proper characterization. Also, the mitigation of harmful gases and particulate matter that are released as a result of combustion is still depending on the development of new gas cleaning technologies including more efficient catalysts to improve its emission profile. On the other hand, biofuels are still struggling to fulfill their role in reducing our high dependence on fossil fuels. Fatty acid alkyl esters (biodiesel) from vegetable oils and ethanol from cane sucrose and corn starch are mature technologies whose market share is partially limited by the availability of their raw materials. For this reason, there has been a great effort to develop "second-generation" technologies to produce methanol, ethanol, butanol, biodiesel, biogas (methane), bio-oils, syngas and synthetic fuels from lower grade renewable feedstocks such as lignocellulosic materials whose consumption would not interfere with the rather sensitive issues of food security. Advanced fermentation processes are envisaged as "third generation" technologies and these are primarily linked to the use of algae feedstocks as well as other organisms that could produce biofuels or simply provide microbial biomass for the processes listed above. Due to the complexity and cost of their production chain, "third generation" technologies usually aim at high value added biofuels such as biojet fuel, biohydrogen and hydrocarbons with a fuel performance similar to diesel or gasoline, situations in which the use of genetically modified organisms is usually required. In general, the main challenges in this field could be summarized as follows: (a) the need for prospecting alternative sources of biomass that are not linked to the food chain; (b) the intensive use of green chemistry principles in our current industrial activities; (c) the development of mature technologies for the production of second and third generation biofuels; (d) the development of safe bioprocesses that are based on environmentally benign microorganisms; (e) the scale-up of potential technologies to a suitable demonstration scale; and (f) the full understanding of the technological and environmental implications of the food vs. fuel debate. On the basis of these, the main objective of this article is to stimulate the discussion and help the decision making regarding "energy security" issues and their challenges for modern society, in such a way to encourage the participation of the Brazilian Chemistry community in the design of a road map for a safer, sustainable and prosper future for our nation.

Optimization of solvent mixtures for extraction from bark of Schinus terebinthifolius by a statistical mixture-design technique and development of a UV-Vis spectrophotometric method for analysis of total polyphenols in the extract

A statistical mixture-design technique was used to study the effects of different solvents and their mixtures on the yield, total polyphenol content, and antioxidant capacity of the crude extracts from the bark of Schinus terebinthifolius Raddi (Anacardiaceae). The experimental results and their response-surface models showed that ternary mixtures with equal portions of all the three solvents (water, ethanol and acetone) were better than the binary mixtures in generating crude extracts with the highest yield (22.04 ± 0.48%), total polyphenol content (29.39 ± 0.39%), and antioxidant capacity (6.38 ± 0.21). An analytical method was developed and validated for the determination of total polyphenols in the extracts. Optimal conditions for the various parameters in this analytical method, namely, the time for the chromophoric reaction to stabilize, wavelength of the absorption maxima to be monitored, the reference standard and the concentration of sodium carbonate were determined to be 5 min, 780 nm, pyrogallol, and 14.06% w v-1, respectively. UV-Vis spectrophotometric monitoring of the reaction under these conditions proved the method to be linear, specific, precise, accurate, reproducible, robust, and easy to perform.

BIOFILMS BASED ON CANIHUA FLOUR (Chenopodium Pallidicaule): DESIGN AND CHARACTERIZATION

This work aims to (1) produce and characterize the flour obtained from two varieties of canihua, cupi and illpa-inia, and (2) evaluate the ability of these flours to form biofilms. The flours produced contain proteins, starches, lipids, organic substances containing phenol groups, and high percentages of unsaturated fatty acids. Films produced from the illpa variety presented lower water vapor permeability and larger Young’s modulus values than the films formed from the cupi variety. Both films were yellowish and displayed a high light blocking ability (as compared with polyethylene films), which can be attributed to the presence of phenolic compounds. Furthermore, they showed lesser solubility and water permeability than other polysaccharide films, which may be the result of the higher protein (12%–13.8%) and lipid (11%) contents in canihua flours, as well as the formation of a larger number of S–S bonds. On the other hand, these films presented a single vitreous transition temperature at low temperatures (< 0 °C), crystallization of the A and Vh types, and an additional diffraction peak at 2 = 7.5º, ascribed to the presence of essential fatty acids in canihua flour. Canihua flour can form films with adequate properties and shows promise for potential applications in food packaging, because it acts as a good barrier to incident ultraviolet light.

RAPID AND SENSITIVE DETERMINATION OF PALLADIUM USING HOMOGENEOUS LIQUID-LIQUID MICROEXTRACTION VIA FLOTATION ASSISTANCE FOLLOWED BY GRAPHITE FURNACE ATOMIC ABSORPTION SPECTROMETRY

A method for the determination of trace amounts of palladium was developed using homogeneous liquid-liquid microextraction via flotation assistance (HLLME-FA) followed by graphite furnace atomic absorption spectrometry (GFAAS). Ammonium pyrrolidine dithiocarbamate (APDC) was used as a complexing agent. This was applied to determine palladium in three types of water samples. In this study, a special extraction cell was designed to facilitate collection of the low-density solvent extraction. No centrifugation was required in this procedure. The water sample solution was added to the extraction cell which contained an appropriate mixture of extraction and homogeneous solvents. By using air flotation, the organic solvent was collected at the conical part of the designed cell. Parameters affecting extraction efficiency were investigated and optimized. Under the optimum conditions, the calibration graph was linear in the range of 1.0-200 µg L-1 with a limit of detection of 0.3 µg L-1. The performance of the method was evaluated for the extraction and determination of palladium in water samples and satisfactory results were obtained. In order to verify the accuracy of the approach, the standard addition method was applied for the determination of palladium in spiked synthetic samples and satisfactory results were obtained.

Uses of nitrate ion sensitive electrodes

Some models of ion-selective electrodes (ISE) and other methods have been elaborated, to quantify nitrate levels in environmental samples (water, fruits, vegetables and others), using direct potentiometry

Modeling of water/steam circulation in Circulating Fluidized Bed boiler

A distinctive design feature of steam boiler with natural circulation is the presence of the steam drum which plays a role of the separator of vapor from the flow of water-and-steam mixture coming into steam drum from the furnace tubes. Steam drum with unheated downcomer tubes, deducing from it, and riser (screen/furnace tubes) inside the furnace is a closed circulation loop in which movement of water (downcomer tubes) and water-and-steam mixture (riser tubes) is organized. The movement of the working fluid is appears due to occurrence of the natural pressure, determined by the difference in hydrostatic pressure and the mass of water and water-and-steam mixtures in downcomer and riser tubes and called the driving pressure of the natural circulation:

Determination of Hg in water by CVAAS using 2-aminothiazole modified silica

This paper discusses a rapid and sensitive method developed to determine trace levels of mercury in natural water samples by cold vapor atomic absorption spectrometry using a preconcentration system composed by mini-column packed with 100 mg of 2-aminothiazol modified silica gel (SiAT) coupled on-line with the spectrometer's cold vapor generator system. The optimum preconcentration conditions are also described here. The preconcentrated Hg(II) ions were eluted directly from the column to the spectrometer's cold vapor generator system using 100 µL of 2 mol L-1 hydrochloric acid and the retention efficiency achieved exceeded 95%. The enrichment factors determined were 29, 38 and 46 using 3, 4 and 5 mL of preconcentrated aqueous solutions containing 400 ng L-1 of Hg. The detection limit calculated was 5 ng L-1. The preconcentration procedure was applied to determine trace level mercury in spiked river water samples.

Sensitive spectrophotometric assessment of carbofuran using dapsone as a new chromogenic reagent in formulations and environmental samples

A simple, sensitive and selective spectrophotometric method for the assessment of carbofuran in various formulations and in environmental water samples is described. The method is based on the coupling of hydrolyzed carbofuran with diazotized dapsone in alkaline medium at 0 ­ 4° C which gives orange red colored product having the absorption maximum at 480 nm. The product is stable for 48 h. Beer's law is obeyed in the concentration range of 0.1 ­ 4.0 µg ml-1. The molar absorptivity and Sandell's Sensitivity are 5.0 x 10(4) L mol-1 cm-1 and 4.4 ng cm-2 respectively. The method is highly reproducible and is confirmed by RSD values (1.144 %). From the recovery studies it is found that this method is accurate and it can be successfully employed for the determination of carbofuran.