Chemiluminescence detection flow cells for flow injection analysis and high-performance liquid chromatography

We have examined a range of new and previously described flow cells for chemiluminescence detection. The reactions of acidic potassium permanganate with morphine and amoxicillin were used as model systems representing the many fast chemiluminescence reactions between oxidising agents and organic analytes, and the preliminary partial reduction of the reagent was exploited to further increase the rates of reaction. The comparison was then extended to high-performance liquid chromatography separations of α- and β-adrenergic agonists, with permanganate chemiluminescence detection. Flow cells constructed by machining novel channel designs into white polymer materials (sealed with transparent films or plates) have enabled improvements in mixing efficiency and overall transmission of light to the photodetector.

3D-printed and CNC milled flow-cells for chemiluminescence detection

Herein we explore modern fabrication techniques for the development of chemiluminescence detection flow-cells with features not attainable using the traditional coiled tubing approach. This includes the first 3D-printed chemiluminescence flow-cells, and a milled flow-cell designed to split the analyte stream into two separate detection zones within the same polymer chip. The flow-cells are compared to conventional detection systems using flow injection analysis (FIA) and high performance liquid chromatography (HPLC), with the fast chemiluminescence reactions of an acidic potassium permanganate reagent with morphine and a series of adrenergic phenolic amines.

A review of recent advances in chemiluminescence detection using nano-colloidal manganese(IV)

The application of 'soluble' (colloidal) manganese(IV) for chemiluminescence detection is reviewed, focussing on papers published since the last comprehensive review of the subject in 2008. Advances in this reagent system include: the on-line formation of manganese(IV); new insight into the light-producing pathway and selectivity of the reagent; its application to assess total antioxidants in plant derived samples and oxidative stress in biological fluids and tissues; and the replacement of the formaldehyde enhancer with ethanol.

Ethanol as an alternative to formaldehyde for the enhancement of manganese(IV) chemiluminescence detection.

Previous applications of manganese(IV) as a chemiluminescence reagent have required the use of formaldehyde to enhance the emission intensity to analytically useful levels. However, this known human carcinogen (by inhalation) is not ideal for routine application. A wide range of alternative enhancers have been examined but to date none have been found to provide the dramatic increase in chemiluminescence intensities obtained using formaldehyde. Herein, we demonstrate that ethanol offers a simple, safe and inexpensive alternative to the use of formaldehyde for manganese(IV) chemiluminescence detection, without compromising signal intensity or sensitivity. For example, chemiluminescence signals for opiate alkaloids using 50-100% ethanol were 0.8-1.6-fold those using 2M formaldehyde. This innocuous alternative enhancer is shown to be a particularly effective for the direct detection of thiols and disulfides by manganese(IV) chemiluminescence, which we have applied to a simple HPLC procedure to determine a series of biomarkers of oxidative stress.

A novel in vitro whole plant system for analysis of polyphenolics and their antioxidant potential in cultivars of Ocimum basilicum

Plants are an important source for medicinal compounds. Chemical screening and selection is critical for identification of compounds of interest. Ocimum basilicum (Basil) is a rich source of polyphenolics and exhibits high diversity, therefore bioprospecting of a suitable cultivar is a necessity. This study reports on the development of a true to type novel "in vitro system" and its comparison with a conventional system for screening and selection of cultivars for high total phenolics, individual polyphenolics, and antioxidant content. We have shown for the first time using online acidic potassium permanganate chemiluminescence that extracts from Ocimum basilicum showed antioxidant potential. The current study identified the cultivar specific composition of polyphenolics and their antioxidant properties. Further, a distinct relationship between plant morphotype and polyphenolic content was also found. Of the 15 cultivars examined, "Holy Green", "Red Rubin", and "Basil Genovese" were identified as high polyphenolic producing cultivars while "Subja" was determined to be a low producer. The "in vitro system" enabled differentiation of the cultivars in their morphology, polyphenolic content, and antioxidant activity and is a cheap and efficient method for bioprospecting studies.

Protocols for finding the most orthogonal dimensions for two-dimensional high performance liquid chromatography

The selection of two high performance liquid chromatography (HPLC) columns with vastly different retention mechanisms is vital for performing effective two-dimensional (2D-) HPLC. This paper reports on a systematic method to select a pair of HPLC columns that provide the most different separations for a given sample. This was completed with the aid of a HPLC simulator that predicted retention profiles on the basis of real experimental data, which is difficult when the contents of sample matrices are largely-or completely-unknown. Peaks from the same compounds must first be matched between chromatograms to compare the retention profiles and optimised 2D-HPLC column selection. In this work, two methods of matching peaks between chromatograms were explored and an optimal pair of chromatography columns was selected for 2D-HPLC. First, a series of 17 antioxidants were selected as an analogue for a coffee extract. The predicted orthogonality of the standards was 39%, according to the fractional surface coverage 'bins' method, which was close to the actual space utilisation of the standard mixture, 44%. Moreover, the orthogonality for the 2D-HPLC of coffee matched the predicted value of 38%. The second method employed a complex sample matrix of urine to optimise the column selections. Seven peaks were confidently matched between chromatograms by comparing relative peak areas of two detection strategies: UV absorbance and potassium permanganate chemiluminescence. It was found that the optimal combinations had an orthogonality of 35% while the actual value was closer to 30%.

Avaliação do processo oxidativo avançado por permanganato de potássio no tratamento de solos contaminados com idrocarbonetos poliaromáticos

The soil contamination with petroleum is one of the major concern of industries operating in the field and also of environmental agencies. The petroleum consists mainly of alkanes and aromatic hydrocarbons. The most common examples of hydrocarbons polyaromatic are: naphthalene, anthracene, phenanthrene, benzopyrene and their various isomers. These substances cause adverse effects on human and the environment. Thus, the main objective of this work is to study the advanced oxidation process using the oxidant potassium permanganate (KMnO4) for remediation of soils contaminated with two polyaromatic hydrocarbons (PAHs): anthracene and phenanthrene. This study was conducted at bench scale, where the first stage was at batch experiment, using the variables: the time and oxidant dosage in the soil. The second stage was the remediation conducted in continous by a fix column, to this stage, the only variable was remediation time. The concentration of oxidant in this stage was based on the best result obtained in the tests at batch, 2,464 mg / L. The results of degradation these contaminants were satisfactory, at the following dosages and time: (a) 5g of oxidant per kg soil for 48 hours, it was obtained residual contaminants 28 mg phenanthrene and 1.25 mg anthracene per kg of soil and (b) for 7g of oxidant per kg soil in 48 hours remaining 24 mg phenanthrene and anthracene 0.77 mg per kg soil, and therefore below the intervention limit residential and industrial proposed by the State Company of Environmental Sao Paulo (CETESB)

Avaliação e modelagem da absorção de H2S do gás natural em coluna de leito estagnado

Natural gas, although basically composed by light hydrocarbons, also presents contaminant gases in its composition, such as CO2 (carbon dioxide) and H2S (hydrogen sulfide). The H2S, which commonly occurs in oil and gas exploration and production activities, causes damages in oil and natural gas pipelines. Consequently, the removal of hydrogen sulfide gas will result in an important reduction in operating costs. Also, it is essential to consider the better quality of the oil to be processed in the refinery, thus resulting in benefits in economic, environmental and social areas. All this facts demonstrate the need for the development and improvement in hydrogen sulfide scavengers. Currently, the oil industry uses several processes for hydrogen sulfide removal from natural gas. However, these processes produce amine derivatives which can cause damage in distillation towers, can cause clogging of pipelines by formation of insoluble precipitates, and also produce residues with great environmental impact. Therefore, it is of great importance the obtaining of a stable system, in inorganic or organic reaction media, able to remove hydrogen sulfide without formation of by-products that can affect the quality and cost of natural gas processing, transport, and distribution steps. Seeking the study, evaluation and modeling of mass transfer and kinetics of hydrogen removal, in this study it was used an absorption column packed with Raschig rings, where the natural gas, with H2S as contaminant, passed through an aqueous solution of inorganic compounds as stagnant liquid, being this contaminant gas absorbed by the liquid phase. This absorption column was coupled with a H2S detection system, with interface with a computer. The data and the model equations were solved by the least squares method, modified by Levemberg-Marquardt. In this study, in addition to the water, it were used the following solutions: sodium hydroxide, potassium permanganate, ferric chloride, copper sulfate, zinc chloride, potassium chromate, and manganese sulfate, all at low concentrations (»10 ppm). These solutions were used looking for the evaluation of the interference between absorption physical and chemical parameters, or even to get a better mass transfer coefficient, as in mixing reactors and absorption columns operating in counterflow. In this context, the evaluation of H2S removal arises as a valuable procedure for the treatment of natural gas and destination of process by-products. The study of the obtained absorption curves makes possible to determine the mass transfer predominant stage in the involved processes, the mass transfer volumetric coefficients, and the equilibrium concentrations. It was also performed a kinetic study. The obtained results showed that the H2S removal kinetics is greater for NaOH. Considering that the study was performed at low concentrations of chemical reagents, it was possible to check the effect of secondary reactions in the other chemicals, especially in the case of KMnO4, which shows that your by-product, MnO2, acts in H2S absorption process. In addition, CuSO4 and FeCl3 also demonstrated to have good efficiency in H2S removal

Melanocitoma dérmico fribroso em bezerra

Melanomas are neoplasm not frequent in rattle. They constitute less than 2% of all the bovine turners. This report describes a 11-month-old female Holstein heifer hearing a subcutaneous mass of tissue approximately 18 x 8 cm surrounding the right eye, extending to the top of the neck. This mass appeared when the animal was 4-month-old. A biopsy sample taken to histopathology revealed neoplastic tissue composed of melanin-loaded cells and not disorganized connective tissue fibers. Partial pigment removal, utilizing potassium permanganate technique, revealed large nucleus in thp melanocitic cells. In some of these cells, a nucleolus was evident. Considering that previous reports on fibrous dermic melanocytoma are rarer in the literature, these findings are documented.

Electrical conductivity of soybean seed and correlation with seed coat lignin content

The effects of soybean genotype and seed coat lignin content on bulk electrical conductivity were investigated. Seeds of nine soybean cultivars were hand harvested at R8 maturation stage in Londrina, PR., Brazil in 1995/96. Seeds were electrical conductivity tested using four replicates of 50 seeds per cultivar soaked in 75 mi of deionized water at 25 degrees C for 24 hours. Seed coat lignin content was determined using the potassium permanganate method. There was a significant relationship (R-2 = 0.84**) between electrical conductivity and seed coat lignin content, the latter being a characteristic that varies among soybean genotypes; the higher the amount of lignin in the seed coat, the lower the levels of seed exudates to the soaking solution and consequently the lower the electrical conductivity. It was concluded that seed soaking electrical conductivity is influenced by the seed coat lignin content, which is a characteristic that varies among soybean genotypes. Additionally, the EC test can be used as a valuable tool in the screening process for this characteristic, which is desirable for genetically improving soybean seed quality.

Conservação frigorificada de pêssegos ‘Tropic beauty’ irradiados com e sem utilização de permanganato de potássio

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Síntese do complexo ferro (III) com ácido pirazina tetracarboxílico e aplicação como catalisador em reação fenton

The amount of waste generated by industries has increased gradually in recent years. The proper disposal of residues has been an area of study of many researchers. Several organic compounds are considered potential contaminants of natural waters due to their high toxicity, difficult natural degradation and long persistence in the environment. Ways of recovery and reutilization as well as concepts that minimize the generation of wastes have been increasing widely. Organometallic compound of pyrazine carboxylic acid has proven to be of great interest in many areas. Herein, we studied the use of pyrazine tetracarboxylic acid ligand for complex formation with iron (Fe). The binder (C 8H4N2O8) was synthetized with the addition of Fe (complex) and tested as a catalyst in oxidation reactions of the organic model compound methylene blue (MB). Tetramethyl pyrazine was used in the synthesis, which was oxidized with potassium permanganate in order to form the ligand. The ligand (C 8H4N2O8) was then characterized to validate its formation. For the complex solution, it was used (C 8H4N2O8) and Fe (NO3)3.9H2O 0,01molL-1. After preliminary tests, it was found that the best ratio of Fe and the ligand was 2: 1. Through the oxidation tests, it could be seen that the complex has great potential for the degradation of different concentrations of MB. During only 20 minutes of reaction, approximately 60% of MB 500 mgL -1 was oxidized. The use of the complex was found to be an attractive alternative for oxidation of effluents with high organic compounds levels and contributes to the minimization of organic contaminants hazards in the environment.

Desenvolvimento de um sistema de injeção em fluxo para a determinação seqüencial de fosfito e fosfato em amostras agroindustriais por espectrofotometria

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Tratamento físico-químico de efluentes de curtume por meio de filtros de membrana seletiva

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)