Simultaneous determination of gemifloxacin and diuretics in bulk, pharmaceutical dosage forms and human serum by RP-HPLC

An isocratic reversed phase high-performance liquid chromatographic (RP-HPLC) method has been developed for the simultaneous determination of gemifloxacin and diuretics (hydrochlorothiazide and furosemide) in bulk, dosage formulations and human serum at 232 nm. Chromatographic separation was achieved on Purospher Start C18 (250 mm x 4.6 mm, 5 µm) column using mobile phase, methanol: water: acetonitrile (70:25:5 v/v/v) adjusted to pH 3.0 via phosphoric acid 85% having flow rate of 0.8 mL min -1 at room temperature. Calibration curves were linear over range of 0.5-10 µg mL -1 with a correlation coefficient ± 0.999. LOD and LOQ were in the ranges of 0.75-2.56 µg mL -1. Intra and inter-run precision and accuracy results were 98.26 to 100.9.

Effect of temperature on the electro-oxidation of ethanol on platinum

We present in this work an experimental investigation of the effect of temperature (from 25 to 180 ºC) in the electro-oxidation of ethanol on platinum in two different phosphoric acid concentrations. We observed that the onset potential for ethanol electro-oxidation shifts to lower values and the reaction rates increase as temperature is increased for both electrolytes. The results were rationalized in terms of the effect of temperature on the adsorption of reaction intermediates, poisons, and anions. The formation of oxygenated species at high potentials, mainly in the more diluted electrolyte, also contributes to increase the electro-oxidation reaction rate.

Quantification of beta-lactam antibiotics in veterinary drugs: amoxicillin and ampicillin determination by high performance liquid chromatography

This work focused on the development and validation of an RP-HPLC-UV method for quantification of beta-lactam antibiotics in three pharmaceutical samples. Active principles analyzed were amoxicillin and ampicillin, in 3 veterinary drugs. Mobile phase comprised 5 mmol L-1 phosphoric acid solution at pH 2.00, acetonitrile with gradient elution mode and detection wavelength at 220 nm. The method was validated according to the Brazilian National Health Surveillance regulation, where linear range and linearity, selectivity, precision, accuracy and ruggedness were evaluated. Inter day precision and accuracy for pharmaceutical samples 1, 2 and 3 were: 1.43 and 1.43%; 4.71 and 3.74%; 2.72 and 1.72%, respectively, while regression coefficients for analytical curves exceeded 0.99. The method had acceptable merit figure values, indicating reliable quantification. Analyzed samples had active principle concentrations varying from -12 to +21% compared to manufacturer label claims, rendering the medicine unsafe for administration to animals.

LC/ESI-MS method applied to characterization of flavonoids glycosides in B. forficata subsp. pruinosa

Bauhinia forficata is used in folk medicine for its hypoglycemiant effect. In the south of Brazil, the subspecies pruinosa is found in a region with the characteristic flora, pampa biome. This species has been consumed by the local population as a tea for diabetes treatment. We studied the chemical composition of hydroethanolic extracts using LC/ESI-MS. The leaf extracts were prepared by percolation with 50% (v/v) ethanol. The chromatographic analyses were performed using a reverse-phase system, gradient elution with acetonitrile:phosphoric acid 0.05%, and ESI-MS in the positive ion mode. The chemical profile of the flavonoids was suggested to involve four quercetin and kaempferol glycosides.

Immersion enthalpy variation of surface-modified mineral activated carbon in lead (II) aqueous solution adsorption: the relation between immersion enthalpy and adsorption capacity

An activated carbon was obtained by chemical activation with phosphoric acid, CM, from a mineral carbon. Afterwards, the carbon was modified with 2 and 5 molL-1, CMox2 and CMox5 nitric acid solutions to increase the surface acid group contents. Immersion enthalpy at pH 4 values and Pb2+ adsorption isotherms were determined by immersing activated carbons in aqueous solution. The surface area values of the adsorbents and total pore volume were approximately 560 m².g-1 and 0.36 cm³g-1, respectively. As regards chemical characteristics, activated carbons had higher acid sites content, 0.92-2.42 meq g-1, than basic sites, 0.63-0.12 meq g-1. pH values were between 7.4 and 4.5 at the point of zero charge, pH PZC. The adsorbed quantity of Pb2+ and the immersion enthalpy in solution of different pH values for CM activated carbon showed that the values are the highest for pH 4, 15.7 mgg-1 and 27.6 Jg-1 respectively. Pb2+ adsorption isotherms and immersion enthalpy were determined for modified activated carbons and the highest values were obtained for the activated carbon that showed the highest content of total acid sites on the surface.

Synthesis and characterization of activated carbon fibers from Kevlar

Kevlar [poly (p-phenilylene terephtalamide)], was used as a precursor in the preparation of activated carbon fibers. For this intention, physical and chemical activations were carried out. Activated fibers were physically prepared from the carbonization of the Kevlar and its later activation with CO2 and steam of water, by the other hand; the chemically activated fibers were obtained by means of the impregnation of the material with phosphoric acid and their later carbonization. Different conditions were used and preliminary analyses of the precursor were taken into account (TGA-DTA / IR). The resulting fibers were characterized by N2 (77K) adsorption, infrared spectroscopy, SEM, and immersion calorimetry. Yields and Burn off were also evaluated. The results shows that if you want to synthesize activated carbon fibers from Kevlar strong conditions respect to the commonly used such as water steam, high phosphoric acid concentrations and methods of impregnation are the ones who allows the development of optimal surface areas and pore volumes.

A pH optode based on thymol blue: application to determination of CO2 using flow injection analysis system

An optode based on thymol blue (TB), an acid-based indicator, has been constructed and evaluated as a detector in FIA system for CO2 determination. The dye was chemically immobilised on the surface of a bifurcated glass optical fibre bundle, using silanisation in organic media. In FIA system, hydrogen carbonate or carbonate samples are injected in a buffer carrier solution, and then are mixed with phosphoric acid solution to generate CO2, which diffuses through a PTFE membrane, in order to be collected in an acceptor carrier fluid, pumped towards to detection cell, in which the optode was adapted. The proposed system presents two linear response ranges, from 1.0 x 10-3 to 1.0 x 10-2 mol l-1, and from 2.0 x 10-2 to 0.10 mol l-1. The sampling frequency was 11 sample h-1, with good repeatability (R.S.D < 4 %, n = 10). In flow conditions the optode lifetime was 170 h. The system was applied in the analysis of commercial mineral water and the results obtained in the hydrogen carbonate determination did not differ significantly from those obtained by potentiometry, at a confidence level of 95 %.

Recovery and refining of manganese as by-product from hydrometallurgical processes

The consumption of manganese is increasing, but huge amounts of manganese still end up in waste in hydrometallurgical processes. The recovery of manganese from multi-metal solutions at low concentrations may not be economical. In addition, poor iron control typically prevents the production of high purity manganese. Separation of iron from manganese can be done with chemical precipitation or solvent extraction methods. Combined carbonate precipitation with air oxidation is a feasible method to separate iron and manganese due to the fast kinetics, good controllability and economical reagents. In addition the leaching of manganese carbonate is easier and less acid consuming than that of hydroxide or sulfide precipitates. Selective iron removal with great efficiency from MnSO4 solution is achieved by combined oxygen or air oxidation and CaCO3 precipitation at pH > 5.8 and at a redox potential of > 200 mV. In order to avoid gypsum formation, soda ash should be used instead of limestone. In such case, however, extra attention needs to be paid on the reagents mole ratios in order to avoid manganese coprecipitation. After iron removal, pure MnSO4 solution was obtained by solvent extraction using organophosphorus reagents, di-(2-ethylhexyl)phosphoric acid (D2EHPA) and bis(2,4,4- trimethylpentyl)phosphinic acid (CYANEX 272). The Mn/Ca and Mn/Mg selectivities can be increased by decreasing the temperature from the commonly used temperatures (40 –60oC) to 5oC. The extraction order of D2EHPA (Ca before Mn) at low temperature remains unchanged but the lowering of temperature causes an increase in viscosity and slower phase separation. Of these regents, CYANEX 272 is selective for Mn over Ca and, therefore, it would be the better choice if there is Ca present in solution. A three-stage Mn extraction followed by a two-stage scrubbing and two-stage sulfuric acid stripping is an effective method of producing a very pure MnSO4 intermediate solution for further processing. From the intermediate MnSO4 some special Mn- products for ion exchange applications were synthesized and studied. Three types of octahedrally coordinated manganese oxide materials as an alternative final product for manganese were chosen for synthesis: layer structured Nabirnessite, tunnel structured Mg-todorokite and K-kryptomelane. As an alternative source of pure MnSO4 intermediate, kryptomelane was synthesized by using a synthetic hydrometallurgical tailings. The results show that the studied OMS materials adsorb selectively Cu, Ni, Cd and K in the presence of Ca and Mg. It was also found that the exchange rates were reasonably high due to the small particle dimensions. Materials are stable in the studied conditions and their maximum Cu uptake capacity was 1.3 mmol/g. Competitive uptake of metals and acid was studied using equilibrium, batch kinetic and fixed-bed measurements. The experimental data was correlated with a dynamic model, which also accounts for the dissolution of the framework manganese. Manganese oxide micro-crystals were also bound onto silica to prepare a composite material having a particle size large enough to be used in column separation experiments. The MnOx/SiO2 ratio was found to affect significantly the properties of the composite. The higher the ratio, the lower is the specific surface area, the pore volume and the pore size. On the other hand, higher amount of silica binder gives composites better mechanical properties. Birnesite and todorokite can be aggregated successfully with colloidal silica at pH 4 and with MnO2/SiO2 weight ratio of 0.7. The best gelation and drying temperature was 110oC and sufficiently strong composites were obtained by additional heat-treatment at 250oC for 2 h. The results show that silica–supported MnO2 materials can be utilized to separate copper from nickel and cadmium. The behavior of the composites can be explained reasonably well with the presented model and the parameters estimated from the data of the unsupported oxides. The metal uptake capacities of the prepared materials were quite small. For example, the final copper loading was 0.14 mmol/gMnO2. According to the results the special MnO2 materials are potential for a specific environmental application to uptake harmful metal ions.

Lannoitetehtaan prosessivesien käsittelyvaihtoehtojen soveltuvuuden arviointi

Phosphorus and nitrogen cause eutrophication of water bodies, causing severe damage to the ecosystem. Eutrophication of the waters causes oxygen depletion, which in turn increases fish mortality, releasing toxins in waters. The released toxins can cause damage to animals and humans, which is the reason in many countries to set emission limits for waste water. Nutrients exist naturally, but due to human activities there is high nutrient leaching to water bodies. Human activity is one of the main reasons to the eutrophication. The aim of this thesis was to estimate the suitability of different water treatment options for Yara Finland’s fertilizer plant’s process waters in Siilinjärvi. The fertilizer plant process waters are high concentrate and especially nitrogen concentrations are high, which bring challenge to the treatment. At the theoretical part was investigated conventional and as well advanced wastewater treatment methods like reverse osmosis, adsorption and ion exchange. Beside different treatment methods corporate environmental requirements, responsibility and strategies were researched. At the empirical part of the thesis the goal was to find out possibil-ities to intensify the efficiency of purification at lamella clarifier with chemical precipitation. In addition possibility to use already existing chemical purifying plant for process waters was estimated. As a result of the research Yara has a possibility to intensify lamella clarifier’s action by addi-tion of calcium hydroxide and thus to obtain the phosphorus and fluorine to precipitate out of the water. But in practice this would be too expensive. It is possible to eliminate nitrogen compounds by adsorption or ammonia stripping, both methods requires additional testing. It is possible to process waters in chemical purifying plant, if ammonium nitrogen has been reduced before. Reverse osmosis is possible to exploit for the phosphoric acid plant’s waters.

Survey of transportation of liquid bulk chemicals in the Baltic Sea

This study is made as a part of the Chembaltic (Risks of Maritime Transportation of Chemicals in Baltic Sea) project which gathers information on the chemicals transported in the Baltic Sea. The purpose of this study is to provide an overview of handling volumes of liquid bulk chemicals (including liquefied gases) in the Baltic Sea ports and to find out what the most transported liquid bulk chemicals in the Baltic Sea are. Oil and oil products are also viewed in this study but only in a general level. Oils and oil products may also include chemical-related substances (e.g. certain bio-fuels which belong to MARPOL annex II category) in some cargo statistics. Chemicals in packaged form are excluded from the study. Most of the facts about the transport volumes of chemicals presented in this study are based on secondary written sources of Scandinavian, Russian, Baltic and international origin. Furthermore, statistical sources, academic journals, periodicals, newspapers and in later years also different homepages on the Internet have been used as sources of information. Chemical handling volumes in Finnish ports were examined in more detail by using a nationwide vessel traffic system called PortNet. Many previous studies have shown that the Baltic Sea ports are annually handling more than 11 million tonnes of liquid chemicals transported in bulk. Based on this study, it appears that the number may be even higher. The liquid bulk chemicals account for approximately 4 % of the total amount of liquid bulk cargoes handled in the Baltic Sea ports. Most of the liquid bulk chemicals are handled in Finnish and Swedish ports and their proportion of all liquid chemicals handled in the Baltic Sea is altogether over 50 %. The most handled chemicals in the Baltic Sea ports are methanol, sodium hydroxide solution, ammonia, sulphuric and phosphoric acid, pentanes, aromatic free solvents, xylenes, methyl tert-butyl ether (MTBE) and ethanol and ethanol solutions. All of these chemicals are handled at least hundred thousand tonnes or some of them even over 1 million tonnes per year, but since chemical-specific data from all the Baltic Sea countries is not available, the exact tonnages could not be calculated in this study. In addition to these above-mentioned chemicals, there are also other high volume chemicals handled in the Baltic Sea ports (e.g. ethylene, propane and butane) but exact tonnes are missing. Furthermore, high amounts of liquid fertilisers, such as solution of urea and ammonium nitrate in water, are transported in the Baltic Sea. The results of the study can be considered indicative. Updated information about transported chemicals in the Baltic Sea is the first step in the risk assessment of the chemicals. The chemical-specific transportation data help to target hazard or e.g. grounding/collision risk evaluations to chemicals that are handled most or have significant environmental hazard potential. Data gathered in this study will be used as background information in later stages of the Chembaltic project when the risks of the chemicals transported in the Baltic Sea are assessed to highlight the chemicals that require special attention from an environmental point of view in potential marine accident situations in the Baltic Sea area.

Intensification of Operation of Inclined Plate Settler at Fertilizer Plant

Fertilizer plant’s process waters contain high concentrations of nitrogen compounds, such as ammonium and nitrate. Phosphorus and fluorine, which originate from phosphoric acid and rock phosphate (apatite) used in fertilizer production, are also present. Phosphorus and nitrogen are the primary nutrients causing eutrophication of surface waters. At fertilizer plant process waters are held in closed internal circulation. In a scrubber system process waters are used for washing exhaust gases from fertilizer reactors and dry gases from granulation drums as well as for cooling down the fertilizer slurry in neutralization reactor. Solids in process waters are separated in an inclined plate settler by gravitational sedimentation. However, the operation of inclined plate settler has been inadequate. The aim of this thesis was to intensify the operation of inclined plate settler and thus the solids separation e.g. through coagulation and/or flocculation process. Chemical precipitation was studied to reduce the amount of dissolved species in process waters. Specific interest was in precipitation of nitrogen, phosphorus, and fluorine containing specimens. Amounts of phosphorus and fluorine were reduced significantly by chemical precipitation. When compared to earlier studies, annual chemical costs were almost eight times lower. Instead, nitrogen compounds are readily dissolved in water, thus being difficult to remove by precipitation. Possible alternative techniques for nitrogen removal are adsorption, ion exchange, and reverse osmosis. Settling velocities of pH adjusted and flocculated process waters were sufficient for the operation of inclined plate settler. Design principles of inclined plate settler are also presented. In continuation studies, flow conditions in inclined plate settler should be modelled with computational fluid dynamics and suitability of adsorbents, ion exchange resins, and membranes should be studied in laboratory scale tests.

Adsorció d'or i zinc amb resines impregnades XAD-2. Superfície d'Equilibri, un nou concepte per a l'adsorció

Dins dels processos de recuperació de metalls de dissolucions diluïdes s'ha realitzat un estudi del procés d'extracció d'or i de zinc mitjançant resines amberlite XAD-2 impregnades amb sulfur de triisobutil fosfina (TIBPS) i àcid di-(2-etilhexil) fosfòric (DEHPA) respectivament. S'ha realitzat un estudi de l'equilibri de l'adsorció d'espècies metàl·liques d'aquests metalls amb les resines indicades anteriorment. Amb la metodologia emprada per a la determinació dels punts d'equilibri dels experiments en batch i en columna, s'ha vist que una única isoterma no podia descriure el fenomen global d'equilibri i que en funció de la metodologia emprada s'obtenien isotermes diferents. Es va introduir una nova variable per poder explicar el fenomen observat, i per tant, amb aquesta nova variable l'equació de la isoterma es converteix amb l'equació d'una supèrfície que s'ha definit com a Superfície d'Equilibri. S'han determinat les equacions de les Suprfícies d'Equilibri dels sistemes d'adsorció estudiats (Au(III) TIBPS/XAD-2 i Zn(II) DEHPA/XAD-2) observan una bona coincidència de tots els punts d'equilibri obtinguts sobre la superfície, així com, un bon ajust de totes les isotermes obtingudes en funció de les diferents metodologies emprades sobre les respectives superfícies d'equilibri. Aquest nou concepte generalitza el concepte d'isoterma d'un procés d'adsorció. Fimalment, s'ha plantejat un model matemàtic d'adsorció per a determinar el coeficient efectiu de difusió (De) i el coeficient de transferància de matèria (kf) per ambdós sistemes d'adsorció estudiats mitjançant l'aplicació del model de difusió de sòlid homogeni (HSDM), utilitzant com a condició de contorn en el model la isoterma de Langmuir obtinguda mitjançant els experiments en columna de llit fix i emprant també l'equació obtinguda mitjançant el nou concepte de Superfície d'Equilibri. Els resultats obtinguts són molt satisfactoris, per tant, es pot concloure que la Superfície d'Equilibri és una bona eina per a descriure l'equilibri en els processos d'adsorció d'or i zinc amb les resines amberlite XAD-2 impregnades amb TIBPS i DEHPA respectivament.

SEM analysis of enamel surface treated by Er : YAG laser: Influence of irradiation distance

Background: Depending on the distance of laser tip to dental surface a specific morphological pattern should be expected. However, there have been limited reports that correlate the Er:YAG irradiation distance with dental morphology. Purpose: To assess the influence of Er:YAG laser irradiation distance on enamel morphology, by means of scanning electron microscopy (SEM). Methods: Sixty human third molars were employed to obtain discs (congruent to 1 mm thick) that were randomly assigned to six groups (n = 10). Five groups received Er:YAG laser irradiation (80 mJ/2 Hz) for 20 s, according to the irradiation distance: 11, 12, 14, 16, or 17 mm. and the control group was treated with 37% phosphoric acid for 15 s. The laser-irradiated discs were bisected. One hemi-disc was separated for superficial analysis without subsequent acid etching, and the other one, received the phosphoric acid for 15 s. Samples were prepared for SEM. Results: Laser irradiation at 11 and 12 min provided an evident ablation of enamel, with evident fissures and some fused areas. At 14, 16 and 17 mm the superficial topography was flatter than in the other distances. The subsequent acid etching on the lased-surface partially removed the disorganized tissue. Conclusions: Er:YAG laser in defocused mode promoted slight morphological alterations and seems more suitable for enamel conditioning than focused irradiation. The application of phosphoric acid on lased-enamel surface, regardless of the irradiation distance, decreased the superficial irregularities.

Shear strength of the bond to primary dentin: influence of Er:YAG laser irradiation distance

The aim of this study was to assess in vitro the influence of Er:YAG laser irradiation distance on the shear strength of the bond between an adhesive restorative system and primary dentin. A total of 60 crowns of primary molars were embedded in acrylic resin and mechanically ground to expose a flat dentin surface and were randomly assigned to six groups (n = 10). The control group was etched with 37% phosphoric acid. The remaining five groups were irradiated (80 mJ, 2 Hz) at different irradiation distances (11, 12, 16, 17 and 20 mm), followed by acid etching. An adhesive agent (Single Bond) was applied to the bonding sites, and resin cylinders (Filtek Z250) were prepared. The shear bond strength tests were performed in a universal testing machine (0.5 mm/min). Data were submitted to statistical analysis using one-way ANOVA and the Kruskal-Wallis test (p < 0.05). The mean shear bond strengths were: 7.32 +/- 3.83, 5.07 +/- 2.62, 6.49 +/- 1.64, 7.71 +/- 0.66, 7.33 +/- 0.02, and 9.65 +/- 2.41 MPa in the control group and the groups irradiated at 11, 12, 16, 17, and 20 mm, respectively. The differences between the bond strengths in groups II and IV and between the bond strengths in groups II and VI were statistically significant (p < 0.05). Increasing the laser irradiation distance resulted in increasing shear strength of the bond to primary dentin.

Bond Strength and Etching Pattern of Adhesive Systems to Enamel: Effects of Conditioning Time and Enamel Preparation

Statement of the problem: The performance of self-etch systems on enamel is controversial and seems to be dependent on the application technique and the enamel preparation. Purpose of the Study: To examine the effects of conditioning time and enamel surface preparation on bond strength and etching pattern of adhesive systems to enamel. Materials and Methods: Ninety-six teeth were divided into 16 conditions (N = 6) in function of enamel preparation and conditioning time for bond strength test. The adhesive systems OptiBond FL (Kerr, Orange, CA, USA), OptiBond SOLO Plus (Kerr), Clearfil SE Bond (Kuraray, Osaka, Japan), and Adper Prompt L-Pop (3M ESPE, St. Paul, MN, USA) were applied on unground or ground enamel following the manufacturers` directions or doubling the conditioning time. Cylinders of Filtek Flow (0.5-mm height) were applied to each bonded enamel surface using a Tygon tube (0.7 mm in diameter; Saint-Gobain Corp., Aurora, OH, USA). After storage (24 h/37 degrees C), the specimens were subjected to shear force (0.5 mm/min). The data were treated by a three-way analysis of variance and Tukey`s test (alpha = 0.05). The failure modes of the debonded interfaces and the etching pattern of adhesives were observed using scanning electron microscopy. Results: Only the main factor ""adhesive"" was statistically significant (p < 0.001). The lowest bond strength value was observed for OptiBond FL. The most defined etching pattern was observed for 35% phosphoric acid and for Adper Prompt L-Pop. Mixed failures were observed for all adhesives, but OptiBond FL showed cohesive failures in resin predominantly. Conclusions: The increase in the conditioning time as well as the enamel pretreatment did not provide an increase in the resin-enamel bond strength values for the studied adhesives. CLINICAL SIGNIFICANCE The surface enamel preparation and the conditioning time do not affect the performance of self-etch systems to enamel. (J Esthet Restor Dent 20:322-336, 2008)