Crystallization of progesterone polymorphs using polymer-induced heteronucleation (PIHn) method

Progesterone is a natural hormone steroid used in humans for several treatments and in livestock for artificial insemination, which exhibits two polymorphic forms at ambient conditions: form 1 and form 2. Form 2 is metastable and more soluble than form 1; however, it is not suitable to use as powder raw material because it transforms into form 1 by the effects of grinding. A polymorphic screening of progesterone based on polymer-induced heteronucleation method was performed as an alternative to prepare the metastable form. Polyvinyl alcohol, hydroxypropyl methylcellulose (HPMC), dextran, gelatin, polyisoprene (PI) and acrylonitrile-butadiene (NBR) copolymer were used. Crystals were prepared from 0.5, 10 and 40?mg/mL solutions in acetone at room temperature by solvent evaporation. The samples were characterized by X-ray powder diffraction, differential scanning calorimetry (DSC), scanning electron microcopy and attenuated total reflectance infrared Fourier transform spectroscopy. Form 1 was nucleated from 40?mg/mL solutions on the six polymers and from 10?mg/mL solutions on PI and NBR. The mixture of form 1 and form 2 was obtained from 10?mg/mL solution on HPMC, dextran and gelatin and from 0.5?mg/mL solution crystallizations. Therefore, the polymeric devices, which crystallized the metastable and more soluble polymorph (2) of progesterone, would be a promissory alternative for the pharmaceutical applications.     

Inhibition of sulfide on the simultaneous removal of nitrate and p‐cresol by a denitrifying sludge

BACKGROUND: Many industrial discharges, such as those generated from petrochemical refineries, contain large amounts of sulfurous, nitrogenous and organic contaminants. Denitrification has emerged as a suitable technology for the simultaneous removal of these pollutants in a single reactor unit; however, more evidence is demanded to clarify the limitations of denitrification on the simultaneous removal of sulfide and phenolic contaminants and to optimize the biological process. The aim of this study was to evaluate the capacity of a denitrifying sludge to simultaneously convert sulfide and p‐cresol via denitrification. RESULTS: Sulfide was the preferred electron donor over p‐cresol, imposing a 5 h lag phase (required for complete sulfide removal) on organotrophic denitrification. Addition of sulfide (20 mg S^2? L^?1) to p‐cresol‐amended denitrifying cultures also decreased the reduction rate of nitrate and nitrite, as well as the production rate of nitrogen gas. Nitrite reduction rate was the most affected step by sulfide, decreasing from 35 to 21 mg N (g VSS d)^?1. A synergistic inhibitory effect of nitrate and sulfide was also observed on nitrite reduction. Despite the effects of sulfide on the respiratory rates monitored, complete removal of nitrate, sulfide and p‐cresol could be achieved after 48 h of incubation. CONCLUSION: Our results suggest that simultaneous removal of sulfide and p‐cresol could be achieved in denitrifying reactors, but a large hydraulic residence time may be required to sustain an efficient process due to inhibitory effects of sulfide. Copyright © 2008 Society of Chemical Industry     

Development of high-performance liquid chromatography criteria for determination of grades of commercial olive oils. Part I. The normal ranges for the triacylglycerols

Criteria for authentic olive oils were developed from isocratic high-performance liquid chromatography analyses of 99 olive oils from the major Mediterranean producers in the 1983–1986 crop years. Authentic olive oils include extra virgin, virgin and pure or refined oils, but exclude all reesterified and adulterated oils. The extra virgin through pure grades will have a combined area for the LOO (C_18:2C_18:1C_18:1), LOP (C_18:2C_18:1C_16:0), OOO (C_18:1C_18:1C_18:1), POO (C_16:0C_18:1C_18:1), POP (C_16:0C_18:1C_18:1), and SOO (C_18:0C_18:1C_18:1) peaks between 82.0 and 92.6% of the total area (L, linoleic; O, oleic; P, palmitic; S, stearic). Authentic oils will have ratios of LOO/LOP and OOO/POO that coincide with a line defined by OOO/POO=0.7844(LOO/LOP)+0.0968; correlation coefficient is 0.885. Authentic oils will not have a trilinolein (LLL) peak over 0.5% in area. Neither triolein (OOO) nor any other single peak suffices to characterize an olive oil sample as one of the authentic grades.     

Analytic expressions for the isosteric heat of adsorption from adsorption isotherm models and two-dimensional SAFT-VR equation of state

The isosteric heat of adsorption is an important thermodynamic property used to characterize and optimize adsorption processes. In this work, analytic expressions for isosteric heats of adsorption are derived for a collection of commonly used isotherm models and a two-dimensional molecular equation of state based on the SAFT-VR approach. The use of these expressions is presented with an example of adsorption of nitrous oxide, N₂O, on biochar, which is a waste biomass charcoal that exhibits high adsorption potential. The results show that accurate fitting of the adsorption isotherms leads to consistent results obtained with different approaches; however, the predicted isosteric heat of adsorption exhibits strong variations in the regions where experimental data is insufficient such in the region of low pressure/low coverage. Convergence on the prediction of the isosteric heat of adsorption by the different models is only observed in the region where no extrapolation of experimental data is needed.     

Development of an Autonomous Robot for Gas Storage Spheres Inspection

Inspection for corrosion of gas storage spheres at the welding seam lines must be done periodically. Until now this inspection is being done manually and has a high cost associated to it and a high risk of inspection personel injuries. The Brazilian Petroleum Company, Petrobras, is seeking cost reduction and personel safety by the use of autonomous robot technology. This paper presents the development of a robot capable of autonomously follow a welding line and transporting corrosion measurement sensors. The robot uses a pair of sensors each composed of a laser source and a video camera that allows the estimation of the center of the welding line. The mechanical robot uses four magnetic wheels to adhere to the sphere’s surface and was constructed in a way that always three wheels are in contact with the sphere’s metallic surface which guarantees enough magnetic atraction to hold the robot in the sphere’s surface all the time. Additionally, an independently actuated table for attaching the corrosion inspection sensors was included for small position corrections. Tests were conducted at the laboratory and in a real sphere showing the validity of the proposed approach and implementation.     

The Impact of Technological Opportunities and Innovative Capabilities on Firms’ Output Innovation

In this study, we analyse the effect that external sources of knowledge and absorptive capacity exert on a firm's output innovation. In addition, we examine the moderating influence of absorptive capacity on the effect that technological opportunities have on output innovation. Empirical research was carried out on a sample of 91 Spanish firms from the ceramic tile industry. Absorptive capacity is operationalized by ‘systematic or continuous R&D’ and output innovation by ‘percentage of sales from new products’. Technological opportunities are divided into several industry and non‐industry related variables. Our results show the positive effect that both the industry's technological opportunities and a systematic approach to R&D exert on output innovation. Moreover, firms with a systematic approach to R&D usually achieve higher innovation output than firms which do not follow this approach. The innovation results of this second group decrease as a result of embedded technology acquisition.     

In vivo remineralization of acid-etched enamel in non-brushing areas as influenced by fluoridated orthodontic adhesive and toothpaste

This study aimed to evaluate the in vivo remineralization of acid-etched enamel in non-brushing areas as influenced by fluoridated orthodontic adhesive and toothpaste. One hundred and twenty teeth from 30 volunteers were selected. The teeth were assigned to four treatments: no treatment (negative control); 37% phosphoric acid-etching (PAE) (positive control); PAE + resin-modified glass ionomer cement (RMGIC); and, PAE + composite resin. Patients brushed teeth with fluoridated (n = 15) or non-fluoridated (n = 15) toothpastes, so that etched enamel was protected with screens and it was not in contact with the brush bristles. Remineralization was evaluated by means of laser fluorescence (LF), environmental scanning electronic microscopy, and energy dispersive spectrometry after extraction. The LF means were compared by means of Wilcoxon and Mann Whitney tests. Environmental scanning electron microscopy scores were compared among the groups using a Kruskal Wallis test, whereas the Ca/P ratio was evaluated by means of an Analysis of Variance with subparcels (treatments) and Tukey's post-hoc test. There were no statistically significant differences between the tooth pastes and between the orthodontic adhesives evaluated. Most teeth presented only partial enamel remineralization. Therefore, the fluoride released by the RMGIC was not enough to cause increased crystal regrowth in the acid-etched enamel. The use of fluoridated toothpaste did not provide positive additional effect.     

Morphology study of progesterone polymorphs prepared by polymer‐induced heteronucleation (PIHn)

In this article, morphology of progesterone polymorphs prepared by polymer‐induced heteronucleation (PIHn) technique was studied. Hydroxypropyl methylcellulose(HPMC), such as dextran T‐500 and gelatin G‐9382, polyisoprene (PI), and acrylonitrile/butadiene copolymer (NBR) were used as substrates. The crystallizations were performed by solvent evaporation at room temperature from 0.5, 10, and 40 mg/ml solutions in chloroform and acetone. Progesterone polymorphs were identified by X‐ray diffraction. Differential scanning calorimetry and total attenuated reflectance infrared spectroscopy were used as complementary techniques in the identification. Depending on the polymeric matrix and the concentration used, form 1, form 2, or mixture of both polymorphs were obtained. Scanning electron microscopy pictures evidenced difference in morphology and in homogeneity of the two progesterone polymorphs. These polymorphs prepared by PIHn, did not present a distinctive morphology that allows identifying polymorph by its crystal habit. Hence, polymeric matrix induced the crystallization, affecting polymorphism and morphology. SCANNING 35:213‐221, 2013. © 2012 Wiley Periodicals, Inc.