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.     

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.     

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.     

A Graphical Method for Fire Design of Reinforced Concrete Beams

Fire Technology - Reinforced concrete beams lose resistance at high temperatures and so as to guarantee their good performance, it is mandatory to consider this accidental action in design. As an...     

Blends composed of poly(N‐isopropylacrylamide) and an ethylene/vinyl alcohol copolymer: Thermal and morphological studies

Blends of poly(N‐isopropylacrylamide) (PNIPAM) and an ethylene/vinyl alcohol copolymer (EVAL) were obtained through casting from dimethyl sulfoxide (DMSO) solutions and phase inversion in 50/50 DMSO/H₂O solutions. The miscibility and morphology of the PNIPAM/EVAL blends were investigated with thermal and morphological analysis. Differential scanning calorimetry indicated that the crystallinity of EVAL decreased with increasing PNIPAM content and that the blends cast from DMSO/H₂O solutions were miscible in the melt state. Measurements of the melting point depression allowed the determination of the interaction energy density (B) and Flory–Huggins interaction parameter (χ₁₂) with the Nishi–Wang equation. The negative B and χ₁₂ values obtained were examined in terms of the specific intermolecular interactions between the polymers. Scanning electron micrographs revealed that blends obtained by the casting method led to dense membranes, whereas the phase‐inversion method rendered typical macroporous membranes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 501–505, 2004     

Novel hybrid block copolymer nanocarrier systems to load lipophilic drugs prepared by microphase inversion method

Nanoparticles based on block copolymers of oligosaccharides [β-cyclodextrin (βCyD) and maltoheptaose (Mal₇)] and poly(ε-caprolactone) (PCL) were prepared by microphase inversion method. Zeta-potential, particle size measurements and morphological analysis of drug-free and drug-loaded nanoparticles were performed by using, respectively, laser-doppler anemometry, dynamic and static light scattering and transmission electron microscopy. ρ-Ratio values were correlated with transmission electron microscopy observations. Both types of amphiphilic block copolymers, βCyD-b-PCL_5k and Mal₇-b-PCL_5k, self-assembled in water to form spherical vesicles, presented a hydrodynamic diameter of 72 and 34 nm, respectively. The incorporation of drugs into nanoparticles did not affect significantly the particle size for βCyD-b-PCL_5k-based nanoparticles with progesterone, unlike the other tested systems. On the other hand, all nanoparticles (with and without drug) were negatively charged. Both nanoparticulate systems showed high drug loading efficiency (higher than 95%), confirming their suitability as delivery system for lipophilic drugs.     

Properties of filmogenic solutions of gliadin crosslinked with 1-(3-dimethyl aminopropyl)-3-ethylcarbodiimidehydrochloride/N-hydroxysuccinimide and cysteine

In this study gliadin solutions were crosslinked with 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride/N-hydroxysuccinimide (EDC/NHS) and cysteine. The filmogenic solutions were studied through rheological, sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) and FTIR analysis. Gliadin modified by EDC/NHS showed lower viscosity values when compared with the gliadin/cysteine system and the non-modified gliadin system. Determination of amino groups in gliadin modified by EDC/NHS was carried out through the trinitrobenzenesulfonic acid (TNBS) method. The cast films were evaluated by FTIR analysis in order to detect structural changes in the secondary structure of protein. SDS-PAGE showed the formation of higher protein aggregates, indicating that cysteine promotes gliadin polymerization through covalent bonds (disulfide bonds). The TNBS analysis showed that non-chemically modified gliadin had higher amounts of ε-amino groups when compared with gliadin treated with EDC/NHS; however, both systems revealed similar amounts of amino groups for the whole range of glycerol content. The FTIR spectra for the films showed that the two crosslinking agents act by different mechanisms, promoting changes in the secondary structure of gliadin.     

The influence of different cross-linking reactions and glycerol addition on thermal and mechanical properties of biodegradable gliadin-based film

In this study gliadin solutions previously cross-linked by 1-(3-dimethylaminopropyl)-3-1-ethylcarbodiimide hydrochloride/n-hydroxysuccinimide (EDC/NHS) and l-cysteine were prepared with different plasticizer concentrations. The obtained films were investigated through mechanical behavior (Young's modulus and elongation at break), thermal characteristics (differential scanning calorimetry and thermogravimetric analysis), swelling and water solubility, FTIR measurements and scanning electron microscopy. The relationships between the gliadin structure and the mechanical, thermal and morphological properties were affected by protein conformational changes during the cross-linking reaction. On the other hand, the reaction mechanism was strongly dependent on the glycerol content.     

In Silico Study,Physicochemical, and In Vitro Lipase Inhibitory Activity of α,β-Amyrenone Inclusion Complexes with Cyclodextrins

α,β-amyrenone (ABAME) is a triterpene derivative with many biological activities; however, its potential pharmacological use is hindered by its low solubility in water. In this context, the present work aimed to develop inclusion complexes (ICs) of ABAME with γ- and β-cyclodextrins (CD), which were systematically characterized through molecular modeling studies as well as FTIR, XRD, DSC, TGA, and SEM analyses. In vitro analyses of lipase activity were performed to evaluate possible anti-obesity properties. Molecular modeling studies indicated that the CD:ABAME ICs prepared at a 2:1 molar ratio would be more stable to the complexation process than those prepared at a 1:1 molar ratio. The physicochemical characterization showed strong evidence that corroborates with the in silico results, and the formation of ICs with CD was capable of inducing changes in ABAME physicochemical properties. ICs was shown to be a stronger inhibitor of lipase activity than Orlistat and to potentiate the inhibitory effects of ABAME on porcine pancreatic enzymes. In conclusion, a new pharmaceutical preparation with potentially improved physicochemical characteristics and inhibitory activity toward lipases was developed in this study, which could prove to be a promising ingredient for future formulations.