Chemical structure, surface properties and biological activities of the biosurfactant produced by Pseudomonas aeruginosa LBI from soapstock

Pseudomonas aeruginosa LBI isolated from petroleum-contaminated soil produced rhamnolipids (RLLBI) when cultivated on soapstock as the sole carbon source. HPLC-MS analysis of the purified culture supernatant identified 6 RL homologues (%): R-2 C-10 C-10 28.9; R-2 C-10 C-12:1 23.0; R-1 C-10 C-10 23.4; R-2 C-10 C-12 11.3; R-2 C-10 C-12 7.9; R-2 C-10 C-12 C-12 5.5. To assess the potential antimicrobial activity of the new rhamnolipid product, RLLBI, its physicochemical properties were studied. RLLBI had a surface tension of 24 mN m(-1) and an interfacial tension 1.31 mN m(-1); the cmc was 120 mg l(-1). RLLBI produced stable emulsions with hydrocarbons and vegetable oils. This product showed good antimicrobial behaviour against bacteria: MIC for Bacillus subtilis, Staphylococcus aureus and Proteus vulgaris was 8 mg l(-1), for Streptococcus faecalis 4 mg l(-1), and for Pseudomonas aeruginosa 32 mg l(-1). RLLBI was active against phytopathogenic fungal species, MIC values of 32 mg l(-1) being found against Penicillium, Alternaria, Gliocadium virens and Chaetonium globosum. Due to its physicochemical properties and antimicrobial behaviour, RLLBI could be used in bioremediation treatment and in the food, cosmetic and pharmaceutical industries.

Xylo-oligosaccharides from lignocellulosic materials: Chemical structure, health benefits and production by chemical and enzymatic hydrolysis

Currently, there is worldwide interest in the technological use of agro-industrial residues as a renewable source of food and biofuels. Lignocellulosic materials (LCMs) are a rich source of cellulose and hemicellulose. Hemicellulose is rich in xylan, a polysaccharide used to develop technology for producing alcohol, xylose, xylitol and xylo-oligosaccharides (XOSs). The XOSs are unusual oligosaccharides whose main constituent is xylose linked by β 1-4 bonds. The XOS applications described in this paper highlight that they are considered soluble dietary fibers that have prebiotic activity, favoring the improvement of bowel functions and immune function and having antimicrobial and other health benefits. These effects open a new perspective on potential applications for animal production and human consumption. The raw materials that are rich in hemicellulose include sugar cane bagasse, corncobs, rice husks, olive pits, barley straw, tobacco stalk, cotton stalk, sunflower stalk and wheat straw. The XOS-yielding treatments that have been studied include acid hydrolysis, alkaline hydrolysis, auto-hydrolysis and enzymatic hydrolysis, but the breaking of bonds present in these compounds is relatively difficult and costly, thus limiting the production of XOS. To obviate this limitation, a thorough evaluation of the most convenient methods and the opportunities for innovation in this area is needed. Another challenge is the screening and taxonomy of microorganisms that produce the xylanolytic complex and enzymes and reaction mechanisms involved. Among the standing out microorganisms involved in lignocellulose degradation are Trichoderma harzianum, Cellulosimicrobium cellulans, Penicillium janczewskii, Penicillium echinulatu, Trichoderma reesei and Aspergillus awamori. The enzyme complex predominantly comprises endoxylanase and enzymes that remove hemicellulose side groups such as the acetyl group. The complex has low β-xylosidase activities because β-xylosidase stimulates the production of xylose instead of XOS; xylose, in turn, inhibits the enzymes that produce XOS. The enzymatic conversion of xylan in XOS is the preferred route for the food industries because of problems associated with chemical technologies (e.g., acid hydrolysis) due to the release of toxic and undesired products, such as furfural. The improvement of the bioprocess for XOS production and its benefits for several applications are discussed in this study. © 2012 Elsevier Ltd.

SUGARCANE BAGASSE PULPING and BLEACHING: THERMAL and CHEMICAL CHARACTERIZATION

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Isolation and chemical characterization of PwTx-II: A novel alkaloid toxin from the venom of the spider Parawixia bistriata (Araneidae, Araneae)

Brazil has many species of spiders belonging to Araneidae family however, very little is known about the composition, chemical structure and mechanisms of action of the main venom components of these spiders. The main objective of this work was to isolate and to perform the chemical characterization of a novel beta-carboline toxin from the venom of the spider Parawixia bistriata, a typical species of the Brazilian 'cerrado'. The toxin was purified by RP-HPLC and structurally elucidated by using a combination of different spectroscopic techniques (UV, ESI-MS/MS and H-1 NMR), which permitted the assignment of the molecular structure of a novel spider venom toxin, identified as 1-4-guanidinobutoxy-6-hydroxy-1,2,3,4-tetrahydro-beta-carboline, and referred to here as PwTx-II. This compound is toxic to insects (LD50 = 12 +/- 3 eta g/mg honeybee), neurotoxic, convulsive and lethal to rats (LD50 = 9.75 mg/kg of male Wistar rat). (c) 2005 Elsevier Ltd. All rights reserved.

Characterization of Si : O : C : H films fabricated using electron emission enhanced chemical vapour deposition

Silicon-based polymers and oxides may be formed when vapours of oxygen-containing organosilicone compounds are exposed to energetic electrons drawn from a hot filament by a bias potential applied to a second electrode in a controlled atmosphere in a vacuum chamber. As little deposition occurs in the absence of the bias potential, electron impact fragmentation is the key mechanism in film fabrication using electron-emission enhanced chemical vapour deposition (EEECVD). The feasibility of depositing amorphous hydrogenated carbon films also containing silicon from plasmas of tetramethylsilane or hexamethyldisiloxane has already been shown. In this work, we report the deposition of diverse films from plasmas of tetraethoxysilane (TEOS)-argon mixtures and the characterization of the materials obtained. The effects of changes in the substrate holder bias (Vs) and of the proportion of TEOS in the mixture (XT) on the chemical structure of the films are examined by infrared-reflection absorption spectroscopy (IRRAS) at near-normal and oblique incidence using unpolarised and p-polarised, light, respectively. The latter is particularly useful in detecting vibrational modes not observed when using conventional near-normal incidence. Elemental analyses of the film were carried out by X-ray photoelectron spectroscopy (XPS), which was also useful in complementary structural investigations. In addition, the dependencies of the deposition rate on Vs and XT are presented. (c) 2007 Elsevier B.V. All rights reserved.

Structure and catalytic mechanism of glucosamine 6-phosphate deaminase from Escherichia coli at 2.1 Å resolution

Background: Glucosamine 6-phosphate deaminase from Escherichia coli is an allosteric hexameric enzyme which catalyzes the reversible conversion of D-glucosamine 6-phosphate into D-fructose 6-phosphate and ammonium ion and is activated by N-acetyl-D-glucosamine 6-phosphate. Mechanistically, it belongs to the group of aldose-ketose isomerases, but its reaction also accomplishes a simultaneous amination/deamination. The determination of the structure of this protein provides fundamental knowledge for understanding its mode of action and the nature of allosteric conformational changes that regulate its function. Results: The crystal structure of glucosamine 6-phosphate deaminase with bound phosphate ions is presented at 2.1 Å resolution together with the refined structures of the enzyme in complexes with its allosteric activator and with a competitive inhibitor. The protein fold can be described as a modified NAD-binding domain. Conclusions: From the similarities between the three presented structures, it is concluded that these represent the enzymatically active R state conformer. A mechanism for the deaminase reaction is proposed. It comprises steps to open the pyranose ring of the substrate and a sequence of general base-catalyzed reactions to bring about isomerization and deamination, with Asp72 playing a key role as a proton exchanger.

Structure of thrombin complexed with selective non-electrophilic inhibitors having cyclohexyl moieties at P1

The crystal structures of five new non-electrophilic β-strand-templated thrombin active-site inhibitors have been determined bound to the enzyme. Four co-crystallize with hirugen and inhibitor isomorphously to produce thrombin-hirugen crystals (monoclinic, space group C2), while one co-crystallizes in the hexagonal system, space group P65. A 1,4-substituted cyclohexyl moiety is conserved at the P1 position of all the inhibitors, along with a fused hetero-bicyclic five- and six-membered ring that occupies the P2 site. Amino, amidino and aminoimidazole groups are attached to the cyclohexyl ring for recognition at the S1 specificity site, while benzylsulfonyl and diphenyl groups enhance the binding at the S3 subsite. The cyclohexyl groups at the P1 positions of three of the inhibitors appear to be in the energetically favored chair conformation, while the imidazole-substituted cyclohexyl rings are in a boat conformation. Somewhat unexpectedly, the two cyclohexyl-aminoimidazole groups bind differently in the specificity site; the unique binding of one is heretofore unreported. The other inhibitors generally mimic arginyl binding at S1. This group of inhibitors combines the nonelectrophilicity and selectivity of DAPA-like compounds and the more optimal binding features of the S1-S3 sites of thrombin for peptidic molecules, which results in highly potent (binding constants 12 nM-16 pM, one being 1.1 μM) and selective (ranging from 140 to 20 000 times more selective compared with trypsin) inhibitors of thrombin. The binding modes of these novel inhibitors are correlated with their binding constants, as is their selectivity, in order to provide further insight for the design of therapeutic antithrombotic agents that inhibit thrombin directly at the active site.

Structure and weak hydrogen bonds in liquid acetaldehyde

Monte Carlo simulations have been performed to investigate the structure and hydrogen bonds formation in liquid acetaldehyde. An all atom model for the acetaldehyde have been optimized in the present work. Theoretical values obtained for heat of vaporisation and density of the liquid are in good agreement with experimental data. Graphics of radial distribution function indicate a well structured liquid compared to other similar dipolar organic liquids. Molecular mechanics minimization in gas phase leads to a trimer of very stable structure. The geometry of this complex is in very good agreement with the rdf. The shortest site-site correlation is between oxygen and the carbonyl hydrogen, suggesting that this correlation play a important role in the liquid structure and properties. The O⋯H average distance and the C-H⋯O angle obtained are characteristic of weak hydrogen bonds.

Investigation of chemical changes in sealers during application of the warm vertical compaction technique

Aim To assess (i) heat generated by pluggers during warm vertical compaction of gutta-percha and investigation of temperature changes on the external root surface during canal filling, and (ii) the chemical changes of root canal sealers induced by heat.Methodology Four sealers, namely AH Plus, MTA Plus and two other experimental sealers based on tricalcium silicate, were characterised. External temperatures generated on the root surface during warm vertical compaction of gutta-percha with different sealers inside the root canal were monitored using an infrared thermography camera. Chemical changes induced by heating the sealers were assessed by Fourier transform infrared (FT-IR) spectroscopy.Results MTA Plus and the experimental sealers were composed of a cement and radiopacifier, with epoxy resin or a water-soluble polymer as dispersant, whilst AH Plus was epoxy resin-based. The heat generated at the tips of the continuous wave pluggers was found to be lower than the temperature set and indicated on the device LCD display. The sealers reduced the heat generated on the external root surfaces during the heating phase. AH Plus sustained changes to its chemical structure after exposure to heat, whilst the other sealers were unaffected.Conclusions The temperatures recorded at the tips of continuous wave pluggers varied with their taper and were lower than the temperature set on the System B LCD display. Root canal sealers reduced the dissipation of heat generated during warm vertical compaction, with the temperature at the external root surface maintained at 37-41 degrees C, a temperature below that is necessary to cause irreversible damage to bone and periodontium. The use of AH Plus sealer during warm vertical compaction techniques results in chemical changes in the sealer. The effect on sealer properties needs to be further investigated.

The effect of power-ultrasound on the pretreatment of acidified aqueous solutions of banana flower-stalk: Structural, chemical and statistical analysis

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Structural Changes of Conjugated Pt-Containing Polymetallaynes Exposed to Gamma Ray Radiation Doses

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Plasma-polymerized hexamethyldisilazane treated by nitrogen plasma immersion ion implantation technique

This paper describes the effect of nitrogen Plasma Immersion Ion Implantation (PIII) on chemical structure, refraction index and surface hardness of plasma-polymerized hexamethyldisilazane (PPHMDSN) thin films. Firstly, polymeric films were deposited at 13.56 MHz radiofrequency (RF) Plasma Enhanced Chemical Vapour Deposition (PECVD) and then, were treated by nitrogen PIII from 15 to 60 min. Fourier Transformed Infrared (FTIR) spectroscopy was employed to analyse the molecular structure of the samples, and it revealed that vibrations modes at 3350 cm(-1), 2960 cm(-1), 1650 cm(-1), 1250 cm(-1) and 1050 cm(-1) were altered by nitrogen PIII. Visible-ultraviolet (vis-UV) spectroscopy was used to evaluate film refractive index and the results showed a slight increase from 1.6 to 1.8 following the implantation time. Nanoindentation revealed a surface hardness rise from 0.5 to 2.3 GPa as PIII treatment time increased. These results indicate nitrogen PIII is very promising in improving optical and mechanical properties of PPHMDSN films.

Amorphous hydrogenated carbon films treated by SF(6) plasma

This work was performed to verify the chemical structure, mechanical and hydrophilic properties of amorphous hydrogenated carbon films prepared by plasma enhanced chemical vapor deposition, using acetylene/argon mixture as monomer. Films were prepared in a cylindrical quartz reactor, fed by 13.56 MHz radiofrequency. The films were grown during 5 min, for power varying from 25 to 125 W at a fixed pressure of 9.5 Pa. After deposition, all samples were treated by SF(6) plasma with the aim of changing their hydrophilic character. Film chemical structure investigated by Raman spectroscopy, revealed the increase of sp(3) hybridized carbon bonds as the plasma power increases. Hardness measurements performed by the nanoindentation technique showed an improvement from 5 GPa to 14 GPa following the increase discharge power. The untreated films presented a hydrophilic character, which slightly diminished after SF(6) plasma treatment.

Rhamnolipid surfactants: An update on the general aspects of these remarkable biomolecules

Pseudomonas strains are able to biosynthesize rhamnose-containing surfactants also known as rhamnolipids. These surface-active compounds are reviewed with respect to chemical structure, properties, biosynthesis, and physiological role, focusing on their production and the use of low-cost substrates such as wastes from food industries as alternative carbon sources. The use of inexpensive raw materials such as agroindustrial wastes is an attractive strategy to reduce the production costs associated with biosurfactant production and, at same time, contribute to the reduction of environmental impact generated by the discard of residues, and the treatment costs. Carbohydrate-rich substrates generated low rhamnolipid levels, whereas oils and lipid-rich wastes have shown excellent potential as alternative carbon sources.

Decolorization of textile dye by Candida albicans isolated from industrial effluents

The aim of the present work was to observe microbial decolorization and biodegradation of the Direct Violet 51 azo dye by Candida albicans isolated from industrial effluents and study the metabolites formed after degradation. C. albicans was used in the removal of the dye in order to further biosorption and biodegradation at different pH values in aqueous solutions. A comparative study of biodegradation analysis was carried out using UV-vis and FTIR spectroscopy, which revealed significant changes in peak positions when compared to the dye spectrum. Theses changes in dye structure appeared after 72 h at pH 2.50; after 240 h at pH 4.50; and after 280 h at pH 6.50, indicating the different by-products formed during the biodegradation process. Hence, the yeast C. albicans was able to remove the color substance, demonstrating a potential enzymatic capacity to modify the chemical structure of pigments found in industrial effluents.