Determination of hemin-binding characteristics of proteins by a combinatorial peptide library approach

Studies of the binding of heme/hemin to proteins or peptides have recently intensified as it became evident that heme serves not only as a prosthetic group, but also as a regulator and effector molecule interacting with transmembrane and cytoplasmic proteins. The iron‐ion‐containing heme group can associate with these proteins in different ways, with the amino acids Cys, His, and Tyr allowing individual modes of binding. Strong coordinate‐covalent binding, such as in cytochrome c, is known, and reversible attachment is also discussed. Ligands for both types of binding have been reported independently, though sometimes with different affinities for similar sequences. We applied a combinatorial approach using the library (X)₄(C/H/Y)(X)₄ to characterize peptide ligands with considerable hemin binding capacities. Some of the library‐selected peptides were comparable in terms of hemin association independently of whether or not a cysteine residue was present in the sequence. Indeed, a preference for His‐based (≈39 %) and Tyr‐based (≈40 %) sequences over Cys‐based ones (≈21 %) was detected. The binding affinities for the library‐selected peptides, as determined by UV/Vis spectroscopy, were in the nanomolar range. Moreover, selected representatives efficiently competed for hemin binding with the human BK channel hSlo1, which is known to be regulated by heme through binding to its heme‐binding domain.     

Mechanistic Investigation of ROS-Induced DNA Damage by Oestrogenic Compounds in Lymphocytes and Sperm Using the Comet Assay

Past research has demonstrated that oestrogenic compounds produce strand breaks in the DNA of sperm and lymphocytes via reactive oxygen species (ROS). In the current investigation, sperm and lymphocytes were treated in vitro with oestrogenic compounds (diethylstilboestrol, progesterone, 17β-oestradiol, noradrenaline and triiodotyronine) and several aspects of DNA damage were investigated. Firstly, mediation of DNA damage by lipid peroxidation was investigated in the presence of BHA (a lipid peroxidation blocker). BHA reduced the DNA damage generated by 17β-oestradiol and diethylstilboestrol in a statistically significant manner. No effects were observed for sperm. Secondly, the presence of oxidized bases employing FPG and EndoIII were detected for lymphocytes and sperm in the negative control and after 24 h recovery in lymphocytes but not immediately after treatment for both cell types. The successful detection of oxidized bases in the negative control (untreated) of sperm provides an opportunity for its application in biomonitoring studies. DNA repair at 24 h after exposure was also studied. A nearly complete recovery to negative control levels was shown in lymphocytes 24 h recovery after oestrogenic exposure and this was statistically significant in all cases. Rapid rejoining of DNA, in a matter of hours, is a characteristic of DNA damaged by ROS.     

Chemical Profiles of Body Surfaces and Nests from Six Bornean Stingless Bee Species

Stingless bees (Apidae: Meliponini) are the most diverse group of Apid bees and represent common pollinators in tropical ecosystems. Like honeybees they live in large eusocial colonies and rely on complex chemical recognition and communication systems. In contrast to honeybees, their ecology and especially their chemical ecology have received only little attention, particularly in the Old World. We previously have analyzed the chemical profiles of six paleotropical stingless bee species from Borneo and revealed the presence of species-specific cuticular terpenes— an environmentally derived compound class so far unique among social insects. Here, we compared the bees’ surface profiles to the chemistry of their nest material. Terpenes, alkanes, and alkenes were the dominant compound groups on both body surfaces and nest material. However, bee profiles and nests strongly differed in their chemical composition. Body surfaces thus did not merely mirror nests, rendering a passive compound transfer from nests to bees unlikely. The difference between nests and bees was particularly pronounced when all resin-derived compounds (terpenes) were excluded and only genetically determined compounds were considered. When terpenes were included, bee profiles and nest material still differed, because whole groups of terpenes (e.g., sesquiterpenes) were found in nest material of some species, but missing in their chemical profile, indicating that bees are able to influence the terpene composition both in their nests and on their surfaces.     

Phosphorus‐containing poly(ester‐imide)–polydimethylsiloxane copolymers

New phosphorus‐containing poly(ester‐imide)‐polydimethylsiloxane copolymers were prepared by solution polycondensation of 1,4‐[2‐(6‐oxido‐6H‐dibenz < c,e > < 1, 2 > oxaphosphorin‐6‐yl)]naphthalene‐bis(trimellitate) dianhydride with a mixture of an aromatic diamine (1,3‐bis(4‐aminophenoxy)benzene) and α,ω‐bis(3‐aminopropyl)oligodimethylsiloxane of controlled molecular weight, in various ratios. Poly(amic acid) intermediates were converted quantitatively to the corresponding polyimide structures using a solution imidization procedure. The polymers are easily soluble in polar organic solvents, such as N‐methyl‐2‐pyrrolidone and N,N‐dimethylformamide, as well as in less polar solvents such as tetrahydrofuran. They show good thermal stability, the decomposition temperature being above 370 °C. The glass transition temperatures are in the range 165–216 °C. Solutions of the polymers in N‐methyl‐2‐pyrrolidone exhibit photoluminescence in the blue region. Copyright © 2010 Society of Chemical Industry     

Optimization of the separation of sulfur hexafluoride and nitrogen by selective adsorption using monte carlo simulations

We present molecular simulations to find the optimal conditions for the separation by adsorption of SF₆ from a gaseous mixture with N₂, a mixture of key interest in electrical applications. The effect of pore size, pressure, and mixture compositions on the selective adsorption of SF₆ was investigated by using Grand Canonical Monte Carlo simulations with simple fluid models and a simplified model of MCM‐41. Simulations performed with multisite fluid models confirm that general trends are predicted using simple models, including a maximum in SF₆ selectivity for pore diameters around 1.1 nm. Simulations were also performed using two atomistic models of zeolite‐templated carbon (ZTC), FAU‐ZTC, and EMT‐ZTC, materials with average pore sizes close to 1.1 nm, obtaining high selectivities for both materials. Selectivities for FAU‐ZTC are approximately four times higher than the best materials published for this mixture separation, opening excellent opportunities to use it for recovering SF₆ from SF₆/N₂ mixtures. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Mechanical performance of hybrid rice straw/sea weed polypropylene composites

Rice straw (Rs)/polypropylene (PP) composites were prepared in the different ratio of 5 : 95, 10 : 90, 15 : 85, 20 : 80, 25 : 75, and 30 : 70 (Rs wt % : PP wt %) by an injection molding process. This work investigated the tensile strength (TS), bending strength (BS), and impact strength (IS) of the composites. From the results, it is observed that Rs20 : PP80 mixture composite showed better performance with mechanical properties (TS = 26.2 MPa, BS = 58 N/mm², and IS = 1.7 KJ/mm²) among the composites prepared. Two hybrid composites were also fabricated using 20% Rs, 10% seaweed with 70% PP and 20% Rs, 30% seaweed with 70% PP. In between the two hybrid composites, superior mechanical behavior showed by the hybrid composite in ratio of Rs20 : Sw10 : PP70 with enhanced results such as TS = 28 MPa, BS = 68 N/mm², and IS = 2.5 KJ/mm². Water uptake, simulating weathering, and soil degradation test of different composites were also performed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of chitosan coatings onto regular cellulose fibers with ultrasound technique

Regenerated cellulose fibers—viscose fibers—were coated with chitosan using an ultrasound technique to improve their accessibility, reactivity and sorption properties. The main purpose of our research was to study the modification of viscose fibers and to determine the effect of the application of chitosan onto viscose fibers. Samples were obtained by treating the fibers with chitosan in a dilute acetic acid solution in an ultrasonic bath. The influences of the chitosan coating on the changes in morphology, supramolecular structure, sorption and tensile properties were studied. The spectra (FTIR analysis) of the treated viscose fibers showed changes and new absorption bands that revealed the existence of the chemical interactions with the chitosan. The scanning electron microscope images confirmed that the surface of the fibers was covered with the chitosan. A decrease in the water retention value and increase in the absorption and moisture content with an increasing concentration of chitosan was noted. Furthermore, the differences in tensile behavior were analyzed using an Instron tensile testing machine. The chitosan coating had no effect on the tensile strength of the viscose fibers, but influenced the tensile strain. Some changes, though not significant, were noted in the structure (crystallinity, orientation) of the treated viscose fibers.     

Anti-fog chitosan/sodium lauryl ether sulfate films

The aim of this study was the preparation and characterization of hydrophobic–hydrophilic chitosan films obtained through interaction between the cationic biopolymer, chitosan (CH), with sodium lauryl ether sulfate (SLES), an anionic surfactant, which has also nonionic surfactant properties. The chitosan flat films were obtained at different concentrations of SLES, in the range of 0.02–0.1 M, where spherical capsules were also obtained. The wettability, quantified by the values of contact angle, indicated the hydrophobic character of the films. The significant values of swelling capacity in water, and in 1 % acetic acid solution confirmed the hydrophilic character of the obtained films. Weight loss of CH/SLES films after 24 h, in water and 1 % acetic acid solution was less than 3 % for the all samples. The structure of CH/SLES complex was determined by FTIR spectroscopy method. The morphology of CH/SLES film surfaces determined by atomic force microscopy showed a film surface with nanoroughness structure, determined by the SLES self-assembled nanostructures. The obtained CH/SLES films are transparent and have anti-fogging properties, compared with CH/sodium lauryl sulfate film, which is also transparent but, it gets fogged when coming in contact with warm air.     

Tuning of defects in ZnO nanorod arrays used in bulk heterojunction solar cells

With particular focus on bulk heterojunction solar cells incorporating ZnO nanorods, we study how different annealing environments (air or Zn environment) and temperatures impact on the photoluminescence response. Our work gives new insight into the complex defect landscape in ZnO, and it also shows how the different defect types can be manipulated. We have determined the emission wavelengths for the two main defects which make up the visible band, the oxygen vacancy emission wavelength at approximately 530 nm and the zinc vacancy emission wavelength at approximately 630 nm. The precise nature of the defect landscape in the bulk of the nanorods is found to be unimportant to photovoltaic cell performance although the surface structure is more critical. Annealing of the nanorods is optimum at 300°C as this is a sufficiently high temperature to decompose Zn(OH)₂ formed at the surface of the nanorods during electrodeposition and sufficiently low to prevent ITO degradation.     

Investigating the Role of Conformational Effects on Laccase Stability and Hyperactivation under Stress Conditions

Fungal laccase from Steccherinum ochraceum 1833 displays remarkable stability under different harsh conditions: organic/buffer mixtures, thermal treatment, and microwave radiation. The behavior is particularly significant in the light of the sharp inactivation observed for two different fungal laccases. Laccase from S. ochraceum 1833 also displays hyperactivation under mild thermal treatment (60 °C). Molecular dynamics simulations at 80 °C explained how this laccase retains the geometry of the electron transfer pathway, thereby assuring electron transfer through the copper ions and thus maintaining its catalytic activity at high temperature. Spectroscopic studies revealed that the thermal activation corresponds to specific conformational changes in the protein. The results indicate that this laccase is potentially applicable under denaturing conditions that might be beneficial for the biotransformation of recalcitrant substrates.