Engineering of functional supramacromolecular complexes of proteins (enzymes) using reversed micelles as matrix microreactors

The size of the inner water cavity of reversed micelles formedin a triple system ‘water-surfactant-organic solvent’can be widely varied by changing the degree of surfactant hydration.This gives grounds to use reversed micelles as matrix microreactorsfor the design of supramolecular complexes of proteins. Usingultracentrifugation analysis, it has been demonstrated thatthe oligomeric composition of various enzymes (ketoglutaratedehydrogenase, alkaline phosphatase, lactic dehydrogenase, glyceraldehyde-3-phosphatedehydrogenase) solubilized in reversed micelles of Aerosol OT[sodium bis(2-ethylehexyl)sulfosuccinate] in octane changesupon variation of the degree of hydration. An oligomeric complexforms under conditions when the radius of the micelle innercavity is big enough to incorporate this complex as a whole.At lower degrees of hydration the micelles ‘uncouple’such complexes to their components. The catalytic propertiesof various oligomeric complexes have been studied. Possibilitiesof using reversed micelles for the separation of subunits ofoligomeric enzymes under non-denaturating conditions have beendemonstrated. In particular, the isolated subunits of alkalinephosphatase, lactic dehydrogenase and glyceralde-hyde-3-phosphatedehydrogenase have been found to be active in Aerosol OT reversedmicelles. The dependences of the catalytic activity of oligomericenzymes represent saw-like curves. The maxima of the catalyticactivity observed at these curves relate to the functioningof various oligomeric forms of an enzyme. The radii of the micelleinner cavity under conditions when these maxima are observedcorrelate with the linear dimensions of the enzyme oligomericforms. Correlation of the position of a maximum with the shapeof an oligomeric complex is discussed.     

Selective separation of yttrium from rare earth elements by ion interaction chromatography. Analytical and larger scale applications

ABSTRACT

New ion interaction chromatographic (IIC) method employing Kromasil 100 C₁₈ column and tetra-n-butylammonium hydroxide (TBAOH) as an ion interaction reagent (IIR) is able to separate yttrium from Rare Earth Elements (REE) as anionic complexes with nitrilotriacetic acid (NTA). New method for the chromatographic determination of Y in REE mixture was devised and validated by the analysis of the certified reference material (CRM). Potential possibilities of the new chromatographic system for larger scale applications including macro-micro events were demonstrated.     

In vivo and in vitro lipid accumulation inBorago officinalis L.

Seeds of 13 accessions of borage (Borago officinalis) varied in total fatty acid content from 28.6 to 35.1% seed weight, with linoleic, γ-linolenic, oleic and palmitic as the predominant fatty acids, averaging 38.1%, 22.8%, 16.3% and 11.3% of total fatty acids, respectively. There was an inverse relation between γ-linolenic acid (25.0 to 17.6%) and oleic acid (14.5 to 21.3%). Fatty acid content of leaf tissues was 9.1% dry weight, with α-linolenic acid 55.2% and γ-linolenic acid 4.4% of total fatty acids. Cotyledons were the major source of fatty acids in seeds. Seed fatty acid content increased from <1 mg at six days postanthesis to about seven mg at maturity (22 to 24 days). Individual fatty acid content of seed was relatively constant after day 8. When immature embryos from 6 to 16 days postanthesis were cultured in a liquid or semisolid basal medium, fatty acid composition was similar to that of in vivo-grown seeds. Growth of cultured embryos decreased as sucrose concentration was increased from 3 to 20% in the basal medium, and most embryos did not survive 30% sucrose; fatty acid as a percentage of dry weight was maximal at 6% sucrose.     

Synthesis of nanodispersed oxides of vanadium, titanium, molybdenum, and tungsten on mesoporous silica using atomic layer deposition

The advantages of the atomic layer deposition (ALD) method for preparation of tungsten, vanadium, titanium, and molybdenum oxide catalyst supported on mesoporous silica are discussed, with emphasis on the importance of synthesis conditions on dispersion, structure and activity of the resulting materials. A suite of complementary techniques such as DRS-UV/Vis, BET, ¹H-NMR, XRD, and TEM were used to study the structural properties of the supported metal oxides, and probe reactions such as 2-butanol dehydration and ethanol partial oxidation were used to demonstrate the potential advantages of the ALD-prepared catalysts. Specifically, highly dispersed oxides of titanium, molybdenum, and tungsten oxide on mesoporous silica were synthesized using the ALD method. It is also demonstrated that attainment of high dispersions of vanadium oxide on mesoporous silica requires the presence of at least a single layer of titanium oxide due to the well-known poor interaction between vanadia and silica. The highly dispersed catalysts prepared here by ALD methods exhibited superior catalytic performance relative to those prepared using conventional incipient wetness impregnation.     

Polyesters containing sulfur. I. Products of melt polycondensation of diphenylmethane-4,4′-di(methylthioacetic acid) with some diols

Several new polyesters containing sulfur in the main chain were obtained by melt polycondensation of diphenylmethane-4,4′-di(methylthioacetic acid) with ethanediol, 1,3-propane diol, 1,4-butanediol, 1,5-pentenediol, 1,6-hexanediol, 1,2-propanediol, and 2,2′-oxydiethanol. The structure of all polyesters was determined from elemental analysis and infrared (IR) spectra. Yield, reduced viscosity, molecular weight, and softening temperature for reaction products have been found. Initial decomposition and initial intensive decomposition temperature were defined from the curves of thermogravimetric analysis.     

Mechanochemical tuning of molecular weight distribution of styrene homopolymers as postpolymerization modification in solvent-free solid-state

Mechanochemical degradation by planetary ball milling (PM) is used for postpolymerization modification of styrene homopolymers (PS). A complete factorial design was chosen to study the effect of radical scavengers, milling time, initial molecular weight, and revolution radius (R_p), on the shape of molecular weight distributions (MWDs) of PS. Size-exclusion chromatography analysis shows the feasibility of fine-tuning MWD of PS at up to 40% conversion. Distributions ranged from unimodal to bimodal in a PM with R_p = 150 mm at different stage of milling, whereas in a PM with R_p of 60.8 mm the adjustment of unimodal distributions is achieved. Initial polydispersity is more important to develop bimodal distributions when compared with initial molecular weight. Fourier transform infrared and X-ray electron spectrometry analysis show some suppression of PS degradation and complete oxidation inhibition of macromolecular radicals with the incorporation of radical scavengers, which we considered as additional aids when adjusting the MWDs.     

Fabrication of hybrid proton-exchange membranes using a brandnew high temperature ionic liquid as charge transporting and clay modifier

The search for more compatibility between ionic liquids (ILs) and polymer matrices in proton-exchange membrane fuel cells (PEMFCs) is one of the ways in which IL leaking from proton-exchange membranes could be minimized. In this work, it is presented the synthesis of an aromatic high temperature ionic liquid (HTIL), which, incorporated into an aromatic matrix such as sulfonated polyether ether ketone (sPEEK), is expected to diminish the IL leaking that normally affects PEMFC. Phenylethylammonium trifluoromethane sulfonate (PhetaTfO) was successfully synthesized and characterized. Its melting point of 88°C makes it to classify as a HTIL and it was employed as modifier of natural Montmorillonite, forming the phenylethylammonium intercalated montmorillonite (MmtPheta) and thus, ternary membranes containing PhetaTfO, MmtPheta, and sPEEK were prepared and characterized. Immersion tests demonstrated a higher compatibility of PhetaTfO with matrix when compared to the reference DemaTfO, which was reflected in up to 30% lower IL loss by the synthesized IL than the DemaTfO; X-rays diffraction (XRD) patterns demonstrated that the modified clay was properly dispersed inside the membranes, while dynamic mechanical analyses (DMA) results indicated a strong plasticizer effect along the increase of PhetaTfO content inside the membrane, while at the same time, the conductivity increased in an exponential manner, which permitted to identify an empiric exponential equation to evaluate the effect of concentration on ionic conductivity. The maximum conductivity obtained at IL concentrations of around 38 wt% was 0.2 mS/cm. It could expect high ionic conductivities of 10 mS/cm when the concentration of this IL is 60%; nevertheless, in order to achieve that, crosslinking treatments should be done to give the membranes enough mechanical resistance.     

CR composites with improved processing safety crosslinked via Heck's reaction

The aim of this study was to optimize the composition of the chloroprene rubber (CR) composites crosslinked via the Heck-type reaction to ensure their safe processing at elevated temperature. The developed curing system consisting of iron (III) acetylacetonate (Fe(acac)) and triethanolamine (TEOA) demonstrates high activity and more eco-friendly composition in comparison with metal oxide system, commercially used for CR crosslinking. However, the high activity of Fe(acac)/TEOA system results in a short scorch time, which is the greatest disadvantage regarding the safe processing of CR rubber and thus, must be improved. Therefore, CR compounds with Fe(acac) in the presence of different additives were studied. The longest scorch times (t₀₂) were observed for rubber compounds with urotropine (U), N-cyclohexyl-2-benzothiazole sulfenamide (CBS) or salicylic acid. Moreover, vulcanizates containing these additives exhibited higher tensile strengths and elongation at breaks compared to CR crosslinked with Fe(acac)/TEOA system.     

3D Surface Reconstruction of Noisy Point Clouds Using Growing Neural Gas: 3D Object/Scene Reconstruction

With the advent of low-cost 3D sensors and 3D printers, scene and object 3D surface reconstruction has become an important research topic in the last years. In this work, we propose an automatic (unsupervised) method for 3D surface reconstruction from raw unorganized point clouds acquired using low-cost 3D sensors. We have modified the growing neural gas network, which is a suitable model because of its flexibility, rapid adaptation and excellent quality of representation, to perform 3D surface reconstruction of different real-world objects and scenes. Some improvements have been made on the original algorithm considering colour and surface normal information of input data during the learning stage and creating complete triangular meshes instead of basic wire-frame representations. The proposed method is able to successfully create 3D faces online, whereas existing 3D reconstruction methods based on self-organizing maps required post-processing steps to close gaps and holes produced during the 3D reconstruction process. A set of quantitative and qualitative experiments were carried out to validate the proposed method. The method has been implemented and tested on real data, and has been found to be effective at reconstructing noisy point clouds obtained using low-cost 3D sensors.