Electronegativity Equalization Method: Parameterization and Validation for Large Sets of Organic,Organohalogene and Organometal Molecule

The Electronegativity Equalization Method (EEM) is a fast approach for charge calculation. A challenging part of the EEM is the parameterization, which is performed using ab initio charges obtained for a set of molecules. The goal of our work was to perform the EEM parameterization for selected sets of organic, organohalogen and organometal molecules. We have performed the most robust parameterization published so far. The EEM parameterization was based on 12 training sets selected from a database of predicted 3D structures (NCI DIS) and from a database of crystallographic structures (CSD). Each set contained from 2000 to 6000 molecules. We have shown that the number of molecules in the training set is very important for quality of the parameters. We have improved EEM parameters (STO-3G MPA charges) for elements that were already parameterized, specifically: C, O, N, H, S, F and Cl. The new parameters provide more accurate charges than those published previously. We have also developed new parameters for elements that were not parameterized yet, specifically for Br, I, Fe and Zn. We have also performed crossover validation of all obtained parameters using all training sets that included relevant elements and confirmed that calculated parameters provide accurate charges.     

Optimization of Physiological Growth Conditions for Maximal Gamma-linolenic Acid Production by Cunninghamella blakesleeana-JSK2

Effects of various cultural conditions on biomass, lipid and Gamma-linolenic acid (GLA) production were investigated in the oleaginous fungus Cunninghamella blakesleeana-JSK2 isolated from soil. The GLA production was influenced by various factors such as growth condition (static and shaken), incubation time, pH, temperature, carbon and nitrogen sources. The results indicated that optimum GLA production (21 %) was obtained when the fungus was grown under shaken condition at 120 rpm for 6 days with optimum pH and temperature of 6 and 28 °C ,respectively. Glucose and potassium nitrate enhanced the GLA production. Urea and sucrose were poor substances for biomass, lipid and GLA production.     

Starch as a Pore‐forming and Body‐forming Agent in Ceramic Technology

Wheat and corn starch can be used for the preparation of porous alumina ceramics via the SCC (starch consolidation casting) process, resulting in porosities ranging from > 20% to approx. 50% (using nominal starch contents of 10 – 50%, v/v), with open porosity dominating (closed porosity < 6.5%). The character of porosity and the shape of the pores corresponds to the starch granules used, but the pore size is determined by a complex interplay between starch swelling (during the body‐forming step) and pore shrinkage (during sintering of the ceramic). Typically, for low starch contents (e.g. nominal starch contents of around 10%, v/v) starch swelling is a significant effect, and the pores after sintering are larger than the size of the starch granules. For higher starch contents swelling is constrained (by limited space and/ or water availability), and the matrix shrinkage during sintering overcompensates the swelling effect, so that the final pores in the ceramic can be significantly smaller than the original starch granule size. In this paper it is shown how porosity is related to pore size. In particular, it is demonstrated that the porosity indirectly determined from image analysis (via the median pore size) is closely related to the porosity directly measured via the Archimedes method. On the other hand, mercury porosimetry measures the distribution of pore throat sizes. With increasing starch content in the suspension, the pore throat size in the as‐fired ceramic materials increases, resulting in a more open microstructure.     

Isolation of alpaca anti-hapten heavy chain single domain antibodies for development of sensitive immunoassay

Some unique subclasses of Camelidae antibodies are devoid of the light chain, and the antigen binding site is comprised exclusively of the variable domain of the heavy chain (VHH). Although conventional antibodies dominate current assay development, recombinant VHHs have a high potential as alternative reagents for the next generation of immunoassay. We expressed VHHs from an immunized alpaca and developed a VHH-based immunoassay using 3-phenoxybenzoic acid (3-PBA), a major metabolite of pyrethroid insecticides as a model system. A phage VHH library was constructed, and seven VHH clones were selected by competitive binding with 3-PBA. The best immunoassay developed with one of these VHHs showed an IC(50) of 1.4 ng/mL (limit of detection (LOD) = 0.1 ng/mL). These parameters were further improved by using the phage borne VHH, IC(50) = 0.1 ng/mL and LOD = 0.01 ng/mL. Both assays showed a similar tolerance to methanol and dimethylsulfoxide up to 50% in assay buffer. The assay was highly specific to 3-PBA and its 4-hydroxylated derivative, 4-hydroxy 3-PBA, (150% cross reactivity) with negligible cross reactivity with other tested structural analogues, and the recovery from spiked urine sample ranged from 80 to 112%. In conclusion, a highly specific and sensitive VHH for 3-PBA was developed using sequences from immunized alpaca and phage display technology for antibody selection.     

Depolymerization of insulin amyloid fibrils by albumin-modified magnetic fluid

Pathogenesis of amyloid-related diseases is associated with the presence of protein amyloid deposits. Insulin amyloids have been reported in a patient with diabetes undergoing treatment by injection of insulin and causes problems in the production and storage of this drug and in pplication of insulin pumps. We have studied the interference of insulin amyloid fibrils with a series of 18 albumin magnetic fluids (MFBSAs) consisting of magnetite nanoparticles modified by different amounts of bovine serum albumin (w/w BSA/Fe?O? from 0.005 up to 15). We have found that MFBSAs are able to destroy amyloid fibrils in vitro. The extent of fibril depolymerization was affected by nanoparticle physical-chemical properties (hydrodynamic diameter, zeta potential and isoelectric point) determined by the BSA amount present in MFBSAs. The most effective were MFBSAs with lower BSA/Fe?O? ratios (from 0.005 to 0.1) characteristic of about 90% depolymerizing activity. For the most active magnetic fluids (ratios 0.01 and 0.02) the DC50 values were determined in the range of low concentrations, indicating their ability to interfere with insulin fibrils at stoichiometric concentrations. We assume that the present findings represent a starting point for the application of the active MFBSAs as therapeutic agents targeting insulin amyloidosis.     

Immunomodulatory efficiency of poly(2-oxazolines)

Poly(2-oxazolines) represent promising polymer materials for biomedical applications. The activation of mouse lymphoid macrophage line P388.D1 (clone 3124) by two selected representatives of poly(2-oxazolines), namely poly(2-ethyl-2-oxazoline) (PETOX100) and poly[2-(4-aminophenyl)-2-oxazoline-co-2-ethyl-2-oxazoline] (AEOX10), was assessed in vitro. The immunomodulatory efficacy of both polymers was evaluated via the induced release of pro-inflammatory cytokines (TNF-α, IL-1α and IL-6) and the acceleration of reactive free radicals. The present study revealed effective structure-immunomodulating associations of AEOX10 and PETOX100, which are desirable in biomedical and pharmaceutical applications of aliphatic and aromatic poly (2-oxazolines) in vivo.     

The influence of zeolite catalysts on the products of rapeseed oil cracking

The article is devoted to the study of rapeseed oil cracking in the presence of zeolite catalysts in order to prepare the liquid fraction with the properties close to fossil diesel.To evaluate the cracking products, the chromatographic methods GL and GC/MS were used, together with the determination of viscosities, acid values and densities. The cracking of rapeseed oil in the presence of zeolite-type catalysts in batch arrangement at temperatures between 350 and 440 °C gave a yield of liquid condensate 85 to 90 wt.%. After removal of volatile components 3 to 9 wt.% by distillation at the temperatures up to 190 °C, the GL chromatogram of treated condensate was similar to that of fossil diesel fuel. The paper deals with the influence of the kind and amount of catalyst on composition and properties of treated products with the use of GL and GC/MS chromatography and with the tests of blends of fossil diesel fuel with cracking products at contents up to 7 vol.%. The blended fuels meet all parameters specified by standard EN 590 for diesel fuel.     

The effect of selected hydrocolloids on the rheological properties of processed cheese analogues made with vegetable fats during the cooling phase

The aim of this work was to observe the influence of different hydrocolloids on changes in the rheological properties of processed cheese and their analogues within the process of cooling depending on the type of the fat used (butter, coconut fat and palm oil). κ‐carrageenan, ι‐carrageenan, λ‐carrageenan, arabic gum and locust bean gum were used at a concentration of 1.0% w/w. With the decreasing temperature during the cooling period, an increase in the complex modulus (G*) was observed in all samples tested. Within the cooling period, the sample with the addition of κ‐carrageenan showed both the most significant increase in G* in comparison with the control and the highest values of hardness after a 7‐day storage period regardless of the type of the fat used. The samples with coconut fat were assessed as the hardest. On the other hand, the samples with palm oil showed the lowest hardness (with the same hydrocolloid used). In the gelling hydrocolloids (κ‐ and ι‐carrageenan), only small changes in temperature of coil‐to‐helix transition were observed (in range of 2–7 °C) as a result of the addition of different types of fat.     

Properties of alkyl esters base on castor oil

Castor oil is a non‐traditional raw material for the preparation of methyl and ethyl esters of higher fatty acids as alternative fuels for diesel engines. Castor oil contains ricinoleic acid (12‐hydroxy octadecene acid) with a major share of about 90%. The article presents the parameters of castor oil‐based methyl esters (COME) and ethyl esters (COEE) defined by the standard EN 14 214. The densities of COME and COEE are higher than the limit defined by the standard EN 14 214. The viscosities are more than twice as high as the limit value. The cetane numbers are lower than defined by the standard EN 14 214. For the remaining parameters, COME and COEE meet, in principle, the standard EN 14 214. The presence of the free hydroxyl group has virtually no effect on the values of such parameters as carbon residue, filterability at low temperatures and oxidation stability, for which some influence was expected. The physicochemical parameters of the castor oil esters are discussed in comparison to the analogous esters of high‐oleic sunflower oil, which contain about 80% of oleic acid. Both the methyl and ethyl esters of high‐oleic sunflower oil meet the standard EN 14 214 in all prescribed parameters.     

Note on powers in three interval exchange transformations

We study repetitions in infinite words coding exchange of three intervals with permutation (3, 2, 1), called 3iet words. The language of such words is determined by two parameters, ε,?. We show that finiteness of the index of 3iet words is equivalent to boundedness of the coefficients of the continued fraction of ε. In this case, we also give an upper and a lower estimate on the index of the corresponding 3iet word. Our main tool is the connection between a 3iet word with parameters ε,? and sturmian words with slope ε.