Structural and Adsorptive Characteristics of Pyrocarbon/Silica Gel Si-60

Pyrocarbon/silica gel adsorbents (carbosils, CS) with mesoporous Si-60 (Merck, granule size 0.2–0.5 mm) modified by pyrolysis of CH₂Cl₂ at 823 K and reaction time from 0.5 to 6 h and then hydrothermally treated at 473 K for 6 h were studied by means of TEM, adsorption and ¹H NMR methods. Changes in the structural and adsorptive characteristics of hybrid adsorbents before and after hydrothermal treatment, which depend on pyrocarbon content (C _C), were analyzed on the basis of TEM micrographs and p-nitrophenol and nitrogen adsorption isotherms treated using a constrained regularization method. Interfacial water layers in aqueous suspension of CS were investigated by means of ¹H NMR with freezing-out of bulk water at T < 273 K showing nonlinear changes in the Gibbs free energy of interfacial water with increasing C _C because of nonlinear dependence of the structural characteristics of pyrocarbon deposits and CS as a whole on C _C.     

Two-dimensional separations and behaviour of alkaloids of various polarities on unmodified silica gel in polar and very polar neutral or acidic mobile phases

Summary New separation procedures for alkaloids of similar polarity and structure or of very different polarity and structure, based upon two-dimensional thin-layer chromatography on unmodified silica gel under mild conditions are described. Separation factors and separation mechanisms based on the structure of the bases and mobile phase composition are discussed for some examples of very efficient procedures.Proportions in solvent mixtures are v/v except where otherwise indicated.     

Biotinylation: A nonradioactive method for the identification of cell surface antigens in immunoprecipitates

A nonradioactive method was employed to detect different cell membrane antigens on human polymorphonuclear granulocytes, monocytes and platelets. We compared the reactivity of one monoclonal antibody, N1III10, assumed to be FcγRII-specific by functional assays, with other well-characterized monoclonal antibodies and human sera. Intact cells were incubated with biotin N-hydroxysulfosuccinimide ester which preferentially reacts with lysine residues in polypeptides. Biotin-labeled cells were lysed and the antigen was isolated from the cell lysate by immunoprecipitation with the antibody bound to Protein A-Sepharose. The precipitates were separated by sodium dodecyl sulfate-polyacrylamide gel electrophoresis, transferred onto nitrocellulose membrane, and visualized by a streptavidin-alkaline phosphatase system with a suitable substrate. Using this biotin-labeling system we could show that N1III10 detects a 40 kDa antigen on monocytes and platelets, comparable to that expected of FcγRII monoclonal antibodies.     

Stability of Suspensions of Bioactive Particles Using Hybrid Organic–Inorganic Solutions as Dispersing Media

Functional coatings incorporating different types of particles developed by the sol–gel method have been proposed in the last few years for diverse applications. This work focuses on the preparation of homogeneous coatings prepared from stable suspensions with 10 wt% of glass and glass ceramic particles in a hybrid organic–inorganic solution as dispersing media. For this purpose, the pH was shifted up to 6–7 by adding tetrapropylammonium hydroxide (TPAH) which behaves as a cationic surfactant being probably adsorbed on the particles surface, while the sol maintains stable. Rheological measurements were performed to study the stability of the suspensions prepared at different conditions such as the kind and concentration of dispersant and the pH conditions. After sintering at 450^∘C/30 min, coatings around 2 μ m in thickness were obtained.     

Surface diffusion in reversed-phase liquid chromatography using silica gels bonded with C1 and C18 ligands of different densities

Surface diffusion in reversed-phase liquid chromatography (RPLC) using silica gels bonded with C₁ and C₁₈ alkyl ligands of different densities was studied from the viewpoints of two extrathermodynamic relationships, i.e., enthalpy-entropy compensation (EEC) and linear free energy relationship (LFER). First, according to the four methods proposed by Krug et al., the values of surface diffusion coefficient (D_s) were analyzed to confirm that an actual EEC resulting from substantial physico-chemical effects takes place for surface diffusion. Then, it was also demonstrated that a LFER is observed between surface diffusion and the retention equilibrium. The establishment of EEC and LFER suggests a mechanistic similarity of molecular migration by surface diffusion, irrespective of the alkyl chain length and the densities of C₁ and C₁₈ ligands. Finally, a thermodynamic model for the LFER based on the real EEC was used to estimate D_s values under various RPLC conditions. The D_s values can be estimated with a mean square deviation of about 25–30%. The agreement between the D_s values estimated and those experimentally measured suggests that the total mass flux by surface diffusion consists of the two contributions due to C₁ and C₁₈ ligands and that the contribution of each ligand is proportional to the ligand density.     

Synthesis of new colloidal formations during the strengthening of different activated hydrated metallurgical slags

This paper reports on a comparison of experimental researches on the hydration hardening of different types of dumped ferrous slag (DFS) (blast furnace, open hearth, electric steel and converter), non-activated and activated with small (2%) additions of Portland cement or lime. Activation was found to accelerate the strengthening processes in the early stages of hydration resulting from the growth of colloidal sol–gel new formations in a more alkaline environment. Over time, these formations became denser and transformed into stone-like amorphous materials with a uniaxial strength of up to 47.6 MPa at 1 year of age. All these types of slag can, therefore, be used in different applications, for example, like traditional binders, such as Portland cement, to different ceramic goods, new construction materials, etc. But till now the results of this research were used only for the preparing of binder materials for natural soils strengthening as road bases in Russia. Highways whose roadbeds were built with these DFS as binder materials have shown excellent performance indices in different parts of Russia, including Siberia and northern regions.     

Pure Organic Phase Phenol Biosensor Based on Tyrosinase Entrapped in a Vapor Deposited Titania Sol‐Gel Membrane

A novel amperometric biosensor was constructed for the determination of phenols in pure organic phase. This biosensor was fabricated by immobilizing tyrosinase in a titania sol‐gel membrane which was obtained with a vapor deposition method. This method was facile and avoided the calcination step needed in conventional titania sol‐gel process. The titania sol‐gel membrane could effectively retain the essential water layer around the enzyme molecule needed for maintaining its activity in organic phase. The experimental parameters such as solvent and operating potential were optimized. At ?100 mV this biosensor showed a good amperometric response to phenols in pure chloroform without any mediator and rehydration of the enzyme. For catechol determination the sensor exhibited a fast response of less than 5 seconds. The sensitivity of different phenols was as follows: catechol > phenol > p‐cresol. Additionally, the apparent Michaelis‐Menten constants of the encapsulated tyrosinase to catechol, phenol and p‐cresol were found to be 0.15±0.003, 0.17±0.008 and 0.21±0.004 mM, respectively. The biosensor had also good reproducibility and stability. This work provided a promising platform for the construction of pure organic phase biosensors and the determination of substrates with poor water solubility.     

Thermoreversible gelation of polyacrylonitrile/dimethylformamide-solution

The thermoreversible gelation of semi-diluted atactic polyacrylnitrile (PAN)/dimethylformamide (DMF)-solutions has been studied. The structural features of PAN/DMF-gels, formed by supercooling have been investigated by DSC-, x-ray- and swelling measurements. A new structural model has been introduced to describe the morphology of the junction zones of PAN/DMF-gels and to also explain the gelation behavior of PAN/DMF-solutions as the structural features of PAN/DMF-gels. The junction zones of a PAN/DMF-gel have been defined as ordered junction zones.A gelation enthalpy of about H=–6 kJ/mol supports the idea that an ordered junction zone is formed by intermolecularly neighboring stereoregular parts of atactic PAN chains due to a nucleation process in the solution. It can be defined as a strongly distributed fringed micelle.     

Evaluation of recombinant green fluorescent protein, under various culture conditions and purification with HiTrap hydrophobic interaction chromatography resins

To determine the influence of various culture conditions, transformed cells of Escherichia coli expressing recombinant green fluorescent protein (GFPuv) were grown in nine cultures with four variable conditions (storage of inoculated broth at 4°C prior to incubation, agitation speed, isopropyl-β-d-thiogalactopyranoside [IPTG] concentration, and induction time). The pelleted cells were resuspended in extraction buffer and subjected to the three-phase partitioning (TPP) extraction method. To determine the most appropriate purification resin, protein extracts were eluted through one of four types of HiTrap hydrophobic interaction chromatography (HIC) columns prepacked with methyl, butyl, octyl, or phenyl resins and analyzed further on a 12% sodium dodecylsulfatepolyacrylamidegel. With Coomassie staining, a single band between 27 (standard GFPuv) and 29 kDa (molecular weight standard) was visualized for every HIC column sample. TPP extraction with HIC elution provided about 90% of the GFPuv recovered and eight-fold GFPuv enrichment related to the specific mass. Rotary speed and IPTG concentration showed, respectively, greater negative and positive influences on GFPuv expression at the beginning of the logarithmic phase for the set culture conditions (37°C, 24-h incubation).     

Formation of sol-gel nanostructured mullite by additions of fluoride ion

Summary The subject of this study was to investigate the effect of fluoride ions addition on the temperature of sol gel mullite formation based on the hypotheses that the presence of fluoride ions can decrease the temperature of mullite formation (in respect to common 980&deg;C, in sol-gel processing). Polymeric sols were prepared by mixing TEOS and aluminum nitrate nanohydrate and by adding fluoride ions (from 2 to 5 mass&percnt;). DTA, TG, XRD and SEM were used for characterisation of mullite gel and crystalline mullite. The experimental results confirmed that the addition of fluoride ions decrease the temperature of mullite formation up to 890&deg;C for the fluorine concentration of 3.5 mass&percnt;. Experimental results showed that the temperature of mullite formation is not a simple function of the fluoride ion content. The mechanism of fluorine effect was discussed in terms of the gelling process, gel structure and the phase separation before the mullite formation.