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Model Substances (model + substance)
Selected AbstractsMetastable zone determination of lipid systems: Ultrasound velocity versus optical back-reflectance measurementsEUROPEAN JOURNAL OF LIPID SCIENCE AND TECHNOLOGY, Issue 5 2010Kesarin Chaleepa Abstract The metastable zone width (MZW) of a multi-component system as influenced by the process parameters cooling rate, agitation speed, and additive concentration was determined via ultrasound velocity measurements. The results were compared with those obtained by optical back-reflectance measurements (ORM) using coconut oil as a model substance. Increasing the cooling rate led to the shift of the nucleation point to lower temperatures. This tendency was better visualized by the ultrasonic curves while a significant disturbance of the ORM signal could be observed. Agitation led to an increase of the nucleation temperature and hence a narrower metastable zone. The influence of an additive on the MZW was found to strongly depend on its concentration. The MZW detected by the ultrasound technique was narrower compared to that obtained by the ORM method, indicating the faster response to the phase transition of the ultrasound technique. Another advantage of the ultrasound technique was the in situ evaluation of the experimental data, while ORM needed a linear fitting to estimate the saturation temperature. Furthermore, ultrasound velocity measurements are based on density determination of the medium whereas the ORM sensor is able to detect only particles that are located within the measuring zone and possess a well-defined size. Practical applications: MZW is one of the most important parameters that determine the characteristics of crystalline products. However, a proper technique that can be used in MZW detection in fat systems has rarely been reported, due to the difficulties in dealing with natural fats. The findings of this study can greatly help those who are involved in the field of fat crystallization from both the academic and the practical point of view. This is due to the fact that new and promising techniques for the online and in situ determination of the MZW of fats, with high accuracy, and reproducibility, under most process conditions, were clarified in this work. The readers can easily follow the procedure developed in this paper. Also information about the influence of process parameters and additives on the MZW is included. [source] Mass spectrometric characterization of 4-oxopentanoic acid and gas-phase ion fragmentation mechanisms studied using a triple quadrupole and time-of-flight analyzer hybrid system and density functional theoryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 14 2008Basem Kanawati 4-Oxopentanoic acid was characterized experimentally by electrospray ionization using a triple quadrupole and time-of-flight analyzer hybrid system. This compound was chosen as a model substance for small organic compounds bearing an acetyl and a carboxyl group. Collision-induced dissociation experiments at different activation energies were performed to elucidate possible fragmentation pathways. These pathways were also studied on the theoretical level using density functional theory (DFT) B3LYP/6-311++G(3df,3pd)//B3LYP/6-31+G(d)+ZPVE calculations. CO2 ejection from the [M,H], anion of 4-oxopentanoic acid was observed and the fragmentation pathway studied by DFT reveals a new concerted mechanism for CO2 elimination accompanied by an intramolecular proton transfer within a pentagonal transition state structure. Successive elimination of water and CO from the [M,H], anion of 4-oxopentanoic acid was also observed. A rearrangement in the primary deprotonated ketene anion produced after water elimination was found on the theoretical level and leads to CO elimination from the primary product anion [M,H,H2O],. Energy diagrams along the reaction coordinates of the fragmentation pathways are presented and discussed in detail. Mulliken charge distributions of some important structures are presented. Copyright © 2008 John Wiley & Sons, Ltd. [source] Columnar Mesophase Formation of Cyclohexa- m -phenylene-Based MacrocyclesCHEMISTRY - AN ASIAN JOURNAL, Issue 1 2007Wojciech Pisula Dr. Abstract Two novel discotic macrocycles, substituted cyclohexa- m -phenylene (CHP) and cyclo-3,6-trisphenanthrylene (CTP), and the linear oligomer 3,3,:6,,3,,-terphenanthrene (TP) as a model substance have been synthesized by repetitive cross-coupling reactions. To correlate the molecular design with the supramolecular architecture and the established macroscopic order, 2D wide-angle X-ray scattering experiments were performed on mechanically extruded filaments. At room temperature in their crystalline phases, all three compounds revealed columnar assemblies in which the macrocycles self-organized by ,-stacking interactions. The degree of macroscopic order was found to depend upon the planarity and stiffness of the aromatic core. The flexible CHP ring showed a poor macroscopic order of the columnar structures and a low isotropization temperature, whereas the more-planar, less-flexible CTP self-assembled into well-defined superstructures. The larger ,-stacking area and the more-pronounced intermolecular interactions for CTP led to the formation of a mesophase over a very large temperature range. The surprising columnar organization of the "open" TP system was explained by back-folding of the molecule into a ringlike structure. [source] Differential Pulse Voltammetric Determination of Selected Nitro-Compounds on Silver, Solid Silver Composite, and Solid Graphite Composite ElectrodesELECTROANALYSIS, Issue 3-5 2009Navrátil Abstract Three different types of solid electrodes, namely silver electrode, silver composite electrode containing 20% (m/m) of silver powder, 20% (m/m) of graphite powder and 60% (m/m) of methacrylate resin and graphite composite electrode containing 30% (m/m) of graphite powder and 70% (m/m) of epoxy resin were tested for differential pulse voltammetric determination of selected genotoxic nitro-compounds using 2-nitronaphthalene, 6-nitroquinoline, and 5-nitrobenzimidazole as model compounds. It was found that all three electrodes can be used for the determination of micromolar concentrations of tested model substances, the limit of detection and other figures of merits being dependent both on the electrode used and the substance to be determined. [source] Rainwater Dissolved Organic Carbon: Characterization of Surface Active Substances by Electrochemical MethodELECTROANALYSIS, Issue 19-20 2007osovi Abstract Surface active substances as organic constituents of bulk precipitation were studied by AC voltammetric method. Adsorption characteristics at the mercury electrode of real rainwater samples are compared with aqueous solutions of a number model substances suggested to be representative of water soluble organic compounds (WSOC) in atmospheric aerosols and droplets: monocarboxylic, dicarboxylic, and polyacidic compounds, levoglucosan, polyaromatic hydrocarbon naphtalene and anionic surfactant sodium dodecylbenzene sulfonate. On the basis of the capacitance vs. potential curves and the surfactant activity normalized to the organic carbon content it is concluded that humic like substances, monocarboxylic acids and polyaromatic hydrocarbons may play an important role in atmospheric aquatic system because of their surface active potential. [source] Microemulsion electrokinetic chromatography of drugs varying in charge and hydrophobicity: I. Impact of parameters on separation performance evaluated by multiple linear regression modelsELECTROPHORESIS, Issue 1 2004Valérie Harang Abstract The separation of anionic, cationic and neutral drugs in microemulsion electrokinetic chromatography (MEEKC) was studied with a statistical experimental design. The concentration of sodium dodecyl sulfate (SDS, surfactant), 1-butanol (co-surfactant) and borate buffer and the factors Brij 35 (surfactant), 2-propanol (organic solvent) and cassette temperature were varied simultaneously, while the parameters pH (9.2), the concentration of octane (oil, 0.8% w/w), the voltage (10 kV) and the dimension of the fused-silica capillary, were kept constant. Eight different model substances were chosen with different hydrophobicities. Two of the analytes were positively charged, two were negatively charged, and the remaining four were neutral or close to neutral at the pH explored. The importance of each parameter on the separation window, the plate height and the retention factor for each of the analytes was studied by means of multiple linear regression (MLR) models. A new response was evaluated for anions, the quotient between the effective mobility in the microemulsion and the effective mobility in the corresponding buffer. Factors affecting selectivity changes were also explored, and it was found that SDS and 2-propanol had the largest effect on selectivity. [source] Evaluation of poly(ethylene-co-vinyl acetate-co-carbon monoxide) and polydimethylsiloxane for equilibrium sampling of polar organic contaminants in waterENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 9 2009Jörgen A Magnér Abstract Abstract-The aim of the present study was to develop a passive a bsorptive equilibrium sampler that would enable the determination of the concentrations of polar organic compound (POC) in water more efficiently than existing techniques. To this end, a novel plastic material, poly(ethylene-co-vinyl acetate-co-carbon monoxide) (PEVAC), was evaluated and the results were compared with an existing silicone-based passive absorptive equilibrium device. Seven compounds (imidacloprid, carbendazim, metoprolol, atrazin, carbamazepine, diazinon, and chlorpyrifos), a mixture of pharmaceuticals, and pesticides with a logarithmic octanol-water partition coefficient ranging from 0.2 to 4.77 were selected as model substances for the experiments. The results showed that six of the seven selected POCs reached distribution equilibrium within 4 d in the two materials tested. A linear relation with a regression coefficient of more than 0.8906 between the established logarithmic absorbent-water partition coefficient and the calculated logarithmic dissociation partition coefficient of the selected compounds in the two polymers was observed. The correlation between these two coefficients was within one order of magnitude for the compounds that reached equilibrium in the two polymers, which demonstrates that both materials are suitable for mimicking biological uptake of POCs. The PEVAC material showed an enhanced sorption for all selected compounds compared to the silicone material and up to five times higher enrichment for the most polar compound. Fluorescence analysis of the sampler cross-section, following the uptake of fluoranthene, and proof that the sorption was independent of surface area variations demonstrated that the PEVAC polymer possessed absorptive rather than adsorptive enrichment of organic compounds. [source] Reaction characteristics of a tooth-bleaching agent containing H2O2 and NaF: in vitro study of crystal structure change in treated hydroxyapatite and chemical states of incorporated fluorineINTERNATIONAL JOURNAL OF COSMETIC SCIENCE, Issue 5 2005Y. Tanizawa This in vitro study was performed to elucidate the reaction mechanism of sodium fluoride (NaF), which is added to tooth-bleaching agents to lessen the adverse effect of hydrogen peroxide (H2O2) on teeth. Both hydroxyapatite (HAP) and dihydrated dicalcium phosphate (DCPD), model substances for dental hard tissues, dissolved easily in a simple H2O2 solution. In the H2O2/NaF solutions, however, fluorine compounds that could not be identified by X-ray diffraction (XRD) due to the smallness of the products were formed on the surface of the HAP. X-ray photoelectron spectroscopy (XPS) studies demonstrated that fluoridated hydroxyapatite (FHAP) was formed on HAP, and that calcium fluoride (CaF2) formation was accelerated by increasing the concentrations of fluorine and H2O2 along with the partial dissolution of HAP. In H2O2/NaF solution, DCPD also transformed easily to FHAP and CaF2, which are favorable to the remineralization process on the tooth surface. Thus, the mechanism of NaF was elucidated, and its use together with H2O2 for tooth bleaching was proved to be effective. Methodologically, the XPS two-dimensional plot made it possible for the first time to directly estimate the ratio of FHAP and CaF2 in the reaction products, in contrast to the conventional wet-analytical method, which is simply based on the difference in solubility of the two components. [source] Reaction characteristics of a tooth-bleaching agent containing H2O2 and NaF: in vitro study of crystal structure change in treated hydroxyapatite and chemical states of incorporated fluorineINTERNATIONAL JOURNAL OF COSMETIC SCIENCE, Issue 4 2005Y. Tanizawa This in vitro study was performed to elucidate the reaction mechanism of sodium fluoride (NaF), which is added to tooth-bleaching agents to lessen the adverse effect of hydrogen peroxide (H2O2) on teeth. Both hydroxyapatite (HAP) and dihydrated dicalcium phosphate (DCPD), model substances for dental hard tissues, dissolved easily in a simple H2O2 solution. In the H2O2/NaF solutions, however, fluorine compounds that could not be identified by X-ray diffraction (XRD) due to the smallness of the products were formed on the surface of the HAP. X-ray photoelectron spectroscopy (XPS) studies demonstrated that fluoridated hydroxyapatite (FHAP) was formed on HAP, and that calcium fluoride (CaF2) formation was accelerated by increasing the concentrations of fluorine and H2O2 along with the partial dissolution of HAP. In H2O2/NaF solution, DCPD also transformed easily to FHAP and CaF2, which are favorable to the remineralization process on the tooth surface. Thus, the mechanism of NaF was elucidated, and its use together with H2O2 for tooth bleaching was proved to be effective. Methodologically, the XPS two-dimensional plot made it possible for the first time to directly estimate the ratio of FHAP and CaF2 in the reaction products, in contrast to the conventional wet-analytical method, which is simply based on the difference in solubility of the two components. [source] Simulation and optimization of supercritical fluid purification of phytosterol estersAICHE JOURNAL, Issue 4 2009Tiziana Fornari Abstract Supercritical carbon dioxide extraction to separate phytosterol esters from fatty acid esters and tocopherols was simulated and optimized using the group contribution equation of state. Experimental extraction data at 328 K, pressures ranging from 200 to 280 bar and solvent-to-feed ratio around 25, was employed to verify the performance of the thermodynamic model. The raw material is the product obtained after a two-step enzymatic reaction carried out on soybean oil deodorizer distillates, and contains mainly fatty-acid ethyl esters, tocopherols and phytosterol esters. The extraction process was simulated using model substances to represent the complex multicomponent feed material. Nonlinear programming techniques were applied to find out optimal process conditions for a steady-state countercurrent process with partial reflux of the extract. The process optimization procedure predicts that a product with 94.2 wt % of phytosterol ester purity and 80% yield could be achieved. © 2009 American Institute of Chemical Engineers AIChE J, 2009 [source] Protein glycosylation analysis by HILIC-LC-MS of Proteinase K-generated N - and O -glycopeptidesJOURNAL OF SEPARATION SCIENCE, JSS, Issue 6-7 2010Gerhild Zauner Abstract Analysis of protein glycosylation is essential in order to correlate certain disease types with oligosaccharide structures on proteins. Here, a method for the MS characterization of site-specific protein glycosylation is presented. Using asialofetuin and fetuin as model substances, a protocol for glycopeptide dissection was developed based on unspecific proteolysis by Proteinase K. The resulting glycopeptides were then resolved by nanoscale hydrophilic interaction liquid chromatography-electrospray multistage MS. The early elution range of O -glycopeptides was clearly separated from the late elution range of N -glycopeptides. Glycopeptides were analyzed by ion trap-MS/MS, which revealed fragmentations of glycosidic linkages and some peptide backbone cleavages; MS3 spectra predominantly exhibited cleavages of the peptide backbone and provided essential information on the peptide sequence. The previously reported N - and O -glycan attachment sites of fetuin could be confirmed; moreover using our method, the occupation of a new, additional O -glycosylation site serine 296 was found. In conclusion, this approach appears to be a valuable technique for in-depth analysis of the site-specific N -glycosylation and O -glycosylation of individual glycoproteins. [source] Brief analysis of the retention process in RP-HPLC systems with a C30 bonded stationary phaseJOURNAL OF SEPARATION SCIENCE, JSS, Issue 13 2008Wojciech Zapa Abstract The influence of the mobile-phase composition on the retention of eight model substances in different RP-HPLC systems with a C30 alkyl bonded stationary phase has been studied. The aim of this study was to compare the performance of four valuable retention models assuming the partition and adsorption mechanism of retention. All the models were verified for different experimental data by four criteria: the sum of squared differences between the experimental and theoretical data; the approximation of the standard deviation; the Fisher test; and the F-test ratio. [source] Evaluation of hepatotropic targeting properties of allogenic and xenogenic erythrocyte ghosts in normal and liver-injured ratsLIVER INTERNATIONAL, Issue 2 2008Olav A. Gressner Abstract Background/Aims: Haemoglobin-depleted erythrocyte ghosts have been recommended as vesicle carriers of drugs with hepatotropic properties. However, the influence of liver injury on ghost elimination and targeting has not been reported so far. Methods: Human and rat ghosts were prepared and loaded with model substances, and the basic parameters were characterized. Ghosts were injected intravenously into rats with acute, subacute and chronic liver injuries. Elimination from circulation, organ distribution and cellular targeting was measured. The uptake of ghosts by liver macrophages/Kupffer cells was determined in cell culture. Results: Ghosts are strong hepatotropic carriers with a recovery of 90% in normal liver. Kupffer cells are the almost exclusive target cell type. Hepatotropic properties remain in rats with chronic liver diseases, but are reduced by 60,70% in acute liver damage as a result of decline of phagocytosis of macrophages/Kupffer cells. Although the uptake of ghosts per gram liver tissue in chronic liver injury was also reduced by about 40%, the increase of liver mass and of macrophages/Kupffer cells compensated for the reduced phagocytotic activity. In subacute injury, the uptake per gram liver tissue was only moderately reduced. Conclusion: Drug targeting with ghosts might be feasible in chronic and subacute liver injuries, e.g. fibrogenesis and tumours, because the content of ingested ghosts is released by Kupffer cells into the micro-environment, providing the uptake by and pharmacological effects on adjacent cells. [source] Red Blood Cell Templated Polyelectrolyte Capsules: A Novel Vehicle for the Stable Encapsulation of DNA and ProteinsMACROMOLECULAR RAPID COMMUNICATIONS, Issue 6 2006Oliver Kreft Abstract Summary: A novel method for the encapsulation of biomacromolecules, such as nucleic acids and proteins, into polyelectrolyte microcapsules is described. Fluorescence-labelled double-stranded DNA and human serum albumin (HSA) are used as model substances for encapsulation in hollow microcapsules templated on human erythrocytes. The encapsulation procedure involves an intermediate drying step. The accumulation of DNA and HSA in the capsules is observed by confocal laser scanning microscopy, UV spectroscopy, and fluorimetry. The mechanism of encapsulation is discussed. Confocal fluorescence microscopy images of encapsulated TRITC-HSA (left) and dsDNA (right). Inserts demonstrate fluorescence profiles for both compounds. [source] Loading of Bacterial Cellulose Aerogels with Bioactive Compounds by Antisolvent Precipitation with Supercritical Carbon DioxideMACROMOLECULAR SYMPOSIA, Issue 2 2010Emmerich Haimer Abstract Bacterial cellulose aerogels overcome the drawback of shrinking during preparation by drying with supercritical CO2. Thus, the pore network of these gels is fully accessible. These materials can be fully rewetted to 100% of its initial water content, without collapsing of the structure due to surface tension of the rewetting solvent. This rehydration property and the high pore volume of these material rendered bacterial cellulose aerogels very interesting as controlled release matrices. Supercritical CO2 drying, the method of choice for aerogel preparation, can simultaneously be used to precipitate solutes within the cellulose matrix and thus to load bacterial cellulose aerogels with active substances. This process, frequently termed supercritical antisolvent precipitation, is able to perform production of the actual aerogel and its loading in one single preparation step. In this work, the loading of a bacterial cellulose aerogel matrix with two model substances, namely dexpanthenol and L-ascorbic acid, and the release behavior from the matrix were studied. A mathematical release model was applied to model the interactions between the solutes and the cellulose matrix. The bacterial cellulose aerogels were easily equipped with the reagents by supercritical antisolvent precipitation. Loading isotherms as well as release kinetics indicated no specific interaction between matrix and loaded substances. Hence, loading and release can be controlled and predicted just by varying the thickness of the gel and the solute concentration in the loading bath. [source] | |||||||||||||||||||