Direct and indirect monitoring of peptide-silica interactions using time-resolved fluorescence anisotropy

The present work extends the application of time-resolved fluorescence anisotropy (TRFA) of a cationic probe rhodamine 6G (R6G) in aqueous Ludox to in situ monitoring of peptide adsorption onto the silica particles. Steady-state anisotropy and TRFA of R6G in Ludox sols were measured to characterize the extent of the ionic binding of the probe to silica particles in the presence of varying levels of tripeptides of varying charge, including Lys-Trp-Lys (KWK), N-acetylated Lys-Trp-Lys (Ac-KWK), Glu-Trp-Glu (EWE), and N-acetylated Glu-Trp-Glu (Ac-EWE). The results were compared to those obtained by direct observation of peptide adsorption using the steady-state anisotropy of the intrinsic tryptophan residue. Ionic binding of the peptides to Ludox particles produced an increase in the steady-state Trp anisotropy that was dependent on the number of cationic groups present, but the limiting anisotropy values were relatively low, indicating significant rotational freedom of the indole residue in the adsorbed peptides. On the other hand, R6G showed significant decreases in anisotropy in the presence of cationic peptides, consistent with the cationic peptides blocking the adsorption of the dye to the silica surface. Thus, R6G is able to indirectly report on the binding of peptides to Ludox particles. It was noteworthy that, while there were similar trends in the data obtained from steady-state anisotropy and TRFA studies of R6G, the use of steady-state anisotropy to assess binding of peptides overestimated the degree of peptide adsorption relative to the value obtained by TRFA. The study shows that the competitive binding method can be used to assess the binding of various biologically relevant compounds onto silica surfaces and demonstrates the potential of TRFA for probing peptide-silica and protein-silica interactions.     

Dichlorocarbene addition to cyclopropenes: a computational study

Reaction paths for addition of dichlorocarbene to 1,2-disubstituted cyclopropenes were calculated using hybrid density functional theory (B3LYP/6-31G) in the gas phase and in the presence of a continuum solvation model corresponding to acetonitrile. In both the gas phase and acetonitrile, :CCl2-cyclopropene addition follows an asymmetric, non-least-motion approach. Barriers to addition range from 0 to 2 kcal/mol. The reactions proceed in concerted fashion in both the gas phase and solution to yield 1,3-dienes or bicyclobutanes. The reaction pathway on this complex potential energy surface of this reaction appears to bifurcate, and the product distribution is believed to be controlled by reaction dynamics. At the present level of theory, there appears to be no minimum on the potential energy surface corresponding to a dipolar intermediate.     

Evaluation of optimization techniques for an extractive alcoholic fermentation process

The mathematical optimization of a continuous alcoholic fermentation process combined with a flash column under vacuum was studied. The objective was to maximize % yield and productivity in the fermentor. The results using surface response analysis combined with modeling and simulation were compared withy those obtained when the problem was written as a nonlinear programming problem and was solved with a successive quadratic programming (SQP) technique. Two process models were evaluated when the process was optimized using the SQP technique. The first one is a deterministic model, whose kinetic parameters were experimentally determined as functions of the temperature, and the second is a statistical model obtained using the factorial design technique combined with simulation. Although the best result was the one obtained using the rigorous model, the values for productivity and % yield obtained using the simplified model are acceptable, and these models can be used when the development of a rigorous model is excessively difficult, slow, or expensive.     

Thiosugars Iii. Stereoselective Approach to β-(1→2)-2,3-Dideoxy-2-C-Acetamidomethyl-2-S-Thiodisaccharides From Levoglucosenone

ABSTRACT

β-(1→2)-2,3-Dideoxy-2-C-acetamidomethyl-2-S-thiodisaccharides were synthesized in four steps by a stereoselective base catalyzed Michael addition reaction of 1-thiosugars to α-nitroalkene 4a, a new chiral synthon from levoglucosenone. It was followed by the reduction of the nitro group with a sodium borohydride/cobalt chloride complex and the hydrolytic opening of the 1,6-anhydro ring.     

Annual effective dose due to 222Rn and evaluation of 238U, 232Th and 40K contents in soil at the south-eastern coastal area of Bangladesh

Journal of Radioanalytical and Nuclear Chemistry - On-site 222Rn concentration at three different soil depths was measured at the south-eastern coastal area of Bangladesh to evaluate the annual...     

Spatially and temporally resolved IR-DFWM measurement of HCN released from gasification of biomass pellets

For the first time, to the best of the authors’ knowledge, nonintrusive quantitative measurement of hydrogen cyanide (HCN) released during the devolatilization phase of straw pellets gasification is demonstrated with high spatial and temporal resolution. Mid-infrared degenerate four-wave mixing (IR-DFWM) measurements of HCN were performed by probing the interference-free P(20) line in the v₁ vibrational band at around 3?µm and the IR-DFWM signal was detected with an upconversion-based detector, providing discrimination of thermal noise and increased sensitivity. A novel single-pellet setup consisting of a multi-jet burner was used to provide hot flue gas environments with an even and well-defined temperature distribution, for single straw pellet gasification at atmospheric pressure. The environments had temperatures of 1380?K, 1540?K and 1630?K with a constant oxygen concentration of 0.5?vol%. In order to quantify the amount of HCN released during the devolatilization of straw pellets, calibration measurements were performed in well-defined HCN gas flows. Selected hot water lines were probed with IR-DFWM in the interrogated volume to obtain the instantaneous temperature, which were used to correct the temperature effect. HCN concentrations up to 1500?ppm were detected during the devolatilization stage, and the results indicate a strong temperature dependence of the HCN release.     

Thermal,antioxidant, morphological and bioactive properties of starchy material extracted from the bacupari (Garcinia brasiliensis (Mart.)) seed using aqueous and alkaline maceration

Journal of Thermal Analysis and Calorimetry - Despite their being rich in bioactive compounds, by-products produced during fruit pulping are usually discarded. The present paper aimed to...     

Trans-cis isomerization of an azoxybenzene liquid crystal

Trans-cis isomerization was investigated in a room temperature liquid crystal mixture of two azoxybenzene compounds. Experiments were performed on isolated molecules in dilute solutions and on the liquid crystal phase composed of the pure compounds. The absorption spectra of the trans and cis isomers were found to be similar to those of azobenzene compounds, as were the birefringence and order parameter of the nematic liquid crystal phase. The photo-optic properties were also similar in that irradiation by ultraviolet light caused the conversion from trans to cis isomers, while short wavelength visible light incident on these compounds resulted in the conversion from cis to trans isomers. The activation energy for thermal relaxation from the cis to trans isomer in the liquid crystal phase was determined to be (66±7) kJ/mole, which is less than for azobenzene in solution. While a photostationary state in a dilute solution with approximately equal numbers of trans and cis isomers was achieved, the nematic-isotropic transition of the mixture of the pure compounds decreased from 70°C to room temperature with a cis concentration of only about 12%. One unusual finding was that the photostationary concentration of trans and cis isomers due to irradiation with light of a specific visible wavelength depended on the starting concentrations of the two isomers, indicating that there may be a molecular conformation that is not photo-responsive and relaxes only thermally.     

Comprehensive stability‐indicating high‐performance liquid chromatography coupled with diode array detection method for simultaneous determination of amprolium hydrochloride and ethopabate in powder dosage form for veterinary use

This research deals with the development of a stability‐indicating high‐performance liquid chromatography method for simultaneous determination of amprolium hydrochloride and ethopabate. To the best of our knowledge, no comprehensive stability‐indicating method has been reported for analysis of this mixture. Separation was achieved using Kromasil cyano column with gradient elution of the mobile phase composed of sodium hexane sulfonate solution and methanol. Quantification was based on measuring peak areas at 266 nm. Amprolium and ethopabate peaks eluted at retention times 10.42 and 18.53 min, respectively. The proposed procedure was validated with respect to system suitability, linearity, ranges, precision, accuracy, specificity, robustness, detection, and quantification limits. Linearity ranges for amprolium and ethopabate were 1.5–240 and 1–160 μg/mL, respectively. Analytes were subjected to stress conditions of hydrolysis, oxidation and thermal degradation. The proposed method enabled resolution of drugs from their forced‐degradation products and amprolium related substance (2‐picoline). Moreover, specificity was verified by resolution of the analytes from about 22 drugs used in antimicrobial veterinary products. The validated method was successfully applied to assay of the combined veterinary powder dosage form, additionally it was implemented in the accelerated stability study of the dosage form when stored for six months at 40°C and 75% relative humidity.