Synthesis and characterization of perfectly alternating polycarbonate‐polydimethylsiloxane multiblock copolymers possessing controlled block lengths

An array of perfectly alternating polycarbonate‐polydimethylsiloxane (PC‐PDMS) multiblock copolymers possessing systematic variations in block molecular weights were successfully produced by coupling preformed PC and PDMS telechelic oligomers using hydrosilylation. Based on gel permeation chromatography results, the multiblock copolymers were essentially void of the oligomeric precursors. Despite the relatively large difference in solubility parameter between PC and PDMS, the multiblock copolymers exhibited significant partial miscibility between the two phases. As expected, the degree of partial miscibility was dependent on the molecular weight of the blocks with the extent of partial miscibility increasing with decreasing block molecular weights. Morphological characterization using small angle X‐ray scattering showed that, at a given PC block molecular weight, the uniformity of the two phase morphology increased with increasing PDMS block molecular weight, which is consistent with a decrease in the extent of phase mixing with increasing PDMS block molecular weight. POLYM. ENG. SCI., 54:1648–1663, 2014. © 2013 Society of Plastics Engineers     

Composition-dependent properties of segmented polyurethanes

We studied segmented polyurethanes (SPU) from poly(diethylene glycol adipate) with molar masses M_SFT = 780, 1365, 1780 and 3200 g/mol (soft fragments, SFT), 2,4-toluene diisocyanate and 2,4-toluene diamine (stiff fragments, STF) with essentially monodisperse molar mass distribution of STF. They were characterized by WAXS, SAXS, heat capacity measurements, mainly from 150–450 K, and enthalpies of solution in dimethyl formamide at room temperature, ΔH_sol. The experimental results may be summarized as follows.

• The glass transition temperatures of SFT decrease with an increase of M_SFT, but remain essentially composition-invariant at fixed M_SFT, whatever the STF volume fraction φ.
• The surface-to-volume ratio of STF domains exhibits sudden, jump-like transitions at volume fractions φ* = 0.23 and φ** = 0.40, respectively.
• Exothermic (i.e., negative) values of ΔH_SOl exhibit a jump-like decrease at φ* = 0.23.

It has been shown that the main cause of the latter effect is the transition of SFT from a somewhat extended to an essentially unperturbed conformation.     

Lipid specificity and location of the sterol carrier protein-2 fatty acid-binding site: A fluorescence displacement and energy transfer study

Although it was recently recognized that sterol carrier protein-2 (SCP-2) interacts with fatty acids, little is known regarding the specificity of SCP-2 for long-chain fatty acids or branched-chain fatty-acid-like molecules. Likewise the location of the fatty-acid binding site within SCP-2 is unresolved. A fluorescent cis-parinaric acid displacement assay was used to show that SCP-2 optimally interacted with 14–22 carbon chain lipidic molecules: polyunsaturated fatty acids > monounsaturated, saturated > branched-chain isoprenoids > branched-chain phytol-derived fatty acids. In contrast, the other major fatty-acid binding protein in liver, fatty-acid binding protein (L-FABP), displayed a much narrower carbon chain preference in general: polyunsaturated fatty acids > branched-chain phytol-derived fatty acids > 14- and 16-carbon saturated > branched-chain isoprenoids. However, both SCP-2 and l-FABP displayed a very similar unsaturated fatty-acid specificity profile. The presence and location of the SCP-2 lipid binding site were investigated by fluorescence energy transfer. The distance between the SCP-2 Trp⁵⁰ and bound cis-parinaric acid was determined to be 40 Å. Thus, the SCP-2 fatty-acid binding site appeared to be located on the opposite side of the SCP-2 Trp⁵⁰. These findings not only contribute to our understanding of the SCP-2 ligand binding site but also provide evidence suggesting a potential role for SCP-2 and/or L-FABP in metabolism of branched-chain fatty acids and isoprenoids.     

CFD predictions for hazardous area classification

This study aimed to describe a Computational Fluid Dynamics(CFD) procedure using the ANSYS CFX software 16.1 and Design of Experiments for the determination of volume and extension of explosive atmospheres due to fugitive emissions of flammable gases.The multidimensional statistical sampling technique Latin Hypercube was used, which defined 100 simulations of random methane gas leak conditions.The CFD model proved to be robust in predicting the extension and volume of the explosive atmosphere for orifice diameters from 0.1 to2.5 mm, pressure from 0.1 MPa to 12 MPa and temperatures from 0 ℃ to 400 ℃.It was found that the calculation domain must be parameterized 8 m in length for each millimeter of the diameter of the source of release to ensure the predictions.In order not to lose precision for very small diameters, the mesh was parameterized with 50 elements along the orifice diameter.It was proved that gravity does not influence the extension and volume of the explosive atmosphere at sonic emissions.The deviation from the ideal gas behavior in the reservoir,achieved by applying the Soave–Redlich–Kwong equation of state, also has not significantly influenced the extension and volume of the explosive atmosphere.The results showed that the size of the explosive atmosphere varies directly with the diameter of the source emission and reservoir pressure, and inversely with the temperature of the reservoir.The diameter of the source is the parameter that has the major effect on the extension of the explosive atmosphere, followed by the pressure and lastly the temperature of the reservoir.     

Self-assembled silver nanoislands formed on glass surface via out-diffusion for multiple usages in SERS applications

We demonstrate that silver nanoisland film self-assembled on the surface of silver-containing glass in the course of thermal processing in hydrogen is capable to detect 10⁻⁷ M concentration of rhodamine 6G in water using surface enhanced Raman spectroscopy (SERS) technique. The film can be multiply restored on the same glass substrate via annealing of the glass in hydrogen. We showed that the film can be self-assembled after as much as ten circles of the substrate cleaning followed by annealing. The proposed technique of the silver nanoisland film formation enables multiple usage of the same glass substrate in SERS experiments.     

Side-chain type benzoxazine-functional cellulose via click chemistry

A side-chain type benzoxazine-functional cellulose has been developed using click chemistry via the reaction of ethynyl-monofunctional benzoxazine monomer and azide-functional cellulose. The synthesis, crosslinking, and thermal properties of the benzoxazine-functional cellulose are studied by NMR, FTIR, DSC, and TGA. The crosslinking reaction of the benzoxazine side-chain unusually takes place at low-temperatures in comparison to an ordinary benzoxazine resins. Upon crosslinking, the polymer shows high char yield of 40%, which is a marked improvement from a mere 4% of the unfunctionalized cellulose. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Kinetics of Soybean Oil Hydrolysis on Niobium Catalysts

The catalytic hydrolysis of soybean oil was used as an alternative for the production of monoglycerides (MG) and diglycerides (DG). The reactions were conducted in a stainless-steel tubular reactor in the temperature range of 240–290 °C, on niobium phosphate (NBP) and niobium oxide (NBO) as catalysts. In the hydrolysis reactions at 270 °C, the maximum selectivities of the products of interest were obtained at 22 % MG and 48 % DG for the reaction with NBP, and 7 % MG and 33 % DG with NBO, for 59 % and 36 % of triglyceride conversion in 10 min, respectively. The proposed kinetic model presented a good fit of the theoretical model with the experimental data, showing that the previous hypotheses considered for the mechanism development are suitable for describing the kinetics of soybean oil hydrolysis.     

Methods and Applications of In Silico Aptamer Design and Modeling

Aptamers are nucleic acid analogues of antibodies with high affinity to different targets, such as cells, viruses, proteins, inorganic materials, and coenzymes. Empirical approaches allow the design of in vitro aptamers that bind particularly to a target molecule with high affinity and selectivity. Theoretical methods allow significant expansion of the possibilities of aptamer design. In this study, we review theoretical and joint theoretical-experimental studies dedicated to aptamer design and modeling. We consider aptamers with different targets, such as proteins, antibiotics, organophosphates, nucleobases, amino acids, and drugs. During nucleic acid modeling and in silico design, a full set of in silico methods can be applied, such as docking, molecular dynamics (MD), and statistical analysis. The typical modeling workflow starts with structure prediction. Then, docking of target and aptamer is performed. Next, MD simulations are performed, which allows for an evaluation of the stability of aptamer/ligand complexes and determination of the binding energies with higher accuracy. Then, aptamer/ligand interactions are analyzed, and mutations of studied aptamers made. Subsequently, the whole procedure of molecular modeling can be reiterated. Thus, the interactions between aptamers and their ligands are complex and difficult to understand using only experimental approaches. Docking and MD are irreplaceable when aptamers are studied in silico.     

Impact of A134 and E218 Amino Acid Residues of Tropomyosin on Its Flexibility and Function

Tropomyosin (Tpm) is one of the major actin-binding proteins that play a crucial role in the regulation of muscle contraction. The flexibility of the Tpm molecule is believed to be vital for its functioning, although its role and significance are under discussion. We choose two sites of the Tpm molecule that presumably have high flexibility and stabilized them with the A134L or E218L substitutions. Applying differential scanning calorimetry (DSC), molecular dynamics (MD), co-sedimentation, trypsin digestion, and in vitro motility assay, we characterized the properties of Tpm molecules with these substitutions. The A134L mutation prevented proteolysis of Tpm molecule by trypsin, and both substitutions increased the thermal stability of Tpm and its bending stiffness estimated from MD simulation. None of these mutations affected the primary binding of Tpm to F-actin; still, both of them increased the thermal stability of the actin-Tpm complex and maximal sliding velocity of regulated thin filaments in vitro at a saturating Ca²⁺ concentration. However, the mutations differently affected the Ca²⁺ sensitivity of the sliding velocity and pulling force produced by myosin heads. The data suggest that both regions of instability are essential for correct regulation and fine-tuning of Ca²⁺-dependent interaction of myosin heads with F-actin.