The structure of an aminosilane coupling agent in aqueous solutions and partially cured solids

The molecular structures of partially cured polyaminopropylsilsesquioxane and aminopropyltriethoxysilane in water have been studied using Fourier-transform infrared, laser Raman, and quasielastic laser light-scattering spectroscopy. A multiply hydrogen-bonded structure is proposed for the intramolecularly interacting amine and silanol groups on the basis of isotope exchange experiment and conformational energy calculations. Conformational restrictions are rather low for the proposed structure, which is thus suitable for the partially cured solid where there are slight perturbations by the surrounding amine and silanol groups. The O.…N distance was experimentally determined to be in the range 2.70–2.67 Å and estimated theoretically as 2.49–2.45 Å. The aminosilane in very dilute solution is found to be mostly monomeric. The isolated monomer-oligomer transition lies around 0.15% by weight and this transition influences the amount of silane uptake by glass fibers. It is also proposed that this phenomenon may be general for surface treatments by silane coupling agents. Hydrolyzed aminosilane oligomers exist in part as submicron aggregates which can be broken up by the addition of an alcohol. The neutralized aminosilane hydrolyzes very slowly although it dissolves in water instantaneously. Micelle formation is also proposed.     

Impact of protein denaturants and stabilizers on water structure

It is of great interest to determine how solutes such as urea, sugars, guanidinium salts, and trimethylamine N-oxide affect the stability, solubility, and solvation of globular proteins. A key hypothesis in this field states that solutes affect protein stability indirectly by making or breaking water structure. We used a new technique, pressure perturbation calorimetry, to measure the temperature dependence of a solute's partial compressibility. Using fundamental thermodynamic relations, we converted these data to the pressure dependence of the partial heat capacity to examine the impact of protein stabilizing and denaturing solutes on water structure by applying the classic two-state mixture model for water. Contrary to widely held expectations, we found no correlation between a solute's impact on water structure and its effect on protein stability. Our results indicate that efforts to explain solute effects should focus on other hypotheses, including those based on preferential interaction and excluded volume.     

RCM approach for the total synthesis of cryptophycin-24 (Arenastatin A)

An efficient total synthesis of cryptophycin-24 (arenastatin A) is reported, which features two novel synthetic strategies, the use of a RCM reaction to form the macrocycle, and the introduction of the styrene epoxide moiety prior to the macrocyclization reaction.     

Molecular modeling of polymers: I. Correct and efficient enumeration of intrachain conformational energetics

Polymer conformational analyses can require being able to model the intramolecular energetics of a very long (infinite) chain employing calculations carried out on a relatively short chain sequence. A method to meet this need, based upon symmetry considerations and molecular mechanics energetics, has been developed. Given N equivalent degrees of freedom in a linear polymer chain, N unique molecular groups are determined within the chain. A molecular unit is defined as a group of atoms containing backbone rotational degrees of conformational freedom on each of its ends. The interaction of these N molecular groups, each with a finite number of nearest neighbors, properly describe the intramolecular energetics of a long (infinite) polymer chain. Thus, conformational energetics arising from arbitrarily distant neighbor interactions can be included in the estimation of statistical and thermodynamic properties of a linear polymeric system. This approach is called the polymer reduced interaction matrix method (PRIMM) and the results of applying it to isotactic polystyrene (I-PS) are presented by way of example.     

Photoconductivity in a photocrosslinkable second-order nonlinear optical polymer

Photoconductivity measurements on a stable photocrosslinkable nonlinear optical polymer — PVCN (polyvinylcinnamate)/CNNB-R (3-cinnamoyloxy-4-[4-N,N-diethylamino)-2-cinnamoyloxy phenylazo] nitrobenzene) are reported. Photoconductivity in this polymer system, in both crosslinked and uncrosslinked states, was observed without introducing any sensitizer or carrier-transport agents. Absorption of CNNB-R (_peak=518 nm) results in photocarrier generation and it is conjectured that CNNB-R also plays a role in the carrier transport. Such polymers are candidate materials for photorefraction.     

Nörlund and Riesz mean of sequences of fuzzy real numbers

In this article we study some properties of the Nörlund and Riesz mean of sequences of fuzzy real numbers. We establish necessary and sufficient conditions for the Nörlund and Riesz means to transform convergent sequences of fuzzy numbers into convergent sequences of fuzzy numbers with limit preserving.     

A model for expansion ratio in liquid-solid fluidized beds

Liquid-solid fluidized beds are used in mineral processing industries to separate particles based on parti- cle size, density, and shape. Understanding the expanded fluidized bed is vital for accurately assessing its performance. Expansion characteristics of the fluidized bed were studied by performing several experi- ments with iron ore, chromite, quartz, and coal samples. Using water as liquid medium, experiments were conducted to study the effects of particle size, particle density, and superficial velocity on fluidized bed expansion. The experimental data were utilized to develop an empirical mathematical model based on dimensional analysis to estimate the expansion ratio of the fluidized bed in terms of particle character- istics, operating and design parameters. The predicted expansion ratio obtained from the mathematical model is in good agreement with the experimental data.     

Effect of Sc substitution on the structure,electrical, and magnetic properties of multiferroic BiFeO3 thin films grown by a sol–gel process

Multiferroic BiFeO₃ (BFO), Bi_1−xSc_xFeO₃ (BSF), and BiFe_1−xSc_xO₃ (BFS) (x=0.3 mol%) thin films are prepared on Pt/Ti/SiO₂/Si substrates using a sol–gel technique. The effect of Sc substitution along with the annealing ambient (N₂ and O₂) on the structure, electrical, and magnetic properties of the films are reported. X-ray diffraction (XRD) analysis reveals that the films can be prepared with the single-phase perovskite structure by annealing at 700 °C for 10 min either in O₂ or N₂ ambient. The unit cell volume increases on the substitution of Sc, which are 61.39, 62.50, and 62.57 (Å)³ for BFO, BSF, and BFS, respectively. X-ray photoelectron spectroscopy (XPS) study reveals that the chemical environments of Bi and Fe are different in BFO, BSF, BFS films. Similarly, XPS spectra for Sc2p lines in BSF and BFS also have different peak positions; this indicates Sc doping has certain chemical impact on BSF and BFS films. Systematic studies of Sc substitution along with the effect of annealing ambient on the dielectric constant (ε) and dielectric loss (tan δ), leakage current, remnant polarization (P_r), coercive field (E_c), and magnetic properties of the films are carried out. The room temperature values of ε and tan δ at 1 kHz for BFO and BFS films annealed in N₂ ambient are (∼208; 0.035) and (∼235; 0.023), respectively. The comparative value of leakage current for the BFO and BFS films at an applied field strength of 50 kV/cm are 2.997×10⁻⁴ and 1.87×10⁻⁵ A/cm², respectively. Room temperature value of coercive magnetization for BFS films has one order small compared to that of the BFO films; this indicates BFS films are magnetically soft and more suitable for potential device applications. Finally, among the studied compositions, the BFS films annealed in N₂ ambient show the best property.