Poly(vinyl alcohol) (PVOH)/clay aerogel composites were fabricated by an environmentally friendly freeze-drying of the aqueous precursor suspensions, followed by cross-linking induced by gamma irradiation without chemical additives. The influences of cross-linking conditions, i.e., absorbed dose and polymer loading as well as density on the aerogel structure and properties, were investigated. The absorbed dose of 30 kGy was found to be the optimum dose for fabricating strong PVOH composites; the compressive modulus of an aerogel prepared from an aqueous suspension containing 2 wt % PVOH/8 wt % clay increased 10-fold, and that containing 1 wt % PVOH/9 wt % clay increased 12 times upon cross-linking with a dose of 30 kGy. Increasing the solids concentration led to an increase in the mechanical strength, in accordance with the changes in microstructure from layered structure to network structure. The increase of absorbed dose also led to decreased porous size of the network structure. Cross-linking and the increase of the PVOH lead to decreased thermal stability. The strengthened PVOH/clay aerogels possess very low flammability, as measured by cone calorimetry, with heat, smoke, and volatile products release value decreasing as increasing clay content. The mechanism of flame retardation in these materials was investigated with weight loss, FTIR, WAXD, and SEM of the burned residues. The proposed mechanism is that with decreasing fuel content (increasing clay content), increased heat and mass transport barriers are developed; simultaneously low levels of thermal conductivity are maintained during the burning.

Anomeric sulfonium ions are attractive glycosyl donors for the stereoselective installation of 1,2-cis glycosides. Although these donors are receiving increasing attention, their mechanism of glycosylation remains controversial. We have investigated the reaction mechanism of glycosylation of a donor modified at C-2 with a (1S)-phenyl-2-(phenylsulfanyl)ethyl chiral auxiliary. Preactivation of this donor results in the formation of a bicyclic β-sulfonium ion that after addition of an alcohol undergoes 1,2-cis-glycosylation. To probe the importance of the thiophenyl moiety, analogs were prepared in which this moiety was replaced by an anisoyl or benzyl moiety. Furthermore, the auxiliaries were installed as S- and R-stereoisomers. It was found that the nature of the heteroatom and chirality of the auxiliary greatly influenced the anomeric outcome and only the one containing a thiophenyl moiety and having S-configuration gave consistently α-anomeric products. The sulfonium ions are sufficiently stable at a temperature at which glycosylations proceed indicating that they are viable glycosylation agents. Time-course NMR experiments with the latter donor showed that the initial rates of glycosylations increase with increases in acceptor concentration and the rate curves could be fitted to a second order rate equation. Collectively, these observations support a mechanism by which a sulfonium ion intermediate is formed as a trans-decalin ring system that can undergo glycosylation through a bimolecular mechanism. DFT calculations have provided further insight into the reaction path of glycosylation and indicate that initially a hydrogen-bonded complex is formed between sulfonium ion and acceptor that undergoes SN2-like glycosylation to give an α-anomeric product.

Abstract. We report on the development of a cavityenhanced aerosol single-scattering albedometer based on incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) combined with an integrating sphere (IS) for simultaneous in situ measurements of aerosol scattering and extinction coefficients in an exact same sample volume. The cavity-enhanced albedometer employed a blue light-emitting-diode (LED)-based IBBCEAS approach for the measurement of wavelength-resolved aerosol optical extinction over the spectral range of 445-480 nm and an integrating sphere nephelometer coupled to the IBBCEAS setup for the measurement of aerosol scattering. The scattering signal was measured with a single-channel photomultiplier tube (PMT), providing an averaged value over a narrow bandwidth (full-width at half-maximum, FWHM, ∼ 9 nm) in the spectral region of 465-474 nm. A scattering coefficient at a wavelength of 470 nm was deduced as an averaged scattering value over the spectral region of 465-474 nm and used for data analysis and instrumental performance comparison. Performance evaluation of the albedometer was carried out using laboratory-generated particles and ambient aerosol. The scattering and extinction measurements of monodisperse polystyrene latex (PSL) spheres generated in the laboratory proved excellent correlation between two channels of the albedometer. The retrieved refractive index (RI) of the PSL particles from the measured scattering and extinction efficiencies agreed well with the values reported in previously published papers. Aerosol light scattering and extinction coefficients, single-scattering albedo (SSA) and NO 2 concentrations in an ambient sample were directly and simultaneously measured using the albedometer developed. The instrument developed was validated via an intercomparison of the measured aerosol scattering coefficients and NO 2 trace gas concentrations to a TSI 3563 integrating nephelometer and a chemiluminescence detector, respectively.

The γ radiolysis behavior of polydimethylsiloxane (PDMS) in the radiation-thermal environments (dose rate, 0.2 Gy/s) is studied to pinpoint the basic knowledge of the temperature (20–70 °C) effects. The non-monotonous temperature effects on the formation of gas products, paramagnetic species in silica, and cross-linking density are proposed to correlate with the complex chemical reaction mechanisms. Besides, molecular dynamics simulation and theoretical calculation are first performed simultaneously based on the radical chemistry and intricate material composition, making it easier to comprehend and further harness the radiolysis mechanisms and structure deterioration of PDMS. The γ radiation-induced primary gas products and dominant cross-linking phenomena are reproduced by the molecular dynamics simulations with a reactive force field, and the reaction mechanisms and physicochemical interactions among PDMS chains, gas products, reactive radicals, and silica fillers are thoroughly studied at the atomic scale. The thermochemistry of the barrierless radical coupling reactions and reactions with explicit high-barrier transition states is calculated at the M06-2X theoretical level with the 6-311g­(d, p) basis set. The barrierless reactions are all exothermal with the heat release of 321–618 kJ/mol, while the potential barriers for reactions with explicit transition states vary between 37 and 229 kJ/mol. The results show that γ radiation-induced radicals are crucial for the ensuing gas formation and cross-linking reactions, especially for the radical coupling reactions. The radical chemistry involved in the radiolytic PDMS is the key to understand and simulate its radiolysis behavior, according to the experimental and simulated results.