Surface Modification of Wood Using Nitric Acid

Surface modification of wood flakes by oxidation with nitric acid has been investigated at three different moisture contents of wood, and two different concentrations of the oxidant. It is shown that a significant number of the acid groups generated are chemically linked to wood. Increasing moisture content in wood has the effect of local dilution of the nitric acid oxidant while reduction in moisture content of wood during drying makes potential oxidation sites less accessible. Thus, two different regimes of oxidation, one of more accessible, and another, of less accessible, sites are observed. The nature of the generated acid is established as carboxylic, which is capable of undergoing a coupling reaction with 2-(l-aziridinyl)ethyl methacrylate. The catalysis of in situ polymerization of furfuryl alcohol by bound acid has also been shown to occur.     

In situ Diamond Anvil Cell–Raman Spectroscopy and Nanoindentation Study of the Pressure‐Induced Phase Transformation in Pure and Zinc‐Doped β‐Eucryptite

β‐eucryptite (LiAlSiO₄), a member of the family of lithium aluminum silicates, is known to undergo a reversible pressure‐induced phase transformation at ~0.8 GPa to ε‐eucryptite. This study correlates the results between two techniques, in situ diamond anvil cell–Raman spectroscopy and nanoindentation experiments, to explore how doping (substituting Zn for Li) influences this pressure‐induced phase transformation. Diamond anvil cell tests carried up to 3 GPa hydrostatic stress under Raman spectroscopy were compared with nanoindentation results, which provide a more localized, multiaxial stress state. The results indicate that the magnitude of hysteresis observed (difference between the pressures required for the forward and reverse transformation) is lower for Zn‐doped β‐eucryptite; however, the onset of the phase transformation is unchanged by doping with Zn. Furthermore, calculations of activation volume from nanoindentation experiments yield similar values (~0.1 nm³) for pure and Zn‐doped β‐eucryptite, suggesting that the nucleation event that establishes the onset of the phase transformation is the same for both materials.     

Local and Regional Secondary Organic Aerosol: Insights from a Year of Semi-Continuous Carbon Measurements at Pittsburgh

We present Scanning Mobility CCN Analysis (SMCA) as a novel method for obtaining rapid measurements of size-resolved cloud condensation nuclei (CCN) distributions and activation kinetics. SMCA involves sampling the monodisperse outlet stream of a Differential Mobility Analyzer (DMA) operated in scanning voltage mode concurrently with CCN and condensation particle counters. By applying the same inversion algorithm as used for obtaining size distributions with a scanning mobility particle sizer (SMPS), CCN concentration and activated droplet size are obtained as a function of mobility size over the timescale of an SMPS scan (typically 60–120 s). Methods to account for multiple charging, particle non-sphericity, and limited counting statistics are presented. SMCA is demonstrated using commercial SMPS and CFSTGC instruments with the manufacturer-provided control software. The method is evaluated for activation of both laboratory aerosol and ambient aerosol obtained during the 2004 NEAQS-ITCT2k4 field campaign. It is shown that SMCA reproduces the results obtained with a DMA operating in voltage “stepping” mode.     

Yellow Beads and Missing Particles: Trouble Ahead for Filter-Based Absorption Measurements

Particulate emissions from low-temperature biomass burning are dominated by organic matter. Here, we show that such emissions have a liquid, bead-like appearance when collected on fibrous filters, and the number of these beads are far less than expected for solid spherical particles. These shapes are in line with published drop-on-fiber theories for liquids entrained on filaments. A smoldering pine sample is yellowish, with organic carbon over 99% of the total carbon, and chars substantially in thermal-optical analysis (TOA), indicating that such liquid organic particles could affect both absorption measurements and TOA of such samples. Similar colored samples collected in the field from rice-straw burning and cook stove emissions also show a similar liquid appearance.     

Synthesis and evaluation of trimethylolpropane triacrylate crosslinked superabsorbent polymers for conserving water and fertilizers

A series of superabsorbent polymers (SAP) were synthesized by free radical thermal copolymerization of acrylic acid and N‐isopropyl acrylamide monomers using trimethylolpropane triacrylate as crosslinker. They were characterized by FT‐IR and thermal stability (TGA/DTG), and evaluated for their water and fertilizer uptake and release characteristics under different crosslinker levels, temperature, pressure, and pH. The observed maximum absorption of water by the SAP was 1130 g/g of polymer. The release was modeled which showed a non‐Fickian mechanism. The water uptake of SAP was correlated with the average molecular weight between the crosslinks and crosslink density. Analysis of the weight loss data from TG in air revealed a zero order kinetics for the initial degradation step with an activation energy (AE) of 70.8 kJ/mol. The AEs for water uptake and release for thermal degradation were also determined through Arrhenius plots. The results inferred that the synthesized SAP can be exploited for commercial agricultural applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Atomistic insights into solvation dynamics and conformational transformation in thermo-sensitive and non-thermo-sensitive oligomers

Solvation dynamics and conformational transformation in oligomers with varying degree of temperature sensitivity is studied using molecular dynamics (MD) simulations. Conformational transformation in three model systems namely poly(N-isopropylacrylamide) (PNIPAM), poly(acrylamide) (PAA), and poly(ethylene glycol) (PEG) are compared and contrasted to understand the origin of a coil-to-globule transformations across the lower critical solution temperature (LCST) in thermo-sensitive oligomers. PNIPAM, PAA, and PEG are water-soluble oligomers. However, for the temperature range used in these simulations, PNIPAM shows an LCST whereas PAA and PEG are non-thermo-sensitive. Oligomers of PNIPAM, PAA, and PEG consisting of 30 monomer units (30-mer) each were simulated at 5 °C (278 K) and 37 °C (310 K). Conformational transformations in the oligomers are evaluated using structural and dynamical correlation functions such as radius of gyration, radial distribution function, residence time probabilities and hydrogen-bonding life-times. Our simulations suggest that the solubility, solvation dynamics, and conformation of the oligomers are dictated by two factors: (a) the local structure of proximal water and (b) the diffusion and exchange kinetics of proximal water with bulk water. In thermo-sensitive oligomer such as PNIPAM, we find that the coil-to-globule transition is closely related to the local ordering and solvation dynamics of PNIPAM. We have identified stable configurations of proximal water molecules for an oligomer undergoing conformational transition. The slow diffusional properties of proximal water molecules near PNIPAM oligomers suggests that water forms a stable network near hydrophilic groups of PNIPAM as compared to the hydrophilic groups of PAA and PEG. Thermal perturbation of this solvated structure results in significant reduction in local ordering of water, which contributes to the globular collapse and the reduced solubility of PNIPAM above its LCST. On the other hand, non-thermo-sensitive oligomers such as PAA and PEG are characterized by much faster diffusion and exchange kinetics of proximal water at the two simulated temperatures compared to PNIPAM. This faster exchange kinetics helps in maintaining higher hydration level of the oligomers and is responsible for the apparent hydrophilic character and thereby the observed solubility at the two simulated temperatures.     

1-[2-(1-Cyclobutylpiperidin-4-yloxy)-6,7-dihydro-4H-thiazolo[5,4-c]pyridin-5-yl]propan-1-one: a Histamine H3 Receptor Inverse Agonist with Efficacy in Animal Models of Cognition

A series of chemical optimizations, which was guided by in vitro affinity at histamine H₃ receptor (H₃R), modulation of lipophilicity, ADME properties and preclinical efficacy resulted in the identification of 1-[2-(1-cyclobutylpiperidin-4-yloxy)-6,7-dihydro-4H-thiazolo[5,4-c]pyridin-5-yl]propan-1-one ( 45 e ) as a potent and selective (K_i=4.0 nM) H₃R inverse agonist. Dipsogenia induced by (R)-α-methylhistamine was dose dependently antagonized by 45 e , confirming its functional antagonism at H₃R. It is devoid of hERG and phospholipidosis issues. Compound 45 e has adequate oral exposures and favorable half-life in both rats and dogs. It has demonstrated high receptor occupancy (ED₈₀=0.22 mg/kg) and robust efficacy in object recognition task and, dose dependently increased acetylcholine levels in brain. The sub-therapeutic doses of 45 e in combination with donepezil significantly increased acetylcholine levels. The potent affinity, selectivity, in vivo efficacy and drug like properties together with safety, warrant for further development of this molecule for potential treatment of cognitive disorders associated with Alzheimer's disease.     

Membrane processing of used frying oils

Studies were conducted with used frying oils in a flat membrane batch cell using five different types of polymeric membranes to decrease the soluble degradation products. During membrane processing, triglycerides permeated preferentially compared to the majority of the polar compounds including oxidation products, polymers, and color compounds. Two of the composite membranes, NTGS-AX and NTGS-2200, selectively rejected polar compounds and oxidation products to the extent of 25–48% and 24–44% respectively. The reduction in Lovibond color values (5R+Y) was in the range of 83–93%. The viscosity of the used frying oil was reduced to the extent of 22%. The composite membranes were effective in reducing the soluble impurities, as well as insoluble particulates, without causing any undesirable changes to the oil. The membrane process appears to improve the life of used frying oils and does not have the disadvantages associated with the active filtration systems, however, for commercial application the permeate flux needs to be improved considerably.