Role of salt on adhesion of an epoxy/aluminum (oxide) interface in aqueous environments

Joints held by polymeric adhesives are commonplace in many engineered products, but normal service can require exposure to environmental conditions that present a significant challenge for maintaining the structural integrity of the interface. In particular, aqueous environments can wreak havoc on the joint strength. Here, a mechanistic approach is used to understand the difference in the debonding behavior of an epoxy/aluminum (oxide) interface when exposed to deionized (DI) water and aqueous sodium chloride by correlating macroscopic failure with the sorption of salt and water into the adhesive and its nanoscale distribution. For the epoxy‐aluminum system examined here, the presence of sodium chloride increases the resistance to crack growth in comparison to DI water. The debonding appears to be controlled by water near the buried interface. Salt water decreases the solubility of water in the epoxy and decreases the concentration of water near the buried interface, but the concentration of salt that enters the epoxy is below the detection limit. Thus, even if ions cannot penetrate or sorb into the adhesive, the presence of salt can significantly alter the water distribution within the adhesive and ultimately the strength of the joint. POLYM. ENG. SCI., 56:18–26, 2016. © 2015 Society of Plastics Engineers     

Optimization of Mixing and Mass Transfer in In-line Multi-Jet Ozone Contactors Using Computational Fluid Dynamics

Typical ozone mixing and mass transfer calculations are lumped approaches based on ideal operating conditions and can misrepresent behavior in real-life installations. This article models the effect of local hydrodynamics and mixing on the overall mass transfer of ozone into water with the aid of multiphase computational fluid dynamics (CFD). CFD models were validated with measured data from a pipeline ozone contactor installation which was optimized for more rapid, uniform mixing and mass transfer. Results emphasize the sensitivity of mixing quality to nozzle placement, size, orientation and spacing relative to main pipeline diameter and flows.     

Electrophilic Aromatic Functionalization of Phenolic Photoresist Polymers

Summary Functionalization of both linear poly(4-hydroxystyrene) (PHS) and branched poly(4-hydroxystyrene) (PHS-B) was accomplished via a Reimer-Tiemann electrophilic aromatic substitution reaction. Linear and branched poly(4-hydroxystyrene-co-5-vinylsalicylaldehyde) (pHS/5VSA and pHS-B/5VSA) copolymers were observed to undergo acid-catalyzed, novolac type self-crosslinking. Both the pHS/5VSA and pHS-B/5VSA copolymer systems possessed a lower deep ultra violet microlithographic sensitivity compared to linear PHS when formulated in negative photoresists. The sluggishness of the negative photoresists containing 5-vinylsalicylaldehyde functionalized copolymers was attributed to a combination of resonance stabilization and steric hindrance effects.     

Design, synthesis and biological evaluation of Trypanosoma brucei trypanothione synthetase inhibitors

Trypanothione synthetase (TryS) is essential for the survival of the protozoan parasite Trypanosoma brucei, which causes human African trypanosomiasis. It is one of only a handful of chemically validated targets for T. brucei in vivo. To identify novel inhibitors of TbTryS we screened our in-house diverse compound library that contains 62,000 compounds. This resulted in the identification of six novel hit series of TbTryS inhibitors. Herein we describe the SAR exploration of these hit series, which gave rise to one common series with potency against the enzyme target. Cellular studies on these inhibitors confirmed on-target activity, and the compounds have proven to be very useful tools for further study of the trypanothione pathway in kinetoplastids.     

State-Resolved Stereodynamics of an Insertion Reaction O(1D2) + H2(v = 0, j) → OH(X2Πi; v′, N′, f′) + H

The product state-resolved stereodynamics of the reaction of O(¹D₂) with H₂ have been studied at 300 K at a mean collision energy of ca. 12 kJ mol⁻¹, using polarized, Doppler-resolved laser-induced fluorescence to probe the scattered products, OH(X²Π_i; v′ = 0, N′, f′), and polarized photodissociation of N₂O to provide the reagent O(¹D₂) atoms. Product state-resolved differential cross sections, rotational polarizations, and excitation functions are in very good qualitative agreement with the results of quasi-classical trajectory (QCT) calculations, conducted on the Schinke-Lester, SL1 ab initio potential energy surface (PES) for the ground electronic state of the collision complex. The experimental and computational results are compared with those obtained in a complementary study of the reaction of O(¹D₂) with CH₄ and remarkable parallels have been exposed. The linear and angular momentum vector correlations are all consistent with an “insertion” mechanism, proceeding over an attractive PES, which presents no entrance barrier.     

Particle size and chemical composition effects on elemental analysis with the nano aerosol mass spectrometer

In the Nano Aerosol Mass Spectrometer (NAMS), particles are irradiated with a high energy laser pulse to produce a plasma that quantitatively disintegrates each particle into positively charged atomic ions. Previous work with this method used electrodynamic focusing and trapping of particles 30 nm dia. and below. In the current work, an aerodynamic focusing inlet was used to study particles between 40 and 150 nm dia. The distribution of atomic ion charge states was found to be particle size dependent, shifting toward lower charges with increasing size. This shift also affected the calibration by which elemental composition was determined from atomic ion signal intensities. Size independent calibration could be achieved by restricting the analysis to particles that gave more than 90% of the total signal intensity as multiply charged ions. This approach worked best for particles smaller than about 100 nm dia. since most spectra met this criterion. For the nanoparticles studied, the elemental mole fractions of Group I and II metals, halogens, and low atomic mass nonmetals could be determined within 10% or less of the expected value when the mole fraction was at the 1% level or greater. Some transition and heavy metals could not be quantified, while others could. Quantification appeared to be dependent on the ability of the element to be vaporized. Elements with high melting and boiling points gave particle mass spectra similar to those obtained by laser desorption ionization—mostly singly charged ions with relative intensities strongly biased toward atoms with low ionization energies.

Copyright © 2017 American Association for Aerosol Research     

Synthesis and Biochemical Evaluation of Biotinylated Conjugates of Largazole Analogues: Selective Class I Histone Deacetylase Inhibitors

The synthesis of biotinylated conjugates of synthetic analogues of the potent and selective histone deacetylase (HDAC) inhibitor largazole is reported. The thiazole moiety of the parent compound's cap group was derivatized to allow the chemical conjugation to biotin. The derivatized largazole analogues were assayed across a panel of HDACs 1–9 and retained potent and selective inhibitory activity towards the class I HDAC isoforms. The biotinylated conjugate was further shown to pull down HDACs 1, 2, and 3.     

Flexible and mechanical strain resistant large area SERS active substrates

We report a cost effective and facile way to synthesize flexible, uniform, and large area surface enhanced Raman scattering (SERS) substrates using an oblique angle deposition (OAD) technique. The flexible SERS substrates consist of 1 μm long, tilted silver nanocolumnar films deposited on flexible polydimethylsiloxane (PDMS) and polyethylene terephthalate (PET) sheets using OAD. The SERS enhancement activity of these flexible substrates was determined using 10(-5) M trans-1,2-bis(4-pyridyl) ethylene (BPE) Raman probe molecules. The in situ SERS measurements on these flexible substrates under mechanical (tensile/bending) strain conditions were performed. Our results show that flexible SERS substrates can withstand a tensile strain (ε) value as high as 30% without losing SERS performance, whereas the similar bending strain decreases the SERS performance by about 13%. A cyclic tensile loading test on flexible PDMS SERS substrates at a pre-specified tensile strain (ε) value of 10% shows that the SERS intensity remains almost constant for more than 100 cycles. These disposable and flexible SERS substrates can be integrated with biological substances and offer a novel and practical method to facilitate biosensing applications.     

Interspecific Comparison of Constitutive Ash Phloem Phenolic Chemistry Reveals Compounds Unique to Manchurian Ash, a Species Resistant to Emerald Ash Borer

The emerald ash borer (Agrilus planipennis, EAB) is an invasive wood-borer indigenous to Asia and is responsible for widespread ash (Fraxinus spp.) mortality in the U.S. and Canada. Resistance and susceptibility to EAB varies among Fraxinus spp., which is a result of their co-evolutionary history with the pest. We characterized constitutive phenolic profiles and lignin levels in the phloem of green, white, black, blue, European, and Manchurian ash. Phloem was sampled twice during the growing season, coinciding with phenology of early and late instar EAB. We identified 66 metabolites that displayed a pattern of variation, which corresponded strongly with phylogeny. Previously identified lignans and lignan derivatives were confirmed to be unique to Manchurian ash, and may contribute to its high level of resistance to EAB. Other compounds that had been considered unique to Manchurian ash, including hydroxycoumarins and the phenylethanoids calceolarioside A and B, were detected in closely related, but susceptible species, and thus are unlikely to contribute to EAB resistance of Manchurian ash. The distinct phenolic profile of blue ash may contribute to its relatively high resistance to EAB.     

Growth of Aitken mode ammonium sulfate particles by α-pinene ozonolysis

The fraction of Aitken mode particles that grow sufficiently large to act as cloud condensation nuclei is an important factor in understanding the climate impact of atmospheric particles. Elucidating the rate of particle growth in this size range requires a detailed understanding of the mechanisms by which these particles grow. Here, a flow tube reactor is described, characterized and then used to study growth of ammonium sulfate seed particles in the Aitken mode size range by α-pinene ozonolysis under dry conditions (10% RH). When size-selected particles starting at 40, 60, or 80?nm diameter were exposed to α-pinene (11?ppbv) and ozone (five separate mixing ratios between 30 and 250?ppbv), particle growth was found to depend on the amount of α-pinene reacted and the condensation sink, but not directly dependent on the initial seed particle diameter. The observed dependencies are consistent with a condensational growth mechanism, which is not surprising since the dry conditions of the experiment minimized the probability of multiphase chemistry within the seed particles. Combining the measured particle growth with a kinetic model gave a molar yield of 13% for condensable organic molecules produced by the ozonolysis reaction. This value is somewhat higher than previously reported molar yields of highly oxidized molecules (HOMs) measured in the gas phase with chemical ionization mass spectrometry, which are in the 3–7% range. The relationship between molar yields determined from gas phase and particle phase measurements is discussed.

Copyright © 2019 American Association for Aerosol Research