Infrared Evidence for the Existence of Nitrate Species on Cu-ZSM5 During Isothermal Rate Oscillations in the Decomposition of N2O

Isothermal oscillations in the rate of decomposition of N₂O were studied on an over-exchanged Cu-ZSM-5 catalyst by mass spectroscopy and in situ transient FTIR. Oscillations in the production of O₂ and N₂ were observed to occur in a temperature range of 410–490°C at a total pressure of 1.0 Torr pure N₂O. FTIR has provided the first spectroscopic evidence that surface nitrate species are present under oscillatory conditions. This study confirmed a previously proposed model that predicts a slow build-up of surface nitrates, followed by a rapid nitrate decomposition coupled with an increase in the rate of N₂O decomposition. The IR signature of the surface nitrates suggests they are monodentate nitrate species bound to Cu²⁺ ions. Temperature-programmed desorption studies reveal a strong correlation between the stability of the surface nitrate species and the temperature range in which oscillations occur.     

Refractive index retrievals for polystyrene latex spheres in the spectral range 220–420 nm

The recent development of an Aerosol Extinction Differential Optical Absorption Spectrometer (AE-DOAS) has allowed for the retrieval of wavelength dependent complex refractive indices for polystyrene latex spheres (PSL). The AE-DOAS is a white-type multi-pass gas cell coupled to a UV-Vis spectrometer. Refractive index values are retrieved for wavelengths between 220 and 420 nm by minimizing the χ² goodness-of-fit between measured extinction for five diameters of PSL and model Mie Theory predictions. Comparison to literature shows agreement at wavelengths >360 nm demonstrating the validity of this new instrumental approach while expanding the known refractive index range for PSLs further into the UV where it is previously unreported. In the studied wavelength range, coefficients for the general Cauchy dispersion relationship (A = 1.538(11); B = 0.0043(16) μm²; C = 0.00094(5) μm⁴) for PSLs were determined using the retrieved real portion of the refractive index and the wavelength in microns. In addition, this work indicates that the precision of retrieved values is impacted by the particle diameters chosen for the experiment where retrievals for shorter wavelengths of light benefit from the study of smaller sized particles.

Copyright © 2017 American Association for Aerosol Research     

Modification of absorbent poly(glycerol‐glutaric acid) films by the addition of monoglycerides

Monoglycerides (MGs) have been incorporated into the matrix of poly(glycerol‐co‐glutaric acid) films to investigate their effect on the thermal, mechanical, and solvent absorption properties of the resultant films. Solvent absorption studies revealed that poly(glycerol‐co‐glutaric acid‐co‐MG) films were able to absorb and resorb solvents better than poly(glycerol‐co‐glutaric acid) films, albeit they had higher erosion levels. Thermogravimetric analysis showed that the incorporated MGs did not affect the thermal stability of the glycerol‐based films. The MG‐incorporated films were observed to be much softer than the poly(glycerol‐co‐glycerol) films which was further proven by a 39‐fold reduction in Young's Modulus and 17‐fold reduction in fracture energy when compared to the poly(glycerol‐co‐glycerol). Mechanical property studies also revealed that the incorporation of MGs increased the elongation % and reduced the tensile strength of poly(glycerol‐co‐glutaric acid) films. Correlation analysis revealed a strong linear relationship between Young's Modulus and fracture energy (R² = 0.9962), and between Young's Modulus and tensile strength (R² = 0.9972). Our study proved that MGs can be successfully incorporated in the polymer matrix of poly(glycerol‐co‐glutaric acid) films to produce softer films with increased elongation and increased solvent absorption capacity. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45381.     

Water permeation and corrosion resistance of single- and two-component hydrophobic polysiloxane barrier coatings

The degradation of corrosion preventative coatings contributes to the high cost and time requirements for maintaining structures in harsh environments. However, the development of new hydrophobic coatings holds the promise of extending the usable life of structures in marine environments. In this work, we quantify the barrier properties and corrosion resistance of two novel highly hydrophobic polysiloxane formulations and the legacy silicone alkyd topcoat used on the topside of Navy’s ships, all with haze gray pigmentation. Based on FTIR-ATR and EIS measurements of the pristine coatings, both the single- (1K) and the two-component (2K) polysiloxane provide significantly improved barrier characteristics (lower water diffusion coefficient and capacitance) than the silicone alkyd. These results were confirmed through a 3-month-long immersion corrosion test, which also showed that the 1K and 2K polysiloxane coatings had comparable degradation characteristic and remained highly hydrophobic.     

Macrocyclization of Organo‐Peptide Hybrids through a Dual Bio‐orthogonal Ligation: Insights from Structure–Reactivity Studies

Macrocycles constitute an attractive structural class of molecules for targeting biomolecular interfaces with high affinity and specificity. Here, we report systematic studies aimed at exploring the scope and mechanism of a novel chemo‐biosynthetic strategy for generating macrocyclic organo‐peptide hybrids (MOrPHs) through a dual oxime‐/intein‐mediated ligation reaction between a recombinant precursor protein and bifunctional, oxyamino/1,3‐amino‐thiol compounds. An efficient synthetic route was developed to access structurally different synthetic precursors incorporating a 2‐amino‐ mercaptomethyl‐aryl (AMA) moiety previously found to be important for macrocyclization. With these compounds, the impact of the synthetic precursor scaffold and of designed mutations within the genetically encoded precursor peptide sequence on macrocyclization efficiency was investigated. Importantly, the desired MOrPHs were obtained as the only product from all the different synthetic precursors probed in this study and across peptide sequences comprising four to 15 amino acids. Systematic mutagenesis of the “i?1” site at the junction between the target peptide sequence and the intein moiety revealed that the majority of the 20 amino acids are compatible with MOrPH formation; this enables the identification of the most and the least favorable residues for this critical position. Furthermore, interesting trends with respect to the positional effect of conformationally constrained (Pro) and flexible (Gly) residues on the reactivity of randomized hexamer peptide sequences were observed. Finally, mechanistic investigations enabled the relative contributions of the two distinct pathways (side‐chain→C‐end ligation versus C‐end→side‐chain ligation) to the macrocyclization process to be dissected. Altogether, these studies demonstrate the versatility and robustness of the methodology to enable the synthesis and diversification of a new class of organo‐peptide macrocycles and provide valuable structure–reactivity insights to inform the construction of macrocycle libraries through this chemo‐biosynthetic strategy.     

Experimental Phase Diagram Determination and Thermodynamic Assessment of the CeO2‐Gd2O3‐CoO System

New phase diagram data and a thermodynamic assessment of the CeO‐Gd₂O₃‐CoO system using the CALPHAD approach are presented. This information is needed to understand the surprisingly low sintering temperature (950°C–1050°C) of CeO₂‐based materials doped with small amounts of transition metal oxide (e.g., CoO). Experimental phase equilibria between 1100°C and 1300°C are reported based on the analysis of annealed and molten samples. No isolated compound exists in the ternary. At 1300°C the Co solubility in the ternary compounds Ce_1?x?yGd_xCo_yO_2?x/2?y (fluorite) is 2.7 mol% and is less than 1 mol% in the Gd_2?xCe_xO_3+x/2 (bixbyite). The Ce solubility in the perovskite GdCoO_3?δ was found to be 1 mol%. The lowest temperature eutectic melt in the ternary has a composition of 57.2 mol% Co and 41.1 mol% Gd melting at an onset temperature of 1303 ± 5°C, which is close to the binary eutectic in the Gd₂O₃‐CoO system at 60 ± 2 mol% Co and 1348 ± 1°C.     

Characterization of Thiol‐Ene Crosslinked PEG Hydrogels

The properties of synthetic hydrogels can be tuned to address the needs of many tissue‐culture applications. This work characterizes the swelling and mechanical properties of thiol‐ene crosslinked PEG hydrogels made with varying prepolymer formulations, demonstrating that hydrogels with a compressive modulus exceeding 600 kPa can be formed. The amount of peptide incorporated into the hydrogel is shown to be proportional to the amount of peptide in the prepolymer solution. Cell attachment and spreading on the surface of the peptide‐functionalized hydrogels is demonstrated. Additionally, a method for bonding distinct layers of cured hydrogels is used to create a microfluidic channel.

     

Characterization of a dimer preparation method for nanoscale organic aerosol

Nanoscale dimers have application in studies of aerosol physicochemical properties such as aerosol viscosity. These particle dimers can be synthesized using the dual tandem differential mobility analyzer (DTDMA) technique, wherein oppositely charged particle streams coagulate to form dimers that can be isolated using electrostatic filtration. Although some characterization of the technique has been published, a detailed thesis on the modes and theory of operation has remained outside the scope of prior work. Here, we present new experimental data characterizing the output DTDMA size distribution and the physical processes underlying its apparent modes. Key experimental limitations for both general applications and for viscosity measurements are identified and quantified in six distinct types of DTDMA experiments. The primary consideration is the production of an adequate number of dimers, which typically requires high mobility-selected number concentration in the range 25,000–100,000?cm^?3. The requisite concentration threshold depends upon the rate of spontaneous monomer decharging, which arises predominately from interactions of the aerosol with ionizing radiation within the coagulation chamber and is instrument location dependent. Lead shielding of the coagulation chamber reduced the first-order decharging constant from ～2.0?×?10^?5 s^?1 to ～0.8?×?10^?5 s^?1 in our laboratory. Dimer production at monomer diameters less than 40?nm is hindered by low bipolar charging efficiency. Results from the characterization experiments shed light on design considerations for general applications and for characterization of viscous aerosol phase transitions.

Copyright © 2019 American Association for Aerosol Research     

Impact of Site-Specific Benzo[a]Pyrene Diol Epoxide-dG Lesions at or near Single/Double-Strand DNA Junctions on DNA Bending

Adducts derived from the binding of the (+)-7R,8S,9S,10R and (?)-7S,8R,9R,10S enantiomers of r7,t8-dihydrodiol-t9,10-epoxy-7,8,9,10-tetrahydrobenzo[a]pyrene (anti-BPDE) to 2′-deoxyguanosine residues in DNA are known to induce mutations due to error-prone DNA replication. Because the conformational properties of these lesions may be important in these phenomena, we have examined the effects of the stereoisomeric (+)- and (?)-trans-anti-[BP]-N ²-dG lesions positioned site-specifically at or near primer/template oligonucleotide junctions on DNA bending using high resolution gel electrophoresis. Remarkable differences in electrophoretic mobilities μ are observed in the two adducts derived from the tumorigenic (+)-anti-BPDE, and the non-tumorigenic (?)-anti-BPDE enantiomer. With the (+)-trans lesion positioned on the template strand adjacent to the 3′-end of the primer strand, a remarkable decrease in μ is observed. This suggests the existence of a bend at the single strand-double strand junction. Only modest decreases in μ are observed in the case of the (?)-trans lesion, or when the 3′-end is opposite to, or more distant from the lesion site. These observations are discussed in terms of the known NMR solution structures of these lesions in the same sequence context, and the properties of primer/template DNA in polymerases.