Estimating the Thermochemistry of Adsorbates Based Upon Gas-Phase Properties

A method for estimating the enthalpy, entropy, and heat capacity for adsorbates on metals is presented. The only input parameters are the binding energy of the adsorbate and the geometric properties of the gas-phase precursor. The method assumes that the vibrational frequencies of the metal lattice and the gas-phase precursor are conserved upon adsorption. Six ??rules of thumb?? are presented to estimate the new vibrational frequencies that correspond to the loss of external translation and rotation upon adsorption. The method is tested against density functional theory calculations for 17 species and 36 reversible reactions for methane steam reforming on Ni(111)[3]. The heats of adsorption and heats of reaction at 800?°C are correctly predicted to within 1?kcal/mol. The entropy of reaction is less accurate, with an average deviation of 3.1?cal/mol/K, but in the context of rapid development for thermodynamically consistent mechanisms and computational catalyst screening for high-temperature applications, this error may be tolerable.     

Partitioning of marine antifoulants in the marine environment

The partitioning behaviour of the organic biocides, Irgarol 1051 and diuron and two inorganic biocides (copper and zinc) was investigated using six sediments of differing physico-chemical properties collected from unimpacted sites along the south coast of England. The kinetics of sorption and equilibrium partitioning between the sediments and seawater were investigated over a period of 20 days. Resulting organic carbon/water partition coefficients (log Koc) were related to suspended sediment concentration and ranged from 2.28 to 5.20 for diuron; and from 2.41 to 4.89 for Irgarol 1051. Sediment/water partition coefficients (log Kp) for copper and zinc varied from 2.46 to 5.08 l/kg and from 2.49 to 4.97 l/kg, respectively. Kinetic data indicated that there were significant interactions between the dissolved and particulate phases at the start of the experiments, just after mixing. This is thought to be a result of redistribution of organic carbon between the two phases.     

Health and performance of Holstein calves that suckled or were hand-fed colostrum and were fed one of three physical forms of starter

Intake of colostrum by neonatal calves and early transition to calf starter are two important factors in successful calf programs. Thirty-one Holstein calves were used to determine health and performance of calves that were 1) allowed to remain with their dams for 3 d and suckle (suckled calves) or were removed from their dams and fed colostrum only by bottle (bottle calves); and were 2) fed ground, pelleted, or textured starters, formulated to be isonitrogenous. Bottle calves were removed from their dams at birth, fed 2.84 L of colostrum, placed in individual hutches, and fed 1.89 L of colostrum 12 h after the first feeding. Suckled calves were removed from their dams after 3 d and placed in individual hutches. Once calves were housed in hutches, they were fed 2 L of whole milk twice daily and were provided starters and water beginning on d 3. Calves were weighed at birth and weekly for 6 wk. Blood samples were obtained at birth, 24 h, and weekly for serum protein determination. Starter intake, fecal scores, and electrolyte treatments were recorded daily. Weaning began when calves had consumed 0.68 kg starter for 2 d consecutively. There were no differences in treatment means between suckled and bottle calves for total gain, grain consumption, days with fecal scores >2, or electrolyte treatments per calf. Average days to weaning was greater for bottle calves compared with suckled calves. Mean serum protein concentration at 24 h was greater for bottle (6.0 g/dl) compared with suckled calves (5.8 g/dl) and only 2 of 15 bottle calves had serum protein concentrations <5.0 g/dl compared with 6 of 16 suckled calves. For starter treatments, calves fed textured starter consumed more total grain, were weaned earlier, and weighed more at 6 wk of age than calves fed pelleted starter. Based on 24-h serum protein concentrations, transfer of passive immunity was greater for bottle calves compared with suckled calves.     

Transitions from functionalization to fragmentation reactions of laboratory secondary organic aerosol (SOA) generated from the OH oxidation of alkane precursors

Functionalization (oxygen addition) and fragmentation (carbon loss) reactions governing secondary organic aerosol (SOA) formation from the OH oxidation of alkane precursors were studied in a flow reactor in the absence of NO(x). SOA precursors were n-decane (n-C10), n-pentadecane (n-C15), n-heptadecane (n-C17), tricyclo[5.2.1.0(2,6)]decane (JP-10), and vapors of diesel fuel and Southern Louisiana crude oil. Aerosol mass spectra were measured with a high-resolution time-of-flight aerosol mass spectrometer, from which normalized SOA yields, hydrogen-to-carbon (H/C) and oxygen-to-carbon (O/C) ratios, and C(x)H(y)+, C(x)H(y)O+, and C(x)H(y)O(2)+ ion abundances were extracted as a function of OH exposure. Normalized SOA yield curves exhibited an increase followed by a decrease as a function of OH exposure, with maximum yields at O/C ratios ranging from 0.29 to 0.74. The decrease in SOA yield correlates with an increase in oxygen content and decrease in carbon content, consistent with transitions from functionalization to fragmentation. For a subset of alkane precursors (n-C10, n-C15, and JP-10), maximum SOA yields were estimated to be 0.39, 0.69, and 1.1. In addition, maximum SOA yields correspond with a maximum in the C(x)H(y)O+ relative abundance. Measured correlations between OH exposure, O/C ratio, and H/C ratio may enable identification of alkane precursor contributions to ambient SOA.     

Infrared and Raman spectroscopy study of alkyl hydroxamic acid and alkyl hydroxamate isomers

The isomeric structures of alkyl hydroxamic acid, as well as its potassium salt, sodium salt, and an alcohol complex, have been characterized in the solid, liquid, and gaseous states by Fourier transform infrared (FT-IR) and FT-Raman spectroscopy. Raman spectroscopy provides insight into the long-standing debate over the isomeric composition of hydroxamates in the solid state and in an aqueous basic solution. IR and Raman results are not consistent with the enol isomer existing in the solid or liquid states of octyl or decyl hydroxamic acid, potassium hydroxamate, and sodium hydroxamate. The infrared and Raman spectra of these compounds provide clear and convincing evidence regarding their chemical structure, mainly from amide-type carbonyl, NH bending, and OH/NH stretching bands. Vibrational spectroscopy is sensitive to polar (FT-IR) and non-polar (FT-Raman) vibrations and the influence of ionic and hydrogen bonding on these vibrations, and these abilities are particularly useful for characterizing keto versus enol and trans versus cis conformations in alkyl hydroxamic acid and its salts. Evolved gas analysis (EGA) in a nitrogen gas environment of alkyl hydroxamic acid and its salts is also discussed. EGA data reveal that water is not incorporated into the solid-state crystal structure of alkyl hydroxamic acid or the potassium salt; however, the sodium salt form is found to have a stable hydrate conformer that is shown to affect the Z isomer (NH trans to carbonyl, OH cis to carbonyl) IR absorbance bands. EGA data also indicates results that could be of interest to bio-pharmaceutical applications involving nitric oxide donation.     

Optimal Control Formulations of Vibration Reduction Problems

Design of controls to move a flexible body such as a robot arm while minimizing unwanted vibrations has been described in many papers and presented in many forms. For the vibration reduction issue alone, it is shown that almost all the proposed designs can be formulated as optimal controls of either the fixed final time or the minimum time type. Furthermore, it is shown that under reasonable assumptions the two types have the same solution and are thus equivalent. Continuous time, tapped-delay-line input shaping filters, and discrete controls are considered. It is shown that the discrete equivalent of the general vibration reduction problem is a convex problem for the fixed final time case and quasi-convex for the free final time problem. The two formulations are compared in terms of computation complexity as well as practical implementation issues.      

The Molecular Basis of COVID-19 Pathogenesis,Conventional and Nanomedicine Therapy

In late 2019, a new member of the Coronaviridae family, officially designated as “severe acute respiratory syndrome coronavirus 2” (SARS-CoV-2), emerged and spread rapidly. The Coronavirus Disease-19 (COVID-19) outbreak was accompanied by a high rate of morbidity and mortality worldwide and was declared a pandemic by the World Health Organization in March 2020. Within the Coronaviridae family, SARS-CoV-2 is considered to be the third most highly pathogenic virus that infects humans, following the severe acute respiratory syndrome coronavirus (SARS-CoV) and the Middle East respiratory syndrome coronavirus (MERS-CoV). Four major mechanisms are thought to be involved in COVID-19 pathogenesis, including the activation of the renin-angiotensin system (RAS) signaling pathway, oxidative stress and cell death, cytokine storm, and endothelial dysfunction. Following virus entry and RAS activation, acute respiratory distress syndrome develops with an oxidative/nitrosative burst. The DNA damage induced by oxidative stress activates poly ADP-ribose polymerase-1 (PARP-1), viral macrodomain of non-structural protein 3, poly (ADP-ribose) glycohydrolase (PARG), and transient receptor potential melastatin type 2 (TRPM2) channel in a sequential manner which results in cell apoptosis or necrosis. In this review, blockers of angiotensin II receptor and/or PARP, PARG, and TRPM2, including vitamin D3, trehalose, tannins, flufenamic and mefenamic acid, and losartan, have been investigated for inhibiting RAS activation and quenching oxidative burst. Moreover, the application of organic and inorganic nanoparticles, including liposomes, dendrimers, quantum dots, and iron oxides, as therapeutic agents for SARS-CoV-2 were fully reviewed. In the present review, the clinical manifestations of COVID-19 are explained by focusing on molecular mechanisms. Potential therapeutic targets, including the RAS signaling pathway, PARP, PARG, and TRPM2, are also discussed in depth.     

Co-Assembly of Nanoparticles in Evaporating Aerosol Droplets: Preparation of Nanoporous Pt/TiO2 Composite Particles

Nanoporous Pt/TiO₂ micro-particles were synthesized via an aerosol assisted co-assembly (AACA) route. Aerosol droplets were produced from a colloidal mixture of 5 nm Pt and 20 nm TiO₂ nanoparticles, which formed spherical micro-aggregates of Pt and TiO₂ with average diameter of around 1.2 μm. The resulting composite micro-particles have very open structure with pore sizes ranging from 20 to 200 nm. Pt nanoparticles were found to be well dispersed on the surface of the supporting TiO₂ particles. Electrocatalytic application of the nanoporous Pt/TiO₂ composites was examined through methanol oxidation reaction. The performance of 20 wt% Pt/TiO₂ particles was found to be comparable to that of commercial 20 wt% Pt/carbon black catalyst.