This study develops synthetic strategies for N,N-trans and N,N-cis Re(O)(LO–N)2Cl complexes and investigates the effects of the coordination spheres and ligand structures on ancillary ligand exchange dynamics and catalytic perchlorate reduction activities of the corresponding [Re(O)(LO–N)2]+ cations. The 2-(2′-hydroxyphenyl)-2-oxazoline (Hhoz) and 2-(2′-hydroxyphenyl)-2-thiazoline (Hhtz) ligands are used to prepare homoleptic N,N-trans and N,N-cis isomers of both Re(O)(hoz)2Cl and Re(O)(htz)2Cl and one heteroleptic N,N-trans Re(O)(hoz)(htz)Cl. Selection of hoz/htzligands determines the preferred isomeric coordination sphere, and the use of substituted pyridine bases with varying degrees of steric hindrance during complex synthesis controls the rate of isomer interconversion. The five corresponding [Re(O)(LO–N)2]+ cations exhibit a wide range of solvent exchange rates (1.4 to 24,000 s–1 at 25 °C) and different LO–N movement patterns, as influenced by the coordination sphere of Re (trans/cis), the noncoordinating heteroatom on LO–N ligands (O/S), and the combination of the two LO–N ligands (homoleptic/heteroleptic). Ligand exchange dynamics also correlate with the activity of catalytic reduction of aqueous ClO4– by H2 when the Re(O)(LO–N)2Cl complexes are immobilized onto Pd/C. Findings from this study provide novel synthetic strategies and mechanistic insights for innovations in catalytic, environmental, and biomedical research.
Aqueous dispersions of iron oxide nanoparticles with a high initial magnetic susceptibility (χi) are of interest as contrast agents in electromagnetic tomography. Nanoclusters composed of iron oxide primary particles were formed by co-precipitation of Fe(II) and Fe(III) chlorides at alkaline conditions and high temperature of 95 °C. Two-step addition of citrate was used to produce large primary particles and then stabilize the nanoclusters. The size of the primary particles was tuned from 5 nm to 15 nm by varying the citrate/iron precursor ratio during the normal phase hydrolysis reaction, while the second iteration of citrate stabilized the nanoclusters with hydrodynamic diameters of 30–75 nm. The crystallinity of the iron oxide nanoparticles was promoted by annealing at 95 °C and systematically studied with Superconducting Quantum Interference Device (SQUID), Vibrating Sample Magnetometer (VSM), Transmission Electron Microscopy (TEM) and X-ray Diffraction (XRD). The dependence of χi was examined over a range of low volume fractions (0.005 < θ < 0.02) to understand the magnetic behavior of dispersions. The χi of the dispersions increased markedly with the size and concentration of the constituent primary particles, reaching an unusually high value of 0.85 at 1.6% v/v for 15 nm primary particles, which is 2–3 times higher than that for typical commercial ferrofluids. The high χi values are favored by the high crystallinity and the large magnetic diameter of 9.3 nm, indicating a relatively thin surface nonmagnetic layer where the spin orientations are disordered.
Coherent thermal phonons (CTPs) play an important role in thermal transport in superlattice (SL) structures. To have a profound understanding of CTP transport in SL, direct measurement of CTP properties is necessary. In this study, coherent phonon spectroscopy has been utilized to generate and detect CTP in Bi2Te3/Sb2Te3 SL. Phonon lifetimes have been extracted from experimental data, with which mode-wise thermal conductivities have been calculated. Comparing with bulk Bi2Te3, the estimated mode-wise thermal conductivity of longitudinal acoustic phonons shifts to higher frequencies, due to constructive coherent phonon interference. Our results suggest that it is possible to use SL structure to manipulate coherent phonon propagation and to tailor thermal conductivity.
BACKGROUND: Dietary canthaxanthin (CX), 25-hydroxycholecalciferol (25-OH-D 3 ) and vitamins have been widely reported to be involved in productive and reproductive performance of broiler breeders. However, limited information is available for duck breeders. In this study, a total of 1,560 Cherry Valley SM3 duck breeder females and 312 males were used to assess if the addition of CX and 25-OH-D3 could increase the performance of duck breeders under two different dietary vitamin regimens. Four diets were used under a 2 x 2 factorial arrangement with 2 kinds of vitamin premixes (REGULAR and HIGH; HIGH premix had higher levels of all vitamins except K3 than REGULAR premix), and with or without the supplementation of the mixture of CX (6 mg/kg) and 25-OH-D3 (0.069 mg/kg). The ducks were fed ad libitum with pelleted diets based on corn-soybean meal from 38 to 77 wk of age. RESULTS: HIGH vitamin premix decreased malondialdehyde (MDA) level (P < 0.001) of egg yolk, increased hatchability of fertile eggs (P = 0.029), increased hatchability of total eggs (P = 0.029), and decreased serum protein carbonyl level (P = 0.037) of breeder males. The mixture of CX and 25-OH-D3 increased serum calcium of breeder females (P = 0.010), decreased the cracked egg rate (P = 0.001), increased the pigmentation of egg yolk (P < 0.001) and male bill (P < 0.001), and decreased MDA level of egg yolk (P < 0.001) and male serum (P = 0.034). Interactive effects were observed in cracked egg rate (P = 0.038), shell thickness (P = 0.011) and serum phosphorus (P = 0.026) of breeder females. HIGH vitamin premix together with the mixture of CX and 25-OH-D3 decreased cracked egg rate and increased shell thickness of duck breeders. Serum phosphorus was decreased in duck breeder females fed REGULAR vitamin premix without the addition of the CX and 25-OH-D3 mixture. CONCLUSIONS: Dietary HIGH vitamin premix increased antioxidant status of eggs and breeder males, and increased hatchability. The mixture of CX and 25-OH-D3 enhanced egg shell quality, and promoted pigmentation and antioxidant status of eggs and breeder males.
The effect of stagger startup on the vibroacoustic loads that form during the end-effects regime of clustered rockets is studied using both full-scale (hot-gas) and laboratory-scale (cold-gas) data with vehicle geometry. Both configurations comprise three nozzles with thrust-optimized parabolic contours that undergo free-shock separated flow and restricted-shock separated flow as well as an end-effects regime before flowing full. Acoustic pressure waveforms recorded at the base of the nozzle cluster are analyzed using various statistical metrics as well as time-frequency analysis. The findings reveal a significant reduction in end-effects regime loads when engine startups are staggered. However, regardless of stagger, both the skewness and kurtosis of the acoustic pressure time derivative elevate to the same levels, thereby demonstrating the intermittence and impulsiveness of the acoustic waveforms during the end effects regime.
A method for the synthesis of electroactive polymers is demonstrated, starting with the synthesis of extended conjugation monomers using a three-step process that finishes with Negishi coupling. Negishi coupling is a cross-coupling process in which a chemical precursor is first lithiated, followed by transmetallation with ZnCl2. The resultant organozinc compound can be coupled to a dibrominated aromatic precursor to give the conjugated monomer. Polymer films can be prepared via electropolymerization of the monomer and characterized using cyclic voltammetry and ultraviolet-visible-near infrared (UV-Vis-NIR) spectroscopy. Nanoparticles (NPs) are prepared via emulsion polymerization of the monomer using a two-surfactant system to yield an aqueous dispersion of the polymer NPs. The NPs are characterized using dynamic light scattering, electron microscopy, and UV-Vis-NIR-spectroscopy. Cytocompatibility of NPs is investigated using the cell viability assay. Finally, the NP suspensions are irradiated with a NIR laser to determine their effectiveness as potential materials for photothermal therapy (PTT).
Ion exchange (IX) is the most common approach to treating nitrate-contaminated drinking water sources, but the cost of salt to make regeneration brine, as well as the cost and environmental burden of waste brine disposal, are major disadvantages. A hybrid ion exchange-catalyst treatment system, in which waste brine is catalytically treated for reuse, shows promise for reducing costs and environmental burdens of the conventional IX system. An IX model with separate treatment and regeneration cycles was developed, and ion selectivity coefficients for each cycle were separately calibrated by fitting experimental data. Of note, selectivity coefficients for the regeneration cycle required fitting the second treatment cycle after incomplete resin regeneration. The calibrated and validated model was used to simulate many cycles of treatment and regeneration using the hybrid system. Simulated waste brines and a real brine obtained from a California utility were also evaluated for catalytic nitrate treatment in a packed-bed, flow-through column with 0.5 wt%Pd–0.05 wt%In/activated carbon support (PdIn/AC). Consistent nitrate removal and no apparent catalyst deactivation were observed over 23 d (synthetic brine) and 45 d (real waste brine) of continuous-flow treatment. Ion exchange and catalyst results were used to evaluate treatment of 1 billion gallons of nitrate-contaminated source water at a 0.5 MGD water treatment plant. Switching from a conventional IX system with a two bed volume regeneration to a hybrid system with the same regeneration length and sequencing batch catalytic reactor treatment would save 76% in salt cost. The results suggest the hybrid system has the potential to address the disadvantages of a conventional IX treatment systems.
The plume produced by a cluster of two large area-ratio thrust-optimized paraboliccontour nozzles is visualized over a range of nozzle pressure ratios by way of retrore-flective shadowgraphy. Both nozzles exhibit free-shock separated flow, restricted-shockseparated flow and an end-effects regime prior to flowing full. Transient (startup) op-erations of the nozzles are studied with the primary focus being the pulsations thatform during the end-effects regime. This occurs at a pressure ratio of 37 for thesenozzles and is associated with elevated sound levels in the immediate vicinity of thenozzles and vehicle. The shadowgraphy images reveal the formation of turbulent largescale structures, on the order of the nozzle diameter, during the end-effects regime.These large scale structures are driven by the intermittent opening of the last trappedannular separation bubble to the ambient and grow rapidly within the first two nozzlediameters.
Foam application in subsurface processes including environmental remediation, geological carbon-sequestration, and gas-injection enhanced oil recovery (EOR) has the potential to enhance contamination remediation, secure CO2">CO2CO2 storage, and improve oil recovery, respectively. Nanoparticles are a promising alternative to surfactants in creating foam in harsh environments. We conducted CO2">CO2CO2-in-brine foam generation experiments in Boise sandstones with surface-treated silica nanoparticle in high-salinity conditions. All the experiments were conducted at the fixed CO2">CO2CO2 volume fraction and fixed flow rate which changed in steps. The steady-state foam apparent viscosity was measured as a function of injection velocity. The foam flowing through the cores showed higher apparent viscosity as the flow rate increased from low to medium and high velocities. At very high velocities, once foam bubbles were finely textured, the foam apparent viscosity was governed by foam rheology rather than foam creation. A noticeable hysteresis occurred when the flow velocity was initially increased and then decreased, implying multiple (coarse and strong) foam states at the same superficial velocity. A normalized generation function was combined with CMG-STARS foam model to cover full spectrum of foam behavior in the experiments. The new model successfully captures foam generation and hysteresis trends in presented experiments in this study and data from the literature. The results indicate once foam is generated in porous media, it is possible to maintain strong foam at low injection rates. This makes foam more feasible in field applications where foam generation is limited by high injection rates that may only exist near the injection well.
The self-assembly of citrate-capped Au nanoparticles (5 nm) resulted in branched nanochains by adding CaCl2 versus spherical nanoclusters for NaCl. These assemblies were formed between 1 s to 30 min by tuning the electrostatic repulsion and the interparticle bridging attraction between the cations and citrate ligands as a function of electrolyte concentration. For dilute Ca2+, strong interparticle bridging favored particle attachment at chain ends. This resulted in the formation of small, branched chains with lengths as short as 20 nm, due to the large Debye length for the diffuse counterions. Furthermore, the bridging produced very small interparticle spacings and sintering, as evident in high-resolution TEM despite the low temperature. This morphology produced a large red shift in the surface plasmon resonance, as characterized by a broad extinction peak with NIR absorption out to 1000 nm, which is unusual for such small particles. Whereas these properties were seen for primary particles with partial citrate monolayers, the degrees of sintering and NIR extinction were small in the case of citrate multilayers. The ability to design the size and shape of nanoparticle clusters as well as the interparticle spacing by tuning bridging and electrostatic interactions may be expected to be quite general and of broad applicability in materials synthesis