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1. Effect of aromatic ring substituents on the ability of catechol to produce brown carbon in iron( iii )-catalyzed reactions

   https://doi.org/10.1039/d0ea00007h  

   Chin, Henry; Hopstock, Katherine S.; Fleming, Lauren T.; Nizkorodov, Sergey A.; Al-Abadleh, Hind A. (February 2021, Environmental Science: Atmospheres)

   null (Ed.)

   Our previous work demonstrated formation of highly insoluble and strongly light-absorbing organic particles in reactions between catechol or guaiacol with Fe( iii ) under pH = 3 conditions characteristic of aerosol liquid water. This work extends these measurements to reactions of Fe( iii ) with 2,4-dinitrophenol, 4-nitrocatechol, 4-methylcatechol, 1,2,4-benzenetriol, 1,2,3-benzenetriol (pyrogallol) and coniferaldehyde to better understand the mechanism of particle formation catalyzed by Fe( iii ). Particles were observed after 2 h of reactions of catechol (43 ± 1% mass yield), 1,2,4-benzenetriol (32 ± 3%), pyrogallol (27 ± 2%) and coniferaldehyde (35 ± 4%), while reactions of 2,4-dinitrophenol and 4-nitrocatechol did not produce any insoluble products. No particles were observed in reaction of 4-methylcatechol after 2 h, however, insoluble products appeared after a 24 h reaction time. Irradiation of a catechol + Fe( iii ) mixture by 405 nm light was found to reduce (but not fully suppress) the particle yield due to a competition between photodegradation and Fe( iii )-catalyzed oligomerization. Particles produced from precursors + Fe( iii ) solutions were dissolved in organic solvents and analyzed with ultra performance liquid chromatography coupled to a photodiode array spectrophotometer and a high resolution mass spectrometer. Major separated chromophores were identified as dimeric, trimeric, and tetrameric products of precursor molecules. Purpurogallin was identified as a major reaction product of pyrogallol reaction with Fe( iii ). To test whether this chemistry can occur in more realistic atmospheric aerosols, reactions of biomass burning organic aerosol (BBOA) extracts with Fe( iii ) were also examined. Two BBOA samples collected under flaming conditions produced no particles, whereas a BBOA sample produced under smoldering conditions resulted in particle formation under both dark and 405 nm irradiation conditions. The results suggest that Fe( iii )-catalyzed chemistry can take place in aging BBOA plumes resulting from smoldering fires and make aerosol particles more light-absorbing. 

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2. Optical and electronic spin properties of fluorescent micro- and nanodiamonds upon prolonged ultrahigh-temperature annealing

   https://doi.org/10.1116/6.0002797  

   Nunn, Nicholas; Milikisiyants, Sergey; Torelli, Marco D.; Monge, Richard; Delord, Tom; Shames, Alexander I.; Meriles, Carlos A.; Ajoy, Ashok; Smirnov, Alex I.; Shenderova, Olga A. (July 2023, Journal of Vacuum Science & Technology B)

   High-temperature annealing is a promising but still mainly unexplored method for enhancing spin properties of negatively charged nitrogen-vacancy (NV) centers in diamond particles. After high-energy irradiation, the formation of NV centers in diamond particles is typically accomplished via annealing at temperatures in the range of 800–900 °C for 1–2 h to promote vacancy diffusion. Here, we investigate the effects of conventional annealing (900 °C for 2 h) against annealing at a much higher temperature of 1600 °C for the same annealing duration for particles ranging in size from 100 nm to 15 μm using electron paramagnetic resonance and optical characterization. At this high temperature, the vacancy-assisted diffusion of nitrogen can occur. Previously, the annealing of diamond particles at this temperature was performed over short time scales because of concerns of particle graphitization. Our results demonstrate that particles that survive this prolonged 1600 °C annealing show increased NV T1 and T2 electron spin relaxation times in 1 and 15 μm particles, due to the removal of fast relaxing spins. Additionally, this high-temperature annealing also boosts magnetically induced fluorescence contrast of NV centers for particle sizes ranging from 100 nm to 15 μm. At the same time, the content of NV centers is decreased fewfold and reaches a level of <0.5 ppm. The results provide guidance for future studies and the optimization of high-temperature annealing of fluorescent diamond particles for applications relying on the spin properties of NV centers in the host crystals. 

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3. Particle Size and Rheology of Silica Particle Networks at the Air–Water Interface

   https://doi.org/10.3390/nano13142114  

   Thakur, Siddharth; Razavi, Sepideh (July 2023, Nanomaterials)

   Silica nanoparticles find utility in different roles within the commercial domain. They are either employed in bulk within pharmaceutical formulations or at interfaces in anti-coalescing agents. Thus, studying the particle attributes contributing to the characteristics of silica particle-laden interfaces is of interest. The present work highlights the impact of particle size (i.e., 250 nm vs. 1000 nm) on the rheological properties of interfacial networks formed by hydrophobically modified silica nanoparticles at the air–water interface. The particle surface properties were examined using mobility measurements, Langmuir trough studies, and interfacial rheology techniques. Optical microscopy imaging along with Langmuir trough studies revealed the microstructure associated with various surface pressures and corresponding surface coverages (ϕ). The 1000 nm silica particle networks gave rise to a higher surface pressure at the same coverage compared to 250 nm particles on account of the stronger attractive capillary interactions. Interfacial rheological characterization revealed that networks with 1000 nm particles possess higher surface modulus and yield stress in comparison to the network obtained with 250 nm particles at the same surface pressure. These findings highlight the effect of particle size on the rheological characteristics of particle-laden interfaces, which is of importance in determining the stability and flow response of formulations comprising particle-stabilized emulsions and foams. 

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4. Viscoelastic Properties of Electrospray‐Deposited Polymer Shells via Quartz Crystal Microbalance With Dissipation (QCM‐D)

   https://doi.org/10.1002/mame.202400224  

   Green‐Warren, Robert A; McAllister, Noah M; Pasupathy, Parameshwaran; Pelegri, Assimina A; Singer, Jonathan P; Murthy, N Sanjeeva (December 2024, Macromolecular Materials and Engineering)

   Multilayer polymer films are extensively used in multiphase separation. Electrospray deposition (ESD) is an important technique for fabricating such films with tunable morphology. Viscoelastic properties of polystyrene (PS) nanoshell coatings produced by ESD on gold and spin‐coated PS surfaces are evaluated using Quartz Crystal Microbalance with Dissipation (QCM‐D). The thickness of PS films on gold increases with flow rate from ∼200 nm at 0.5 to ∼400 nm at 1.5 mL h^−1, accompanied by an order‐of‐magnitude increase in dissipation due to larger particle sizes from shorter droplet flight times. This effect is absent on spin–coated PS films, suggesting the onset of the self‐limiting effect of charges. Although the shear moduli for ESD films calculated from Voigt models is only 0.08%–0.20% of the bulk PS modulus, the stiffness ratio of spray‐coated PS to a single shell is (5.00–13.3) × 10^3  m^−1, due to shell–shell and shell–substrate interactions. These are novel results related to the interparticle friction obtained using QCM‐D for the first time. This work demonstrates  that mechanical properties of particulate viscoelastic films with potential applications in high surface area sensors, such as size‐selective membranes for protein or electrolyte adsorption, can be evaluated by QCM‐D with nanograms of material. 

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5. Nanoparticle dynamics in hydrogel networks with controlled defects

   https://doi.org/10.1039/d2sm01224c  

   Rose, Katie A.; Marino, Emanuele; O'Bryan, Christopher S.; Murray, Christopher B.; Lee, Daeyeon; Composto, Russell J. (December 2022, Soft Matter)

   The effect of nanoscale defects on nanoparticle dynamics in defective tetra-poly(ethylene glycol) (tetra-PEG) hydrogels is investigated using single particle tracking. In a swollen nearly homogeneous hydrogel, PEG-functionalized quantum dot (QD) probes with a similar hydrodynamic diameter ( d h = 15.1 nm) to the mesh size (〈 ξ s 〉 = 16.3 nm), are primarily immobile. As defects are introduced to the network by reaction-tuning, both the percentage of mobile QDs and the size of displacements increase as the number and size of the defects increase with hydrolysis time, although a large portion of the QDs remain immobile. To probe the effect of nanoparticle size on dynamics in defective networks, the transport of d h = 47.1 nm fluorescent polystyrene (PS) and d h = 9.6 nm PEG-functionalized QDs is investigated. The PS nanoparticles are immobile in all hydrogels, even in highly defective networks with an open structure. Conversely, the smaller QDs are more sensitive to perturbations in the network structure with an increased percentage of mobile particles and larger diffusion coefficients compared to the larger QDs and PS nanoparticles. The differences in nanoparticle mobility as a function of size suggests that particles of different sizes probe different length scales of the defects, indicating that metrics such as the confinement ratio alone cannot predict bulk dynamics in these systems. This study provides insight into designing hydrogels with controlled transport properties, with particular importance for degradable hydrogels for drug delivery applications. 

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