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1. Absorption spectra of benzoic acid in water at different pH and in the presence of salts: insights from the integration of experimental data and theoretical cluster models

   https://doi.org/10.1039/C9CP06728K  

   Karimova, Natalia V.; Luo, Man; Grassian, Vicki H.; Gerber, R. Benny (March 2020, Physical Chemistry Chemical Physics)

   The absorption spectra of molecular organic chromophores in aqueous media are of considerable importance in environmental chemistry. In this work, the UV-vis spectra of benzoic acid (BA), the simplest aromatic carboxylic acid, in aqueous solutions at varying pH and in the presence of salts are measured experimentally. The solutions of different pH provide insights into the contributions from both the non-dissociated acid molecule and the deprotonated anionic species. The microscopic interpretation of these spectra is then provided by quantum chemical calculations for small cluster models of benzoic species (benzoic acid and benzoate anion) with water molecules. Calculations of the UV-vis absorbance spectra are then carried out for different clusters such as C 6 H 5 COOH·(H 2 O) n and C 6 H 5 COO − ·(H 2 O) n , where n = 0–8. The following main conclusions from these calculations and the comparison to experimental results can be made: (i) the small water cluster yields good quantitative agreement with observed solution experiments; (ii) the main peak position is found to be very similar at different levels of theory and is in excellent agreement with the experimental value, however, a weaker feature about 1 eV to lower energy (red shift) of the main peak is correctly reproduced only by using high level of theory, such as Algebraic Diagrammatic Construction (ADC); (iii) dissociation of the BA into ions is found to occur with a minimum of water molecules of n = 8; (iv) the deprotonation of BA has an influence on the computed spectrum and the energetics of the lowest energy electronic transitions; (v) the effect of the water on the spectra is much larger for the deprotonated species than for the non-dissociated acid. It was found that to reproduce experimental spectrum at pH 8.0, additional continuum representation for the extended solvent environment must be included in combination with explicit solvent molecules ( n ≥ 3); (vi) salts (NaCl and CaCl 2 ) have minimal effect on the absorption spectrum and; (vii) experimental results showed that B-band of neutral BA is not sensitive to the solvent effects whereas the effect of the water on the C-band is significant. The water effects blue-shift this band up to ∼0.2 eV. Overall, the results demonstrate the ability to further our understanding of the microscopic interpretation of the electronic structure and absorption spectra of BA in aqueous media through calculations restricted to small cluster models. 

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2. Nanoparticle filtration through microporous ECTFE membrane in an alcoholic solution

   https://doi.org/https://doi.org/10.1016/j.seppur.2018.08.022  

   Na Yao, Boris Khusid (October 2018, Separation and purification technology)

   Organic solvent filtration is an important industrial process. It is widely used in pharmaceutical manufacturing, chemical processing industry, semiconductor industry, auto assembly etc. Most of the particle filtration studies reported in open literature dealt with aqueous suspension medium. The current work has initiated a study of cross-flow solvent filtration behavior of microporous ethylene chlorotrifluoroethylene (ECTFE) membranes using 12 nm silica nanoparticles suspended in an aqueous solution containing 25% ethanol. In the constant pressure mode of operation of cross-flow microfiltration (MF), permeate samples were collected at different time intervals. The permeate particle size distribution (PSD) results for different experiments were identical. Particle agglomerates having less than 100 nm size can pass through the membrane; some fouling was observed. The governing fouling mechanisms for tests operated using 3.8×10−3 kg/m3 (3.8 ppm) at 6.9×103 Pag and 1.4×104 Pag were pore blocking. For tests conducted using 3.8×10−3 kg/m3 (3.8 ppm) at 27.6×103 Pag (4 psig) and 1.9×10−3 kg/m3 (1.9 ppm) at 6.9×103, 13.8×103 and 27.6×103 Pag (1, 2 and 4 psig), the mechanism was membrane resistance control. Less particles got embedded in membrane pores in experiments operated using suspensions with lower or higher particle concentrations with a higher transmembrane pressure. This is in good agreement with the values of the shear rate in the pore flow and scanning electron microscope images of the membrane after MF. In the dead-end mode of operation of solvent filtration using methanol, ethanol and 2-propanol, the permeate flux behavior follows Jmethanol > Jethanol > J2-propanol at all testing pressures. The values of permeance (kg/m2-s-Pa) determined from the slope of the linear plot of filtration flux vs. the applied pressure difference across the membrane, were 3.9×10−4, 2.3×10−4 and 3.0×10−5 for methanol, ethanol and 2-propanol, respectively. Further exploration was made on solvent sorption results reported earlier. The critical temperature of selected solvents shows a better correlation with solvent sorption rather than the solubility parameter. 

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3. Emerging investigator series: sunlight photolysis of 2,4-D herbicides in systems simulating leaf surfaces

   https://doi.org/10.1039/C8EM00186C  

   Su, Lei; Sivey, John D.; Dai, Ning (January 2018, Environmental Science: Processes & Impacts)

   Pesticides are commonly applied on foliage, forming dry deposits on the leaf cuticular wax. However, their photochemical transformation in this lipophilic environment is much less understood compared with that in surface water. In this work, sunlight photolysis of six chlorinated phenoxyacetic acid herbicides ( i.e. , 2,4-D and structural analogues) was evaluated in four organic solvents, on quartz, and on paraffin wax. In solvents of low polarity ( i.e. , n -heptane and 2-propanol), direct photolysis of 2,4-D herbicides was enhanced due to the relatively high quantum yields in these solvents. Photolysis on paraffin wax was slower than photolysis on quartz by a factor of 3–9, but was comparable with that in solvents of low polarity. With environmentally relevant irradiation and surface loading, the half-lives of 2,4-D herbicides on paraffin wax were 27–159 h, which are within the same range reported for biodegradation, the dominant dissipation pathway in the current 2,4-D fate model. Product analyses showed that photoreductive dechlorination is the dominant pathway in organic solvents, accounting for 68–100% of parent compound decay. On quartz and paraffin wax surfaces, however, photoreductive dechlorination products accounted for <60% of parent compound decay. Combining kinetic modeling and product analyses, it was shown that neither could the two additional putative pathways (photosubstitution of chlorine by hydroxyl group and cleavage of the ether bond) fully account for the total phototransformation on surfaces. These results suggest that rapid photolysis on surfaces can be attributed to unique pathways that are absent in the organic solvent phase. 

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4. Fine-Tuning of Molecular Structures to Generate Carbohydrate Based Super Gelators and Their Applications for Drug Delivery and Dye Absorption

   https://doi.org/10.3390/gels7030134  

   Bietsch, Jonathan; Olson, Mary; Wang, Guijun (September 2021, Gels)

   Carbohydrate-based low molecular weight gelators (LMWGs) exhibit many desirable properties making them useful in various fields including applications as drug delivery carriers. In order to further understand the structural connection to gelation properties, especially the influence of halide substitutions, we have designed and synthesized a series of para-chlorobenzylidene acetal protected D-glucosamine amide derivatives. Fifteen different amides were synthesized, and their self-assembling properties were assessed in multiple organic solvents, as well as mixtures of organic solvents with water. All derivatives were found to be gelators for at least one solvent and majority formed gels in multiple solvents at concentrations lower than 2 wt%. A few derivatives rendered remarkably stable gels in aqueous solutions at concentrations below 0.1 wt%. The benzamide 13 formed gels in water and in EtOH/H2O (v/v 1:2) at 0.36 mg/mL. The gels were characterized using optical microscopy and atomic force microscopy, and the self-assembly mechanism was probed using variable temperature 1H-NMR spectroscopy. Gel extrusion studies using H2O/DMSO gels successfully printed lines of gels on glass slides, which retained viscoelasticity based on rheology. Gels formed by the benzamide 13 were used for encapsulation and the controlled release of chloramphenicol and naproxen, as well as for dye removal for toluidine blue aqueous solutions. 

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5. Kinetics and Mass Yields of Aqueous Secondary Organic Aerosol from Highly Substituted Phenols Reacting with a Triplet Excited State

   https://doi.org/10.1021/acs.est.1c00575  

   Ma, Lan; Guzman, Chrystal; Niedek, Christopher; Tran, Theodore; Zhang, Qi; Anastasio, Cort. (January 2021, Environmental science technology)

   null (Ed.)

   Biomass burning emits large amounts of phenols, which can partition into cloud/fog drops and aerosol liquid water (ALW) and react to form aqueous secondary organic aerosol (aqSOA). Triplet excited states of organic compounds (3C*) are a likely oxidant, but there are no rate constants with highly substituted phenols that have high Henry’s law constants (KH) and are likely important in ALW. To address this gap, we investigated the kinetics of six highly substituted phenols with the triplet excited state of 3,4-dimethoxybenzaldehyde. Second-order rate constants at pH 2 are all fast, (2.6 - 4.6)E9 M-1 s-1, while values at pH 5 are 2 to 5 times smaller. Rate constants are reasonably described by a quantitative structure-activity relationship with phenol oxidation potentials, allowing rate constants of other phenols to be predicted. Triplet-phenol kinetics are unaffected by ammonium sulfate, sodium chloride, galactose (a biomass-burning sugar), or Fe(III). In contrast, ammonium nitrate increases the rate of phenol loss by making hydroxyl radical, while Cu(II) inhibits phenol decay. Mass yields of aqueous SOA from triplet reactions are large and range from 59 to 99%. Calculations using our data along with previous oxidant measurements indicate that phenols with high KH can be an important source of aqSOA in ALW, with 3C* typically the dominant oxidant. 

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