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1. Natural organic matter adsorption conditions influence photocatalytic reaction pathways of phosphate-treated titanium dioxide nanoparticles

   https://doi.org/10.1039/D1EN00433F  

   Mathew, Riya A.; Wu, Gang; Zhang, Ye; Shakiba, Sheyda; Yao, Yan; Tsai, Ah-Lim; Louie, Stacey M. (August 2021, Environmental Science: Nano)

   Titanium dioxide (TiO 2 ) nanoparticles have been widely studied for water treatment applications; however, natural organic matter (NOM) is often reported to hamper the efficiency of the nanoparticles toward the degradation of target pollutants. Phosphate treatment has been proposed as a potentially facile solution to this problem, as phosphate competes for TiO 2 surface sites to diminish the NOM adsorption. However, the potential importance of the conditions of the NOM exposure and the residual NOM remaining after phosphate treatment have not been fully explored. Here, we investigate the reactivity of phosphate-treated TiO 2 nanoparticles with NOM coatings adsorbed from two background water chemistries, deionized water (TiO 2 –NOM DIW ) and moderately hard water (TiO 2 –NOM MHW ). Thorough characterization by size exclusion chromatography revealed that the adsorbed NOM was only partially displaced after phosphate treatment, with a higher adsorbed mass and wider variety of NOM species persisting on TiO 2 –NOM MHW compared to TiO 2 –NOM DIW . Although the remaining adsorbed NOM did not significantly influence the degradation rate of phenol as a model pollutant, remarkably distinct effects were observed in the degradation of catechol as an oxidative byproduct of phenol, with TiO 2 –NOM MHW hindering catechol degradation and TiO 2 –NOM DIW accelerating catechol degradation. The suppressed reactivity for TiO 2 –NOM MHW was attributed to hindrance of the physical adsorption of catechol to the TiO 2 surface by the NOM MHW layer as well as changes in the reactive oxygen species profile as measured by electron paramagnetic resonance (EPR) spectroscopy, whereas the enhanced reactivity for TiO 2 –NOM DIW was attributed to higher hole formation, suggesting participation of the NOM DIW layer in electron transfer processes. This research highlights the critical importance of the NOM surface coating in directing the mechanisms for pollutant degradation in photocatalytic nano-enabled water treatment applications. 

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2. Natural organic matter composition determines the molecular nature of silver nanomaterial-NOM corona

   https://doi.org/10.1039/c8en00018b  

   Baalousha, Mohammed; Afshinnia, Kamelia; Guo, Laodong (January 2018, Environmental Science: Nano)

   Adsorption of natural organic matter (NOM) on nanomaterials (NMs) results in the formation of interfacial area between NMs and the surrounding environment (referred to as NOM-corona), giving rise to NMs' unique surface identity. This unique surface identity is determined by the ligands and their interactions with NM surfaces. Since the chemical structure and functionality is heterogeneous and polydisperse, the molecular composition of NOM-corona is the result of competitive adsorption of NOM molecules on the NM surface. Here, we investigate the molecular composition of NOM-corona formed from two different NOM samples (isolated from the Yukon River and Milwaukee River) on the surface of AgNMs using electrospray ionization-Fourier-transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS). The composition of AgNM-NOM corona varied with the composition of the original NOM. In general, AgNM-NOM corona is rich with N- and S-containing compounds. Furthermore, AgNM-NOM corona is rich with compounds with high molecular weight, high unsaturation, and high number of oxygenated groups. However, CHOS (carbon, hydrogen, oxygen and sulfur) compounds adsorbed on AgNMs from the Yukon River NOM have low molecular weight (LMW) and low saturation index, which might be due to selective adsorption via chemical complexation (Ag–S). On the other hand, NOM compounds with LMW and low unsaturation or compounds containing few oxygenated groups (mainly alcohols and ethers) are preferentially maintained in solution phase. The results here provide evidence of molecular interactions between NOM and NMs, which are critical to understanding NM behavior and toxicity in natural environments. 

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3. Probing protein aggregation at buried interfaces: distinguishing between adsorbed protein monomers, dimers, and a monomer–dimer mixture in situ

   https://doi.org/10.1039/d1sc04300e  

   Lu, Tieyi; Guo, Wen; Datar, Prathamesh M.; Xin, Yue; Marsh, E. Neil; Chen, Zhan (January 2022, Chemical Science)

   Protein adsorption on surfaces greatly impacts many applications such as biomedical materials, anti-biofouling coatings, bio-separation membranes, biosensors, antibody protein drugs etc. For example, protein drug adsorption on the widely used lubricant silicone oil surface may induce protein aggregation and thus affect the protein drug efficacy. It is therefore important to investigate the molecular behavior of proteins at the silicone oil/solution interface. Such an interfacial study is challenging because the targeted interface is buried. By using sum frequency generation vibrational spectroscopy (SFG) with Hamiltonian local mode approximation method analysis, we studied protein adsorption at the silicone oil/protein solution interface in situ in real time, using bovine serum albumin (BSA) as a model. The results showed that the interface was mainly covered by BSA dimers. The deduced BSA dimer orientation on the silicone oil surface from the SFG study can be explained by the surface distribution of certain amino acids. To confirm the BSA dimer adsorption, we treated adsorbed BSA dimer molecules with dithiothreitol (DTT) to dissociate these dimers. SFG studies on adsorbed BSA after the DTT treatment indicated that the silicone oil surface is covered by BSA dimers and BSA monomers in an approximate 6 : 4 ratio. That is to say, about 25% of the adsorbed BSA dimers were converted to monomers after the DTT treatment. Extensive research has been reported in the literature to determine adsorbed protein dimer formation using ex situ experiments, e.g. , by washing off the adsorbed proteins from the surface then analyzing the washed-off proteins, which may induce substantial errors in the washing process. Dimerization is a crucial initial step for protein aggregation. This research developed a new methodology to investigate protein aggregation at a solid/liquid (or liquid/liquid) interface in situ in real time using BSA dimer as an example, which will greatly impact many research fields and applications involving interfacial biological molecules. 

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4. Polyvinyl chloride (PVC) ultrafiltration membrane fouling and defouling behavior: EDLVO theory and interface adhesion force analysis

   https://doi.org/https://doi.org/10.1016/j.memsci.2018.07.020  

   Wanyi Fu, Lan Wang (October 2018, Journal of membrane science)

   To unravel fouling and defouling mechanisms of protein, saccharides and natural organic matters (NOM) on polymeric membrane during filtration, this study investigated filtration characteristics on polyvinyl chloride (PVC) ultrafiltration membranes with bovine serum albumin, dextran, humic acid as model foulants. Membrane fouling and defouling performances were analyzed through monitoring the flux decline during filtration and flux recovery during physical backwash. Physico-chemical properties (e.g., hydrophobicity and surface charge) of PVC membrane and foulants were characterized, which were used in the extended Derjaguin–Landau–Verwey–Overbeek (EDLVO) theory to calculate the interaction energies between membrane foulant and foulant-foulant. The results showed that at the later filtration stages the fouling rate was strongly correlated with the deposition rate, which was determined by the interaction energy profile calculated by EDLVO. Moreover, the adhesion forces of membrane–foulant and foulant–foulant were further measured by atomic force microscopy (AFM) with modified colloidal probes. A positive correlation (R2 =0.845) between particle detachment rate (determined by adhesion force) and defouling rate was developed for BSA and HA foulants that led to cake layer formation. By contrast, dextran defouling rate was off this correlation as dextran partially clogged membrane pores due to its smaller size. 

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5. Thermodynamics of Protein-Surface Binding- the Model Makes all the Difference

   Nicholas C. Fitzkee, Kayla D (February 2020, Biophysical journal)

   null (Ed.)

   Gold nanoparticles (AuNPs) are now being used in such areas as diagnostics, drug delivery, and biological sensing. In these applications, AuNPs are frequently exposed to biological fluids. These fluids contain many different proteins, any of which may interfere with the intended function of the nanoparticle. In this work, we examine the thermodynamic consequences of proteinnanoparticle binding using a combined spectroscopic and calorimetric approach. We monitored binding using UV-Vis spectroscopy, differential scanning calorimetry (DSC), and isothermal titration calorimetry (ITC). Six proteins were studied based on their differing chemical properties, and both 15 nm and 30 nm citrate-coated AuNPs were investigated. We interpreted the UV-Vis data using two different models: the commonly-used Langmuir isotherm model and a more complex mass transport model. Both models can be used to determine Kd values for the 30 nm AuNP data; however, the mass transport model is more appropriate for 15 nm AuNPs. This is because, when fitting the Langmuir model, it is commonly assumed that most proteins are not surface-associated, and this assumption fails for 15 nm AuNPs. The DSC thermograms show two transitions for a globular protein adsorbed to a 15 nm AuNP: one high-temperature transition that is similar to global protein unfolding (68 C), and one low-temperature transition that may correspond to unfolding at the surface (56 C). Conversely, ITC experiments show no net heat of adsorption for GB3, even at high protein/AuNP concentrations. Together, the spectroscopic and calorimetric data suggest a complex, multi-step process for protein-nanoparticle adsorption. Moreover, for the proteins studied, both AuNP curvature and protein chemistry contribute to protein adsorption, with proteins generally binding more weakly to the larger nanoparticles. In the future, this work may lead to principles for improving the design of AuNPbased therapeutics and sensors. 

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