HUMIC MACROMOLECULES IN NATURAL WATERS

Abstract

Humic substances are the major organic constituents of soils and sediments. They also occur in small concentrations in natural surface waters and groundwaters. They form through the breakdown of plant and animal tissues by chemical and biological processes that tend to produce complex chemical structures that are more stable than the original material from which they were derived. One of the more important characteristics of humic substances is their ability to form water-soluble and water-insoluble complexes with metal ions and hydrous oxides and to interact with clay minerals and various organic compounds such as alkanes, fatty acids, and toxic organic substances such as pesticides.     

Altering protein surface charge with chemical modification modulates protein–gold nanoparticle aggregation

Gold nanoparticles (AuNP) can interact with a wide range of molecules including proteins. Whereas significant attention has focused on modifying the nanoparticle surface to regulate protein–AuNP assembly or influence the formation of the protein “corona,” modification of the protein surface as a mechanism to modulate protein–AuNP interaction has been less explored. Here, we examine this possibility utilizing three small globular proteins—lysozyme with high isoelectric point (pI) and established interactions with AuNP; α-lactalbumin with similar tertiary fold to lysozyme but low pI; and myoglobin with a different globular fold and an intermediate pI. We first chemically modified these proteins to alter their charged surface functionalities, and thereby shift protein pI, and then applied multiple methods to assess protein–AuNP assembly. At pH values lower than the anticipated pI of the modified protein, AuNP exposure elicits changes in the optical absorbance of the protein–NP solutions and other properties due to aggregate formation. Above the expected pI, however, protein–AuNP interaction is minimal, and both components remain isolated, presumably because both species are negatively charged. These data demonstrate that protein modification provides a powerful tool for modulating whether nanoparticle–protein interactions result in material aggregation. The results also underscore that naturally occurring protein modifications found in vivo may be critical in defining nanoparticle–protein corona compositions.     

Slow dynamics and aging of a colloidal hard sphere glass

The intermediate scattering function (ISF) is measured for a colloidal hard-sphere glass as functions of the scattering vector and waiting time. For scattering vectors near the structure factor peak, we show that the ISF and the stretching index, defined at the crossover time between the fast and slow processes, depend algebraically on the waiting time. By contrast, the Debye-Waller factor is independent of the waiting time.     

Photoinitiated Energy Transfer in Porous-Cage-Stabilised Silver Nanoparticles

We report a new composite material consisting of silver nanoparticles decorated with three-dimensional molecular organic cages based on light-absorbing porphyrins. The porphyrin cages serve to both stabilize the particles and allow diffusion and trapping of small molecules close to the metallic surface. Combining these two photoactive components results in a Fano-resonant interaction between the porphyrin Soret band and the nanoparticle-localised surface-plasmon resonance. Time-resolved spectroscopy revealed the silver nanoparticles transfer up to 37 % of their excited-state energy to the stabilising layer of porphyrin cages. These unusual photophysics cause a 2-fold current increase in photoelectrochemical water-splitting measurements. The composite structure provides a compelling proof of concept for advanced photosensitiser systems with intrinsic porosity for photocatalytic and sensing applications.