Bacteria secrete small molecules known as siderophores to acquire iron from their surroundings. For over 60 years, investigations into the bioinorganic chemistry of these molecules, including fundamental coordination chemistry studies, have provided insight into the crucial role that siderophores play in bacterial iron homeostasis. The importance of understanding the fundamental chemistry underlying bacterial life has been highlighted evermore in recent years because of the emergence of antibiotic-resistant bacteria and the need to prevent the global rise of these superbugs. Increasing reports of siderophores functioning in capacities other than iron transport have appeared recently, but reports of “non-classical” siderophore functions have long paralleled those of iron transport. One particular non-classical function of these iron chelators, namely antibiotic activity, was documented before the role of siderophores in iron transport was established. In this Perspective, we present an exposition of past and current work into non-classical functions of siderophores and highlight the directions in which we anticipate that this research is headed. Examples include the ability of siderophores to function as zincophores, chalkophores, and metallophores for a variety of other metals, sequester heavy metal toxins, transport boron, act as signalling molecules, regulate oxidative stress, and provide antibacterial activity.

/pdf/beyond-iron-non-classical-biological-functions-of-bacterial-559xy9rh0d.pdf

Beyond iron: non-classical biological functions of bacterial siderophores

Despite the possible occurrence of metal nanoparticles in the environment due to the discharge of engineered nanoparticles and the natural transformation of metal ions into metal nanoparticles, little is known about the transformation mechanism, fates, behaviors, and effects of these nanoparticles in the environment. Here, we show that dissolved organic matter (DOM) in environmental waters can mediate the reduction of ionic Ag and Au to their metallic nanoparticles under natural sunlight, suggesting that this process may be general for metals with high reduction potential. We demonstrated that the reduction was mediated by superoxide from photoirradiation of the phenol group in DOM, and the dissolved O2 significantly enhanced the formation of Ag nanoparticles. These results imply that previous knowledge about O2-induced dissolution and its effect on persistence of Ag nanoparticles should be reconsidered in a sunlit DOM-rich aqueous environment. This study can also shed light on understanding possible natu...

Sunlight-Induced Reduction of Ionic Ag and Au to Metallic Nanoparticles by Dissolved Organic Matter

Microorganisms produce and secrete secondary metabolites to assist in their survival. We report that the gold resident bacterium Delftia acidovorans produces a secondary metabolite that protects from soluble gold through the generation of solid gold forms. This finding is the first demonstration that a secreted metabolite can protect against toxic gold and cause gold biomineralization.

Gold biomineralization by a metallophore from a gold-associated microbe

Bacteria are essential components of all natural and many engineered systems. The most active fractions of bacteria are now recognized to occur as ‘biofilms’, where cells are attached and surrounded by a secreted matrix of “sticky” extracellular polymeric substances (EPS). Recent investigations have established that significant accumulation of nanoparticles (NPs) occurs in aquatic biofilms. These studies point to the emerging roles of biofilms for influencing partitioning and possibly transformations of NPs in both natural and engineered systems. While attached biofilms are efficient “sponges” for NPs, efforts to elucidate the fundamental mechanisms guiding interactions between NPs and biofilms have just begun. In this mini review, special attention is focused on NP-biofilm interactions within the aquatic environment. We highlight key physical, chemical and biological processes that affect interactions and accumulation of NPs by bacterial biofilms. We posit that these biofilm processes present the likely possibility for unique biological and chemical transformations of NPs. Ultimately, the environmental fate of NPs is influenced by biofilms, and therefore requires a more-in depth understanding of their fundamental properties.

/pdf/when-nanoparticles-meet-biofilms-interactions-guiding-the-34vgpnu53o.pdf

When nanoparticles meet biofilms—interactions guiding the environmental fate and accumulation of nanoparticles

Biofilms living on gold (Au) grains play a key role in the biogeochemical cycle of Au by promoting the dispersion of Au via the formation of Au nanoparticles as well as the formation of secondary biomorphic Au. Gold grains from Queensland, Australia, are covered by a polymorphic, organic-inorganic layer that is up to 40 μm thick. It consists of a bacterial biofilm containing Au nanoparticles associated with extracellular polymeric substances as well as bacterioform Au. Focused ion beam (FIB) sectioning through the biofilm revealed that aggregates of nanoparticulate Au line open spaces beneath the active biofilm layer. These aggregates (bacterioform Au type 1) resulted from the reprecipitation of dissolved Au, and their internal growth structures provide direct evidence for coarsening of the Au grains. At the contact between the polymorphic layer and the primary Au, bacterioform Au type 2 is present. It consists of solid rounded forms into which crystal boundaries of underlying primary Au extend, and is the result of dealloying and Ag dissolution from the primary Au. This study demonstrates that (1) microbially driven dissolution, precipitation, and aggregation lead to the formation of bacterioform Au and contribute to the growth of Au grains under supergene conditions, and (2) the microbially driven mobilization of coarse Au into nanoparticles plays a key role in mediating the mobility of Au in surface environments, because the release of nanoparticulate Au upon biofilm disintegration greatly enhances environmental mobility compared to Au complexes only.

Nanoparticle factories: Biofilms hold the key to gold dispersion and nugget formation

Secondary gold structures: Relics of past biogeochemical transformations and implications for colloidal gold dispersion in subtropical environments

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Nanoparticle factories: Biofilms hold the key to gold dispersion and nugget formation

Secondary gold structures: Relics of past biogeochemical transformations and implications for colloidal gold dispersion in subtropical environments