Nanoscale Dynamic Readout of a Chemical Redox Process Using Radicals Coupled with Nitrogen-Vacancy Centers in Nanodiamonds.

Biocompatible nanoscale probes for sensitive detection of paramagnetic species and molecules associated with their (bio)chemical transformations would provide a desirable tool for a better understanding of cellular redox processes. Here, we describe an analytical tool based on quantum sensing techniques. We magnetically coupled negatively charged nitrogen-vacancy (NV) centers in nanodiamonds (NDs) with nitroxide radicals present in a bioinert polymer coating of the NDs. We demonstrated that the T1 spin relaxation time of the NV centers is very sensitive to the number of nitroxide radicals, with a resolution down to ∼10 spins per ND (detection of approximately 10-23 mol in a localized volume). The detection is based on T1 shortening upon the radical attachment, and we propose a theoretical model describing this phenomenon. We further show that this colloidally stable, water-soluble system can be used dynamically for spatiotemporal readout of a redox chemical process (oxidation of ascorbic acid) occurring near the ND surface in an aqueous environment under ambient conditions.

Proton-Gradient-Driven Oriented Motion of Nanodiamonds Grafted to Graphene by Dynamic Covalent Bonds.

Manipulating nanoscopic objects by external stimuli is the cornerstone of nanoscience. Here, we report the implementation of dynamic covalent chemistry in the reversible binding and directional motion of fluorescent nanodiamond particles at a functionalized graphene surface via imine linkages. The dynamic connections allow for controlling the formation and rupture of these linkages by external stimuli. By introduction of pH gradients, the nanoparticles are driven to move along the gradient due to the different rates of the imine condensation and hydrolysis in the two environments. The multivalent nature of the particle-to-surface connection ensures that particles remain attached to the surface, whereas its dynamic character allows for exchange reaction, thus leading to displacement yet bound behavior in two-dimensional space. These results open a pathway for thermodynamically controlled manipulation of objects on the nanoscale.

Efficiency and stability of spectral sensitization of boron-doped-diamond electrodes through covalent anchoring of a donor-acceptor organic chromophore (P1).

A novel procedure is developed for chemical modification of H-terminated B-doped diamond surfaces with a donor-π-bridge-acceptor molecule (P1). A cathodic photocurrent near 1 µA cm(-2) flows under 1 Sun (AM 1.5) illumination at the interface between the diamond electrode and aqueous electrolyte solution containing dimethylviologen (electron mediator). The efficiency of this new electrode outperforms that of the non-covalently modified diamond with the same dye. The found external quantum efficiency of the P1-sensitized diamond is not far from that of the flat titania electrode sensitized by a standard organometallic dye used in solar cells. However, the P1 dye, both pure and diamond-anchored, shows significant instability during illumination by solar light. The degradation is a two-stage process in which the initially photo-generated products further decompose in complicated dark reactions. These findings need to be taken into account for optimization of organic chromophores for solar cells in general.

Visible-light sensitization of boron-doped nanocrystalline diamond through non-covalent surface modification.

A novel simple and versatile synthetic strategy is developed for the surface modification of boron-doped diamond. In a two-step procedure, polyethyleneimine is adsorbed on the hydrogenated diamond surface and subsequently modified with a model light-harvesting donor-π-bridge-acceptor molecule (coded P1). The sensitized diamond exhibits stable cathodic photocurrents under visible-light illumination in aqueous electrolyte solution with dimethylviologen serving as an electron mediator. In spite of the simplicity of the surface sensitization protocol, the photoelectrochemical performance is similar to or better than that of other sensitized diamond electrodes which were reported in previous studies (2008-2014).

Predicting the likely response of data-poor ecosystems to climate change using space-for-time substitution across domains.

Predicting ecological response to climate change is often limited by a lack of relevant local data from which directly applicable mechanistic models can be developed. This limits predictions to qualitative assessments or simplistic rules of thumb in data-poor regions, making management of the relevant systems difficult. We demonstrate a method for developing quantitative predictions of ecological response in data-poor ecosystems based on a space-for-time substitution, using distant, well-studied systems across an inherent climatic gradient to predict ecological response. Changes in biophysical data across the spatial gradient are used to generate quantitative hypotheses of temporal ecological responses that are then tested in a target region. Transferability of predictions among distant locations, the novel outcome of this method, is demonstrated via simple quantitative relationships that identify direct and indirect impacts of climate change on physical, chemical and ecological variables using commonly available data sources. Based on a limited subset of data, these relationships were demonstrably plausible in similar yet distant (>2000 km) ecosystems. Quantitative forecasts of ecological change based on climate-ecosystem relationships from distant regions provides a basis for research planning and informed management decisions, especially in the many ecosystems for which there are few data. This application of gradient studies across domains - to investigate ecological response to climate change - allows for the quantification of effects on potentially numerous, interacting and complex ecosystem components and how they may vary, especially over long time periods (e.g. decades). These quantitative and integrated long-term predictions will be of significant value to natural resource practitioners attempting to manage data-poor ecosystems to prevent or limit the loss of ecological value. The method is likely to be applicable to many ecosystem types, providing a robust scientific basis for estimating likely impacts of future climate change in ecosystems where no such method currently exists.

The development of biological objectives for streams in a single catchment: a case study on the catchment of Western Port Bay, Victoria, Australia.

Government environment protection policies for waterways have traditionally relied on water quality indicators and their objectives. In this paper we describe the development of biological objectives based on invertebrate indicators for inclusion in a government policy for the catchment of Western Port Bay, Victoria. The first step of defining segments (areas with streams in which the same objectives are applied) was problematic, requiring two different approaches, as follows. Site groups initially based on invertebrate community composition derived using multivariate techniques (ordination and classification) proved to be unsuitable for policy segments. Segment boundaries were subsequently defined using topographical (e.g. boundary of foothills and lowland plains), climate (e.g. rainfall) and land-use (e.g. urban) features. We used information and data from reference sites inside as well outside the catchment to derive specific biological objectives based on aquatic invertebrates for these segments. Objectives were specified for the following four indicators--number of invertebrate families, the SIGNAL index, the AUSRIVAS predictive model and the number of key families.