Only in the last 30 years of science have we discovered that not all life on Earth is based upon photosynthesis. The deep biosphere has emerged as an incredibly diverse ecosystem with life thriving in environmental conditions ranging from sub-zero to 120°C+ temperatures, hyper saline brine pools to low pH environments. This body of work contributes to several key questions about life in the deep biosphere: 1) Which microbes are present in the deep biosphere, 2) what are their sources of energy, 3) how do they attain required nutrients for metabolic function and growth and 4) what is the effect of substrate composition on each of the above questions. In order to address these first order questions, we focused our efforts on Loihi Seamount, off the SE coast of the Big Island of Hawai'i, which provides us with raw materials and microbes for laboratory experiments as well as an in- situ deep-sea laboratory so that we can study effects of microbiology on basalt weathering. Due to the high iron content (̃10-12%), basalts are an attractive source of reduced iron as an energy source for chemolithoautotrophic growth. We explored microbial diversity associated with basaltic glass substrates across a range of different environments in and around Loihi using t-RFLP, clone library data, and culturing/isolation techniques. Results show that [gamma]- and [alpha]-Proteobacteria tend to dominate these surfaces and one of our Fe(II)-oxidizing isolates, a Pseudomonas sp. LOB-7, is represented as one of the most dominant members of the microbial communities on several basalts indicating that perhaps Fe(II)- oxidizing microbes are important players in the microbially mediated dissolution and alteration of basaltic glass. Investigations into substrate specificity by microbes under energy- and nutrient-limiting conditions reveal that Pseudomonas and Shewanella isolates are able to obtain Fe and/or phosphorus directly from a basaltic glass silicate matrix. This finding provides a direct relationship between substrate composition and the activity of particular microbes, which will allow us to provide insights into how substrate composition can control microbial diversity and consequently chemical fluxes between seawater and the basaltic ocean crust

Rapid, efficient development of homogeneous catalysts featuring desired performance is critical to numerous catalytic transformations but remains a key challenge. Typically, this task relies heavily on ligand design that is often based on trial and error. Herein, we demonstrate a catalyst editing strategy in Ni-catalyzed ethylene/acrylate copolymerization. Specifically, alkylation of a pendant phosphine followed by anion exchange provides a high yield strategy for a large number of cationic Ni phosphonium catalysts with varying electronic and steric profiles. These catalysts are highly active in ethylene/acrylate copolymerization, and their behaviors are correlated with the electrophile and the anion used in late-stage functionalization.

Polar monomer-induced β-H elimination is a key elementary step in polar polyolefin synthesis by coordination polymerization but remains underexplored. Herein, we show that a bulky neutral Ni catalyst, 1Ph, is not only a high-performance catalyst in ethylene/acrylate copolymerization (activity up to ∼37,000 kg/(mol·h) at 130 °C in a batch reactor, mol % tBA ∼ 0.3) but also a suitable platform for investigation of acrylate-induced β-H elimination. 4Ph-tBu, a novel Ni alkyl complex generated after acrylate-induced β-H elimination and subsequent acrylate insertion, was identified and characterized by crystallography. A combination of catalysis and mechanistic studies reveals effects of the acrylate monomer, bidentate ligand, and the labile ligand (e.g., pyridine) on the kinetics of β-H elimination, the role of β-H elimination in copolymerization catalysis as a chain-termination pathway, and its potential in controlling the polymer microstructure in polar polyolefin synthesis.