Lithium Ion Battery Materials as Tunable, Redox Non-Innocent Catalyst Supports

The development of general strategies for the electronic tuning of a catalyst’s active site is an ongoing challenge in heterogeneous catalysis. To this end, herein we describe the application of Li-ion battery cathode and anode materials as redox non-innocent catalyst supports that can be continuously modulated as a function of lithium intercalation. A zero-valent nickel complex was oxidatively grafted onto the surface of lithium manganese oxide (LixMn2O4) to yield isolated Ni(II) occupying the vacant interstitial octahedral site in the Li diffusion channel on the surface and subsurface of the spinel structure (Ni/LixMn2O4). The activity of Ni/LixMn2O4 for olefin hydrogenation, as a representative probe reaction, was found to increase monotonically as a function of support reductive lithiation. Simulation of Ni/LixMn2O4 reveals the dramatic impact of surface redox states on the viability of the homolytic oxidative addition mechanism for H2 activation. Catalyst control through support lithiation was extended to an organotantalum complex on LixTiO2, demonstrating the generality of this phenomenon.

Inner-sphere electron transfer at the ruthenium-azo interface

Metal complexes exhibiting multiple reversible redox states have drawn continuing research interest due to their electron reservoir features. In this context, the present article described ruthenium-acac complexes (acac=acetylacetonate) incorporating redox-active...

Experimental Evolution Reveals Redox State Modulates Mycobacterial Pathogenicity

Understanding how Mycobacterium tuberculosis has evolved into a professional pathogen is helpful in studying its pathogenesis and for designing vaccines. We investigated how the evolutionary adaptation of M. smegmatis mc251 to an important clinical stressor H2O2 allows bacteria undergo coordinated genetic mutations, resulting in increased pathogenicity. Whole-genome sequencing identified a mutation site in the fur gene, which caused increased expression of katG. Using a Wayne dormancy model, mc251 showed a growth advantage over its parental strain mc2155 in recovering from dormancy under anaerobic conditions. Meanwhile, the high level of KatG in mc251 was accompanied by a low level of ATP, which meant that mc251 is at a low respiratory level. Additionally, the redox-related protein Rv1996 showed different phenotypes in different specific redox states in M. smegmatis mc2155, mc251, M. bovis BCG and M. tuberculosis mc27000. In conclusion, our study shows that the same gene presents different phenotypes under different physiological conditions. This may partly explain why M. smegmatis and M. tuberculosis have similar virulence factors and signaling transduction systems such as two-component systems and sigma factors, but due to the different redox states in the corresponding bacteria, M. smegmatis is a nonpathogen, while M. tuberculosis is a pathogen. As mc251 overcomes its shortcomings of rapid removal, it can be potentially developed as a vaccine vector.

Iron Formations as Palaeoenvironmental Archives

Ancient iron formations - iron and silica-rich chemical sedimentary rocks that formed throughout the Precambrian eons - provide a significant part of the evidence for the modern scientific understanding of palaeoenvironmental conditions in Archaean (4.0–2.5 billion years ago) and Proterozoic (2.5–0.539 billion years ago) times. Despite controversies regarding their formation mechanisms, iron formations are a testament to the influence of the Precambrian biosphere on early ocean chemistry. As many iron formations are pure chemical sediments that reflect the composition of the waters from which they precipitated, they can also serve as nuanced geochemical archives for the study of ancient marine temperatures, redox states, and elemental cycling, if proper care is taken to understand their sedimentological context.

A crystalline radical cation derived from Thiele’s hydrocarbon with redox range beyond 1 V

Thiele’s hydrocarbon occupies a central role as an open-shell platform for new organic materials, however little is known about its redox behaviour. While recent synthetic approaches involving symmetrical carbene substitution of the CPh2 termini yield isolable neutral/dicationic analogues, the intervening radical cations are much more difficult to isolate, due to narrow compatible redox ranges (typically < 0.25 V). Here we show that a hybrid BN/carbene approach allows access to an unsymmetrical analogue of Thiele’s hydrocarbon 1, and that this strategy confers markedly enhanced stability on the radical cation. 1•+ is stable across an exceptionally wide redox range (> 1 V), permitting its isolation in crystalline form. Further single-electron oxidation affords borenium dication 12+, thereby establishing an organoboron redox system fully characterized in all three redox states. We perceive that this strategy can be extended to other transient organic radicals to widen their redox stability window and facilitate their isolation.

Rational Design of Stable Four-Electron-Accepting Carbonyl-N-methylpyridinium Species for High-Performance Lithium-Ion Batteries

Development of novel organics that exhibit multiple and stable redox states, limited solubility and improved conductivity is a highly rewarding direction for improving the performance of lithium-ion batteries (LIBs). As biologically derived organic molecules, carbonylpyridinium compounds have desirable and tunable redox properties, making them suitable candidates for battery applications. In this work, we report a structural evolution of carbonylpyridinium-based redox-active organics, from 2-electron accepting BMP to 4-electron accepting small, conjugated molecules (1, 2), and then to the corresponding conjugated polymers (CP1, CP2). Through suppression of dissolution and increasing electrochemical conductivity, the LIBs performance can be gradually enhanced. At a relatively high current of 0.5 A g-1, high specific capacities for 1 (100 mAh g-1), 2 (260 mAh g-1), CP1 (360 mAh g-1) and CP2 (540 mAh g-1) can be reached after 240 cycles. Particularly, the rate performance and cycling stability of CP2 surpasses many reported commercial inorganic and organic electrode materials. This work provides a promising new carbonylpyridinium-based building block featured with multiple redox centers, on the way to high performance Li-organic batteries.

Oxidative Stress and Inflammatory Mediators in Exhaled Breath Condensate of Patients with Pulmonary Tuberculosis. A Pilot Study with a Biomarker Perspective

Tuberculosis (TB) is one of the highest infectious burdens worldwide. An excess of inflammation and inadequate antioxidant defense mechanisms are believed to lead to chronic inflammation and lung damage in tuberculosis (TB). However, circulating metabolites do not always replicate lung-associated biomarkers that define the pathobiology of the disease. The objective of this study was to determine the utility of exhaled breath condensate (EBC), a non-invasive and straightforward sample, to evaluate alveolar space-derived metabolites of redox state and inflammation. We assessed the levels of exhaled oxidant/antioxidant parameters (8-isoprostane, MDA, GSH), inflammatory markers, such as nucleosomes, cytokines (IL-2, IL-4, IL-6 and IL-8, IL-10, GM-CSF, TNF-α, and IFN-γ) and lipid mediators (PGE2, LTB4, RvD1, and Mar1), in patients with recently diagnosed pulmonary TB and healthy controls’ EBC and serum. The TB patients showed 36% lower GSH levels, and 2-, 1.4-, 1.1-, and 50-fold higher levels of 8-isoprostanes, nucleosomes, IL-6, and LTB4, respectively, in EBC. There was no correlation between EBC and serum, highlighting the importance of measuring local biomarkers. Quantitation of local inflammatory molecules and redox states in EBC would help find biomarkers useful for pharmacological and follow-up studies in pulmonary tuberculosis.

Thermodynamics of Potential CHO Metabolites in a Reducing Environment

How did metabolism arise and evolve? What chemical compounds might be suitable to support and sustain a proto-metabolism before the advent of more complex co-factors? We explore these questions by using first-principles quantum chemistry to calculate the free energies of CHO compounds in aqueous solution, allowing us to probe the thermodynamics of core extant cycles and their closely related chemical cousins. By framing our analysis in terms of the simplest feasible cycle and its permutations, we analyze potentially favorable thermodynamic cycles for CO2 fixation with H2 as a reductant. We find that paying attention to redox states illuminates which reactions are endergonic or exergonic. Our results highlight the role of acetate in proto-metabolic cycles, and its connection to other prebiotic molecules such as glyoxalate, glycolaldehyde, and glycolic acid.