Cable bacteria embed a network of conductive protein fibers in their cell envelope that efficiently guides electron transport over distances spanning up to several centimeters. This form of long-distance electron transport is unique in biology and is mediated by a metalloprotein with a sulfur-coordinated nickel (Ni) cofactor. However, the molecular structure of this cofactor remains presently unknown. Here, we applied multi-wavelength Raman microscopy to identify cell compounds linked to the unique cable bacterium physiology, combined with stable isotope labeling, and orientation-dependent and ultralow-frequency Raman microscopy to gain insight into the structure and organization of this novel Ni-cofactor. Raman spectra of native cable bacterium filaments reveal vibrational modes originating from cytochromes, polyphosphate granules, proteins, as well as the Ni-cofactor. After selective extraction of the conductive fiber network from the cell envelope, the Raman spectrum becomes simpler, and primarily retains vibrational modes associated with the Ni-cofactor. These Ni-cofactor modes exhibit intense Raman scattering as well as a strong orientation-dependent response. The signal intensity is particularly elevated when the polarization of incident laser light is parallel to the direction of the conductive fibers. This orientation dependence allows to selectively identify the modes that are associated with the Ni-cofactor. We identified 13 such modes, some of which display strong Raman signals across the entire range of applied wavelengths (405-1,064 nm). Assignment of vibrational modes, supported by stable isotope labeling, suggest that the structure of the Ni-cofactor shares a resemblance with that of nickel bis(1,2-dithiolene) complexes. Overall, our results indicate that cable bacteria have evolved a unique cofactor structure that does not resemble any of the known Ni-cofactors in biology.
The great oxidation event (GOE), ~2.4 billion years ago, caused fundamental changes to the chemistry of Earth's surface environments. However, the effect of these changes on the biosphere is unknown, due to a worldwide lack of well-preserved fossils from this time. Here, we investigate exceptionally preserved, large spherical aggregate (SA) microfossils permineralised in chert from the c. 2.4 Ga Turee Creek Group in Western Australia. Field and petrographic observations, Raman spectroscopic mapping, and in situ carbon isotopic analyses uncover insights into the morphology, habitat, reproduction and metabolism of this unusual form, whose distinctive, SA morphology has no known counterpart in the fossil record. Comparative analysis with microfossils from before the GOE reveals the large SA microfossils represent a step-up in cellular organisation. Morphological comparison to extant micro-organisms indicates the SAs have more in common with coenobial algae than coccoidal bacteria, emphasising the complexity of this microfossil form. The remarkable preservation here provides a unique window into the biosphere, revealing an increase in the complexity of life coinciding with the GOE.
Ecosystem , Fossils , Bacteria , Carbon Isotopes , Carbon
There is tremendous interest in employing collective excitations of the lattice, spin, charge, and orbitals to tune strongly correlated electronic phenomena. We report such an effect in a ruthenate, Ca3Ru2O7, where two phonons with strong electron-phonon coupling modulate the electronic pseudogap as well as mediate charge and spin density wave fluctuations. Combining temperature-dependent Raman spectroscopy with density functional theory reveals two phonons, B2P and B2M, that are strongly coupled to electrons and whose scattering intensities respectively dominate in the pseudogap versus the metallic phases. The B2P squeezes the octahedra along the out of plane c-axis, while the B2M elongates it, thus modulating the Ru 4d orbital splitting and the bandwidth of the in-plane electron hopping; Thus, B2P opens the pseudogap, while B2M closes it. Moreover, the B2 phonons mediate incoherent charge and spin density wave fluctuations, as evidenced by changes in the background electronic Raman scattering that exhibit unique symmetry signatures. The polar order breaks inversion symmetry, enabling infrared activity of these phonons, paving the way for coherent light-driven control of electronic transport.
The lubricity of hydrogenated diamond-like carbon (HDLC) films is highly sensitive to the hydrogen (H) content in the film and the oxidizing gas in the environment. The tribochemical knowledge of HDLC films with two different H-contents (mildly hydrogenated vs highly hydrogenated) was deduced from the analysis of the transfer layers formed on the counter-surface during friction tests in O2 and H2O using Raman spectroscopic imaging and X-ray photoelectron spectroscopy (XPS). The results showed that, regardless of H-content in the film, shear-induced graphitization and oxidation take place readily. By analyzing the O2 and H2O partial pressure dependence of friction of HDLC with a Langmuir-type reaction kinetics model, the oxidation probability of the HDLC surface exposed by friction as well as the removal probability of the oxidized species by friction were determined. The HDLC film with more H-content exhibited a lower oxidation probability than the film with less H-content. The atomistic origin of this H-content dependence was investigated using reactive molecular dynamics simulations, which showed that the fraction of undercoordinated carbon species decreased as the H-content in the film increased, corroborating the lower oxidation probability of the highly-hydrogenated film. The H-content in the HDLC film influenced the probabilities of oxidation and material removal, both of which vary with the environmental condition.
Low-frequency shear and breathing modes are important Raman signatures of two-dimensional (2D) materials, providing information on the number of layers and insights into interlayer interactions. We elucidate the nature of low-frequency modes in a 2D polar metal-2D Ga covalently bonded to a SiC substrate, using a first-principles Green's function-based approach. The low-frequency Raman modes are dominated by surface resonance modes, consisting primarily of out-of-phase shear modes in Ga, coupled to SiC phonons. Breathing modes are strongly coupled to the substrate and do not give rise to peaks in the phonon spectra. The highest-frequency shear mode blue-shifts significantly with increasing thickness, reflecting both an increase in the number of Ga layers and an increase in the effective interlayer force constant. The surface resonance modes evolve into localized 2D Ga modes as the phonon momentum increases. The predicted low-frequency modes are consistent with Raman measurements on 2D polar Ga.
Chemically stable quantum-confined 2D metals are of interest in next-generation nanoscale quantum devices. Bottom-up design and synthesis of such metals could enable the creation of materials with tailored, on-demand, electronic and optical properties for applications that utilize tunable plasmonic coupling, optical nonlinearity, epsilon-near-zero behavior, or wavelength-specific light trapping. In this work, it is demonstrated that the electronic, superconducting, and optical properties of air-stable 2D metals can be controllably tuned by the formation of alloys. Environmentally robust large-area 2D-Inx Ga1- x alloys are synthesized byConfinement Heteroepitaxy (CHet). Near-complete solid solubility is achieved with no evidence of phase segregation, and the composition is tunable over the full range of x by changing the relative elemental composition of the precursor. The optical and electronic properties directly correlate with alloy composition, wherein the dielectric function, band structure, superconductivity, and charge transfer from the metal to graphene are all controlled by the indium/gallium ratio in the 2D metal layer.
