An alcove at the acetyl-CoA synthase nickel active site is required for productive substrate CO binding and anaerobic carbon fixation.

One of the seven natural CO fixation pathways, the anaerobic Wood-Ljungdahl pathway (WLP) is unique in generating CO as a metabolic intermediate, operating through organometallic intermediates, and in conserving (versus utilizing) net ATP. The key enzyme in the WLP is acetyl-CoA synthase (ACS), which uses an active site [2Ni-4Fe-4S] cluster (A-cluster), a CO tunnel, and an organometallic (Ni-CO, Ni-methyl, and Ni-acetyl) reaction sequence to generate acetyl-CoA. Here, we reveal that an alcove, which interfaces the tunnel and the A-cluster, is essential for CO fixation and autotrophic growth by the WLP.

Spectroscopic and computational investigations of organometallic complexation of group 12 transition metals by methanobactins from Methylocystis sp. SB2.

Methanotrophic bacteria catalyze the aerobic oxidation of methane to methanol using Cu-containing enzymes, thereby exerting a modulating influence on the global methane cycle. To facilitate the acquisition of Cu ions, some methanotrophic bacteria secrete small modified peptides known as "methanobactins," which strongly bind Cu and function as an extracellular Cu recruitment relay, analogous to siderophores and Fe. In addition to Cu, methanobactins form complexes with other late transition metals, including the Group 12 transition metals Zn, Cd, and Hg, although the interplay among solution-phase configurations, metal interactions, and the spectroscopic signatures of methanobactin-metal complexes remains ambiguous.

Design and development of the efficient anguilliform swimming robot- MAR.

Propulsion of swimming robots at the surface and underwater is largely dominated by rotary propellers due to high thrust, but at the cost of low efficiency. Due to their inherently high speed turning motion, sharp propeller blades and generated noise, they also present a disturbance to maritime ecosystems. Our work presents a bio-inspired approach to efficient and eco-friendly swimming with moderate to high thrust.

Qualitative and quantitative differences in estrogen biotransformation in human breast glandular and adipose tissues: implications for studies using mammary biospecimens.

Because of its assumed role in breast cancer etiology, estrogen biotransformation (and interaction of compounds therewith) has been investigated in human biospecimens for decades. However, little attention has been paid to the well-known fact that large inter-individual variations exist in the proportion of breast glandular (GLT) and adipose (ADT) tissues and less to adequate tissue characterization. To assess the relevance of this, the present study compares estrogen biotransformation in GLT and ADT.

Solvent Quality Controls Macromolecular Structural Dynamics of a Dendrimeric Hydrogenase Model.

We report a spectroscopic investigation of the ultrafast dynamics of the second-generation poly(aryl ether) dendritic hydrogenase model using two-dimensional infrared (2D-IR) spectroscopy to probe the metal carbonyl vibrations of the dendrimer and a reference small molecule, [Fe(μ-S)(CO)]. We find that the structural dynamics of the dendrimer are reflected in a slow phase of the spectral diffusion, which is absent from [Fe(μ-S)(CO)] and we relate the slow phase to the quality of the solvent for poly(aryl ether) dendrimers. We observe a solvent-dependent modulation of the initial phase of vibrational relaxation of the carbonyl groups, which we attribute to an inhibition of solvent assistance in the intramolecular vibrational redistribution process for the dendrimer.

Oncilla Robot: A Versatile Open-Source Quadruped Research Robot With Compliant Pantograph Legs.

We present Oncilla robot, a novel mobile, quadruped legged locomotion machine. This large-cat sized, 5.1 kg robot is one of a kind of a recent, bioinspired legged robot class designed with the capability of model-free locomotion control.

Oxidation-State-Dependent Vibrational Dynamics Probed with 2D-IR.

In an effort to examine the role of electronic structure and oxidation states in potentially modifying intramolecular vibrational dynamics and intermolecular solvation, we have used 2D-IR to study two distinct oxidation states of an organometallic complex. The complex, [1,1'-bis(diphenylphosphino)ferrocene]tetracarbonyl chromium (DPPFCr), consists of a catalytic diphenylphosphino ferrocene redox-active component as well as a Cr that can be switched from a Cr(0) to a Cr(I) oxidation state using a chemical oxidant in dichloromethane (DCM) solution. The DPPFCr(I) radical cation is sufficiently stable to investigate with 2D-IR spectroscopy, which provides dynamical information such as vibrational relaxation, intramolecular vibrational redistribution, as well as solvation dynamics manifested as spectral diffusion.

Dynamic Flexibility of Hydrogenase Active Site Models Studied with 2D-IR Spectroscopy.

Hydrogenase enzymes enable organisms to use H as an energy source, having evolved extremely efficient biological catalysts for the reversible oxidation of molecular hydrogen. Small-molecule mimics of these enzymes provide both simplified models of the catalysis reactions and potential artificial catalysts that might be used to facilitate a hydrogen economy. We have studied two diiron hydrogenase mimics, μ-pdt-[Fe(CO)] and μ-edt-[Fe(CO)] (pdt = propanedithiolate, edt = ethanedithiolate), in a series of alkane solvents and have observed significant ultrafast spectral dynamics using two-dimensional infrared (2D-IR) spectroscopy.

Molecular selectivity of brown carbon chromophores.

Complementary methods of high-resolution mass spectrometry and microspectroscopy were utilized for molecular analysis of secondary organic aerosol (SOA) generated from ozonolysis of two structural monoterpene isomers: D-limonene SOA (LSOA) and α-pinene SOA (PSOA). The LSOA compounds readily formed adducts with Na(+) under electrospray ionization conditions, with only a small fraction of compounds detected in the protonated form. In contrast, a significant fraction of PSOA compounds appeared in the protonated form because of their increased molecular rigidity.

Chemical analysis of complex organic mixtures using reactive nanospray desorption electrospray ionization mass spectrometry.

Reactive nanospray desorption electrospray ionization (nano-DESI) combined with high-resolution mass spectrometry was utilized for the analysis of secondary organic aerosol produced through ozonolysis of limonene (LSOA). Previous studies have shown that LSOA constituents are multifunctional compounds containing at least one aldehyde or ketone groups. In this study, we used the selectivity of the Girard's reagent T (GT) toward carbonyl compounds to examine the utility of reactive nano-DESI for the analysis of complex organic mixtures.

Chemical characterization of crude petroleum using nanospray desorption electrospray ionization coupled with high-resolution mass spectrometry.

Nanospray desorption electrospray ionization (nano-DESI) combined with high-resolution mass spectrometry was used for the first time for the analysis of the polar constituents of liquid petroleum crude oil samples. The analysis was performed in both positive and negative ionization modes using three solvents, one of which (acetonitrile/toluene mixture) is commonly used in petroleomics studies while two other polar solvents (acetonitrile/water and methanol/water mixtures) are generally not compatible with petroleum characterization using mass spectrometry. The results demonstrate that nano-DESI analysis efficiently ionizes petroleum constituents soluble in a particular solvent.