Prebiotic dimer and trimer peptide formation in gas-phase atmospheric nanoclusters of water.

Insight into the origin of prebiotic molecules is key to our understanding of how living systems evolved into the complex network of biological processes on Earth. By modelling diglycine and triglycine peptide formation in the prebiotic atmosphere, we provide a plausible pathway for peptide growth. By examining different transition states (TSs), we conclude that the formation of diglycine and triglycine in atmospheric nanoclusters of water in the prebiotic atmosphere kinetically favors peptide growth by an N-to-C synthesis of glycines through a trans conformation. Addition of water stabilizes the TS structures and lowers the Gibbs free activation energies. At temperatures that model the prebiotic atmosphere, the free energies of activation with a six water nanocluster as part of the TS are predicted to be 16 kcal mol-1 relative to the prereactive complex. Examination of the trans vs. cis six water transition states reveals that a homodromic water network that maximizes the acceptor/donor nature of the six waters is responsible for enhanced kinetic favorability of the trans N-to-C pathway. Compared to the non-hydrated trans TS, the trans six-water TS accelerates the reaction of diglycine and glycine to form triglycine by 13 orders of magnitude at 217 K. Nature uses the trans N-to-C pathway to synthesize proteins in the ribosome, and we note the similarities in hydrogen bond stabilization between the transition state for peptide synthesis in the ribosome and the transition states formed in nanoclusters of water in the same pathway. These results support the hypothesis that small oligomers formed in the prebiotic atmosphere and rained onto earth's surface.

Photochemistry and Photophysics of Charge-Transfer Excited States in Emissive d10/d0 Heterobimetallic Titanocene Tweezer Complexes.

Transition-metal complexes that undergo ligand-to-metal charge transfer (LMCT) to d0 metals are of interest as possible photocatalysts due to the lack of deactivating d-d states. Herein, the synthesis and characterization of nine titanocene complexes of the formula Cp2Ti(C2Ar)2·MX (where Ar = phenyl, dimethylaniline, or triphenylamine; and MX = CuCl, CuBr, or AgCl) are presented. Solid-state structural characterization demonstrates that MX coordinates to the alkyne tweezers and CuX coordination has a greater structural impact than AgCl. All complexes, including the parent complexes without coordinated MX, are brightly emissive at 77 K (emission max between 575 and 767 nm), with the coordination of MX redshifting the emission in all cases except for the coordination of AgCl into Cp2Ti(C2Ph)2. TDDFT investigations suggest that emission is dominated by arylalkynyl-to-titanium 3LMCT in all cases except Cp2Ti(C2Ph)2·CuBr, which is dominated by CuBr-to-Ti charge transfer. In room-temperature fluid solution, only Cp2Ti(C2Ph)2 and Cp2Ti(C2Ph)2·AgCl are emissive, albeit with photoluminescent quantum yields ≤2 × 10-4. The parent complexes photodecompose in room-temperature solution with quantum yields, Φrxn, between 0.25 and 0.99. The coordination of MX decreases Φrxn by two to three orders of magnitude. There is a clear trend that Φrxn increases as the emission energy increases. This trend is consistent with a competition between energy-gap-law controlled nonradiative decay and thermally activated intersystem crossing between the 3LMCT state and the singlet transition state for decomposition.

Hydrogen-Bond Topology Is More Important Than Acid/Base Strength in Atmospheric Prenucleation Clusters.

We explored the hypothesis that on the nanoscale level, acids and bases might exhibit different behavior than in bulk solution. Our study system consisted of sulfuric acid, formic acid, ammonia, and water. We calculated highly accurate Domain-based Local pair-Natural Orbital- Coupled-Cluster/Complete Basis Set (DLPNO-CCSD(T)/CBS) energies on DFT geometries and used the resulting Gibbs free energies for cluster formation to compute the overall equilibrium constants for every possible cluster. The equilibrium constants combined with the initial monomer concentrations were used to predict the formation of clusters at the top and the bottom of the troposphere. Our results show that formic acid is as effective as ammonia at forming clusters with sulfuric acid and water. The structure of formic acid is uniquely suited to form hydrogen bonds with sulfuric acid. Additionally, it can partner with water to form bridges from one side of sulfuric acid to the other, hence demonstrating that hydrogen bonding topology is more important than acid/base strength in these atmospheric prenucleation clusters.