Publications

Absorption of ultraviolet (UV) radiation can trigger a variety of photophysical and photochemical reactions in nucleic acids. In the prebiotic era, on the surface of the early Earth, UV light could have played a major role in the selection of the building blocks of life via a balance between synthetic and destructive pathways. As nucleic acid monomers assembled into polymers, their survival and facility for non-enzymatic replication hinged on their photostability and the ability for self-repair of lesions, e. g., by UV-induced charge transfer. Such photoprocesses are known to be sequence-dependent and could have led to an additional prebiotic selection of the genetic sequence pools available to the earliest life forms. This review summarizes the photophysical processes in nucleic acids upon the absorption of a UV photon and their implications for chemical and genetic selection at the emergence of life and the origin of translation.

Ultraviolet (UV) light plays a key role in surficial theories of the origin of life, and numerous studies have focused on constraining the atmospheric transmission of UV radiation on early Earth. However, the UV transmission of the natural waters in which origins-of-life chemistry (prebiotic chemistry) is postulated to have occurred is poorly constrained. In this work, we combine laboratory and literature-derived absorption spectra of potential aqueous-phase prebiotic UV absorbers with literature estimates of their concentrations on early Earth to constrain the prebiotic UV environment in marine and terrestrial natural waters, and we consider the implications for prebiotic chemistry. We find that prebiotic freshwaters were largely transparent in the UV, contrary to assumptions in some models of prebiotic chemistry. Some waters, such as high-salinity waters like carbonate lakes, may be deficient in shortwave (≤220 nm) UV flux. More dramatically, ferrous waters can be strongly UV-shielded, particularly if the Fe²⁺ forms highly UV-absorbent species such as . Such waters may be compelling venues for UV-averse origin-of-life scenarios but are unfavorable for some UV-dependent prebiotic chemistries. UV light can trigger photochemistry even if attenuated through photochemical transformations of the absorber (e.g.,  production from halide irradiation), which may have both constructive and destructive effects for prebiotic syntheses. Prebiotic chemistries that invoke waters that contain such absorbers must self-consistently account for the chemical effects of these transformations. The speciation and abundance of Fe²⁺ in natural waters on early Earth is a major uncertainty and should be prioritized for further investigation, as it played a major role in UV transmission in prebiotic natural waters.

Substitution of exocyclic oxygen with sulfur was shown to substantially influence the properties of RNA/DNA bases, which are crucial for prebiotic chemistry and photodynamic therapies. Upon UV irradiation, thionucleobases were shown to efficiently populate triplet excited states and can be involved in characteristic photochemistry or generation of singlet oxygen. Here, we show that the photochemistry of a thionucleobase can be considerably modified in a nucleoside, that is, by the presence of ribose. Our transient absorption spectroscopy experiments demonstrate that thiocytosine exhibits 5 times longer excited-state lifetime and different excited-state absorption features than thiocytidine. On the basis of accurate quantum chemical simulations, we assign these differences to the dominant population of a shorter-lived triplet nπ* state in the nucleoside and longer-lived triplet ππ* states in the nucleobase. This explains the distinctive photoanomerziation of thiocytidine and indicates that the nucleoside will be a less efficient phototherapeutic agent with regard to singlet oxygen generation.

Radial velocity (RV) searches for Earth-mass exoplanets in the habitable zone around Sun-like stars are limited by the effects of stellar variability on the host star. In particular, suppression of convective blueshift and brightness inhomogeneities due to photospheric faculae/plage and starspots are the dominant contribution to the variability of such stellar RVs. Gaussian process (GP) regression is a powerful tool for statistically modeling these quasi-periodic variations. We investigate the limits of this technique using 800 days of RVs from the solar telescope on the High Accuracy Radial velocity Planet Searcher for the Northern hemisphere (HARPS-N) spectrograph. These data provide a well-sampled time series of stellar RV variations. Into this data set, we inject Keplerian signals with periods between 100 and 500 days and amplitudes between 0.6 and 2.4 m s^-1. We use GP regression to fit the resulting RVs and determine the statistical significance of recovered periods and amplitudes. We then generate synthetic RVs with the same covariance properties as the solar data to determine a lower bound on the observational baseline necessary to detect low-mass planets in Venus-like orbits around a Sun-like star. Our simulations show that discovering planets with a larger mass (∼0.5 m s^-1) using current-generation spectrographs and GP regression will require more than 12 yr of densely sampled RV observations. Furthermore, even with a perfect model of stellar variability, discovering a true exo-Venus (∼0.1 m s^-1) with current instruments would take over 15 yr. Therefore, next-generation spectrographs and better models of stellar variability are required for detection of such planets.

The seven planets orbiting TRAPPIST-1 in a compact near-resonant chain offer a unique case to study in planet formation theory. We demonstrate in this paper that the remarkable flatness of the system, exceeding that of any other known planetary system, is an important constraint on the mass of the gaseous disk in which it formed and attained its current configuration. We use three-dimensional hydrodynamic simulations of the gas and planets to study specific formation models. In particular, we report simulations motivated by the model proposed by Ormel et al.—in this model, the dispersal of the gas disk pushes the planets from an initial resonant chain into their present configuration. We find that a disk with the mass used in this model is consistent with the flatness of the TRAPPIST-1 system, but a more massive disk is not, with the transition occurring between 15 and 50 times the mass of the Ormel et al. disk. This upper limit on mass rules out certain models of the formation of the system, namely in situ formation and disk migration on long timescales.

Based on HARPS-N radial velocities (RVs) and TESS photometry, we present a full characterization of the planetary system orbiting the late G dwarf TOI-561. After the identification of three transiting candidates by TESS, we discovered two additional external planets from RV analysis. RVs cannot confirm the outer TESS transiting candidate, which would also make the system dynamically unstable. We demonstrate that the two transits initially associated with this candidate are instead due to single transits of the two planets discovered using RVs. The four planets orbiting TOI-561 include an ultra-short period (USP) super-Earth (TOI-561 b) with period P_b = 0.45 d, mass M_b = 1.59 ± 0.36 M_⊕ and radius R_b = 1.42 ± 0.07 R_⊕, and three mini-Neptunes: TOI-561 c, with P_c = 10.78 d, M_c = 5.40 ± 0.98 M_⊕, R_c = 2.88 ± 0.09 R_⊕; TOI-561 d, with P_d = 25.6 d, M_d = 11.9 ± 1.3 M_⊕, R_d = 2.53 ± 0.13 R_⊕; and TOI-561 e, with P_e = 77.2 d, M_e = 16.0 ± 2.3 M_⊕, R_e = 2.67 ± 0.11 R_⊕. Having a density of 3.0 ± 0.8 g cm^-3, TOI-561 b is the lowest density USP planet known to date. Our N-body simulations confirm the stability of the system and predict a strong, anti-correlated, long-term transit time variation signal between planets d and e. The unusual density of the inner super-Earth and the dynamical interactions between the outer planets make TOI-561 an interesting follow-up target.

UV light has been invoked as a source of energy for driving prebiotic chemistry, but such high energy photons are also known to cause damage to biomolecules and their precursors. One potential mechanism for increasing the lifetime of UV-photounstable molecules is to invoke a protection or shielding mechanism. UV shielding could either occur by the molecule in question itself (self-shielding) or by the presence of other UV-absorbing molecules. We investigate and illustrate these two shielding mechanisms as means of increasing the lifetime of 2-aminooxazole (AO), a prebiotic precursor molecule moderately susceptible to UV photodamage, with an expected half-life of 7 h on the surface of the early Earth. AO can be protected by being present in high concentrations, such that it self-shields. AO can similarly be protected by the presence of UV-absorbing nucleosides; the degree of protection depends on the concentration and identity of the nucleoside. The purine nucleosides (A, G, and I) confer more protection than the pyrimidines (C and U). We find that 0.1 mM purine ribonucleosides affords AO about the same protection as 1 mM AO self-shielding, corresponding to a lifetime enhancement of 2–3×. This suggests that only a modest yield of nucleosides can potentially allow for protection of UV photounstable molecules, and therefore this could be a plausible mechanism for protecting sensitive molecules while prebiotic synthesis is occurring simultaneously. Our findings suggest that both synthetic and degradative reactions can proceed at the same time, given various degrees of shielding.

Carbon dioxide (CO₂) is the major carbonaceous component of many planetary atmospheres, which includes the Earth throughout its history. Carbon fixation chemistry—which reduces CO₂ to organics, utilizing hydrogen as the stoichiometric reductant—usually requires high pressures and temperatures, and the yields of products of potential use to nascent biology are low. Here we demonstrate an efficient ultraviolet photoredox chemistry between CO₂ and sulfite that generates organics and sulfate. The chemistry is initiated by electron photodetachment from sulfite to give sulfite radicals and hydrated electrons, which reduce CO₂ to its radical anion. A network of reactions that generates citrate, malate, succinate and tartrate by irradiation of glycolate in the presence of sulfite was also revealed. The simplicity of this carboxysulfitic chemistry and the widespread occurrence and abundance of its feedstocks suggest that it could have readily taken place on the surfaces of rocky planets. The availability of the carboxylate products on early Earth could have driven the development of central carbon metabolism before the advent of biological CO₂ fixation.

Delivery of water and organics by asteroid and comet impacts may have influenced prebiotic chemistry on the early Earth. Some recent prebiotic chemistry experiments emphasize hydrogen cyanide (HCN) as a feedstock molecule for the formation of sugars, ribonucleotides, amino acids, and lipid precursors. Here, we assess how much HCN originally contained in a comet would survive impact, using parametric temperature and pressure profiles together with a time-dependent chemistry model. We find that HCN survival mainly depends on whether the impact is hot enough to thermally decompose H₂O into reactive radicals, and HCN is therefore rather insensitive to the details of the chemistry. In the most favorable impacts (low impact angle, low velocity, small radius), this temperature threshold is not reached, and intact delivery of HCN is possible. We estimate the global delivery of HCN during a period of Early and Late Heavy Bombardment of the early Earth, as well as local HCN concentrations achieved by individual impacts. In the latter case, comet impacts can provide prebiotically interesting HCN levels for thousands to millions of years, depending on properties of the impactor and of the local environment.

A previously proposed synthesis of pyrimidine ribonucleotides makes use of ultraviolet (UV) light to convert β-uc(d)-ribocytidine-2',3'-cyclic phosphate to β-uc(d)-ribouridine-2',3'-cyclic phosphate, while simultaneously selectively degrading synthetic byproducts. Past studies of the photochemical reactions of pyrimidines have employed mercury arc lamps, characterized by narrowband emission centered at 254 nm, which is not representative of the UV environment of the early Earth. To further assess this process under more realistic circumstances, we investigated the wavelength dependence of the UV-driven conversion of β-uc(d)-ribocytidine-2',3'-cyclic phosphate to β-uc(d)-ribouridine-2',3'-cyclic phosphate. We used constraints provided by planetary environments to assess the implications for pyrimidine nucleotides on the early Earth. We found that the wavelengths of light (255-285 nm) that most efficiently drive the deamination of β-uc(d)-ribocytidine-2',3'-cyclic phosphate to β-uc(d)-ribouridine-2',3'-cyclic phosphate are accessible on planetary surfaces such as those of the Hadean-Archaean Earth for CO₂-N₂-dominated atmospheres. However, continued irradiation could eventually lead to low levels of ribocytidine in a low-temperature, highly irradiated environment, if production rates are slow.

Charge transfer has proven to be an important mechanism in DNA photochemistry. In particular, guanine (dG) plays a major role as an electron donor, but the photophysical dynamics of dG‐containing charge‐transfer states have not been extensively investigated so far. Here, we use UV pump (266 nm) and picosecond IR probe (∼5–7 μm) spectroscopy to study ultrafast dynamics in dG‐containing short oligonucleotides as a function of sequence and length. For the pure purine oligomers, we observed lifetimes for the charge‐transfer states of the order of several hundreds of picoseconds, regardless of the oligonucleotide length. In contrast, pyrimidine‐containing dinucleotides d(GT) and d(GC) show much faster relaxation dynamics in the 10 to 30 ps range. In all studied nucleotides, the charge‐transfer states are formed with an efficiency of the order of ∼50 %. These photophysical characteristics will lead to an improved understanding of DNA damage and repair processes.

We advocate an integrative approach between laboratory experiments in prebiotic chemistry and geologic, geochemical, and astrophysical observations to help assemble a robust chemical pathway to life that can be reproduced in the laboratory. The cyanosulfidic chemistry scenario described here was developed by such an integrative iterative process. We discuss how it maps onto evolving planetary surface environments on early Earth and Mars and the value of comparative planetary evolution. The results indicate that Mars can offer direct evidence for geochemical conditions similar to prebiotic Earth, whose early record has been erased. The Jezero crater is now the chosen landing site for NASA’s Mars 2020 rover, making this an extraordinary opportunity for a breakthrough in understanding life’s origins.

Three related molecules in the 2-aminoazole family are potentially important for prebiotic chemistry: 2-aminooxazole, 2-aminoimidazole, and 2-aminothiazole, which can provide critical functions as an intermediate in nucleotide synthesis, a nucleotide activating agent, and a selective agent, respectively. Here, we examine the wavelength-dependent photodegradation of these three molecules under mid-range UV light (210–290 nm). We then assess the implications of the observed degradation rates for the proposed prebiotic roles of these compounds. We find that all three 2-aminoazoles degrade under UV light, with half lives ranging from ≈7–100 hours under a solar-like spectrum. 2-Aminooxazole is the least photostable, while 2-aminoimidazole is the most photostable. The relative photostabilities are consistent with the order in which these molecules would be used prebiotically: AO is used first to build nucleotides and AI is used last to activate them.

Measures of exoplanet bulk densities indicate that small exoplanets with radius less than 3 Earth radii (R_⊕) range from low-density sub-Neptunes containing volatile elements¹ to higher-density rocky planets with Earth-like² or iron-rich³ (Mercury-like) compositions. Such astonishing diversity in observed small exoplanet compositions may be the product of different initial conditions of the planet-formation process or different evolutionary paths that altered the planetary properties after formation⁴. Planet evolution may be especially affected by either photoevaporative mass loss induced by high stellar X-ray and extreme ultraviolet (XUV) flux⁵ or giant impacts⁶. Although there is some evidence for the former^7,8, there are no unambiguous findings so far about the occurrence of giant impacts in an exoplanet system. Here, we characterize the two innermost planets of the compact and near-resonant system Kepler-107 (ref. ⁹). We show that they have nearly identical radii (about 1.5–1.6R_⊕), but the outer planet Kepler-107 c is more than twice as dense (about 12.6 g cm^–3) as the innermost Kepler-107 b (about 5.3 g cm⁻³). In consequence, Kepler-107 c must have a larger iron core fraction than Kepler-107 b. This imbalance cannot be explained by the stellar XUV irradiation, which would conversely make the more-irradiated and less-massive planet Kepler-107 b denser than Kepler-107 c. Instead, the dissimilar densities are consistent with a giant impact event on Kepler-107 c that would have stripped off part of its silicate mantle. This hypothesis is supported by theoretical predictions from collisional mantle stripping¹⁰, which match the mass and radius of Kepler-107 c.

The radii and orbital periods of 4,000+ confirmed/candidate exoplanets have been precisely measured by the Kepler mission. The radii show a bimodal distribution, with two peaks corresponding to smaller planets (likely rocky) and larger intermediate-size planets, respectively. While only the masses of the planets orbiting the brightest stars can be determined by ground-based spectroscopic observations, these observations allow calculation of their average densities placing constraints on the bulk compositions and internal structures. However, an important question about the composition of planets ranging from 2 to 4 Earth radii (R_⊕) still remains. They may either have a rocky core enveloped in a H₂–He gaseous envelope (gas dwarfs) or contain a significant amount of multicomponent, H₂O-dominated ices/fluids (water worlds). Planets in the mass range of 10–15 M_⊕, if half-ice and half-rock by mass, have radii of 2.5 R_⊕, which exactly match the second peak of the exoplanet radius bimodal distribution. Any planet in the 2- to 4-R_⊕ range requires a gas envelope of at most a few mass percentage points, regardless of the core composition. To resolve the ambiguity of internal compositions, we use a growth model and conduct Monte Carlo simulations to demonstrate that many intermediate-size planets are “water worlds.”