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Results for “molecular evolution”

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At least 559 records · Page 31
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Aberrant light sensing and motility in the green alga Chlamydomonas priscuii from the ice-covered Antarctic Lake Bonney

The Antarctic green alga Chlamydomonas priscuii is an obligate psychrophile and an emerging model for photosynthetic adaptation to extreme conditions. Endemic to the ice-covered Lake Bonney, this alga thrives at highly unusual light conditions characterized by very low light irradiance (<15 μmol m -2 s -1 ), a narrow wavelength spectrum enriched in blue light, and an extreme photoperiod. Genome sequencing of C. priscuii exposed an unusually large genome, with hundreds of highly similar gene duplicates and expanded gene families, some of which could be aiding its survival in extreme conditions. In contrast to the described expansion in the genetic repertoire in C. priscuii, here we suggest that the gene family encoding for photoreceptors is reduced when compared to related green algae. This alga also possesses a very small eyespot and exhibits an aberrant phototactic response, compared to the model Chlamydomonas reinhardtii. We also investigated the genome and behavior of the closely related psychrophilic alga Chlamydomonas sp. ICE-MDV, that is found throughout the photic zone of Lake Bonney and is naturally exposed to higher light levels. Our analyses revealed a photoreceptor gene family and a robust phototactic response similar to those in the model Chlamydomonas reinhardtii. These results suggest that the aberrant phototactic response in C. priscuii is a result of life under extreme shading rather than a common feature of all psychrophilic algae. We discuss the implications of these results on the evolution and survival of shade adapted polar algae.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Cobalt(II) Phthalocyanine Substituents Tune the Electrocatalytic CO 2 Conversion to Methanol

Cobalt phthalocyanine (Co(II)Pc) and its derivatives are promising molecular electrocatalysts for the electrochemical reduction of CO 2 to CO and methanol (CH 3 OH). Despite increasing interest, a detailed mechanistic understanding of how ligand substituents influence catalytic activity, selectivity, and efficiency remains limited. In this study, we employ density functional theory (DFT) to systematically investigate the influence of electron-donating groups (EDGs) and electron-withdrawing groups (EWGs) on the electronic structure and redox properties of the Co(II)Pc electrocatalyst, and to elucidate CO 2 RR mechanistic pathways. Our results reveal that EWGs cause a positive shift in the reduction potentials, favor CO 2 binding over protonation of the Co metal center and promote downstream methanol formation at mild potentials. EDGs show opposite trends including favorable protonation steps, promoting a negative shift in the reduction potential, and facilitating the hydrogen evolution reaction (HER), which competes with the desired CO 2 RR pathway. Notably, CO dissociation is thermodynamically and kinetically unfavorable across all systems, positioning the redox potential versus CO dissociation energy as a key factor for methanol selectivity. Furthermore, these insights provide a predictive framework for rational catalyst design and underscore the critical role of electronic tuning in advancing molecular electrocatalysts for sustainable CO 2 conversion.

Alcohols↗
DOE OSTI2026

Probing the atomic dynamics of ultrafast melting with femtosecond electron diffraction

Melting is an every-day phase transition that is determined by thermodynamic parameters like temperature and pressure. In contrast, ultra-fast melting is governed by the microscopic response to a rapid energy input and, thus, can reveal the strength and dynamics of atomic bonds as well as the energy flow rate to the lattice. Accurately describing these processes remains challenging and requires detailed insights into transient states encountered. Here, we present data from femtosecond electron diffraction measurements that capture the structural evolution of copper during the ultrafast solid-to-liquid phase transformations. At absorbed energy densities 2-4 times the melting threshold, melting begins at the surface slightly below the nominal melting point followed by rapid homogeneous melting throughout the volume. Molecular dynamics simulations reproduce these observations and reveal a weak electron-lattice energy transfer rate for the given experimental conditions. Both simulations and experiments show no indications of rapid lattice collapse when its temperature surpasses proposed limits of superheating, providing evidence that the inherent dynamics limits the speed of disordering in ultrafast melting of metals.

FOS: Physical sciences↗
DOE OSTI2023

CO and [C ii] line emission of molecular clouds: the impact of stellar feedback and non-equilibrium chemistry

We analyse synthetic 12 CO, 13 CO, and [C ii] emission maps of molecular cloud (MC) simulations from the SILCC-Zoom project. We present radiation, magnetohydrodynamic zoom-in simulations of individual clouds, both with and without radiative stellar feedback, forming in a turbulent multiphase interstellar medium following on-the-fly the evolution of e.g. H 2 , CO, and C + . We introduce a novel post-processing routine based on cloudy which accounts for higher ionization states of carbon due to stellar radiation in H ii regions. Synthetic emission maps of [C ii] in and around feedback bubbles show that the bubbles are largely devoid of [C ii], as recently found in observations, which we attribute to the further ionization of C+ into C 2+ . For both 12 CO and 13 CO, the cloud-averaged luminosity ratio, $L_\rm {CO}/L_\rm {[C\, \small {II}]}$, can neither be used as a reliable measure of the H 2 mass fraction nor of the evolutionary stage of the clouds. We note a relation between the $I_\rm {CO}/I_\rm {[C\, \small {II}]}$ intensity ratio and the H 2 mass fraction for individual pixels of our synthetic maps. The scatter, however, is too large to reliably infer the H 2 mass fraction. Finally, the assumption of chemical equilibrium overestimates H2 and CO masses by up to 150 and 50 per cent, respectively, and $L_\rm {CO}$ by up to 60 per cent. The masses of H and C + would be underestimated by 65 and 30 per cent, respectively, and $L_\rm {[C\, \small {II}]}$ by up to 35 per cent. Hence, the assumption of chemical equilibrium in MC simulations introduces intrinsic errors of a factor of 2 in chemical abundances, luminosities, and luminosity ratios.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Tracking surface charge dynamics on single nanoparticles

Surface charges play a fundamental role in physics and chemistry, in particular in shaping the catalytic properties of nanomaterials. However, tracking nanoscale surface charge dynamics remains challenging due to the involved length and time scales. Here, we demonstrate time-resolved access to the nanoscale charge dynamics on dielectric nanoparticles using reaction nanoscopy. We present a four-dimensional visualization of the spatiotemporal evolution of the charge density on individual SiO 2 nanoparticles under strong-field irradiation with femtosecond-nanometer resolution. The initially localized surface charges exhibit a biexponential redistribution over time. Our findings reveal the influence of surface charges on surface molecular bonding through quantum dynamical simulations. We performed semi-classical simulations to uncover the roles of diffusion and charge loss in the surface charge redistribution process. Understanding nanoscale surface charge dynamics and its influence on chemical bonding on a single-nanoparticle level unlocks an increased ability to address global needs in renewable energy and advanced health care.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2024

Diverse signatures of convergent evolution in cactus-associated yeasts

Many distantly related organisms have convergently evolved traits and lifestyles that enable them to live in similar ecological environments. However, the extent of phenotypic convergence evolving through the same or distinct genetic trajectories remains an open question. Here, we leverage a comprehensive dataset of genomic and phenotypic data from 1,049 yeast species in the subphylum Saccharomycotina (Kingdom Fungi, Phylum Ascomycota) to explore signatures of convergent evolution in cactophilic yeasts, ecological specialists associated with cacti. We inferred that the ecological association of yeasts with cacti arose independently approximately 17 times. Using a machine learning–based approach, we further found that cactophily can be predicted with 76% accuracy from both functional genomic and phenotypic data. The most informative feature for predicting cactophily was thermotolerance, which we found to be likely associated with altered evolutionary rates of genes impacting the cell envelope in several cactophilic lineages. We also identified horizontal gene transfer and duplication events of plant cell wall–degrading enzymes in distantly related cactophilic clades, suggesting that putatively adaptive traits evolved independently through disparate molecular mechanisms. Notably, we found that multiple cactophilic species and their close relatives have been reported as emerging human opportunistic pathogens, suggesting that the cactophilic lifestyle—and perhaps more generally lifestyles favoring thermotolerance—might preadapt yeasts to cause human disease. This work underscores the potential of a multifaceted approach involving high-throughput genomic and phenotypic data to shed light onto ecological adaptation and highlights how convergent evolution to wild environments could facilitate the transition to human pathogenicity.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

Anion-dependent phase behavior of methylimidazolium-based ionic liquids mixed with water: Correlation between local molecular structure and mesoscale behaviors

The mesoscopic phase behavior of decylmethylimidazolium (C 10 mim) ionic liquids (ILs) bearing three monovalent anions—thiocyanate (SCN − ), nitrate (NO 3 − ), and chloride (Cl − )—mixed with water at relatively high IL contents (50–95 wt%) was investigated. Small-angle and wide-angle X-ray scattering (SAXS/WAXS) were employed to follow the evolution of both local and mesoscale structures across this composition range. In the absence of water, C 10 mimSCN and C 10 mimCl behaved as disordered liquids, whereas C 10 mimNO 3 spontaneously formed a hexagonally ordered cylindrical mesophase and displayed a sticky-solid macroscopic appearance. Upon addition of water, C 10 mimSCN remained a viscous liquid and only weakly ordered lamellar domains were observed. This limited ordering is attributed to the lack of hydrogen bonding and weak interaction energy between SCN − anions and C 10 mim + cations. In contrast, the trigonal-planar NO 3 − and point-like Cl − anions promoted the formation of well-defined hexagonal mesophases up to 35–45 wt% water. The formation of hydrogen bonding of the two anions with imidazolium ring protons likely enabled the creation of compact ion clusters that effectively exclude water molecules from the immediate vicinity of the IL aggregates. These findings demonstrate that the interaction energy between ion pairs dictate IL-water interactions and therefore control the transition from disordered liquids to ordered mesophases in IL/water mixtures with high IL contents. In conclusion, the combined SAXS/WAXS analysis reveals a correlation between local intermolecular structure and the emergence of mesoscopic order, providing a systematic framework for tailoring mesoscale structures in alkylimidazolium-based IL/water systems.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Electron shuttle in the MOF derived TiO 2 /CuO heterojunction boosts light driven hydrogen evolution

Metal organic frameworks (MOFs) have emerged as a novel template to develop porous photocatalytic materials for solar fuel conversion. In this work, we report the synthesis, charge separation dynamics, and photocatalytic performance of the TiO 2 /CuO heterostructure derived from mixed-phase MOFs based on Ti and Cu metal nodes, which demonstrates significantly enhanced catalytic activity for the hydrogen evolution reaction (HER) compared to metal oxides derived from single node MOFs. More importantly, using transient absorption spectroscopy, we identified the specific role each component in the heterostructure plays and unravelled the key intermediate species that is responsible for the exceptional photocatalytic activity of the heterostructure. We found that the HER is initiated with ultrafast electron transfer (<150 fs) from the molecular photosensitizer to the conduction band of TiO 2 , where TiO 2 acts as an electron mediator and shuttles the electron to the CuO cocatalyst, facilitating charge separation and ultimately boosting the HER efficiency. Overall, these results not only demonstrate the great potential of using mixed-phase MOFs as templates to synthesize mesoporous heterostructure photocatalysts but also provide important insight into the HER mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Effects of processing temperature, pressure, and fiber volume fraction on mechanical and morphological behaviors of fully-recyclable uni-directional thermoplastic polymer-fiber-reinforced polymers

This work explores a type of composite called thermoplastic polymer-fiber-reinforced polymers (PFRPs), often referred to as self-reinforced composites (SRCs). A representative PFRP was exemplified using unidirectional (UD) ultra-high-molecular-weight polyethylene (UHMWPE) fibers embedded in a high-density polyethylene (HDPE) matrix. The effects of compression molding temperature and pressure on the mechanical and morphological behaviors of the filament-wound PFRPs with various fiber volume fractions (V f ) were experimentally investigated. The results elucidate the evolution of morphologies and tensile properties of the PFRPs due to thermal melting, fiber misalignment from pressure, and (V f )-induced structural variance, which has not been comprehensively reported yet. The highest specific tensile strength and modulus of the PFRP laminae reach 600 MPa/(g/cm 3 ) and 31 GPa/(g/cm 3 ), respectively. These properties are comparable to glass-/aramid-fiber-reinforced polymers (GFRPs, GFRTPs, AFRPs, and AFRTPs), with PFRPs exhibiting better ductility (specific strain at peak load ≈ 4%/(g/cm 3 )) than other common polymer composites. The motivation for this work was the high recyclability of PFRPs, which can be recycled by melting both the fibers and the matrix, and then reshaped them for re-manufacturing composites to maximize the efficiency in material reuse. This process simplifies the implementation of closed-loop recycling, re-manufacturing, and reuse to support sustainability in composites. This work aims to contribute to advancing thermoplastic PFRPs for their potential applications in various industries.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Molecular bond stabilization in the strong-field dissociation of O 2 +

We theoretically examine the rotational and vibrational dynamics of O 2 + molecular ions exposed to intense, short laser pulses for conditions realized in contemporary pump-probe experiments. We solve the time-dependent Schrödinger equation within the Born-Oppenheimer approximation for an initial distribution of randomly aligned molecular ions. For fixed peak intensities, our numerical results show that total, angle-integrated O 2 + → O( 3 P) + O + ( 4 S 0 ) dissociation yields do not monotonically increase with increasing infrared-probe pulse duration. We find this pulse-duration-dependent stabilization to be consistent with the transient trapping of nuclear probability density in a light-induced (bond-hardening) potential-energy surface and robust against rotational excitation. We analyze this stabilization effect and its underlying bond-hardening mechanism (i) in the time domain, by following the evolution of partial nuclear probability densities associated with the dipole-coupled O 2 + (a 4 Π u ) and O 2 + (f 4 Π g ) cationic states, and (ii) in the frequency domain, by examining rovibrational quantum-beat spectra for the evolution of the partial nuclear probability densities associated with these states. In this work, our analysis reveals the characteristic timescale for the bond-hardening mechanism in O 2 + and explains the onset of bond stabilization for sufficiently long pulse durations.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

Structure/property relationship of semicrystalline polymers during tensile deformation: a molecular dynamics approach

Molecular dynamics (MD) simulation with an ab initio numerical model is conducted to study the structure–property relationship of semicrystalline polymers during uniaxial deformation. The effects of chain length, temperature, and strain rate on mechanical properties are discussed. The influences of microstructural evolution such as bond length, entanglement density, and chain orientation are also studied quantitatively. The temperature will greatly affect the chain conformation in amorphous domains, and the results revealed that the interaction of amorphous and crystalline domains played a crucial role during stretching. Accordingly, the yielding of semicrystalline polymers follows different mechanisms at temperatures above and below T g . A melt-recrystallization scheme is observed during yielding at higher temperatures, while destruction of crystal structures is observed at lower temperatures at the yield point. The correlated effects of different temperatures and strain rates on mechanical properties are examined. This research is part of our efforts to develop a digital twin of a real experiment for efficient optimization of polymer material properties.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Biomimetic Metal-Free Hydride Donor Catalysts for CO 2 Reduction

The catalytic reduction of carbon dioxide to fuels and value-added chemicals is of significance for the development of carbon recycling technologies. One of the main challenges associated with catalytic CO 2 reduction is product selectivity: the formation of carbon monoxide, molecular hydrogen, formate, methanol, and other products occurs with similar thermodynamic driving forces, making it difficult to selectively reduce CO 2 to the target product. Significant scientific effort has been aimed at the development of catalysts that can suppress the undesired hydrogen evolution reaction and direct the reaction toward the selective formation of the desired products, which are easy to handle and store. Inspired by natural photosynthesis, where the CO 2 reduction is achieved using NADPH cofactors in the Calvin cycle, in this study we explore biomimetic metal-free hydride donors as catalysts for the selective reduction of CO 2 to formate. Here, we outline our recent findings on the thermodynamic and kinetic parameters that control the hydride transfer from metal-free hydrides to CO 2 . By experimentally measuring and theoretically calculating the thermodynamic hydricities of a range of metal-free hydride donors, we derive structural and electronic factors that affect their hydride-donating abilities. Two dominant factors that contribute to the stronger hydride donors are identified to be (i) the stabilization of the positive charge formed upon HT via aromatization or by the presence of electron-donating groups and (ii) the destabilization of hydride donors through the anomeric effect or in the presence of significant structural constrains in the hydride molecule. Hydride donors with appropriate thermodynamic hydricities were reacted with CO 2 , and the formation of the formate ion (the first reduction step in CO 2 reduction to methanol) was confirmed experimentally, providing an important proof of principle that organocatalytic CO 2 reduction is feasible. The kinetics of hydride transfer to CO 2 were found to be slow, and the sluggish kinetics were assigned in part to the large self-exchange reorganization energy associated with the organic hydrides in the DMSO solvent. Finally, we outline our approaches to the closure of the catalytic cycle via the electrochemical and photochemical regeneration of the hydride (R–H) from the conjugate hydride acceptors (R + ). We illustrate how proton-coupled electron transfer can be efficiently utilized not only to lower the electrochemical potential at which the hydride regeneration takes place but also to suppress the unwanted dimerization that neutral radical intermediates tend to undergo. Overall, this account provides a summary of important milestones achieved in organocatalytic CO 2 reduction and provides insights into the future research directions needed for the discovery of inexpensive catalysts for carbon recycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Insights into the Reactivity of Brookite TiO 2 Nanorods in Liquid Water from Ab Initio Molecular Dynamics Simulations

Brookite TiO 2 , a rare natural polymorph of TiO 2 , has been reported to be an excellent photocatalyst for the production of hydrogen from water and aqueous alcohol solutions, especially when it is reduced and synthesized in the form of nanorods. Here, we investigate the reactivity of stoichiometric and reduced brookite nanorods in liquid water using ab initio molecular dynamics and hybrid density functional theory calculations. Our simulations show a much higher water dissociation fraction on reduced nanorods than on stoichiometric ones, with an accumulation of the resulting bridging hydroxyls (O br H) and terminal hydroxyls (Ti –OH) on different facets of the nanorod. ObrH groups accumulate preferentially on low-energy (210) facets, where they are stabilized by adjacent reduced Ti (Ti 3+ ) sites, while Ti –OH groups prefer to form at the four-fold coordinated Ti atoms on high-energy (010) facets. This hydroxylation pattern also favors the spatial localization of excited holes on the (010) facets. This coupling between water-induced surface chemistry and charge separation underpins the enhanced photocatalytic activity of brookite nanorods, providing useful information for the design of more efficient TiO2-based nanostructures for solar-driven hydrogen evolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Platinum Surface Water Orientation Dictates Hydrogen Evolution Reaction Kinetics in Alkaline Media

The fundamental understanding of sluggish hydrogen evolution reaction (HER) kinetics on a platinum (Pt) surface in alkaline media is a topic of considerable debate. Herein, we combine cyclic voltammetry (CV) and electrical transport spectroscopy (ETS) approaches to probe the Pt surface at different pH values and develop molecular-level insights into the pH-dependent HER kinetics in alkaline media. The change in HER Tafel slope from ~110 mV/decade in pH 7–10 to ~53 mV/decade in pH 11–13 suggests considerably enhanced kinetics at higher pH. The ETS studies reveal a similar pH-dependent switch in the ETS conductance signal at around pH 10, suggesting a notable change of surface adsorbates. Fixed-potential calculations and chemical bonding analysis suggest that this switch is attributed to a change in interfacial water orientation, shifting from primarily an O-down configuration below pH 10 to a H-down configuration above pH 10. This reorientation weakens the O–H bond in the interfacial water molecules and modifies the reaction pathway, leading to considerably accelerated HER kinetics at higher pH. Finally, our integrated studies provide an unprecedented molecular-level understanding of the nontrivial pH-dependent HER kinetics in alkaline media.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Irradiation-induced grain boundary facet motion: In situ observations and atomic-scale mechanisms

Metals subjected to irradiation environments undergo microstructural evolution and concomitant degradation, yet the nanoscale mechanisms for such evolution remain elusive. Here, we combine in situ heavy ion irradiation, atomic resolution microscopy, and atomistic simulation to elucidate how radiation damage and interfacial defects interplay to control grain boundary (GB) motion. While classical notions of boundary evolution under irradiation rest on simple ideas of curvature-driven motion, the reality is far more complex. Focusing on an ion-irradiated Pt Σ3 GB, we show how this boundary evolves by the motion of 120° facet junctions separating nanoscale {112} facets. Our analysis considers the short- and mid-range ion interactions, which roughen the facets and induce local motion, and longer-range interactions associated with interfacial disconnections, which accommodate the intergranular misorientation. We suggest how climb of these disconnections could drive coordinated facet junction motion. These findings emphasize that both local and longer-range, collective interactions are important to understanding irradiation-induced interfacial evolution.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Conservation of endo -glucanase 16 (EG16) activity across highly divergent plant lineages

Plant cell walls are highly dynamic structures that are composed predominately of polysaccharides. As such, endogenous carbohydrate active enzymes (CAZymes) are central to the synthesis and subsequent modification of plant cells during morphogenesis. The endo-glucanase 16 (EG16) members constitute a distinct group of plant CAZymes, angiosperm orthologs of which were recently shown to have dual β-glucan/xyloglucan hydrolase activity. Molecular phylogeny indicates that EG16 members comprise a sister clade with a deep evolutionary relationship to the widely studied apoplastic xyloglucan endo-transglycosylases/hydrolases (XTH). A cross-genome survey indicated that EG16 members occur as a single ortholog across species and are widespread in early diverging plants, including the non-vascular bryophytes, for which functional data were previously lacking. Remarkably, enzymological characterization of an EG16 ortholog from the model moss Physcomitrella patens (PpEG16) revealed that EG16 activity and sequence/structure are highly conserved across 500 million years of plant evolution, vis-à-vis orthologs from grapevine and poplar. Ex vivo biomechanical assays demonstrated that the application of EG16 gene products caused abrupt breakage of etiolated hypocotyls rather than slow extension, thereby indicating a mode-of-action distinct from endogenous expansins and microbial endo-glucanases. As a result, the biochemical data presented here will inform future genomic, genetic, and physiological studies of EG16 enzymes.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Radiation-induced vacancy injection in heterogeneous multiphase materials

Understanding the synergy between corrosion and defect dynamics is a key consideration in the development of advanced materials for extreme environments. Here, we reveal a surprising phenomenon for the transport of point defects induced by irradiation in a heterogeneous multiphase structure of a metal and an oxide, similar to that formed under metal corrosion that takes place in most environments. Despite the confinement of the produced damage within the oxide, vacancies were injected into the unirradiated metal and coarsened with dose. Furthermore, the results show that the nature of the oxide layer dictates the defect evolution in the metal layer. This work reveals an interesting mechanism for point defect interactions in multiphase materials, with broad implications in many fields, while also emphasizing the complex coupling between corrosion and irradiation. Corrosion leads to the formation of multiphase materials, while irradiation enhances diffusion within the heterogeneous phases, which can impact corrosion rates.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Understanding Metal–Organic Framework Nucleation from a Solution with Evolving Graphs

A mechanistic understanding of metal–organic framework (MOF) synthesis and scale-up remains underexplored due to the complex nature of the interactions of their building blocks. In this work, we investigate the collective assembly of building units at the early stages of MOF nucleation, using MIL-101(Cr) as a prototypical example. Using large-scale molecular dynamics simulations, we observe that the choice of solvent (water and N,N-dimethylformamide), the introduction of ions (Na+ and F–) and the relative populations of MIL-101(Cr) half-secondary building unit (half-SBU) isomers have a strong influence on the cluster formation process. Additionally, the shape, size, nucleation and growth rates, crystallinity, and short and long-range order largely vary depending on the synthesis conditions. We evaluate these properties as they naturally emerge when interpreting the self-assembly of MOF nuclei as the time evolution of an undirected graph. Solution-induced conformational complexity and ionic concentration have a dramatic effect on the morphology of clusters emerging during assembly. While pure solvents lead to the rapid formation of a small number of large clusters, the presence of ions in aqueous solutions results in smaller clusters and slower nucleation. This diversity is captured by the key features of the graph representation. Principle component analysis on graph properties reveals that only a small number of molecular descriptors is needed to deconvolute MOF self-assembly. Furthermore, descriptors such as the average coordination number between half-SBUs and fractal dimension are of particular interest as they can be can be followed experimentally by techniques like by time-resolved spectroscopy. Ultimately, graph theory emerges as an approach that can be used to understand complex processes revealing molecular descriptors accessible by both simulation and experiment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗