Metal ion binding by humic substances as emergent functions of labile supramolecular assemblies
Bibliographic record
Abstract
Environmental context The fundamental basis for the high flexibility of humic substances is still unclear, though it is crucial for the understanding of metal bioavailability and toxicity in soil and aqueous environments. We show at the molecular level how characteristics of organic matter affect metal binding depending on the environmental conditions. Such understanding will help in the modulation of metal availability in soil and water in changing environmental situations. Abstract In this work, we explore the hypothesis that humic substances (HS) can be perceived as labile supramolecular assemblages, the functioning of which is mainly determined by chemical composition and characteristics, the size of molecular units and weak intermolecular forces, rather than the exact primary structure of molecular moieties and their spatial configuration. To test the hypothesis, 72 computational models of three different organic mixtures were composed. The formation of inner and outer sphere metal–ligand complexes, metal binding sites, complex configurations, binding energies and aggregation/dissolution as emergent properties of HS were determined under various conditions. The results of computational modelling revealed that: (i) the highest Cu2+ binding (55.6 %) was by the SRFA-22 organic model, which represents low-molecular-weight fulvic acids. In contrast, the highest amount of inner-sphere Mg–organic matter complex (63.4 %) was formed in SRHA-6, which has higher-molecular-weight constituents. Therefore, a correlation between the type of cation, the system aromaticity and the extent of metal complexation is proposed. (ii) Increase of metal ion concentration and decrease of water content resulted in an increase in the number of hydrogen bonds and more compact and stable aggregates with lower hydrophilic and higher hydrophobic surface areas in SRFA-22. However, in SRHA-6, the results varied owing to the competition between metal binding, H-bonding and non-polar interactions in the structural arrangement of the aggregates. In general, the aggregation process, driven by metal complexation and water removal, resulted in the formation of more stable conformers, with lower potential energy, with the only exception of SRHA-6–Cu.
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How this classification was reachedexpand
Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.030 | 0.001 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; both teacher heads agree on what is shown here.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".