The original Miller-Urey experiment demonstrated the abiotic synthesis of organic compounds under early Earth conditions, yet the physicochemical properties and internal organization of the associated insoluble solid organic films (SOFs) remain poorly constrained. Here we present a spatially resolved characterization of SOFs formed in prebiotic discharge experiments, focusing on their chemical heterogeneity, structural organization, and role in the emergence of hollow organic biomorphs. Using a combination of electron microscopy and spectroscopic techniques, we show that the insoluble SOF is a continuous but chemically heterogeneous matrix whose molecular composition varies systematically across the reactor as a function of local gas-liquid-solid interactions. Distinct regions of the SOF are enriched in aliphatic amine-rich polymers, aromatic carbon domains, cyanide-derived intermediates, and amorphous carbon, indicating that hydrogen cyanide (HCN)-derived chemistry evolves differently within specific microenvironments rather than proceeding uniformly throughout the system. We further demonstrate that spherical, caterpillar-like, and polyp-like hollow biomorphs preferentially emerge at hydrated interfacial regions of the SOF, thereby directly linking their morphogenesis to spatial chemical heterogeneity and phase-boundary chemistry in spark-driven systems. The SOF's capacity to shield chemically fragile solutes and emerging biopolymers through near-ultraviolet chromophore absorption, combined with its abiotic compartmentalization properties, suggests a potentially important role in abiogenesis.

Plants can exhibit phosphorus luxury uptake, absorbing several-fold more P than required under P-sufficient conditions. Harnessing this underutilized capacity helps to overcome substrate adsorption saturation and improve the phosphorus removal efficiency and sustainability of subsurface flow constructed wetlands (SFCWs). Here, we engineered a dense, fiber filter-like mat-structured root system to replace conventional inert substrates and systematically investigated its P removal performance, mechanisms, and engineering feasibility. From late spring to early winter, the root-mat system more than halved the effluent P compared with a conventional SFCW despite operating at an eight-fold hydraulic loading. Root-exudated aliphatic and carboxylic compounds scavenged the root-surface hydroxyl radicals, protecting the significantly more exudated histidine and lysine from being degraded. During the daytime, these amino acids coordinated with Fe3O4 and FeOOH in root-surface iron plaque via Fe(III)-COOH bonding, and their protonation formed a positively charged coating that increased P accumulation capacity by 77.8% through electrostatic attraction. The coordination enhanced the electron-transfer capacity of Fe by 62.9%, and increased nighttime Fe(III) reduction by 75%. The cleavage of Fe(III)-COOH released coordinated lysine and histidine, and their subsequent degradation at the iron plaque-water interface released electrostatically bound P, substantially elevating root-surface P supply and triggering plant luxury uptake. This pathway accounted for 91.2% of total P removal, with microorganisms assimilating the remainder. The root mat increased auxin and cytokinin synthesis, rebalanced their root-shoot allocation, and facilitated the growth of P storage sites. At the pilot scale, the root-mat system outperformed conventional SFCWs under 67% higher hydraulic loading, and seasonal stability can be improved using cold-hardy plants. Overall, these results advanced the current understanding and provide a scalable substrate-independent strategy that leverages plant luxury uptake to achieve efficient, economical, and sustainable P removal in SFCWs.

Biomass burning produces extensive pyrogenic dissolved organic matter (PyDOM), but the differences in compositions and photoactivities between PyDOM from char residues and smoke aerosols (referred to as PyDOMchar and PyDOMaerosol) remain poorly understood. Here, we systematically compared the composition and photoactivity of PyDOMchar and PyDOMaerosol coproduced by open-air burning of rice straw. At the bulk level, PyDOMaerosol exhibited lower ultraviolet-visible absorption but higher fluorescence intensity than PyDOMchar. Additionally, PyDOMaerosol had a lower weight-averaged molecular weight (1940 Da) than PyDOMchar (2601 Da). At the molecular level, 3594 and 2734 molecular formulae were identified for PyDOMaerosol and PyDOMchar, indicating greater chemical diversity of PyDOMaerosol. PyDOMaerosol was enriched in aromatic compounds (19.1% vs. 15.8%), aliphatic compounds (12.3% vs. 5.3%), carbohydrate-like compounds (3.9% vs. 0.02%), and N/S-containing molecules (43.9% vs. 20.6%) compared to PyDOMchar. Accordingly, PyDOMaerosol more effectively promoted [3]DOM* and [1]O2 formation under simulated sunlight. Our findings revealed structural and photoactivity differences between PyDOMchar and PyDOMaerosol, informing their environmental effects.

Aliphatic N-unprotected α-fluoroamines are unstable due to dehydrofluorination. Here, we show that the incorporation of the CH2-group into the elusive α-fluoropiperidine provides a stable α-fluoroamine with the 2-azabicyclo[2.2.1]heptane core. The latter does not eliminate HF because of Bredt's rule. The high stability of this α-fluoroamine allows its wide chemical modifications and use in medicinal chemistry.

Access to strongly quantum-confined lead bromide perovskite quantum dots (QDs) remains limited by the rapid formation kinetics of the perovskite phase. A major advance was achieved by introducing tri-n-octylphosphine oxide (TOPO) to coordinate PbBr2 and slow QD growth, although obtaining sub-5 nm CsPbBr3 QDs still required extreme dilution and yielded only tens of micrograms of isolable QDs per milliliter of reaction solution. Here, we introduce molecular design of the A-site cation precursor as a practical handle for controlling QD growth. Using cesium phosphinates, phosphonates, and phosphates with systematically varied aliphatic substituents, we show that the headgroup has only a minor influence on QD growth, whereas the precursor tail length governs the final QD size in a nonmonotonic manner, with a threshold around C8 attributed to changes in precursor organization. Steric tuning of the cesium precursor enabled size control of CsPbBr3 QDs from 18 to 3 nm with up to 40-fold increase in yield relative to the conventional route. In practical terms, the difference is 0.8 mg mL[-1] vs. 18 µg mL[-1] of isolable 3 nm QDs, with improved size dispersion (26 nm absorption linewidth). Even smaller CsPbBr3 species, estimated at 3-4 PbBr6 octahedra in width, are resolved by in situ absorption spectroscopy, opening the way to interrogate their nucleation and growth. The same strategy is extended to the more challenging FAPbBr3 system, enabling monodisperse QDs as small as 3.8 nm and allowing construction of a practical sizing curve relating FAPbBr3 QD size to the first excitonic absorption peak over the 3.8-12 nm size range.

Native aliphatic alcohols are highly abundant feedstocks for organic synthesis but remain challenging as alkyl donors. Herein, a new class of electrochemically triggered deoxygenative substitution of aliphatic alcohols is described. In the presence of diphenyl sulfide, the protocol furnishes alkyl chloride products under mild conditions and tolerates functional groups such as amines, carbamates, heteroaromatic rings, sulfones and free carboxylic acids. Mechanistic studies indicate that the reaction proceeds via nucleophilic substitution of alkoxysulfonium intermediates with inversion of configuration at the hydroxyl carbon, representing a new avenue for deoxyfunctionalization of aliphatic alcohols under electrochemical conditions.

Bark and ambrosia beetles are associated with various filamentous fungi, whose roles range from mutualists to antagonists. Mutualists can provide various benefits and are typically selectively dispersed by these wood-boring beetles. However, it is currently unknown how such bark and ambrosia beetles distinguish their fungal mutualists from other fungal associates, including insect pathogens. We hypothesized that volatile organic compounds might help maintain the mutualisms between beetles and specific fungal partners. Here, we compared the volatiles emitted by 30 fungi known to act as mutualists, commensals or antagonists for their beetle hosts. GC-MS analysis showed that all the fungi had characteristic volatile profiles with beneficial fungi emitting a greater diversity of volatiles than other fungal species. The volatile profiles of beneficial fungi were dominated by aliphatic and aromatic alcohols and esters in terms of both diversity and abundance. Furthermore, we demonstrated that the larvae and adults of two ambrosia beetle species can distinguish their mutualistic fungi from others based on volatile cues. Our results highlight the importance of aliphatic and aromatic alcohols and esters as recognition cues for mutualist fungi by wood-boring beetles. Volatiles likely play key roles in maintaining beetle associations with fungi that are essential to their insect host.

Organic hydrogen carriers are attractive for hydrogen storage because the reaction enthalpies of many systems are favorable for the realization of a storage cycle. Recent studies have shown that this thermodynamic advantage can be further enhanced through the formation of an aromatic organic salt system. This study investigates the physicochemical properties of sodium phenoxide and sodium cyclohexanolate. The enthalpies of formation in the solid phase at 298.15 K were determined using solution calorimetry and validated using quantum-chemical methods applied to calculate the enthalpy of formation in the gas phase and the sublimation enthalpy. Replacing the hydroxyl proton with a sodium ion in the studied compounds lowers the standard enthalpy of formation in the solid phase by about 160 kJ mol[-1] for the aromatic phenol and roughly 130 kJ mol[-1] for the aliphatic cyclohexanol. This 30 kJ mol[-1] difference highlights a stronger thermodynamic stabilization of the phenolate anion relative to cyclohexanolate, arising from the charge delocalization in the aromatic system upon substitution of the hydroxyl proton with a sodium ion. Therefore, the reaction enthalpy for the dehydrogenation of the organic sodium salt system is significantly lower compared to that of the phenol-cyclohexanol system, with a decrease of approximately 10 kJ per mole of hydrogen. Furthermore, heat capacity measurements by DSC demonstrated that the temperature dependence of the hydrogenation enthalpy of solid sodium phenoxide follows the same trend as that of typical liquid hydrogen carriers, indicating that this reduction in reaction enthalpy remains stable at least up to the maximum investigated temperature of 473 K.

Despite massive advances in mass spectrometric technologies, there remains a class of materials largely impervious to analysis: high molecular weight aliphatic hydrocarbons. Electrospray ionization mass spectrometry (ESI-MS) is used extensively as a tool in petroleomics to identify and fingerprint the polar constituents of oil, but the non-polar constituents remain challenging to analyze with ESI-MS due to poor ionization efficiency. Derivatization methods which bond electrospray-active tags to analytes impart charge and increase analyte response and have been developed for many different classes of petrochemicals, but not hydrocarbons. In this work, a method is described which renders aliphatic hydrocarbons amenable to ESI-MS analysis through C-H insertion into a substrate molecule of a diazirine-derived carbene, which is bound to a pendant alkyne. Subsequent electrospray-tagging occurs through copper-catalyzed azide alkyne cycloaddition, appending a triphenylphosphonium cation to the derivatized compound. The process was developed and benchmarked with cyclododecane as a model substrate to evaluate tagging efficiency and product distribution and then applied to characterize several commercial products composed of aliphatic compounds. While derivatization efficiency and ionization response may vary across substrates, the method provides a complementary route to established ionization techniques by enabling hydrocarbon analysis within ESI-based high-resolution mass spectrometric workflows. Its primary utility lies in enabling ESI-compatible fingerprinting of unfunctionalized compounds.

[This corrects the article DOI: 10.1039/D6RA04846C.].

Increasing helminth drug resistance necessitates novel anthelmintic agents. Lichens, historically used to treat parasitic infections, represent a promising natural resource. This study evaluated eight lichen extracts and 17 metabolites against the model organism Caenorhabditis elegans (wild-type strain N2). Extracts of Hypogymnia physodes, Nephroma arcticum, and Stereocaulon grande showed significant efficacy, while Sphaerophorus fragilis and Ophioparma ventosa caused 100% nematode mortality on day 11 (at 25 and 100 μg/mL, respectively). Chemical workup of S. fragilis yielded squamatic acid, sphaerophorin, and its monocyclic degradation products. Among the tested compounds, the depside sphaerophorin exhibited the highest nematocidal activity (LC50 = 22.07 μM), followed by divaricatic acid (LC50 = 77.27 μM). Physodic acid (LC50 > 200 μM) and evernic acid showed moderate effects. Sphaerophorin and divaricatic acid demonstrated moderate to low selectivity, generally exhibiting lower cytotoxicity toward human CCD-18Co cells (CC50 values of 88.5 μM and 91.7 μM, respectively) than toward nematodes. Given a panel of 17 structurally related compounds, we conducted a structure-activity relationship (SAR) analysis to identify molecular patterns associated with observed nematocidal activity. The analysis suggested the importance of the intact depside structure together with the presence of aliphatic chains and a carboxylic group, as isolated monocyclic fragments lacked antinematode efficacy. This first report on the nematocidal activity of H. physodes, N. arcticum, S. grande, and S. fragilis extracts, alongside evernic acid, physodic acid, and sphaerophorin, against the model organism C. elegans identifies them as promising scaffolds that warrant further investigation against parasitic species.

Immunotherapy has markedly advanced cancer treatment, with Th1-biased natural killer T (NKT) cell agonists emerging as promising candidates owing to their ability to induce potent antitumor immunity. However, α-galactosylceramide (αGalCer), the prototypical NKT agonist, induces mixed Th1/Th2 responses with antagonistic cytokine effects, limiting therapeutic selectivity. The development of potent immunostimulatory agents promote Th1 polarization remains a major challenge. Herein, we convert the linear aliphatic chain of αGalCer into a conformationally constrained all-hydrocarbon macrocyclic scaffold, establishing the first report of a purely hydrocarbon macrocycle pharmacophore. Guided by the structural architecture of the CD1d antigen-binding groove, this design preorganizes the aliphatic chain to optimize A' pocket occupancy, reduce entropic penalties, and enhance binding stability. αGalCer macrocyclized (GCC) analogs GCC-1 and GCC-2 elicited potent Th1-biased responses, with an approximately 12-fold increase in in vivo IFN-γ production relative to αGalCer, establishing them as highly potent Th1-biased NKT cell agonists. They exhibited potent immunological activity as effective antitumor immunotherapeutic agents and antiviral SARS-CoV-2 vaccine adjuvants, while retaining robust responsiveness in human NKT cells. Collectively, these findings establish the all-hydrocarbon macrocycle as a rational conformational constraint strategy for selectively biasing NKT cell responses, with potential applications in cancer immunotherapy and vaccine development.

Microbial consortia are essential for the degradation of complex hydrocarbon mixtures in coastal environments, yet the functional basis of consortium performance rarely resolved at strain level. In this study, we employed a Plackett-Burman experimental design to rationally assemble and optimize a synthetic consortium for the degradation of medium-grade crude oil in a sand-seawater microcosm. Six strains were selected: Stutzerimonas stutzeri CBC1 and CBC2, S. balearica GOM11, Pseudomonas sp. CBC3, Halomonas litopenaei GOM23 and Enterobacter kobei GOM24. After 45 days, the consortium removed 15.72% of total hydrocarbons relative to the abiotic control, with markedly higher fraction-specific removal determined by GC-MS: 94.7% of phenanthrene, 63.1% and 41.0% of the C8-C27 and C18-C27 aliphatic fractions respectively. Comparative genomic analysis revealed a non-uniform distribution of catabolic functions consistent with metabolic complementary. Stutzerimonas and Pseudomonas strains carried ring-hydroxylating dioxygenases (nah/nag-like clusters) together alkane-degrading alcohol/aldehyde dehydrogenases (alkJ, alkH), whereas H. litopenaei GOM23 and E. kobei GOM24 encoded alternative long-chain alkane-hydroxylating systems (ladA). GOM24 further carried an expanded repertoire of ABC transporters and oxidative-stress genes (ahpC/ahpF), consistent with a role in substrate uptake and stress tolerance rather than in primary ring cleavage. Enzymatic assays supported this partitioning, catechol 1,2-dioxygenase activity was confined to the same four strain that encoded the gene and was highest in CBC1 and GOM11 (0.0472 and 0.0443 U·mg[-][1] protein, respectively). No genome carried the classical alkB alkane-monooxygenase, pointing to alternative and partially redundant alkane-oxidation routes. By combining statistically guided assembly with comparative genomics and targeted enzyme assays, this work identifies a six-strain combination that removes more crude oil than the full eleven-isolate community and resolves how its catabolic functions are partitioned among strains.

A stereo- and regioselective Fe-(II)-catalyzed hydroboration of both terminal and internal alkynes with pinacolborane (HBpin) is described. The hydroboration reaction is in all cases highly syn-selective. The reaction requires no additives and proceeds with a catalyst loading of 1-2 mol % at 45-55 °C. An active pre-catalyst is the bench-stable alkyl Fe-(II) complex [Fe-(PCP[CH2]-iPr)-(CH2CH2CH3)-(CO)2]. This complex reacts with an excess of HBpin to form the Fe-(II) pinacolborane complex [Fe-(PCP[CH2]-iPr)-(κ[2]-H2BPin)-(CO)], which is an equally active pre-catalyst but more difficult to handle, as it decomposes in the absence of substrates. Both pre-catalysts afford the highly reactive hydride catalyst [Fe-(PCP[CH2]-iPr)-(H)-(CO)] under catalytic conditions. A broad variety of aromatic and aliphatic alkynes were efficiently and selectively borylated. Mechanistic insights are provided based on experimental data and DFT calculations.