Commonality in Functional Groups on Trace Compounds in High Explosives
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Imine Reductase-Catalyzed, Radical-Mediated Asymmetric Cyano Group Migration
Functional group migration (FGM) reactions represent a fundamental class of transformations in organic chemistry, enabling the repositioning of functional moieties in nonobvious ways. However, catalytic asymmetric radical-mediated FGMs remain rare due to the inherent challenges of achieving catalyst-controlled enantioselectivity over free radical intermediates. Herein, we repurpose imine reductases (IREDs), a class of biotechnologically important enzymes known for their substrate promiscuity, to enable the first examples of catalytic asymmetric cyano group migration via a radical mechanism. An orthogonal set of radical enzymes, including PbaIREDCym and SmiIREDCym, was engineered, allowing both 1,4- and 1,5-cyano group migration reactions to occur in an enantiodivergent fashion. The use of the nonionic surfactant TPGS-1000 was found to improve both the yield and enantioselectivity of these cyano migration reactions. Furthermore, this biocatalytic process exhibited a broad substrate scope and is readily scalable, affording a rare example of chiral nonamine product assembly with imine reductases. More broadly, stereoselective radical biocatalysis with engineered IREDs and other versatile enzymes provides a potentially general solution to challenging asymmetric FGM reactions.
Biocatalysis↗
Experimental and fuel-surrogates modeling study of the high-pressure pyrolysis of specialty cetane number fuels: implications for fall-off in ethylene unimolecular dissociation
Single pulse shock tube experiments were conducted at 50 atm nominal pressure and 4 ms nominal reaction time over a temperature range of 900–1800 K, to study the pyrolysis speciation of a multi-component jet fuel, F-24, and six cetane number (CN) specialty fuels - CN30, CN35, CN40, CN45, CN50, and CN55. Gas chromatography (GC) was used to qualitatively and quantitatively analyze the post shock gases. The relationship between the formation of key pyrolysis species and the chemically controlled combustion propensity as reflected by the cetane number of each fuel was examined. A surrogate-based mechanism from the CRECK Modelling Group and chemical-functional group based optimized surrogates (CFGO) were used to simulate the pyrolysis speciation results. The model was able to capture the chemistry of most species except two important pyrolysis intermediates – ethylene and acetylene. Chemical kinetic analyses were performed to identify the important reactions which affect the chemistry of these species; however, the rate parameters of critical reactions were found to be unsuitable for simulating the present high-pressure studies. Here, to address this unsuitability, a theory-based fall-off analysis for three reactions representing the decomposition of ethylene and subsequent formation of acetylene was performed, and these are included in an updated version of the CRECK mechanism. This update resolves discrepancies between the experimental results and simulations for ethylene and acetylene. Reaction flux analyses using the updated surrogate model were also performed to identify the important reaction pathways responsible for the formation of crucial species and to provide an analysis of the chemistry of complex multi-component fuel systems. The fundamental reactions responsible for driving pyrolysis chemistry were greatly influenced by the chemical functional groups present in these fuels. In addition to updating the rate parameters of specific reactions to improve modeling, this study also emphasizes the effectiveness of the fuel-surrogate approach, where surrogates representing the chemical functional group composition of the parent fuel serve as a valuable tool for predicting the combustion chemistry of novel fuels.
Chemical Kinetics↗
Evaluating the Structural Response of Amphiphilic Monolayers to Environmental Stimuli
Amphiphilic monolayers composed of end groups with distinct polar and nonpolar functional groups offer rapid and reversible interfacial adaptation in response to environmental stimuli such as a change in interfacial medium polarity. We have synthesized and characterized a suite of monolayers with functional groups of competing polarity designed to reconfigure their interfacial chemical composition in response to solvent polarity. In these films, the end group is designed to be able to reorient and expose the functional groups that minimize the interfacial free energy between the film and the environment. Using a combination of spectroscopic, computational, and wettability studies, we have investigated the responsive interfacial behavior of different end groups upon exposure to environments with varying polarities. Contact angle measurements across a series of polar and dispersive probe liquids reveal trends that reflect the underlying molecular flexibility and composition. Vibrational sum frequency generation (SFG) spectroscopy and atomistic molecular dynamics (MD) simulations confirm solvent-driven reorientation of the end groups, with restructuring observed at the interface. To quantify these effects, we have developed a surface energy calculation model that incorporates solvent-induced surface rearrangements into the estimations. Our findings reveal a strong dependence of surface energy and switching behavior on the length and flexibility of the functionalities in the end group, which affects the exposure of certain interfacial compositions under different solvents. These results offer new insights into the design of adaptive monolayers and provide a framework for evaluating solvent-responsive surfaces.
functional groups↗
Refractive index matching base resin for extremely fine three-dimensional ceramic structures
An optically clear resin for additive manufacturing includes an optically clear ceramic precursor having a pre-defined refractive index. Each molecule of the ceramic precursor has at least two photopolymerizable functional groups, at least one of the photopolymerizable functional groups being functionalized with a refractive index-tuning group thereby causing the ceramic precursor to have the pre-defined refractive index.
Mettry, Magi↗
Data for Photoenzymatic Stereoablative Enantioconvergence of γ-chiral Oximes via Hydrogen Atom Transfer
Producing enantioenriched molecules from racemic mixtures is essential for manufacturing. Traditional methods such as resolution, deracemization and enantioconvergent catalysis primarily involve separating or converting enantiomers without altering their structures, or functionalization of stereocentres at or proximal to functional groups. However, there are challenges in enantioselectively forging C–H bonds that are remote from functional groups via hydrogen atom transfer (HAT) with these methods. Here we introduce a strategy for the photoenzymatic stereoablative enantioconvergence of γ-chiral oximes using repurposed flavin-dependent ene-reductases. A photoinduced single-electron reduction of the γ-chiral oxime by an ene-reductase generates an iminyl radical, which then undergoes stereoablative 1,5-HAT at the γ-stereocentre. Subsequent chiral reconstruction through enzymatic HAT and spontaneous imine hydrolysis yields the γ-chiral ketone with high enantioselectivity. This work provides a robust method for remote stereoablative enantioconvergent HAT and broadens the synthetic utility of photobiocatalysis.
Bioproducts↗
Selective single-atom adsorption for precision separation of lead ions in tap water via capacitive deionization
Capacitive deionization (CDI) offers a cost-effective and low-energy method for selective removal of Pb 2+ from drinking water. Modifying CDI electrode surfaces with functional groups presents a versatile approach to enhancing selective ion adsorption capacity. However, a comprehensive understanding of the selectivity and removal efficiency of Pb 2+ among diverse functional groups remains unexplored. Here, we investigated the effects of different functional groups (-SH, -COOH, and -NH 2 ) attached to the graphene oxide (GO) electrode surfaces on Pb 2+ selectivity and removal efficiency. Surprisingly, GO-COOH demonstrated single-atom adsorption of Pb 2+ , displaying superior removal efficiency and selectivity compared with -SH and -NH 2 , although -SH possesses significant chelation capability for Pb 2+ . Both density functional theory (DFT) calculations and X-ray pair distribution function (PDF) analyses confirmed that Pb 2+ exhibits a theoretically higher affinity to -COOH. Further, this research deepens our understanding of the interactions between functional groups and heavy metal ions, enabling selective and rapid separation of target cations for water purification.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Probing the External Surface Chemistry of Imine-Based Covalent Organic Frameworks Using Reactive Organic Dyes
The external surfaces of covalent organic frameworks (COFs) are presumably composed of free terminal functional groups from their constituent monomers. These terminal groups have been utilized to immobilize molecules onto COF surfaces for a variety of studies and potential applications. Despite the utility of these latent functional groups for COF functionalization and composite formation, the surface chemistry of the COFs has not been quantitatively investigated and is not well understood. In this work, fluorescent organic dyes bearing reactive amine and aldehyde functional groups are used to probe the surface chemistry of representative two-dimensional (2D) imine-based COFs. Furthermore, systematic dye binding and displacement experiments provide new insights into the characteristics of COF surfaces and the reactivity of different molecules with the surface groups on the COF crystallites.
COFs↗
Bidirectional Suzuki Catalyst Transfer Polymerization of Poly( p -phenylene)
Suzuki catalyst transfer polymerization (SCTP) has emerged as an effective method for accessing length-controlled π-conjugated poly(p-phenylene). Regio-controlled functional group sequencing along the backbone and the chain ends of synthetic polymers remains a challenge for the successful integration of organic semiconductors in sensors and electronic devices. Here, we report a bidirectional SCTP system based on dinuclear palladium(II) initiators. Functional groups transferred during the initiation and termination steps unlock independently addressable synthetic handles at the polymer core and respective chain ends. These functional groups open opportunities for late-stage regio-controlled and chemoselective derivatizations. Control over key polymer parameters, including molecular weight (M n ), dispersity ( Đ = M w /M n ), degree of polymerization ( DP ), termination efficiency, and functional group interconversion, is corroborated by size exclusion chromatography (SEC) and NMR spectroscopy. The modular design of SCTP initiators, in combination with commercially available terminating groups, represents a highly flexible toolbox for late-stage polymer conjugation, e.g., chemoselective anchoring groups for integration with functional electronics or bioorthogonal conjugation for molecular sensing.
Aldehydes↗
Blocky Selective Postpolymerization C–H Functionalization of Polyolefins
C–H functionalization of commodity polyolefins affords functional materials derived from a high-volume, low-cost resource. However, current postpolymerization modification strategies result in randomly distributed functionalization along the length of the polymer backbone, which has a negative impact on the crystallinity of the resultant polymers, and thus the thermomechanical properties. Here, we demonstrate an amidyl radical mediated C–H functionalization of polyolefins to access blocky microstructures, which exhibit a higher crystalline fraction, larger crystallite size, and improved mechanical properties compared to their randomly functionalized analogues. Taking inspiration from the site-selective C–H functionalization of small molecules, we leverage the steric protection provided by crystallites and target polymer functionalization to amorphous domains in a semicrystalline polyolefin gel. The beneficial outcomes of blocky functionalization are independent of the identity of the pendant functional group that is installed through functionalization. Here, the decoupling of functional group incorporation and crystallinity highlights the promise in accessing nonrandom microstructures through selective functionalization to circumvent traditional tradeoffs in postpolymerization modification, with potential impact in advanced materials and upcycling plastic waste.
Neidhart, Eliza K. [The University of North Caroli↗
Tuning the Lifetimes of Photoinduced Deligation in a Metal–Organic Framework via Linker Functionalization
Recently photoinduced dynamic ligation in a metal–organic frameworks (MOFs) was reported, where a long-lived charge-transfer excited state (ca. 30 μs) featuring partial dissociation between the carboxylate linker and metal-based node was probed by time-resolved infrared (TRIR) spectroscopy. The study offers a new mechanistic perspective to evaluate the potential contribution from the excited state molecular configuration to the performance of MOF photocatalysts. In this work, by employing MIL-101(Fe) as the study platform, we have further explored the influence of intramolecular interactions on the stability of relevant excited states and demonstrated the effective tuning of their lifetimes through the incorporation of different functional groups into the system. The correlations between the varied excited state lifetimes and coordination configurations with specific functional groups (−NH 2 or −NO 2 ) was inferred from the analyses of infrared spectroscopic data and theoretical calculations, revealing the essential role of the intramolecular interactions (i.e., between the added functional groups and the carboxylate group) in the modulation of system energetics. Overall, the work presents a pathway to tune the excited state dynamics and expands the knowledge regarding the photoinduced dynamic ligation in carboxylate-based MOFs.
excited states↗
Experimental investigation into coal wettability changes caused by reactions with scCO 2 -H 2 O
Geological CO 2 sequestration (GCS) can help mitigate global warming and enhance methane recovery from coal beds. However, few studies have linked the effects of CO 2 to surface chemistry changes controlling wetting behavior in deep coal beds. Contact angles (CAs) of CO 2 /N 2 -high volatile bituminous coal-water systems were measured under different temperatures and pressures. The surface chemistry and physical structure of coals were characterized to investigate changes in physicochemical properties and their relations with wettability after reactions. For N 2 treatment, the time-dependence of static and dynamic CAs were insignificant, ranging within 4°. For gaseous CO 2 treatment, the static CAs and the average advancing angles increased slightly. With supercritical (sc) CO 2 , both the static and dynamic CAs increased significantly, and θ adv changed to intermediate-wet (92°). Reactions with minerals exposed to scCO 2 resulted in greater surface roughness and heterogeneity, greater contact angle hysteresis and more surface sites occupied by scCO 2 rather than H 2 O. Increases in hydrophobic functional groups and decreases in hydrophilicity were shown by FTIR spectra, reflecting the shedding of polar oxygen-containing functional groups, reduction of hydrogen bonds, and increasing percentage of hydrocarbons. XRD patterns obtained following scCO 2 -treatment showed that crystallite growth and molecular polymerization were higher toward graphite-like. The calculated structural parameters of functional groups and crystallites both showed elevated coal rank. Changes in crystallite structure, notably higher carbon content and decreased negative surface charge, are unfavorable for water-wetting. Finally, this study contributes to understanding surface chemistry changes responsible for decreased wettability during CO 2 -enhanced coal bed methane recovery and GCS in coal reservoirs.
01 COAL, LIGNITE, AND PEAT↗
Elucidating the Interfacial Effects of Nonmetallic Elements on the Dehydrogenation Behavior of Nanoconfined NaAlH 4 in Zeolite-Templated Carbon
Confining materials within nanoscale volumes alters their physical and chemical properties, with positive consequences for energy storage, conversion, and catalysis. The pore structure and composition of scaffolds are essential variables for optimizing these properties, with carbon-based materials being preferred due to their tunable porous structures and chemical versatility. This study investigates the influence of surface functional groups on the dehydrogenation kinetics of nanoconfined NaAlH4 using zeolite-templated carbons (ZTCs). Here we focus on oxygen functional groups commonly present as intrinsic impurities on carbon scaffolds, analyzing three ZTC scaffolds to determine how their concentrations and configurations affect dehydrogenation behavior. Our findings reveal that carbonyl groups enhance charge transfer and destabilize Al–H bonds more effectively than ether or phenol groups. This indicates that the type of oxygen functional group is more critical than the quantity, highlighting the importance of properly tailoring oxygen defects to improve hydrogen storage performance in nanoconfined systems.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Late-Stage Oxidation of C( sp 3 )─H Bonds with High Efficiency and Alkyl Group Dihydroxylation of Complex Molecules
Here, the late-stage oxidation of C(sp 3 )─H bonds is highly valuable for modulating the solubility and binding of bioactive compounds and for diversification of complex molecules. Undirected methods for C(sp 3 )─H oxidation are valuable for the installation of hydroxyl groups at sites remote from other functional groups present in the molecule, but existing catalysts are limited by low turnover numbers and lengthy ligand syntheses. Perfluorinated ruthenium porphyrins are highly active catalysts for the oxidation of alkyl C─H bonds, but the scope of the transformation with complex molecules under conditions of limiting substrate has not been investigated. We report that carbonylruthenium(II) tetrakis(pentafluorophenyl)porphyrin [Ru(TPFPP)(CO)] catalyzes the selective oxidation of tertiary C(sp 3 )─H bonds in a broad range of complex natural products and drugs, with turnover numbers as high as 1000, and the tolerance of the reaction to various functional groups was rapidly assessed by performing a model reaction in the presence of additives. We show how the combination of this undirected C(sp 3 )─H oxidation and a directed C(sp 3 )─H silylation and oxidation provides rapid access to highly oxidized, 1,2-diol derivatives of natural products by a formal dihydroxylation of an alkyl group.
Alcohols↗
Two-Dimensional Siloxene Nanosheets: Understanding the Effect of Heat Treatment on the Surface Chemistry and Resulting Electrochemistry in Lithium-Based Batteries
Two-dimensional (2D) silicon materials are conceptually appealing as negative electrode materials in lithium-ion batteries due to their layered morphology, which can accommodate (de)lithiation-induced volume changes. Herein, heat treatment of 2D Siloxene materials was used to modify the surface functional groups to determine the impact on the electrochemical behavior. Spectroscopic characterization of the heat-treated nanosheets confirmed the loss of oxygenated and hydride surface functional groups with an increased annealing temperature. Formation and disproportionation of the amorphous suboxides with increasing heat treatment were affirmed with lab and synchrotron-based measurements. A reduced irreversible capacity was observed for Siloxene with a higher temperature heat treatment consistent with the formation of a more favorable surface electrolyte interphase (SEI). A Siloxene-400||NMC622 full cell (prepared with 400 °C-annealed Siloxene (Siloxene-400) and LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622)) showed significantly enhanced capacity and rate capability compared to a nano Si||NMC622 cell. Finally, these results illustrate the ability of thermal annealing to modify the surface functional groups of Siloxene and highlight the favorable impact of the appropriate surface functionality on the electrochemistry of Siloxene in lithium cells.
25 ENERGY STORAGE↗
High-Pressure Rate Rules for Ether Alkylperoxy Radical Isomerization
The first isomerization reaction of an alkylperoxy (RO 2 ) radical holds significant importance in low-temperature oxidation, as it governs the branching ratios of the hydroperoxyalkyl (QOOH) radicals, which influence the competition between the chain-propagation and chain-branching reactions. In this study, we systematically calculated high-pressure rate rules for the RO 2 isomerization reaction of monoethers, exploring 5-, 6-, 7-, and 8-membered ring transition states. Primary, secondary, and tertiary carbon sites, where both the abstracting peroxy group and the abstracted hydrogen are located, were considered, with particular emphasis on distinguishing between secondary carbons adjacent (alpha) and nonadjacent to the ether functional group. Using the G4//B3LYP/6-311++G(2df,2pd) level of theory and the transition state theory, we estimated the rate constants and the Arrhenius coefficient for over 120 possible isomerization reactions. We examined the effect of ring size and ring atoms, revealing that 6- and 7-membered ring isomerizations were generally the fastest. The impact of the ether functional group on transition states was investigated by comparing reactions with identical ring size, peroxy, and radical positions, but with the ether functional group positioned either outside (i.e., out) or inside (i.e., in) the transition state ring, leading to differences in the rate constants. When comparing to analogous alkane rate constants, differences of up to an order of magnitude were observed, underscoring the need for caution when assigning rate rules by analogy. We applied our rate constants in the di-iso-butyl ether kinetic model and evaluated their influence on low-temperature chemistry finding that they altered the branching ratios by up to a factor of 9, highlighting the significance of site-specific rate constants for more accurate low-temperature modeling.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Demystifying In Situ Pyrolysis Chemistry for High-Performance Polyanionic Cathodes in Sodium-Ion Batteries
In this article, the carbon coating strategy has emerged as an indispensable approach to improve the conductivity of polyanionic cathodes. However, owing to the complex reaction process between precursors of carbon and cathode, establishing a unified screening principle for carbonaceous precursors remains a technical challenge. Herein, we reveal that carbonaceous precursor pyrolysis chemistry undeniably influences the formation process and performance of Na 3 V 2 (PO 4 ) 3 (NVP) cathodes from in situ insights. By investigating three types of carbonaceous precursors, it is found that O/H-containing functional groups can provide more bonding sites for cathode precursors and generate a reducing atmosphere by pyrolysis, which is beneficial to the formation of polyanionic materials and a uniform carbon coating layer. Conversely, excessive pyrolysis of functional groups leads to a significant amount of gas, which is detrimental to the compactness of the carbon layer. Furthermore, the substantial presence of residual heteroatoms diminishes graphitization. In this case, it is demonstrated that carbon dots (CDs) precursors with suitable functional groups can comprehensively enhance the Na+ migration rate, reversibility, and interface stability of the cathode material. As a result, the NVP/CDs cathode displays outstanding capacity retention, maintaining 92% after 10,000 cycles at a high rate of 50 C. Altogether, these findings provide a valuable benchmark for carbon source selection for polyanionic cathodes.
25 ENERGY STORAGE↗
A Structurally Diverse Compound Screening Library to Identify Substrates for Diamine, Polyamine, and Related Acetyltransferases
Spermidine/spermine N-acetyltransferases (SSATs) and other types of polyamine acetyltransferases (PAATs) acetylate diamines and/or polyamines. These enzymes are evolutionarily related and belong to the Gcn5-related N-acetyltransferase (GNAT) superfamily, yet we lack a fundamental understanding of their substrate specificity and/or promiscuity toward different compounds. Many of these enzymes are known or are predicted to acetylate polyamines, but in the cell there are other types of compounds that contain moieties derived from polyamines that may be the native substrates for these enzymes. To learn more about the identity of substrates that are acetylated, we selected and screened 17 different GNAT enzymes for activity toward a set of structurally diverse compounds that contained different types of amine moieties (e.g., aminopropyl, aminobutyl, etc.). These compounds included diamines, triamines, and polyamines containing primary amino groups, and they had structural diversity with variation of the chain length and presence or absence of internal amino groups and other functional groups. We found 12 of the 17 enzymes acetylated at least one of the compounds. Some enzymes were selective toward acetylating only one compound while others exhibited substrate promiscuity toward numerous compounds. Our experimental results ultimately allowed us to pinpoint specific substrates that could be further investigated to more fully understand substrate specificity versus promiscuity of GNAT enzymes and the role of acetylated small molecules in cells.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗