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For many chemical reactions, it remains notoriously difficult to predict and experimentally determine the rates and branching ratios between different reaction channels. This is particularly the case for reactions involving short-lived intermediates, whose observation requires ultrafast methods. The UV photochemistry of bromoform (CHBr3) is among the most intensely studied photoreactions. Yet, a detailed understanding of the chemical pathways leading to the production of atomic Br and molecular Br2 fragments has proven challenging. In particular, the role of isomerization and/or roaming and their competition with direct C-Br bond scission has been a matter of continued debate. Here, gas-phase ultrafast megaelectronvolt electron diffraction (MeV-UED) is used to directly study structural dynamics in bromoform after single 267 nm photon excitation with femtosecond temporal resolution. The results show unambiguously that isomerization contributes significantly to the early stages of the UV photochemistry of bromoform. In addition to direct C-Br bond breaking within 1.1 ps. The branching ratio between direct dissociation and isomerization is determined to be 0.4 ± 0.2:0.6 ± 0.2, i.e., approximately 60% of molecules undergo isomerization within the first few hundred femtoseconds after UV excitation. The structure and time of formation of iso-CHBr3 compare favorably with the results of an ab initio molecular dynamics simulation. The lifetime and interatomic distances of the isomer are consistent with the involvement of a roaming reaction mechanism.

Polymeric materials bearing Frustrated Lewis Pair (FLP) functionality are promising candidates for use as heterogeneous catalysts and adaptive materials, but synthetic access to FLP-functional polymers remains limited due to the incompatibility of FLPs with standard polymerization chemistries. Herein, we describe a synthetic approach that "cages" highly reactive vicinal phosphine-borane FLPs as covalent alkene adducts, which are stable to Ni-mediated vinyl addition polymerization. We discovered that the caged FLP adducts can be photochemically activated to liberate vicinal FLPs, enabling spatiotemporally controlled release of FLPs from polymeric precursors.

Monomethylamine (NH2CH3), dimethylamine (NH(CH3)2), and trimethylamine (N(CH3)3) are important chemical feedstocks that are produced industrially as an azeotropic mixture and must be separated using an energy-intensive thermal distillation. While solid adsorbents have been proposed as alternatives to distillation for separating various industrial gas mixtures, methylamine separations remain largely unexplored in this context. Here, we investigate two isoreticular frameworks Cu(cyhdc) (cyhdc2- = trans-1,4-cyclohexanedicarboxylate) and Cu(bdc) (bdc2- = 1,4-benzenedicarboxylate) as prospective candidates for this challenging separation, motivated by the recent discovery that Cu(cyhdc) reversibly captures ammonia through a unique framework-to-coordination polymer phase change. Through a combination of gas adsorption and powder X-ray diffraction analyses, we find that Cu(cyhdc) and Cu(bdc) reversibly bind large quantities of mono- and dimethylamine through framework-to-coordination polymer phase change mechanisms, although both frameworks adsorb only moderate amounts of trimethylamine via physisorption. Single-crystal X-ray diffraction analysis of select mono- and dimethylamine containing phases suggests that the number of hydrogen bond donors available and the linker donor strength are key factors influencing amine uptake. Finally, investigation of the tricomponent adsorption behavior of both materials reveals that Cu(cyhdc) is selective for the capture of monomethylamine from a range of mono-, di-, and trimethylamine mixtures.

Chromium and arsenic are two of the most problematic water pollutants due to their high toxicity and prevalence in various water streams. While adsorption and ion-exchange processes have been applied for the efficient removal of numerous toxic contaminants, including heavy metals, from water, these technologies display relatively low overall performances and stabilities for the remediation of chromium and arsenic oxyanions. This work presents the use of polyol-functionalized porous aromatic framework (PAF) adsorbent materials that use chelation, ion-exchange, redox activity, and hydrogen-bonding interactions for the highly selective capture of chromium and arsenic from water. The chromium and arsenic binding mechanisms within these materials are probed using an array of characterization techniques, including X-ray absorption and X-ray photoelectron spectroscopies. Adsorption studies reveal that the functionalized porous aromatic frameworks (PAFs) achieve selective, near-instantaneous (reaching equilibrium capacity within 10 s), and high-capacity (2.5 mmol/g) binding performances owing to their targeted chemistries, high porosities, and high functional group loadings. Cycling tests further demonstrate that the top-performing PAF material can be recycled using mild acid and base washes without any measurable performance loss over at least ten adsorption-desorption cycles. Finally, we establish chemical design principles enabling the selective removal of chromium, arsenic, and boron from water. To achieve this, we show that PAFs appended with analogous binding groups exhibit differences in adsorption behavior, revealing the importance of binding group length and chemical identity.

Nanowires have emerged as an important family of one-dimensional (1D) nanomaterials owing to their exceptional optical, electrical, and chemical properties. In particular, Cu nanowires (NWs) show promising applications in catalyzing the challenging electrochemical CO2 reduction reaction (CO2RR) to valuable chemical fuels. Despite early reports showing morphological changes of Cu NWs after CO2RR processes, their structural evolution and the resulting exact nature of active Cu sites remain largely elusive, which calls for the development of multimodal operando time-resolved nm-scale methods. Here, we report that well-defined 1D copper nanowires, with a diameter of around 30 nm, have a metallic 5-fold twinned Cu core and around 4 nm Cu2O shell. Operando electrochemical liquid-cell scanning transmission electron microscopy (EC-STEM) showed that as-synthesized Cu@Cu2O NWs experienced electroreduction of surface Cu2O to disordered (spongy) metallic Cu shell (Cu@CuS NWs) under CO2RR relevant conditions. Cu@CuS NWs further underwent a CO-driven Cu migration leading to a complete evolution to polycrystalline metallic Cu nanograins. Operando electrochemical four-dimensional (4D) STEM in liquid, assisted by machine learning, interrogates the complex structures of Cu nanograin boundaries. Correlative operando synchrotron-based high-energy-resolution X-ray absorption spectroscopy unambiguously probes the electroreduction of Cu@Cu2O to fully metallic Cu nanograins followed by partial reoxidation of surface Cu during postelectrolysis air exposure. This study shows that Cu nanowires evolve into completely different metallic Cu nanograin structures supporting the operando (operating) active sites for the CO2RR.

Aggregation of protein-based therapeutics can occur during development, production, or storage and can lead to loss of efficacy and potential toxicity. Native mass spectrometry of a covalently linked pentameric monoclonal antibody complex with a mass of ∼800 kDa reveals several distinct conformations, smaller complexes, and abundant higher-order aggregates of the pentameric species. Charge detection mass spectrometry (CDMS) reveals individual oligomers up to the pentamer mAb trimer (15 individual mAb molecules; ∼2.4 MDa) whereas intermediate aggregates composed of 6-9 mAb molecules and aggregates larger than the pentameric dimer (1.6 MDa) were not detected/resolved by standard mass spectrometry, size exclusion chromatography (SEC), capillary electrophoresis (CE-SDS), or by mass photometry. Conventional quadrupole time-of-flight mass spectrometry (QTOF MS), mass photometry, SEC, and CE-SDS did not resolve partially or more fully unfolded conformations of each oligomer that were readily identified using CDMS by their significantly higher extents of charging. Trends in the charge-state distributions of individual oligomers provides detailed insight into how the structures of compact and elongated mAb aggregates change as a function of aggregate size. These results demonstrate the advantages of CDMS for obtaining accurate masses and information about the conformations of large antibody aggregates despite extensive overlapping m/z values. These results open up the ability to investigate structural changes that occur in small, soluble oligomers during the earliest stages of aggregation for antibodies or other proteins.

The formation and preservation of the active phase of the catalysts at the triple-phase interface during CO2 capture and reduction is essential for improving the conversion efficiency of CO2 electroreduction toward value-added chemicals and fuels under operational conditions. Designing such ideal catalysts that can mitigate parasitic hydrogen generation and prevent active phase degradation during the CO2 reduction reaction (CO2RR), however, remains a significant challenge. Herein, we developed an interfacial engineering strategy to build a new SnOx catalyst by invoking multiscale approaches. This catalyst features a hierarchically nanoporous structure coated with an organic F-monolayer that modifies the triple-phase interface in aqueous electrolytes, substantially reducing competing hydrogen generation (less than 5%) and enhancing CO2RR selectivity (∼90%). This rationally designed triple-phase interface overcomes the issue of limited CO2 solubility in aqueous electrolytes via proactive CO2 capture and reduction. Concurrently, we utilized pulsed square-wave potentials to dynamically recover the active phase for the CO2RR to regulate the production of C1 products such as formate and carbon monoxide (CO). This protocol ensures profoundly enhanced CO2RR selectivity (∼90%) compared with constant potential (∼70%) applied at -0.8 V (V vs RHE). We further achieved a mechanistic understanding of the CO2 capture and reduction processes under pulsed square-wave potentials via in situ Raman spectroscopy, thereby observing the potential-dependent intensity of Raman vibrational modes of the active phase and CO2RR intermediates. This work will inspire material design strategies by leveraging triple-phase interface engineering for emerging electrochemical processes, as technology moves toward electrification and decarbonization.

In the context of carbon reutilization, the direct electroreduction of captured CO2 (c-CO2RR) appears as an appealing approach since it avoids the energetically costly separation of CO2 from the capture agent. In this process, CO2 is directly reduced from its captured form. Here, we investigate the influence of the capture agent and proton source on that reaction from a combination of theory and experiment. Specifically, we consider methoxide-captured CO2, NH3-captured CO2, and bicarbonate on silver electrocatalysts. We show that the proton source plays a key role in the interplay of the chemistries for the electroreduction of protons, free CO2, and captured CO2. Our density functional theory calculations, including the influence of the potential, demonstrate that a proton source with smaller pKa improves the reactivity for c-CO2RR, but also increases the selectivity toward the hydrogen evolution reaction (HER) on silver surfaces. Since c-CO2RR requires an additional chemical protonation step, the influence of the proton source is stronger than that of the HER. However, c-CO2RR cannot compete with the HER on Ag, Experimentally, the dominant product observed is H2 with low amounts of CO being produced. Through a rotating cylinder electrode cell of well-defined mass-transport properties, we conclude that although methanol solvent exhibits a lower HER activity, HER remains dominant over c-CO2RR. Our work suggests that methoxide is a potential alternative capture agent to NH3 for direct reduction of captured CO2, though challenges in catalyst design, particularly in reducing the onset potential of c-CO2RR to surpass the HER, remain to be addressed.

Catalyst-free and reversible step-growth Diels-Alder (DA) polymerization has a wide range of applications in polymer synthesis and is a promising method for fabricating recyclable thermoplastics. The effectiveness of polymerization and depolymerization relies on the chemical building blocks, often utilizing furan as the diene and maleimide as the dienophile. Compared to the traditional diene-dienophile or two-component approach that requires precise stoichiometry, cyclopentadiene (Cp) can serve dual roles via self-dimerization. This internally balanced platform offers a route to access high-molecular-weight polymers and a dynamic handle for polymer recycling, which has yet to be explored. Herein, through a reactivity investigation of different telechelic Cp derivatives, the uncontrolled cross-linking of Cp was addressed, revealing the first successful DA homopolymerization. To demonstrate the generality of our methodology, we synthesized and characterized six Cp homopolymers with backbones derived from common thermoplastics, such as poly(dimethylsiloxane), hydrogenated polybutadiene, and ethylene phthalate. Among these materials, the hydrogenated polybutadiene-Cp analog can be thermally depolymerized (Mn = 68 to 23 kDa) and repolymerized to the parent polymer (Mn = 68 kDa) under solvent- and catalyst-free conditions. This process was repeated over three cycles without intermediate purification, confirming the efficient thermo-selective recyclability. The varied degradable properties of the other four Cp-incorporated thermoplastics were also examined. Overall, this work provides a general methodology for accessing a new class of reversible homopolymers, potentially expanding the design and construction of sustainable thermoplastics.

This study presents a Ni-photoredox method for indole N-arylation, broadening the range of substrates to include indoles with unprotected C3-positions and base-sensitive groups. Through detailed mechanistic inquiries, a Ni(I/III) mechanism was uncovered, distinct from those commonly proposed for Ni-catalyzed amine, thiol, and alcohol arylation, as well as from the Ni(0/II/III) cycle identified for amide arylation under almost identical conditions. The key finding is the formation of a Ni(I) intermediate bearing the indole nucleophile as a ligand prior to oxidative addition, which is rare for Ni-photoredox carbon-heteroatom coupling and has a profound impact on the reaction kinetics and scope. The pre-coordination of indole renders a more electron-rich Ni(I) intermediate, which broadens the scope by enabling fast reactivity even with challenging electron-rich aryl bromide substrates. Thus, this work highlights the often-overlooked influence of X-type ligands on Ni oxidative addition rates and illustrates yet another mechanistic divergence in Ni-photoredox C-heteroatom couplings.

Pendent metals bound to heterocubanes are components of well-known active sites in enzymes that mediate difficult chemical transformations. Investigations into the specific role of these metal ions, sometimes referred to as "danglers", have been hindered by a paucity of rational synthetic routes to appropriate model structures. To generate pendent metal ions bonded to an oxo cubane through a carboxylate bridge, the cubane Co4(μ3-O)4(OAc)4(t-Bupy)4 (OAc = acetate, t-Bupy = 4-tert-butylpyridine) was exposed to various metal acetate complexes. Reaction with Cu(OAc)2 gave the structurally characterized (by X-ray diffraction) dicopper dangler Cu2Co4(μ4-O)2(μ3-O)2(OAc)6(Cl)2(t-Bupy)4. In contrast, the analogous reaction with Mn(OAc)2 produced the MnIV-containing cubane cation [MnCo3(μ3-O)4(OAc)4(t-Bupy)4]+ by way of a metal-metal exchange that gives Co(OAc)2 and [CoIII(μ-OH)(OAc)]n oligomers as byproducts. Additionally, reaction of the formally CoIV cubane complex [Co4(μ3-O)4(OAc)4(t-Bupy)4][PF6] with Mn(OAc)2 gave the corresponding Mn-containing cubane in 80% yield. A mechanistic examination of the related metal-metal exchange reaction between Co4(μ3-O)4(OBz)4(py)4 (OBz = benzoate) and [Mn(acac)2(py)2][PF6] by ultraviolet-visible (UV-vis) spectroscopy provided support for a process involving rate-determining association of the reactants and electron transfer through a μ-oxo bridge in the adduct intermediate. The rates of exchange correlate with the donor strength of the cubane pyridine and benzoate ligand substituents; more electron-donating pyridine ligands accelerate metal-metal exchange, while both electron-donating and -withdrawing benzoate ligands can accelerate exchange. These experiments suggest that the basicity of the cubane oxo ligands promotes metal-metal exchange reactivity. The redox potentials of the Mn and cubane starting materials and isotopic labeling studies suggest an inner-sphere electron-transfer mechanism in a dangler intermediate.

Phosphine oxides and arsine oxides are common laboratory reagents with diverse applications that stem from the chemistry exhibited by these monomeric species. Stibine oxides are, in contrast, generally dimeric or oligomeric species because of the reactivity-quenching self-association of the highly polarized stiboryl (Sb=O/Sb+-O-) group. We recently isolated Dipp3SbO (Dipp = 2,6-diisopropylphenyl), the first example of a kinetically stabilized monomeric stibine oxide, which exists as a bench-stable solid and bears an unperturbed stiboryl group. Herein, we report the isolation of Mes3SbO (Mes = mesityl), in which the less bulky substituents maintain the monomeric nature of the compound but unlock access to a wider range of reactivity at the unperturbed stiboryl group relative to Dipp3SbO. Mes3SbO was found to be a potent Lewis base in the formation of adducts with the main-group Lewis acids PbMe3Cl and SnMe3Cl. The accessible Lewis acidity at the Sb atom results in a change in the reactivity with GeMe3Cl, SiMe3Cl, and CPh3Cl. With these species, Mes3SbO formally adds the E-Cl (E = Ge, Si, C) bond across the unsaturated stiboryl group to form a 5-coordinate stiborane. The biphilicity of Mes3SbO is sufficiently potent to activate even the C-F and Si-F bonds of C(p-MeOPh)3F and SiEt3F, respectively. These results mark a significant contribution to an increasingly rich literature on the reactivity of polar, unsaturated main-group motifs. Furthermore, these results highlight the utility of a kinetic stabilization approach to access unusual bonding motifs with unquenched reactivity that can be leveraged for small-molecule activation.

ConspectusDNA-stabilized silver nanoclusters (AgN-DNAs) are sequence-encoded fluorophores. Like other noble metal nanoclusters, the optical properties of AgN-DNAs are dictated by their atomically precise sizes and shapes. What makes AgN-DNAs unique is that nanocluster size and shape are controlled by nucleobase sequence of the templating DNA oligomer. By choice of DNA sequence, it is possible to synthesize a wide range of AgN-DNAs with diverse emission colors and other intriguing photophysical properties. AgN-DNAs hold significant potential as "programmable" emitters for biological imaging due to their combination of small molecular-like sizes, bright and sequence-tuned fluorescence, low toxicities, and cost-effective synthesis. In particular, the potential to extend AgN-DNAs into the second near-infrared region (NIR-II) is promising for deep tissue imaging, which is a major area of interest for advancing biomedical imaging. Achieving this goal requires a deep understanding of the structure-property relationships that govern AgN-DNAs in order to design AgN-DNA emitters with sizes and geometries that support NIR-II emission.In recent years, major advances have been made in understanding the structure and composition of AgN-DNAs, enabling new insights into the correlation of nanocluster structure and photophysical properties. These advances have hinged on combined innovations in mass characterization and crystallography of compositionally pure AgN-DNAs, together with combinatorial experiments and machine learning-guided design. A combined approach is essential due to the major challenge of growing suitable AgN-DNA crystals for diffraction and to the labor-intensive nature of preparing and solving the molecular formulas of atomically precise AgN-DNAs by mass spectrometry. These approaches alone are not feasibly scaled to explore the large sequence space of DNA oligomer templates for AgN-DNAs.This account describes recent fundamental advances in AgN-DNA science that have been enabled by high throughput synthesis and fluorimetry together with detailed analytical studies of purified AgN-DNAs. First, short introductions to nanocluster chemistry and AgN-DNA basics are presented. Then, we review recent large-scale studies that have screened thousands of DNA templates for AgN-DNAs, leading to discovery of distinct classes of these emitters with unique cluster core compositions and ligand chemistries. In particular, the discovery of a new class of chloride-stabilized AgN-DNAs enabled the first ab initio calculations of AgN-DNA electronic structure and present new approaches to stabilize these emitters in biologically relevant conditions. Near-infrared (NIR) emissive AgN-DNAs are also found to exhibit diverse structures and properties. Finally, we conclude by highlighting recent proof-of-principle demonstrations of NIR AgN-DNAs for targeted fluorescence imaging. Continued efforts may future push AgN-DNAs into the tissue transparency window for fluorescence imaging in the NIR-II tissue transparency window.

Healthcare facilities produce millions of tons of waste annually, with a significant portion consisting of diagnostic plasticware. Here, we introduce a new detection platform that completely replaces traditional assay plates with a piece of membrane, offering a much greener and more sustainable alternative. The membrane, integrated within the portable vortex fluidic device (P-VFD), enables rapid detection of a clinically relevant protein biomarker, urinary p75ECD. This biomarker is utilized to evaluate the prognosis, disease severity, and progression of amyotrophic lateral sclerosis (ALS). This assay has a limit-of-detection (LOD) of 4.03 pg, which is comparable to the plate-based assay (2.24 pg) and has been optimised through a full factorial design of experiments (DOE) and response surface methodology (RSM). P-VFD has great potential in quantifying p75ECD in human biofluids and can significantly reduce the assay time to 5 min compared to the current plate-based p75ECD ELISA assay (3 days), with at least a 4.4-fold reduction in the usage of the detection antibody.

Metals are important cofactors in the metabolic processes of cyanobacteria, including photosynthesis, cellular respiration, DNA replication, and the biosynthesis of primary and secondary metabolites. In adaptation to the marine environment, cyanobacteria use metallophores to acquire trace metals when necessary as well as to reduce potential toxicity from excessive metal concentrations. Leptochelins A-C were identified as structurally novel metallophores from three geographically dispersed cyanobacteria of the genus Leptothoe. Determination of the complex structures of these metabolites presented numerous challenges, but they were ultimately solved using integrated data from NMR, mass spectrometry and deductions from the biosynthetic gene cluster. The leptochelins are comprised of halogenated linear NRPS-PKS hybrid products with multiple heterocycles that have potential for hexadentate and tetradentate coordination with metal ions. The genomes of the three leptochelin producers were sequenced, and retrobiosynthetic analysis revealed one candidate biosynthetic gene cluster (BGC) consistent with the structure of leptochelin. The putative BGC is highly homologous in all three Leptothoe strains, and all possess genetic signatures associated with metallophores. Postcolumn infusion of metals using an LC-MS metabolomics workflow performed with leptochelins A and B revealed promiscuous binding of iron, copper, cobalt, and zinc, with greatest preference for copper. Iron depletion and copper toxicity experiments support the hypothesis that leptochelin metallophores may play key ecological roles in iron acquisition and in copper detoxification. In addition, the leptochelins possess significant cytotoxicity against several cancer cell lines.

A 7-tungstabicyclo[4.3.0]nonane complex forms slowly upon addition of cyclohexene to the ethylene complex, W(NAr)(OSiPh3)2(C2H4), at 22 °C. A single-crystal X-ray study showed its structure to be closest to a square pyramid (τ = 0.23). At 22 °C, loss of cyclohexene or ring contraction of the 7-tungstabicyclo[4.3.0]nonane complex is slow. Above ∼80 °C, cyclohexene is ejected to give W(NAr)(OSiPh3)2(C2H4), but a sufficient amount of 7-tungstabicyclo[4.3.0]nonane complex remains in the presence of cyclohexene and the ring contracts to yield methylenecyclohexane and a methylidene complex or ethylene and a cyclohexylidene complex. Other complexes that have been observed include an 8-tungstabicyclo[4.3.0]nonane complex formed from 1,7-octadiene, a 7-tungstabicyclo[4.2.0]octane complex (formed from a methylidene complex and cyclohexene), and a methylenecyclohexane complex. 13C-Labeling studies show that the exo-methylene group in methylenecyclohexane and the α positions in the 8-tungstabicyclo[4.3.0]nonane come from ethylene. An alternative ring contraction of a tungstacyclopentane made from two molecules of cyclohexene cannot be excluded when concentrations of ethylene are low. A cyclohexylidene complex could also form from two cyclohexenes via a newly proposed "alkyl/allyl" mechanism. The results reported here are the first experimental confirmations that a tungstacyclopentane can ring-contract thermally at a substituted WCα position to form a tungstacyclobutane and therefore metathesis-active alkylidenes.

To unravel why computational design fails in creating viable enzymes, while directed evolution (DE) succeeds, our research delves into the laboratory evolution of protoglobin. DE has adapted this protein to efficiently catalyze carbene transfer reactions. We show that the previously proposed enhanced substrate access and binding alone cannot account for increased yields during DE. The 3D electric field in the entire active site is tracked through protein dynamics, clustered using the affinity propagation algorithm, and subjected to principal component analysis. This analysis reveals notable changes in the electric field with DE, where distinct field topologies influence transition state energetics and mechanism. A chemically meaningful field component emerges and takes the lead during DE and facilitates crossing the barrier to carbene transfer. Our findings underscore intrinsic electric field dynamic's influence on enzyme function, the ability of the field to switch mechanisms within the same protein, and the crucial role of the field in enzyme design.

The dynamic restructuring of Cu has been observed under electrochemical conditions, and it has been hypothesized to underlie the unique reactivity of Cu toward CO2 electroreduction. Roughening is one of the key surface phenomena for Cu activation, whereby numerous atomic vacancies and adatoms form. However, the atomic structure of such surface motifs in the presence of relevant adsorbates has remained elusive. Here, we explore the chemical space of Cu surface restructuring under coverage of CO and H in realistic electroreduction conditions, by combining grand canonical DFT and global optimization techniques, from which we construct a potential-dependent grand canonical ensemble representation. The regime of intermediate and mixed CO and H coverage─where structures exhibit some elevated surface Cu─is thermodynamically unfavorable yet kinetically inevitable. Therefore, we develop a quasi-kinetic Monte Carlo simulation to track the system's evolution during a simulated cathodic scan. We reveal the evolution path of the system across coverage space and identify the accessible metastable structures formed along the way. Chemical bonding analysis is performed on the metastable structures with elevated Cu*CO species to understand their formation mechanism. By molecular dynamics simulations and free energy calculations, the surface chemistry of the Cu*CO species is explored, and we identify plausible mechanisms via which the Cu*CO species may diffuse or dimerize. This work provides rich atomistic insights into the phenomenon of surface roughening and the structure of involved species. It also features generalizable methods to explore the chemical space of restructuring surfaces with mixed adsorbates and their nonequilibrium evolution.

The integration of low-energy states into bottom-up engineered graphene nanoribbons (GNRs) is a robust strategy for realizing materials with tailored electronic band structure for nanoelectronics. Low-energy zero-modes (ZMs) can be introduced into nanographenes (NGs) by creating an imbalance between the two sublattices of graphene. This phenomenon is exemplified by the family of [n]triangulenes (n ∈ N). Here, we demonstrate the synthesis of [3]triangulene-GNRs, a regioregular one-dimensional (1D) chain of [3]triangulenes linked by five-membered rings. Hybridization between ZMs on adjacent [3]triangulenes leads to the emergence of a narrow band gap, Eg,exp ∼ 0.7 eV, and topological end states that are experimentally verified using scanning tunneling spectroscopy. Tight-binding and first-principles density functional theory calculations within the local density approximation corroborate our experimental observations. Our synthetic design takes advantage of a selective on-surface head-to-tail coupling of monomer building blocks enabling the regioselective synthesis of [3]triangulene-GNRs. Detailed ab initio theory provides insights into the mechanism of on-surface radical polymerization, revealing the pivotal role of Au-C bond formation/breakage in driving selectivity.

Amphiphilic bottlebrush block copolymers (BBCPs), having a hydrophilic bottlebrush polymer (BP) linked covalently to a hydrophobic BP, were found to segregate to liquid-liquid interfaces to minimize the free energy of the system. The key parameter influencing the outcome of the experiments is the ratio between the degree of polymerization of the backbone (NBB) and that of the side-chain brushes (NSC). Specifically, a spherical, star-like configuration results when NBB < NSC, while a cylindrical, bottlebrush-like shape is preferred when NBB > NSC. Dynamic interfacial tension (γ) and fluorescence recovery after photobleaching (FRAP) measurements show that the BBCP configuration influences the areal density and in-plane diffusion at the fluid interface. The characteristic relaxation times associated with BBCP adsorption (τA) and reorganization (τR) were determined by fitting time-dependent interfacial tension measurements to a sum of two exponential relaxation functions. Both τA and τR initially increased with NBB up to 92 repeat units, due to the larger hydrodynamic radius in solution and slower in-plane diffusivity, attributed to a shorter cross-sectional diameter of the side-chains near the block junction. This trend reversed at NBB = 190, with shorter τA and τR attributed to increased segregation strength and exposure of the bare water/toluene interface due to tilting and/or wiggling of the backbone chains, respectively. The adsorption energy barrier decreased with higher NBB, due to a reduced BBCP packing density at the fluid interface. This study provides fundamental insights into macromolecular assembly at fluid interfaces, as it pertains to unique bottlebrush block architectures.

Spectator ions have known and emerging roles in aqueous metal-cation chemistry, respectively directing solubility, speciation, and reactivity. Here, we isolate and structurally characterize the last two metastable members of the alkali uranyl triperoxide series, the Rb+ and Cs+ salts (Cs-U1 and Rb-U1). We document their rapid solution polymerization via small-angle X-ray scattering, which is compared to the more stable Li+, Na+ and K+ analogues. To understand the role of the alkalis, we also quantify alkali-hydroxide promoted peroxide deprotonation and decomposition, which generally exhibits increasing reactivity with increasing alkali size. Cs-U1, the most unstable of the uranyl triperoxide monomers, undergoes ambient direct air capture of CO2 in the solid-state, converting to Cs4[UVIO2(CO3)3], evidenced by single-crystal X-ray diffraction, transmission electron microscopy, and Raman spectroscopy. We have attempted to benchmark the evolution of Cs-U1 to uranyl tricarbonate, which involves a transient, unstable hygroscopic solid that contains predominantly pentavalent uranium, quantified by X-ray photoelectron spectroscopy. Powder X-ray diffraction suggests this intermediate state contains a hydrous derivative of CsUVO3, where the parent phase has been computationally predicted, but not yet synthesized.

Through mechanistic work and rational design, we have developed the fastest organometallic abiotic Cys bioconjugation. As a result, the developed organometallic Au(III) bioconjugation reagents enable selective labeling of Cys moieties down to picomolar concentrations and allow for the rapid construction of complex heterostructures from peptides, proteins, and oligonucleotides. This work showcases how organometallic chemistry can be interfaced with biomolecules and lead to a range of reactivities that are largely unmatched by classical organic chemistry tools.

Sulfuric acid in the atmosphere can participate in acid-catalyzed and acid-driven reactions, including those within secondary organic aerosols (SOA). Previous studies have observed enhanced absorption at visible wavelengths and significant changes in the chemical composition when SOA was exposed to sulfuric acid. However, the specific chromophores responsible for these changes could not be identified. The goals of this study are to identify the chromophores and determine the mechanism of browning in highly acidified α-pinene SOA by following the behavior of specific common α-pinene oxidation products, namely, cis-pinonic acid and cis-pinonaldehyde, when they are exposed to highly acidic conditions. The products of these reactions were analyzed with ultra-performance liquid chromatography coupled with photodiode array spectrophotometry and high-resolution mass spectrometry, UV-vis spectrophotometry, and nuclear magnetic resonance spectroscopy. cis-Pinonic acid (2) was found to form homoterpenyl methyl ketone (4), which does not absorb visible radiation, while cis-pinonaldehyde (3) formed weakly absorbing 1-(4-(propan-2-ylidene)cyclopent-1-en-1-yl)ethan-1-one (5) and 1-(4-isopropylcyclopenta-1,3-dien-1-yl)ethan-1-one (6) via an acid-catalyzed aldol condensation. This chemistry could be relevant for environments characterized by high sulfuric acid concentrations, for example, during the transport of organic compounds from the lower to the upper atmosphere by fast updrafts.

Direct imaging of single molecules at nanostructured interfaces is a grand challenge with potential to enable new, precise material architectures and technologies. Of particular interest are the structural morphology and spectroscopic signatures of the adsorbed molecule, where modern probes are only now being developed with the necessary spatial and energetic resolution to provide detailed information at the molecule-surface interface. Here, we directly characterize the adsorption of individual m-terphenyl isocyanide ligands on a reconstructed Au(111) surface through scanning tunneling microscopy and inelastic electron tunneling spectroscopy. The site-dependent steric pressure of the various surface features alters the vibrational fingerprints of the m-terphenyl isocyanides, which are characterized with single-molecule precision through joint experimental and theoretical approaches. This study provides molecular-level insights into the steric-pressure-enabled surface binding selectivity as well as its effect on the chemical properties of individual surface-binding ligands.

Nonaqueous organic redox flow batteries (N-ORFBs) are a promising technology for grid-scale storage of energy generated from intermittent renewable sources. Their primary benefit over traditional aqueous RFBs is the wide electrochemical stability window of organic solvents, but the design of catholyte materials, which can exploit the upper range of this window, has proven challenging. We report herein a new class of N-ORFB catholytes in the form of squaric acid quinoxaline (SQX) and squaric acid amide (SQA) materials. Mechanistic investigation of decomposition in battery-relevant conditions via NMR, HRMS, and electrochemical methods enabled a rational design approach to optimizing these scaffolds. Three lead compounds were developed: a highly stable one-electron SQX material with an oxidation potential of 0.51 V vs Fc/Fc+ that maintained 99% of peak capacity after 102 cycles (51 h) when incorporated into a 1.58 V flow battery; a high-potential one-electron SQA material with an oxidation potential of 0.81 V vs Fc/Fc+ that demonstrated negligible loss of redox active material as measured by pre- and postcycling CV peak currents when incorporated in a 1.63 V flow battery for 110 cycles over 29 h; and a proof-of-concept two-electron SQA catholyte material with oxidation potentials of 0.48 and 0.85 V vs Fc/Fc+ that demonstrated a capacity fade of just 0.56% per hour during static H-cell cycling. These findings expand the previously reported space of high-potential catholyte materials and showcase the power of mechanistically informed synthetic design for N-ORFB materials development.

The valorization of lignin, a currently underutilized component of lignocellulosic biomass, has attracted attention to promote a stable and circular bioeconomy. Successful approaches including thermochemical, biological, and catalytic lignin depolymerization have been demonstrated, enabling opportunities for lignino-refineries and lignocellulosic biorefineries. Although significant progress in lignin valorization has been made, this review describes unexplored opportunities in chemical and biological routes for lignin depolymerization and thereby contributes to economically and environmentally sustainable lignin-utilizing biorefineries. This review also highlights the integration of chemical and biological lignin depolymerization and identifies research gaps while also recommending future directions for scaling processes to establish a lignino-chemical industry.

This comprehensive Review delves into the chemical principles governing RNA-mediated crowding events, commonly referred to as granules or biological condensates. We explore the pivotal role played by RNA sequence, structure, and chemical modifications in these processes, uncovering their correlation with crowding phenomena under physiological conditions. Additionally, we investigate instances where crowding deviates from its intended function, leading to pathological consequences. By deepening our understanding of the delicate balance that governs molecular crowding driven by RNA and its implications for cellular homeostasis, we aim to shed light on this intriguing area of research. Our exploration extends to the methodologies employed to decipher the composition and structural intricacies of RNA granules, offering a comprehensive overview of the techniques used to characterize them, including relevant computational approaches. Through two detailed examples highlighting the significance of noncoding RNAs, NEAT1 and XIST, in the formation of phase-separated assemblies and their influence on the cellular landscape, we emphasize their crucial role in cellular organization and function. By elucidating the chemical underpinnings of RNA-mediated molecular crowding, investigating the role of modifications, structures, and composition of RNA granules, and exploring both physiological and aberrant phase separation phenomena, this Review provides a multifaceted understanding of the intriguing world of RNA-mediated biological condensates.

Transition-metal-catalyzed carbene insertion reactions of a nitrogen-hydrogen bond have emerged as robust and versatile methods for the construction of C-N bonds. While significant progress of homogeneous catalytic metal carbene N-H insertions has been achieved, the control of chemoselectivity in the field remains challenging due to the high electrophilicity of the metal carbene intermediates. Herein, we present an efficient strategy for the synthesis of a rhodium single-atom-site catalyst (Rh-SA) that incorporates a Rh atom surrounded by three nitrogen atoms and one phosphorus atom doped in a carbon support. This Rh-SA catalyst, with a catalyst loading of only 0.15 mol %, exhibited exceptional catalytic performance for heterogeneous carbene insertion with various anilines and heteroaryl amines in combination with diazo esters. Importantly, the heterogeneous catalyst selectively transformed aniline derivatives bearing multiple nucleophilic moieties into single N-H insertion isomers, while the popular homogeneous Rh2(OAc)4 catalyst produced a mixture of overfunctionalized side products. Additionally, similar selectivities for N-H bond insertion with a set of stereoelectronically diverse diazo esters were obtained, highlighting the general applicability of this heterogeneous catalysis approach. On the basis of density functional theory calculations, the observed selectivity of the Rh-SA catalyst was attributed to the insertion barriers and the accelerated proton transfer assisted by the phosphorus atom in the support. Overall, this investigation of heterogeneous metal-catalyzed carbene insertion underscores the potential of single-atom-site catalysis as a powerful and complementary tool in organic synthesis.

The chemical bond is the cornerstone of chemistry, providing a conceptual framework to understand and predict the behavior of molecules in complex systems. However, the fundamental origin of chemical bonding remains controversial and has been responsible for fierce debate over the past century. Here, we present a unified theory of bonding, using a separation of electron delocalization effects from orbital relaxation to identify three mechanisms [node-induced confinement (typically associated with Pauli repulsion, though more general), orbital contraction, and polarization] that each modulate kinetic energy during bond formation. Through analysis of a series of archetypal bonds, we show that an exquisite balance of energy-lowering delocalizing and localizing effects are dictated simply by atomic electron configurations, nodal structure, and electronegativities. The utility of this unified bonding theory is demonstrated by its application to explain observed trends in bond strengths throughout the periodic table, including main group and transition metal elements.

Conventional ligands for CsPbBr3 perovskite nanocrystals (NCs), composed of polar, coordinating head groups (e.g., ammonium or zwitterionic) and aliphatic tails, are instrumental in stabilizing the NCs against sintering and aggregation. Nonetheless, the aliphatic (insulating) nature of these ligands represents drawbacks with respect to objectives in optoelectronics, and yet removing these ligands typically leads to a loss of colloidal stability. In this paper, we describe the preparation of CsPbBr3 NCs in the presence of discrete conjugated oligomers that were prepared by an iterative synthetic approach and capped at their chain ends with sulfobetaine zwitterions for perovskite coordination. Notably, these zwitterionic oligofluorenes are compatible with the hot injection and ligand exchange conditions used to prepare CsPbBr3 NCs, yielding stable NC dispersions with high photoluminescence quantum yields (PLQY, >90%) and spectral features representative of both the perovskite core and conjugated ligand shell. Controlling the chain length of these capping ligands effectively regulated inter-NC spacing and packing geometry when cast into solid films, with evidence derived from both transmission electron microscopy (TEM) and grazing incidence X-ray scattering measurements.

High entropy alloys (HEAs) are a highly promising class of materials for electrocatalysis as their unique active site distributions break the scaling relations that limit the activity of conventional transition metal catalysts. Existing Bayesian optimization (BO)-based virtual screening approaches focus on catalytic activity as the sole objective and correspondingly tend to identify promising materials that are unlikely to be entropically stabilized. Here, we overcome this limitation with a multiobjective BO framework for HEAs that simultaneously targets activity, cost-effectiveness, and entropic stabilization. With diversity-guided batch selection further boosting its data efficiency, the framework readily identifies numerous promising candidates for the oxygen reduction reaction that strike the balance between all three objectives in hitherto unchartered HEA design spaces comprising up to 10 elements.

Gallium phosphide is an established photoelectrode material for H2 or O2 evolution from water, but particle-based GaP photocatalysts for H2 evolution are very rare. To understand the reasons, we investigated the photocatalytic H2 evolution reaction (HER) of suspended n-type GaP particles with iodide, sulfite, ferricyanide, ferrous ion, and hydrosulfide as sacrificial electron donors, and using Pt, RhyCr2-yO3, and Ni2P HER cocatalysts. A record apparent quantum efficiency of 14.8% at 525 nm was achieved after removing gallium and oxide charge trapping states from the GaP surface, adding a Ni2P cocatalyst to reduce the proton reduction overpotential, lowering the Schottky-barrier at the GaP-cocatalyst interface, adjusting the polarity of the depletion layer at the GaP-liquid interface, and optimizing the electrochemical potential of the electron donor. The work not only showcases the main factors that control charge separation in suspended photocatalysts, but it also explains why most known HER photocatalysts in the literature are based on n-type and not p-type semiconductors.

Diamine-appended Mg2(dobpdc) (dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) metal-organic frameworks are promising candidates for carbon capture that exhibit exceptional selectivities and high capacities for CO2. To date, CO2 uptake in these materials has been shown to occur predominantly via a chemisorption mechanism involving CO2 insertion at the amine-appended metal sites, a mechanism that limits the capacity of the material to ∼1 equiv of CO2 per diamine. Herein, we report a new framework, pip2-Mg2(dobpdc) (pip2 = 1-(2-aminoethyl)piperidine), that exhibits two-step CO2 uptake and achieves an unusually high CO2 capacity approaching 1.5 CO2 per diamine at saturation. Analysis of variable-pressure CO2 uptake in the material using solid-state nuclear magnetic resonance (NMR) spectroscopy and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) reveals that pip2-Mg2(dobpdc) captures CO2 via an unprecedented mechanism involving the initial insertion of CO2 to form ammonium carbamate chains at half of the sites in the material, followed by tandem cooperative chemisorption and physisorption. Powder X-ray diffraction analysis, supported by van der Waals-corrected density functional theory, reveals that physisorbed CO2 occupies a pocket formed by adjacent ammonium carbamate chains and the linker. Based on breakthrough and extended cycling experiments, pip2-Mg2(dobpdc) exhibits exceptional performance for CO2 capture under conditions relevant to the separation of CO2 from landfill gas. More broadly, these results highlight new opportunities for the fundamental design of diamine-Mg2(dobpdc) materials with even higher capacities than those predicted based on CO2 chemisorption alone.

The catalytic transformation of C-H to C-N bonds offers rapid access to fine chemicals and high-performance materials, but achieving high selectivity from undirected aminations of unactivated C(sp3)-H bonds remains an outstanding challenge. We report the origins of the reactivity and selectivity of a Cu-catalyzed C-H amidation of simple alkanes. Using a combination of experimental and computational mechanistic studies and energy decomposition techniques, we uncover a switch in mechanism from inner-sphere to outer-sphere coupling between alkyl radicals and the active Cu(II) catalyst with increasing substitution of the alkyl radical. The combination of computational predictions and detailed experimental validation shows that simultaneous minimization of both Cu-C covalency and alkyl radical size increases the rate of reductive elimination and that both strongly electron-donating and electron-withdrawing substituents on the catalyst accelerate the selectivity-determining C-N bond formation process as a result of a change in mechanism. These findings offer design principles for the development of improved catalyst scaffolds for radical C-H functionalization reactions.

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. Our integrated studies provide an unprecedented molecular-level understanding of the nontrivial pH-dependent HER kinetics in alkaline media.

ConspectusThere is considerable recent interest in the synthesis and development of peptide-based materials as mimics of natural biological assemblies that utilize proteins and peptides to form organized structures and develop beneficial properties. Due to their potential compatibility with living organisms, synthetic peptide materials are also being developed for applications such as cell grafting, therapeutic delivery, and implantable diagnostic devices. One desirable feature for such applications is the ability to design materials that can respond to stimuli by changes in their structure or properties under biologically relevant conditions. Peptide and protein assemblies can respond to stimuli, such as changes in temperature, solution pH, ions present in media, or interactions with other biomacromolecules. An exciting area of emerging research is focused on how biology uses the chemistry of sulfur-containing amino acids as a means to regulate biological processes. These concepts have been utilized and expanded in recent years to enable the development of peptide materials with readily switchable properties.The incorporation of sulfur atoms in polypeptides, peptides, and proteins provides unique sites that can be used to alter the physical and biological properties of these materials. Sulfur-containing amino acid residues, most often cysteine and methionine, are able to undergo a variety of selective chemical and enzyme-mediated reactions, which can be broadly characterized as redox or alkylation processes. These reactions often proceed under physiologically relevant conditions, can be reversible, and are significant in that they can alter residue polarity as well as conformations of peptide chains. These sulfur-based reactions are able to switch molecular and macromolecular properties of peptides and proteins in living systems and recently have been applied to synthetic peptide materials. Naturally occurring "sulfur switches" can be reversible or irreversible and are often triggered by enzymatic activity. Sulfur switches in peptide materials can also be triggered in vitro using oxidation/reduction and alkylation as well as photochemical reactions. The application of sulfur switches to peptide materials has greatly expanded the scope of these switches due to the ability to readily incorporate a wide variety of noncanonical sulfur-containing synthetic amino acids.Sulfur switches have been shown to provide considerable potential to reversibly alter peptide material properties under mild physiologically relevant conditions. An important molecular feature of sulfur-containing amino acid residues was found to be the location of sulfur atoms in the side chains. The variation of sulfur atom positions from the backbone by single bond lengths was found to significantly affect polypeptide chain conformations upon oxidation-reduction or alkylation/dealkylation reactions. With the successful adaptation of sulfur switches to peptide materials, future studies can explore how these switches affect how these materials interact with biological systems. This Account provides an overview of the different types of sulfur switch reactions found in biology and their properties and the elaboration of these switches in synthetic systems with a focus on recent developments and applications of reversible sulfur switches in peptide materials.

Concentrated water-in-salt electrolytes (WiSEs) are used in aqueous batteries and to control electrochemical reactions for fuel production. The hydrogen evolution reaction is a parasitic reaction at the negative electrode that limits cell voltage in WiSE batteries and leads to self-discharge, and affects selectivity for electrosynthesis. Mitigating and modulating these processes is hampered by a limited fundamental understanding of HER kinetics in WiSEs. Here, we quantitatively assess how thermodynamics, kinetics, and interface layers control the apparent HER activities in 20 m LiTFSI. When the LiTFSI concentration is increased from 1 to 20 m, an increase in proton activity causes a positive shift in the HER equilibrium potential of 71 mV. The exchange current density, io, derived from the HER branch for 20 m LiTFSI in 98% purity (0.56 ± 0.05 μA/cmPt2), however, is 8 times lower than for 20 m LiTFSI in 99.95% (4.7 ± 0.2 μA/cmPt2) and 32 times lower than for 1 m LiTFSI in 98% purity (18 ± 1 μA/cmPt2), demonstrating that the WiSE's impurities and concentration are both central in significantly suppressing HER kinetics. The ability and applicability of the reported methods are extended by examining additional WiSEs formulations made of acetates and nitrates.

High or enriched-purity O2 is used in numerous industries and is predominantly produced from the cryogenic distillation of air, an extremely capital- and energy-intensive process. There is significant interest in the development of new approaches for O2-selective air separations, including the use of metal-organic frameworks featuring coordinatively unsaturated metal sites that can selectively bind O2 over N2 via electron transfer. However, most of these materials exhibit appreciable and/or reversible O2 uptake only at low temperatures, and their open metal sites are also potential strong binding sites for the water present in air. Here, we study the framework CuI-MFU-4l (CuxZn5-xCl4-x(btdd)3; H2btdd = bis(1H-1,2,3-triazolo[4,5-b],[4',5'-i])dibenzo[1,4]dioxin), which binds O2 reversibly at ambient temperature. We develop an optimized synthesis for the material to access a high density of trigonal pyramidal CuI sites, and we show that this material reversibly captures O2 from air at 25 °C, even in the presence of water. When exposed to air up to 100% relative humidity, CuI-MFU-4l retains a constant O2 capacity over the course of repeated cycling under dynamic breakthrough conditions. While this material simultaneously adsorbs N2, differences in O2 and N2 desorption kinetics allow for the isolation of high-purity O2 (>99%) under relatively mild regeneration conditions. Spectroscopic, magnetic, and computational analyses reveal that O2 binds to the copper(I) sites to form copper(II)-superoxide moieties that exhibit temperature-dependent side-on and end-on binding modes. Overall, these results suggest that CuI-MFU-4l is a promising material for the separation of O2 from ambient air, even without dehumidification.

Selective hydrogenation of α,β-unsaturated aldehydes to produce unsaturated alcohols remains a challenge in catalysis. Here, we explore, on the basis of first-principles simulations, single-atom alloy (SAA) catalysts on copper as a class of catalytic materials to enhance the selectivity for C═O bond hydrogenation in unsaturated aldehydes by controlling the binding strength of the C═C and C═O bonds. We show that on SAA of early transition metals such as Ti, Zr, and Hf, the C═O binding mode of acrolein is favored but the strong binding renders subsequent hydrogenation and desorption impossible. On SAA of late-transition metals, on the other hand, the C═C binding mode is favored and C═C bond hydrogenation follows, resulting in the production of undesired saturated aldehydes. Mid-transition metals (Cr and Mn) in Cu(111) appear as the optimal systems, since they favor acrolein adsorption via the C═O bond but with a moderate binding strength, compatible with catalysis. Additionally, acrolein migration from the C═O to the C═C binding mode, which would open the low energy path for C═C bond hydrogenation, is prevented by a large barrier for this process. SAA of Cr in Cu appears as an optimal candidate, and kinetic simulations show that the selectivity for propenol formation is controlled by preventing the acrolein migration from the more stable C═O to the less stable C═C binding mode and subsequent H-migration and by the formation of the O-H bond from the monohydrogenated intermediate. Dilute alloy catalysts therefore enable tuning the binding strength of intermediates and transition states, opening control of catalytic activity and selectivity.

We theoretically investigate the influence of diradical electron spin coupling on the time-resolved X-ray absorption spectra of the photochemical ring opening of furanone. We predict geometry-dependent carbon K-edge signals involving transitions from core orbitals to both singly and unoccupied molecular orbitals. The most obvious features of the ring opening come from the carbon atom directly involved in the bond breaking through its transition to both the newly formed singly occupied and the available lowest unoccupied molecular orbitals (SOMO and LUMO, respectively). In addition to this primary feature, the singlet spin coupling of four unpaired electrons that arises in the core-to-LUMO states creates additional geometry dependence in some spectral features with both oscillator strengths and relative excitation energies varying observably as a function of the ring opening. We attribute this behavior to a spin-occupancy-induced selection rule, which occurs when singlet spin coupling is enforced in the diradical state. Notably, one of these geometry-sensitive core-to-LUMO transitions excites core electrons from a backbone carbon not involved in the bond breaking, providing a novel nonlocal X-ray probe of chemical dynamics arising from electron spin coupling.

Natural proteins are highly optimized for function but are often difficult to produce at a scale suitable for biotechnological applications due to poor expression in heterologous systems, limited solubility, and sensitivity to temperature. Thus, a general method that improves the physical properties of native proteins while maintaining function could have wide utility for protein-based technologies. Here, we show that the deep neural network ProteinMPNN, together with evolutionary and structural information, provides a route to increasing protein expression, stability, and function. For both myoglobin and tobacco etch virus (TEV) protease, we generated designs with improved expression, elevated melting temperatures, and improved function. For TEV protease, we identified multiple designs with improved catalytic activity as compared to the parent sequence and previously reported TEV variants. Our approach should be broadly useful for improving the expression, stability, and function of biotechnologically important proteins.

We herein describe the synthesis of a new class of axially chiral aza/boracyclophanes (BDN1, BXN1, BDB1 and BXB1) using binaphthyls as chiral building blocks and the main-group (B/N) chemistry with tunable electronic effects. All macrocycles substituted with triarylamine donors or triarylborane acceptors are strongly luminescent. These macrocycles showed two distinct meta and para π-conjugation pathways, leading to the formation of quasi figure-of-eight and square-shaped conformations. Interestingly, comparison of such structural models revealed that the former type of macrocycles BXN1 and BXB1 gave higher racemization barriers relative to the other ones. The results reported here may provide a new approach to engineer the optical stability of π-conjugated chiral macrocycles by controlling π-substitution patterns. The ring constraints induced by macrocyclization were also demonstrated to contribute to the configurational persistence as compared with the open-chain analogues p-BTT and m-BTT.

Sialic acids are fascinating negatively charged nine-carbon monosaccharides. Sialic acid-containing glycans and glycoconjugates are structurally diverse, functionally important, and synthetically challenging molecules. We have developed highly efficient chemoenzymatic strategies that combine the power of chemical synthesis and enzyme catalysis to make sialic acids, sialyl glycans, sialyl glycoconjugates, and their derivatives more accessible, enabling the efforts to explore their functions and applications. The Account starts with a brief description of the structural diversity and the functional importance of naturally occurring sialic acids and sialosides. The development of one-pot multienzyme (OPME) chemoenzymatic sialylation strategies is then introduced, highlighting its advantages in synthesizing structurally diverse sialosides with a sialyltransferase donor substrate engineering tactic. With the strategy, systematic access to sialosides containing different sialic acid forms with modifications at C3/4/5/7/8/9, various internal glycans, and diverse sialyl linkages is now possible. Also briefly described is the combination of the OPME sialylation strategy with bacterial sialidases for synthesizing sialidase inhibitors. With the goal of simplifying the product purification process for enzymatic glycosylation reactions, glycosphingolipids that contain a naturally existing hydrophobic tag are attractive targets for chemoenzymatic total synthesis. A user-friendly highly efficient chemoenzymatic strategy is developed which involves three main processes, including chemical synthesis of lactosyl sphingosine as a water-soluble hydrophobic tag-containing intermediate, OPME enzymatic extension of its glycan component with a single C18-cartridge purification of the product, followed by a facile chemical acylation reaction. The strategy allows the introduction of different sialic acid forms and diverse fatty acyl chains into the products. Gram-scale synthesis has been demonstrated. OPME sialylation has also been demonstrated for the chemoenzymatic synthesis of sialyl glycopeptides and in vitro enzymatic N-glycan processing for the formation of glycoproteins with disialylated biantennary complex-type N-glycans. For synthesizing human milk oligosaccharides (HMOs) which are glycans with a free reducing end, acceptor substrate engineering and process engineering strategies are developed, which involve the design of a hydrophobic tag that can be easily installed into the acceptor substrate to allow facile purification of the product from enzymatic reactions and can be conveniently removed in the final step to produce target molecules. The process engineering involves heat-inactivation of enzymes in the intermediate steps in multistep OPME reactions for the production of long-chain sialoside targets in a single reaction pot and with a single C18-cartridge purification process. In addition, a chemoenzymatic synthon strategy has been developed. It involves the design of a derivative of the sialyltransferase donor substrate precursor, which is tolerated by enzymes in OPME reactions, introduced to enzymatic products, and then chemically converted to the desired target structures in the final step. The chemoenzymatic synthon approach has been used together with the acceptor substrate engineering method in the synthesis of complex bacterial glycans containing sialic acids, legionaminic acids, and derivatives. The biocatalysts characterized and their engineered mutants developed by the Chen group are described, with highlights on synthetically useful enzymes. We anticipate further development of chemoenzymatic strategies and biocatalysts to enable exploration of the sialic acid space.

Students come into the classroom with a variety of background knowledge. Therefore, it is imperative that educators are able to help all students, regardless of their familiarity with the content. Since it can be challenging for some large enrollment classes to schedule recitation classes after lectures due to logistical constraints, this study attempts to determine if there are differences in performance based on when content is introduced first, recitation or lecture. This study found that students who were introduced to content in recitation before a lecture typically scored statistically higher across three mid-term exams, in a first-term general chemistry course. This difference in performance suggests that students who are introduced to content in recitation, versus simply hearing about a topic in a lecture, might get more out of the lecture, thus leading to higher performance on exams. Students who are introduced to topics that are tested by way of definition-based questions or basic calculations benefit from being introduced to this content in recitation before the lecture. However, when introducing more challenging and abstract chemistry topics, our results indicate it may benefit students to be introduced to these topics in the lecture first, so they can begin developing their conceptual understanding in the lecture. [ABSTRACT FROM AUTHOR]

Mixed results have been reported on the correlation between clickers and performance. This study investigates the usage of clickers in a voluntary context to answer in-class questions in a General Chemistry class. Scores on an internal chemistry placement exam were used to estimate cognitive ability, as a factor that students can no longer control, and average participation on clicker questions was considered as a behavioral aspect that students are able to change. While placement exam scores and clicker usage do not correlate with each other, both positively correlate with performance (midterm average grades and final course grades) in the cohorts of this study (2017, 2018, and 2019). Independent of placement exam scores, students who answered more clicker questions performed better on midterm exams and had a higher final course grade. Students who obtained course grades of A, B, or C answered more clicker questions on average (68% of questions) than students who earned course grades of D or F (51% of questions). Those who answered more than the average number of the clicker questions were at least 2.6 times more likely to achieve course proficiency. These results suggest that students who choose to engage by answering questions in class (answer correctness not required) are more likely to perform well in general chemistry courses, regardless of cognitive ability. [ABSTRACT FROM AUTHOR]

General Chemistry is the first of the 12 core courses in the Chemistry "101 Plan" of the Ministry of Education, and serves as the foundation of university-level chemistry courses. It has a unique position in the university chemistry curriculum system. This article provides a detailed introduction to the design ideas and construction of the General Chemistry course in the Chemistry "101 Plan" from the aspects of course information, knowledge modules and knowledge points, core faculty team building, and construction of core textbook and teaching plans. Taking the Chemistry "101 Plan" as an opportunity, we aim to build a first-class core course, a core textbook, and a core faculty team, in order to improve the quality of talent cultivation in the field of chemistry. [ABSTRACT FROM AUTHOR]

This study examined the relationship between the time students spend on practice problems and their performance on exams in various chemistry topics, considering their demographics. The researchers divided 91 general chemistry students into three groups based on the time allotted for solving intervention questions: Minimum, Average, and Maximum. The results showed that the Minimum and Average time groups benefited almost equally, but the performance of the Maximum time group declined. This suggests that, while additional practice is beneficial, there could be an optimal amount of time that students should spend on each question. Spending too much time on a single question can lead to mental and emotional fatigue, resulting in a decline in performance. Additionally, the researchers noted variations in performance across different chemistry topics and student groups, and they examined the relationship between student demographics and their problem-solving performances. The study provides recommendations for educators, testing services, and online homework systems to improve the effectiveness of chemistry instruction, highlighting the importance of finding the right balance between practice time and student engagement, and suggesting that a uniform approach to practice problems may not be ideal for every student. [ABSTRACT FROM AUTHOR]

When General Chemistry at West Point switched from interactive lectures to guided inquiry, it provided an opportunity to examine what was expected of students in classrooms and on assessments. Learning objectives and questions on mid-term exams for four semesters of General Chemistry I (two traditional semesters and two guided inquiry semesters) were analyzed by the Cognitive Process and Knowledge dimensions of Bloom's revised taxonomy. The results of this comparison showed the learning objectives for the guided inquiry semesters had a higher proportion of Conceptual and Understand with a corresponding decrease of Factual, Procedural, Remember and Apply learning objectives. On mid-term exams, the proportion of Remember, Understand, Analyze/Evaluate, Factual, and Conceptual questions increased. We found that guided inquiry learning objectives and mid-term exam questions are more conceptual than traditional courses and may help explain how active learning improves equity in introductory chemistry. [ABSTRACT FROM AUTHOR]

A program for writing words (or personal names) by combining chemical element symbols is developed in the context of classroom activity to introduce the periodic table, properties of elements, and periodic trends. We provide multiple examples and possible ideas to improve student engagement and create an inclusive environment in the classroom. Common confusions and mistakes made when learning the periodic table are tabulated and discussed. In addition to spelling words and creating graphics using element symbols, the program can display and print out properties of elements as part of the word-building game. [ABSTRACT FROM AUTHOR]

Bonding interactions and spin-orbit coupling in the topological insulator SrAg4 Sb2 are investigated using DFT with orbital projection analysis. Ag-Ag delta bonding is a key ingredient in the topological insulating state because the 4dxy+4dx2-y2${4d_{xy} + 4d_{x^2 - y^2 } }$ delta antibonding band forms a band inversion with the 5 s sigma bonding band. Spin-orbit coupling is required to lift d orbital degeneracies and lower the antibonding band enough to create the band inversion. These bonding effects are enabled by a longer-than-covalent Ag-Ag distance in the crystal lattice, which might be a structural characteristic of other transition metal based topological insulators. A simplified model of the topological bands is constructed to capture the essence of the topological insulating state in a way that may be engineered in other materials.