College of Chemistry

Deployment of large numbers of low capital cost sensors to increase the spatial density of air quality measurements enables applications that build on mapping air at neighborhood scales. Effective deployment requires not only low capital costs for observations but also a simultaneous reduction in labor costs. The Berkeley Environmental Air Quality and CO2 Network (BEACO2N) is a sensor network measuring O3, CO, NO, and NO2, particulate matter (PM2.5), and CO2 at dozens of locations in cities where it is deployed. Here, we describe a low labor cost in situ field calibration for the BEACO2N O3, CO, NO, and NO2 sensors. This method identifies and leverages uniform periods in concentrations across the network for calibration. The calibration achieves high accuracy and low biases with respect to temperature, humidity, and concentration, with coefficients of determination and root mean square errors of 0.88 and 3.70 ppb for O3, 0.66 and 3.16 ppb for NO2, and 0.79 and 1.58 ppb for NO. Performance of the CO sensor is 0.90 and 33.3 ppb at a site colocated with reference measurements. The method is a crucial step toward lowering operational costs of delivering accurate measurements in dense networks employing large numbers of inexpensive air quality sensors.

The construction of thin film heterostructures has been a widely successful archetype for fabricating materials with emergent physical properties. This strategy is of particular importance for the design of multilayer magnetic architectures in which direct interfacial spin-spin interactions between magnetic phases in dissimilar layers lead to emergent and controllable magnetic behavior. However, crystallographic incommensurability and atomic-scale interfacial disorder can severely limit the types of materials amenable to this strategy, as well as the performance of these systems. Here, we demonstrate a method for synthesizing heterostructures comprising magnetic intercalation compounds of transition metal dichalcogenides (TMDs), through directed topotactic reaction of the TMD with a metal oxide. The mechanism of the intercalation reaction enables thermally initiated intercalation of the TMD from lithographically patterned oxide films, giving access to a family of multi-component magnetic architectures through the combination of deterministic van der Waals assembly and directed intercalation chemistry.

Sciences broader impacts and the historic social, political, and geographic implications of these impacts are rarely discussed in graduate STEM curricula. A new required Scientific Responsibility and Citizenship course for first year chemistry graduate students was developed and taught at UC Berkeley. The course examined a series of case studies in which basic chemistry research led to societal impacts and discussed the diversity and equity of the research process and resulting consequences. The impact of the course was examined through pre- and post-surveys and interviews with participants. The course was found to have raised students awareness and sense of responsibility for the impacts of their research and the importance of diversity, equity, and inclusion. Students also expressed an increased sense of identity and value alignment with the community as a result of the course. This study shows that even a relatively low-commitment intervention (6 hours in total), can have a large positive impact on students awareness of the social context of science and their perceptions of department values.

Controlling the reactivity of bonds along polymer chains enables both functionalization and deconstruction with relevance to chemical recycling and circularity. Because the substrate is a macromolecule, however, understanding the effects of chain conformation on the reactivity of polymer bonds emerges as important yet underexplored. Here, we show how oxy-functionalization of chemically recyclable condensation polymers affects acidolysis to monomers through control over distortion and interaction energies in the rate-limiting transition states. Oxy-functionalization of polydiketoenamines at specific sites on either the amine or triketone monomer segments increased acidolysis rates by more than three orders of magnitude, opening the door to efficient deconstruction of linear chain architectures. These insights substantially broaden the scope of applications for polydiketoenamines in a circular manufacturing economy, including chemically recyclable adhesives for a diverse range of surfaces.

Understanding the chemistry of the inert actinide oxo bond in actinyl ions AnO22+ is important for controlling actinide behavior in the environment, during separations, and in nuclear waste (An = U, Np, Pu). The thioether calixarene TC4A (4-tert-butyltetrathiacalix[4]arene) binds equatorially to [AnO2]n+ (An = U, Np) forming a conical pocket that differentiates the two trans-oxo groups. The 'ate' complexes, [A]2[UO2(TC4A)] (A = [Li(DME)2], HNEt3) and [HNEt3]2[NpO2(TC4A)], enable selective oxo chemistry. Silylation of the UVI oxo groups by bis(trimethylsilyl)pyrazine occurs first at only the unencapsulated exo oxo and only one silylation is needed to enable migration of the endo oxo out of the cone, whereupon a second silylation affords the stable UIV cis-bis(siloxide) [A]2[U(OSiMe3)2(TC4A)]. Calculations confirm that only one silylation event is needed to initiate oxo rearrangement, and that the putative cis dioxo isomer of [UO2(TC4A)]2- would be stable if it could be accessed synthetically, at only 23 kcal.mol-1 in energy above the classical trans dioxo. The aryloxide (OAr) groups of the macrocycle are essential in stabilizing this as-yet unseen uranyl geometry, with further bonding in the TC4A U-OAr groups stabilizing the U=O 'yl' bonds, explaining the stability of a calculated cis[UO2(TC4A)]2- in this ligand framework.

Developing multicharge and spin stabilization strategies is fundamental to enhancing the lifetime of functional organic materials, particularly for long-term energy storage in multiredox organic redox flow batteries. Current approaches are limited to the incorporation of electronic substituents to increase or decrease the overall electron density or bulky substituents to sterically shield reactive sites. With the aim to further expand the molecular toolbox for charge and spin stabilization, we introduce regioisomerism as a scaffold-diversifying design element that considers the collective and cumulative electronic and steric contributions from all of the substituents based on their relative regioisomeric arrangements. Through a systematic study of regioisomers of near-planar aromatic cyclic triindoles and nonplanar nonaromatic cyclic tetraindoles, we demonstrate that this regioisomeric engineering strategy significantly enhances the H-cell cycling stability in the above two new classes of 2e- catholytes, even when current strategies failed to stabilize the multicharged species. Density functional theory calculations reveal that the strategy operates by redistributing the charge and spin densities while highlighting the role of aromaticity in charge stabilization. The most stable 2e- catholyte candidate was paired with a viologen derivative anolyte to achieve a proof-of-concept all-organic flow battery with 1.26-1.49 V, 98% capacity retention, and only 0.0117% fade/h and 0.00563% fade/cycle over 400 cycles (192 h), which is the highest capacity retention ever reported over 400 cycles in a multielectron all-organic flow battery setup. We anticipate regioisomeric engineering to be a promising strategy complementary to conventional electronic and steric approaches for multicharge and spin stabilization in other functional organic materials.

Dioxygen (O2) is a potent oxidant used by aerobic organisms for energy transduction and critical biosynthetic processes. Numerous metalloenzymes harness O2 to mediate C-H bond hydroxylation reactions, but most commonly feature iron or copper ions in their active site cofactors. In contrast, many manganese-activated enzymes─such as glutamine synthetase and isocitrate lyase─perform redox neutral chemical transformations and very few are known to activate O2 or C-H bonds. Here, we report that the dimanganese-metalated form of the cambialistic monooxygenase SfbO (Mn2-SfbO) can efficiently mediate enzymatic C-H bond hydroxylation. The activity of the dimanganese form of SfbO toward substrate hydroxylation is comparable to that of its heterobimetallic Mn/Fe form but exhibits distinct kinetic profiles. Kinetic, spectroscopic, and structural studies invoke a mixed-valent dimanganese cofactor (MnIIMnIII) in O2 activation and evidence a stoichiometric role for superoxide in maturing an O2-inert MnII2 cofactor. Computational studies support a hypothesis wherein superoxide addition to the MnII2 cofactor installs a critical bridging hydroxide ligand that stabilizes higher-valent manganese oxidation states. These findings establish the viability of proteinaceous dimanganese cofactors in mediating complex, multistep redox transformations.

In Nature, the four-electron reduction of O₂ is catalyzed at preorganized multimetallic active sites. These complex active sites often feature low-coordinate, redox-active metal centers precisely positioned to facilitate rapid O₂ activation processes that obviate the generation of toxic, partially reduced oxygen species. Very few biomimetic constructs simultaneously recapitulate the complexity and reactivity of these biological cofactors. Herein, we report solid-state O₂ activation at a triiron(II) active site templated by phosphinimide ligands. Insight into the structure of the O₂ reduction intermediates was obtained via in crystallo O₂ dosing experiments in conjunction with spectroscopic, structural, magnetic, and computational studies. These data support the in situ formation of an Fe₂^IIIFe^IV-dioxo intermediate upon exposure to O₂ that participates in oxygen atom and hydrogen atom transfer reactivity with exogenous substrates to furnish a stable Fe^IIFe₂^III-oxo species. Combined, these studies provide an extraordinary level of detail into the dynamics of bond-forming and -breaking processes operative at complex multimetallic active sites.

Unraveling vulnerabilities in chronic lymphocytic leukemia (CLL) represents a key approach to understand molecular basis for its indolence and a path toward developing tailored therapeutic approaches. In this study, we found that CLL cells are particularly sensitive to the inhibitory action of abundant serum protein, apolipoprotein E (ApoE). Physiological concentrations of ApoE affect CLL cell viability and inhibit CD40-driven proliferation. Transcriptomics of ApoE-treated CLL cells revealed a signature of redox and metal disbalance which prompted us to explore the underlying mechanism of cell death. We discover, on one hand, that ApoE treatment of CLL cells induces lipid peroxidation and ferroptosis. On the other hand, we find that ApoE is a copper-binding protein and that intracellular copper regulates ApoE toxicity. ApoE regulation tends to be lost in aggressive CLL. CLL cells from patients with high leukocyte counts are less sensitive to ApoE inhibition, while resistance to ApoE is possible in transformed CLL cells from patients with Richter syndrome (RS). Nevertheless, both aggressive CLL and RS cells maintain sensitivity to drug-induced ferroptosis. Our findings suggest a natural suppression axis that mediates ferroptotic disruption of CLL cell proliferation, building up the rationale for choosing ferroptosis as a therapeutic target in CLL and RS.

Cryogenic transmission electron microscopy (cryo-TEM) combined with single particle analysis (SPA) is an emerging imaging approach for soft materials. However, the accuracy of SPA-reconstructed nanostructures, particularly those formed by synthetic polymers, remains uncertain due to potential packing heterogeneity of the nanostructures. In this study, the combination of molecular dynamics (MD) simulations and image simulations is utilized to validate the accuracy of cryo-TEM 3D reconstructions of self-assembled polypeptoid fibril nanostructures. Using CryoSPARC software, image simulations, 2D classifications, ab initio reconstructions, and homogenous refinements are performed. By comparing the results with atomic models, the recovery of molecular details is assessed, heterogeneous structures are identified, and the influence of extraction location on the reconstructions is evaluated. These findings confirm the fidelity of single particle analysis in accurately resolving complex structural characteristics and heterogeneous structures, exhibiting its potential as a valuable tool for detailed structural analysis of synthetic polymers and soft materials.