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Open Access Publications from the University of California

College of Chemistry

UC Berkeley

This series is automatically populated with publications deposited by UC Berkeley College of Chemistry Department of Chemistry researchers in accordance with the University of California’s open access policies. For more information see Open Access Policy Deposits and the UC Publication Management System.

Cover page of Sodium Carbonate ion complexes modify water structure at electrode interfaces

Sodium Carbonate ion complexes modify water structure at electrode interfaces

(2024)

Water structure near electrode interfaces may play an important role in controlling CO2 electroreduction. Using plasmon-enhanced vibrational sum frequency generation spectroscopy, we demonstrate the emergence of an interfacial water subpopulation with large electric fields along their OH bonds, when Na2CO3 ions are present near the electrode under applied potential. With molecular dynamics simulations, we show that the approach of aqueous Na2CO3 to electrodes is coupled to the formation of structured and oriented ion complexes, and that the emergent water population is associated with the first solvation shell of these complexes. This water subpopulation is seen even when the sole source of CO32− is its in-situ generation from CO2, indicating that the interfacial species investigated here are likely ubiquitous in CO2 electroreduction contexts.

Cover page of A tandem activity-based sensing and labeling strategy reveals antioxidant response element regulation of labile iron pools.

A tandem activity-based sensing and labeling strategy reveals antioxidant response element regulation of labile iron pools.

(2024)

Iron is an essential element for life owing to its ability to participate in a diverse array of oxidation-reduction reactions. However, misregulation of iron-dependent redox cycling can also produce oxidative stress, contributing to cell growth, proliferation, and death pathways underlying aging, cancer, neurodegeneration, and metabolic diseases. Fluorescent probes that selectively monitor loosely bound Fe(II) ions, termed the labile iron pool, are potentially powerful tools for studies of this metal nutrient; however, the dynamic spatiotemporal nature and potent fluorescence quenching capacity of these bioavailable metal stores pose challenges for their detection. Here, we report a tandem activity-based sensing and labeling strategy that enables imaging of labile iron pools in live cells through enhancement in cellular retention. Iron green-1 fluoromethyl (IG1-FM) reacts selectively with Fe(II) using an endoperoxide trigger to release a quinone methide dye for subsequent attachment to proximal biological nucleophiles, providing a permanent fluorescent stain at sites of elevated labile iron. IG1-FM imaging reveals that degradation of the major iron storage protein ferritin through ferritinophagy expands the labile iron pool, while activation of nuclear factor-erythroid 2-related factor 2 (NRF2) antioxidant response elements (AREs) depletes it. We further show that lung cancer cells with heightened NRF2 activation, and thus lower basal labile iron, have reduced viability when treated with an iron chelator. By connecting labile iron pools and NRF2-ARE activity to a druggable metal-dependent vulnerability in cancer, this work provides a starting point for broader investigations into the roles of transition metal and antioxidant signaling pathways in health and disease.

Cover page of Scanning electrochemical probe microscopy investigation of two-dimensional materials

Scanning electrochemical probe microscopy investigation of two-dimensional materials

(2024)

Research interests in two-dimensional (2D) materials have seen exponential growth owing to their unique and fascinating properties. The highly exposed lattice planes coupled with tunable electronic states of 2D materials have created manifold opportunities in the design of new platforms for energy conversion and sensing applications. Still, challenges in understanding the electrochemical (EC) characteristics of these materials arise from the complexity of both intrinsic and extrinsic heterogeneities that can obscure structure-activity correlations. Scanning EC probe microscopic investigations offer unique benefits in disclosing local EC reactivities at the nanoscale level that are otherwise inaccessible with macroscale methods. This review summarizes recent progress in applying techniques of scanning EC microscopy (SECM) and scanning EC cell microscopy (SECCM) to obtain distinctive insights into the fundamentals of 2D electrodes. We showcase the capabilities of EC microscopies in addressing the roles of defects, thickness, environments, strain, phase, stacking, and many other aspects in the heterogeneous electron transfer, ion transport, electrocatalysis, and photoelectrochemistry of representative 2D materials and their derivatives. Perspectives for the advantages, challenges, and future opportunities of scanning EC probe microscopy investigation of 2D structures are discussed.

Cover page of Photolysis-driven bond activation by thorium and uranium tetraosmate polyhydride complexes

Photolysis-driven bond activation by thorium and uranium tetraosmate polyhydride complexes

(2024)

Transition metal multimetallic complexes have seen intense study due to their unique bonding and potential for cooperative reactivity, but actinide-transition metal (An-TM) species are far less understood. We have synthesized uranium- and thorium-osmium heterometallic polyhydride complexes in order to study An-Os bonding and investigate the reactivity of An-Os interactions. Computational studies suggest the presence of a significant bonding interaction between the actinide center and the four coordinated osmium centers supported by bridging hydrides. Upon photolysis, these complexes undergo intramolecular C-H activation with the formation of an Os-Os bond, while the thorium complex may activate an additional C-H bond of the benzene solvent, resulting in a μ-η11 phenyl ligand across one Th-Os interaction.

Cover page of Characterization of Mass, Diameter, Density, and Surface Properties of Colloidal Nanoparticles Enabled by Charge Detection Mass Spectrometry

Characterization of Mass, Diameter, Density, and Surface Properties of Colloidal Nanoparticles Enabled by Charge Detection Mass Spectrometry

(2024)

A variety of scattering-based, microscopy-based, and mobility-based methods are frequently used to probe the size distributions of colloidal nanoparticles with transmission electron microscopy (TEM) often considered to be the "gold standard". Charge detection mass spectrometry (CDMS) is an alternative method for nanoparticle characterization that can rapidly measure the mass and charge of individual nanoparticle ions with high accuracy. Two low polydispersity, ∼100 nm diameter nanoparticle size standards with different compositions (polymethyl methacrylate/polystyrene copolymer and 100% polystyrene) were characterized using both TEM and CDMS to explore the merits and complementary aspects of both methods. Mass and diameter distributions are rapidly obtained from CDMS measurements of thousands of individual ions of known spherical shape, requiring less time than TEM sample preparation and image analysis. TEM image-to-image variations resulted in a ∼1-2 nm range in the determined mean diameters whereas the CDMS mass precision of ∼1% in these experiments leads to a diameter uncertainty of just 0.3 nm. For the 100% polystyrene nanoparticles with known density, the CDMS and TEM particle diameter distributions were in excellent agreement. For the copolymer nanoparticles with unknown density, the diameter from TEM measurements combined with the mass from CDMS measurements enabled an accurate measurement of nanoparticle density. Differing extents of charging for the two nanoparticle standards measured by CDMS show that charging is sensitive to nanoparticle surface properties. A mixture of the two samples was separated based on their different extents of charging despite having overlapping mass distributions centered at 341.5 and 331.0 MDa.

Cover page of α-Phenylthioaldehydes for the effective generation of acyl azolium and azolium enolate intermediates

α-Phenylthioaldehydes for the effective generation of acyl azolium and azolium enolate intermediates

(2024)

α-Phenylthioaldehydes are readily prepared using a simple multi-step procedure and herein are introduced as a new precursor for the NHC-catalysed generation of acyl azolium and azolium enolate intermediates that are of widespread synthetic interest and utility. Treatment of α-phenylthioaldehydes with an NHC precatalyst and base produces an efficient redox rearrangement via a Breslow intermediate, elimination of thiophenolate, and subsequent rebound addition to the generated acyl azolium to give the corresponding thiol ester. In the presence of an external alcohol, competition between redox rearrangement and redox esterification can be controlled through judicious choice of the N-aryl substituent within the NHC precatalyst and the base used in the reaction. With NEt3 as base, NHCs bearing electron-withdrawing (N-C6F5 or N-C6H2Cl3) substituents favour redox rearrangement, while triazolium precatalysts with electron-rich N-aryl substituents (N-Ph, N-Mes) result in preferential redox esterification. Using DBU, redox esterification is preferred due to transesterification of the initially formed thiol ester product. Additionally, α-phenylthioaldehyde-derived azolium enolates have been used in enantioselective formal [4 + 2]-cycloaddition reactions to access dihydropyridinone heterocycles with high enantioselectivity (up to >95 : 5 dr, 98 : 2 er).

Cover page of Anion and Cation Migration at 2D/3D Halide Perovskite Interfaces

Anion and Cation Migration at 2D/3D Halide Perovskite Interfaces

(2024)

This study explores the ionic dynamics in 2D/3D perovskite solar cells, which are known for their improved efficiency and stability. The focus is on the impact of halide choice in 3D perovskites treated with phenethylammonium halide salts (PEAX, X = Br and I). Our findings reveal that light and heat drive ionic migration in these structures, with PEA+ species diffusing into the 3D film in PEABr-treated samples. Mixed-halide 3D perovskites show halide interdiffusion, with bromine migrating to the surface and iodine diffusing into the film. Cathodoluminescence microscopy reveals localized 2D phases on the 3D perovskite, which become more evenly distributed after thermal treatment. Both PEAX salts enhance the performance of photovoltaic devices. This improvement is attributed to the passivation capabilities of the salts themselves and their respective Ruddlesden−Popper (RP) phases. Annealed PEAI-treated devices show a better balance between efficiency and statistical distribution of photovoltaic parameters.

Cover page of Long Duration Energy Storage Using Hydrogen in Metal–Organic Frameworks: Opportunities and Challenges

Long Duration Energy Storage Using Hydrogen in Metal–Organic Frameworks: Opportunities and Challenges

(2024)

Materials-based H2 storage plays a critical role in facilitating H2 as a low-carbon energy carrier, but there remains limited guidance on the technical performance necessary for specific applications. Metal-organic framework (MOF) adsorbents have shown potential in power applications, but need to demonstrate economic promises against incumbent compressed H2 storage. Herein, we evaluate the potential impact of material properties, charge/discharge patterns, and propose targets for MOFs' deployment in long-duration energy storage applications including backup, load optimization, and hybrid power. We find that state-of-the-art MOF could outperform cryogenic storage and 350 bar compressed storage in applications requiring ≤8 cycles per year, but need ≥5 g/L increase in uptake to be cost-competitive for applications that require ≥30 cycles per year. Existing challenges include manufacturing at scale and quantifying the economic value of lower-pressure storage. Lastly, future research needs are identified including integrating thermodynamic effects and degradation mechanisms.

Cover page of Utopia Point Bayesian Optimization Finds Condition-Dependent Selectivity for N-Methyl Pyrazole Condensation.

Utopia Point Bayesian Optimization Finds Condition-Dependent Selectivity for N-Methyl Pyrazole Condensation.

(2024)

Utopia Point Bayesian Optimization (UPBO) was used to identify reaction conditions that are highly selective for the formation of N1 and N2-methyl-3-aryl pyrazole constitutional isomers. UPBO was used to explore a wide chemical space and identify basic reaction conditions for a typically acid-catalyzed Knorr pyrazole condensation. These studies revealed that selectivity in the reaction stems from a condition-dependent equilibrium of intermediates prior to dehydration. For the N2-methyl isomer reaction pathway, a hemiaminal intermediate was found to form reversibly under the reaction conditions, enabling a highly selective synthesis of the N2 isomer upon dehydrative workup. UPBO was able to successfully optimize conversion and selectivity simultaneously with search spaces of >1 million potential variable combinations without the need for high-performance computational resources.

Cover page of Regioselective On-Surface Synthesis of [3]Triangulene Graphene Nanoribbons

Regioselective On-Surface Synthesis of [3]Triangulene Graphene Nanoribbons

(2024)

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.