Publications

Metals are essential for life, playing critical roles in all aspects of the central dogma of biology (e.g., the transcription and translation of nucleic acids and synthesis of proteins). Redox-inactive alkali, alkaline earth, and transition metals such as sodium, potassium, calcium, and zinc are widely recognized as dynamic signals, whereas redox-active transition metals such as copper and iron are traditionally thought of as sequestered by protein ligands, including as static enzyme cofactors, in part because of their potential to trigger oxidative stress and damage via Fenton chemistry. Metals in biology can be broadly categorized into two pools: static and labile. In the former, proteins and other macromolecules tightly bind metals; in the latter, metals are bound relatively weakly to cellular ligands, including proteins and low molecular weight ligands. Fluorescent probes can be useful tools for studying the roles of transition metals in their labile forms. Probes for imaging transition metal dynamics in living systems must meet several stringent criteria. In addition to exhibiting desirable photophysical properties and biocompatibility, they must be selective and show a fluorescence turn-on response to the metal of interest. To meet this challenge, we have pursued two general strategies for metal detection, termed "recognition" and "reactivity". Our design of transition metal probes makes use of a recognition-based approach for copper and nickel and a reactivity-based approach for cobalt and iron. This Account summarizes progress in our laboratory on both the development and application of fluorescent probes to identify and study the signaling roles of transition metals in biology. In conjunction with complementary methods for direct metal detection and genetic and/or pharmacological manipulations, fluorescent probes for transition metals have helped reveal a number of principles underlying transition metal dynamics. In this Account, we give three recent examples from our laboratory and collaborations in which applications of chemical probes reveal that labile copper contributes to various physiologies. The first example shows that copper is an endogenous regulator of neuronal activity, the second illustrates cellular prioritization of mitochondrial copper homeostasis, and the third identifies the "cuprosome" as a new copper storage compartment in Chlamydomonas reinhardtii green algae. Indeed, recognition- and reactivity-based fluorescent probes have helped to uncover new biological roles for labile transition metals, and the further development of fluorescent probes, including ones with varied Kd values and new reaction triggers and recognition receptors, will continue to reveal exciting and new biological roles for labile transition metals.

The various proposed DHT routing algorithms embody several different underlying routing geometries. These geometries include hypercubes, rings, tree-like structures, and butterfly networks. In this paper we focus on how these basic geometric approaches affect the resilience and proximity properties of DHTs. One factor that distinguishes these geometries is the degree of flexibility they provide in the selection of neighbors and routes. Flexibility is an important factor in achieving good static resilience and effective proximity neighbor and route selection. Our basic finding is that, despite our initial preference for more complex geometries, the ring geometry allows the greatest flexibility, and hence achieves the best resilience and proximity performance.

Auf der Suche nach dem Limit: Die einzigartige Koordinationschemie von ECHE-Liganden (E=Si, Ge) mit Übergangsmetallen der 9. Gruppe (Ir, Rh) sowie die Anwendung der Komplexe in der katalytischen C-H-Borylierung von Arenen wurden untersucht. Ein Vergleich von Iridiumkomplexen zeigt, dass die divalenten Si- und Ge-Pinzettenliganden in ihren σ-Donoreigenschaften den isoelektronischen PIII-Ligandsystemen überlegen sind.

We compare the characteristics of the armored scales of three large fish, namely the Arapaima gigas (arapaima), Latimeria chalumnae (coelacanth), and Atractosteus spatula (alligator gar), with specific focus on their unique structure-mechanical property relationships and their specialized ability to provide protection from predatory pressures, with the ultimate goal of providing bio-inspiration for manmade materials. The arapaima has flexible and overlapping cycloid scales which consist of a tough Bouligand-type arrangement of collagen layers in the base and a hard external mineralized surface, protecting it from piranha, a predator with extremely sharp teeth. The coelacanth has overlapping elasmoid scales that consist of adjacent Bouligand-type pairs, forming a double-twisted Bouligand-type structure. The collagenous layers are connected by collagen fibril struts which significantly contribute to the energy dissipation, so that the scales have the capability to defend from predators such as sharks. The alligator gar has inflexible articulating ganoid scales made of a hard and highly mineralized enamel-like outer surface and a tough dentine-like bony base, which resist powerful bite forces of self-predation and attack by alligators. The structural differences between the three scales correspond with the attack of their predators, and show refined mechanisms which may be imitated and incorporated into superior bioinspired and biomimetic designs that are specialized to resist specific modes of predation.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Halide materials are promising superionic conductors for ASSBs but require moisture-free synthesis, limiting throughput due to manual operation in gloveboxes or dry rooms. An automated robotic system for handling air-sensitive materials in an inert atmosphere would greatly accelerate discovery. Here, we present a fully automated lab for high-throughput solid-state synthesis of halide conductors and other air-sensitive materials. Compact and modular, it operates entirely within an N 2 -protected double-station glovebox. The system includes five automated workstations for solid-state synthesis, with two six-axis robot arms seamlessly handling and transferring samples. By eliminating manual operation in confined spaces, it enhances efficiency and increases throughput. Many halide ionic conductors rely on rare-earth metals or mechanochemical treatments, raising costs and complicating scale-up. Developing compositions synthesizable via conventional heating with earth-abundant precursors is essential. Using our automated platform, we will systematically explore aliovalent substitution in close-packed halides, mapping synthesis accessibility by analyzing polymorph energetics, dopant effects, and heating conditions. This approach enables cost-effective, scalable ionic conductors, advancing solid-state battery technology.

An entry from the Inorganic Crystal Structure Database, the world’s repository for inorganic crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the joint CCDC and FIZ Karlsruhe Access Structures service and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.