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.

A lift-off technique for epitaxial layers with subsequent deposition on a different substrate was applied to InP/InGaAs devices, demonstrating the ability to combine long-wavelength optoelectronic devices with electronic components from different material systems, e.g. GaAs. Furthermore, it was found that a passivation layer and an interconnecting final metal layer can be applied to the devices after lift-off on the new host substrate. The lift-off process is described in detail.

Using electron-beam-induced deposition and focused-ion-beam milling, we have fabricated and demonstrated a nanofocusing optical transformer with a 3-dimensionally tapered tip. At the tip, the light is confined to 13-by-80-nm area with intensity enhancement exceeding 1500.

Comparing photosynthetic and photovoltaic efficiencies is not a simple issue. Although both processes harvest the energy in sunlight, they operate in distinctly different ways and produce different types of products: biomass or chemical fuels in the case of natural photosynthesis and nonstored electrical current in the case of photovoltaics. In order to find common ground for evaluating energy-conversion efficiency, we compare natural photosynthesis with present technologies for photovoltaic-driven electrolysis of water to produce hydrogen. Photovoltaic-driven electrolysis is the more efficient process when measured on an annual basis, yet short-term yields for photosynthetic conversion under optimal conditions come within a factor of 2 or 3 of the photovoltaic benchmark. We consider opportunities in which the frontiers of synthetic biology might be used to enhance natural photosynthesis for improved solar energy conversion efficiency.

To analyze the effect of lithium and microstructure on the pitting corrosion behavior of aluminum alloys, three types of aluminum alloys were studied via scanning electron microscopy, transmission electron microscopy, electrochemical polarization, and by immersion tests coupled with in-situ observation of pitting and statistical analysis of pit depths measured by surface profilometry. It was found that, with increasing lithium content, the resistance to pitting corrosion was enhanced and the passive range was enlarged. In-situ observation revealed that the development of pitting corrosion exhibited three stages, including an initial slow nucleation stage (Stage I), a fast development stage (Stage II), and a stabilized growth stage (Stage III). Higher lithium content contributed to shorter time periods of Stages I and II, resulting in faster pitting evolution and a higher number of pits. However, the pits were generally shallower for the specimen with the highest lithium content, which is in agreement with the results of the electrochemical analysis.

Noniridescent coloration by the spongy keratin in parrot feather barbs has fascinated scientists. Nonetheless, its ultimate origin remains as yet unanswered, and a quantitative structural and optical description is still lacking. Here we report on structural and optical characterizations and numerical simulations of the blue feather barbs of the scarlet macaw. We found that the sponge in the feather barbs is an amorphous diamond-structured photonic crystal with only short-range order. It possesses an isotropic photonic pseudogap that is ultimately responsible for the brilliant noniridescent coloration. We further unravel an ingenious structural optimization for attaining maximum coloration apparently resulting from natural evolution. Upon increasing the material refractive index above the level provided by nature, there is an interesting transition from a photonic pseudogap to a complete bandgap.

A panel of seventeen experts from academia, industry, and government laboratories share their thoughts on a variety of matters of importance to the readership of Organometallics. These include directions for the field and recent breakthroughs (illustrated with selected examples), the interface with green chemistry, the quest for reproducible experimental procedures, data and research integrity, laboratory safety, the preparation of coworkers for non-academic careers, and needs regarding instrumentation, infrastructure, shared facilities, and computational methods. A lively give and take is evident in the edited transcript, which continues a biennial tradition initiated in 2011.