Publications

Studying bacteria-nanostructure interactions is crucial to gaining controllable interfacing of biotic and abiotic components in advanced biotechnologies. For bioelectrochemical systems, tunable cell-electrode architectures offer a path toward improving performance and discovering emergent properties. As such, Sporomusa ovata cells cultured on vertical silicon nanowire arrays formed filamentous cells and aligned parallel to the nanowires when grown in increasing ionic concentrations. Here, we propose a model describing the kinetic and the thermodynamic driving forces of bacteria-nanowire interactions.

New soluble quinacridone-based molecules have been developed as electron donor materials for solution-processed organic solar cells. By functionalizing the pristine pigment core of quinacridone with solubilizing alkyl chains and light absorbing/charge transporting thiophene units, i.e., bithiophene (BT) and thienylbenzo[c][1,2,5]thiadiazolethienyl (BTD), we prepared a series of multifunctional quinacridone-based molecules. These molecular donors show intense absorption in the visible spectral region, and the absorption range and intensity are well-tuned by the interaction between the quinacridone core and the incorporated thiophene units. The thin film absorption edge extends with the expansion of molecular conjugation, i.e., 552 nm for N,N'-di(2-ethylhexyl)quinacridone (QA), 592 nm for 2,9-Bis(5'-hexyl-2,2'-bithiophene)-N,N'-di(2-ethylhexyl)quinacridone (QA-BT), and 637 nm for 4-(5-hexylthiophen-2-yl)-7-(thiophen-2-yl)benzo[c][1,2,5]thiadiazole (QA-BTD). The change of molecular structure also influences the electrochemical properties. Observed from cyclic voltammetry measurements, the oxidation and reduction potentials (vs ferrocene) are 0.7 and -1.83 V for QA, 0.54 and -1.76 V for QA-BT, and 0.45 and -1.68 V for QA-BTD. Uniform thin films can be generated from both single component molecular solutions and blend solutions of these molecules with [6,6]-phenyl C70-butyric acid methyl ester (PC70BM). The blend films exhibit space-charge limited current (SCLC) hole mobilities on the order of 1×10(-4) cm(2) V(-1) S(-1). Bulk heterojunction (BHJ) solar cells using these soluble molecules as donors and PC70BM as the acceptor were fabricated. Power conversion efficiencies (PCEs) of up to 2.22% under AM 1.5 G simulated 1 sun solar illumination have been achieved and external quantum efficiencies (EQEs) reach as high as ∼45%.

The introduction of computational resources at the network edge allows application designers to offload computation from clients and/or servers, thereby reducing response latency and backbone bandwidth. More fundamentally, edge-computing moves applications from a client-server model to a client-edge-server model. While this is an attractive paradigm for many use cases, it raises the question of how to design client-edge-server systems so they can tolerate edge failures and client mobility. This is particularly challenging when edge processing is strongly stateful. In this paper we propose a design for meeting this challenge called the Client-Edge-Server for Stateful Network Applications (CESSNA).

Plesiadapiform mammals, as stem primates, are key to understanding the evolutionary and ecological origins of Pan-Primates and Euarchonta. The Purgatoriidae, as the geologically oldest and most primitive known plesiadapiforms and one of the oldest known placental groups, are also central to the evolutionary radiation of placentals and the Cretaceous-Palaeogene biotic recovery on land. Here, we report new dental fossils of Purgatorius from early Palaeocene (early Puercan) age deposits in northeastern Montana that represent the earliest dated occurrences of plesiadapiforms. We constrain the age of these earliest purgatoriids to magnetochron C29R and most likely to within 105–139 thousand years post-K/Pg boundary. Given the occurrence of at least two species, Purgatorius janisae and a new species, at the locality, we provide the strongest support to date that purgatoriids and, by extension, Pan-Primates, Euarchonta and Placentalia probably originated by the Late Cretaceous. Within 1 million years of their arrival in northeastern Montana, plesiadapiforms outstripped archaic ungulates in numerical abundance and dominated the arboreal omnivore–frugivore niche in mammalian local faunas.

Bicarbonate-based electrolytes are ubiquitous in aqueous electrochemical CO2 reduction, particularly in heterogenous catalysis, where they demonstrate improved catalytic performance relative to other buffers. In contrast, the presence of bicarbonate in organic electrolytes and its roles in homogenous electrocatalysis remain underexplored. Here, we investigate the influence of bicarbonate on iron porphyrin-catalyzed electrochemical CO2 reduction. We show that bicarbonate is a viable proton donor in organic electrolyte (pKa = 20.8 in DMSO) and that urea pendants in the second coordination sphere can be used to template bicarbonate in the vicinity of a molecular iron porphyrin catalyst. The templated binding of bicarbonate decreases its acidity, resulting in a 1500-fold enhancement in catalytic rates relative to unmodified parent iron porphyrin. This work emphasizes the importance of bicarbonate speciation in wet organic electrolytes and establishes second-sphere bicarbonate templating as a design strategy to harness this adventitious acid and enhance CO2 reduction catalysis.

The main challenge in P2P computing is to design and implement a robust and scalable distributed system composed of inexpensive, individually unreliable computers in unrelated administrative domains. The participants in a typical P2P system might include computers at homes, schools, and businesses, and can grow to several million concurrent participants.

Catalytic borylations of sp3 C–H bonds occur with high selectivities for primary C–H bonds or secondary C–H bonds that are activated by nearby electron-withdrawing substituents. The catalytic borylation at tertiary C–H bonds has not been observed. We describe a broadly applicable method for the synthesis of boron-substituted bicyclo[1.1.1]pentanes (BCPs) and (hetero)bicyclo[2.1.1]hexanes (BCHs) by an iridium-catalyzed borylation of the bridgehead tertiary C–H bond. This reaction is highly selective for the formation of bridgehead boronic esters and is compatible with a broad range of functional groups (>35 examples). The method is applicable to the late-stage modification of pharmaceuticals containing this substructure and the synthesis of novel bicyclic building blocks. Kinetic and computational studies suggest that C–H bond cleavage occurs with a modest barrier and that the turnover-limiting step of this reaction is an isomerization that occurs prior to reductive elimination that forms the C–B bond.

The reabsorption of photoluminescence within a medium, an effect known as the inner filter effect (IFE), has been well studied in solutions, but has garnered less attention in regards to solid-state nanocomposites. Photoluminescence from a quantum dot (QD) can selectively excite larger QDs around it resulting in a net red-shift in the reemitted photon. In CdSe/CdS core/shell QD-polymer nanocomposites, we observe a large spectral red-shift of over a third of the line width of the photoluminescence of the nanocomposites over a distance of 100 μm resulting from the IFE. Unlike fluorescent dyes, which do not show a large IFE red-shift, QDs have a component of inhomogeneous broadening that originates from their size distribution and quantum confinement. By controlling the photoluminescence broadening as well as the sample dispersion and concentration, we show that the magnitude of the IFE within the nanocomposite can be tuned. We further demonstrate that this shift can be exploited in order to spectroscopically monitor the vertical displacement of a nanocomposite in a fluorescence microscope. Large energetic shifts in the measured emission with displacement can be maximized, resulting in a displacement sensor with submicrometer resolution. We further show that the composite can be easily attached to biological samples and is able to measure deformations with high temporal and spatial precision.

We present the design and performance of a homebuilt high-pressure and high-temperature reactor equipped with a high-resolution scanning tunneling microscope (STM) for catalytic studies. In this design, the STM body, sample, and tip are placed in a small high pressure reactor (∼19 cm3) located within an ultrahigh vacuum (UHV) chamber. A sealable port on the wall of the reactor separates the high pressure environment in the reactor from the vacuum environment of the STM chamber and permits sample transfer and tip change in UHV. A combination of a sample transfer arm, wobble stick, and sample load-lock system allows fast transfer of samples and tips between the preparation chamber, high pressure reactor, and ambient environment. This STM reactor can work as a batch or flowing reactor at a pressure range of 10−13 to several bars and a temperature range of 300–700 K. Experiments performed on two samples both in vacuum and in high pressure conditions demonstrate the capability of in situ investigations of heterogeneous catalysis and surface chemistry at atomic resolution at a wide pressure range from UHV to a pressure higher than 1 atm.