Publications

High-capacity polymer dielectrics that operate with high efficiencies under harsh electrification conditions are essential components for advanced electronics and power systems. It is, however, fundamentally challenging to design polymer dielectrics that can reliably withstand demanding temperatures and electric fields, which necessitate the balance of key electronic, electrical, and thermal parameters. Herein, we demonstrate that polysulfates, synthesized by sulfur(VI) fluoride exchange (SuFEx) catalysis, another near-perfect click chemistry reaction, serve as high-performing dielectric polymers that overcome such bottlenecks. Free-standing polysulfate thin films from convenient solution processes exhibit superior insulating properties and dielectric stability at elevated temperatures, which are further enhanced when ultrathin (∼5 nm) oxide coatings are deposited by atomic layer deposition. The corresponding electrostatic film capacitors display high breakdown strength (>700 MV m−1) and discharged energy density of 8.64 J cm−3 at 150°C, outperforming state-of-the-art free-standing capacitor films based on commercial and synthetic dielectric polymers and nanocomposites.

We present a water-in-oil droplet microfluidic platform for transformation, culture and expression of recombinant proteins in multiple host organisms including bacteria, yeast and fungi. The platform consists of a hybrid digital microfluidic/channel-based droplet chip with integrated temperature control to allow complete automation and integration of plasmid addition, heat-shock transformation, addition of selection medium, culture, and protein expression. The microfluidic format permitted significant reduction in consumption (100-fold) of expensive reagents such as DNA and enzymes compared to the benchtop method. The chip contains a channel to continuously replenish oil to the culture chamber to provide a fresh supply of oxygen to the cells for long-term (∼5 days) cell culture. The flow channel also replenished oil lost to evaporation and increased the number of droplets that could be processed and cultured. The platform was validated by transforming several plasmids into Escherichia coli including plasmids containing genes for fluorescent proteins GFP, BFP and RFP; plasmids with selectable markers for ampicillin or kanamycin resistance; and a Golden Gate DNA assembly reaction. We also demonstrate the applicability of this platform for transformation in widely used eukaryotic organisms such as Saccharomyces cerevisiae and Aspergillus niger. Duration and temperatures of the microfluidic heat-shock procedures were optimized to yield transformation efficiencies comparable to those obtained by benchtop methods with a throughput up to 6 droplets/min. The proposed platform offers potential for automation of molecular biology experiments significantly reducing cost, time and variability while improving throughput.

Abstract The effective mass is a convenient descriptor of the electronic band structure used to characterize the density of states and electron transport based on a free electron model. While effective mass is an excellent first-order descriptor in real systems, the exact value can have several definitions, each of which describe a different aspect of electron transport. Here we use Boltzmann transport calculations applied to ab initio band structures to extract a density-of-states effective mass from the Seebeck Coefficient and an inertial mass from the electrical conductivity to characterize the band structure irrespective of the exact scattering mechanism. We identify a Fermi Surface Complexity Factor: $${N}_{{\rm{v}}}^{\ast }{K}^{\ast }$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:msubsup> <mml:mrow> <mml:mi>N</mml:mi> </mml:mrow> <mml:mrow> <mml:mi>v</mml:mi> </mml:mrow> <mml:mrow> <mml:mo>*</mml:mo> </mml:mrow> </mml:msubsup> <mml:msup> <mml:mrow> <mml:mi>K</mml:mi> </mml:mrow> <mml:mrow> <mml:mo>*</mml:mo> </mml:mrow> </mml:msup> </mml:math> from the ratio of these two masses, which in simple cases depends on the number of Fermi surface pockets $$({N}_{{\rm{v}}}^{\ast })$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:mrow> <mml:mo>(</mml:mo> <mml:mrow> <mml:msubsup> <mml:mrow> <mml:mi>N</mml:mi> </mml:mrow> <mml:mrow> <mml:mi>v</mml:mi> </mml:mrow> <mml:mrow> <mml:mo>*</mml:mo> </mml:mrow> </mml:msubsup> </mml:mrow> <mml:mo>)</mml:mo> </mml:mrow> </mml:math> and their anisotropy K * , both of which are beneficial to high thermoelectric performance as exemplified by the high values found in PbTe. The Fermi Surface Complexity factor can be used in high-throughput search of promising thermoelectric materials.

BiFeO3 (BFO) is a next-generation non-toxic multiferroic material with applications in sensors, memory devices, and spintronics, where its crystallinity and crystal structure directly influence its functional properties. Designing sol-gel syntheses that result in phase-pure BFO remains a challenge due to the complex interactions between metal complexes in the precursor solution. Here, we combine text-mined data and chemical reaction network (CRN) analysis to obtain novel insight into BFO sol-gel precursor chemistry. We perform text-mining analysis of 340 synthesis recipes with the emphasis on phase-pure BFO and identify trends in the use of precursor materials, including that nitrates are the preferred metal salts, 2-methoxyethanol (2ME) is the dominant solvent, and adding citric acid as a chelating agent frequently leads to phase-pure BFO. Our CRN analysis reveals that the thermodynamically favored reaction mechanism between bismuth nitrate and 2ME interaction involves partial solvation followed by dimerization, contradicting assumptions in previous literature. We suggest that further oligomerization, facilitated by nitrite ion bridging, is critical for achieving the pure BFO phase.

Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

We study how the intrinsic anomalous Hall conductivity is modified in two-dimensional crystals with broken time-reversal symmetry due to weak inhomogeneity of the applied electric field. Focusing on a clean noninteracting two-band system without band crossings, we derive the general expression for the Hall conductivity at small finite wave vector q to order q^{2}, which governs the Hall response to the second gradient of the electric field. Using the Kubo formula, we show that the answer can be expressed through the Berry curvature, Fubini-Study quantum metric, and the rank-3 symmetric tensor which is related to the quantum geometric connection and physically corresponds to the gauge-invariant part of the third cumulant of the position operator. We further compare our results with the predictions made within the semiclassical approach. By deriving the semiclassical equations of motion, we reproduce the result obtained from the Kubo formula in some limits. We also find, however, that the conventional semiclassical description in terms of the definite position and momentum of the electron is not fully consistent because of singular terms originating from the Heisenberg uncertainty principle. We thus present a clear example of a case when the semiclassical approach inherently suffers from the uncertainty principle, implying that it should be applied to systems in nonuniform fields with extra care.

It is well-known that BGP, the current inter-domain routing protocol, has many deficiencies. This paper describes a hybrid link-state and path-vector protocol called HLP as an alternative to BGP that has vastly better scalability, isolation and convergence properties. Using current BGP routing information, we show that HLP, in comparison to BGP, can reduce the churn-rate of route updates by a factor 400 as well as isolate the effect of routing events to a region 100 times smaller than that of BGP. For a majority of Internet routes, HLP guarantees worst-case linear-time convergence. We also describe a prototype implementation of HLP on top of the XORP router platform. HLP is not intended to be a finished and final proposal for a replacement for BGP, but is instead offered as a starting point for debates about the nature of the next-generation inter-domain routing protocol.

Size-tunable monodisperse Rh nanocrystals can offer unique properties for many heterogeneous catalytic reactions (such as hydrogenation, hydroformylation, and hydrocarbonylation) of both scientific and technological interest. In this article, we report the synthesis of monodisperse, well-shaped Rh nanocrystals in a range of 5−15 nm by a one-step polyol reduction at temperatures of 170−230 °C under Ar, using rhodium(III) acetylacetonate [Rh(acac)3] as the source of metal ions, 1,4-butanediol as the reducing solvent, and poly(vinylpyrrolidone) as the capping agent. Two-dimensional projects of the nanocrystals are polygons, dominated by hexagons, pentagons, and triangles with catalytically active (111) surfaces (>65% yield). Over 45% of the polygons are multiple (111) twinned particles (hexagons and pentagons), favored by thermodynamics. To achieve size uniformity, adjustment of the reduction kinetics of Rh(acac)3 in the nucleation and crystal growth stages has been shown to depend upon several synthetic parameters including an Ar or air atmosphere, reaction temperature and time, and Rh(acac)3 concentration. Due to the present well-controlled polyol reduction kinetics, the size of the Rh nanocrystals can be tuned by changing the Rh(acac)3 concentration in a proper range. Monolayer films of the Rh polygons have been formed on silicon wafers by the Langmuir−Blodgett method and have been used as model heterogeneous catalysts for the study of ethylene hydrogenation.

Abstract not Available.

Task-based distributed frameworks (e.g., Ray, Dask, Hydro) have become increasingly popular for distributed applications that contain asynchronous and dynamic workloads, including asynchronous gradient descent, reinforcement learning, and model serving. As more data-intensive applications move to run on top of task-based systems, collective communication efficiency has become an important problem. Unfortunately, traditional collective communication libraries (e.g., MPI, Horovod, NCCL) are an ill fit, because they require the communication schedule to be known before runtime and they do not provide fault tolerance.

Reactive oxygen species (ROS) are important factors mediating aging according to the free radical theory of aging. Few studies have systematically measured ROS levels in relationship to aging, partly due to the lack of tools for detection of specific ROS in live animals. By using the H₂O₂-specific fluorescence probe Peroxy Orange 1, we assayed the H₂O₂ levels of live Caenorhabditis elegans with 41 aging-related genes being individually knocked down by RNAi. Knockdown of 14 genes extends the lifespan but increases H₂O₂ level or shortens the lifespan but decreases H₂O₂ level, contradicting the free radical theory of aging. Strikingly, a significant inverse correlation between lifespan and the normalized standard deviation of H₂O₂ levels was observed (p < 0.0001). Such inverse correlation was also observed in worms cultured under heat shock conditions. An oxidative fluctuation hypothesis of aging is thus proposed and suggests that the ability of animals to homeostatically maintain the ROS levels within a narrow range is more important for lifespan extension than just minimizing the ROS levels though the latter still being crucial.

Abstract This chapter examines the Mio-Pliocene volcanic materials exposed along the western margin of the Middle Awash area, with a primary focus on the late Miocene deposits of the Adu-Asa Formation. The primary goals of this chapter are to: define the different types of volcanic material preserved in the Adu-Asa Formation; present a working composite stratigraphic view of the Adu-Asa Formation volcanic horizons; present the existing geochemical data for western margin volcanic samples, including some with uncertain chronostratigraphic context; illustrate the data and observations that provided the basis for previous correlations and naming of key volcanic marker horizons; and illustrate the data and observations that provide new regional correlations and hence the establishment of newly named volcanic horizons.