Kinetic modeling of Pt-catalyzed glycolaldehyde decomposition to syngas

Fundamental knowledge of the elementary reaction mechanisms involved in oxygenate decomposition on transition metal catalysts can facilitate the optimization of future catalyst and reactor systems for biomass upgrade to fuels and chemicals. Pt-catalyzed decomposition of glycolaldehyde, as the smallest oxygenate with alcohol and aldehyde functionality, was studied via a DFT-based microkinetic model. It was found that two decomposition pathways exist. Under conditions of low hydrogen surface coverage, the initial C-H bond breaking reaction to HOCH(2)CO* is prevalent, while under conditions of high hydrogen coverage, the rather unexpected O-H bond forming reaction to HOCH(2)CHOH* is more active (subsequent decomposition is energetically favorable from HOCH(2)CHOH*). Our results indicate the possibility that (de)hydrogenation chemistry is rate-controlling in many small polyoxygenate biomass derivatives, and suitable catalysts are needed. Finally, DFT was used to understand the increased decomposition activity observed on the surface segregated Ni-Pt-Pt bimetallic catalyst. It was found that the initial O-H bond breaking of glycolaldehyde to OCH(2)CHO* has an activation barrier of just 0.21 eV. This barrier is lower than that of any glycolaldehyde consuming reaction on Pt. These computational predictions are in qualitative agreement with experimental results.     

Efficient gradient estimation using finite differencing and likelihood ratios for kinetic Monte Carlo simulations

While many optimization and control methods for stochastic processes require gradient information from the process of interest, obtaining gradient information from experiments is prohibitively expensive and time-consuming. As a result, such information is often obtained from stochastic process simulations. Computing gradients efficiently and accurately from stochastic simulations is challenging, especially for simulations involving computationally expensive models with significant inherent noise. In this work, we analyze and characterize the applicability of two gradient estimation methods for kinetic Monte Carlo simulations: finite differencing and likelihood ratio. We developed a systematic method for choosing an optimal perturbation size for finite differencing and discuss, for both methods, important implementation issues such as scaling with respect to the number of elements in the gradient vector. Through a series of numerical experiments, the methods were compared across different time and size regimes to characterize the precision and accuracy associated with each method. We determined that the likelihood ratio method is appropriate for estimating gradients at short (transient) times or for systems with small population sizes, whereas finite differencing is better-suited for gradient estimation at long times (steady state) or for systems with large population sizes.     

Single-lobed frequency-dependent beam shape in an echolocating false killer whale (Pseudorca crassidens)

Recent studies indicate some odontocetes may produce echolocation beams with a dual-lobed vertical structure. The shape of the odontocete echolocation beam was further investigated in a false killer whale performing an echolocation discrimination task. Clicks were recorded with an array of 16 hydrophones and frequency-dependent amplitude plots were constructed to assess beam shape. The majority of the echolocation clicks were single-lobed in structure with most energy located between 20 and 80 kHz. These data indicate the false killer whale does not produce a dual-lobed structure, as has been shown in bottlenose dolphins, which may be a function of lowered frequencies in the emitted signal due to hearing loss.     

Imaging Caenorhabditis elegans embryogenesis by third-harmonic generation microscopy

In this study, third-harmonic generation (THG) imaging measurements were performed to characterize different developmental stages of the nematode Caenorhabditis elegans (C. elegans) embryos. Femtosecond laser pulses (1028 nm) were utilized for excitation. THG image contrast modality proved as a powerful diagnostic tool, providing valuable information and offering new insights into the complex developmental process of C. elegans embryogenesis.     

20-GHz broadly tunable and stable mode-locked semiconductor amplifier fiber ring laser

We present an actively mode-locked fiber ring laser that uses a single active semiconductor optical amplifier device to provide both gain and gain modulation from an external optical pulse train. The laser source generated 4.3-ps pulses at 20 GHz over a 16-nm tuning range and is stable against environmental changes and simple to build.     

Heterocyclic reactive mesogens: synthesis, characterisation and mesomorphic behaviour

Novel heterocyclic and photopolymerizable liquid crystalline materials (reactive mesogens) with smectic phases have been synthesized and characterized. A selection of heterocyclic rings, such as benzothiazole, benzothiadiazole and pyrimidine, has been incorporated into the aromatic core to control the electrochemical/luminescence properties and the structural geometry. Particular emphasis is focused on structure-property relationships, in which the variation of molecular structure and its subsequent effect on the liquid crystalline transition temperatures have been investigated.     

Homology vanishing theorems for submanifolds

We relate intrinsic and extrinsic curvature invariants to the homology groups of submanifolds in space forms of nonnegative curvature. More precisely, we provide bounds for the squared length of the second fundamental form, or the Ricci curvature in terms of the mean curvature, which force homology to vanish in a range of intermediate dimensions. Moreover, we give examples which show that these conditions are sharp.

     

Complete Minimal Hypersurfaces in a Sphere

In this paper we investigate complete minimal hypersurfaces f : Mⁿ? \Bbb Sⁿ⁺¹f : M^{n}\rightarrow {\Bbb S}^{n+1} with at most two principal curvatures. We prove that if the squared norm S of the second fundamental form satisfies S ≥ n, then S = n and f(Mⁿ) is a minimal Clifford torus.     

SOA-Based Multi-Wavelength Laser Sources

We present recent advances in multi-wavelength, power-equalized laser sources that incorporate a semiconductor optical amplifier (SOA) and simple optical filters, such as Lyot-type and Fabry-Perot, for comb generation. Both linear and ring-cavity configurations are presented, and single-pass optical feedback technique is proposed to improve the performance in terms of the number of simultaneously oscillating lines and output channel power equalization. This technique resulted in a broadened oscillating spectrum of 52 lines spaced at 50 GHz, power-equalized within 0.3 dB. Finally, a simplified version that uses only an uncoated SOA for both gain and comb generation is demonstrated.     

Knitting neutrino mass textures with or without Tri-Bi maximal mixing

The solar and baseline neutrino oscillation data suggest bimaximal neutrino mixing among the first two generations, and trimaximal mixing between all three neutrino flavors. It has been conjectured that this indicates the existence of an underlying symmetry for the leptonic fermion mass textures. The experimentally measured quantities, however, are associated to the latter indirectly and in a rather complicated way through the mixing matrices of the charged leptons and neutrinos. Motivated by these facts, we derive exact analytical expressions which directly link the charged lepton and neutrino mass and mixing parameters to measured quantities and obtain constraints on the parameter space. We discuss deviations from Tri-Bi mixing matrices and present minimal extensions of the Harrison, Perkins and Scott matrices capable of interpreting all neutrino data.