Preparation of I2@SWNTs: synthesis and spectroscopic characterization of I2-loaded SWNTs

X-ray photoelectron spectroscopy (XPS) along with inductively coupled plasma analysis (ICP-AE) and Raman spectroscopy have been used to define the location and to quantify the amount of iodine in HiPco SWNT samples loaded with molecular I(2) via sublimation (I(2)-SWNTs). The exterior-adsorbed I(2) can be removed (as I(-)) by reducing the sample of filled nanotubes with Na(0)/THF or by heating the I(2)-SWNTs to 300 degrees C (without reduction), leaving I(2) contained only within the interior of the SWNTs (I(2)@SWNTs) as proven by XPS. These I(2)@SWNTs contain approximately 25 wt % of I(2) and are stable without the loss of I(2) even after exposure to additional reduction with Na(0)/THF or upon heating to ca. 500 degrees C.     

On Modular Edge-Graceful Graphs

Let G be a connected graph of order \({n\ge 3}\) and size m and \({f:E(G)\to \mathbb{Z}_n}\) an edge labeling of G. Define a vertex labeling \({f': V(G)\to \mathbb{Z}_n}\) by \({f'(v)= \sum_{u\in N(v)}f(uv)}\) where the sum is computed in \({\mathbb{Z}_n}\) . If f′ is one-to-one, then f is called a modular edge-graceful labeling and G is a modular edge-graceful graph. A graph G is modular edge-graceful if G contains a modular edge-graceful spanning tree. Several classes of modular edge-graceful trees are determined. For a tree T of order n where \({n\not\equiv 2 \pmod 4}\) , it is shown that if T contains at most two even vertices or the set of even vertices of T induces a path, then T is modular edge-graceful. It is also shown that every tree of order n where \({n\not\equiv 2\pmod 4}\) having diameter at most 5 is modular edge-graceful.     

Inverse analysis and regularisation in conditional source-term estimation modelling

Conditional Source-term Estimation (CSE) obtains the conditional species mass fractions by inverting a Fredholm integral equation of the first kind. In the present work, a Bayesian framework is used to compare two different regularisation methods: zeroth-order temporal Tikhonov regulatisation and first-order spatial Tikhonov regularisation. The objectives of the current study are: (i) to elucidate the ill-posedness of the inverse problem; (ii) to understand the origin of the perturbations in the data and quantify their magnitude; (iii) to quantify the uncertainty in the solution using different priors; and (iv) to determine the regularisation method best suited to this problem. A singular value decomposition shows that the current inverse problem is ill-posed. Perturbations to the data may be caused by the use of a discrete mixture fraction grid for calculating the mixture fraction PDF. The magnitude of the perturbations is estimated using a box filter and the uncertainty in the solution is determined based on the width of the credible intervals. The width of the credible intervals is significantly reduced with the inclusion of a smoothing prior and the recovered solution is in better agreement with the exact solution. The credible intervals for temporal and spatial smoothing are shown to be similar. Credible intervals for temporal smoothing depend on the solution from the previous time step and a smooth solution is not guaranteed. For spatial smoothing, the credible intervals are not dependent upon a previous solution and better predict characteristics for higher mixture fraction values. These characteristics make spatial smoothing a promising alternative method for recovering a solution from the CSE inversion process.     

Investigation into the molecular structure and energetic stability of endohedral and exohedral metallofullerene derivatives of C24

Density-functional theory was applied to the investigation of the structural and electronic properties of C₂₄ fullerene derivatives. Transition metals (TMs) from groups 11 and 12, in various oxidation and spin-states, are inserted at either endohedral (TM@C₂₄) or exohedral (TM-C₂₄) sites and their subsequent energetic stabilities are assessed. With the exception of Ag@C₂₄, all derivatives are predicted to occupy a minimum on the potential energy surface. The optimized exohedral TM-C₂₄ geometries yield TM-C bond lengths that are consistent with comparable carbon-metal bond lengths, and the overwhelming majority of the derivatives result in a slight deformation of the C₂₄ cage as the bonding carbon takes on more sp³ character. All of the TM@C₂₄ equilibrium structures maintain the integrity of the cage structure with a moderate increase in the diameter. All neutral exohedral and endohedral complexes favor the low spin-state; conversely, all of the charged exohedral complexes prefer the high spin-state, with the exception of Cu-C₂₄¹⁺ molecular ion. The Group 12 charged endohedral derivatives prefer the low spin-state, whereas the Group 11 molecular ions do not necessarily exhibit a definitive trend. Analysis of the energetic data predicts that of the lowest energy endohedral molecular species only four are predicted to be energetically favorable in terms of insertion energy and an advantageous HOMO-LUMO gap: Cu@C₂₄²⁺, Ag@C₂₄¹⁺, Au@C₂₄³⁺, and Zn@C₂₄²⁺.     

Photolytic Reductive Elimination of White Phosphorus from a Mononuclear cyclo‐P4 Transition Metal Complex

Elemental white phosphorus (P₄) is well recognized as a critical precursor to organophosphorus compounds. However, regulatory constraints stemming from the toxic and pyrophoric nature of white phosphorus have significantly limited its accessibility. Herein is described a new approach to white phosphorus storage and release based on a unique example of photolytic reductive elimination of the tetrahedral P₄ molecule from a mononuclear cyclo‐P₄ molybdenum complex. The latter functions as an air‐stable, chemically‐deactivated source of white phosphorus. The system features efficient photo‐release of white phosphorus using inexpensive violet LED sources. Additionally, high‐yield recapture of unspent white phosphorus by the molybdenum center can be achieved by post‐photolysis heating at convenient temperatures.     

The impact of water column variability on horizontal wave number estimation and mode based geoacoustic inversion results

The influence of water column variability on low-frequency, shallow water geoacoustic inversion results is considered. The data are estimates of modal eigenvalues obtained from measurements of a point source acoustic field using a horizontal aperture array in the water column. The inversion algorithm is based on perturbations to a background waveguide model with seabed properties consistent with the measured eigenvalues. Water column properties in the background model are assumed to be known, as would be obtained from conductivity, temperature, and depth measurements. The scope of this work in addressing the impact of water column variability on inversion is twofold. Range-dependent propagation effects as they pertain to eigenvalue estimation are first considered. It is shown that mode coupling is important even for weak internal waves and can enhance modal eigenvalue estimates. Second, the effect of the choice of background sound speed profile in the water column is considered for its impact on the estimated bottom acoustic properties. It is shown that a range-averaged sound velocity profile yields the best geoacoustic parameter estimates.     

Chemical Synthesis and Immunological Evaluation of a Pentasaccharide Bearing Multiple Rare Sugars as a Potential Anti-pertussis Vaccine

With the infection rate of Bordetella pertussis at a 60-year high, there is an urgent need for new anti-pertussis vaccines. The lipopolysaccharide (LPS) of B. pertussis is an attractive antigen for vaccine development. With the presence of multiple rare sugars and unusual glycosyl linkages, the B. pertussis LPS is a highly challenging synthetic target. In this work, aided by molecular dynamics simulation and modeling, a pertussis-LPS-like pentasaccharide was chemically synthesized for the first time. The pentasaccharide was conjugated with a powerful carrier, bacteriophage Qβ, as a vaccine candidate. Immunization of mice with the conjugate induced robust anti-glycan IgG responses with IgG titers reaching several million enzyme-linked immunosorbent assay (ELISA) units. The antibodies generated were long lasting and boostable and could recognize multiple clinical strains of B. pertussis, highlighting the potential of Qβ-glycan as a new anti-pertussis vaccine.     

Development of efficient and accurate skeletal mechanisms for hydrocarbon fuels and kerosene surrogate

In this paper,the methodology of the directed relation graph with error propagation and sensitivity analysis(DRGEPSA),proposed by Niemeyer et al.(Combust Flame 157:1760-1770.2010).and its differences to the original directed relation graph method are described.Using DRGEPSA,the detailed mechanism of ethylene containing 71 species and 395 reaction steps is reduced to several skeletal mechanisms with different error thresholds.The 25-species and 131-step mechanism and the 24-species and115-step mechanism are found to be accurate for the predictions of ignition delay time and laminar flame speed.Although further reduction leads to a smaller skeletal mechanism with 19 species and 68 steps,it is no longer able to represent the correct reaction processes.With the DRGEPSA method,a detailed mechanism for n-dodecane considering low-temperature chemistry and containing 2115 species and8157 steps is reduced to a much smaller mechanism with249 species and 910 steps while retaining good accuracy.If considering only high-temperature(higher than 1000 K)applications,the detailed mechanism can be simplified to even smaller mechanisms with 65 species and 340 steps or48 species and 220 steps.Furthermore,a detailed mechanism for a kerosene surrogate having 207 species and 1592 steps is reduced with various error thresholds and the results show that the 72-species and 429-step mechanism and the66-species and 392-step mechanism are capable of predicting correct combustion properties compared to those of the detailed mechanism.It is well recognized that kinetic mechanisms can be effectively used in computations only after they are reduced to an acceptable size level for computation capacity and at the same time retaining accuracy.Thus,the skeletal mechanisms generated from the present work are expected to be useful for the application of kinetic mechanisms of hydrocarbons to numerical simulations of turbulent or supersonic combustion.