Atmospheric oxidation of reduced sulfur species

The kinetics of elementary gas phase reactions involved in the oxidation of reduced sulfur species, H₂S, CS₂, OCS, CH₃SH, CH₃SCH₃, and CH₃SSCH₃, to SO₂ (or other products) are reviewed. The reactions with OH and NO₃ which are the processes that initiate the degradation of the above compounds have been evaluated. Reactions of key intermediates, HS, HSO, CH₃S, and CH₃SO, are discussed. Whenever possible, recommendations for the rate coefficients are made and the need for further work indicated. The review has been carried out with the atmospheric chemistry in mind by looking at the laboratory based kinetics data. This review also provides information that will help model the Earth's sulfur cycle.     

Comparison of a subrank to a full-rank time-reversal operator in a dynamic ocean

This paper investigates the application of time-reversal techniques to the detection and ensonification of a target of interest. The focusing method is based on a generalization of time-reversal operator techniques. A subrank time-reversal operator is derived and implemented using a discrete set of transmission beams to ensonify a region of interest. In a dynamic ocean simulation, target focusing using a subrank matrix is shown to be superior to using a full-rank matrix, specifically when the subrank matrix is captured in a period shorter than the coherence time of the modeled environment. Backscatter from the point target was propagated to a vertical 64-element source-receiver array and processed to form the sub-rank time-reversal operator matrix. The eigenvector corresponding to the strongest eigenvalue of the time-reversal operator was shown to focus energy on the target in simulation. Modeled results will be augmented by a limited at-sea experiment conducted on the New Jersey shelf in April-May 2004 measured low-frequency backscattered signal from an artificial target (echo repeater).     

An Approximate Analytical Solution for Counter-Current Spontaneous Imbibition

An approximate analytical solution is provided for one-dimensional, counter- current, spontaneous imbibition of a wetting phase (water) into a semi-infinite porous medium. The solution is based on the assumption that a similarity solution exists for the displacement process. This assumption, in turn, rests on the assumption that the set of relative permeability and capillary pressures curves are unique functions of saturation and do not depend on the nature of the displacement. It further rests on the assumption that the saturation at the imbibition face does not vary with time. It is demonstrated that the solution is in agreement with results obtained from experiments and also numerical analyses of these experiments. The experiments utilize cylindrical samples with the radial surface and one end-face sealed, and with counter-current imbibition occurring at the open end-face. The stage of the experiment that is modeled by the present solution is the period before the imbibition front contacts the sealed end-face. An important finding of the present analysis is that the pressure upstream of the advancing invasion front is a constant. A second, improved solution is also presented; this solution is an iterative, series solution of an integral-differential equation. It converges to a stable solution in very few terms.     

Synthesis of an [(NHC)2Pd(SiMe3)2] Complex and Catalytic cis‐Bis(silyl)ations of Alkynes with Unactivated Disilanes

The novel complex cis‐[(ITMe)₂Pd(SiMe₃)₂ (ITMe=1,3,4,5‐tetramethylimidazol‐2‐ylidene) has been synthesized by mild oxidative cleavage of Me₃SiSiMe₃ using [(ITMe)₂Pd⁰]. The use of this complex as precatalyst for the cis‐bis(silyl)ation of alkynes using unactivated disilanes is reported.     

Two‐Photon Voltmeter for Measuring a Molecular Electric Field

We present a new approach for determining the strength of the dipolar solute‐induced reaction field, along with the ground‐ and excited‐state electrostatic dipole moments and polarizability of a solvated chromophore, using exclusively one‐photon and two‐photon absorption measurements. We verify the approach on two benchmark chromophores N,N‐dimethyl‐6‐propionyl‐2‐naphthylamine (prodan) and coumarin 153 (C153) in a series of toluene/dimethyl sulfoxide (DMSO) mixtures and find that the experimental values show good quantitative agreement with literature and our quantum‐chemical calculations. Our results indicate that the reaction field varies in a surprisingly broad range, 0–10⁷ V cm^?1, and that at close proximity, on the order of the chromophore radius, the effective dielectric constant of the solute–solvent system displays a unique functional dependence on the bulk dielectric constant, offering new insight into the close‐range molecular interaction.     

Insights into the Catalytic Activity of Nitridated Fibrous Silica (KCC‐1) Nanocatalysts from 15N and 29Si NMR Spectroscopy Enhanced by Dynamic Nuclear Polarization

Fibrous nanosilica (KCC‐1) oxynitrides are promising solid‐base catalysts. Paradoxically, when their nitrogen content increases, their catalytic activity decreases. This counterintuitive observation is explained here for the first time using ¹⁵N‐solid‐state NMR spectroscopy enhanced by dynamic nuclear polarization.     

Encapsulation of Functional Organic Compounds in Nanoglass for Optically Anisotropic Coatings

A novel approach is presented for the encapsulation of organic functional molecules between two sheets of 1 nm thin silicate layers, which like glass are transparent and chemically stable. An ordered heterostructure with organic interlayers strictly alternating with osmotically swelling sodium interlayers can be spontaneously delaminated into double stacks with the organic interlayers sandwiched between two silicate layers. The double stacks show high aspect ratios of >1000 (typical lateral extension 5000 nm, thickness 4.5 nm). This newly developed technique can be used to mask hydrophobic functional molecules and render them completely dispersible in water. The combination of the structural anisotropy of the silicate layers and a preferred orientation of molecules confined in the interlayer space allows polymer nanocomposite films to be cast with a well‐defined orientation of the encapsulated molecules, thus rendering the optical properties of the nanocoatings anisotropic.     

Tetraarylborate polymer networks as single-ion conducting solid electrolytes

A new family of solid polymer electrolytes based upon anionic tetrakis(phenyl)borate tetrahedral nodes and linear bis-alkyne linkers is reported. Sonogashira polymerizations using tetrakis(4-iodophenyl)borate, tetrakis(4-iodo-2,3,5,6-tetrafluorophenyl)borate and tetrakis(4-bromo-2,3,5,6-tetrafluorophenyl)borate delivered highly cross-linked polymer networks with both 1,4-diethynylbeznene and a tri(ethylene glycol) substituted derivative. Promising initial conductivity metrics have been observed, including high room temperature conductivities (up to 2.7 × 10^–4 S cm^–1), moderate activation energies (0.25–0.28 eV), and high lithium ion transport numbers (up to t _Li⁺ = 0.93). Initial investigations into the effects of important materials parameters such as bulk morphology, porosity, fluorination, and other chemical modification, provide starting design parameters for further development of this new class of solid electrolytes.     

Semigroup graded algebras and graded PI-exponent

Let S be a semigroup. We study the structure of graded-simple S-graded algebras A and the exponential rate PIexp ^S-gr(A):= lim_n→∞ \(\sqrt[n]{{c_n^{S - gr}\left( A \right)}}\) of growth of codimensions c _n ^S-gr (A) of their graded polynomial identities. This is of great interest since such algebras can have non-integer PIexp ^S-gr(A) despite being finite dimensional and associative. In addition, such algebras can have a non-trivial Jacobson radical J(A). All this is in strong contrast with the case when S is a group since in the group case J(A) is trivial, PIexp ^S-gr(A) is always integer and, if the base field is algebraically closed, then PIexp ^S-gr(A) equals dimA. Without any restrictions on the base field F, we classify graded-simple S-graded algebras A for a class of semigroups S which is complementary to the class of groups. We explicitly describe the structure of J(A) showing that J(A) is built up of pieces of a maximal S-graded semisimple subalgebra of A which turns out to be simple. When F is algebraically closed, we get an upper bound for \({\overline {\lim } _{n \to \infty }}\sqrt[n]{{c_n^{S - gr}\left( A \right)}}\). If A/J(A) ≈ M ₂(F) and S is a right zero band, we show that this upper bound is sharp and PIexp ^S-gr(A) indeed exists. In particular, we present an infinite family of graded-simple algebras A with arbitrarily large non-integer PIexp ^S-gr(A).