Analytical detection methodologies for methane and related hydrocarbons

The determination of methane is of strong interest to the analytical community due to its natural abundance, its potential to cause explosions and its known greenhouse effect. The current report gives a brief overview into the environmental significance of methane and an account of the existing detection protocols for methane in air and environmental samples.     

N-activated β-lactams as versatile reagents for acyl carrier protein labeling

Acyl carrier proteins are critical components of fatty acid and polyketide biosynthesis. Their primary function is to shuttle intermediates between active sites via a covalently bound phosphopantetheine arm. Small molecules capable of acylating this prosthetic group will provide a simple and reversible means of introducing novel functionality onto carrier protein domains. A series of N-activated β-lactams are prepared to examine site-specific acylation of the phosphopantetheine-thiol. In general, β-lactams are found to be significantly more reactive than our previously studied β-lactones. Selectivity for the holo over apo-form of acyl carrier proteins is demonstrated indicating that only the phosphopantetheine-thiol is modified. Incorporation of an N-propargyloxycarbonyl group provides an alkyne handle for conjugation to fluorophores and affinity labels. The utility of these groups for mechanistic interrogation of a critical step in polyketide biosynthesis is examined through comparison to traditional probes. In all, we expect the probes described in this study to serve as valuable and versatile tools for mechanistic interrogation.     

ChemBead Enabled High-Throughput Cross-Electrophile Coupling Reveals a New Complementary Ligand

High-throughput experimentation (HTE) methods are central to modern medicinal chemistry. While many HTE approaches to C−N and Csp²−Csp² bonds are available, options for Csp²−Csp³ bonds are limited. We report here how the adaptation of nickel-catalyzed cross-electrophile coupling of aryl bromides with alkyl halides to HTE is enabled by AbbVie ChemBeads technology. By using this approach, we were able to quickly map out the reactivity space at a global level with a challenging array of 3×222 micromolar reactions. The observed hit rate (56 %) is competitive with other often-used HTE reactions and the results are scalable. A key to this level of success was the finding that bipyridine 6-carboxamidine (BpyCam), a ligand that had not previously been shown to be optimal in any reaction, is as general as the best-known ligands with complementary reactivity. Such “cryptic” catalysts may be common and modern HTE methods should facilitate the process of finding these catalysts.     

Light- and pH-regulated Water-soluble Pseudorotaxanes Comprising a Cucurbit[7]uril and a Flavylium-based Axle

A linear double pyridinium-terminated thread comprising a central chalcone moiety is shown to provide two independent binding sites with similar affinity for cucurbit[7]uril (CB7) macrocycles in water as judged from NMR, UV-Visible and fluorescence spectroscopies. Association results in [2] and [3]pseudorotaxanes, which are both pH and photosensitive. Switching from the neutral chalcone to the cationic flavylium form upon irradiation at 365 nm under acidic conditions provided an enhanced CB7 association (K_1:1 increases from 1.2×10⁵ M⁻¹ to 1.5×10⁸ M⁻¹), limiting spontaneous on-thread cucurbituril shuttling. This co-conformational change in the [2]pseudorotaxane is reversible in the dark with k_obs=4.1×10⁻⁴ s⁻¹. Threading the flavylium moiety into CB7 leads to a dramatic increase in the fluorescence quantum yield, from 0.29 in the free axle to 0.97 in the [2]pseudorotaxane and 1.0 in the [3]pseudorotaxane.     

Modeling,Simulation, and Implementation of Solar‐Driven Water‐Splitting Devices

An integrated cell for the solar‐driven splitting of water consists of multiple functional components and couples various photoelectrochemical (PEC) processes at different length and time scales. The overall solar‐to‐hydrogen (STH) conversion efficiency of such a system depends on the performance and materials properties of the individual components as well as on the component integration, overall device architecture, and system operating conditions. This Review focuses on the modeling‐ and simulation‐guided development and implementation of solar‐driven water‐splitting prototypes from a holistic viewpoint that explores the various interplays between the components. The underlying physics and interactions at the cell level is are reviewed and discussed, followed by an overview of the use of the cell model to provide target properties of materials and guide the design of a range of traditional and unique device architectures.     

H2 Formation on Cosmic Grain Siliceous Surfaces Grafted with Fe+: A Silsesquioxanes‐Based Computational Model

Cosmic siliceous dust grains are involved in the synthesis of H₂ in the inter‐stellar medium. In this work, the dust grain siliceous surface is represented by a hydrogen Fe‐metalla‐silsesquioxane model of general formula: [Fe(H₇Si₇O_12?n)(OH)_n]⁺ (n=0,1,2) where Fe⁺ behaves like a single‐site heterogeneous catalyst grafted on a siliceous surface synthesizing H₂ from H. A computational analysis is performed using two levels of theory (B3LYP‐D3BJ and MP2‐F12) to quantify the thermodynamic driving force of the reaction: [Fe‐T7H₇]⁺+4H→[Fe‐T7H₇(OH)₂]⁺+H₂. The general outcomes are: 1) H₂ synthesis is thermodynamically strongly favored; 2) Fe‐H / Fe‐H₂ barrier‐less formation potential; 3) chemisorbed H‐Fe leads to facile H₂ synthesis at 20≤T≤100 K; 4) relative spin energetics and thermodynamic quantities between the B3LYP‐D3BJ and MP2‐F12 levels of theory are in qualitative agreement. The metalla‐silsesquioxane model shows how Fe⁺ fixed on a siliceous surface can potentially catalyze H₂ formation in space.     

Direct realism: Proximate causation and the missing object

Direct Realists believe that perception involves direct awareness of an object not dependent for its existence on the perceiver. Howard Robinson rejects this doctrine in favour of a Sense-Datum theory of perception. His argument against Direct Realism invokes the principle ‘same proximate cause, same immediate effect’. Since there are cases in which direct awareness has the same proximate cerebral cause as awareness of a sense datum, the Direct Realist is, he thinks, obliged to deny this causal principle. I suggest that although Direct Realism is in more than one respect implausible, it does not succumb to Robinson’s argument. The causal principle is true only if ‘proximate cause’ means ‘proximate sufficient cause’, and the Direct Realist need not concede that there is a sufficient cerebral cause for direct awareness of independent objects.     

Multiphase laminates of extremal effective conductivity in two dimensions

This paper deals with two-dimensional composites made of several isotropic linearly conducting phases in prescribed volume fractions. The primary focus is on the three-phase case; the generalization to a larger number of phases is straightforward.A class of high- but finite-rank laminates is introduced. The laminates saturate the known inequality bounds—due to the work of Hashin and Shtrikman, Lurie and Cherkaev, Tartar, and Murat and Tartar—on the effective conductivity tensor of any composite. These bounds depend only on the constituent material properties and volume fractions and not on the placement of these materials in the composite. The bounds are known not to be optimal for all admissible choices of the conductivities and volume fractions. However, they are now known to be realizable in a much larger range of these parameters than was previously known.The range of effective properties of our multiphase laminates strictly includes those corresponding to the composites found earlier by Milton and Kohn, Lurie and Cherkaev, and Gibiansky and Sigmund. The new optimal laminates are found in a systematic fashion by satisfying sufficient conditions on the fields in each layer. This leads to a simple algorithm for generating optimal laminates.In addition a new supplementary bound for multiphase structures is also proven which must be satisfied by composites with smooth interfaces.     

Simultaneous measurements of the release of atomic sodium, particle diameter and particle temperature for a single burning coal particle

The temporal history of the release of volatile alkali species during coal combustion is a significant, but poorly understood factor in the fouling and corrosion of heat transfer surfaces within industrial coal-fired boilers. We present new results of the simultaneous measurement of particle temperature, particle size and the atomic sodium concentration in the plume of a burning coal particle. During the char phase, the sodium concentration in the plume was found to be linearly dependent on the inverse of particle diameter, but during the ash phase the sodium concentration was found to decay exponentially with decreasing particle temperature. The centreline decay of Na within the plume above the burning particle consists of one region controlled by a first order chemical reaction and a second region controlled by diffusion.