Metal-catalyzed nitrogen-atom transfer methods for the oxidation of aliphatic C-H bonds

For more than a century, chemists have endeavored to discover and develop reaction processes that enable the selective oxidation of hydrocarbons. In the 1970s, Abramovitch and Yamada described the synthesis and electrophilic reactivity of sulfonyliminoiodinanes (RSO(2)N═IPh), demonstrating the utility of this new class of reagents to function as nitrene equivalents. Subsequent investigations by Breslow, Mansuy, and Müller would show such oxidants to be competent for alkene and saturated hydrocarbon functionalization when combined with transition metal salts or metal complexes, namely those of Mn, Fe, and Rh. Here, we trace our own studies to develop N-atom transfer technologies for C-H and π-bond oxidation. This Account discusses advances in both intra- and intermolecular amination processes mediated by dirhodium and diruthenium complexes, as well as the mechanistic foundations of catalyst reactivity and arrest. Explicit reference is given to questions that remain unanswered and to problem areas that are rich for discovery. A fundamental advance in amination technology has been the recognition that iminoiodinane oxidants can be generated in situ in the presence of a metal catalyst that elicits subsequent N-atom transfer. Under these conditions, both dirhodium and diruthenium lantern complexes function as competent catalysts for C-H bond oxidation with a range of nitrogen sources (e.g., carbamates, sulfamates, sulfamides, etc.), many of which will not form isolable iminoiodinane equivalents. Practical synthetic methods and applications thereof have evolved in parallel with inquiries into the operative reaction mechanism(s). For the intramolecular dirhodium-catalyzed process, the body of experimental and computational data is consistent with a concerted asynchronous C-H insertion pathway, analogous to the consensus mechanism for Rh-carbene transfer. Other studies reveal that the bridging tetracarboxylate ligand groups, which shroud the dirhodium core, are labile to exchange under standard reaction conditions. This information has led to the generation of chelating dicarboxylate dinuclear rhodium complexes, exemplified by Rh(2)(esp)(2). The performance of this catalyst system is unmatched by other dirhodium complexes in both intra- and intermolecular C-H amination reactions. Tetra-bridged, mixed-valent diruthenium complexes function as effective promoters of sulfamate ester oxidative cyclization. These catalysts can be crafted with ligand sets other than carboxylates and are more resistant to oxidation than their dirhodium counterparts. A range of experimental and computational mechanistic data amassed with the tetra-2-oxypyridinate diruthenium chloride complex, [Ru(2)(hp)(4)Cl], has established the insertion event as a stepwise pathway involving a discrete radical intermediate. These data contrast dirhodium-catalyzed C-H amination and offer a cogent model for understanding the divergent chemoselectivity trends observed between the two catalyst types. This work constitutes an important step toward the ultimate goal of achieving predictable, reagent-level control over product selectivity.     

Direct-writing of PbS nanoparticles inside transparent porous silica monoliths using pulsed femtosecond laser irradiation

Pulsed femtosecond laser irradiation at low repetition rate, without any annealing, has been used to localize the growth of PbS nanoparticles, for the first time, inside a transparent porous silica matrix prepared by a sol-gel route. Before the irradiation, the porous silica host has been soaked within a solution containing PbS precursors. The effect of the incident laser power on the particle size was studied. X-ray diffraction was used to identify the PbS crystallites inside the irradiated areas and to estimate the average particle size. The localized laser irradiation led to PbS crystallite size ranging between 4 and 8 nm, depending on the incident femtosecond laser power. The optical properties of the obtained PbS-silica nanocomposites have been investigated using absorption and photoluminescence spectroscopies. Finally, the stability of PbS nanoparticles embedded inside the host matrices has been followed as a function of time, and it has been shown that this stability depends on the nanoparticle mean size.     

Chemical and Biological Tools for the Study of Voltage-Gated Sodium Channels in Electrogenesis and Nociception

The malfunction and misregulation of voltage-gated sodium channels (Na_Vs) underlie in large part the electrical hyperexcitability characteristic of chronic inflammatory and neuropathic pain. Na_Vs are responsible for the initiation and propagation of electrical impulses (action potentials) in cells. Tissue and nerve injury alter the expression and localization of multiple Na_V isoforms, including Na_V1.1, 1.3, and 1.6–1.9, resulting in aberrant action potential firing patterns. To better understand the role of Na_V regulation, localization, and trafficking in electrogenesis and pain pathogenesis, a number of chemical and biological reagents for interrogating Na_V function have been advanced. The development and application of such tools for understanding Na_V physiology are the focus of this review.     

Population toxicokinetics of tetrachloroethylene

In assessing the distribution and metabolism of toxic compounds in the body, measurements are not always feasible for ethical or technical reasons. Computer modeling offers a reasonable alternative, but the variability and complexity of biological systems pose unique challenges in model building and adjustment. Recent tools from population pharmacokinetics, Bayesian statistical inference, and physiological modeling can be brought together to solve these problems. As an example, we modeled the distribution and metabolism of tetrachloroethylene (PERC) in humans. We derive statistical distributions for the parameters of a physiological model of PERC, on the basis of data from Monster et al. (1979). The model adequately fits both prior physiological information and experimental data. An estimate of the relationship between PERC exposure and fraction metabolized is obtained. Our median population estimate for the fraction of inhaled tetrachloroethylene that is metabolized, at exposure levels exceeding current occupational standards, is 1.5% [95% confidence interval (0.52%, 4.1%)]. At levels approaching ambient inhalation exposure (0.001 ppm), the median estimate of the fraction metabolized is much higher, at 36% [95% confidence interval (15%, 58%)]. This disproportionality should be taken into account when deriving safe exposure limits for tetrachloroethylene and deserves to be verified by further experiments.     

A vision-based strategy for autonomous aerial refueling tasks

Autonomous aerial refueling is a key enabling technology for both manned and unmanned aircraft where extended flight duration or range are required. The results presented within this paper offer one potential vision-based sensing solution, together with a unique test environment. A hierarchical visual tracking algorithm based on direct methods is proposed and developed for the purposes of tracking a drogue during the capture stage of autonomous aerial refueling, and of estimating its 3D position. Intended to be applied in real time to a video stream from a single monocular camera mounted on the receiver aircraft, the algorithm is shown to be highly robust, and capable of tracking large, rapid drogue motions within the frame of reference. The proposed strategy has been tested using a complex robotic testbed and with actual flight hardware consisting of a full size probe and drogue. Results show that the vision tracking algorithm can detect and track the drogue at real-time frame rates of more than thirty frames per second, obtaining a robust position estimation even with strong motions and multiple occlusions of the drogue.     

Silica, carbon and boron nitride monoliths with hierarchical porosity prepared by spark plasma sintering process

Silica SBA-15, carbon CMK-3, boron nitride (BN), the latter synthesized from the first two compounds as templates, are mesoporous materials in the form of powders. They have a high specific surface area and an important mesoporous volume. The porosity is organized with the hexagonal symmetric space group p6mm. For selected applications, it could be interesting to preserve these characteristics with materials in a well-defined shape at a macroscopic scale (few millimeters to centimeter). Spark plasma sintering (SPS) is a well-known technique which allows to prepare monoliths with relatively mild conditions. The SPS technique has been used on these mesoporous powders without charge or with a uniaxial charge and at temperatures of 600 °C, 800 °C for silica, 1100 °C, 1300 °C for carbon and 1600 °C, 1700 °C for boron nitride during 1–5 min. The nitrogen adsorption/desorption isotherms reveal that the obtained monoliths present high specific surface area (300–500 m²/g) and important mesoporous volume. The coexistence of interconnected mesoporosity and macroporosity (with volume’s close value) was observed by SEM and TEM, while the XRD and TEM characterization show that the mesoporosity organization is partially preserved.     

Dielectric plug-loaded two-port transmission line measurementtechnique for dielectric property characterization of granular andliquid materials

There are numerous dielectric property characterization techniques available in the microwave regime each with its own uniqueness, advantages and disadvantages. The two-port completely-filled waveguide (transmission line) technique is a robust measurement approach which is well suited for solid dielectric materials. In this case, the dielectric material can be relatively easily machined to fit inside the waveguide and the subsequent measurement of the scattering parameters of this two-port device renders the dielectric properties of the material filling the waveguide. However, this technique is not well suited for measuring the dielectric properties of granular and liquid materials. These materials are used in the production of various composites which are increasingly replacing the use of metals in many environments. If this technique is directly applied to these types of materials, several approximations either in the measurement apparatus or the formulation must be made. To overcome this problem, this paper describes a modification to this measurement technique utilizing two dielectric plugs which are used to house the granular or the liquid dielectric material. In this approach no approximation to the measurement apparatus is made while the presence of the plugs are fully accounted for in the derivations. Using this technique, the dielectric properties of cement powder, corn oil, antifreeze solution and tap water, constituting low- and high-loss dielectric materials (granular and liquid) were measured. In addition, the important issue of measurement uncertainty associated with this technique is also fully addressed. The issue of optimal choice of various measurement parameters is also discussed as it relates to the measurement uncertainty