Multielectron Redox Reactions between Manganese Porphyrins Mediated by Nitrogen Atom Transfer

From the pioneering work of Taube, 1 electron-transfer reactions can be mechanistically categorized into either inner sphere or outer sphere processes. The most well-studied systems in either case typically involve one-electron changes. Redox processes involving transfers of a multiple number of electrons, especially between two metals, are much less prevalent and consequently less well understood. The most extensive studies on multiple electron changes have involved atom transfer processes.2 These are typically two electron-transfer reactions mediated by either a bridging halogen3•4 or a bridging oxo5 ligand. The consideration of a nitrido ligand as a bridging species in redox reactions has received little attention.6 In this regard, we initiated studies on the bridging capabilities of the nitrido complexes of metalloporphyrins. We report herein the first example of a reversible net three electron redox process mediated by nitrogen atom transfer

3-dimensional electrode patterning within a microfluidic channel using metal ion implantation

The application of electrical fields within a microfluidic channel enables many forms of manipulation necessary for lab-on-a-chip devices. Patterning electrodes inside the microfluidic channel generally requires multi-step optical lithography. Here, we utilize an ion-implantation process to pattern 3D electrodes within a fluidic channel made of polydimethylsiloxane (PDMS). Electrode structuring within the channel is achieved by ion implantation at a 40° angle with a metal shadow mask. The advantages of three-dimensional structuring of electrodes within a fluidic channel over traditional planar electrode designs are discussed. Two possible applications are presented: asymmetric particles can be aligned in any of the three axial dimensions with electro-orientation; colloidal focusing and concentration within a fluidic channel can be achieved through dielectrophoresis. Demonstrations are shown with E. coli, a rod shaped bacteria, and indicate the potential that ion-implanted microfluidic channels have for manipulations in the context of lab-on-a-chip devices

Oxo-Transfer Reactions of Chromium and Titanium Porphyrins

Examples of intermetal oxygen atom transfer are rare. In general, inner-sphere electron transfer mediated through an oxo ligand typically leads to formation of .u-oxo-bridged products.1 For example, when (TPP)Cr1v=O is treated with Cr11(TPP) in toluene, formation of (TPP)Cr111-0-Cr111(TPP) is observed. 2•3 lntermetal oxo transfer thus far has been limited to molybdenum and tungsten complexes.4 Oxo transfer between two ruthenium centers has been implicated in the aerobic epoxidation of olefins by ruthenium porphyrins.5 As an extension of our studies on inner-sphere redox reactions and nitrogen atom transfer,6 we have initiated an investigation of oxygen atom transfer. Our approach to oxo transfer developed as a result of our recent finding that nitrogen atom transfer occurs reversibly between (OEP)Mn==N and (TTP)Mn-CI as shown in eq 1

An ammonia sensor based on Lossy Mode Resonances on a tapered optical fibre coated with porphyrin-incorporated titanium dioxide

The development of a highly sensitive ammonia sensor is described. The sensor is formed by deposition of a nanoscale coating of titanium dioxide, containing a porphyrin as a functional material, onto a tapered optical fibre. The titanium dioxide coating allows coupling of light from the fundamental core mode to a lossy mode supported by the coating, thus creating a Lossy Mode Resonance (LMR) in the transmission spectrum. A change in the refractive index of the coating caused by the interaction of the porphyrin with ammonia causes a change in the centre wavelength of the LMR, allowing concentrations of ammonia in water as low as 0.1 ppm to be detected, with a response time of less than 30 s

Ammonia sensing using lossy mode resonances in a tapered optical fibre coated with porphyrin-incorporated titanium dioxide

The development of an ammonia sensor, formed by the deposition of a functionalised titanium dioxide film onto a tapered optical fibre is presented. The titanium dioxide coating allows the coupling of light from the fundamental core mode to a lossy mode supported by the coating, thus creating lossy mode resonance (LMR) in the transmission spectrum. The porphyrin compound that was used to functionalise the coating was removed from the titanium dioxide coating upon exposure to ammonia, causing a change in the refractive index of the coating and a concomitant shift in the central wavelength of the lossy mode resonance. Concentrations of ammonia as small as 1ppm was detected with a response time of less than 1min. © (2016) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE). Downloading of the abstract is permitted for personal use only

Effects of Beaver Dams on Subarctic Wetland Hydrology

Beaver dams are ubiquitous in subarctic wetlands, where runoff in the flat terrain is highly prone to changes as the stream courses are modified by beaver activities. Depending on the state of preservation, stream flow can overtop or funnel through gaps in the dams, leak from the bottom of the dams or seep through the entire structure. Peak and low flows are regulated by these dams to a varying extent. The formation of beaver ponds causes local flooding, while the open water surfaces of the ponds increase water loss from the wetlands. Water spilled from the dams may cause diversion channels to produce complex drainage patterns. Comparing the water balance of basins with and without a beaver dam at its outlet confirms that the dammed basin lost more water to evaporation, suppressed the outflow and increased the basin water storage.

Oxygen Atom Transfer Reactions of Chromium Porphyrins: An Electronic Rationale for Oxo Transfer versus μ-Oxo Product Formation

Treatment of (meso-tetra-p-tolylporphyrinato)chromium(IV) oxide, {TTP)Cr=O, with (octaethylporphyrinato)chromium( III) chloride, (OEP)Cr-Cl, in benzene results in the reversible exchange of axial ligands to form (TTP)Cr-Cl and (OEP)Cr=O. The net result is a formal one-electron redox process. This occurs with a second-order rate constant of 0.14 :1:: 0.01 M-1 s-1 to form an equilibrium mixture with K = 2.7 :1:: 0.1 at 30 °C (ill/* = 15.4 :1:: 0.7 kcaljmol, M* = -12 :1:: 2 cal/ (mol·K), ill/0 = -2.0 :1:: 0.4 kcaljmol, and M 0 = -4.6 :1:: 1.2 cal/ (mol·K)). Use of pivalate in place of chloride on the Cr(III) complex causes no significant change in the rate of this one-electron redox process. The sterically protected Baldwin\u27s C2-capped {porphyrinato)chromium(III) complex, (CAP)Cr-Cl, also undergoes oxygen atom transfer with (OEP)Cr=O at a similar rate. In addition, excess chloride inhibits the rate of oxygen transfer with chlorochromium(III) complexes. These results support an inner-sphere mechanism involving a ~-oxo intermediate which is formed after an initial ligand (chloride or pivalate) dissociation from the chromium(III) reductant