A Photophysical Study of Sensitization‐Initiated Electron Transfer: Insights into the Mechanism of Photoredox Activity

The development of photocatalytic reactions has provided many novel opportunities to expand the scope of synthetic organic chemistry. In parallel with progress towards uncovering new reactivity, there is consensus that efforts focused on providing detailed mechanistic insight in order to uncover underlying excited‐state reactions are essential to maximise formation of desired products. With this in mind, we have investigated the recently reported sensitization‐initiated electron transfer (SenI‐ET) reaction for the C?H arylation of activated aryl halides. Using a variety of techniques, and in particular nanosecond transient absorption spectroscopy, we are able to distinguish several characteristic signals from the excited‐state species involved in the reaction, and subsequent kinetic analysis under various conditions has facilitated a detailed insight into the likely reaction mechanism.     

Mass Spectrometric Strategies to Improve the Identification of Pt(II)-Modification Sites on Peptides and Proteins

To further explore the binding chemistry of cisplatin (cis-Pt(NH₃)₂Cl₂) to peptides and also establish mass spectrometry (MS) strategies to quickly assign the platinum-binding sites, a series of peptides with potential cisplatin binding sites (Met(S), His(N), Cys(S), disulfide, carboxyl groups of Asp and Glu, and amine groups of Arg and Lys, were reacted with cisplatin, then analyzed by electron capture dissociation (ECD) in a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS). Radical-mediated side-chain losses from the charge-reduced Pt-binding species (such as CH₃S^? or CH₃SH from Met, SH^? from Cys, CO₂ from Glu or Asp, and NH₂ ^? from amine groups) were found to be characteristic indicators for rapid and unambiguous localization of the Pt-binding sites to certain amino acid residues. The method was then successfully applied to interpret the top-down ECD spectrum of an inter-chain Pt-crosslinked insulin dimer, insulin?+?Pt(NH₃)₂?+?insulin (>10 kDa). In addition, ion mobility MS shows that Pt binds to multiple sites in Substance P, generating multiple conformers, which can be partially localized by collisionally activated dissociation (CAD). Platinum(II) (Pt(II)) was found to coordinate to amine groups of Arg and Lys, but not to disulfide bonds under the conditions used. The coordination of Pt to Arg or Lys appears to arise from the migration of Pt(II) from Met(S) as shown by monitoring the reaction products at different pH values by ECD. No direct binding of cisplatin to amine groups was observed at pH 3?~?10 unless Met residues were present in the sequence, but noncovalent interactions between cisplatin hydrolysis and amination [Pt(NH₃)₄]²⁺ products and these peptides were found regardless of pH.

A Photophysical Study of Sensitization-Initiated Electron Transfer: Insights into the Mechanism of Photoredox Activity

The development of photocatalytic reactions has provided many novel opportunities to expand the scope of synthetic organic chemistry. In parallel with progress towards uncovering new reactivity, there is consensus that efforts focused on providing detailed mechanistic insight in order to uncover underlying excited-state reactions are essential to maximise formation of desired products. With this in mind, we have investigated the recently reported sensitization-initiated electron transfer (SenI-ET) reaction for the C−H arylation of activated aryl halides. Using a variety of techniques, and in particular nanosecond transient absorption spectroscopy, we are able to distinguish several characteristic signals from the excited-state species involved in the reaction, and subsequent kinetic analysis under various conditions has facilitated a detailed insight into the likely reaction mechanism.     

Strategies and tactics for the metal-directed synthesis of rotaxanes, knots, catenanes, and higher order links

More than a quarter of a century after the first metal template synthesis of a [2]catenane in Strasbourg, there now exists a plethora of strategies available for the construction of mechanically bonded and entwined molecular level structures. Catenanes, rotaxanes, knots and Borromean rings have all been successfully accessed by methods in which metal ions play a pivotal role. Originally metal ions were used solely for their coordination chemistry; acting either to gather and position the building blocks such that subsequent reactions generated the interlocked products or by being an integral part of the rings or "stoppers" of the interlocked assembly. Recently the role of the metal has evolved to encompass catalysis: the metal ions not only organize the building blocks in an entwined or threaded arrangement but also actively promote the reaction that covalently captures the interlocked structure. This Review outlines the diverse strategies that currently exist for forming mechanically bonded molecular structures with metal ions and details the tactics that the chemist can utilize for creating cross-over points, maximizing the yield of interlocked over non-interlocked products, and the reactions-of-choice for the covalent capture of threaded and entwined intermediates.     

MnO2/TiN heterogeneous nanostructure design for electrochemical energy storage

MnO(2)/TiN nanotubes are fabricated using facile deposition techniques to maximize the surface area of the electroactive material for use in electrochemical capacitors. Atomic layer deposition is used to deposit conformal nanotubes within an anodic aluminium oxide template. After template removal, the inner and outer surfaces of the TiN nanotubes are exposed for electrochemical deposition of manganese oxide. Electron microscopy shows that the MnO(2) is deposited on both the inside and outside of TiN nanotubes, forming the MnO(2)/TiN nanotubes. Cyclic voltammetry and galvanostatic charge-discharge curves are used to characterize the electrochemical properties of the MnO(2)/TiN nanotubes. Due to the close proximity of MnO(2) with the highly conductive TiN as well as the overall high surface area, the nanotubes show very high specific capacitance (662 F g(-1) reported at 45 A g(-1)) as a supercapacitor electrode material. The highly conductive and mechanically stable TiN greatly enhances the flow of electrons to the MnO(2) material, while the high aspect ratio nanostructure of TiN creates a large surface area for short diffusion paths for cations thus improving high power. Combining the favourable structural, electrical and energy properties of MnO(2) and TiN into one system allows for a promising electrode material for supercapacitors.     

Heterogeneous nanostructured electrode materials for electrochemical energy storage

In order to fulfil the future requirements of electrochemical energy storage, such as high energy density at high power demands, heterogeneous nanostructured materials are currently studied as promising electrode materials due to their synergic properties, which arise from integrating multi-nanocomponents, each tailored to address a different demand (e.g., high energy density, high conductivity, and excellent mechanical stability). In this article, we discuss these heterogeneous nanomaterials based on their structural complexity: zero-dimensional (0-D) (e.g. core-shell nanoparticles), one-dimensional (1-D) (e.g. coaxial nanowires), two-dimensional (2-D) (e.g. graphene based composites), three-dimensional (3-D) (e.g. mesoporous carbon based composites) and the even more complex hierarchical 3-D nanostructured networks. This review tends to focus more on ordered arrays of 1-D heterogeneous nanomaterials due to their unique merits. Examples of different types of structures are listed and their advantages and disadvantages are compared. Finally a future 3-D heterogeneous nanostructure is proposed, which may set a goal toward developing ideal nano-architectured electrodes for future electrochemical energy storage devices.     

Highly flexible pseudocapacitor based on freestanding heterogeneous MnO2/conductive polymer nanowire arrays

Flexible electronics such as wearable electronic clothing, paper-like electronic devices, and flexible biomedical diagnostic devices are expected to be commercialized in the near future. Flexible energy storage will be needed to power these devices. Supercapacitor devices based on freestanding nanowire arrays are promising high power sources for these flexible electronics. Electrodes for these supercapacitor devices consisting of heterogeneous coaxial nanowires of poly (3,4-ethylenedioxythiophene) (PEDOT)-shell and MnO(2)-core materials have been shown in a half cell system to have improved capacitance and rate capabilities when compared to their pure nanomaterials; however, their performance in a full cell system has not been fully investigated. Herein, these coaxial nanowires are tested in both a symmetric and an asymmetric (utilizing a PEDOT nanowire anode) full cell configuration in the aspect of charge storage, charge rate, and flexibility without using any carbon additives and polymer binders. It is found that the asymmetric cell outperforms the symmetric cell in terms of energy density, rate capability, and cycle ability. The asymmetric device's electrode materials display an energy density of 9.8 Wh/kg even at a high power density of 850 W kg(-1). This device is highly flexible and shows fast charging and discharging while still maintaining 86% of its energy density even under a highly flexed state. The total device is shown to have a total capacitance of 0.26 F at a maximum voltage of 1.7 V, which is capable of providing enough energy to power small portable devices.     

Using soluble polymers in latent biphasic systems

A new strategy for carrying out reactions with a soluble polymer-bound reagent or catalyst is described. In this latent biphasic process, a solvent mixture at the cusp of immiscibility is prepared and used to carry out a reaction under homogeneous conditions. Then, after the reaction is complete, this mixture is perturbed by the addition of solvent or some other perturbing agent to produce a biphasic mixture. The product-containing phase is then separated under liquid/liquid conditions from the polymer-containing phase. The generality of this process is demonstrated using both dye-labeled polymers as surrogates for polymer-bound catalysts and with various polymer-bound organic and transition metal catalysts or reagents. In cases where a polymeric catalyst is used, the addition of fresh solvent and substrate reforms the original mixture allowing facile reuse of the catalyst.