Issues Relevant to C-H Activation at Platinum(II): Comparative Studies between Cationic, Zwitterionic, and Neutral Platinum(II) Compounds in Benzene Solution

Cationic late metal systems are being highly scrutinized due to their propensity to mediate so-called electrophilic C-H activation reactions. This contribution compares the reactivity of highly reactive cationic platinum(II) systems with structurally related but neutral species. Our experimental design exploits isostructural neutral and cationic complexes supported by bis(phosphine) ligands amenable to mechanistic examination in benzene solution. The data presented herein collectively suggests that neutral platinum complexes can be equally if not more reactive towards benzene than their cationic counter-parts. Moreover, a number of unexpected mechanistic distinctions between the two systems arise that help to explain their respective reactivity

Reply to "Unrealistic nonphysiological amounts of reagents and a disregard for published literature"

Peer reviewedPublisher PD

Mitochondria and neuroprotection in stroke: Cationic arginine-rich peptides (CARPs) as a novel class of mitochondria-targeted neuroprotective therapeutics

Stroke is the second leading cause of death globally and represents a major cause of devastating long-term disability. Despite sustained efforts to develop clinically effective neuroprotective therapies, presently there is no clinically available neuroprotective agent for stroke. As a central mediator of neurodamaging events in stroke, mitochondria are recognised as a critical neuroprotective target, and as such, provide a focus for developing mitochondrial-targeted therapeutics. In recent years, cationic arginine-rich peptides (CARPs) have been identified as a novel class of neuroprotective agent with several demonstrated mechanisms of action, including their ability to target mitochondria and exert positive effects on the organelle. This review provides an overview on neuronal mitochondrial dysfunction in ischaemic stroke pathophysiology and highlights the potential beneficial effects of CARPs on mitochondria in the ischaemic brain following stroke

Nanotoxicity of polyelectrolyte-functionalized titania nanoparticles towards microalgae and yeast: Role of the particle concentration, size and surface charge

We studied the nanotoxicity of titania nanoparticles (TiO₂NPs) of various hydrodynamic diameters and crystallite sizes towards C. reinhardtii microalgae and S. cerevisiae (yeast) upon illumination with UV and visible light. The cell viability was assessed for a range of nanoparticle concentrations and incubation times. We found that bare TiO₂NPs affect the C. reinhardtii cell viability at much lower particle concentrations than for yeast. We observed an increase of the TiO₂NPs toxicity upon illumination with UV light compared with that in dark conditions due to the oxidative stress of the produced reactive oxygen species. We also found an increased TiO₂NPs nanotoxicity upon illumination with visible light which indicates that they may also interfere with the microalgae's photosynthetic system leading to decreased chlorophyll content upon exposure to TiO₂NPs. The results indicate that the larger the hydrodynamic diameter of the TiO₂NPs the lower is their nanotoxicity, with anatase TiO₂NPs generally being more toxic than rutile TiO₂NPs. We also prepared a range of polyelectrolyte-coated TiO₂NPs using a layer by-layer method and studied their nanotoxicity towards yeast and microalgae. We found that the toxicity of the coated TiO₂NPs changes with their surface charge. TiO₂NPs coated with cationic polyelectrolyte as an outer layer exhibit much higher nanotoxicity than the ones with an outer layer of anionic polyelectrolyte. TEM images of sectioned microalgae and yeast cells exposed to different polyelectrolyte-coated TiO₂NPs confirmed the formation of a significant build-up of nanoparticles on the cell surface for bare and cationic polyelectrolyte-coated TiO₂NPs. The effect comes from the increased adhesion of cationic nanoparticles to the cell walls. Significantly, coating the TiO₂NPs with anionic polyelectrolyte as an outer layer led to a reduced adhesion and much lower nanotoxicity due to electrostatic repulsion with the cell walls. This suggest a new way of making cationic TiO₂NPs safer for use in different formulations by pre-coating them with anionic polyelectrolytes. The results of this study give important insights into the various factors controlling the nanotoxicity of TiO₂NPs

Immobilized photosensitizers for antimicrobial applications

Photodynamic antimicrobial chemotherapy (PACT) is a very promising alternative to conventional antibiotics for the efficient inactivation of pathogenic microorganisms; this is due to the fact that it is virtually impossible for resistant strains to develop due to the mode of action employed. PACT employs a photosensitizer, which preferentially associates with the microorganism, and is then activated with non-thermal visible light of appropriate wavelength(s) to generate high localized concentrations of reactive oxygen species (ROS), inactivating the microorganism. The concept of using photosensitizers immobilized on a surface for this purpose is intended to address a range of economic, ecological and public health issues. Photosensitising molecules that have been immobilized on solid support for PACT applications are described herein. Different supports have been analyzed as well as the target microorganism and the effectiveness of particular combinations of support and photosensitiser

Mechanisms underlying the exquisite sensitivity of Candida albicans to combinatorial cationic and oxidative stress that enhances the potent fungicidal activity of phagocytes

Copyright © 2014 Kaloriti et al.Peer reviewedPublisher PD

Ionic Liquid-functionalized Mesoporous Sorbents And Their Use In The Capture Of Polluting Gases

A composite structure for capturing a gaseous electrophilic species, the composite structure comprising mesoporous refractory sorbent particles on which an ionic liquid is covalently attached, wherein said ionic liquid includes an accessible functional group that is capable of binding to said gaseous electrophilic species. In particular embodiments, the mesoporous sorbent particles are contained within refractory hollow fibers. Also described is a method for capturing a gaseous electrophilic species by use of the above-described composite structure, wherein the gaseous electrophilic species is contacted with the composite structure. In particular embodiments thereof, cooling water is passed through the refractory hollow fibers containing the IL-functionalized sorbent particles in order to facilitate capture of the gaseous electrophilic species, and then steam is passed through the refractory hollow fibers to facilitate release of the gaseous electrophilic species such that the composite structure can be re-used to capture additional gas.Ut-battelle, LLCGeorgia Tech Research Corporatio

Rate and Mechanism of the Oxidative Addition of Benzoic Anhydride to Palladium(0) Complexes in DMF

The rate constant of the oxidative addition of the benzoic anhydride (PhCO)2O to [Pd0(PPh3)4] has been determined in DMF and compared to that of phenyl halides and phenyl triflate. The following reactivity order has been established: PhI >> (PhCO)2O > PhOTf > PhBr. The oxidative addition of (PhCO)2O proceeds by activation of one C−O bond. Two acyl-PdII complexes are formed: a neutral complex trans-[(PhCO)Pd(OCOPh)(PPh3)2] and a cationic complex trans-[(PhCO)PdS(PPh3)2]+ (S = DMF) showing that the decarbonylation process is highly endergonic. The exchange of PPh3 by the bidentate ligand dppp does not favor the decarbonylation process.

Adsorption of Ethylene on Neutral, Anionic and Cationic Gold Clusters

The adsorption of ethylene molecule on neutral, anionic and cationic gold clusters consisting of up to 10 atoms has been investigated using density-functional theory. It is demonstrated that C2H4 can be adsorbed on small gold clusters in two different configurations, corresponding to the pi- and di-sigma-bonded species. Adsorption in the pi-bonded mode dominates over the di-sigma mode over all considered cluster sizes n, with the exception of the neutral C2H4-Au5 system. A striking difference is found in the size-dependence of the adsorption energy of C2H4 bonded to the neutral gold clusters in the pi and di-sigma configurations. The important role of the electronic shell effects in the di-sigma mode of ethylene adsorption on neutral gold clusters is demonstrated. It is shown that the interaction of C2H4 with small gold clusters strongly depends on their charge. The typical shift in the vibrational frequencies of C2H4 adsorbed in the pi- and the di-sigma configurations gives a guidance to experimentally distinguish between the two modes of adsorption.Comment: 30 pages, 10 figure

Kinetic and Thermodynamic Studies of Carbenium Ion Additions Towards Alkenes

The ionisation (Ar2CHCl + BC13 v=± Ar2CH+BCi;) and dissociation (Ar2CH+BCi; ^=*Ar2CH+ + BCl^) equilibria of diarylmethyl chlorides i n boron trichloride/ dichloromethane solution have been studied by conductimetry, photometry and *H NMR spectroscopy. Small differences i n the UV-vis spectra of diarylcarbenium tetrachloroborates, which have been observed i n solutions of low and high tetrachloroborate concentration, can be attributed to the formation of 1 :1 ion-pairs i n the more concentrated solutions. Low temperature calorimetry was used to determine the heats of addition of diarylcarbenium tetrachloroborates to 2~methyl-1 -pentene (Ar2CH+BCi; + H2C=CRRT ArjCH-CHj-CRR'Cl + BC13), and it is estimated that the standard free enthalpy of t h i s reaction is greater than 0 for systems with pKR+ > -2.6. Kinetic studies have shown that paired and unpaired diarylcarbenium tetrachloroborates exhibit identical reactivity towards alkenes. A rationalisation for the different situation in carbocationic and carbanionic polymerisation i s presented. The rate constants for the initiation of isobutene, styrene and isoprene polymerisation by diarylcarbenium ions have been determined, and it is shown, how propagation rate constants can be estimated from linear free energy relationships