Oxidation of biogenic and water-soluble compounds in aqueous and organic aerosol droplets by ozone: a kinetic and product analysis approach using laser Raman tweezers

The results of an experimental study into the oxidative degradation of proxies for atmospheric aerosol are presented. We demonstrate that the laser Raman tweezers method can be used successfully to obtain uptake coeffcients for gaseous oxidants on individual aqueous and organic droplets, whilst the size and composition of the droplets is simultaneously followed. A laser tweezers system was used to trap individual droplets containing an unsaturated organic compound in either an aqueous or organic ( alkane) solvent. The droplet was exposed to gas- phase ozone and the reaction kinetics and products followed using Raman spectroscopy. The reactions of three different organic compounds with ozone were studied: fumarate anions, benzoate anions and alpha pinene. The fumarate and benzoate anions in aqueous solution were used to represent components of humic- like substances, HULIS; a alpha- pinene in an alkane solvent was studied as a proxy for biogenic aerosol. The kinetic analysis shows that for these systems the diffusive transport and mass accommodation of ozone is relatively fast, and that liquid- phase di. ffusion and reaction are the rate determining steps. Uptake coe. ffcients, g, were found to be ( 1.1 +/- 0.7) x 10(-5), ( 1.5 +/- 0.7) x 10 (-5) and ( 3.0 - 7.5) x 10 (-3) for the reactions of ozone with the fumarate, benzoate and a- pinene containing droplets, respectively. Liquid- phase bimolecular rate coe. cients for reactions of dissolved ozone molecules with fumarate, benzoate and a- pinene were also obtained: k(fumarate) = ( 2.7 +/- 2) x 10 (5), k(benzoate) = ( 3.5 +/- 3) x 10 (5) and k(alpha-pinene) = ( 1-3) x 10(7) dm(3) mol (-1) s (- 1). The droplet size was found to remain stable over the course of the oxidation process for the HULIS- proxies and for the oxidation of a- pinene in pentadecane. The study of the alpha- pinene/ ozone system is the first using organic seed particles to show that the hygroscopicity of the particle does not increase dramatically over the course of the oxidation. No products were detected by Raman spectroscopy for the reaction of benzoate ions with ozone. One product peak, consistent with aqueous carbonate anions, was observed when following the oxidation of fumarate ions by ozone. Product peaks observed in the reaction of ozone with alpha- pinene suggest the formation of new species containing carbonyl groups

Geometric isomerism in coordination cages based on tris-chelate vertices: a tool to control both assembly and host/guest chemistry.

This 'Perspective' article summarises recent work from the authors' research group on the exploitation of the simple fac/mer geometric isomerism of octahedral metal tris-chelates as a tool to control the chemistry of coordination cages based on bis(pyrazolyl-pyridine) ligands, in two different respects. Firstly this geometric isomerism plays a major role in controlling the guest binding properties of cages because a fac tris-chelate arrangement of pyrazolyl-pyridine chelates around a metal ion vertex results in formation of a convergent set of inwardly-directed C-H protons in a region of high positive electrostatic potential close to a metal cation. This collection of δ+ protons therefore provides a charge-assisted hydrogen-bond donor site, which interacts with the electron-rich regions of guest molecules that are of the correct size and shape to occupy the cage cavity, and the strength of this hydrogen-bonding interaction plays a major role in guest recognition in non-aqueous solvents. Secondly the ability to prepare mononuclear complexes with either a fac or mer arrangement of ligands provides an entry into the controlled, stepwise assembly of heterometallic cages based on a combination of kinetically inert and kinetically labile metal ions at different sites. This has allowed introduction of useful physical properties such as redox activity or luminescence, commonly associated with inert metal ions which are not amenable to participation in thermodynamic self-assembly processes, to be incorporated in a predictable way into the superstructures of coordination cages at specific sites

D→f energy transfer in heteronuclear Ir(III)/Ln(III) near-infrared luminescent complexes

A series of d/f dinuclear complexes Ir•Ln [where Ln = Eu(III), Gd(III), Yb(III) and Nd(III)] are reported. The core structure consists of a rigid skeleton containing two different types of receptor site in a single molecular motif designed to combine a transition metal ion [Ir(III)] and a lanthanide ion [Ln(III)] in different binding sites at either end of fully conjugated bridge to facilitate d→f energy-transfer following photoexcitation of the Ir(III)-based antenna unit. Steady state and time-resolved photophysical experiments on these compounds revealed that the energy-transfer is feasible only in case of Ir•Yb and Ir•Nd systems, affording sensitized emission from the Yb(III) or Nd(III) centres. Such EnT is not possible in the Ir•Eu dyad as the excited state energy of the Ir(III) unit is insufficient to sensitise the excited state of the Eu(III) centre

Predicting the failure of ultrasonic spot welds by pull-out from sheet metal

AbstractA methodology for determining the cohesive fracture parameters associated with pull-out of spot welds is presented. Since failure of a spot weld by pull-out occurs by mixed-mode fracture of the base metal, the cohesive parameters for ductile fracture of an aluminum alloy were determined and then used to predict the failure of two very different spot-welded geometries. The fracture parameters (characteristic strength and toughness) associated with the shear and normal modes of ductile fracture in thin aluminum alloy coupons were determined by comparing experimental observations to numerical simulations in which a cohesive-fracture zone was embedded within a continuum representation of the sheet metal. These parameters were then used to predict the load–displacement curves for ultrasonically spot-welded joints in T-peel and lap-shear configurations. The predictions were in excellent agreement with the experimental data. The results of the present work indicate that cohesive-zone models may be very useful for design purposes, since both the strength and the energy absorbed by plastic deformation during weld pull-out can be predicted quite accurately

The static and dynamic response of SU-8 electrothermal microgrippers of varying thickness

This work presents an investigation into the effect on dynamic response of SU-8 microgrippers due to varying thickness, and subsequent validation via COMSOL Multiphysics simulations and thermal camera profiling during actuation. The tweezer-like microgrippers can easily manipulate, with a high degree of control, cells and particles with diameters as small as 10 μm, without using an impractical operating voltage or generating excessive heat. However, in order to fully exploit the versatility of the devices, their response characteristics must be fully understood as material and/or dimension parameters change. Therefore an investigation took place to determine the effects of device thickness on functionality of the device, including the drive current required to actuate the gripper and the speed of actuation. Furthermore, an infrared camera was used to characterise the thermal response of the device. Finally, a simulation of the temperature profile and deflection dimension has been developed in order to verify the findings and further investigate and predict the effects of design variations

Pharmacological targeting of phosphoinositide lipid kinases and phosphatases in the immune system:Success, disappointment, and new opportunities

The predominant expression of the γ and δ isoforms of PI3K in cells of hematopoietic lineage prompted speculation that inhibitors of these isoforms could offer opportunities for selective targeting of PI3K in the immune system in a range of immune-related pathologies. While there has been some success in developing PI3Kδ inhibitors, progress in developing selective inhibitors of PI3Kγ has been rather disappointing. This has prompted the search for alternative targets with which to modulate PI3K signalling specifically in the immune system. One such target is the SH2-domain containing inositol-5-phosphatase-1 (SHIP-1) which de-phosphorylates PI(3,4,5)P3 at the D5 position of the inositol ring to create PI(3,4)P2. In this article, we first describe the current state of PI3K isoform-selective inhibitor development. We then focus on the structure of SHIP-1 and its function in the immune system. Finally, we consider the current state of development of small molecule compounds that potently and selectively modulate SHIP activity and which offer novel opportunities to manipulate PI3K mediated signalling in the immune system

Coordination‐cage‐catalysed hydrolysis of organophosphates : cavity‐ or surface‐based?

The hydrophobic central cavity of a water‐soluble M8L12 cubic coordination cage can accommodate a range of phospho‐diester and phospho‐triester guests such as the insecticide “dichlorvos” (2,2‐dichlorovinyl dimethyl phosphate) and the chemical warfare agent analogue di(isopropyl) chlorophosphate. The accumulation of hydroxide ions around the cationic cage surface due to ion‐pairing in solution generates a high local pH around the cage, resulting in catalysed hydrolysis of the phospho‐triester guests. A series of control experiments unexpectedly demonstrates that—in marked contrast to previous cases—it is not necessary for the phospho‐triester substrates to be bound inside the cavity for catalysed hydrolysis to occur. This suggests that catalysis can occur on the exterior surface of the cage as well as the interior surface, with the exterior‐binding catalysis pathway dominating here because of the small binding constants for these phospho‐triester substrates in the cage cavity. These observations suggest that cationic but hydrophobic surfaces could act as quite general catalysts in water by bringing substrates into contact with the surface (via the hydrophobic effect) where there is also a high local concentration of anions (due to ion pairing/electrostatic effects)

Stepwise assembly of mixed-metal coordination cages containing both kinetically inert and kinetically labile metal ions: introduction of metal-centred redox and photophysical activity at specific sites

Stepwise preparation of the heterometallic octanuclear coordination cages [(Ma)4(Mb)4L12]16+ is reported, in which Ma = Ru or Os and Mb = Cd or Co (all in their +2 oxidation state). This requires initial preparation of the kinetically inert mononuclear complexes [(Ma)L3]2+ in which L is a ditopic ligand with two bidentate chelating pyrazolyl-pyridine units: in the complexes [(Ma)L3]2+ one terminus of each ligand is bound to the metal ion, such that the complex has three pendant bidentate sites at which cage assembly can propagate by coordination to additional labile ions Mb in a separate step. Thus, combination of four [(Ma)L3]2+ units and four [Mb]2+ ions results in assembly of the complete cages [(Ma)4(Mb)4L12]16+ in which a metal ion lies at each of the eight vertices, and a bridging ligand spans each of the twelve edges, of a cube. The different types of metal ion necessarily alternate around the periphery with each bridging ligand bound to one metal ion of each type. All four cages have been structurally characterised: in the Ru(II)/Cd(II) cage (reported in a recent communication) the Ru(II) and Cd(II) ions are crystallographically distinct; in the other three cages [Ru(II)/Co(II), Os(II)/Cd(II) and Os(II)/Co(II), reported here] the ions are disordered around the periphery such that every metal site refines as a 50 : 50 mixture of the two metal atom types. The incorporation of Os(II) units into the cages results in both redox activity [a reversible Os(II)/Os(III) couple for all four metal ions simultaneously, at a modest potential] and luminescence [the Os(II) units have luminescent 3MLCT excited states which will be good photo-electron donors] being incorporated into the cage superstructure

Ir(III) and Ir(III)/Re(I) complexes of a new bis(pyrazolyl-pyridine) bridging ligand containing a naphthalene-2,7-diyl spacer: Structural and photophysical properties

A new bridging ligand has been prepared in which two chelating bidentate pyrazolyl-pyridine termini are connected to a central naphthalene-2,7-diyl core via methylene spacer units. This ligand has been used to prepared mononuclear and dinuclear Ir(III) complexes in which {Ir(F2ppy)2} [F2ppy = cyclometallating anion of 2-(3,5-difluorophenyl)-pyridine] complex fragments are coordinated to one or both of the pyrazolyl-pyridine termini; in addition a heterodinuclear complex has been prepared containing one {Ir(F2ppy)2} unit and one {Re(CO)3Cl} unit in the two binding sites. X-ray crystallographic studies show that the bridging naphthyl group lies stacked with a coordinated F2ppy ligand from a terminal {Ir(F2ppy)2} unit in every case. Luminescence measurements show that the usual strong Ir(III)-centred blue luminescence is substantially quenched by the presence of a low-lying triplet state on the naphthyl group; in the Ir(III)/Re(I) dyad we observe both weak Ir(III)-based emission as well as lower-energy Re(I)-based emission which overlap; Ir(III) → Re(I) energy-transfer occurs on a timescale of <1 ns as no rise-time for sensitised Re(I)-based emission could be detected, in contrast to other Ir(III)/Re(I) dyads in which the Ir(III) → Re(I) energy-transfer is slower (10–100 ns timescale). We ascribe this to the spatial and energetic intermediacy of the naphthyl group whose triplet energy lies between that of the Ir(III) and Re(I) termini, providing an effective conduit for energy-transfer to occur

A note on brain actuated spelling with the Berlin brain-computer interface

Brain-Computer Interfaces (BCIs) are systems capable of decoding neural activity in real time, thereby allowing a computer application to be directly controlled by the brain. Since the characteristics of such direct brain-tocomputer interaction are limited in several aspects, one major challenge in BCI research is intelligent front-end design. Here we present the mental text entry application ‘Hex-o-Spell’ which incorporates principles of Human-Computer Interaction research into BCI feedback design. The system utilises the high visual display bandwidth to help compensate for the extremely limited control bandwidth which operates with only two mental states, where the timing of the state changes encodes most of the information. The display is visually appealing, and control is robust. The effectiveness and robustness of the interface was demonstrated at the CeBIT 2006 (world’s largest IT fair) where two subjects operated the mental text entry system at a speed of up to 7.6 char/min