Laser Guide Star for Large Segmented-Aperture Space Telescopes, Part I: Implications for Terrestrial Exoplanet Detection and Observatory Stability

Precision wavefront control on future segmented-aperture space telescopes presents significant challenges, particularly in the context of high-contrast exoplanet direct imaging. We present a new wavefront control architecture that translates the ground-based artificial guide star concept to space with a laser source aboard a second spacecraft, formation flying within the telescope field-of-view. We describe the motivating problem of mirror segment motion and develop wavefront sensing requirements as a function of guide star magnitude and segment motion power spectrum. Several sample cases with different values for transmitter power, pointing jitter, and wavelength are presented to illustrate the advantages and challenges of having a non-stellar-magnitude noise limited wavefront sensor for space telescopes. These notional designs allow increased control authority, potentially relaxing spacecraft stability requirements by two orders of magnitude, and increasing terrestrial exoplanet discovery space by allowing high-contrast observations of stars of arbitrary brightness.Comment: Submitted to A

A Short, Versatile Route Towards Benzothiadiazinyl Radicals

A family of substituted 1,2,4-benzothiadiazine 1-chlorides have been prepared by treatment of N-arylamidines in neat thionyl chloride at reflux. The S(IV) 1-chlorides are readily reduced under mild conditions to persistent 1,2,4- benzothiadiazinyl radicals which have been characterised by EPR spectroscopy and cyclic voltammetry. Crystallographic studies on isolated radicals indicate that the radicals dimerise via pancake bonding in the solid-state, resulting in spin-pairing and net diamagnetism

Adducts of Donor—Functionalized Ar3P with the Soft Lewis—Acid I2: Probing Simultaneous Lewis Acidity and Basicity at Internally Solvated P(III) Centers

The enhancement of donor strength of ortho—functionalized triarylphosphanes is shown to occur via different mechanisms for O- and N- donor substituents, with internal solvation of the phosphorus center observed for N—- donors. Nevertheless, the steric congestion about the P— center is shown to significantly oppose the increase in donor ability, leading to donation weaker than that expected. A series of mono- and bis-aryl -substituted Ar3PI2 adducts—[(Ph3—-?n (o-OMe-C6H4) n PI2, Ph3—-?n (o-NMe2-C6H4) n PI2, Ph3—-?n (o-CH2NMe2-C6H4) n PI2 (n =—1——,21, 2—)]) have been synthesized via the 1:1 reaction of donor-functionalized phosphanes with diiodine. These soft Lewis acid/base adducts exhibit apparent internal solvation of the donor phosphorus by the pendant donor moieties, giving rise to five- or six-coordinate phosphorus atoms acting as both Lewis base and Lewis acid; the first neutral six-coordinate simultaneous P(III) Lewis acid and Lewis base adduct is reported. Single -crystal X-ray diffraction studies reveal unexpectedly weak donor strength for one of the phosphanes, indicating significant steric hindrance as a consequence of internal solvation. Crystallographic interrogation of the corresponding iodophosphonium salts [Ar3PI]X (X = I3, BArF) shows that the cationic complexes experience a still greater influence of the steric bulk of the donor moieties than their neutral precursors. The steric and electronic contributions to bonding have been analyzed through computational studies, determining the factors governing the basicity of these donor—functionalized phosphanes, and show that enhancement of P-centered donor strength occurs by conjugation of lone pairs through the arene rings for oxygen substituents, and via internal solvation for the nitrogen donors

Exploring the reactivity of donor-stabilised phosphenium cations: Lewis acid catalysed reduction of chlorophosphanes by silanes

Phosphane-stabilised phosphenium cations react with silanes to effect either reduction to primary or secondary phosphanes, or formation of P-P bonded species depending upon counter-anion. This operates for in situ generated phosphenium cations, allowing catalytic reduction of P(III)-Cl bonds in the absence of strong reducing agents. Anion and substituent dependence studies have allowed insight into the competing mechanisms involved

Diverse Cooperative Reactivity at a Square Planar Aluminium Complex and Catalytic Reduction of CO 2

The use of a sterically demanding pincer ligand to prepare an unusual square planar aluminium complex is reported. Due to the constrained geometry imposed by the ligand scaffold, this four‐coordinate aluminium centre remains Lewis acidic and reacts via differing metal‐ligand cooperative pathways for activating ketones and CO2. It is also a rare example of a single‐component aluminium system for the catalytic reduction of CO2 to a methanol equivalent at room temperature

Supramolecular Behaviour and Fluorescence of Rhodamine-Functionalised ROMP Polymers

Inherently fluorescent polymers are of interest in materials and medicine. We report a ring-opening metathesis polymerisation (ROMP) platform for creation of amphiphilic block copolymers in which one block is formed from rhodamine B-containing monomers. The polymers self-assemble into well-defined micelles which are able to sequester molecular dyes and further interact with them by energy transfer. Despite incorporating a cationic dye known to bind DNA, the polymer micelles do not interact with DNA, indicating that they are potentially safe for use in bioanalytical applications

Dual-specificity phosphatase 1 and tristetraprolin cooperate to regulate macrophage responses to lipopolysaccharide

Dual-specificity phosphatase (DUSP) 1 dephosphorylates and inactivates members of the MAPK superfamily, in particular, JNKs, p38a, and p38b MAPKs. It functions as an essential negative regulator of innate immune responses, hence disruption of the Dusp1 gene renders mice extremely sensitive to a wide variety of experimental inflammatory challenges. The principal mechanisms behind the overexpression of inflammatory mediators by Dusp12/2 cells are not known. In this study, we use a genetic approach to identify an important mechanism of action of DUSP1, involving the modulation of the activity of the mRNA-destabilizing protein tristetraprolin. This mechanism is key to the control of essential early mediators of inflammation, TNF, CXCL1, and CXCL2, as well as the anti-inflammatory cytokine IL-10. The same mechanism also contributes to the regulation of a large number of transcripts induced by treatment of macrophages with LPS. These findings demonstrate that modulation of the phosphorylation status of tristetraprolin is an important physiological mechanism by which innate immune responses can be controlled

Gain-of-function mutation of tristetraprolin impairs negative feedback control of macrophages in vitro yet has overwhelmingly anti-inflammatory consequences in vivo

The mRNA-destabilizing factor tristetraprolin (TTP) binds in a sequencespecific manner to the 3= untranslated regions of many proinflammatory mRNAs and recruits complexes of nucleases to promote rapid mRNA turnover. Mice lacking TTP develop a severe, spontaneous inflammatory syndrome characterized by the overexpression of tumor necrosis factor and other inflammatory mediators. However, TTP also employs the same mechanism to inhibit the expression of the potent antiinflammatory cytokine interleukin 10 (IL-10). Perturbation of TTP function may therefore have mixed effects on inflammatory responses, either increasing or decreasing the expression of proinflammatory factors via direct or indirect mechanisms. We recently described a knock-in mouse strain in which the substitution of 2 amino acids of the endogenous TTP protein renders it constitutively active as an mRNA-destabilizing factor. Here we investigate the impact on the IL-10-mediated anti-inflammatory response. It is shown that the gain-of-function mutation of TTP impairs IL-10-mediated negative feedback control of macrophage function in vitro. However, the in vivo effects of TTP mutation are uniformly anti-inflammatory despite the decreased expression of IL-10

Dominant suppression of inflammation via targeted mutation of the mRNA destabilizing protein tristetraprolin

In myeloid cells, the mRNA-destabilizing protein tristetraprolin (TTP) is induced and extensively phosphorylated in response to LPS. To investigate the role of two specific phosphorylations, at serines 52 and 178, we created a mouse strain in which those residues were replaced by nonphosphorylatable alanine residues. The mutant form of TTP was constitutively degraded by the proteasome and therefore expressed at low levels, yet it functioned as a potent mRNA destabilizing factor and inhibitor of the expression of many inflammatory mediators. Mice expressing only the mutant form of TTP were healthy and fertile, and their systemic inflammatory responses to LPS were strongly attenuated. Adaptive immune responses and protection against infection by Salmonella typhimurium were spared. A single allele encoding the mutant form of TTP was sufficient for enhanced mRNA degradation and underexpression of inflammatory mediators. Therefore, the equilibrium between unphosphorylated and phosphorylated TTP is a critical determinant of the inflammatory response, and manipulation of this equilibrium may be a means of treating inflammatory pathologies

Influencing the Optoelectronic Properties of a Heteroleptic Iridium Complex by Second-Sphere H-Bonding Interactions

The use of a new second-sphere coordination methodology for emission color tuning of iridium complexes is presented. We demonstrate that a complimentary H-bonding guest molecule binding through contiguous triple H-bonding interactions can induce a shift in the emission of the iridium complex from green to blue without the need to alter the ligand structure around the metal centre, while simultaneously increasing the photoluminescence quantum yield in solution. The association constant for this host-guest interaction was determined to be Ka = 4.3 x 103 M-1 in a solution of 2% dimethylsulfoxide in chloroform by UV-Vis titration analysis and the impact of the hydrogen bonding interaction further probed by photoluminescence, electrochemical, and computational methods. Our findings suggest that directed self-assemblies are an effective approach to influencing emission properties of phosphorescent iridium (III) complexes