Micron-sized biogenic and synthetic hollow mineral spheres occlude additives within single crystals

Incorporating additives within host single crystals is an effective strategy for producing composite materials with tunable mechanical, magnetic and optical properties. The type of guest materials that can be occluded can be limited, however, as incorporation is a complex process depending on many factors including binding of the additive to the crystal surface, the rate of crystal growth and the stability of the additives in the crystallisation solution. In particular, the size of occluded guests has been restricted to a few angstroms – as for single molecules – to a few hundred nanometers – as for polymer vesicles and particles. Here, we present a synthetic approach for occluding micrometer-scale objects, including high-complexity unicellular organisms and synthetic hollow calcite spheres within calcite single crystals. Both of these objects can transport functional additives, including organic molecules and nanoparticles that would not otherwise occlude within calcite. Therefore, this method constitutes a generic approach using calcite as a delivery system for active compounds, while providing them with effective protection against environmental factors that could cause degradation

Polymeric Frustrated Lewis Pairs

Frustrated Lewis Pair (FLP) chemistry is a significant and growing field since it offers a novel non-metal catalyst for hydrogenation and small molecule activation. Once it was discovered, different FLPs with varying reactivity towards small molecules have been extensively investigated. Its research has mainly focused on small molecule-based FLPs, however, especially in the aspect of hydrogenation reactions. In the field of polymer chemistry, several examples of conventional Lewis pair adduct containing polymers have been reported but there has yet been no exploration of FLPs incorporated into polymers up to the date of this project. Dynamic crosslinked polymeric networks have attracted more attention in recent years as their shape can be post-modified after polymerisation due to their exchangeable crosslinks. This dynamic crosslinking also makes the material stimuli-responsive and provides self-healing properties. This thesis introduces the synthesis of a polymeric network with combined features of frustrated Lewis pairs and dynamic crosslinking. New monomers containing Lewis acid or Lewis base centres were designed and synthesised successfully. For the pair 4- styryl-diphenylborane and 4-styryl-diphenylphosphine, the two monomers were found to be able to bind together at high concentration in toluene so as to form a weak conventional Lewis pair (CLP) adduct. An FLP can be obtained when the phosphine monomer was replaced to its more hindered analogue, 4-styryl-dimesitylphosphine, which is reactive enough to form a complex with diethyl azodicarboxylate (DEAD), where the DEAD bridges the boron and phosphorous centres. The monomers obtained were copolymerised with styrene by RAFT polymerisations. It was also found to be possible to control both the molecular weight and the dispersity. The FLP polymers synthesised in this way were characterised by NMR spectroscopy and gel permission chromatography. The Lewis acidity of both the monomer and resultant polymer were tested using the Gutmann-Beckett Method, and a decrease in Lewis acidity was observed when the boron monomer was polymerised. The network was synthesised by addition of DEAD into the solution containing both Lewis acid and Lewis base polymers. A gel was quickly generated (in 10 seconds). The mechanical properties of the network formed were determined by rheology. The gel was responsive to heat, in that it would break and return to a polymer solution at high temperatures. The gel formed also shows the ability to self-heal with the assistance of a solvent after physical cracking. The synthesis of the next generation of polymeric FLPs was also examined. A much more Lewis acidic boron monomer, (2,3,5,6-tetrafluorostyryl)- bis(pentafluorophenyl)borane was synthesised. This boron monomer was paired with 4-styryl-dimesitylphosphine to form a reactive FLP that was able to activate small molecules, including dihydrogen molecules and carbon dioxide. The catalysis reactivity of the hydrogenation reactions of this FLP was also explored. The copolymers made from these reactions readily formed a supramolecular gel upon mixing, which also proved temperature responsive. These early-stage results proved that this new boron-monomer is capable of generating a novel stimuli-responsive smart polymer for carbon capture and hydrogenation catalysis. Except for the polymeric FLP, some early-stage research about polymeric CLP and novel synthetic methods for boron-monomers were also introduced and discussed

Iron-Catalyzed Heck-Type Alkenylation of Functionalized Alkyl Bromides

The ability of iron to controllably generate alkyl radicals from alkyl halides as a key step in atom transfer radical polymerization (ATRP) has been adapted to facilitate a formal Heck cross-coupling between styrenes and functionalized alkyl bromides. A simple FeCl₂ catalyst in a coordinating solvent gave excellent activity without the need for expensive ligands. Tertiary, secondary, and even primary alkyl bromides are tolerated to give the products in moderate to good yields (up to 94% yield). The easily accessible reagents and operational simplicity make this reaction a method of choice for the alkenylation of alkyl halides, especially for functionalized tertiary alkyl halides, which are difficult to target by classic palladium-catalyzed Heck reactions because of the competing β-hydride elimination

Binary Quasars in the Sloan Digital Sky Survey: Evidence for Excess Clustering on Small Scales

We present a sample of 218 new quasar pairs with proper transverse separations R_prop < 1 Mpc/h over the redshift range 0.5 < z < 3.0, discovered from an extensive follow up campaign to find companions around the Sloan Digital Sky Survey and 2dF Quasar Redshift Survey quasars. This sample includes 26 new binary quasars with separations R_prop < 50 kpc/h (theta < 10 arcseconds), more than doubling the number of such systems known. We define a statistical sample of binaries selected with homogeneous criteria and compute its selection function, taking into account sources of incompleteness. The first measurement of the quasar correlation function on scales 10 kpc/h < R_prop < 400 kpc/h is presented. For R_prop < 40 kpc/h, we detect an order of magnitude excess clustering over the expectation from the large scale R_prop > 3 Mpc/h quasar correlation function, extrapolated down as a power law to the separations probed by our binaries. The excess grows to ~ 30 at R_prop ~ 10 kpc/h, and provides compelling evidence that the quasar autocorrelation function gets progressively steeper on sub-Mpc scales. This small scale excess can likely be attributed to dissipative interaction events which trigger quasar activity in rich environments. Recent small scale measurements of galaxy clustering and quasar-galaxy clustering are reviewed and discussed in relation to our measurement of small scale quasar clustering.Comment: 25 pages, 12 figures, 9 tables. Submitted to the Astronomical Journa

Clustering of High Redshift (z≥2.9z\ge 2.9) Quasars from the Sloan Digital Sky Survey

(Abridged) We study the two-point correlation function of a uniformly selected sample of 4,426 luminous optical quasars with redshift $2.9 \le z\le 5.4$ selected over 4041 deg$^2$ from the Fifth Data Release of the Sloan Digital Sky Survey. For a real-space correlation function of the form $\xi(r)=(r/r_0)^{-\gamma}$, the fitted parameters in comoving coordinates are $r_0 = 15.2 \pm 2.7 h^{-1}$ Mpc and $\gamma = 2.0 \pm 0.3$, over a scale range $4\le r_p\le 150 h^{-1}$ Mpc. Thus high-redshift quasars are appreciably more strongly clustered than their $z \approx 1.5$ counterparts, which have a comoving clustering length $r_0 \approx 6.5 h^{-1}$ Mpc. Dividing our sample into two redshift bins: $2.9\le z\le 3.5$ and $z\ge 3.5$, and assuming a power-law index $\gamma=2.0$, we find a correlation length of $r_0 = 16.9 \pm 1.7 h^{-1}$ Mpc for the former, and $r_0 = 24.3 \pm 2.4 h^{-1}$ Mpc for the latter. Following Martini & Weinberg, we relate the clustering strength and quasar number density to the quasar lifetimes and duty cycle. Using the Sheth & Tormen halo mass function, the quasar lifetime is estimated to lie in the range $4\sim 50$ Myr for quasars with $2.9\le z\le 3.5$; and $30\sim 600$ Myr for quasars with $z\ge 3.5$. The corresponding duty cycles are $0.004\sim 0.05$ for the lower redshift bin and $0.03\sim 0.6$ for the higher redshift bin. The minimum mass of halos in which these quasars reside is $2-3\times 10^{12}\ h^{-1}M_\odot$for quasars with$2.9\le z\le 3.5$and$4-6\times 10^{12}\ h^{-1}M_\odot$for quasars with$z\ge 3.5$.Comment: To appear in AJ; 20 emulateapj pages; supplemental materials can be found at http://www.astro.princeton.edu/~yshen/highz_qso_clustering/qso_clustering.ht

Adult Romantic Attachment, Negative Emotionality, and Depressive Symptoms in Middle Aged Men: A Multivariate Genetic Analysis

Adult romantic attachment styles reflect ways of relating in close relationships and are associated with depression and negative emotionality. We estimated the extent to which dimensions of romantic attachment and negative emotionality share genetic or environmental risk factors in 1,237 middle-aged men in the Vietnam Era Twin Study of Aging (VETSA). A common genetic factor largely explained the covariance between attachment-related anxiety, attachment-related avoidance, depressive symptoms, and two measures of negative emotionality: Stress-Reaction (anxiety), and Alienation. Multivariate results supported genetic and environmental differences in attachment. Attachment-related anxiety and attachment-related avoidance were each influenced by additional genetic factors not shared with other measures; the genetic correlation between the attachment measure-specific genetic factors was 0.41, indicating some, but not complete overlap of genetic factors. Genetically informative longitudinal studies on attachment relationship dimensions can help to illuminate the role of relationship-based risk factors in healthy aging

Mismatches in Scale Between Highly Mobile Marine Megafauna and Marine Protected Areas

Marine protected areas (MPAs), particularly large MPAs, are increasing in number and size around the globe in part to facilitate the conservation of marine megafauna under the assumption that large-scale MPAs better align with vagile life histories; however, this alignment is not well established. Using a global tracking dataset from 36 species across five taxa, chosen to reflect the span of home range size in highly mobile marine megafauna, we show most MPAs are too small to encompass complete home ranges of most species. Based on size alone, 40% of existing MPAs could encompass the home ranges of the smallest ranged species, while only \u3c 1% of existing MPAs could encompass those of the largest ranged species. Further, where home ranges and MPAs overlapped in real geographic space, MPAs encompassed \u3c 5% of core areas used by all species. Despite most home ranges of mobile marine megafauna being much larger than existing MPAs, we demonstrate how benefits from MPAs are still likely to accrue by targeting seasonal aggregations and critical life history stages and through other management techniques

Mismatches in Scale Between Highly Mobile Marine Megafauna and Marine Protected Areas

Marine protected areas (MPAs), particularly large MPAs, are increasing in number and size around the globe in part to facilitate the conservation of marine megafauna under the assumption that large-scale MPAs better align with vagile life histories; however, this alignment is not well established. Using a global tracking dataset from 36 species across five taxa, chosen to reflect the span of home range size in highly mobile marine megafauna, we show most MPAs are too small to encompass complete home ranges of most species. Based on size alone, 40% of existing MPAs could encompass the home ranges of the smallest ranged species, while only \u3c 1% of existing MPAs could encompass those of the largest ranged species. Further, where home ranges and MPAs overlapped in real geographic space, MPAs encompassed \u3c 5% of core areas used by all species. Despite most home ranges of mobile marine megafauna being much larger than existing MPAs, we demonstrate how benefits from MPAs are still likely to accrue by targeting seasonal aggregations and critical life history stages and through other management techniques