Synthesis, Oxidation and Photophysics of Perfluoroborated Tetrakis(pyrophosphito)diplatinate (II) and Density Functional Theory (DFT) Study of Electrochemical CO2 Reduction by Mn Catalysts

In the first part of this thesis (Chapters I and II), the synthesis, characterization, reactivity and photophysics of per(difluoroborated) tetrakis(pyrophosphito)diplatinate(II) (Pt(POPBF₂)) are discussed. Pt(POP-BF₂) was obtained by reaction of [Pt₂(POP)₄]^4- with neat boron trifluoride diethyl etherate (BF₃·Et₂O). While Pt(POP-BF₂) and [Pt₂(POP)₄]^4- have similar structures and absorption spectra, they differ in significant ways. Firstly, as discussed in Chapter I, the former is less susceptible to oxidation, as evidenced by the reversibility of its oxidation by I2. Secondly, while the first excited triplet states (T₁) of both Pt(POP-BF₂) and [Pt₂(POP)₄]^4- exhibit long lifetimes (ca. 0.01 ms at room temperature) and substantial zero-field splitting (40 cm^-1), Pt(POP-BF₂) also has a remarkably long-lived (1.6 ns at room temperature) singlet excited state (S₁), indicating slow intersystem crossing (ISC). Fluorescence lifetime and quantum yield (QY) of Pt(POP-BF₂) were measured over a range of temperatures, providing insight into the slow ISC process. The remarkable spectroscopic and photophysical properties of Pt(POP-BF₂), both in solution and as a microcrystalline powder, form the theme of Chapter II.

In the second part of the thesis (Chapters III and IV), the electrochemical reduction of CO₂ to CO by [(L)Mn(CO)₃]^- catalysts is investigated using density functional theory (DFT). As discussed in Chapter III, the turnover frequency (TOF)-limiting step is the dehydroxylation of [(bpy)Mn(CO)₃(CO₂H)]^0/- (bpy = bipyridine) by trifluoroethanol (TFEH) to form [(bpy)Mn(CO)₄]^+/0. Because the dehydroxylation of [(bpy)Mn(CO)₃(CO₂H)]^- is faster, maximum TOF (TOF_max) is achieved at potentials sufficient to completely reduce [(bpy)Mn(CO)₃(CO₂H)]⁰ to [(bpy)Mn(CO)₃(CO₂H)]^-. Substitution of bipyridine with bipyrimidine reduces the overpotential needed, but at the expense of TOF_max. In Chapter IV, the decoration of the bipyrimidine ligand with a pendant alcohol is discussed as a strategy to increase CO₂ reduction activity. Our calculations predict that the pendant alcohol acts in concert with an external TFEH molecule, the latter acidifying the former, resulting in a ~ 80,000-fold improvement in the rate of TOF-limiting dehydroxylation of [(L)Mn(CO)₃(CO₂H)]^-.

An interesting strategy for the co-upgrading of light olefins and alkanes into heavier alkanes is the subject of Appendix B. The proposed scheme involves dimerization of the light olefin, operating in tandem with transfer hydrogenation between the olefin dimer and the light alkane. The work presented therein involved a Ta olefin dimerization catalyst and a silica-supported Ir transfer hydrogenation catalyst. Olefin dimer was formed under reaction conditions; however, this did not undergo transfer hydrogenation with the light alkane. A significant challenge is that the Ta catalyst selectively produces highly branched dimers, which are unable to undergo transfer hydrogenation.

Routing scheme, permutation properties, and optical implementation of a four-shuffle-exchange-based Omega network

The routing scheme and some permutation properties of a four-shuffle-exchange-based Omega network are discussed. The corresponding optical setup, which is composed of 2-D phase spatial light modulators and calcite plates, is proposed and demonstrated through mapping the inputs to a 2-D array. Instead of one shuffle-exchange followed by one switching operation as in ordinary Omega networks, in our presented system, the shuffle interconnection embraced in the switches is accomplished simply by varying the switching structure of each stage. For the proposed polarization-optical modules, the system is compact in structure, efficient in performance, and insensitive to the environment. (C) 1997 Society of Photo-Optical Instrumentation Engineers.

Experiments using an artificial stream to investigate the seasonal growth of chalk-stream algae

Research into the production ecology of chalk streams using a large artificial recirculating stream is described. Physical chemical processes including calcium and inorganic phosphate levels, and exchange of gaseous carbon dioxide in both a simple closed system and a circulating system with gravel substrate have been monitored in both light and dark conditions. Further experiments were concerned with the seasonal changes in algal growth over the gravel substrate with constant water velocities and replenishment. The algal population, composed mainly of the diatoms Achnanthes minutissima, Meridion circulare, Nitzschia fonticola and Synedra ulna reached a peak in mid May and declined rapidly during June. Concentrations of phosphate phosphorus fell as the diatoms grew but was not thought to limit growth. Silicate concentrations followed the diatom cycle closely but never fell below 0.8 mg/l Si. It is possible that one of the nutrients may have been limiting the rate of growth due to steep diffusion gradients through the algal mat. In the last summer and autumn a hard calcareous crust composed of the green alga Gongrosira incrustans and the blue green alga Homeothrix varians , developed. The channel stream is compared with the natural conditions found in chalk streams.

Systematic Studies on 3d- and 4f-Metal Containing Polyoxometalates Suitable for Organic Derivatization

232 p.

Spectroscopic and thermal properties of short wavelength metal (II) complexes containing alpha-isoxazolylazo-beta-diketones as co-ligands

Two new azo dyes of alpha-isoxazolylazo-beta-dilcetones and their Ni(II) and Cu(II) complexes with blue-violet light wavelength were synthesized using a coupling component, different diazo components and metal (II) ions (Ni2+ and Cu2+). Based on the elemental analysis, MS spectra and FT-IR spectral analyses, azo dyes were unequivocally shown to exist as hydrazoketo and azoenol forms which were respectively obtained from the solution forms and from the solid forms. The action of sodium methoxide (NaOMe) on azo dyes in solutions converts hydrazoketo form into azoenol form, so azo dyes are coordinated with metal (II) ions as co-ligands in the azoenol forms. The solubility of all the compounds in common organic solvents such as 2,2,3,3-tetrafluoro-1-propanol (TFP) or chloroform (CHCl3) and absorption properties of spin-coating thin films were measured. The difference of absorption maxima from the complexes to their ligands was discussed. In addition, the TG analysis of the complexes was also determined, and their thermal stability was evaluated. It is found that these new metal (II) complexes had potential application for high-density digital versatile disc-recordable (HD-DVD-R) system due to their good solubility in organic solvents, reasonable and controllable absorption spectra in blue-violet light region and high thermal stability. (c) 2004 Elsevier B.V. All rights reserved.

Characteristics and optical spectra of V : YAG crystal grown in reducing atmosphere

A V:YAG single crystal was grown by the temperature gradient technique (TGT) with graphite-heating elements. The as-grown crystal has different colorations of light green and yellow brown in different parts. Distribution of vanadium in three samples with different colorations was determined by inductively coupled plasma-mass spectrometry. From the absorption spectrum of the yellow-brown part with peaks at 370, 820 and 1320nm, we can deduce that the reducing atmosphere of carbon diffused from the heating elements can increase the concentration of tetrahedral V3+ ions and induce F color centers. All three samples exhibited light-green color after annealing in vacuum or H-2 atmospheres. In the vacuum annealing process, the V3+ ions in tetrahedral positions were enhanced through two methods: one method is the exchanging of octahedral V3+ and tetrahedral Al3+ ions in neighboring sites under thermal excitation, the other is that F color centers were thoroughly eliminated and the escaped free electrons could be captured by V ions with higher valance states to further improve the concentration of tetrahedral V3+ ions. Besides the two mechanisms, the H-2 annealing process greatly improved the V-tetra(3+) ions through the reduction effect of H-2. (c) 2006 Elsevier B.V. All rights reserved.

Benthic habitats of Fish Bay, Coral Bay and the St. Thomas East End Reserve

NOAA’s National Centers for Coastal Ocean Science Biogeography Branch has mapped and characterized large portions of the coral reef ecosystems inside the U.S. coastal and territorial waters, including the U.S. Caribbean. The complementary protocols used in these efforts have enabled scientists and managers to quantitatively and qualitatively compare marine ecosystems in tropical U.S. waters. The Biogeography Branch used similar protocols to generate new benthic habitat maps for Fish Bay, Coral Bay and the St. Thomas East End Reserve (STEER). While this mapping effort marks the third time that some of these shallow-water habitats (≤40 m) have been mapped, it is the first time that nearly 100% of the seafloor has been characterized in each of these areas. It is also the first time that high resolution imagery describing seafloor depth has been collected in each of these areas. Consequently, these datasets provide new information describing the distribution of coral reef ecosystems and serve as a spatial baseline for monitoring change in the Fish Bay, Coral Bay and the STEER. Benthic habitat maps were developed for approximately 64.3 square kilometers of seafloor in and around Fish Bay, Coral Bay and the STEER. Twenty seven percent (17.5 square kilometers) of these habitat maps describe the seafloor inside the boundaries of the STEER, the Virgin Islands National Park and the Virgin Islands Coral Reef National Monument. The remaining 73% (46.8 square kilometers) describe the seafloor outside of these MPA boundaries. These habitat maps were developed using a combination of semi-automated and manual classification methods. Habitats were interpreted from aerial photographs and LiDAR (Light Detection and Ranging) imagery. In total, 155 distinct combinations of habitat classes describing the geology and biology of the seafloor were identified from the source imagery.

Current velocity and catch efficiency in sampling settlement-stage larvae of coral-reef fishes

Light traps and channel nets are fixed-position devices that involve active and passive sampling, respectively, in the collection of settlement-stage larvae of coral-reef fishes. We compared the abundance, taxonomic composition, and size of such larvae caught by each device deployed simultaneously near two sites that differed substantially in current velocity. Light traps were more selective taxonomically, and the two sampling devices differed significantly in the abundance but not size of taxa caught. Most importantly, light traps and channel nets differed greatly in their catch efficiency between sites: light traps were ineffective in collecting larvae at the relatively high-current site, and channel nets were less efficient in collecting larvae at the low-current site. Use of only one of these sampling methods would clearly result in biased and inaccurate estimates of the spatial variation in larval abundance among locations that differ in current velocity. When selecting a larval sampling device, one must consider not only how well a particular taxon may be represented, but also the environmental conditions under which the device will be deployed.

Studies on cultural conditions of marine Chromatium buderi Truper and Jannasch 1968

Photosynthetic characteristics of a purple sulfur bacterium, Chromatium buderi, cultured under different ranges of pH, temperature, light intensities and ammonium chloride concentrations were examined. Maximum bacteriochlorophyll a synthesis was observed at pH 6.5 whereas the optimum growth was at pH 8.0. In general, higher temperature tended to inhibit the chlorophyll a synthesis and growth. 30°C is the optimum temperature both for chlorophyll a synthesis and growth. At 25µE mˉ²Sˉ¹ the bacteriochlorophyll a content and growth attained maximum level. The response to this low light intensity is an adaptation that ensures a high photosynthetic rate for the purple sulfur bacterium that usually occurs in dimly lit environment. Besides these, ammonium chloride at low concentration enhances both chlorophyll a synthesis and growth. Above 0.5% of it causes the nitrogen-chlorosis and also retards the growth of the bacterium. Possible chemical and structural mechanisms involved are discussed.

Characterization of the sleep architecture in two species of fruit bat

Bats (Chiroptera) are the second-most abundant mammalian order in the world, occupying a diverse range of habitats and exhibiting many different life history traits. In order to contribute to this highly underrepresented group we describe the sleep architecture of two species of frugivorous bat, the greater short-nosed fruit bat (Cynopterus sphinx) and the lesser dawn fruit bat (Eonycteris spelaea). Electroencephalogram (EEG) and electromyogram (EMG) data were recorded from multiple individuals (>= 5) by telemetry over a 72-h period in a laboratory setting with light/dark cycles equivalent to those found in the wild. Our results show that over a 24-h period both species spent more time asleep than awake (mean 15 h), less than previous reported for Chiroptera (20 h). C sphinx spent significantly more of its non-rapid eye movement sleep (NREM) and rapid eye movement sleep (REM) quotas during the light phase, while E. spelaea divided its sleep-wake architecture equally between both light and dark phases. Comparing the sleep patterns of the two species found that C. sphinx had significantly fewer NREM and REM episodes than E. spelaea but each episode lasted for a significantly longer period of time. Potential hypotheses to explain the differences in the sleep architecture of C. sphinx with E. spelaea, including risk of predation and social interaction are discussed. (C) 2010 Published by Elsevier B.V.

Changes in phytoplankton communities and primary production

Lake Victoria is the second largest lake in the world (69000km2) by surface area, but it is the shallowest (69m maximum depth) of the African Great Lakes. It is situated across the equator at an altitude of 1240m and lies in a shallow basin between two uplifted ridges of the eastern and western rift valleys (Beadle 1974). Despite their tropical locations, African lakes exhibit considerable seasonality related to the alteration of warm, wet and cool, dry seasons and the accompanying changes in lucustrine stratification and mixing (Tailing, 1965; 1966; Melack 1979; Hecky& Fee 1981; Hecky& Kling,1981; 1987; Bootsma 1993; Mugidde 1992; 1993). Phytoplankton productivity, biomass and species composition change seasonally in response to variations in light environment and nutrient availability which accompany changes in mixed layer depth and erosion or stabilization of the metalimnion / hypolimnion (Spigel & Coulter 1996; Hecky et al., 1991; Tailing 1987). Over longer, millennial time scales, the phytoplankton communities of the African Great Lakes have responded to variability in the EastAfrican climate (Johnson 1996; Haberyan& Hecky, 1986) which also alters the same ecological factors (Kilham et al., 1986). Recently, over the last few decades, changes in external and or internal factors in Lake Victoria and its basin have had a profound inlluence on the planktic community of this lake (Hecky, 1993; Lipiatou et al., 1996). The lake has experienced 2-10x increases in chlorophyll and 2x increase in primary productivity since Tailing's observations in the early 1960s (Mugidde 1992, 1993). In addition to observed changes in the lake nutrient chemistry (Hecky & Mungoma, 1990; Hecky & Bugenyi 1992; Hecky 1993; Bootsma & Hecky 1993), the deep waters previouslyoxygenated to the sediment surface through most of the year are now regularly anoxic(Hecky et al., 1994).

Precise modal excitation in multimode fibre for control of modal dispersion and mode-group division multiplexing

Each mode of a multimode fibre is excited using binary phase patterns on a Spatial Light Modulator and verified by observation of the near-field leaving the fibre and analysis of the step response. © 2011 OSA.

Advanced spatial light modulator technology

This paper will review the advances which have been made in both electrically and optically addressed spatial light modulators and coding algorithms, which bring the realization of advanced optical systems such as 3D display closer. © OSA 2012.

Optically activated shutter using a photo-tunable short-pitch chiral nematic liquid crystal

We report the demonstration of an optically activated shutter based upon a short-pitch chiral nematic liquid crystal (LC) device sandwiched between crossed polarizers. This LC is comprised of photo-active chiral dopants. In the trans-state, the LC appears dark between crossed polarizers due to the very short pitch. As the pitch is extended through exposure to ultraviolet light, the device becomes transmissive reaching a maximum for a particular value of the pitch. As a result, it is possible to switch between the light and dark states by subjecting the device to visible light so as to cause a cis-trans photo-isomerisation. © 2013 AIP Publishing LLC.