Design and synthesis of quasi-diastereomeric molecules with unchanging central, regenerating axial and switchable helical chirality via cleavage and formation of Ni(II)–O and Ni(II)–N coordination bonds

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Spatial filtering in tone reproduction and vision

This thesis is concerned with spatial filtering. What is its utility in tone reproduction? Does it exist in vision, and if so, what constraints does it impose on the nervous system?

Tone reproduction is just the art and science of taking a picture and then displaying it. The sensors available to capture an image have a greater dynamic range than the media that may be used to display it. Conventionally, spatial filtering is used to boost contrast; it ameliorates the loss of contrast that results when the sensor signal range is scaled down to fit the display range. In this thesis, a type of nonlinear spatial filtering is discussed that results in direct range reduction without range scaling. This filtering process is instantiated in a real-time image processor built using analog CMOS VLSI.

Spatial filtering must be applied with care in both artificial and natural vision systems. It is argued that the nervous system does not simply filter linearly across an image. Rather, the way that we see things implies that the nervous system filters nonlinearly. Further, many models for color vision include a high-pass filtering step in which the DC information is lost. A real-time study of filtering in color space leads to the conclusion that the nervous system is not that simple, and that it maintains DC information by referencing to white.

Marine spatial planning approaches at the state level: Similarities and differences between MSP efforts across the country

Competing uses, sensitive and valuable marine resources, and overlapping jurisdictions complicate management decision making in the marine environment. States are developing marine spatial planning capacity to help make better decisions, particularly as demand for ocean space and resources is growing because of emerging human uses (renewable energy, aquaculture) and traditional human uses (commercial fishing, commerce). This paper offers perspectives on marine spatial planning efforts being carried out in four states across the US, and demonstrates similarities and differences between them. The approach to marine spatial planning in each state is discussed with specific attention given to issues such as what is driving the effort, data availability, maturity of the effort, and level of resources devoted to it. Highlighting the similarities and differences illustrates state and region specific challenges and the approaches being used to meet them. (PDF contains 4 pages)

Intersexual and spatial heterogeneity in trophic attributes of the sleeper, Bostrychus africanus (Eleotridae) in the Qua Iboe Estuary, Nigeria

There was variation in the ingestion of the food objects by the sexes. Despite the similarity in rank-order of the food objects, the ingestion of the objects vary significantly (rg=0.320, P>0.05). Dipterans adult and Hymenoptera were the only food objects not eaten by the males whereas insect remains and unidentified bivalves were absent from the trophics spectrum of the females. There was significant increase in feeding intensity by females than males. There was significant increase in GRI by specimens from Nipa Creek whereas individuals from mangrove creek recorded higher MGF and vice-versa. Dipterans adult. Hymenoptera, insect remains, Neritina glabrata and unid bivalves were absent from dietaries for nipa creek whereas a complete array of the food objects were eaten in the mangrove creek. The present findings highlights the importance of the mangrove ecosystem as the native vegetation encompassing great diversity of food resources and living conditions than the succeeding alien nipa vegetation

An ultra-broadband spatially dispersed regenerative amplifier free from spatial chirp

An ultra-broadband Ti:sapphire regenerative amplifier based on spatially dispersed amplification is demonstrated experimentally. Departing from previous reports, a new design of the cavity gets the amplified pulse free from spatial chirp. Utilizing this new regenerative amplifier, chirped pulses with bandwidth (FWHM) of about 80 nm are obtained, and the bandwidth is limited only by that of the incident seed pulses.

Experimental and theoretical studies of Notch signaling-mediated spatial pattern

Notch signaling acts in many diverse developmental spatial patterning processes. To better understand why this particular pathway is employed where it is and how downstream feedbacks interact with the signaling system to drive patterning, we have pursued three aims: (i) to quantitatively measure the Notch system's signal input/output (I/O) relationship in cell culture, (ii) to use the quantitative I/O relationship to computationally predict patterning outcomes of downstream feedbacks, and (iii) to reconstitute a Notch-mediated lateral induction feedback (in which Notch signaling upregulates the expression of Delta) in cell culture. The quantitative Notch I/O relationship revealed that in addition to the trans-activation between Notch and Delta on neighboring cells there is also a strong, mutual cis-inactivation between Notch and Delta on the same cell. This feature tends to amplify small differences between cells. Incorporating our improved understanding of the signaling system into simulations of different types of downstream feedbacks and boundary conditions lent us several insights into their function. The Notch system converts a shallow gradient of Delta expression into a sharp band of Notch signaling without any sort of feedback at all, in a system motivated by the Drosophila wing vein. It also improves the robustness of lateral inhibition patterning, where signal downregulates ligand expression, by removing the requirement for explicit cooperativity in the feedback and permitting an exceptionally simple mechanism for the pattern. When coupled to a downstream lateral induction feedback, the Notch system supports the propagation of a signaling front across a tissue to convert a large area from one state to another with only a local source of initial stimulation. It is also capable of converting a slowly-varying gradient in parameters into a sharp delineation between high- and low-ligand populations of cells, a pattern reminiscent of smooth muscle specification around artery walls. Finally, by implementing a version of the lateral induction feedback architecture modified with the addition of an autoregulatory positive feedback loop, we were able to generate cells that produce enough cis ligand when stimulated by trans ligand to themselves transmit signal to neighboring cells, which is the hallmark of lateral induction.

Reactions of oxygen containing ligands in the coordination sphere of permethylhafnocene and permethyltantalocene

A series of terl-butylperoxide complexes of hafnium, Cp*₂Hf(R)(OOCMe₃) (Cp* = ((η⁵-C₅Me₅); R = Cl, H, CH₃, CH₂CH₃, CH₂CH₂CH₃, CH₂CH₂CH₂CH₃, CH₂CHMe₂, CH=CHCMe₃, C₆H₅, meta-C₆H₃(CH₂)2) and Cp*(η⁵-C₅(CH₃)₄CH₂CH₂CH₂)Hf(OOCMe₃), has been synthesized. One example has been structurally characterized, Cp*₂Hf(OOCMe₃)CH₂CH₃ crystallizes in space group P2₁/c, with a = 19.890(7)Å, b = 8.746(4)Å, c = 17.532(6)Å, β = 124.987(24)°, V = 2498(2)ų, Z = 4 and R_F = 0.054 (2222 reflections, I > 0). Despite the coordinative unsaturation of the hafnium center, the terl-butylperoxide ligand is coordinated in a mono-dentate ligand. The mode of decomposition of these species is highly dependent on the substituent R. For R = H, CH₂CH₃, CH₂CH₂CH₃, CH₂CH₂CH₂CH₃, CH₂CHMe₂ a clean first order conversion to Cp*₂Hf(OCMe₃)(OR) is observed (for R CH₂CH₃, ΔHǂ = 19.6 kcal•mol^-1, ΔSǂ = -13 e.u.). These results are discussed in terms of a two step mechanism involving η²-coordination of the terl-butylperoxide ligand. Homolytic O-O bond cleavage is observed upon heating of Cp*₂Hf(OOCMe₃) R (R = C₆H₆, meta-C₆H₃(CH₃)₂). In the presence of excess 9,10-dihydroanthracene thermolysis of Cp*₂Hf(OOCMe₃)C₆H₆ cleanly affords Cp*₂Hf(C₆H₆)OH and HOCMe₃ (ΔHǂ = 22.6 kcal•mol^-1, ΔSǂ = -9 e.u.). The O-O bond strength in these complexes is thus estimated to be 22 kcal•mol^-1.

Cp*₂Ta(CH₂)H, Cp*₂Ta(CHC₆H₅)H, Cp*₂Ta(C₆H₄)H, Cp*₂Ta(CH₂=CH₂)H and Cp*₂Ta(CH₂=CHMe)H react, presumably through Cp*₂Ta-R intermediates, with H₂O to give Cp*₂Ta(O)H and alkane. Cp*₂Ta(O)H was structurally characterized: space group P2₁/n, a= 13.073(3)Å, b = 19.337(4)Å, c = 16.002(3)Å, β = 108.66(2)°, V = 3832(1)ų, Z = 8 and R_F = 0.0672 (6730 reflections). Reaction of terlbutylhydroperoxide with these same starting materials ultimately yields Cp*₂Ta(O)R and HOCMe₃. Cp*₂Ta(CH₂=CHR)OH species are proposed as intermediates in the olefin hydride reactions. Cp*₂Ta(O₂)R species can be generated from the reaction of the same starting materials and O₂. Lewis acids have been shown to promote oxygen insertion in these complexes.