A series of tetradentate amine(bisphenolate) ligands have been synthesized and complexed to Ti(IV), Zr(IV), and Hf(IV) centers. Two distinct ligand sets have been synthesized both exhibiting ONNO
coordination. The steric bulk of the ligands was varied to assess the impact of sterics on the catalytic performance
in the ring-opening-polymerization (ROP) of cyclic esters. In all cases the metal centers are pseudo octahedral in
geometry. Several group 4 amine(bisphenolate) complexes have been characterized by single-crystal X-ray
diffraction. The complexes were tested for the ROP of ε-caprolactone and L/rac-lactide, with significant activity
seen for complexes of all group 4 metals. For Ti(IV), complexes of sterically demanding ligands were more
effective initiators, whereas sterically less demanding ligands were more successful for Zr(IV) complexes.
Copolymers of poly(ε-caprolactone) and poly-l-lactide were produced utilizing the Zr(IV) initiators. The
polymerization of rac-lactide was also studied allowing stereoselectivity of a range of metal−ligand combinations
to be assessed. Isotactic polymer was produced with both Zr(IV) and Hf(IV) centers whereas Ti(IV) produced an
atactic polymer.
A kinetic study has been made of the polymerization of butadiene and styrene in an aliphatic hydrocarbon solvent with the use of butyllithium as an initiator. It is shown that the anomalous behavior in the initiation reaction exhibited by isoprene under these conditions is also found for these two monomers. These monomers give a sigmoidal rate curve in the initiation reaction in cyclohexane solution, and the reaction appears to be auto‐catalytic. The propagation reactions were studied also, and the results compared with the rather discordant sets of data published by other authors.
Previous analyses of natural image statistics have dealt mainly with their Fourier power spectra. Here we explore image statistics by examining responses to biologically motivated filters that are spatially localized and respond to first-order (luminance-defined) and second-order (contrast- or texture-defined) characteristics. We compare the distribution of natural image responses across filter parameters for first- and second-order information. We find that second-order information in natural scenes shows the same self-similarity previously described for first-order information but has substantially less orientational anisotropy. The magnitudes of the two kinds of information, as well as their mutual unsigned correlation, are much stronger for particular combinations of filter parameters in natural images but not in unstructured fractal images having the same power spectra.
The contrast response function of early visual evoked potentials elicited by sinusoidal gratings is known to exhibit characteristic potentials closely associated with the processes of parvocellular and magnocellular pathways. Specifically, the N1 component has been linked with parvocellular processes, while the P1 component has been linked with magnocellular processes. However, little is known regarding the response properties of the N1 and P1 components during the processing and encoding of complex (i.e., broadband) stimuli such as natural scenes. Here, we examine how established physical characteristics of natural scene imagery modulate the N1 and P1 components in humans by providing a systematic investigation of component modulation as visual stimuli are gradually built up from simple sinusoidal gratings to highly complex natural scene imagery. The results suggest that the relative dominance in signal output of the N1 and P1 components is dependent on spatial frequency (SF) luminance contrast for simple stimuli up to natural scene imagery possessing few edges. However, such a dependency shifts to a dominant N1 signal for natural scenes possessing abundant edge content and operates independently of SF luminance contrast.
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