Intelligent manipulation technique for multi-branch robotic systems

New analytical development in kinematics planning is reported. The INtelligent KInematics Planner (INKIP) consists of the kinematics spline theory and the adaptive logic annealing process. Also, a novel framework of robot learning mechanism is introduced. The FUzzy LOgic Self Organized Neural Networks (FULOSONN) integrates fuzzy logic in commands, control, searching, and reasoning, the embedded expert system for nominal robotics knowledge implementation, and the self organized neural networks for the dynamic knowledge evolutionary process. Progress on the mechanical construction of SRA Advanced Robotic System (SRAARS) and the real time robot vision system is also reported. A decision was made to incorporate the Local Area Network (LAN) technology in the overall communication system

Decoherence, Branching, and the Born Rule in a Mixed-State Everettian Multiverse

In Everettian quantum mechanics, justifications for the Born rule appeal to self-locating uncertainty or decision theory. Such justifications have focused exclusively on a pure-state Everettian multiverse, represented by a wave function. Recent works in quantum foundations suggest that it is viable to consider a mixed-state Everettian multiverse, represented by a (mixed-state) density matrix. Here, we develop the conceptual foundations for decoherence and branching in a mixed-state multiverse, and extend the standard Everettian justifications for the Born rule to this setting. This extended framework provides a unification of 'classical' and 'quantum' probabilities, and additional theoretical benefits, for the Everettian picture.Comment: 29 page

Stereoselectivity in Metallocene-Catalyzed Coordination Polymerization of Renewable Methylene Butyrolactones: From Stereo-random to Stereo-perfect Polymers

Coordination polymerization of renewable α-methylene-γ-(methyl)butyrolactones by chiral C2-symmetric zirconocene catalysts produces stereo-random, highly stereo-regular, or perfectly stereo-regular polymers, depending on the monomer and catalyst structures. Computational studies yield a fundamental understanding of the stereocontrol mechanism governing these new polymerization reactions mediated by chiral metallocenium catalysts

Analysis of enhanced diffusion in Taylor dispersion via a model problem

We consider a simple model of the evolution of the concentration of a tracer, subject to a background shear flow by a fluid with viscosity $\nu \ll 1$ in an infinite channel. Taylor observed in the 1950's that, in such a setting, the tracer diffuses at a rate proportional to $1/\nu$, rather than the expected rate proportional to $\nu$. We provide a mathematical explanation for this enhanced diffusion using a combination of Fourier analysis and center manifold theory. More precisely, we show that, while the high modes of the concentration decay exponentially, the low modes decay algebraically, but at an enhanced rate. Moreover, the behavior of the low modes is governed by finite-dimensional dynamics on an appropriate center manifold, which corresponds exactly to diffusion by a fluid with viscosity proportional to $1/\nu$

Unusual C–C Bond Cleavage in the Formation of Amine-Bis(phenoxy) Group 4 Benzyl Complexes: Mechanism of Formation and Application to Stereospecific Polymerization

Group 4 tetrabenzyl compounds MBn4 (M = Zr, Ti), upon protonolysis with an equimolar amount of the tetradentate amine-tris(phenol) ligand N[(2,4-tBu2C6H2(CH2)OH]3 in toluene from −30 to 25 °C, unexpectedly lead to amine-bis(phenoxy) dibenzyl complexes, BnCH2N[(2,4-tBu2C6H2(CH2)O]2MBn2 (M = Zr (1), Ti (2)) in 80% (1) and 75% (2) yields. This reaction involves an apparent cleavage of the >NCH2–ArOH bond (loss of the phenol in the ligand) and formation of the >NCH2–CH2Bn bond (gain of the benzyl group in the ligand). Structural characterization of 1 by X-ray diffraction analysis confirms that the complex formed is a bis(benzyl) complex of Zr coordinated by a newly derived tridentate amine-bis(phenoxy) ligand arranged in a mer configuration in the solid state. The abstractive activation of 1 and 2 with B(C6F5)3·THF in CD2Cl2 at room temperature generates the corresponding benzyl cations {BnCH2N[(2,4-tBu2C6H2(CH2)O]2MBn(THF)}+[BnB(C6F5)3]− (M = Zr (3), Ti, (4)). These cationic complexes, along with their analogues derived from (imino)phenoxy tri- and dibenzyl complexes, [(2,6-iPr2C6H3)N═C(3,5-tBu2C6H2)O]ZrBn3 (5) and [2,4-Br2C6H2(O)(6-CH2(NC5H9))CH2N═CH(2-adamantyl-4-MeC6H2O)]ZrBn2 (6), have been found to effectively polymerize the biomass-derived renewable β-methyl-α-methylene-γ-butyrolactone (βMMBL) at room temperature into the highly stereoregular polymer PβMMBL with an isotacticity up to 99% mm. A combined experimental and DFT study has yielded a mechanistic pathway for the observed unusual C–C bond cleavage in the present protonolysis reaction between ZrBn4 and N[(2,4-tBu2C6H2(CH2)OH]3 for the formation of complex 1, which involves the benzyl radical and the Zr(III) species, resulting from thermal and photochemical decomposition of ZrBn4, followed by a series of reaction sequences consisting of protonolysis, tautomerization, H-transfer, oxidation, elimination, and radical coupling

PPARs and the Cardiovascular System

Abstract Peroxisome proliferator-activated receptors (PPARs) belong to the nuclear hormone-receptor superfamily. Originally cloned in 1990, PPARs were found to be mediators of pharmacologic agents that induce hepatocyte peroxisome proliferation. PPARs also are expressed in cells of the cardiovascular system. PPARγ appears to be highly expressed during atherosclerotic lesion formation, suggesting that increased PPARγ expression may be a vascular compensatory response. Also, ligand-activated PPARγ decreases the inflammatory response in cardiovascular cells, particularly in endothelial cells. PPARα, similar to PPARγ, also has pleiotropic effects in the cardiovascular system, including antiinflammatory and antiatherosclerotic properties. PPARα activation inhibits vascular smooth muscle proinflammatory responses, attenuating the development of atherosclerosis. However, PPARδ overexpression may lead to elevated macrophage inflammation and atherosclerosis. Conversely, PPARδ ligands are shown to attenuate the pathogenesis of atherosclerosis by improving endothelial cell proliferation and survival while decreasing endothelial cell inflammation and vascular smooth muscle cell proliferation. Furthermore, the administration of PPAR ligands in the form of TZDs and fibrates has been disappointing in terms of markedly reducing cardiovascular events in the clinical setting. Therefore, a better understanding of PPAR-dependent and -independent signaling will provide the foundation for future research on the role of PPARs in human cardiovascular biology. Antioxid. Redox Signal. 11, 1415-1452.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/78115/1/ars.2008.2280.pd

Organocatalytic Conjugate-Addition Polymerization of Linear and Cyclic Acrylic Monomers by N-Heterocyclic Carbenes: Mechanisms of Chain Initiation, Propagation, and Termination

This contribution presents a full account of experimental and theoretical/computational investigations into the mechanisms of chain initiation, propagation, and termination of the recently discovered N-heterocyclic carbene (NHC)-mediated organocatalytic conjugate-addition polymerization of acrylic monomers. The current study specifically focuses on three commonly used NHCs of vastly different nucleophilicity, 1,3-di-tert-butylimidazolin-2-ylidene (ItBu), 1,3-dimesitylimidazolin-2-ylidene (IMes), and 1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene (TPT), and two representative acrylic monomers, the linear methyl methacrylate (MMA) and its cyclic analog, biomass-derived renewable γ-methyl-α-methylene-γ-butyrolactone (MMBL). For MMA, there exhibits an exquisite selectivity of the NHC structure for the three types of reactions it promotes: enamine formation (single-monomer addition) by IMes, dimerization (tail-to-tail) by TPT, and polymerization by ItBu. For MMBL, all three NHCs promote no dimerization but polymerization, with the polymerization activity being highly sensitive to the NHC structure and the solvent polarity. Thus, ItBu is the most active catalyst of the series and converts quantitatively 1000–3000 equiv of MMBL in 1 min or 10 000 equiv in 5 min at room temperature to MMBL-based bioplastics with a narrow range of molecular weights of Mn = 70–85 kg/mol, regardless of the [MMBL]/[ItBu] ratio employed. The ItBu-catalyzed MMBL polymerization reaches an exceptionally high turnover frequency up to 122 s–1 and a high initiator efficiency value up to 1600%. Unique chain-termination mechanisms have been revealed, accounting for the production of relative high-molecular-weight linear polymers and the catalytic nature of this NHC-mediated conjugate-addition polymerization. Computational studies have provided mechanistic insights into reactivity and selectivity between two competing pathways for each NHC-monomer zwitterionic adduct, namely enamine formation/dimerization through proton transfer vs polymerization through conjugate addition, and mapped out extensive energy profiles for chain initiation, propagation, and termination steps, thereby satisfactorily explaining the experimental observations

Decoherence, Branching, and the Born Rule in a Mixed-State Everettian Multiverse

In Everettian quantum mechanics, justifications for the Born rule appeal to self-locating uncertainty or decision theory. Such justifications have focused exclusively on a pure-state Everettian multiverse, represented by a wave function. Recent works in quantum foundations suggest that it is viable to consider a mixed-state Everettian multiverse, represented by a (mixed-state) density matrix. Here, we develop the conceptual foundations for decoherence and branching in a mixed-state multiverse, and extend the standard Everettian justifications for the Born rule to this setting. This extended framework provides a unification of 'classical' and 'quantum' probabilities, and additional theoretical benefits, for the Everettian picture