Kinetic analysis of copper(I)/feringa-phosphoramidite catalysed AlEt3 1,4-addition to cyclohex-2-en-1-one

ReactIR studies of mixtures of AlEt3 (A) and cyclohex-2-en-1-one (CX) in Et2O indicate immediate formation of the Lewis acid-base complex (CX.A) at -40 oC (K = 12.0 M-1, ΔGo react -1.1 kcal mol-1). Copper(I) catalysts, derived from pre-catalytic Cu(OAc)2 (up to 5 mol- %) and (R,S,S)-P(binaphtholate){N(CHMePh)2} [Feringa’s ligand (L), up to 5 mol-%] convert CX.A (0.04-0.3 M) into its 1,4-addition product enolate (E) within 2000 sec at -40 oC. Kinetic studies (ReactIR and chiral GC) of CX.A, CX and (R)-3-ethylcyclohexanone (P, the H+ quench product of enolate E) show that the true catalyst is formed in the first 300 sec and this subsequently provides P in 82% ee. This true catalyst converts CX.A to E with a rate law [Cu]1.5[L]0.66[CX.A]1 when [L]/[Cu] ≤ 3.5. Above this ligand ratio inhibition by added ligand with order [L]-2.5 is observed. A rate determining step (rds) of Cu3L2(CX.A)2 stoichiometry is shown to be most consistent with the rate law. The presence of the enolate in the active catalyst (Graphical Abstract) best accounts for the reaction’s induction period and molecularity as [E] ≡ [CX.A]. Catalysis proceeds through a ‘shuttling mechanism’ between two C2 symmetry related ground state intermediates. Each turnover consumes one equivalent of CX.A, expels one molecule of E and forms the new Cu-Et bond needed for the next cycle (Graphic Abstract). The observed ligand (L) inhibition and a non-linear ligand Lee effect on the ee of P are all well simulated by the kinetic model. DFT studies [ωB97X-D/SRSC] support coordination of CX.A to the groundstate Cu-trimer and its rapid conversion to E

A proper understanding of Millikan

Ruth Millikan’s teleological theory of mental content is complex and often misunderstood. This paper motivates and clarifies some of the complexities of the theory, and shows that paying careful attention to its details yields answers to a number of common objections to teleological theories, in particular, the problem of novel mental states, the problem of functionally false beliefs, and problems about indeterminacy or multiplicity of function

The Preliminary Evaluation of Liquid Lubricants for Space Applications by Vacuum Tribometry

Four different vacuum tribometers for the evaluation of liquid lubricants for space applications are described. These range from simple ball-on-flat sliders with maximum in-situ control and surface characterization to an instrument bearing apparatus having no in-situ characterization. Thus, the former provides an abundance of surface chemical information but is not particularly simulative of most triboelements. On the other hand, the instrument bearing apparatus is completely simulative, but only allows post-mortem surface chemical information. Two other devices, a four-ball apparatus and a ball-on-plate tribometer, provide varying degrees of surface chemical information and tribo-simulation. Examples of data from each device are presented

Prenatal hypoxia induces increased cardiac contractility on a background of decreased capillary density.

Background: Chronic hypoxia in utero (CHU) is one of the most common insults to fetal development and may be associated with poor cardiac recovery from ischaemia-reperfusion injury,yet the effects on normal cardiac mechanical performance are poorly understood. Methods: Pregnant female wistar rats were exposed to hypoxia (12% oxygen, balance nitrogen)for days 10–20 of pregnancy. Pups were born into normal room air and weaned normally. At 10 weeks of age, hearts were excised under anaesthesia and underwent retrograde 'Langendorff' perfusion. Mechanical performance was measured at constant filling pressure (100 cm H2O) with intraventricular balloon. Left ventricular free wall was dissected away and capillary density estimated following alkaline phosphatase staining. Expression of SERCA2a and Nitric Oxide Synthases (NOS) proteins were estimated by immunoblotting. Results: CHU significantly increased body mass (P < 0.001) compared with age-matched control rats but was without effect on relative cardiac mass. For incremental increases in left ventricular balloon volume, diastolic pressure was preserved. However, systolic pressure was significantly greater following CHU for balloon volume = 50 μl (P < 0.01) and up to 200 μl (P < 0.05). For higher balloon volumes systolic pressure was not significantly different from control. Developed pressures were correspondingly increased relative to controls for balloon volumes up to 250 μl (P < 0.05).Left ventricular free wall capillary density was significantly decreased in both epicardium (18%; P <0.05) and endocardium (11%; P < 0.05) despite preserved coronary flow. Western blot analysis revealed no change to the expression of SERCA2a or nNOS but immuno-detectable eNOS protein was significantly decreased (P < 0.001) in cardiac tissue following chronic hypoxia in utero. Conclusion: These data offer potential mechanisms for poor recovery following ischaemia, including decreased coronary flow reserve and impaired angiogenesis with subsequent detrimental effects of post-natal cardiac performance

The rocky shore biology of Bantry Bay: a re-survey

A survey of the distribution and abundance of intertidal rocky shore animals and plants of Bantry Bay was carried out in 1970 and 1971 by G. B. Crapp and published in 1973. A re-survey was carried out during 1975 and early 1976 and a number of changes were noted. In an attempt to explain these the possible effects of changing weather conditions, the occurrence of oil spillages and the use of dispersants were examined. In most cases, the changes were not obviously attributable to visible oil pollution and seem more likely to result from a variety of natural factors. The re-survey highlighted a number of problems associated with this type of biological monitoring. The problems are discussed and some alternative approaches suggested

Three-Dimensional Object Registration Using Wavelet Features

Recent developments in shape-based modeling and data acquisition have brought three-dimensional models to the forefront of computer graphics and visualization research. New data acquisition methods are producing large numbers of models in a variety of fields. Three-dimensional registration (alignment) is key to the useful application of such models in areas from automated surface inspection to cancer detection and surgery. The algorithms developed in this research accomplish automatic registration of three-dimensional voxelized models. We employ features in a wavelet transform domain to accomplish registration. The features are extracted in a multi-resolutional format, thus delineating features at various scales for robust and rapid matching. Registration is achieved by using a voting scheme to select peaks in sets of rotation quaternions, then separately identifying translation. The method is robust to occlusion, clutter, and noise. The efficacy of the algorithm is demonstrated through examples from solid modeling and medical imaging applications

Microstructured catalytic hollow fiber reactor for methane steam reforming

Microstructured alumina hollow fibers, which contain a plurality of radial microchannels with significant openings on the inner surface, have been fabricated in this study and used to develop an efficient catalytic hollow fiber reactor. Apart from low mass-transfer resistance, a unique structure of this type facilitates the incorporation of Ni-based catalysts, which can be with or without the aged secondary support, SBA-15. In contrast to a fixed bed reactor, the catalytic hollow fiber reactor shows similar methane conversion, with a gas hourly space velocity that is approximately 6.5 times higher, a significantly greater CO2 selectivity, and better productivity rates. These results demonstrate the advantages of dispersing the catalyst inside the microstructured hollow fiber as well as the potential to reduce the required quantity of catalyst

Implementing EM and Viterbi algorithms for Hidden Markov Model in linear memory

<p>Abstract</p> <p>Background</p> <p>The Baum-Welch learning procedure for Hidden Markov Models (HMMs) provides a powerful tool for tailoring HMM topologies to data for use in knowledge discovery and clustering. A linear memory procedure recently proposed by <it>Miklós, I. and Meyer, I.M. </it>describes a memory sparse version of the Baum-Welch algorithm with modifications to the original probabilistic table topologies to make memory use independent of sequence length (and linearly dependent on state number). The original description of the technique has some errors that we amend. We then compare the corrected implementation on a variety of data sets with conventional and checkpointing implementations.</p> <p>Results</p> <p>We provide a correct recurrence relation for the emission parameter estimate and extend it to parameter estimates of the Normal distribution. To accelerate estimation of the prior state probabilities, and decrease memory use, we reverse the originally proposed forward sweep. We describe different scaling strategies necessary in all real implementations of the algorithm to prevent underflow. In this paper we also describe our approach to a linear memory implementation of the Viterbi decoding algorithm (with linearity in the sequence length, while memory use is approximately independent of state number). We demonstrate the use of the linear memory implementation on an extended Duration Hidden Markov Model (DHMM) and on an HMM with a spike detection topology. Comparing the various implementations of the Baum-Welch procedure we find that the checkpointing algorithm produces the best overall tradeoff between memory use and speed. In cases where sequence length is very large (for Baum-Welch), or state number is very large (for Viterbi), the linear memory methods outlined may offer some utility.</p> <p>Conclusion</p> <p>Our performance-optimized Java implementations of Baum-Welch algorithm are available at <url>http://logos.cs.uno.edu/~achurban</url>. The described method and implementations will aid sequence alignment, gene structure prediction, HMM profile training, nanopore ionic flow blockades analysis and many other domains that require efficient HMM training with EM.</p