Kinetics and mechanism of ?-caprolactone and l,l-lactide polymerization coinitiated with zinc octoate or aluminum acetylacetonate: The next proofs for the general alkoxide mechanism and synthetic applications

Following our previous papers on mechanism of cyclic esters' polymerization coinitiated by tin(II) octoate [tin(II) bis-(2-ethylhexanoate), (Sn(Oct)₂)] in the presence of either the low molar mass coinitiator (an alcohol, hydroxy acid, or H₂O) or a macromolecule fitted with a hydroxy end group (ROH), the present work deals with ?-caprolactone (CL) and l,l-lactide (LA) polymerizations coinitiated with zinc octoate (Zn(Oct)₂) or aluminum acetylacetonate (Al(Acac)₃). A series of kinetic measurements revealed that similarly as in the Sn(Oct)₂ coinitiated process, these polymerizations proceed by simple monomer insertion into the …Mt-OR bond, reversibly formed in the reaction -Mt-L + ROH ? …-Mt-OR + LH (where Mt = Sn, Zn or Al; L = Oct or Acac), taking place throughout the whole polymerization process. MtL_n itself does not play an active role in the polymerization. Applicability of the commercially available Zn(Oct)₂ or Al(Acac)₃ for the aliphatic polyester (10³ ≤ M_n ≤ 4 × 10⁵) synthesis is also discussed.     

What localizes beneath: A metric multisensor localization and mapping system for autonomous underground mining vehicles

Robustly and accurately localizing vehicles in underground mines is particularly challenging due to the unavailability of GPS, variable and often poor lighting conditions, visual aliasing in long tunnels, and airborne dust and water. In this paper, we present a novel, infrastructure‐less, multisensor localization method for robust autonomous operation within underground mines. The proposed method integrates with existing mine site commissioning and operation procedures and includes both an offline map‐building process and an online localization algorithm. The approach combines the strengths of visual‐based place recognition, LIDAR‐based localization, and odometry in a particle filter fusion process. We provide an extensive experimental validation using new large data sets acquired in two operational Australian underground hard‐rock mines (including a 600m‐deep multilevel mine with approximately 33 km of mapping data and 7 km of vehicle localization) by actual mining vehicles during production operations. We demonstrate a significant increase in localization accuracy over prior state‐of‐the‐art SLAM research systems and real‐time operation, with processing times in the order of 10 Hz. We present results showing a mean error of 0.68 m from the Queensland Mine data set and 1.32 m from the New South Wales Mine data set and at least 86% reduction in error compared with prior state of the art. We also analyze the impact of the particle filter parameters with respect to localization accuracy. Together this study represents a new approach to positioning systems for currently deployed autonomous vehicles within underground mine environments.     

Kinetic analysis of cellular internalization and expulsion of unstructured D-chirality cell penetrating peptides

Most cell penetrating peptides (CPPs) are unstructured and susceptible to proteolytic degradation. One alternative is to incorporate D-chirality amino acids into unstructured CPPs to allow for enhanced uptake and intracellular stability. This work investigates CPP internalization using a series of time, concentration, temperature, and energy dependent studies, resulting in a three-fold increase in uptake and 50-fold increase in stability of D-chirality peptides over L-chirality counterparts. CPP internalization occurred via a combination of direct penetration and endocytosis, with a percentage of internalized CPP expelling from cells in a time-dependent manner. Mechanistic studies identified that cells exported the intact internalized D-chirality CPPs via an exocytosis independent pathway, analogous to a direct penetration method out of the cells. These findings highlight the potential of a D-chirality CPP as bio-vector in therapeutic and biosensing applications, but also identify a new expulsion method suggesting a relationship between uptake kinetics, intracellular stability, and export kinetics.     

Modeling drop breakage using the full energy spectrum and a specific realization of turbulence anisotropy

The assumption of homogeneous isotropic turbulence when modeling drop breakage in industrially relevant geometries is questionable. We describe the development of an anisotropic breakage model, where the anisotropy is introduced via the inclusion of a perturbed turbulence spectrum. The selection of the perturbed spectrum is itself motivated by our previous large-eddy simulations of high-pressure homogenizers. The model redistributes energy from small to large scales, and assumes that the anisotropic part of the Reynolds stresses is confined to the energy-containing range. The second-order structure function arising from the perturbed spectrum is used in the standard framework of Coulaloglou and Tavlarides to calculate breakage frequency. While the base model exhibits non-monotonic behavior (by predicting a maximum value for a certain drop size), the effect of anisotropy is shown to increase breakage frequency in length scales larger than this peak, thereby reducing non-monotonicity. This effect is more pronounced for small turbulence Reynolds numbers.     

Host Plant Constancy in Ovipositing Manduca sexta

Journal of Chemical Ecology - Many pollinating insects exhibit flower constancy, i.e. they target flower species they have already experienced and fed from. While the insects might profit from...     

The mechanical milling of Al/TiO2 composite powders

The processing of Al/TiO₂ composite powders produced by high-energy mechanical milling leads to production of a range of valuable, titanium-based materials. They include Ti(Al,O)/Al₂O₃ and Ti_xAl_y(O)/Al₂O₃ composite powders, bulk composites and Ti₃Al/TiAl alloy powders, and corresponding bulk materials. The strength of the Ti(Al,O)/Al₂O₃ and Ti_xAl_y(O)/Al₂O₃ composites is moderate, but their high-temperature oxidation resistance is exceptionally high, making the titanium-based composite powders favorable feedstock materials for protective coatings. The hardness of the Ti(Al,O)/Al₂O₃ and Ti₃Al(O)/Al₂O₃ composites is also very high (10–16 GPa). For more information, contact D.L. Zhang, University of Waikato, Waikato Centre for Advanced Materials, Department of Materials and Process Engineering, Private Bag 3105, Hamilton, New Zealand; 011-64-7-838-4783; fax 011-64-7-838-4835; e-mail d.zhang@waikato.ac.nz.     

Numerical simulation of non-linear chatter vibration in turning

In this paper, basic relationships and algorithms for numerical simulation of non-linear, self-excited vibrations in single degree-of-freedom cutting systems are presented. Non-linearities due to the tool leaving the cut, as well as interference between the cutting tool clearance face and cutting surface waviness, were taken into consideration. Examples of vibration simulation results are shown.     

An improved factor based approach to precedential constraint

In this article I argue for rule-based, non-monotonic theories of common law judicial reasoning and improve upon one such theory offered by Horty and Bench-Capon. The improvements reveal some of the interconnections between formal theories of judicial reasoning and traditional issues within jurisprudence regarding the notions of the ratio decidendi and obiter dicta. Though I do not purport to resolve the long-standing jurisprudential issues here, it is beneficial for theorists both of legal philosophy and formalizing legal reasoning to see where the two projects interact.     

Think,feel, bid: the impact of environmental conditions on the role of bidders’ cognitive and affective processes in auction bidding

Environmental conditions and the interplay of cognitive and affective processes both exert influences on bidding behavior. This paper brings the above together, considering how the (external) auction environment determines the impact of (internal) cognitive and affective processes on bidding behavior, assessed in comparison to the optimal bid. Two aspects of the auction environment were considered, namely auction dynamics (low: first-price sealed-bid auction, high: Dutch auction) and value uncertainty (low, high). In a laboratory experiment, we assess bidders’ cognitive workload and emotional arousal through physiological measurements. We find that higher auction dynamics increase the impact of emotional arousal on bid deviations, but not that of cognitive workload. Higher value uncertainty, conversely, increases the impact of cognitive workload on bid deviations, but not that of emotional arousal. Taken together, the auction environment is a critical factor in understanding the nature of the underlying decision process and its impact on bids.     

Constructive quantum scaling of unitary matrices

In this work, we present a method of decomposition of arbitrary unitary matrix \(U\in \mathbf {U}(2^k)\) into a product of single-qubit negator and controlled-\(\sqrt{\text{ NOT }}\) gates. Since the product results with negator matrix, which can be treated as complex analogue of bistochastic matrix, our method can be seen as complex analogue of Sinkhorn–Knopp algorithm, where diagonal matrices are replaced by adding and removing an one-qubit ancilla. The decomposition can be found constructively, and resulting circuit consists of \(O(4^k)\) entangling gates, which is proved to be optimal. An example of such transformation is presented.