Labelling Studies to Determine Product Formation from Reactions of CO and Hydrogen Catalysed by Ru Clusters and Rh Complexes

Reaction of CO with hydrogen in the presence of [Ru₃(CO)₁₂], KI and N-methylpyrrolidone produces small amounts of methanol under mild conditions. Using D₂ the methanol is CD₃OD confirming that it is a product of CO hydrogenation. In the presence of added H₂O, CH _x D_1-y OH/D (y=0–3) are produced. Carrying out the same reaction in the presence of MeI water and RhCl₃·xH₂O (x=3–4) produces ethanoic acid in a slow reaction which continues for at least 64 h. The effects of different reaction parameters are discussed and labelling using ¹³CH₃I shows that some of the ethanoic acid originates from sources other than MeI whilst labelling with D₂, CD₃I, and/or D₂O suggest that some originates from CO and H₂. Electrospray mass spectrometry and high pressure infra-red spectroscopic studies show that the main species present in catalytic solutions are [HRu₃(CO)₁₁]⁻, [HRu₄(CO)₁₃]⁻ and [Ru(CO)₃I₃]⁻ for methanol carbonylation, [Ru(CO)₃I₃]⁻ and [RhI₂(CO)₂]⁻ for ethanoic acid production. A reaction carried out in the absence of [Ru₃(CO)₁₂] gave similar results to a reaction in which it was added, suggesting that the entire process may be catalysed by rhodium complexes alone. Electronic Supplementary Material  Supplementary material for this article is available at and is accessible for authorized users.

Reference classes and relational learning

This paper studies the connections between relational probabilistic models and reference classes, with specific focus on the ability of these models to generate the correct answers to probabilistic queries. We distinguish between relational models that represent only observed relations and those which additionally represent latent properties of individuals. We show how both types of relational models can be understood in terms of reference classes, and that learning such models correspond to different ways of identifying reference classes. Rather than examining the impact of philosophical issues associated with reference classes on relational learning, we directly assess whether relational models can represent the correct probabilities of a simple generative process for relational data. We show that models with only observed properties and relations can only represent the correct probabilities under restrictive conditions, whilst models that also represent latent properties avoids such restrictions. As such, methods for acquiring latent-property models are an attractive alternatives to traditional ways of identifying reference classes. Our experiments on synthetic as well as real-world domains support the analysis, demonstrating that models with latent relations are significantly more accurate than those without latent relations.     

THz optical pulses from a coupled-cavity quantum-dot laser

Optical pulses are generated from a coupled-cavity quantum-dot (QD) laser consisting of a short QD-waveguide Fabry–Perot (F–P) cavity and three long external fiber Bragg grating (FBG) cavities. When the laser is biased at low operation current, the feedback from the external cavities dominates and laser pulses have a 1.01 THz repetition rate, determined by the equal frequency difference of the three FBGs. We are thus able to decouple the repetition rate of a mode-locked laser from the cavity length. With much higher bias current, the QD F–P cavity dominates and the repetition rate is switched to 43.8 GHz, defined by the length of the F–P cavity.     

Fusion around the barrier for 7Li+12C

Fusion cross-sections for the ⁷Li + ¹²C reaction have been measured at energies above the Coulomb barrier by the direct detection of evaporation residues. The heavy evaporation residues with energies below 3 MeV could not be separated out from the α-particles in the spectrum and hence their contribution was estimated using statistical model calculations. The present work indicates that suppression of fusion cross-sections due to the breakup of ⁷Li may not be significant for ⁷Li + ¹²C reaction at energies around the barrier.     

Identification of cloud phase from PICASSO-CENA lidar depolarization: a multiple scattering sensitivity study

A fast Monte Carlo simulation scheme is developed to assess the impact of multiple scattering on space-based lidar backscattering depolarization measurements. The specific application of our methodology is to determine cloud thermodynamic phase from satellite-based lidar depolarization measurements. Model results indicate that multiple scattering significantly depolarizes backscatter return from water clouds. Multiple scattering depolarization is less significant for non-spherical particles. There are sharp contrasts in the depolarization profile between a layer of spherical particles and a layer of non-spherical particles. Although it is not as obvious as ground-based lidar observations, it is likely that we can identify cloud phase not only for a uniform cloud layer, but also for overlapping cloud layers where one layer contains ice and the other water droplets.     

Balancing Ligand Flexibility versus Rigidity for the Stepwise Self-Assembly of M12L24 via M6L12 Metal–Organic Cages

Non-covalent interactions are important for directing protein folding across multiple intermediates and can even provide access to multiple stable structures with different properties and functions. Herein, we describe an approach for mimicking this behavior in the self-assembly of metal–organic cages. Two ligands, the bend angles of which are controlled by non-covalent interactions and one ligand lacking the above-mentioned interactions, were synthesized and used for self-assembly with Pd²⁺. As these weak interactions are easily broken, the bend angles have a controlled flexibility giving access to M₂( L1 )₄, M₆( L2 )₁₂, and M₁₂( L2 )₂₄ cages. By controlling the self-assembly conditions this process can be directed in a stepwise fashion. Additionally, the multiple endohedral hydrogen-bonding sites on the ligand were found to play a role in the binding and discrimination of neutral guests.     

Concerted Nucleophilic Aromatic Substitution Reactions

Recent developments in experimental and computational chemistry have identified a rapidly growing class of nucleophilic aromatic substitutions that proceed by concerted (cS_NAr) rather than classical, two‐step, S_NAr mechanisms. Whereas traditional S_NAr reactions require substantial activation of the aromatic ring by electron‐withdrawing substituents, such activating groups are not mandatory in the concerted pathways.     

Correlation Analysis of the Alternating Step Generator

The alternating step generator is a well-known keystream generator consisting of two stop/go clocked LFSRs, LFSR₁ and LFSR₂, whose clocks are controlled by another LFSR, LFSR₃, which is clocked regularly. A probabilistic analysis of this generator is conducted which shows that the posterior probabilites of individual bits of the first derivatives of the regularly clocked LFSR₁ and LFSR₂ sequences, when conditioned on a given segment of the first derivative of the keystream sequence, can be computed efficiently in a number of probabilistic models of interest. The expected values of these probabilities, for a random keystream sequence, are derived by an approximate theoretical analysis and are also verified by systematic computer experiments. It is pointed out that these posterior probabilities can be enhanced in a resynchronization scenario and thus used for a low-complexity fast correlation attack on the two LFSRs. More generally, it is argued that even without resynchronization these probabilities may be significantly different from one half for fast correlation attacks based on iterative decoding algorithms to be successful, although with incresead complexity. A related method for computing the posterior probabilities of individual bits of the LFSR₃ sequence, when conditioned on both the keystream sequence and the LFSR₁ and LFSR₂ sequences, is also developed. As these posterior probabilities are much more different from one half, they can be used for a low-complexity fast correlation attack on LFSR₃, provided that the initial states of LFSR₁ and LFSR₂ are previously reconstructed.     

An Improved Upper Bound for Leo Moser's Worm Problem

Abstract. A worm ω is a continuous rectifiable arc of unit length in the Cartesian plane. Let W denote the class of all worms. A planar region C is called a cover for W if it contains a copy of every worm in W . That is, C will cover or contain any member ω of W after an appropriate translation and/ or rotation of ω is completed (no reflections). The open problem of determining a cover C of smallest area is attributed to Leo Moser [7], [8]. This paper reduces the smallest known upper bound for this area from 0.275237 [10] to 0.260437.