Mechanochemical interconversion between discrete complexes and coordination networks - formal hydration/dehydration by LAG

Using a small planetary ball mill, liquid-assisted grinding (LAG) of metal salts or oxides (ZnO, CdO, CdCO3, Cu(OAc)(2)center dot H2O, Co(OAc)(2)center dot 4H(2)O, Mn(OAc)(2)center dot 4H(2)O, Ni(OAc)(2)center dot 4H(2)O, FeSO4 center dot 7H(2)O) with two equivalents of isonicotinic acid (HINA) and small amounts of water ( up to 5.6 molar equivalents) gave discrete aquo complexes trans-[M(INA)(2)(OH2)(4)] (M = Zn, Cd, Cu, Fe, Co, Ni, Mn) efficiently within 30 min. For M = Zn, Cd and Cu these complexes readily undergo reversible formal dehydration to the extended network structures [M(INA)(2)] (M = Zn, Cu) or [Cd(INA)(2)(OH2)]center dot DMF by further LAG with non-aqueous liquids such as methanol or DMF. Overall, the mechanochemical dehydrations are more effective than heating or immersion in bulk solvents. The work demonstrates a two-step mechanochemical synthesis of coordination networks via discrete aquo complexes which may be preferable to single step reactions or grinding-annealing procedures in some cases. For example, the two step method was the only way to prepare [Cd(INA)(2)(OH2)]center dot DMF mechanochemically and the porous network Cu(INA)(2) could not be obtained from the aquo complex by heating.

Moving with Beats and Loops: The Structure of Auditory Events and Sensorimotor Timing

Traditionally, audio-motor timing processes have been understood as motor output from an internal clock, the speed of which is set by heard sound pulses. In contrast, this paper proposes a more ecologically-grounded approach, arguing that audio-motor processes are better characterized as performed actions on the perceived structure of auditory events. This position is explored in the context of auditory sensorimotor synchronization and continuation timing. Empirical research shows that the structure of sounds as auditory events can lead to marked differences in movement timing performance. The nature of these effects is discussed in the context of perceived action-relevance of auditory event structure. It is proposed that different forms of sound invite or support different patterns of sensorimotor timing. Hence, the temporal information in looped auditory signals is more than just the interval durations between onsets: all metronomes are not created equal. The potential implications for auditory guides in motor performance enhancement are also described.

A Coordination and Ligand Replacement Based Three-Input Colorimetric Logic Gate Sensing Platform for Melamine, Mercury Ions, and Cysteine

Discrimination of different species in various target scopes within a single sensing platform can provide many advantages such as simplicity, rapidness, and cost effectiveness. Here we design a three-input colorimetric logic gate based on the aggregation and anti-aggregation of gold nanoparticles (Au NPs) for the sensing of melamine, cysteine, and Hg2+. The concept takes advantages of the highly specific coordination and ligand replacement reactions between melamine, cysteine, Hg2+, and Au NPs. Different outputs are obtained with the combinational inputs in the logic gates, which can serve as a reference to discriminate different analytes within a single sensing platform. Furthermore, besides the intrinsic sensitivity and selectivity of Au NPs to melamine-like compounds, the “INH” gates of melamine/cysteine and melamine/Hg2+ in this logic system can be employed for sensitive and selective detections of cysteine and Hg2+, respectively.

Liquid coordination complexes: a new class of Lewis acids as safer alternatives to BF3 in synthesis of polyalphaolefins

Liquid coordination complexes (LCCs) are a new class of liquid Lewis acids, prepared by combining an excess of a metal halide (e.g. GaCl3) with a basic donor molecule (e.g. amides, amines or phosphines). LCCs were used to catalyse oligomerisation of 1-decene to polyalphaolefins (PAOs). Molecular weight distribution and physical properties of the produced oils were compliant with those required for low viscosity synthetic (Group IV) lubricant base oils. Kinematic viscosities at 100 °C of ca. 4 or 6 cSt were obtained, along with viscosity indexes above 120 and pour points below −57 °C. In industry, to achieve similar properties, BF3 gas is used as a catalyst. LCCs are proposed as a safer and economically attractive alternative to BF3 gas for the production of polyalphaolefins.

Friedel–Crafts alkylation catalysed by GaCl3-based liquid coordination complexes

Friedel–Crafts alkylation of benzene with 1-decene was catalysed by a new family of liquid Lewis acids: liquid coordination complexes (LCCs). LCCs are prepared by mixing a metal halide (e.g. GaCl3) and a donor molecule (e.g. N,N-dimethylacetamide, urea, or trioctylphosphine oxide), with the metal halide typically used in excess. This leads to the formation of a eutectic mixture comprised of charged and neutral species in a dynamic equilibrium. GaCl3-based LCCs were used in catalytic amounts, giving high reaction rates under ambient conditions, with selectivities to 2-phenyldecane superior to those previously reported in the literature. The influence of reaction conditions and catalyst composition on the reaction rate and selectivity was investigated. Optimised reaction conditions were suggested. This exploratory study offers promise with regard to the development of safer, LCC-based alternatives to HF in industrial alkylations.

The 4Cs of Disaster Partnering: Communication, Coordination, Cooperation and Collaboration

Public, nonprofit and private organisations respond to large-scale disasters domestically and overseas. Critics of these assistance efforts, as well as those involved, often cite poor interorganisational partnering as an obstacle to successful disaster response. Observers frequently call for ‘more’ and ‘better’ partnering. We found important qualitative distinctions existed within partnering behaviours. We identified four different types of interorganisational partnering activities often referred to interchangeably: communication, cooperation, coordination and collaboration—the Four Cs. We derived definitions of the Four Cs from the partnering literature. We then tested them in a case study of the response to the 2010 Haiti earthquake. We suggest that the Four Cs are distinct activities, that organisations are typically strong or weak in one or more for various reasons, and that the four terms represent a continuum of increased interorganisational embeddedness in partnering activities.

International Coordination in Cross-Border Bank Bail-ins: Problems and Prospects

Bail-in is quickly becoming a predominant approach to banking resolution. The EU Bank Recovery Resolution Directive and the US Federal Deposit Insurance Corporation’s single point of entry strategy envisage creditors’ recapitalisations
to resolve a failing financial institution. However, this legislation focuses on the domestic aspects of bail-in, leaving the question of how it is applied
to a cross-border banking group open. Cross-border banking resolution has been historically subject to coordination failures, which have resulted in disorderly resolutions with dangerous systemic effects. The goal of this article is to assess whether bail-in is subject to the same coordination problems that affect other resolution tools, and to discuss the logic of international legal cooperation in bail-in policies. We demonstrate that, in spite of the evident benefit in terms of fiscal sustainability, bail-in suffers from complex coordination problems which, if not addressed, might lead to regulatory arbitrage and lengthy court battles, and, ultimately, may disrupt resolutions. We argue that only a binding legal regime can address those problems. In doing so, we discuss the recent Financial Stability
Board’s proposal on cross-border recognition of resolution action, and the role of international law in promoting cooperation in banking resolution.

Global Systemic Risk and International Regulatory Coordination: Squaring Sovereignty and Financial Stability

In recent years much attention has been given to systemic risk and maintaining financial stability. Much of the focus, rightly, has been on market failures and the role of regulation in addressing them. This article looks at the role of domestic policies and government actions as sources of global instability. The global financial system is built upon global markets controlled by national financial and macroeconomic policies. In this context, regulatory asymmetries, diverging policy preferences, and government failures add a further dimension to global systemic risk not present at the national level.
Systemic risk is a result of the interplay between two independent variables: an underlying trigger event, in this analysis a domestic policy measure, and a transmission channel. The solution to systemic risk requires tackling one of these variables. In a domestic setting, the centralization of regulatory power into one single authority makes it easier to balance the delicate equilibrium between enhancing efficiency and reducing instability. However, in a global financial system in which national financial policies serve to maximize economic welfare, regulators will be confronted with difficult policy and legal tradeoffs.
We investigate the role that financial regulation plays in addressing domestic policy failures and in controlling the danger of global financial interdependence. To do so we analyse global financial interconnectedness, and explain its role in transmitting instability; we investigate the political economy dynamics at the origin of regulatory asymmetries and government failures; and we discuss the limits of regulation.